Spintronics

THIN FILM OXIDES AND HETEROSTRUCTURES FOR SPINTRONICS
Sourav Chattopadhyay
THIN FILM OXIDES AND HETEROSTRUCTURES FOR SPINTRONICS
Thesis submitted to the Indian Institute of Technology, Kharagpur For award of the degree
of
Doctor of Philosophy
by
Under the guidance of Dr. T. K. Nath & Dr. P. Banerji
DEPARTMENT OF PHYSICS AND METEOROLOGY INDIAN INSTITUTE OF TECHNOLOGY KHARAGPUR MAY 2011
2011 Sourav Chattopadhyay. All rights reserved.
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APPROVAL OF THE VIVA-VOCE BOARD
Certified that the thesis entitled THIN FILM OXIDES AND HETEROSTRUCTURES FOR SPINTRONICS submitted by SOURAV CHATTOAPDHYAY to the Indian Institute of Technology, Kharagpur, for the award of the degree Doctor of Philosophy has been accepted by the external examiners and that the student has successfully defended the thesis in the viva-voce examination held today.
(Member of the DSC)
(Member of the DSC)
(Member of the DSC)
(Supervisor)
(Supervisor)
(External Examiner)
(Chairman)
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CERTIFICATE
This is to certify that the thesis entitled Thin film oxides and heterostructures for spintronics, submitted by Mr. Sourav Chattopadhyay to Indian Institute of Technology, Kharagpur, is a record of bona fide research work under my supervision and is worthy of consideration for the award of the degree of Doctor of Philosophy of the Institute.
__________________________ Superviser
______________________ Superviser
Date:
Date:
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Acknowledgements
I wish to thank Dr. T. K. Nath (supervisor) for introducing the research field and discussion about my research work. He has not only supervised my work but was also a source of constant inspiration. I find him approachable, communicative, open to ideas and suggestions, and very encouraging. He has prepared the base of my understanding regarding the experimental techniques and findings. I heartily acknowledge his friendly introduction to every field including both official and academic. Above all, I acknowledge him for the independence, presented by him, during my research work that enable me to learn the skill of work self sufficiently to certain extent. I wish to thank Dr. Pallab Banerji (co-supervisor) also. It is a pleasure to thank the members of my Doctoral Scrutiny Committee (DSC), Dr. C Jacob, Dr. A Dhar and Dr. S. Das for their constant encouragement. I would like to thank present Head of the Department, Prof. B. K. Mathur and former Head of the department, Prof. R. N P. Choudhary for providing me the research facility. I wish to express my deep appreciation to Prof. G. A. Gehring, Prof. A. M. Fox, Dr. A. J. Behan, Dr. J. R. Neal, D. Score and Q. Feng, University of Sheffield, UK, for their kind help in arranging several measurements and encouragement and suggestions about my research work. I would like to thank Indian Nanoelectronic Users Program, IIT Bombay, for enormous helping for deposition and growth of device structures in clean room environment and giving some measurement facilities. I also would also like to thank all of my lab mates (Sourav Kundu, Samir Kumar Giri, Pampa Rani Mandal, Proloy Taran Das, Jaganandha Panda and Dhiren Kumar Prodhan) and seniors (Sanjay Kumar Mandal and Puja De) for their continuous help to carry out the research work. I would like to acknowledge Central Research Facility, FIST facility, IIT Kharagpur for different measurements and DST-NSTI (No. SR/S5/NM-04/2005), India for use of PLD and FE-SEM experimental facility. I would like to acknowledge Advance Technology Development Center (ATDC) for allowing me to measure thickness using ellipsometry.
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I also would like to thank Mr. Mohanlal Ghosh (Technician, MMM lab) for making the pressure contact set ups and other electrical measurement set ups and Mr. Kisto Mallik (Technician, Hall lab) for helping to carry out different kind of works. I would like to thank DST, India for financial support to buy several measurement equipments through Project No. - IR/S2/PU-04/2006. I am thankful to Indian Institute of Technology Kharagpur for financial support during the course of this study.
DECLARATION
I certify that a. The work contained in the thesis is original and has been done by myself under the general supervision of my supervisor(s). b. The work has not been submitted to any other Institute for any degree or diploma. c. I have followed the guidelines provided by the Institute in writing the thesis. d. I have conformed to the norms and guidelines given in the Ethical Code of Conduct of the Institute. e. Whenever I have used materials (data, theoretical analysis, and text) from other sources, I have given due credit to them by citing them in the text of the thesis and giving their details in the references. f. Whenever I have quoted written materials from other sources, I have put them under quotation marks and given due credit to the sources by citing them and giving required details in the references.
Signature of the Student
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Curriculum Vitae
Name Date of birth : Sourav Chattopadhyay : 31st day of December 1979
ACADEMIC CREDENTIALS Degree M. Tech M. Sc. B. Sc. University/ Institute Jadavpur University University of Calcutta University of Calcutta Subject Nano Science and Nano Technology Electronic Science Electronics Year of passing 2006 2003 2001
ACADEMIC AWARDS Award of Institute Research Scholarship from Indian Institute of Technology Kharagpur, India on 21st Aug, 2006.
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LIST OF PUBLICATIONS A. Research Papers Published in International Journals 1. Electrical and magnetoelectronic properties of La0.7Sr0.3MnO3/SiO2/p-Si heterostructure for spintronics application, S. Chattopadhyay, P. Dey and T. K. Nath, Current Applied Physicsdoi:10.1016/j.cap.2011.02.00 (accepted) 2. Enhancement of room temperature ferromagnetism of Fe-doped ZnO epitaxial thin films with Al co-doping, S. Chattopadhyay, T.K. Nath, A.J. Behan, J.R. Neal, D. Score, Q. Feng, A.M. Fox, G.A. Gehring, Journal of Magnetism and Magnetic Materials vol. 323, pp. 1033 (2011) 3. Temperature dependent carrier induced ferromagnetism in Zn(Fe)O and Zn(FeAl)O thin films by S. Chattopadhyay, T.K. Nath, A.J. Behan, J.R. Neal, D. Score, Q. Feng, A.M. Fox, G.A. Gehring Applied Surface Science vol. 257, pp. 381 (2010) 4. Room temperature enhanced positive magnetoresistance in Pt and carrier induced Zn(Fe)O and Zn(Fe,Al)O dilute magnetic semiconductor junction) by S. Chattopadhyay, T. K. Nath Journal of Applied Physics vol. 108, pp. 083904 (2010). Selected for Virtual Journal of Nanoscale Science & Technology for the October 25, 2010. 5. Electrical properties of Pulsed Laser Deposited ZnO thin films by Sourav Chattopadhyay and Tapan Kumar Nath Advanced Materials Research Vol. 67 , pp. 121 (2009) 6. Electrical characterization of p-ZnO/p-Si heterojunction by S. Majumdar, S. Chattopadhyay and P. Banerji Applied surface science vol. 255, pp. 6141 (2009) 7. Tunneling current at the interface of silicon and silicon dioxide partly embedded with silicon nanocrystals in metal oxide semiconductor structures by G. Chakraborty, S. Chattopadhyay, C. K. Sarkar and C. Pramanik Journal of Applied Physics vol. 101, pp. 24315 (2007) B. Research Papers communicated in International Journals 1. On investigation of origin of junction magnetoresistance in La0.7Sr0.3MnO3/SiO2/p-Si heterostructures, S. Chattopadhyay and T. K. Nath, Journal of Physics D:Applied Physics 2. Enhanced temperature dependent junction magnetoresistance in the heterojunctions with La0.7Sr0.3MnO3 and iron doped ZnO carrier induced dilute magnetic semiconductors by S. Chattopadhyay, J. Panda, T. K. Nath, Journal of Applied Physics. 3. Extraordinary Hall effect, electronic-and Magneto-transport behavior of carrier induced dilute magnetic Zn(Fe)O and Zn(Fe,Al)O thin film by S. Chattopadhyay and T. K. Nath, Physical Review B.
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4. Low-temperature resistivity minima in colossal magnetoresistive La0.7Sr0.3MnO3 thin film: A quantum interference effect by S. Chattopadhyay and T. K. Nath, Solid state communications. B. Papers presented in Conferences/Symposia
1.
2.
3.
4.
5.
6. 7. 8. 9.
10.
Temperature dependent anomalous Hall Effects in DMS Zn(Fe,Al)O epitaxial thin film by S. Chattopadhyay and T. K. Nath, 55th DAE Solid State Physics Symposium 2010 (2010). Temperature dependent junction magnetoresistance behavior of LSMO/Zn(Fe,Al)O heterojunction for spintronics by J. Panda, S. Chattopadhyay and T. K. Nath, 55th DAE Solid State Physics Symposium 2010 (2010). J.Panda,S.Chatopadhyay,T.K. Nath,Temperature dependent junction magnetoresistance behavior of the Ni nanoparticle in TiN with p-Si heterojunction,ICONQUEST, NPL, 2010. Investigation on La0.7Ca0.3MnO3/SiO2/n-Si and La0.7Sr0.3MnO3/SiO2/p-Si MOS like heterostructures for Spintronics by S. Chattopadhyay, S. K. Giri and T. K. Nath, International Conference on Fundamental & Applications of Nanoscience and Technology (ICFANT) (2010). Magnetoresistive behavior of epitaxial Zinc oxide thin films doped with iron by S. Chattopadhyay, T. K. Nath International Conference on Magnetic Materials (ICMM2010) (2010) Room temperature magnetic sensors with Zn(FeAl)O by Pt Schottky contact by S. Chattopadhyay, T. K. Nath 54th DAE Solid State Physics Symposium (2009) Electrical properties of Zn/La0.7Sr0.3MnO3/Pt Schottky device for spintronics by S. Chattopadhyay, T. K. Nath Condensed Matter Days (CMDAYS09) (2009) Electrical properties of La0.7Sr0.3MnO3/SiO2/Si MOS structure by S. Chattopadhyay, P. Dey, T. K. Nath 53rd DAE Solid State Physics Symposium (2008) Electrical properties of Pulsed Laser Deposited ZnO thin films by S. Chattopadhyay, T. K. Nath International Conference on Nanomaterials and Devices Processes and applications (2008) I-V characteristics of La0.7Sr0.3MnO3/SiO2/Si MOS structure by S. Chattopadhyay, P. Dey, T. K. Nath National Seminar on Advanced Nanomaterials and its Applications (2008)
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Abstract
This work contains the study of the properties of two kinds of spintronics materials, namely, dilute magnetic semiconductor (DMS) and colossal magnetoresistive (CMR) half metallic ferromagnetic manganites with very high spin polarization. The DMS materials, namely, wide band gap Zn(Fe)O and Zn(Fe,Al)O epitaxial films have been chosen with different Fe concentrations (5, 7 and 10%). The structural (XRD, FESEM, TEM, AFM etc), magnetic (M(H,T), Anomalous Hall Effect), Optical (UV-VIS absorption spectroscopy down to 5 K), electrical (resistivity, Hall, Magnetoresistance etc.) properties have been investigated explicitly and the room temperature carrier induced ferromagnetic behavior have been observed in these DMS systems. The junction properties of Zn(Fe)O and Zn(Fe,Al)O with Pt have been studied and all the junction shows positive junction magnetoresistance and this behavior is strictly found to depend on the magnetic moments of the DMS materials. It can be well described using spin injection theory. Highly spin polarized, half metallic, ferromagnetic CMR manganites, La0.7Sr0.3MnO3 thin films have been chosen as a potential spintronic electrode materials and its structural, magnetic, electronic- and magneto-transport properties have been investigated in details. Temperature dependent electrical and magneto-transport studies have been carried out on those films and possible transport models have been examined. The La0.7Sr0.3MnO3/Si/SiO2 MOS like junctions show positive junction magnetoresistance and it is temperature dependent where the dominating current transport mechanism through the junctions is found to be Frenkel-Poole type tunneling. The origin of positive MR has been explicitly investigated for these junctions. The junction properties of La0.7Sr0.3MnO3 with ZnO, Zn(Fe)O and Zn(Fe,Al)O heterojunctions have also been studied in details and the junctions show high positive to negative junction magnetoresistance depending on temperature and magnetic field. The appearance of junction magnetoresistance in all these Schottky and heterojunctions are best explained using standard spin injection theory. Keywords: Semiconductor Spintronics, Dilute magnetic semiconductors, magnetoresistive manganite, Spin injection, Magnetic heterojunction. Colossal
List of Symbols
A* A B D Ec Eg Ev H Ihkl Iohkl j j J J0 k m* M MRint MRspt n

Richardson constant Area of junction Magnetic flux Diffusivity Conduction band Band gap Valence band Magnetic field diffraction intensity of the crystal plane (hkl) of the deposited film diffraction intensity of the crystal plane (hkl) of the bulk standard samples Spin up current density Spin down current density Current density Reverse saturation current density Boltzmann constant Effective mass Magnetization Intrinsic magnetoresistance Spin polarized tunneling magnetoresistance Spin up electron concentration Spin down electron concentarion Acceptor ion concentration Carrier Concentration Donor ion concentration Intrinsic carrier concentartions Spin polarization Current spin polarization Electronic charge Majority spin up electron Minority spin down electron Normal Hall co-efficient Anti-parallel resistance
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n NA nc ND ni P PjF(0) q RFM RFM R0 RAP
rc rF rFN rN RP Rs RS S T* T TM TP V V0 vd 0 s D F(0) n(0) B dia para
Contact resistance Ferromagnetic resistence Effective equilibrium resistance Non-ferromagnetic resistance Parallel resistance Anomalous Hall co-efficient Series resistance Spin Cross over temperature Temperature Low temperature minima Metal-insulator transition temperature Voltage Turn on voltage Drift velocity Total conductance Spin down conductance Spin up conductance Vacuum permittivity Dielectric constant Ideality factor Debye temperature Mobility Ferromagnetic sides of the junctions of junction Electrochemical potentials for non-magnetic side of junction Resistivity Conductivity Barrier height Diamagnetic susceptibility Paramagnetic susceptibility
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List of abbreviations
AFM AHE BMP CIP CMR CPP DE DI DMS DOS EDAX EVRH F/N FC FESEM FET FM F-N F-P FWHM GMR HRTEM HRXRD I-V JMR J-V MR MRAM MTJ NEXAFS NM OHE PLD RKKY RT RTFM Atomic force microscope Anomalous Hall Effect Bound magnetic polaron Current-In-Plane Colossal magnetoresistance Current Perpendicular-to-Plane Double-exchange De-ionized Dilute magnetic semiconductor Densities of states Energy dispersive X-ray Efros varieable range hopping Ferromagnet/nonmagnet interfaces Field cooled Field emission scanning electron microscopic Field effect transistor Ferromagnetic Fowler-Nordheim Frenkel-Poole Full width at half maximum Giant magnetoresistance High resolution transmission electron microscope High resolution X-ray diffraction Current-Voltage Junction magnetoresistance Current density-Voltage Magnetoresistance Magnetoresistive random-access-memory Magnetic tunnel junction Near edge x-ray absorption fine structure Nonmagnetic Ordinary Hall Effect Pulsed Laser Deviation Ruderman-Kittel-Kasuya-Yosida Room temperature Room temperature ferromagnetism xiii
SCLC SQUID TC 2DEG TM TMR UV-Vis VRH VTI XAS ZFC
Space Charge Limited current Superconducting quantum interference device Texture coefficients Two dimensional electron gas Transition metal Tunneling magnetoresistance Ultra violet-visible spectroscopy Variable range hopping Variable temperature insert X-ray absorption spectroscopy Zero field cooled
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Contents
Title page Certificate of Approval Certificate Acknowledgement Declaration Curriculum Vitae List of Publications Abstract List of Symbols List of Abbreviations Content Chapter 1: Introduction and Literature overview 1.1. Introduction 1.2. Literature Overview 1.2.1. Spintronic materials and devices 1.2.1.1. Giant magnetoresistance 1.2.1.2. Tunneling magnetoresistance 1.2.1.3. Colossal magnetoresistance 1.2.1.4. Dilute magnetic semiconductor 1.2.1.4.1. Origin of ferromagnetism in DMS 1.2.1.5. Organic spintronics 1.2.2. Spin transport mechanism 1.2.2.1. Spin drift and diffusion 1.2.2.2. Spin injection and spin tunneling 1.2.2.2.1. Spin injection and spin extraction 1.2.2.2.2. Silsbee-Johnson spin-charge coupling 1.2.2.2.3. Spin injection into semiconductors 1.2.3. Active magneto-electronic devices 1.2.3.1. Spin field effect transistor 1.2.3.2. Spin diodes 1.2.3.3. Spin bipolar transistor 1.3. Scope of the thesis References Chapter 2: Experimental equipments and techniques 2.1. Introduction 2.2. Brief description of used equipments i ii iii iv vi vii viii x xi xiii xv 1 2 2 2 4 7 11 13 16 17 17 18 19 20 21 23 23 24 25 26 27 33 33
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2.2.1. Thin film deposition unit: Pulsed Laser Deposition (PLD) 2.2.2. Characterization equipments 2.2.2.1. Structural and surface morphology 2.2.2.1.1. High resolution x-ray diffraction technique (HRXRD) 2.2.2.1.2. High resolution transmission electron microscopy (HRTEM) 2.2.2.1.3. High resolution field emission scanning electron microscopy (FE-SEM) 2.2.2.1.4. Energy dispersive x-ray analysis (EDAX) 2.2.2.1.5. X-ray absorption spectroscopy (XAS) 2.2.2.1.6. Atomic force microscope (AFM) 2.2.2.2. Optical characterizations 2.2.2.3. Magnetic characterizations 2.2.2.4. Electrical characterization 2.2.2.4.1. Cryogen free high magnetic field (Superconducting magnet) VTI system 2.2.2.4.2. Electrical Measurement Instruments 2.2.2.4.3. Temperature readouts and controller Instruments 2.3. Brief description of experimental technique 2.3.1. Four probe resistivity measurements 2.3.2. Hall Effect measurements References Chapter 3: Properties of room temperature ferromagnetic Zn(Fe)O and Zn(Fe,Al)O epitaxial thin film 3.1. Introduction 3.2 Experimental procedures 3.2.1. Preparation of targets 3.2.2. Cleaning of substrates 3.2.3. Preparation of thin films 3.2.4. Characterization of thin films 3.3. Results and discussions 3.3.1 Chemical properties study 3.3.2. Structural properties 3.3.3. Surface morphology 3.3.4. Optical properties 3.3.5. Magnetic properties 3.3.5.1. Room temperature magnetic properties 3.3.5.2. Low temperature magnetic properties 3.3.5.3. Carrier dependent ferromagnetism properties 3.3.6. Electrical properties 3.3.6.1. Electrical transport properties xvi
33 34 34 34 35 35 35 36 37 37 38 39 39 40 40 40 41 42 43
44 45 45 46 46 46 47 47 47 49 50 51 51 53 59 63 64
3.3.6.2. Hall Effect study 3.3.6.2.1. Ordinary Hall Effect 3.3.6.2.2. Anomalous Hall Effect 3.3.6.3. Magnetoresistance properties 3.4. Summary References Chapter 4: Junction magnetoresistance of Pt/Zn(Fe)O and Pt/Zn(Fe,Al)O metaldilute magnetic semiconductorjunction 4.1. Introduction 4.2. Experimental procedure 4.3. Results and discussion 4.3.1. Structural properties 4.3.2. Magnetic properties 4.3.3 Current-voltage characteristics without applied magnetic field 4.3.4. Current-voltage characteristics with applied magnetic field 4.3.5. Junction magneto-resistance properties 4.4. Summary References Chapter 5: Structural, magnetic and electrical behavior of La0.7Sr0.3MnO3 thin films on p-Si 5.1. Introduction 5.2. Experimental procedure 5.2.1. Preparation of Targets 5.2.2. Cleaning of substrates 5.2.3. Deposition of La0.7Sr0.3MnO3 film 5.3. Results and discussion 5.3.1. Structural study 5.3.2. Surface morphology 5.3.3. Magnetic properties 5.3.4. Electrical transport properties 5.3.4.1. -T properties without applied magnetic field 5.3.4.2. -T properties with applied magnetic field 5.3.4.2.1. -T properties lower TM 5.3.4.2.2. -T properties above TM 5.4. Summary References Chapter 6: Junction magnetoresistance study in La0.7Sr0.3MnO3/SiO2/p-Si heterostructures 6.1. Introduction 6.2. Experimental procedure 6.3 Results and discussion 6.3.1 Structural properties xvii
67 68 71 73 76 77
81 81 82 82 83 84 85 88 90 90
93 94 94 94 96 96 96 99 100 101 101 102 105 107 108 109
111 112 114 114
6.3.2. Electrical properties of LSMO/SiO2/p-Si hereostructure without applied magnetic field 6.3.2.1. Current-Voltage study using diode characteristics 6.3.2.2. Tunneling Characteristics 6.3.3. Electrical properties of LSMO/SiO2/p-Si hereostructure with applied magnetic field 6.3.3.1. Current-Voltage properties under magnetic field study using diode characteristics 6.3.3.2. Tunneling Characteristics under1 T applied magnetic field 6.3.4. Junction magnetoresistance properties study 6.4. Summary References Chapter 7: Electronic-and magneto transport of La0.7Sr0.3MnO3/ZnO, La0.7Sr0.3MnO3/Zn(Fe)O and La0.7Sr0.3MnO3/Zn(Fe,Al)O heterostructures 7.1. Introduction 7.2. Experimental Procedure 7.2.1. Preparation of target 7.2.2. Cleaning of substrate 7.2.3. Preparation of heterojunction 7.2.4. Characterization of heterostructure 7.3. Results and Discussion 7.3.1. Structural and surface study 7.3.2. Electrical properties study 7.3.3. Junction Magnetoresistance properties 7.4. Summary References Chapter 8: Conclusions 8.1. Conclusions of thesis 8.2. Scope of future work 8.3. Contribution of thesis
114 114 118 120 121 124 125 129 130
132 133 133 133 133 134 134 134 136 141 145 145 147 148 148
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Chapter 1
Introduction and Literature overview
IntroductionandLiteratureoverview Chapter1
1.1. Introduction It has been argued with considerable justification that the last half of the 20th century could be called the microelectronics era. The Moores law even starts to run out of its momentum one day, as the size of individual bits approaches the dimensions of atoms. This has been called the end of silicon road map. For this reason and also to enhance multifunctionality of devices, investigators have been eager to exploit another property of the electron characteristics known as spin. Spin is a purely quantum phenomenon. Electrons should spin clockwise and anticlockwise directions. Spin therefore acts as binary logic one and zero. The movement of spin, like flow of charge, can also carry information among devices. The spin relaxation and spin transport phenomena are fundamentally important not only as basic physics questions but also of their demonstrated value in electronic technology. In recent years, spintronics has been initiated and is progressing outstandingly. It is an idea to use the spin of electrons in electronic devices for high-speed, high-density, non-volatile memories and quantum computation in the future. Spintronics is one which refers normally to phenomena of electrons playing the decisive role. In wider sense spintronics is a promising research field of electronics. The physical mechanisms of electronic spin in semiconductors may ultimately lead to multifunctional device based on photonics, electronics, and magnetic devices [1]. Using the coherent spin phenomena in semiconductors [2], this may be fundamental for the viewpoint of quantum computation. The electrical spin injection into semiconductors using both ferromagnetic and paramagnetic semiconductors, and more recently with Zener tunneling processes are intended for potential spin based electronics [3-5]. Though the metal spintronics, such as giant magnetoresistance (GMR) systems have already been used in the computer hard disk read heads memories the semiconductor spintronics is yet to demonstrate its full potential in computer industries. Semiconductor spintronics depends on the concepts of spin transport, spin injection, spin dependent tunneling, as well as spin relaxation and spin dynamics. Spin injection from a ferromagnetic material into a semiconductor attracts massive attentions to the researchers in this field. The injection and detection of a spin-polarized current in semiconductors could combine magnetic storage of information with electronic readout in a single 1
Chapter1 IntroductionandLiteratureoverview
semiconductor device, yielding many obvious advantages. Based on the crystal symmetries of the materials and the structural properties of semiconductor based heterostructures, the spin-orbit coupling takes on different functional forms and can give an effective spin-orbit Hamiltonians in the systems. Most magnetic semiconductor devices are still theoretical concepts and thus waiting for experimental demonstrations. A review of selected and few devices is presented. 1.2. Literature Overview
Electron s p in
Electron Charge
Spintronics
Photon Polarization
Fig. 1.1. The spin based electronics containing both electron spin and electron charge domain. Spintronics can be defined as the art and science of utilizing the spin of the electron (as well as its charge) to achieve a few ideas [shown in Fig. 1.1]. In a broad sense spintronics is a study of spin phenomena in solids, in particular metals and semiconductors and semiconductor heterostructures. Such studies characterize electrical, optical, and magnetic properties of solids due to the presence of equilibrium and nonequilibrium spin populations, as well as spin dynamics. These fundamental aspects of spintronics give us important insights about the nature of spin interactions or spin exchange couplings in solids. We also learn about the microscopic processes leading to spin relaxation. The goal of this applied spintronics is to find the effective ways of controlling electronic properties by spin or magnetic field, as well as of controlling spin or magnetic properties by electric currents or gate voltages. 1.2.1. Spintronic materials and devices 1.2.1.1. Giant magnetoresistance The giant magnetoresistance, a beginning of spin electronics, is actually multilayers of magnetic and non-magnetic metals with individual thicknesses comparable 2
to the mean free paths. The giant magnetoresistance (GMR) effect was discovered at the end of 80s [6,7]. Investigation of magnetoresistance in thin magnetic multilayers in the so-called Current-In-Plane (CIP) geometry have revealed a very large change of the resistance in the antiferromagnetically coupled Fe/Cr multilayers. The effect was much larger than the observed magnetoresistance in any metallic multilayer before. The same effect was observed in the so-called Current Perpendicular-to-Plane (CPP) geometry as shown in Fig 1.2(a) [8]. The fundamental physical phenomenon lying behind such large change of resistance is the so-called spin valve effect. Fig. 1.2 (b) shows the spin valve effect in CPP geometry.
FM FM
Field
NM Field NM FM
(a) (b) Fig. 1.2. Giant magnetoresistance structure in (a) CIP and (b) CPP geometry The simplest device is metallic multilayer consisting of two ferromagnetic layers separated by a non-magnetic conductive layer. This layer has ability to change the metallic interaction between ferromagnetic layers and allows changing their relative magnetization by an external magnetic field. Such properties can be realized having the ferromagnetic layers with different coercivity. As the GMR structure consists of nonmagnetic separator in between ferromagnetic layers, it results in the antiferromagnetic coupling between ferromagnetic layers themselves. If the bias voltage is applied the electron transport occurs from one ferromagnet to another as shown in Fig. 1.3. In this case, in the ferromagnetic metal all current is carried by majority spin-up electrons
( R FM < R FM ) and thus is spin-polarized. If the FM/NM interface does not contain large
number of spin scattering, the spin polarized electrons are injected into non-magnetic layer.
E
R FM R FM
R FM
R FM
EF
FM
R FM
N M
N(E)
NM
FM
FM
(b) (a) Fig. 1.3. Electron spin transport in GMR junction formed by ferromagnetic metal; (a) layered circuit diagram, (b) band diagram for spin injection process in GMR.
If the layer is thin the spin flips and the spin polarized electrons arrived at second ferromagnetic interface with preferred spin orientation that backed to the first ferromagnetic layer. It causes an antiferromagnetic configuration and acts causes high resistance at the junction. In case of parallel alignment, the current in second ferromagnetic metal is also carried by spin-up electron and it causes a small junction resistance. However, the CPP geometry is the easiest for practical realization, since the resistance of device in CPP geometry is too low to allow direct measurements. A large number of technological solutions like, superconducting leads [9], sub micron pillars or rods [10,11] and V-groove [12] have been implemented in order to over come this limitation. The typical material combinations in GMR devices are ferromagnetic Fe, Co, NiFe separated by Cr, Cu, Ag, Au, Re, Ru with typical thickness of ~ 1 to 5 nm. The magnetic sensitivity can be increased combining a large number of such magnetic multilayers. These GMR junctions in the relatively week external magnetic fields show extremely large change of the resistance 220% at low temperatures [13] and 100% at room temperature [14]. 1.2.1.2. Tunneling magnetoresistance A magnetic tunnel junction (MTJ), which consists of a thin insulating layer sandwiched between two ferromagnetic electrode layers, shows tunnelling magnetoresistance (TMR) properties due to spin-dependent electron tunneling through the barrier. Tunneling magnetoresistance was first reported by Julliere in 1975 [15]. Making with CoGeFe sandwich layer Julliere showed the change in electrical resistance with applying a field and switching the relative alignment of the magnetic moments of Co and Fe from parallel 4
to anti-parallel directions. He reported a 14% increase in resistance at a temperature of 4.2 K. Jullieres work may have been inspired in part by the work of Tedrow and Meservey [16,17] who had earlier measured the spin-dependence of tunneling currents through an amorphous aluminum oxide tunnel barrier separating various ferromagnetic electrodes from superconducting aluminum. Tunneling magnetoresistance received much more attention in later periods. In 1995 Miyazaki et al. [18] and Moodera et al. [19] reported TMR in excess of 10% at room temperature which was sufficient for making TMR applicable. FM Barrier FM FM Barrier FM
e e e e
(a) EF EF
e e
(b)
(c)
(d)
Fig. 1.4. Typical TMR structure, (a) parallel and (b) anti-parallel alignment of magnetic spins. (c) and (d) are the corresponding conduction band density of state structures for TMR junction. The resistance of a magnetic tunnel junction (MTJ), which consists of a thin insulating layer (a tunnel barrier) sandwiched between two ferromagnetic (FM) metal layers (electrodes), depends on the relative magnetic alignment (parallel or antiparallel) of the electrodes as shown in Fig. 1.4. The resistance R of the junction is lower when the magnetizations are parallel [Fig. 1.4(a)], and it is higher when the magnetizations are antiparallel [Fig. 1.4(b)] i.e. R P < R AP . This change in resistance with the relative orientation of the two magnetic layers, called the TMR effect, is one of the most important phenomena in spintronics. The size of this effect is measured by the fractional 5
R AP R P RP
change in resistance,
, which is called the magnetoresistance ratio (or MR
ratio). In 2001 first-principle calculations predicted that epitaxial MTJs with a crystalline magnesium oxide (MgO) tunnel barrier would have MR ratios of over 1000%, and in 2004 MR ratios of about 200% were obtained at RT in MTJs with a crystalline MgO (0 0 1) barrier. The huge TMR effect in MgO-based MTJs is nowcalled the giant TMR effect and is of great importance not only for device applications but also for clarifying the physics of spin-dependent tunnelling. MR ratios of above 200% have recently been observed at room temperature in fully epitaxial MTJs with MgO (0 0 1) tunnel barrier and Heusler-alloy electrodes [20]. This large TMR effect, however, is thought to originate from the coherent tunnelling in a crystalline MgO (0 0 1) barrier rather than from the half-metallic nature of the electrodes. When a crystalline MgO (0 0 1) barrier is used with simple ferromagnetic electrodes such as bcc Fe, Co and CoFeB yield MTJs with MR ratios from 180% to 500% at RT [21-24]. Sakuraba et al. [25] observed a MR ratio of 570% at low temperature in MTJs with an amorphous aluminium oxide barrier and Heusler-alloy electrodes. They also observed a feature characteristic of a spin-dependent tunnelling in those MTJs. This giant TMR effect at low temperature is therefore thought to be due to the half-metallic nature of Heusler-alloy electrodes. The best explanation of TMR effect is proposed by Julliere. This famous paper proposed a simple phenomenological model, in which the TMR effect is due to spindependent electron tunneling. According to this model, the MR ratio of an MTJ can be expressed in terms of the spin polarizations P of the ferromagnetic electrodes,
MR = 2 P1 P2 1 P1 P2
(1.1) ; = 1 and 2. (1.2)
P =
D ( E F ) D ( E F ) D ( E F ) + D ( E F )
Here P is the spin polarization of a ferromagnetic electrode, and D ( E F ) and

D ( E F ) are, respectively, the densities of states (DOS) of the electrode at the Fermi
energy for the majority-spin and minority-spin bands.
Word line (WL) Bit line (BL) MJT MTJ FM electrode Tunnel barrier FM electrode MOSFET
(b)
(a)
Write WL WL
n+
n+
Resistance of MTJ (R)

Upper lead Tunnel Barrier Cap layer
RAP
FM electrode (free layer)
SyF structure
AF layer Seed layer
FM electrode (pinned layer)
RP
(d)
MR ratio = (RAP -RP) /
(c)
Lower lead
0Magnetic field
Fig. 1.5(a) Schematic circuit diagram and (b) typical cross-sectional structure of a MRAM cell, (c) typical cross-sectional structure of a MTJ for practical applications, (d) A typical magnetoresistance curve of a MTJ and the definition of MR ratio. Magnetoresistive random-access-memory (MRAM) cells with very large ratios of parallel to anti-parallel conductance can enable a new type of computer architecture. This kind of MRAM structure can be achieved by TMR structures. Such kind of devices would be similar to a field programmable gate array that could be reprogrammed on a nanosecond timescale. High density MRAM cells (Fig. 1.5 (b)), should have MR ratios higher than 150% at room temperature, and the read head in the next generation ultrahigh-density hard disk drive should have both a high MR ratio and an ultra low tunnelling resistance in TMR structures [26]. 1.2.1.3. Colossal magnetoresistance Half-metallic properties were first discovered by Groot et al. [27] based on band structure calculations in NiMnSb and PtMnSb crystals. Later the perovskite manganites doped with alkali metals attracts much attention of researchers due to their half-metallic behavior with unusual high spin polarized (~ 100%) electronic band structure. During last decades, numbers of different compounds derived from LaMnO3 inspire researchers due to their Colossal Magnetoresistive (CMR) response to applied magnetic fields [28-30]. This CMR effect and the correlated degrees of freedom of 7
magnetic structure, crystallographic structure and electrical resistivity in CMR materials, in addition to being of fundamental scientific interest, appears to provide some scope for engineering more sensitive magnetoresistive response. The colossal magnetoresistance (CMR) rare earth manganites display a fascinating diversity of behaviors including several forms of magnetic, orbital and charge ordering [31-33]. The materials also exhibit dramatic variations of physical properties with frequency, temperature, chemical composition and applied strain, as well as the magnetoresistive properties, which give them their colloquial name. The particular MR phenomena to be described here are the gigantic decrease of resistance by application of a magnetic field [29,34-35]. This CMR effects are observed in manganites sparked a great amount of effort aimed at understanding the electronic and magnetic properties of these materials. At low temperatures, optimally hole doped manganites exhibit ferromagnetic metallic or nearly metallic behavior, while at high temperatures they exhibit a paramagnetic insulating behavior. In addition to the CMR effect, the manganites have been found to exhibit a very wide range of exotic and interesting phenomena, including many types of magnetic ordering, metal-insulator transitions, charge and orbital ordering and pressure induced phase transitions. It should also be remembered that the manganites belong to the class of materials where electron correlations are deemed important.
3d orbitals
eg t2g
S= (x2-y2, 3z2-r2) Conduction Electron spin
1 eV
So = 3/2 (xy, yz, zx) Core spin
Cubic crystal field splitting EJT
eg
Jahn Teller distortion

Fig. 1.6. Crystal field splitting of five fold degenerate atomic 3-d levels 8
CMR materials are compounds of manganese (Mn), oxygen (O) and other elements. The electrically and magnetically important ion is Mn; the Mn is connected by oxygen, and the other elements play a role in determining the exact crystal structure and the charge density of the Mn. The important electronic states are the Mn d-levels. The manganese (Mn) ion in the CMR manganites is surrounded by the oxygen octahedron. In free space the d-levels are five-fold degenerate, but in a solid, crystal field effects coming from hybridization and the electrostatic interaction with neighboring ions will partially or wholly lift the degeneracy. In the ideal perovskite structure the crystal field has cubic symmetry and splits the d-multiplet into a doublet transforming as the eg representation of the cubic group Oh and a triplet transforming as the t2g representation as shown in Fig. 1.6. The lower-lying orbitals, t2g states, are dxy, dyz and dzx, while the higher-lying ones, eg states, are dx2-y2 and d3z2-r2. The crystal field splitting between the t2g and eg states is about 1 eV. In the Mn3+ based compounds, the Mn site shows the
3 1 electronic configuration of t 2 g e g (total spin number S = 2). All the 3d electrons are
subject to electron repulsion interaction or the electron correlation effect. Even the eg state electrons, hybridized strongly with oxygen 2p states, are strongly affected by such a correlation effect, and tend to localize in the carrier undoped or the parent Mn3+ based compound, forming the so called Mott insulator. However, the eg electrons can be itinerant and hence play a role of conduction electrons, when electron vacancies or holes are created in the eg orbital states of the crystal. The latter hole-doping procedure corresponds to creation of mobile Mn4+ species on the Mn sites. In contrast, the t2g electrons, less hybridized with 2p states and stabilized by the crystal field splitting, are viewed as always localized by the strong correlation effect and as forming the local spin (S = 3/2) even in the metallic state. The important consequence of the apparent separation into the spin and charge sectors in the 3d orbital states are the effective strong coupling between the eg conduction electron spin (S = ) and t2g localized electron spin (S = 3/2).
eg t2g
LaMnO3 AFM Insulator
eg t2g
La1-x SrxMnO3 (T <<Tc) FM
Mn3+ tij Mn4+ ij
eg t2g
La1-x SrxMnO3 (T ~Tc)
H
La1-x SrxMnO3 (T ~Tc)
eg t2g
Fig. 1.7. Schematic diagram of double exchange mechanism This on-site ferromagnetic coupling is nothing but the Hunds rule. The exchange energy JH (Hunds rule coupling energy) is as large as 2-3 eV for the manganites and exceeds the
0 of the eg electron between the neighbouring sites, i and j. intersite hopping interaction t ij
In the case of the strong coupling limit ( J H / t ij ) , the effective interaction tij can be expressed in terms of Anderson-Hasegawa relation,
ij 0 cos t ij = t ij 2
(1.3)
That is the absolute magnitude of the effective hoping depends on the relative angle ij between the neighbouring (classic) spins. The ferromagnetic interaction via the exchange of the conduction electron whose spin shows the on-site (Hunds rule) coupling with the local spin is called double-exchange interaction after the naming by Zener. This terminology comes from the fact that Zener considered the double exchange process of the electron between the two Mn sites via the oxygen 2p state as shown in Fig. 1.7 By creating hole doping, the eg electron can hop depending on the relative configuration of the local spins. The ferromagnetic metallic state is stabilized by maximizing the kinetic energy of the conduction electrons (ij = 0). When temperature is raised up to near or above TC, the configuration of the spin is dynamically disordered and accordingly the 10
effective hopping interaction is also subject to disorder and reduced on average. This would lead to enhancement of the resistivity near and above TC. Therefore, the large MR can be expected around TC, since the local spins are relatively easily aligned by an external field and hence the randomness of the eg hopping interaction is reduced. This is the simplest explanation of the MR observed for the manganites around TC in terms of the double-exchange (DE) model [36]. The physics of the colossal magnetoresiatance (CMR) is obviously more complex. There are other important factors than in the above simplest DE scenario, e.g. electron-lattice interaction, antiferromagnetic superexchange interaction between the t2g local spins, inter-site exchange interaction between the eg orbitals (orbital ordering tendency), intra-site and inter-site Coulomb repulsion interactions among the eg electrons etc. Among the above interactions other than the DE interaction, the important electron-lattice interaction stems from the Jahn-Teller type coupling of the conduction eg electrons with oxygen displacement [37]. The Jahn-Teller type lattice distortion that lifts the orbital degeneracy and lowers the electronic energy is frequently observed for the orbital degenerate d-electron configuration. In the crystal, such a Jahn-Teller distortion is collective and a coherent distortion of metal (e.g. Mn) oxygen network is realized, as typically seen in LaMnO3. Typically doped perovskite oxides with alkali metals are half-metallic in nature and show good magnetic as well as electronic properties. The Sr doped LaMnO3 manganites or La1-xSrxMnO3 shows Tc above room temperature which drive this CMR manganite towards technological applications. 1.2.1.4. Dilute magnetic semiconductor There is an emerging field of semiconductor spin transfer electronics (spintronics) which aims to utilize the charge carrier spin in dilute magnetic semiconductor. Ferromagnetic semiconductors are well established materials since long [38]. Some known ferromagnetic semiconductors are EuS, EuO, CdCr2S4 etc. The main problem with this materials are there Tc does not cross the temperature over 100 K. The crystal structures of such materials are quite different and the growth is very difficult. A typical dilute ferromagnetic semiconductor would consist of a nonmagnetic semiconductor doped with small amount of transition metals [39-42]. This would hence be known as a 11
dilute magnetic semiconductor (DMS). For the material to be true DMS, its magnetic dopant spins should retain remanent alignment when influenced by spin polarized free carriers. Early studies of DMS materials start with Mn-doped II-VI alloys like (CdTe, ZnS, HgTe etc) in the 80s decade [43]. The ternary structures of these compounds make them amendable to tuning the lattice and band parameters by varing alloy composition. The IIVI compounds are formed by sp3 bonding, incorporating the valance s-electron from group-II and p-electron from group-VI element. The elemental Mn has half filled 3d shell and two valance (4s2) electrons. Mn replaces the group-II element by Mn2+. Since the 3dshell of Mn is half filled, it requires considerable energy to add an electron. The magnetic properties of theses alloys are directed by exchange interactions between local atomic moment and sp-band electrons. In early 90s, the technological advancement in DMS materials occurred with discovery of ferromagnetism in Mn doped InAs [44,45]. After that the DMS properties have been found in other III-V semiconductors also. Unfortunately, the highest Tc reported for GaAs was 110 K [46]. Later GaP [47], GaN [48-50], AlN [51,52] showed room temperature ferromagnetism. The main problem with the DMS investigated at this point is clearly the Tc. A theoretical paper by Dietl et al. [53] calculated that manganese doped semiconductors had ability to be ferromagnetic at room temperature. The theory is based on the concept that how carriers in association with localized spins can make it long range ferromagnetic interactions in a DMS. The localized spins are Mn2+ spins, of the d5 configuration, and the carriers are holes that originate from shallow acceptors. The interaction is parameterized by the p-d exchange term which is in exchange energy n0, where n0 is the total cation site number density and is p-d exchange integral of the system. When Mn spins are aligned there is an energy difference between the carriers and Mn spins caused by magnetic moment. This energy difference will lower the decreasing temperature until they are equal at Tc. An equation for Tc of a system is then obtained by equating the two energies. The formula shows that high value of p-d exchange integral is required to achieve the high value of Tc. The data in Fig. 1.8 show the calculated Tc for various semiconductors with 5% Mn doping and hole concentration 3.5 1020 cm-3. This
12
interesting work encourages huge efforts to achieve room temperature ferromagnetism and better understanding of the systems.
Curie temperature (K) Fig 1.8. Calculated Curie temperature values for various p-type semiconductors with the hole concentration of 3.5 1020 and 5% Mn. The main disadvantages of DMS in III-V semiconductors are the solubility of transition metal ion in it. In wide band gap semiconductors still there is a controversy whether the ferrogmanetism arrises from the secondary impurity phase or not. After the acceptance of ZnO as a II-VI semiconductor with Wurtzite structure and wide band gap, the transition metal doped ZnO has been well studied as a dilute magnetic semiconductor. The interest in ZnO was originally prompted by theoretical predictions concerning hole mediated magnetism though the experimental work has been almost entirely concerned with n-type materials, which raises important and interesting scientific issues concerning the carrier-mediated magnetism. Except Mn, there are several reports on room temperature ferromagnetism in ZnO doped with other transition metals like Fe, Ni, Cu etc. also [54-57]. ZnO doped with rare earth element like V, Gd etc. also shows ferromagnetism at room temperature [58]. 1.2.1.4.1. Origin of ferromagnetism in DMS Understanding the physical mechanism behind magnetic ordering in DMS materials is an essential ingredient to their further development. However, there is an incomplete understanding of the origin of ferromagnetism in transition metal doped semiconductors. There are some theories which is used to describe the ferromagnetism in the DMS systems. 13
Dietls mean field theory: The model assumes that the ferromagnetic exchange interactions occur between localized spin doped into the semiconductor matrix and are mediated by charge carriers. This spins are assumed randomly oriented through out the semiconductors. As shown in Fig. 1.9 the localized spins are aligned with the interaction with free carrier and causes ferromagnetism in the system [59].
Mn+2
h+
Mn+2
J s(i) s(j)
si t e j site i Fig.1.9. Magnetic exchange between two Mn ions mediated by delocalized hole First principle design: Sato and Katayama have employed first principles design to investigate the appearance of ferromagnetism in both semiconductor and oxide spintronics [60,61]. The magnetic stability was calculated using density functional theory within the frame work of local density approximation. Their results were consistent with Dietls theory in case of Mn doping. Their work also pointed about the contribution of d state at the Fermi level. Ferromagnetism in a localized carrier regime: In this proposed model ferromagnetism in the localized spins can be originated from localized carrier. Ferromagnetism in the localized carrier regime can be explained through the formation of bound magnetic polarons (BMP). A BMP is a quasi-particle comprised of the localized carrier and the magnetic atoms encompassed within its radius as shown in Fig 1.10. The localized carriers are bound to its associated defects. The exchange between the bound carrier and the magnetic moments tend to align to parallel moment of another inside the BMP. With lower temperature the radius of BMP grows and starts to overlap to each other. The overlapping BMPs become correlated and create a long range ferromagnetic ordering [62,63].
14
Ferromagnetism in spin-split conduction band: Coey et al. [64] have proposed a model for appearing of ferromagnetism in ZnO like DMS semiconducting materials based on the spin-split donor impurity band. In this model, the donor defect (i.e. Oxygen vacancy etc) overlaps on large concentration to form an impurity band. This impurity band can interact with local magnetic moment through bound magnetic polarons (BMP) and creates a long range ferromagnetic interaction.
Isolated BMPs
Isolated ion
Overlapping BMPs Antiferromagnetic pair
Fig.1.10. Illustration of bound magnetic polaron Free carrier mediated ferromagnetism: In Zener mean field approximation, the inclination of the ferromagnetic alignment of d electron spins is due to the spin coupling between the incomplete d shell and conduction electron (or hole). Due to the negligible roaming of magnetic electron and the quantum oscillations of the electron spin polarization around the localized spins, this model was ultimately abandoned. Dietl et al. [53] pointed out on this model that, for semiconductor, the effect of quantum oscillations averages out to zero since the mean distance between the carriers is greater than that between spins and hence the Zener mean field model becomes equivalent to RudermanKittel-Kasuya-Yosida (RKKY) interaction model. Considering this model, high carrier 15
density was shown to drive paramagnetic-ferromagnetic phase transition in DMS materials [65]. Polaron Percolation model: The polaron percolation model tells that when the concentration of carriers is much smaller than the magnetic impurity, exchange interaction between the localized carriers and magnetic impurities lead to their mutual polarization [66]. Due to this interaction BMP is formed and with decreasing temperature the radius grows and forms a ferromagnetic ordering in DMS. 1.2.1.5. Organic spintronics Organic spintronics is a new and promising research field where organic materials are applied to mediate or control a spin-polarized signal. It is hence a fusion of organic electronics and spin electronics. Organic materials, on the one hand, open the way to cheap, low-weight, mechanically flexible, chemically interactive, and bottom-up fabricated electronics. Phenomena in organic semiconductors seem considerably more complicated than in their inorganic semiconductors. In particular, the characterization techniques that have proved so successful for inorganic spin electronics cannot be used for organic materials. Tris-8-hydroxy-quinoline aluminium (Alq3) sandwiched between transition metal and La0.7Sr0.3MnO3 half metal, establish a clear correlation between spinpolarization loss in the organic material and the spin-valve signal [67,68]. The n-alkane-dithiolate and 1,4-n-phenyl-dithiolate molecules shows large magnetoresistance in both the tunnelling and metallic regime. In the case of nickel contacts the first molecules show tunnelling behaviour with the spin-polarization of the current mainly given by surface states at the interface between the nickel and the molecule as shown in Fig. 1.11 [69].
Nickel Sulphur Carbon Hydrogen
Nickel
Sulphur
Carbon
Hydrogen
Fig. 1.11. Structural and electronic properties of (a) Ni(001)/octane/Ni(001) Ni(001)/tricene/Ni(001) spin-valve.
and (b)
16
In contrast, in 1,4-n-phenyl-dithiolate the transport is by means of states extending across the whole molecule, which determine the spin-polarization of the junction. There have been several investigations of spin-transport through organic molecules. These include carbon nanotube spin valves [70], electron coherent spin transfer across molecular bridges [71], spin injection in -conjugated molecules [72,73] and organic tunneling junctions [74]. Although these works demonstrate convincingly that spinpolarized currents can be injected into organic materials with reasonably high efficiency, there is a general lack of control over the magnetic response of the devices. 1.2.2. Spin transport mechanism 1.2.2.1. Spin drift and diffusion The total number of electrons is assumed to be preserved and if the electron densities are n and n for the spin up and spin down states, the total electron density is,
n = n + n
while the spin density is, s = n n
Considering the spin flip probability, w << 1 over a length l (shown in Fig. 1.12), which is justified for the conduction electrons, one can easily employ the balance equation using Taylor expansion,
n t
n t
=D
2 n x
2
vd
vd
n x
n x
w(n n )
w(n n )
(1.4) (1.5)
=D
2 n x
2
P+
wP+
x-l x
wPX+
Fig. 1.12. Random walk scheme with indicated spin-flip probabilities Adding the two equations the drift-diffusion equation for the density n, can be written as,
s 2s s s = D 2 vd t x s x
where
2w
(1.6)
17
s is the spin relaxation time. Writing the spin drift-diffusion equation in terms of
mobility and employing the continuity equation one can easily get the spin continuity equation as,
s s j s = + s t x
(1.7)
Where, J s = ej s = seE + De
s x
is the spin current density and is the electron spin
mobility. The right hand side represents the spin relaxation. The spin in a given volume can decrease either by spin current flowing away from the volume, or by spin relaxation. The current spin polarization can be expressed as,
Pj = j j j = js j
(1.8)
1.2.2.2. Spin injection and spin tunneling First spin injection model has been proposed by Aronov in 1976 [75]. The thermodynamics of spin injection has been developed by Johnson and Silsbee for spin transport across ferromagnet/nonmagnet (F/N) interfaces [76,77]. The theory of spin injection has been further developed by several researchers [78-83]. In the following treatments, the formulations of the spin injection problems by Johnson-Silsbee and Rashba are discussed. Our goal is to find the current spin polarization, P jF (0) , which determines the spin accumulation, sN (0) , in the normal conductor. We will assume that the lengths of the ferromagnet and the nonmagnetic regions are greater than the corresponding spin diffusion lengths. The spin injection scheme is exemplified in Fig. 1.13 assuming that the nonequilibrium spin vanishes at the far ends of the junction.
F >>Ls
N
x
Fig. 1.13. Scheme of our spin-injection geometry; The ferromagnetic conductor (F) forms a junction with the nonmagnetic conductor (N). The contact region (C) is assumed to be infinitely narrow, forming the discontinuity at x = 0. It is assumed that the physical widths of the conductors are greater than the corresponding spin diffusion lengths. 18
>>Ls Contact N
1.2.2.2.1. Spin injection and spin extraction As shown in Fig. 1.13 there are three distinct regime in ferromagnetic / nonmagnetic junction, i.e. ferromagnetic layer with length L sF , non magneric layer with length L sN and contact. The P jF (0) at the ferromagnetic regime can be expressed as;
P jF (0) = PF +
1 sF (0) j RF
(1.9)
RF is an effective resistance that appears in the spin-polarized transport and is roughly equal to the actual resistance of the region of length L sF . The spin accumulation sN (0) at the non magnetic regime can be expressed as:
sN (0) = jP jN (0) R N
(1.10)
The Spin accumulation is proportional to the spin current which pumps the spin into the system. RN is the effective resistance. The greater is the spin diffusion length, the greater is the spin accumulation. The advantage of the quasi-chemical potential model over continuous drift-diffusion equations for charge and spin current, is in describing the spinpolarized transport across the contact region at x = 0. Employing this equation one can write the spin polarization at the contact:
P jC = P +
1 s (0) j RC
(1.11)
where, P =
and . = +
and are the conductance of spin up and spin down electrons, respectively and
RC =
. 4
(1.12)
To solve these three equations of spin polarization electrons one needs to assume the condition that P j = P jF (0) = P jN (0) = P jC (1.13)
The above equalities are justified if spin-flip scattering can be neglected in the contact. Using the spin current continuity equations, we can solve our algebraic system and readily obtain for the spin injection efficiency,
Pj = R F PF + RC P . R F + RC + R N
(1.14)
19
The spin injection efficiency is the averaged conductivity spin polarization over the three regions, weighted by the effective resistances. Using the spin accumulation equation in non magnetic regime, if j < 0, so that electrons flow from F to N, the spin accumulation is positive, sN (0) > 0 ; it is spin injection. If j > 0, the electrons flow from N to F, and sN (0) < 0 ; it is called spin extraction. If we look at the density of spin polarization, Pn = s/n, we get for the density of spin polarization in the nonmagnetic region,
Pn (0) = e sN (0) gN g = jeR N N P j n n
(1.15)
Since the injected spin polarization is proportional to the charge current, the electrical spin injection is an example of spin pumping. 1.2.2.2.2. Silsbee-Johnson spin-charge coupling In electrical spin injection we drive spin-polarized electrons from a ferromagnet into a nonmagnetic conductor. Nonequilibrium spin accumulates in the nonmagnetic conductor. The opposite is also true. If a spin accumulation is generated in a nonmagnetic conductor that is in proximity of a ferromagnet, a current flows in a closed circuit, or an electromotive force (emf) appears in an open circuit (shown in Fig.1.14). This inverse effect is called the Silsbee-Johnson spin-charge coupling. This coupling was first proposed by Silsbee (1980) and experimentally demonstrated by Johnson and Silsbee (1985) in the first electrical spin injection experiment.
V
Spininjection Spin detection

Fig. 1.14. The Johnson-Silsbee non-local spin injection and detection scheme. Spin injected through one F/N junction. The spin detection is done by a different F/N junction, by the Silsbee-Johnson spin charge coupling. Spin diffusion from the injector is indicated by the different shades of grey. Considering an F/N junction with a special boundary condition: a nonequilibrium spin is maintained at the far right boundary of the nonmagnetic conductor, one can write
sN () 0 . Accordingly, at the far left boundary of the ferromagnetic region, the spin is
assumed to be in equilibrium, i.e. sF () = 0 . The emf is sN () sF () . One of our 20
goals is to find the spatial profile of the spin accumulation inside the junction. The e.m.f. represents the drop of the quasi-chemical potential, , across the junction. If such a drop is present, the system acts as a battery: by closing the circuit, charge current flows. In electrical and spin equilibrium, the quasichemical potential drop must vanish. From the drift-diffusion model, since j = 0 the integrating of the equation in the F region, from 1 to 0, and putting sF (1) = 0 , one can wirte F () F (0) = PF sF (0) . Similarly, for the N region N () N (0) = 0 . There is a drop of the quasi chemical potential in the F region, due to the spin-polarization of the conductivity, while the quasi chemical potential is constant over the N region. The s can be expressed as,
sN ( x) = sN () + [ sN (0) sN ()]e x / LsN
(1.16) (1.17)
The above equation gives, sN (0) =
1 [ sN (0) sN ()] . L sN
Using the condition of j = 0, and assuming again that the spin is conserved across the interface at x = 0, i.e. j s = j sF (0) = j sc = j sN (0) , one can obtain the following set of equations for the spin currents at x = 0; (0) = quasichemical potential can be obtained, sF (0) =
RC P + R F PgF sF (0) RF
and the
RF sN () < sN () . R F + RC + R N
This allows writing the spin current at the contact as,

j s (0) =
1 sN () R F + RC + R N
(1.18)
The electrostatic potential drop across the contact is due to the spin polarization of the ferromagnet as well as due to the spin filtering effects of the contact. The emf can be developed if an equilibrium spin (Pj) is in electrically contact with a nonequilibrium spin. This effect allows detection of nonequilibrium spin, by putting a ferromagnetic electrode over the region of spin accumulation. By measuring the emf across this junction, we obtain information about the spin in the nonmagnetic conductor. 1.2.2.2.3. Spin injection into semiconductors In contrast to normal metals and superconductors, creating a substantial current polarization
Pj
by direct electrical spin injection from a metallic ferromagnet into a 21
semiconductor proved to be more difficult [84-86]. The conductivity mismatch problem has been demonstrated by Schmidt et al. [87]. Even in the absence of the resistive contacts, effective spin injection into a semiconductor can be achieved if the resistance mismatch is reduced by using for spin injectors either a magnetic semiconductor or a highly spin-polarized ferromagnet. For spin injection in non-degenerate semiconductors, there can be large effects due to built-in fields and deviation from local charge neutrality and space charge region. Interfaces making up a semiconductor often develop a spacecharge region. Typical examples are the Schottky contact and the depletion layer in p-n junctions. Microscopic studies of spin-polarized transport and spin-resolved tunneling through space-charge regions are still limited in scope. The difficulty lies in the need to consider self consistently simultaneous charge accumulation and electric field generation, both affecting transport. Non-self-consistent analyses of a Schottky-barrier spin injection were performed by Albrecht and Smith [88] and Prins et al. [89], while Osipov and Bratkovsky proposed an efficient spin injection method using a -doped Schottky contact [90].
P region Space charge n region
+
X=-l
X=0
X=l
Fig. 1.15. Schematic diagram of spin injection through space charge region in magnetic p-n junction The system is depicted in Fig.1.15. The p-n junction has a magnetic n region with a net equilibrium electron spin Pn 0 n , where n stands for the n region. Holes are assumed to be unpolarized. At small biases, in which the injected carrier density through the depletion region is still smaller than the equilibrium carrier density, there is no spin injection. Only with bias increasing to the high injection limit, the spin is injected. The following formula was obtained for spin injection [91],
PnL =
R PnL 0 1 Pn 0
( ) + P (1 P P ) 1 (P ) + P (P P )
2 R n L R n0 n0 R n0 R 2 n0 R n L n0
(1.19) 22
where L (left) and R (right) label the edges of the space-charge (depletion) region of a p-n junction. Correspondingly, PnR represents the nonequilibrium electron polarization, evaluated at R, arising from a spin source. 1.2.3. Active magneto-electronic devices The spin valve and the magnetic tunnel junction involve ferromagnetic and non magnetic metal films with or without insulating tunnel barrier. They are compatible with CMOS technology. But the devices are passive and are not capable to power gain. The passive devices are adequate for memory applications if the output voltages are sufficiently large. An active device which have power gain, are of bigger utility and figure the spine of semiconductor electronics. Recently researches are focused on integrate spintronics directly with semiconductors by incorporating a semiconductor spintronics materials in a device structures. This can be able to develop a spintronics device with power gain and therefore they will be capable to maintain a large fan out which is necessary to form a high density electronic logic applications. 1.2.3.1. Spin field effect transistor One attempt to semiconductor spintronics involves a spintronics device and an application of spin injection theory to semiconducting channel of a field effect transistor (FET) had proposed by Datta and Das. In Datta-Das structure [92], a ferromagnetic source and a drain were connected by 2D electron gas channel (2DEG) with a fixed source to drain distance (Lx) as shown as schematic diagram in Fig 1.16. A magnetization of both source and drain were oriented along the axis of the channel and an internal electric field (E) was perpendicular to the 2DEG plane. Carriers were injected at the source with their spin axis (along x axes) proceed under the applied magnetic field. By applying a gate voltage to the channel, the internal electric field (E), the effective magnetic field (H*) and spin phase () can be varied. Increase of gate voltage sweeps the magnitude of H* to values that causes spin precessions of multiples of and 2, and thereby causes a periodic source to drain conductance. In the past few years, much research has been carried out involving the spin injection FET using ferromagnetic semiconductors for spin injection [93], but, unfortunately, these materials cannot be able
23
to show the characteristics necessary for the device applications because of their low Curie temperatures.
Source
Fe contact
Gate
Drain
Fe contact 2DEG
InGaAs
InGaAs
Fig. 1.16. A schematic diagram of Dutta-Das field effect transistor Though the spin injection FET has not yet been realized, progress had been made and significant problems relating to device applications are understood. 1.2.3.2. Spin diodes To understand the mechanism of spin injection through the complex heterostructures it is more convincing to start with magnetic p-n junction. Consider the fact that the electrons are spin polarized, not holes. Fig.1.17 shows the p-n junction of different magnetic semiconductor junctions. Spin injection can happen from magnetic n-side [Fig. 1.17(a)] and spin extraction are expected to happen to the magnetic p-side [Fig. 1.17(b)]. An external field causes spin splitting of the magnetic n-region and spin up subband is more populated with carriers. At a low bias (below built-in potential) there is no spin injection. While there are more spin up carrier in n, the barrier for crossing the space charge region is exponentially larger for spin up electrons. These two exponential factors cancelled and there is no net spin injection. As the bias voltage increases, the barrier for crossing the space charge region reduced and the spin injection become larger. The same effect pursues the analogous reasoning for spin extraction from a magnetic p-region. Figure 1.17(c) and (d) shows another mechanism for larger magnetoresistance. If nonequilibrium population of is created in the n-side, the opposing external factors are minimized and the large spin injection can be expected.
24
P nonmagnetic
n magnetic
P nonmagnetic
n nonmagnetic
(a) (b)
P magnetic
n spin-polarized
(c)
(d)
X=
Fig.1.17. Band diagram for magnetic p-n junction; (a) electrons from magnetic nregion, (b) electrons from magnetic p-region, (c) spin injection extraction through spin polarized n to magnetic p-region, (d) The scheme where the spin is injected from magnetic heterostructure N into the non magnetic n-region which forms a p-n junction in with magnetic p-region 1.2.3.3. Spin bipolar transistor The more complex and interesting device is the bipolar junction transistor with non-magnetic n/magnetic p/non-magnetic n emitter-base-collector configuration as shown in Fig. 1.18 [94]. Forward bias is applied to base to emitter to lowering the baseemitter barrier for electron. Reverse bias is applied to base to collector which increases the barrier for electron transport from base to collector. A population of nonequilibrium spin is maintained at the emitter using circularly polarized light or spin injection from ferromagnetic electrode. Nonequilibrium spin is maintained through the emitter-base narrow depletion layer, and it causes nonequilibrium spin at magnetic base region. This causes a spin split in base which depends on external magnetic field. Carrier recombination in the base is negligible and the base current is formed by holes flow to the emitter. On the other hand, collector current depends on the electron spin injection from emitter to base, and then to collector. Increasing the external field increases the spin splitting and nonequilibrium spin electron to the base increases. It results a sensitive current gain in the bipolar junction transistor under applied magnetic field. 25
XP
Xn
forwar
N P
reverse
N
(a)
emitter
base
collector
je
jb
jc
Spin up electron Spin down electron hole
wc
(b)
we
wb
Fig.1.18. Magnetic bipolar junction transistor with magnetic base (a) Schematic diagram, (b) band diagram
1.3. Scope of the thesis Though the metal spintronics, such as giant magnetoresistance (GMR), tunneling magnetoresistance (TMR) etc. systems have already been used in the computer hard disk, read heads memories, spin valves, sensor applications and other technological applications in computer industries, the semiconductor spintronics is still questionable according to both scientific and technological field. The integrated spintronics allied with semiconductors can be able to lead the semiconductor industries towards a new era. In this thesis, an attempt has been made to find out the properties of dilute magnetic semiconductors (ZnO doped with Fe and sometime co-doped with Al) and halfmetallic highly spin polarized ferromagnetic mangnaites (La0.7Sr0.3MnO3) having Curie temperature above room temperature. Moreover, these materials have been used to fabricate magnetic heterojunctions and metal-semiconductor junctions for possible spintronics applications. The temperature dependent spin injection process through the junctions by applying varying magnetic field has been focused in this thesis. Chapter-1 discusses about the brief overview of spintronics materials and devices. Chapter-2 describes in brief the experimental details and different equipments used for characterization. In chapter-3, the structural, 26 magnetic, electronic transport,
magnetotransport, Hall Effect etc. properties of iron doped ZnO and in some cases codoped with Al have been discussed in details. The high crystalline quality epitaxial Fe doped ZnO dilute magnetic semiconductor thin films deposited on (0001) c-plane single crystalline sapphire substrates show room temperature ferromagnetic behavior with carrier mediated ferromagnetism properties where the majority carrier is electron. The spin injection through the Pt and Fe doped and Al co-doped ZnO junctions have been estimated from the magnetic field dependent current voltage behavior in chapter-4. The appearance of positive junction magnetoresistance and dependence of magnetoresistance on the magnetic moment of ZnO doped with Fe have been explained using Ferromagnetic/Non-magnetic spin injection theory. Chapter-5 discusses about the structural, magnetic and electronic properties of non epitaxial La0.7Sr0.3MnO3 thin films on (100) p-Si substrate. The films show room temperature ferromagnetism with colossal magnetoresistive behavior. In chapter-6, a detailed study of electrical transport mechanism through the La0.7Sr0.3MnO3/SiO2/p-Si heterojunction with different type of SiO2 layers and appearance of junction magnetoresistance have been carried out. The dependency of junction magnetoresistance on trap charges, leakage currents and defects in SiO2 have been estimated in this chapter. Chaper-7 deals with the p-n heterojuction formed using p-type La0.7Sr0.3MnO3 half-metallic ferromagnet and n-type Fe doped ZnO dilute magnetic semiconductor. The spin injection theory through magnetic semiconductor p-n junction has been employed to describe the junction magnetoresistance of such heterostructures. References [1] S. A. Wolf, D. D. Awschalom, R. A. Buhrman, J. M. Daughton, S. von Molnar, M. L. Roukes, A. Y. Chtchelkanova, and D. M. Treger, Spintronics: A Spin-Based Electronics Vision for the Future, Science 294, 1488 (2001). [2] D. D. Awschalom and J. M. Kikkawa, Electron Spin and Optical Coherence in Semiconductors, Phys. Today 52, 33 (1999). [3] Y. Ohno, D. K. Young, B. Beschoten, F. Matsukura, H. Ohno, and D. D. Awschalom, Electrical spin injection in a ferromagnetic semiconductor heterostructure, Nature (London) 402, 790 (1999). [4] R. Fierderling, M. Keim, G. Reushcer, W. Ossau, G. Schmidt, A. Waag, and L. W. Molenkamp, Injection and detection of a spin-polarized current in a light-emitting diode, Nature (London) 402, 787 (1999).
27
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Chapter 2
Experimental equipments and techniques
Experimentalequipmentsandtechniques Chapter2
2.1. Introduction In this chapter, we have discussed about detailed experimental techniques and some major equipments which have been used to carry out our work on oxide thin films and heterostructures. First we have used pulsed laser deposition (PLD) unit for depositing the thin films and heterojunctions. The structural and surface morphological characterizations have been carried out using high resolution x-ray diffraction (HRXRD) technique, high resolution transmission electron microscope (HRTEM), high resolution field emission scanning electron microscope (FESEM), energy-dispersive x-ray spectroscopy (EDAX) and near edge x-ray absorption fine structure (NEXAFS); the optical properties have been studied using UV-VIS spectrophotometer and magnetic characterizations have been done using superconducting quantum interference device (SQUID). The electronic-transport, magneto-electronic, Hall Effect and magneto-transport properties have been investigated using cryogen free high magnetic field low temperature VTI system with closed cycle helium refrigeration compressor unit. Current and voltage source-meter have been used for the current voltage (I-V), resistivity [(T,H)] and Hall resistivity [H(T,H)] etc. characterizations. 2.2. Brief description of used equipments 2.2.1. Thin film deposition unit: Pulsed Laser Deposition (PLD) The photograph of experimental set up of the PLD system for thin film oxide films and heterostuctures deposition has been shown in Fig. 2.1.
Fig. 2.1. The experimental set-up of PLD chamber

33
Chapter2
Experimentalequipmentsandtechniques
A. Laser System: COMPexPro 201, High-Pulse-Energy KrF Excimer Laser manufactured by Coherent, Inc. 5100 Patrick Henry Drive, Santa Clara, CA 95054 has been used for pulsed laser. The wavelength, Pulse Energy and Maximum Average Power of the laser source are 248 nm (KrF), 700 mJ and 7 W, respectively. Maximum Repetition Rate is 10 Hz. B. Deposition Chamber: Deposition chamber with software control unit has been made by Excel Instruments, Mumbai - 93. For substrate temperature we have used PID Temperature Controller, Dynamic Control System and substrate heater for a maximum temperature of 850 C. C. Vacuum Components: We have used a turbo molecular pump, TMH/TMU 261, and a rotary vane pump DUO 10/ MC made by Pfeiffer Vacuum Technology AG; Headquarters/Germany to evacuate the thin film deposition unit to obtain very high vacuum (~ 10-7 Torr) and to control the oxygen pressure while depositing the various films. 2.2.2. Characterization equipments Mainly, the structural, surface morphology, optical, magnetic and electrical characterizations have been carried out for all our thin film samples and heterostructures. A brief description of all the techniques used has been presented here. 2.2.2.1. Structural and surface morphology 2.2.2.1.1. High resolution x-ray diffraction technique (HRXRD)
Structural characterizations of our thin films and heterostructures have been carried out using high resolution x-ray diffractometer (Model: Philips, PW-1729) with monochromatic Cu-K radiation at room temperature. The tube voltage and current have been kept at 40 kV and 30 mA respectively. The wavelength of the K line, which is 1.541 in this present case, is basically the weighted average of the wavelengths of its components K1and K2, K1 being twice the wave length of K2 [1],
1 (2 1.540 + 1.554) = 1.541 3
(2.1)
In order to obtain as closely monochromatic K1 radiation as possible, Ni filter was used to absorb undesirable K component. During measurements, the resolution of the instrument i.e. K 1 is 0.5
K 2
34
and accuracy of 2 value is 0.03o.
2.2.2.1.2. High resolution transmission electron microscopy (HRTEM) High resolution transmission electron microscopy (HRTEM) images of our films and heterostructures were recorded employing JEOL, lEM-2010 ultra - high resolution (UHR) microscope using a LaB6 filament. During experiment the instrument was operated with an accelerating voltage of electron, E=200 kV. Corresponding relativistic wavelength of electrons depends on this accelerating voltage E and its value can be obtained using the modified De Broglie wavelength [2],
[2m eE{1 + eE / 2m c }]
0 0
(2.2)
2 1/ 2
where, h is Planck's constant, m0 the rest mass, e the charge of the electron and c the velocity of light. Thus obtained corresponding to E=200 kV, is 0.025 . For low magnification bright field image, this instrument can resolve a minimum dimension of 2 nm of the specimen
under study and the minimum diameter of electron beam can be ~ 20 nm.
2.2.2.1.3. High resolution field emission scanning electron microscopy (FE-SEM) High resolution field emission scanning electron microscopy (FE-SEM) has been done using Carl Zeiss SMT Ltd. SUPRATM 40 [Emitter: Thermal field emission type, Standard Detectors : High efficiency In-lens detector, Everhart-Thomley Secondary Electron Detector]. The chamber pressure was maintained at ~ 10-5 mbar and gun pressure at~ 10-5 mbar. During experiment the instrument was operated with an accelerating voltage of electron, E=5.28 kV. Corresponding relativistic wavelength of electrons, as obtained using Eq. 2.2, is 0.168 . This instrument can resolve a minimum dimension of ~ 1 nm at our working accelerating voltage of E=5.28 kV. We have used gold coated pelletized samples as specimens for FE-SEM study. 2.2.2.1.4. Energy dispersive x-ray analysis (EDAX) Energy dispersive x-ray analysis (EDAX) unit of Oxford instruments is attached with high resolution field emission scanning electron microscope (Carl Zeiss SMT Ltd .SUPRATM40). During x-ray analysis of our specimen, the working distance was maintained at 15 mm, the chamber pressure at ~ 10-5 mbar and gun pressure at ~ 10-9 mbar. Both point EDAX
35
Chapter2
and bulk EDAX were performed on our samples, depending, upon specific requirement. We have employed INCA EDS hardware and INCA software, which provides a stable microanalysis platform. This EDAX unit promises a < 1 eV shift in peak position and resolution between count rates of 1 kcps and 10 kcps in microanalysis of our samples. 2.2.2.1.5. X-ray absorption spectroscopy (XAS) If a high energy x-ray (0.1-100 eV photon energy) excites an electron from core level of an atom, the resultant photoelectron will jump into unoccupied higher energy states. The created core hole filled either via an Auger process or by capture of electron from another state which is then followed by the fluorescent photon. There are three main regions found on a spectrum generated by XAS data (Figure 2). The dominant feature is called the "rising edge", and is sometimes referred to as X-ray Absorption Near-Edge Structure (XANES) or Near-edge X-ray Absorption Fine Structure (NEXAFS). The pre-edge region is at energies lower than the rising edge. The fluorescent photon or Auger electron which is inelastically scattered photoelectron is been measured to obtain NEXAFS spectra as shown in Fig. 2.2. Photoelectron VB n xray n n n Fluorescent photon
Augerelectron VB n VB n
(c) (b) (a) Fig. 2.2. The processes of NEXAFS spectra: (a) photo absorption of an x-ray into a core level followed by photoelectron emission, followed by either (b) filling of the core hole by an electron in another level, accompanied by fluorescence; or (c) filling of the core hole by an electron in another level followed by emission of an Auger electron. NEXAFS spectra are usually measured either through the fluorescent, in which emitted photons are monitored, or total electron yield, in which neutralization current is monitored [3]. The XAS spectra are measured for a solid sample with some standard and a comparative study gives the present states of the element in the system.
36
2.2.2.1.6. Atomic force microscope (AFM) The atomic force microscope (naming by Scanning Probe Microscope (SPM) [Model: Multiview- 1000TM by Nanonics Imaging Ltd. Malcha Jerusalem 91487 Israel] has been used to characterized the surface morphology of the thin films. It consists of 70 m AFM/ NSOM Scanner, 200 nm200 nm STM Scanner, Varian Turbo molecular pump and Ion pump, Nd: YAG Laser for NSOM, Normal Si AFM and also optical fiber tip, Liquid Cell Accessories, Avalanche Photo Diode, Leica microscope etc. An atomically sharp tip is scanned over a surface with feedback mechanisms to maintain the tip at a constant force (contact mode), or at constant oscillation amplitude (non-contact & tapping mode). A laser is focused to the back of the reflective cantilever. As the tip scans the surface of the sample, moving up and down with the topographical feature of the surface, the laser beam is deflected into a multi-sectioned PSD which measures the difference in light intensities and their incident positions to measure the height of sample surface at that position. 2.2.2.2. Optical characterizations For optical characterization, absorbance spectra of the nanocrystalline sample are recorded using UV - visible spectrophotometer (Micro pack, DH-2000, Deuterium Halogen Light Sources) combine the continuous spectrum of an RF-excited deuterium UV-Visual source and a halogen VIS-NIR light source in a single optical path (fiber optical path). The combined spectrum sources produce stable spectral output from ~ 200 - 1200 mm in a compact package). We have done the global correction of measuring instrument using the bulk ZnO sample with Integration Time: 5000 msec Average: 10, Box car: 10 and Flash Delay: 100.The global correction is done through the reflection mode placing the beam of the light at the perpendicular or 60 angle with the sample surface. After this we have recorded absorbance spectra of all samples fixing the globalize conditions. Optical transmission spectra of the thin films are recorded at room temperature in an energy variation of 1 - 4 eV. The band gaps of all the DMS thin films are estimated from the measured spectra. The optical absorption measurements are carried out on a large number of samples of various thicknesses. A steep rise in the absorbance near the absorption edge hints a direct type transition. In a crystalline material with polycrystalline structure both direct or
37
Chapter2
indirect optical transitions are possible depending on the band structure of the material. Assuming parabolic bands, the relation between and Eg for the direct transition is given by,
h ( h E g ) n
and for indirect transition by
h =
A(h E g + E P ) n exp( D / T ) 1 + B ( h E g E P ) n 1 exp( D / T )
(2.3)
(2.4)
where, Ep is the phonon energy assisting the transition, D the Debye temperature and are constants: For a direct transition n = 1/2 or 3/2 depending on whether the transition is allowed or forbidden in quantum mechanical sense. Similarly, n = 2 or 3 for indirect allowed and forbidden transition, respectively. The usual method of determining band gap is to plot a graph between (h )1 / n and h and look for that value of n which gives best linear graph in the band edge region. 2.2.2.3. Magnetic characterizations Magnetic measurements [Magnetization (M) as a function of magnetic field (H) and Magnetization (M) as a function of temperature (T)] have been carried out using Quantum Design superconducting quantum interferometer device, commonly known as SQUID magnetometer, in the dc magnetic field range of 0 55 kOe and in the temperature range of 2 330 K. The Quantum Design MPMS SQUID VSM Ever-Cool system is an integrated pulse-tube cryocooler system. This eliminates the need to use any liquid cryogens for the operation of the MPMS SQUID VSM. The SQUID VSM utilizes a 7 Tesla, superconducting, helium-cooled magnet and accomplishes rapid switching between charging and discharging states and stable fields with a unique superconducting switching element called the Quick Switch, which changes, between superconducting and normal states in less than one second. This allows rapid collection of high precision data. Typical M-H loop up to 5 T would take ~ 60 mins and M-T measurement in the temperature range of 4 300 K would take ~70 mins. Temperature Accuracy of the SQUID is lesser of 1% or 0.5 K
38
2.2.2.4. Electrical characterization The electrical characterizations of all our oxides thin films and heterostructures have been done mainly using the high magnetic field (8 T) cryogen free superconducting magnet with variable temperature insert (VTI) system which is operated down to 2 K temperature along with other devices, e.g., Keithley-2182 nanovoltmeter, Keithley-2612 source-meter (with 1V
resolution) and Keithley-6221 AC and DC current source. Temperature has been controlled using
Lakeshore (Model 331) temperature controller with the temperature stability better than 50 mK.
2.2.2.4.1. Cryogen free high magnetic field (Superconducting magnet) VTI system The photograph of Cryogen free high magnetic field VTI system set up has been shown in Fig. 2.3 (a) and (b). Figure 2.3 (c) shows the schematic VTI circuit and the probe that has been used for different electrical measurements has been shown in Fig. 2.3 (d). The cryogen free high field measurement system combines the latest cryogen free technology with sophisticated measurement techniques. It is comprised of the following main components: (1) Cryo-cooler system with compressor, (2) Cryostat and Magnet, (3) Variable temperature insert (VTI), (3) Electronics rack with measuring devices, (4) Measurement System Software and (5) Water chiller with compressor for the cooling of the Cryo-cooler compressor. (a) (c)
(b) (d)
Fig. 2.3. (a) and (b) The photograph of Cryogen free high magnetic field VTI system set up. (c) The schematic VTI circuit and (d) the probe that has been used for different electrical measurements. The cryo-cooler system is the Gifford McMahon (GM) cryocooler which has the advantage of greater thermodynamic efficiency and reliable operation in any orientation. It uses
39
Chapter2
the compressor to drive moving pistons with regenerators. This cryocooler can provide more than 50 watts of cooling power on the 60 K stage (the first stage) and up to 1.5 watts of cooling power at 4 K stage (the second stage). The main function of the first stage is to cool the radiation shield around the low temperature parts of the system. Cooling for the magnet and the VTI is provided by the second stage as shown in Fig. 2.3 (c). 2.2.2.4.2. Electrical Measurement Instruments The electrical characterizations was made mainly using (i) Keithley 2182 nanovoltmeter: Measure voltage from 1nV to 120V (channel 1); 10nV to 12V (channel 2) with 6 and digit display. (ii) Keithley 2612 source-meter: Maximum output power and source/sink limits to 30.603 W per channel maximum. 20.2 V at 1.515 A, 202 V at 101 mA, four quadrant source or sink operation. Voltage regulation is 0.01% of range. Load: (0.01% of range + 100 V). (iii)Keithley 6221AC and DC current source: Current ranges from 2 nA to 100 mA with 0.1 to 0.4% accuracy. 2.2.2.4.3. Temperature readouts and controller Instruments Lakeshore (Model 331) temperature controller has been used to control and measure the temperature. It is Proportional-Integral-Derivative type temperature controller (PID) with 0 to 1000 with 0.1 setting (proportional), 1 to 1000 (1000/s) (integral) with 0.1 setting and 1 to 200% (derivative) with 1% resolution. The sensor is used here is diode (Silicon, GaAlAs Most thermocouple types RTDs: 100 ) Platinum, Platinum, Germanium, Carbon-Glass, Cernox, and Rox sensor with 50 heater load power. All the electrical measuring systems are automated using the LABVIEW software (version 8.5) through GPIB interfacing cables with a PC. 2.3. Brief description of experimental technique Mainly the electrical characterizations such as resistivity, Hall Effect, magnetoresistance and current-voltage measurements have been done on oxides thin films and heterostructures in the entire thesis work along with some optical and magnetic measurements. Brief descriptions of
40
such measuring techniques have been presented here. In order to make these electrical measurements, low resistance contacts should be made between the films and the connecting wires in the sample holder. This is done by pressing tiny In (indium) piece onto the sample corners and then the fine Cu wires are bonded into this for Fe and Fe,Al doped ZnO thin films grown epitaxially on sapphire substrates. Wire bonding for La0.7Sr0.3MnO3 samples have been done connecting Ag and Cu wires. Wires bonding for p-Si have been done using Al which have been deposited by thermal evaporation method. Then the Cu wires have been connected on Al with Ag paste. 2.3.1. Four probe resistivity measurements
The purpose of the 4-point probe is to measure the resistivity and magnetoresistance of the films of any semiconductor materials. It can measure either bulk or thin film specimen, each of which consists of a different expression. The 4-point probe setup for bulk or thick films and thin films has been shown in Fig. 2.4 (a) and (b).
I I V
(b) (a) V
Fig. 2.3. (a) Four probe method for measuring resistivity; (b) van der Pauw geometry for measuring resistivity of thin films.
For bulk or thick film samples where the sample thickness (t) >>spacing between two probes (s) we can assume a spherical projection of current coming to sample and differential resistance is,
dx R = dA
(2.5)
If we carry out the integrations between the spaces where voltage is measured (s), we can write,
41
Chapter2
R =
x1
x2
dx 1 = 2 2 s 2 2x
(2.6)
where probe spacing is uniformly s. Due to the superposition of current at the outer two tips, R = V/2I. Thus, we arrive at the expression for bulk resistivity,
= 2s
V I
(2.7)
Thin film measurements are generally done using the Van der Pauw geometry as shown in Fig. 2.4.
(b). For a very thin layer (thickness t <<s) we get current rings instead of spheres. The derivation is
as follows,
x2
R=
x1
2xt = 2t ln 2
t V
dx
(2.8)
Consequently, for R = V/2I, the resistivity for a thin sheet is,
ln 2 I
(2.9)
2.3.2. Hall Effect measurements When the current flows along the x-axis, with a magnetic field (B) applied in the y axis, electron starts to drift from current line due to Lorentz force, ev B , v is drift velocity. The basic Hall geometry has been shown in Fig. 2.4 (a). The electrons are therefore deflected from traveling line (x-axis) and create a potential drop across the surface along z-axis, which is called Hall voltage (VH).
B V=0 j
z
V = VH V (b) Fig. 2.4. (a) Hall Effect geometry in a semiconductor bar; (b) van der Pauw geometry for measuring the Hall Effect in thin films
42
(a)
For the steady state, we can write following equations for the x and y directions, with e the electric charge and n the carrier concentration, me v x / = eE x (2.10)
0 = e( E y v x B )
E y = v x B with v x = j x /(ne) and thus, E y = j x B /( ne) Combining those equations with E H = E y and j = j x yields
(2.11)
(2.12)
RH =
1 ne
(2.13)
RH is Hall coefficient. The measurement is very complex in case of measuring the thin films and it can be done by van der Pauw geometry as shown in Fig. 2.4 (b). A series of resistances in the crossed geometry altering voltage and current directions can be made as a function of magnetic field. The measured resistances are then multiplied by the film thickness and plotted with magnetic field. The gradient of the plot gives the Hall coefficient for all the thin film samples.
References
[1] B.D. Cullity Elements of x-ray diffraction, Addison-Wesley Publishing Company Inc., 2nd Edition, California (1978). [2] G. Thomas and M. J. Joringe, Transmission Electron Microscopy of materials, WileyInterscience Publication, John Wiley & sons, New York (1979). [3] http://en.wikipedia.org/wiki/XANES.
43
Chapter 3
Properties of room temperature ferromagnetic Zn(Fe)O and Zn(Fe,Al)O epitaxial thin film
Thischapterisbasedon Internationaljournals 1. Enhancement of room temperature ferromagnetism of Fedoped ZnO epitaxial thin films with Al codoping, T.K. Nath, A.J. Behan, J.R. Neal, D. Score, Q. Feng, A.M. Fox, G.A. Gehring, Journal of Magnetism and Magnetic Materials vol. 323, pp. 1033(2011) 2. Temperature dependent carrier induced ferromagnetism in Zn(Fe)O and Zn(FeAl)O thin films by S. Chattopadhyay, T.K. Nath,A.J.Behan,J.R.Neal,D.Score,Q.Feng,A.M.Fox,G.A.Gehring,AppliedSurfaceSciencevol.257,pp.381(2010) 3. Extraordinary Hall effect, electronicand Magnetotransport behavior of carrier induced dilute magnetic Zn(Fe)O and Zn(Fe,Al)OthinfilmbyS.ChattopadhyayandT.K.Nath,PhysicalReviewB.(communicated) Conferences/Symposia 1. Temperature dependent anomalous Hall Effects in DMS Zn(Fe,Al)O epitaxial thin film by S. Chattopadhyay and T. K. Nath, 55thDAESolidStatePhysicsSymposium2010(2010) 2. Magnetoresistive behavior of epitaxial Zinc oxide thin films doped with iron by S. Chattopadhyay, T. K. Nath International ConferenceonMagneticMaterials(ICMM2010)(2010)
Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm
3.1. Introduction There has been a great interest in transition-metal-doped diluted magnetic semiconductors (DMS), which exploit both the spin and the charge of carriers, because the combination of two degrees of freedom promises new functionality of memory, detectors, light-emitting sources and possible use in next generation spintronic devices, e.g., spin-valve transistors, spin light-emitting diodes, non-volatile storage and logic devices. A theoretical study by Dietl et al. [1] has predicted that some of the manganese doped semiconductors have the ability to be ferromagnetic at or above room temperature (e.g. GaN and ZnO). The low magnetic ordering temperature in most of the DMS materials limits the potential spintronic device applications at room temperature. There is an ongoing quest for ferromagnetic DMS with Curie temperatures, Tc, far in excess of 300 K for the second generation of spin electronics, as well as a search for transparent ferromagnets which could add an optoelectronic dimension. It is also possible to control the ferromagnetic interactions between the localized spins by the carriers [2-5], as well as the demonstration of efficient spin injections into normal semiconductors [6, 7]. In spite of several progresses on transition metal doped ZnO diluted magnetic semiconductor as a spintronic material, much controversy remains concerning the mechanism that causes the ferromagnetism. The carrier-induced ferromagnetism has been observed in different III-V [8-10] and II-VI [11-14] semiconductors. The interest in ZnO was originally prompted by theoretical predictions concerning hole mediated magnetism. However, the experimental work has been almost entirely concerned with n-type materials, which raises important and interesting scientific issues concerning the carrier-mediated magnetism. DMS are mixed spin-fermion systems, involving randomly distributed localized magnetic and mobile carriers in the semiconductor band. With carrier concentration much smaller than the magnetic impurity concentration, the DMS systems provide a complimentary limit to Kondo systems. The coupling between localized impurity spin (S) and mobile valence band holes can be represented by the exchange interaction J S., where is the fermion spin operator. A theoretical approach has been made by S. Singh et al. [15] to explain the carrier induced ferromagnetism in DMS system by using diluted Hubbard model. The origin of FM in these materials is still an issue of debate. In the currently accepted picture
44
Chapter3
Propertiesofroomtemperatureferromagnetic Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm
for DMS the presence of carriers is essential to mediate the interaction between the magnetic ions. An investigation with additional dopants to enhance or induce ferromagnetism in these DMS materials will be an interesting approach to establish the theoretical picture of carrier induced FM. Some efforts have been made with various doping element to enhance both the electrical conductivity and ferromagnetism. In some literature the coexistence of ferromagnetic and paramagnetic component is reported due to some defect states present in the doped ZnO systems. Sharma et al. [10] observed that there is coexistence of ferromagnetic contribution and paramagnetic contribution in Zn(Fe)O system and the paramagnetic behavior increased with increasing doping concentrations. They have showed it by the Mossbauer spectra for Zn(Fe)O samples recorded at room temperature in order to probe local magnetic environment around the Fe sites and to determine the oxidation state of the Fe in ZnO matrix. Each spectrum shows a paramagnetic doublet with isomer shift (IS). This coexistence of ferromagnetic and paramagnetic components in other DMS systems has also been established by different researchers [16-18]. In this chapter, a systematic study of carrier concentration dependent room temperature ferromagnetism (RTFM) in pulsed laser deposited epitaxial thin films of iron doped zinc oxide [Zn(Fe)O] and iron doped zinc oxide incorporated with 1% aluminium [Zn(Fe,Al)O] has been presented. We have investigated explicitly the presence of temperature dependent paramagnetic component and its effect on room temperature ferromagnetism in Zn(Fe)O and Zn(Fe,Al)O dilute magnetic semiconductors (DMS) using low temperature SQUID measurements. The structural and optical absorption properties have also been studied for these DMS thin films. Moreover, the electrical and magneto-electrical properties have also been investigated for those DMS thin films. The Anomalous Hall Effect and magnetoresistance behavior of these DMS films have been studied and the sp-d exchange behavior of such DMS systems in different temperatures has been found. 3.2. Experimental procedures 3.2.1. Preparation of targets Required amount of high purity ZnO, Fe2O3 powder has been well mixed with hand grinder repeatedly and sintered at 450 C till the required phase appeared with 5%
45
Fe. Required amount of high purity Al2O3 powder were mixed with the ZnO and Fe2O3 powder to dope 5% of Fe and 1% aluminum in the zinc oxide target. The well mixed powder after repeated grinding is sintered at the same 450 C. Finally, the Zn0.95Fe0.05O and Zn0.94Fe0.04Al0.01O powders were palletized and used as the target for pulsed laser deposition. The same procedures have been followed to dope ZnO with 7 and 10% Fe also. 3.2.2. Cleaning of substrates The c-plane (0001) sapphire substrate has been cleaned repeatedly with Deionized water, Acetone and Propanol using ultrasonic vibrator. Each cleaning process has been carrier out for 20 min. 3.2.3. Preparation of thin films The films are grown on well cleaned c-plane (0001) sapphire substrate by pulsed laser deposition technique at several substrate temperatures (300 to 600 C) and different ambient oxygen pressures (from base pressure ~10-5 to 10-1 Torr). The optimized deposition parameters used in obtaining the Zn(Fe,Al)O films having highest magnetic moment at room temperature are - substrate temperature of 450 C and 10-5 Torr ambient oxygen atmospheres for 30 min at a laser pulse frequency (repetition rate) of 10 Hz. The XeCl ( = 308 nm) pulsed mode excimer laser has been used at an average pulsed laser energy of 150 mJ. 3.2.4. Characterization of thin films The concentrations of Fe were estimated by EDAX. The structural studies have been done by high resolution x-ray diffraction (XRD), cross-sectional High Resolution Transmission Electron Microscope (HRTEM). Atomic Force Microscope (AFM) image have been taken for estimate the surface roughness of the films. Room temperature XAS spectra have been taken to estimate the valence state of Fe ion and the content of metallic Fe in the films. The magnetic properties have been carried out using SQUID measurements at room temperature and low temperatures down to 5 K. The thicknesses of the films have been measured with Dektak profilometer and found to lie in the range of 150 450 nm. Hall Effect and magnetoresistance measurements at room temperature and
46
Chapter3
low temperature have been performed using the van-der Pauw four-probe configuration with magnetic fields up to 8 T. The band gap and crystallinity have been estimated using transmission curve of UV spectroscopy recorded at different temperatures. 3.3. Results and discussions 3.3.1 Chemical properties study The concentrations of Fe were established by energy dispersive x-ray analysis (EDAX). The actual values of the Fe concentration in different films have been listed in the Table-3.1. Table-3.1: The actual Fe concentration in the Zn(Fe)O and Zn(Fe,Al)O thin films Sample Zn(Fe)O with 5% Fe Zn(Fe,Al)O with 5% Fe Zn(Fe)O with 7% Fe Zn(Fe,Al)O with 7% Fe Zn(Fe)O with 10% Fe Zn(Fe,Al)O with 10% Fe 3.3.2. Structural properties In Fig. 3.1(a) the recorded XRD patterns (normal - 2 scan) using Cu-K radiation ( = 1.542 ) show that the Zn(Fe)O and Zn(Fe,Al)O films with 5% Fe of thickness 420 and 300 nm respectively, are perfectly epitaxial on (0001) c-plane sapphire in the (0001) direction of the films. The observed XRD patterns also confirm that there is no iron oxide or any other secondary impurity phases present in the films. The ionic radii of aluminum (Al3+) is smaller compared to zinc (Zn2+) but ionic radii of iron (Fe2+) is larger than Zn. So on doping with iron in Zn(Fe)O a stress will develop in ZnO. The FWHM of (0002) film peak and c-axis parameter are obtained to be 0.47 and 5.253 , respectively. On co-doping with Fe and Al in ZnO as Zn(Fe,Al)O, the FWHM of (0002)
47
Actual Fe concentration 2.85% 3.28% 6.12% 6.24% 8.56% 8.51%
film peak is obtained as 0.39 and c-axis parameter so obtained is 5.218 . The FWHM and c-axis parameter are found to reduce slightly on co-doping as stress developed due to doping of Fe and strain developed due to doping with Al. This development of stress and strain compels the reduction of FWHM and c-axis parameter of the Zn(FeAl)O film compared to FWHM and c parameter of the Zn(Fe)O film with 5% Fe. The XRD pattern of Zn(Fe)O and Zn(Fe,Al)O thin films with different doping concentrations have been shown in Fig. 3.1(b) and Fig.3.1(c), respectively.
Zn(Fe)O 5% Fe Intensity
(a)
Zn(Fe)O 5% Fe Intensity
(b)
Zn(FeAl)O 5% Fe
Zn(Fe)O 7% Fe
ZnO
40
Zn(Fe)O 10% Fe 40 50 60 70
2 (degree)
50
60
70
2 (degree)
(c)
Intensity
Zn(Fe,Al)O 5% Fe
(d)
Zn(Fe,Al)O 7% Fe
Zn(Fe,Al)O 10% Fe
40
50
60
2 (degree)
Fig. 3.1. (a) The XRD pattern of as grown ZnO, Fe- doped and Fe and Al doped epitaxial films for 5% Fe. (b) The XRD pattern of Zn(Fe)O epitaxial films for different Fe concentrations. (c) The XRD pattern of Zn(Fe,Al)O epitaxial films for different Fe concentrations. (d) the cross-sectional HRTEM of the junction. Fig. 3.1(d) shows the high resolution transmission electron microscope (HRTEM) image revealing very sharp film-substrate interface. The d spacing of the film calculated from the HRTEM image is 0.261 which well matches with the d spacing of (0002) plane of ZnO. The micrograph taken in [10-10]s || [2-1-10]f zone axes clearly indicates the high degree of texturing of this epitaxial film with the substrate having an atomically sharp interface with no mixed layer near the interface.
48
Chapter3
1.5
Normalized (E)
1.0
Fe2O3 maghemite Zn(Fe)O Zn(FeAl)O FeO Fe2O3 Hametite
0.5
0.0 7110
7120
7130
7140
7150
7160
Energy (eV)
Fig.3.2. (a) Room temperature near edges XAS spectra for both Zn(Fe)O and Zn(Fe,Al)O epitaxial films compared to some standards (Fe2O3 Hematite, Fe2O3 Maghemite and FeO). The valence looks to be Fe2+ for both the ZnO films. Figure 3.2 shows the room temperature XAS spectra for both the Fe and Fe with Al doped epitaxial films along with some standards. The valence of Fe in both the DMS films appears to be Fe2+ as the band edge positions are similar to FeO spectra. The small pre-edge peak of the films is likely due to the less symmetric environment in the Zn site compared to the octahedral coordination in FeO. 3.3.3. Surface morphology
1.2 1 0.8 Y[m]
39.13 nm
54.99 nm
1.2 1 0.8 Y[m] 0.6 0.4 0.2 0
(a)
(b)
0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1
0.00 nm
0.2
0.4
0.6
0.8
1.2
1.4
0.00 nm
X[m]
X[m]
1.6 1.4 1.2 1 Y[m] 0.8 0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 X[m] 1 1.2 1.4 1.6
59.16 nm
(c)
(d)
(d)
0.00 nm
Fig.3.3. (a), (b), (c) The AFM image of Zn(Fe)O and Zn(Fe,Al)O thin films. (d) 3-d view of one of the films. 49
The AFM image of the films recorded for 1 m 1 m scan area have been shown in Fig. 3.3 (a) to (c) for Zn(Fe)O and Zn(Fe,Al)O thin films. The measured r.m.s roughnesses of the films have been obtained to be 1 to 2 nm. Fig. 3.3 (d) is the 3-d view of one of the scanned AFM image of Zn(Fe)O film. 3.3.4. Optical properties To obtain an idea of the band gap of the films and its temperature variation, the temperature dependent absorption spectra in UV regime have been recorded. The UV transmission spectrum of Zn(Fe)O and Zn(Fe,Al)O films with 5% Fe at room temperature are shown in the inset of Fig. 3.4(a). Fig. 3.4(b) and (c) are the same plot for 7 and 10 % Fe concentrations, respectively. The transmittance spectra show the well crystalline nature (sharp drop at the band edges) of all the films. The band gap is determined to be about 3.20 eV for all the films at room temperature.
90 85 80 5% 75 70 65 60 55 50 45 40 35 200 400
% Transmittance
% Transmittance
90
90
% Transmittance
80 70 60 50 40 30
7%
80 70 60 50 40 30
10%
Zn(Fe)O Zn(Fe,Al)O
Zn(Fe)O Zn(Fe,Al)O
Zn(Fe)O Zn(Fe,Al)O
(a)
600 800 1000
(b)
300 600 900
(c)
300 600 900
Wavelength (nm)
Fig.3.4. Room temperature transmission spectra of UV absorption spectroscopy for Zn(Fe)O and Zn(Fe,Al)O films (a) 5% Fe, (b) 7% Fe and (c) 10% Fe. (d) Room temperature transmission spectra of UV absorption spectroscopy for Zn(Fe)O films with different Fe concentrations. The temperature dependence of the direct band gap, determined from the absorption edge, can be described well by Varshnis equation,
Wavelength (nm)
Wavelength (nm)
E g (T ) = E g (0)
T 2 T +
(3.1)
The temperature dependent band gap shown in Fig. 3.5(b) can be fitted by Varshnis equation with Eg(0) = 3.55 eV, = 2.41 meV/K, and = 935 K. In Varshnis equation, is physically associated with the Debye temperature of the crystal and associated with
50
Chapter3
thermal expansion. The Debye temperature obtained for Fe, Al co-doped ZnO is comparable to bulk undoped ZnO (920 K) [19].
600
400 (h)2
200
10 K 50 K 100 K 150 K 200 K 250 K 300 K 350 K 400 K

2.5 3.0 3.5 Energy (eV)
Band gap (eV)
(a)
3.55 3.50 3.45 3.40 3.35 3.30 3.25 0 100 200 300
(b)
0 2.0
400
4.0
Temperature (K)
Fig. 3.5. (a) (h)2 vs. energy plot of Zn(Fe,Al)O films at different temperatures. (b) Temperature dependent band gap plot for Zn(Fe,Al)O sample. 3.3.5. Magnetic properties The ferromagnetic M(H) behavior of both the Zn(Fe)O and Zn(Fe,Al)O films grown on sapphire substrate at optimum deposition condition have been characterized using a SQUID magnetometer in the magnetic field range of 0 - 5 T. The SQUID measurements have been carried out down to 5 K operating temperature. 3.3.5.1. Room temperature magnetic properties The ferromagnetic M(H) behavior at room temperature of both the Zn(Fe)O films for different Fe doping concentrations have been shown in Fig. 3.6. The diamagnetic contributions of sapphire substrate have been subtracted carefully at each magnetic field from the net magnetization [uncorrected raw data (shown in the inset of Fig. 3.6.)] to estimate the actual ferromagnetic contribution of each ferromagnetic film at 300 K. After correcting the substrate contributions in SQUID raw data a ferromagnetic hysteretic M(H) behavior at room temperature is observed for both the films. The coercive field and saturation magnetization for the Zn(Fe)O samples have been listed in Table-3.2.
51
M X10 (emu)
0.15 0.10
M (B/Fe2+)
Zn(Fe)O on sapphire
5% 7%
-4
0.05 0.00
-1
-10000
-2
-5000
5000
10000
H (Oe)
0.04
M (B/Fe2+)
10%
0.02 0.00 -0.02 -0.04 -400 -200 0 H (Oe) 200 400
-0.05 -0.10 -0.15 -10000 -5000
Fig.3.6. Room temperature ferromagnetic M(H) hysteresis loops for Zn0(Fe)O epitaxial films with 5, 7 and 10% Fe concentrations. Lower inset shows the same M(H) plot at 300 K in low field regime. Upper inset shows the uncorrected (from substrate contribution) SQUID raw data Table-3.2: List of saturation magnetization and coercive field of Zn(Fe)O thin films with different Fe concentrations Fe concentrations in Zn(Fe)O thin films 5% 7% 10% Saturation magnetization (B/Fe2+) 0.18 0.04 0.02 135 93 87 Coercive field (Oe)
0 H (Oe)
5000
10000
If all the Fe2+ spins are aligned in high moment state one should expect to attain their full saturation moment value of 4 B/Fe2+ for all the films. The rather small value for saturation magnetization suggests that only a small portion of Fe spins are probably coupled ferromagnetically and that a significant paramagnetic and antiferromagnetic fraction of Fe remains: this is seen explicitly from the observation that the diamagnetic term subtracted from the total signal differs from what should be expected for a sapphire substrate. Moreover, it is also well known fact that the oxygen vacancies produce shallow donor states (defect states) while the zinc vacancies produce shallow acceptor states in
52
Chapter3
ZnO thin films. These states are delocalized due to the hybridization with the Fe d states. The enhanced electron due to oxygen vacancy accommodates in the minority spin channel (let say spin up), so minority spin channels become fully occupied e level and singly occupied t2 levels. On the other hand, Zn vacancies introduces holes into the system, resulting in a completely empty minority spin channel and one hole in the majority spin channel [18]. If the d orbital is partly occupied, the electrons in that orbital then hop to the neighboring d orbital, and make the neighboring Fe atoms in parallel spin configuration. It causes ferromagnetism in the film. On the other hand, if the d cell is completely occupied, energy starts reduced via hoping process which causes antiferromagnetic ordering in the system. This may be the cause of the loss of huge amount of ferromagnetic moment from its expected value in our Fe doped ZnO films. The low temperature M-H loop establishes the fact that the films may contain high order of antiferromagnetic and paramagnetic moments. The decrease of ferromagnetic moment with increasing concentration of iron may be due to the increase of antiferromagnetic coupling between Fe pairs in the matrix. With increase in the Fe doping in ZnO, the average distance between adjacent Fe2+ ions reduces. As the antiferromagnetic energy is less than ferromagnetic energy, the antiferromagnetic coupling between Fe2+Fe2+ ions dominates at higher Fe concentrations and act as a ferromagnetic moment killer reducing average magnetic moment per Fe ion. Similar results are obtained for Mn doped and Ni doped ZnO films [20,21]. 3.3.5.2. Low temperature magnetic properties The temperature dependent M(H) raw SQUID data has been shown in Fig. 3.7(a). The resulting graph of film magnetization versus magnetic field consists of contributions from both the sample and the substrate. Measurements of uncoated sapphire substrates show a large diamagnetic contribution [inset of Fig. 3.7(a)]. The raw SQUID data from a Zn(Fe)O on sapphire shows two clear contributions [shown in Fig. 3.7(a)]. There is a prominent low field ferromagnetic contribution from the epitaxial film. A high field linear dependency with negative slope of diamagnetic contribution from substrate is also observed. There can be a paramagnetic contribution from unreacted components in the films which is also linear in this range. To separate out the ferromagnetic contribution
53
from the rest, we use the fact that it saturates at higher magnetic fields. The magnetization is linear above a certain field in the high field region and a straight line with negative slope can be best fitted. At each temperature the slope of this line has been calculated from the linear fit and subtracted from each point to leave the ferromagnetic contribution. Thus obtained the ferromagnetic moment at different temperatures has been shown in Fig. 3.7(b). The top-left inset of Fig. 3.7(b) shows the clear hysteresis loop at temperature 5 and 300 K confirms the ferromagnetic behavior of the system. The bottomright inset of Fig. 3.7(b) shows the temperature dependent coercive field of Zn(Fe)O samples.
Moment(x 10-4emu)
6 Moment (x10 emu) 4 2 0 -2 -4 -6 5K 50 K 100 K 300 K

-4
1.5
8
0.2
Ferromagnetic moment -4 (x 10 emu)
4 0 -4 -8
1.0 0.5 0.0 -0.5 -1.0
0.0
-0.2
5K 300 K
2000
800
5K 50 K 100 K 300 K
Magnetic field (x 10 Oe)
-4
-2
-2000 -1000 0 1000 Magnetic field (Oe)
(a)
(b)
0
HC (Oe)
600 400 200 0
50
Magnetic field (Oe) Fig. 3.7. (a) Raw SQUID data at different temperature of Zn(Fe)O epitaxial thin film grown on c-sapphire substrate. Inset shows the SQUID data of blank substrate. (b) Ferromagnetism in different temperature. The top left inset is the low field hysteresis loop of Zn(Fe)O at temperature 5 K and 300 K. Right bottom inset shows the temperature dependent coercive field.
-40000-20000 0 20000 40000 Magnetic field (Oe)
-1.5 -60000 -40000 -20000
Temperature (K)
100 150 200 250 300
20000
40000
60000
The change of slope of the raw SQUID [M(H)] data in the high field region with temperature as shown in Fig. 3.7(a) implies that the films contain not only the diamagnetic substrate component (which is temperature independent) but also a huge paramagnetic component in it. To separate out the susceptibility of paramagnetic component at each temperature we consider that the high field slope of the linear fit ( dia + para ) contains both the diamagnetic and paramagnetic components. So,
dia + para = dia + para
(3.2)
54
Chapter3
where the slopes from raw SQUID data at a particular temperature in the very high field regime give dia + para . dia and para are the susceptibilities of diamagnetic component from the substrate and film paramagnetic components which is most likely present from unreacted component in the films. Now, dia is a temperature independent parameter and
para depends on temperature with simple Curie law,
para =
C T
(3.3)
where C is Curie constant and T is temperature in absolute scale (K). Combining Eq. (3.1) and (3.2) we can write,
T dia + para = C + T dia
(3.4)
The plot of T dia + para with temperature [shown in Fig. 3.8(a)] gives a straight line plot whose slope and intercept to y-axis gives the dia and C, respectively. The constant C and dia has been found to be 8.3810-7 emu/Oe/K and -2.7410-8 emu/Oe, respectively. We have also extracted the ferro, para and diamagnetic components of the same Zn(Fe)O film by employing the M-H curve of blank (uncoated) c-sapphire substrate as shown in inset of Fig. 3.7(a). The temperature dependent paramagnetic moment has been shown in Fig. 3.8(b). The comparative studies of diamagnetic, paramagnetic and ferromagnetic moment at 5 K and 300 K have been shown in upper left and lower right insets of Fig. 3.8(b). The magnetization in ferromagnetic materials is generally expressed as,
M = Ng B JBJ ( x) where, Brillouin function BJ (x ) =
x= g B JB k BT
2J + 1 2J + 1 1 1 x) x and coth( coth 2J 2J 2J 2J
. N is the number of atoms per unit volume, g is the g-factor and B is the Bohr
magneton. J is described as the total angular momentum quantum number of the microscopic magnetic moments of the material The saturating nature of paramagnetic moment at higher fields measured at 5 K fits well with the expression of the magnetization containing Brillouin function term keeping g =2 as shown in Fig. 3.8 (c). The rest constant part (NgB) in the expression of the magnetization has been described as constant A.
55
0 -6 Tcdia+para (x 10 ) -2 -4 -6 -8 0
8 Paramagnetic moment (x 10-4emu) 4 0 -4 -8 -0.8 -0.4
/kBT
para
Paramagnetic -5 moment (x10 emu)
(a)
8 6 4 2 0 -2 -4 -6 -8
8
Moment (x10-4 emu)
8 4 0
Para
T=5 K
Ferro
0
(b)
-4 -8
Dia
35000 70000
-70000 -35000
Magnetic field (Oe)

20
Monent (x 10-5emu)
300 K Ferro
Dia
10
5K 50K 100K 300K
-10
Para
-8000 -4000 0 4000 8000
-20
Magnetic field (Oe)
50 100 150 200 250 300 Temperature (K)

(x10-9 emu/Oe)
-10000 -5000 0 5000 Magnetic field (Oe)

I
10000
(d)
6 4 2 0 1.2 0.9 0.6 0.3 0 50 100 150
5K
(c)
0.0 0.4 0.8
Ms (x10-4emu)
II
Fig. 3.8. (a) The plot of T dia + para T . (b) Extracted paramagnetic moment at different temperatures. Insets are the comparative study of diamagnetic, paramagnetic and ferromagnetic moments at 5 K (upper left inset) and 300 K (lower left inset) of the same film. (c) The paramagnetic moment at 5 K fitted with Brillouin function keeping g=2. (d) Paramagnetic susceptibility (I) and saturation magnetization (II) vs. temperature plots of Zn(Fe)O film. Table-3.3: Obtained fit parameters from the Brillouin function fit keeping g =2 at different temperatures. Temperature (K) 5 50 100 300 J 1.21 0.04 1.19 0.13 0.98 0.11 0.991 0.12 A 0.0011 1 10-5 0.0008 5 10-5 0.0007 4 10-5 0.00034 2 10-5 R2(Goodness of fit) 0.99975 0.99978 0.99986 0.99979
Temperature (K)
200
250
300
We get J~1 with excellent goodness of fitting (R2= 0.99975). We have also fitted the paramagnetic moments with the Brillouin function keeping g = 2 for different temperatures also. The fitted parameters for different temperatures (5 K, 50 K, 100 K and
56
Chapter3
300 K) have been summarized in Table-3.3. The J values obtained from the fit for all temperatures are found to be ~ 1.0. From the excellent fit (R2 1) as shown in Table-3.3, it concludes that the paramagnetic moments at different temperatures can be fitted well with a single Brillouin function with a constant value of J (~1). The small value of J indicates that it does not approach towards classical limits (Langevin function). The parameters extracted from the Eq. (3.3) and experimental result has been shown in the Table-3.4. The diamagnetic susceptibility contribution is almost comparable (Table-3.4) but mismatch of the paramagnetic susceptibilities has been found in the system. Table-3.4: Comparative study of paramagnetic susceptibilities at different temperatures Temperature (K) Paramagnetic susceptibility calculated using the measurement of diamagnetic susceptibility of sapphire substrate(-3.1110-7 (emu/gm)/Oe) 4.4310-9 1.7810-9 14.7310-10 3.0210-10 Paramagnetic susceptibility calculated using the Eq. (3.4). Calculated diamagnetic susceptibility (-8.3210-7 (emu/gm)/Oe) 1.6710-7 1.6710-8 8.3510-9 2.7810-9
5 50 100 300
The mismatches of the paramagnetic susceptibilities of the films, estimated from Eq. 3.4 and experiment, imply that the simple Curie law cannot be applicable directly for the DMS systems. The temperature dependent ferromagnetic saturation moment (Ms) and paramagnetic susceptibility (para) has been shown in Fig 3.8 (d). Both ferromagnetic saturation moment and paramagnetic susceptibility decrease with temperature and they do not follow standard Curie law ( 1/T). A sharp exponential rise of both ferromagnetic moment and paramagnetic susceptibility in the low temperature regime reveals more like the insulating type DMS behavior of the film [8,22]. This huge paramagnetic moment may also appear in the films by defects. As discussed earlier it is well known fact that the oxygen vacancies produce shallow donor states (defect states) while the zinc vacancies produce shallow acceptor states in ZnO thin films. These states are delocalized due to the hybridization with the Fe d-states. The
57
enhanced electron due to oxygen vacancy accommodates in the minority spin channel (spin up) of Fe, so minority spin channels become fully occupied eg level and singly occupied t2g levels. On the other hand, Zn vacancies introduce holes into the system, resulting in a completely empty minority spin channel and one hole in the majority spin channel. If the d orbital is partly occupied, the electrons in that orbital then hop to the neighboring d orbital, and make the neighboring Fe atoms in parallel spin configuration. It causes ferromagnetism in the film. On the other hand, if the d cell is completely occupied, energy starts reducing via hoping process which causes antiferromagnetic ordering in the system. From the temperature dependent M-H loop in Fig. 3.7(b), it is found that the magnetization saturates at higher field at lower temperatures compared to same at room temperature. According to the conventional theory of magnetization when thermal energy (kBT) is less, the magnetization should saturate at lower fields. But the situation is completely different in this case. This can be explained by the properties of pinning-type magnets [23]. In pinning type magnet, the Bloch walls cannot travel freely throughout the whole grain because of magnetic inhomogeneities present in the grains. These magnetic inhomogeneities act as pinning centers for the domain walls motion. Apart from the change in magnetization associated with some wall bending, this pinning will prevent further magnetization. Wall displacement (other than bending) can occur only when the force exerted on the wall becomes sufficiently strong. When the strength of the external field exceeds the pinning field strength then only the saturation magnetization occurs. As being very low thermal energy in low temperatures the saturation magnetic fields are higher than the room temperature. So the M-H curve at 300 K saturates earlier than the curves recorded at lower temperatures. The isothermal M2 vs H/M plots (Arrott-Belov plot) have been shown in Fig. 3.9 (a) to confirm the presence of intrinsic spontaneous magnetization [M1/ vs. (H/M)1/ isothermal plots where = 0.5 and =1 in the mean-field limit]. Each plot clearly shows the positive intercept at y-axis for all the temperatures confirming the presence of ferromagnetic spontaneous magnetization in the film for all the temperatures up to 300 K.
58
Chapter3
1.8
Arrott-Belov plot 2 -2 M2 (emu g )
spontaneous magnetization (emu/g)
5K
1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 50 100 150 200 250 300
10
(b)
50 K 100 K
10
-1
300 K (a)
0.0
4.0x10 8.0x10 1.2x10 H/M (Oe-g/emu)
1.6x10
Temperature (K)
Fig. 3.9. (a) Arrott-Belov plots for of Zn(Fe)O epitaxial thin film at different temperatures. (b) Temperature dependent spontaneous magnetization of Zn(Fe)O sample. The temperature dependent spontaneous magnetization obtained from Arrott-Belov plots has been shown in Fig. 3.9 (b). The temperature dependent spontaneous magnetization curve follows the same sharp rise at low temperature behavior as saturation magnetization follows with temperature [shown in Fig. 3.8 (d)]. The temperature dependent behavior of spontaneous magnetization has been found to be similar to an insulating type DMS material.
3.3.5.3. Carrier dependent ferromagnetism properties

Incorporating 1% of Al in the Zn(Fe)O matrix the room temperature ferromagnetic component increases almost four times at room temperature as shown in Fig 3.10(a). However, the understanding of the effect of the additional dopants on the enhancement of ferromagnetism in the DMSs is still an issue of debate. In some literature it has been reported that the additional carrier causes enhancement of ferromagnetism [14]. Li et al. [24] suggest that introducing of Al in Mn doped ZnO results not the increase of carrier concentration but it could break the metastable structures that formed in Mn doped ZnO, leading to spinodal decomposition and lead to Mn rich regions.
59
0.4 0.3
0.6 Paramagneic moment (emu/gm)
M ( /Fe2+) B
0.2 0.1 0.0
Zn(FeAl)O
Zn(Fe)O
(a)
0.4 0.2 0.0 -0.2 -0.4 -0.6 -10000 -5000 0
Zn(Fe)O
Zn(FeAl)O
(b)
-0.1 -0.2 -0.3 -0.4 -10000 -5000 0 5000
10000
5000
10000
H (Oe)
1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 -0.2
Magnetic field (Oe)

10 8 6 4 2 0 0.0 0.2 0.4
(d)
M (emu/gm)
(c)
para (x10
-9emu.gm-1Oe-1)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
nc/ni
nc/ni
0.6
0.8
1.0
1.2
Fig. 3.10. (a) Room temperature ferromagnetic moment M-H loop of Zn(Fe)O and Zn(Fe,Al)O films, (b) room temperature magnetic field dependent paramagnetic moment contribution of those films. (c) and (d) are carrier dependent (nc/ni) room temperature ferromagnetic moment and paramagnetic susceptibility, respectively. The Mn rich region could be the cause of enhancement of ferromagnetic ordering. In our case, we observe that the (Fe, Al) doped ZnO films show the higher carrier concentration ( ~ 8.02 1026 m-3) than the Fe doped one ( ~ 3.34 1026 m-3). The carrier concentrations of all our DMS films were estimated from the magnetic field dependent Hall voltage measurements at room temperature. As discussed in XRD results, it has been observed that the introduction of Al in Fe doped ZnO releases the strain or lattice distortion in our films. Al in Fe doped ZnO results in increase in its carrier density and also break the metastable structures that formed in Fe doped ZnO, leading to spinodal decomposition, which may cause the Fe rich regions. These regions may also be the cause of enhancement of ferromagnetism due to incorporation of Al in iron doped ZnO films. We
60
Chapter3
have also studied the other Al incorporated films which have much higher carrier concentrations (listed in Table-3.5). Table 3.5. Comparative FWHM and carrier concentrations with magnetic moment Samples Zn(Fe)O 5% Fe Zn(Fe)O 5% Fe Zn(Fe)O 5% Fe Zn(Fe)O 5% Fe Zn(Fe,Al)O 5% Fe Zn(Fe,Al)O 5% Fe Zn(Fe,Al)O 5% Fe Zn(Fe,Al)O 5% Fe Zn(Fe,Al)O 5% Fe Zn(Fe,Al)O 5% Fe Carrier Concentrations 1.61 1020 2.08 1020 2.93 1020 3.34 1020 3.09 1020 7.02 1020 7.64 1020 1.08 1020 1.25 1020 2.22 1020 nc/ni 0.076 0.099 0.139 0.158 0.147 0.333 0.362 0.513 0.593 1.051 FWHM 0.472 0.471 0.471 0.472 0.394 0.395 0.394 0.393 0.394 0.394 Magnetic moment 0.04000 0.03896 0.08980 0.08560 0.00000 0.38000 0.20500 0.04686 0.01976 0
The XRD study of those films also shows the strain relaxation which should cause the spinodal decomposition, and hence should enhance the magnetic moment. But, those films with higher carrier concentrations show lower moment which contradict the previously discussed spinodal decomposition theory [24]. Hence, the observation of room temperature ferromagnetic behavior in our DMS films probably can be best explained through the standard theory of carrier induced ferromagnetism. Carrying out the low temperature SQUID measurements and separating out the diamagnetic, paramagnetic, ferromagnetic components as already discussed above, it is clearly seen that the ferromagnetic exchange interaction (magnetization) increases with carrier concentration and reaches to a maximum beyond which it falls drastically at higher carrier concentrations as shown in Fig. 3.10(c). Standard theory of DMS predicts that the exchange is maximized when the nc/ni ratio is in between 0.3 to 0.5 [14]. The reduction of the moment with increasing carrier density ratio of the films occurs when nc/ni > 0.4. In addition, from the low temperature SQUID analysis the extracted paramagnetic
61
susceptibility with carrier concentration shows exactly opposite nature as shown in Fig. 3.10(d).
d4 d4 d4 d4 d4 d4 d4 d4 d4 d4 d4 d4
d4 d4
d4 d4
(a)
ed5 d5 d5 d5 d5 d5 d5 d5 d5 d5 d5 d5
ed5 d10 d10 d5 d10 d10
(b)
d10 d10 d10 d10 d5 d10
d5 d5
d5 d5
d10 d10
d10 d5
Fig.3.11.(a) Electronic band structure for high Tc oxides proposed by Coey et al. [25], (b) The magnetic region in Zn(Fe)O sample. (c) After introducing excess carrier to the system within the limit. The excess electrons sit on the unfilled d state and enhance the up spin population of the polarons. (d) Condition when the carrier density is much higher. The carrier density is higher (cross the limit of nc/ni) the d cell starts to be filled by electrons and decreases up spin population. It causes decrease of magnetic moment. When the electron concentration is very high the d cells of maximum polarons become completely filled and the polaron-polaron distance increases which causes reduction of magnetic moment. The defect such as anion vacancy plays an important role in ferromagnetism in ZnO as this defect forms shallow donor and provides n-type conduction. Zn interstitial is also cause the shallow donor level. The cation vacancy can introduce an electronic defect on neighboring oxygen and creates an O-2p5 anion. The oxygen vacancies are strongly correlated, and they can form extended molecular orbit around the defect site, which couples ferromagnetically. The proposed electronic structure with impurity band splits at higher Curie temperature has been proposed by Coey et al. [25] as shown in Fig. 3.11(a). Doping with Fe2+ splits d level of shallow impurity band which moves down to the 2p band of oxygen. Hence, two region forms: one near the beginning of the series where 3d state cross Fermi level in the impurity band, and one towards the end where 3d state
62
(c)
(d)
Chapter3
cross the Fermi level. If the impurity band is sufficiently narrow, the donor electrons become localized and interact with core spin. Hence, if the localized electron interacts with many magnetic cations it shows completely spin polarization. As the net moment of iron doped samples are much less as expected (4B), one can concludes that the localized electrons are not completely able to interact with all magnetic cations. We also observed that with increasing carrier concentration the magnetization increases. But additional doping of electron kills the magnetic moment beyond a certain value of carrier concentration (nc/ni ~ 0.4). In Fig. 3.11(b), (c) and (d) we have discussed this mechanism. The iron doped ZnO films contains magnetic cation with partially filled d4 states (Fig. 3.11(b)). The magnetization occurs from the interaction of those cations with localized electrons. If free carrier increased in the limit nc/ni < 0.4, the additional electrons transfers to the unfilled d cell and increase net magnetic moment (Fig 3.11(c)). If the carrier concentrations increases further beyond the limit, the excess carriers enter to d states and decreases half field d shell. Net magnetization starts decreasing. At very high carrier concentration d shells become completely filled and net Fe2+ ions available in the system is reduced. So, the distance between nearest magnetically active ions become so large that cannot mediate long range magnetic ordering. The films become eventually paramagnetic in nature. 3.3.6. Electrical properties The presence of magnetic ions such as 3d transition metal (TM) ions in these materials leads to an exchange interaction between traveling sp band electrons or holes and the d electron spins localized at the magnetic ions, resulting in versatile magneticfield-induced functionalities [26]. DMS based materials demonstrated several spin related phenomena such as a spin-polarized transport and luminescence attributable to a sp-d exchange interaction [27]. In the recent years, ZnO based dilute magnetic semiconductors have attracts a lot because of huge controversy between the DMS researchers. So, ZnO based DMS study has a great opening for the researchers. The anomalous Hall Effect (AHE) has been recognized as a powerful technique for demonstrating the ferromagnetic ordering to be intrinsic due to spin-polarized carriers, which mediate ferromagnetic exchange interaction with localized magnetic
63
moments. AHE is well-known to be caused by the emergence of voltage transverse to both an applied current and an external magnetic field proportional to magnetization [28]. The anomalous Hall Effect is attributed to asymmetric scattering involving in spin orbit interaction between conduction electrons and the magnetic moments [29,30]. So this analysis is widely used to study the magnetic behavior of dilute magnetic semiconductors [31,32]. However, the exact mechanism is not clear so far. The questions arise whether the mechanism is intrinsic or extrinsic. Karplus and Luttinger [33] have proposed the phenomenon of Anomalous Hall Effect is intrinsic. On the other hand, some theories attribute the impurity scattering modified by spin orbit interaction namely the skew scattering [34] and the side jump mechanism [35]. This extrinsic mechanism is rather complicated and depends on the impurities and band structures of the DMS materials [36]. One of the characteristics of features of magnetic semiconductors is the sp-d exchange between sp band of the semiconductor and the localized d electrons associated with magnetic ions. Magneto-transport measurements in the DMS systems are extensively used for studying the sp-d interactions of ferromagnetic semiconductors [37, 38]. It is well known fact that the magneto-transport is completely dependent of free carrier concentration of n-type ferromagnetic semiconductors like ZnO [39-41]. The change in carrier concentrations and as well as temperature the characterization of wave function changes from delocalized to localized states which are responsible for change in magnetoresistances (MR) in the DMS systems [42]. Several different mechanisms have been proposed for the spin-dependent MR effect [43,44]. One of the mechanisms is the formation of magnetic polarons [45]. The concept of magnetic polarons can be understood as the variations in the magnetization created by those doped magnetic ions around the localized carriers [46]. If the electrons want to travel through the lattice with low resistance, it must carry the same spin polarization as the surrounding magnetization. Clearly, the transport behavior is influenced by the magnetization condition of the films.
3.3.6.1. Electrical transport properties

The temperature dependent resistivity of the films has been shown in Fig. 3.12 for the temperature range of 1.5 to 300 K. The resistivity drops with temperature for all the
64
Chapter3
films. Figure 3.12(a) and Fig. 3.12(b) are the temperature dependent resistivity plot of the Zn(Fe)O and Zn(Fe,Al)O films with different iron doping.
8.0x10 7.0x10 6.0x10 5.0x10 4.0x10 3.0x10
-4
2.4x10
-4 -4 -4 -4 -4 -4 -4 -4 -5 -5
-4
Zn(Fe)O
10% Fe
2.2x10 2.0x10
Zn(FeAl)O
5% Fe
-4
(m)
1.8x10 1.6x10 1.4x10 1.2x10
(b)
(m)
-4
-4
-4
(a)
0 50 100 150
10%Fe 7%Fe
5% F e
200 250
7% Fe
300
1.0x10 8.0x10
2.0x10
-4
6.0x10
50
100
150
200
250
300
-7.2 -7.6 -8.0 -8.4 -8.8 -9.2 -9.6 -10.0 -10.4 -10.8
Temperature (T)
Zn(Fe)O Zn(FeAl)O
-7.2 -7.6 -8.0 -8.4 -8.8 -9.2 -9.6
Zn(Fe)O
-7.2 -7.6 -8.0

ln ()
Temperature (K)
Zn(Fe)O
ln ()
-8.4 -8.8 -9.2 -9.6

Zn(FeAl)O
ln ()
(c)
0.2 0.3
Zn(FeAl)O
T-1/2(K )
-1/2
(d)
4 5 6
0.120 0.144 0.168 0.192
0.4
0.5
T-1/4 (K
-1/4
0.6 )
0.7
0.8
-10.0
7 8 -1 1000/T (K )
10
Fig. 3.12. (a) Temperature dependent resistivity plot of Zn(Fe)O thin films with 5, 7 and 10% Fe, (b) The same plot for the 1% Al incorporated samples, (c) ln() - T-1/4 plot of Zn(Fe)O and Zn(Fe,Al)O thin films with 5% Fe to test the VRH mechanism. Inset is the ln() - T-1/2 plot of those same films to test the EVRH mechanism and (d) ln() 1000/T plot of those samples which satisfies the thermal excitation process of transport. The conduction mechanism in these DMS films can be best explained by the combination of three types of conduction models (i) variable range hopping (VHR), VRH = 0VRH
T 0 exp VRH T
1/ 4
(3.5),
which describes carrier hopping in localized states. (ii) Efros variable range hopping (EVRH), EVRH = 0 EVRH
T 0 exp EVRH T
1/ 2
(3.6) due to the electron-electron Coulomb interaction at lower temperature range.
65
(iii)
Thermal
excitation
model,
th = 0th exp
EA kT
(3.7),
which describes carriers that have been thermally excited from localized sate to conduction band.
0VRH , T0VRH , 0 EVRH , T0 EVRH and 0th are constants. EA is the thermal activation energy. The
total resistivity can be expressed as,

= ( VRH + EVRH + th )1
(3.8)
The parameters evaluated from the best non-linear 2 fitting method have been listed in the Table-3.6. Table-3.6. Evaluated fit parameters of -T behavior of the Zn(Fe)O and Zn(Fe,Al)O samples using Eq. (3.8). Samples Zn(Fe)O 5% Fe 7% Fe 10% Fe Zn(Fe,Al)O 5% Fe 7% Fe 10% Fe
0VRH (m)-1
42423 12707 2968 2650208 830367 13230
T0VRH (K) 32591 15105 2474 367993 203006 2474
0EVRH (m)-1
1572 1619 1429 6035 6295 6368
T0VRH (K) 0.032 0.015 0.045 0.29 0.031 0.045
0Th (m)-1
19426 21912 4673 1345018 2075335 20828
EA (eV) 0.08256 0.0903 0.05779 0.31743 0.21689 0.05779
Adj. R2
0.99986 0.99927 0.99993 0.99895 0.99972 0.99993
To investigate the temperature dependent transport process in the films we plot ln() with T-1/4, T-1/2, and 1000/T in different temperature ranges. Figure 3.12(c) shows the ln() vs T-1/4 plot of Zn(Fe)O film doped with 5% Fe to find the cross over temperature (T*) and T0. The resistivity rises at low temperature and passes the VRH test (T*<T0) at very low temperature range (1.6 to 4 K). Inset of Fig. 3.12(c) shows the ln() plot with T-1/2 of the same film which gives a straight line in the temperature range 25 to 150 K, implies the Efross variable range hopping due to the electron-electron Coulomb interaction at low temperature range [50]. In between 4 to 25 K the VRH is classed as intermediate [14]. ln() with 1000/T plot of the Zn(Fe)O film has been shown in Fig. 3.12(d) for the temperature range 150 to 300 K. It suggests that the conduction in these
66
Chapter3
thin films is due to the thermally assisted tunneling of the charge carriers through the grain boundary barrier and transition from donor level to conduction band. The transport mechanism at different temperature ranges has been tabulated in Table-3.7.
Table-3.7. The summarized transport mechanism in different temperature ranges Sample Zn(Fe)O Temperature Range 1.6-5 K 5 -40 K 40-150 K 150 300 K Zn(Fe,Al)O 1.6-5 K 5 -40 K 40-150 K 150 -300 K Transport mechanism Variable range hopping [T* < T0] Intermediate[T* >T0] Efross VRH [ = 0 exp (T0/T)1/2 ] Thermal excitation [ ~1000/T] Variable range hopping [T* < T0] Intermediate [T* >T0] Efross VRH [ = 0 exp (T0/T)1/2 ] Thermal excitation [ ~1000/T] Best fit R2 value VRH test passed VRH test failed 0.970 0.0987 VRH test passed VRH test failed 0.988 0.0992
3.3.6.2. Hall Effect study

The hall resistivity with magnetic field plot of Zn(Fe,Al)O film with 5% Fe at different isothermal temperatures has been shown in Fig. 3.13(a). Fig. 3.13(b) and Fig. 3.13(c) are the same plot of the Zn(Fe)O and Zn(Fe,Al)O, respectively for different iron concentrations at 2 K and 300 K (corresponding insets). All the films show the n-type nature of the films. Saturating nature of the Hall resistivity at higher magnetic field range in Fig. 3.13(a) confirms the anomalous Hall Effect behavior of iron doped epitaxial ZnO films. The anomalous Hall Effect can be described by,
H = R0 B + 0 R s M
(3.9)
67
Where, H , R0 and Rs are the Hall resistivity, ordinary Hall co-efficient and anomalous Hall co-efficient, respectively. M is the magnetization of the film. The plot of ordinary Hall co-efficient with temperature of all the films evaluated from temperature dependent Hall measurements have been shown in Fig. 3.13(d) and its insets.
2.0
hall (-m)
hall (m)
1.5 1.0 0.5 0.0 0

2.5 2.0
2K 5K 10 K 50 K 100 K 150 K 200 K 250 K 300 K
Zn(Fe,Al)O with 5% Fe
3.5
(a)
3.0 2.5 2.0 1.5 1.0 0.5 0.0
5% 7% 10%
Zn(Fe)O
hall(m)
(b)
0.5 0.4 0.3 0.2 0.1 0.0 0 2 4 6 8

T = 300 K
T=2K
B (T)
4 B (T)
5% 7% 10%
2
0.5 0.4 R0 (m) 0.3 0.2 0.1 0.0
4 B (T)
8
5%Fe 7%Fe 10%Fe
(c)
R0 (m3/C)
0.5 0.4 0.3 0.2 0.1

9
hall (-m)
1.5 1.0
Zn(Fe,Al)O
0.3
hall (m)
Zn(FeAl)O
T =2 K
0.2 0.1 0.0
T =300 K
0.5 0.0 0 1 2 3
50 100 150 200 250 300 Temperature (T)
4 B (T)
(d)
0
Zn(Fe)O
4 5 B(T)
0.0
50 100 150 200 250 300 Temperature (T)
Fig.3.13. (a) Magnetic field dependent Hall resistivity of Zn(Fe,Al)O thin film with 5% Fe measured at different isothermal temperatures. (b) and (c) are the magnetic field dependent Hall resistivity plots of Zn(Fe)O and Zn(Fe,Al)O thin films, respectively for different Fe concentrations measured at 2 K. Corresponding insets are the same plots measured at 300 K. (d) Temperature dependent ordinary Hall co-efficient of Zn(Fe)O thin films with different Fe concentration. Inset is the same plot for Zn(Fe,Al)O sample.
3.3.6.2.1. Ordinary Hall Effect

From the ordinary Hall co-efficient one can easily find the carrier concentrations and Hall mobility of these DMS films. The calculated temperature dependent carrier concentration of Zn(Fe)O and Zn(Fe,Al)O films for different iron concentrations have been plotted in Fig. 3.14(a) and Fig. 3.14(b), respectively. The increase of carrier concentration with
68
Chapter3
temperature shows semiconducting behavior of the films. To analyze the temperature dependent carrier concentration behavior we have used the multi-donor charge balance equation so that shallow electrically active defect concentrations and activation energies could be extracted [47].
1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0
1.4
(a)
FeAl5 FeAl7 FeAl10
1.2 n (x 1026 m-3) 1.0 0.8 0.6 0.4 0.2 0.0
(b)
Fe5 Fe7 Fe10
n (x 1026 m-3)
100
200 300 1000/T
400
500
100
200
1000/T
300
400
500
Hall mobility (x10-4 m2/V-s)
7 Hall mobility (x10 m /V-s) 6 5 4 3 2 1 0 50 100 150 200 250 300 Temperature (K)
Zn(Fe)O
28 24 20 16 12 8 4 0 50 100 150 200 250 300 Temperature (K)

Zn(Fe,Al)O
(c)
(d)
Fig. 3.14. (a) and (b) are the carrier concentration evaluated from R0 plot with 1000/T for Zn(Fe)O and Zn(Fe,Al)O thin films with different Fe doping. (c) and (d) are the Hall mobility of those films.
For non-degenerate n-type conduction, the charge balance equation adopts the form,
n+ NA =
-4
i =1
g nT 1 + Di Nc
N Di 3 / 2
E Di exp k T B
(3.10)
where n is the carrier concentration, NA is the total acceptor concentration and NDi, EDi and gDi are the concentration, activation energy and donor degeneracy factor of the ith donor Di, respectively. We consider gDi = 2, NC is the effective density of states in the
69
conduction band at 1 K given by N c = 2(m * k B /(2h 2 )) 3 / 2 , where m* is the density of states effective mass, kB is Boltzmanns constant. To fit the temperature dependent carrier concentration we have considered that the acceptor concentration is very less and ND n. The fitted parameters for k = 2 have been shown in the Table-3.8. Table-3.8. The evaluated fit parameters from temperature dependent carrier concentration using Eq. (3.10) Sample Zn(Fe)O 5% 7% 10% Zn(Fe,Al)O 5% 7% 10% ND1 (m-3) 1.071028 9.83 1027 2.15 1028 1.09 1028 2.16 1028 9.54 1026 ND2 (m-3) 3.47 1025 1.89 1025 1.61 1025 3.9 1025 3.36 1025 1.30 1025 ED1 (meV) 181.79 133.61 151.79 75.59 108.92 545.11 ED2 (meV) 217.41 156.15 208.26 315.80 333.59 72.89
The temperature dependent Hall mobility has been plotted in Fig. 3.14(c) and Fig. 3.14(d) for Zn(Fe)O and Zn(Fe,Al)O, respectively. The mobility first decreases with increasing temperature up to a certain temperature. After that it starts to increase up to a certain temperature and then starts decreasing. The mobility of electrons in nondegenerate single crystal ZnO is limited primarily by scattering due to ionized impurities, deformation potential and piezoelectric acoustic phonons, and polar optic phonons. Grain boundary scattering has to be considered as well for such films. The carrier mobility also depends on free carrier concentration of the films. At very low temperature range the electron-electron scattering dominates over other. With increasing temperature free carrier concentration increases and causes a decrease of mobility. The electron-electron collision do not affect the current density directly as they can not alter the total momentum. They just randomize the carrier distribution and the momentum randomly distributed to different velocity groups. The electron-electron collision gives rise to a net
70
Chapter3
transfer of momentum, and results greater rate of momentum transfer and lower the mobility. The electron-electron scattering mobility is inversely proportional to free electron concentration [ e e 1 / n(T ) ] [48]. In the comparatively higher temperature range the electron-electron scattering does not dominates and the impurity scattering as well as grain boundary scattering starts to dominate. In the moderate low temperature region impurity scattering dominates. With increasing temperature the localized impurity scattering start decrease which causes an increase of mobility. The impurity scattering is given by [49],
2 AT 3 / 2 BT 2 BT I = 1+ ln 2 NI N I N I + BT 1
(3.11)
Where, A and B are constants and NI is the ionized impurity scattering. The electron can face some grain boundary scattering also. The mobility due to grain boundary scattering is given by,
B = 0 exp( B / k B T )
(3.12)
where 0 = qc l / 8k B T . The l is the grain size and c = (8k B T / m * )1 / 2 is the thermal velocity. B is the effective barrier height between two grains. At higher temperature lattice scattering dominates which causes again decrease of mobility. The temperature dependent mobility due to lattice scattering can be expressed as [50],
L = C
D T
(3.13)
Where C, D and are constants. The total Hall mobility can be expressed using Matthiessens rule,
1 1 1 1 1
ee
(3.14)
3.3.6.2.2. Anomalous Hall Effect

Figure 3.15(a) shows the temperature dependence of anomalous Hall coefficient, Rs of the Zn(Fe,Al)O film with 5% Fe, exhibiting decrease of Rs with increasing temperature. The observation of anomalous Hall Effect in this DMS film also provides
71
evidence of intrinsic carrier-mediated ferromagnetism [51]. The AHE observed in other Zn(Fe)O and Zn(Fe,Al)O films with higher Fe doping is very weak compared to Zn(Fe,Al)O film with 5% Fe. One of the possible reasons might be the relatively large R0 and low magnetic moments in other Zn(Fe)O and Zn(Fe,Al)O thin films due to smaller carrier concentration [52]. The origin of the anomalous Hall Effect is believed to be the spin-orbit interaction between the carrier angular momentum and the localized spin. Rs has a power law relationship with the ohmic resistivity and is given by,
R s = C n
(3.15)
where, C is a constant. The exponent n=1 corresponds to the skew scattering and n=2 corresponds the quantum mechanical side jump scattering [53]. Considering the both mechanism one can write [54],
R s = a sk + b sj 2
(3.16)
where sk ~ a sk 0 M represents the average deflection of a charge carrier at a scattering center. The bsj is associated with a side-jump mechanism where the charge carriers trajectory is displaced a fixed distance perpendicular to its original path at each scattering centers.
0.03
(a) Rs (m3/C)
0.03
Rs (m /C)
0.01
0.01
Rs=b
0.02
=a
2
0.02
+b
(b)
0.00 0 50 100 150 200 250 300

Temperature (K)
0.00 1.0x10
-4
1.5x10
Fig. 3.15. (a) Anomalous Hall co-efficient (Rs), evaluated from Fig. 3.13(a), plot with temperature for the Zn(Fe,Al)O thin films with 5% Fe doping. (b) Relation between Rs with linear resistivity of the film. The red line is the best fit curve with the Eq. 3.16 and the green line is the fitted curve with skew scattering . Red line fit describes well the Rs vs. behavior of this Zn(Fe,Al)O DMS film with 5 % Fe doping.
72
2.0x10 (-m)
-4
-4
2.5x10
-4
Chapter3
Fig. 3.15(b) shows the Rs vs plot. The fitted curve using R s = a sk + bsj 2 has been shown by red line and R s = bsj 2 has been shown by green line. The red curve fits very well with the experimental data as shown in Fig. 3.15(b) and it confirms that both the mechanisms are presents in the Zn(Fe,Al)O with 5% Fe film. The negative ask value (~268 units) is widely observed in ferromagnetic Transition Metals.
3.3.6.3. Magnetoresistance behaviors

4 3 % MR 2 1 0 -1 -8 -6 -4 Zn(Fe)O -2 0 2 4 Magnetic field (T) 6 8
1.6 K 2.3 K 4.2 K 6.2 K 8.4 K 9.4 K 10 K
1.6 K 10 K 20 K 30 K 40 K 50 K 60 K 70 K 80 K 90 K 100 K
(a)
6 4 2 % MR 0 -2 -4 -6 -8 -6 Zn(Fe,Al)O
(b)
2K 10 K 20 K 30 K 40 K 50 K 60 K 70 K 80 K 90 K 100 K
-4 -2 0 2 4 Magnetic field (T)
4.0 3.5 (c) 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Zn(Fe)O -0.5 -1.0 -10 -8 -6 -4 -2 0 2 4 6 Magnetic field (T)
6 4 2
% MR
% MR
0 -2 -4
Zn(Fe,Al)O
8 10
-6 -10 -8 -6 -4 -2 0 2 4 6 Magnetic field (T)
1.6 K 2.3 K 4.2 K 6.2 K 8.4 K 9.4 K 10 K
(d)
8 10
Fig.3.16. (a) and (b) The magnetic field dependent %MR measured at different isothermal temperature of Zn(Fe)O and Zn(Fe,Al)O with 5% Fe concentration, respectively. (c) and (d) The %MR plot with magnetic field measured at lower temperatures upto 10 K for those same samples, respectively. Having a single-valley conduction band and the possibility of heavy n-type carrier doping, ZnO is a suitable material for the study of magnetotransport. Isothermal MR has been measured at different temperatures with the magnetic field parallel to the c-axis of the films. Figure 3.16(a) and Fig. 3.16(b) are the nature of % of MR of the 5% Fe doped Zn(Fe)O and Zn(Fe,Al)O films measured at different temperatures. Figure 3.16(c) and Fig. 3.16(d) are the same for those films at lower temperature ranges. The magnetic field
73
dependent % of MR plot shows different behavior at different temperatures for all the doped films as shown in Fig. 3.17.
Fig. 3.17. %MR plot with magnetic field of Zn(Fe)O and Zn(Fe,Al)O thin films with different Fe concentrations. (a), (c) and (e) are the %MR nature of Zn(Fe)O thin films with different Fe concentrations at temperatures 1.6 K, 10 K and 20 K, respectively and (b), (d) and (f) are the %MR nature of Zn(Fe,Al)O samples at temperatures 1.6 K, 10 K and 20 K, respectively. The magnetoresistance (MR) of the films have been measured at different temperatures to investigate the sd exchange interaction between the conducting s-electron spins and the d-electron spins localized at the magnetic Fe impurities [55]. We have observed the positive MR at low magnetic field and negative MR at higher magnetic field. The s-d exchange-induced spin splitting of the conduction band could account for positive MR while suppression of electrons at weak localization of impurity centers could account for the negative MR of the iron doped ZnO films. The behavior of MR at different field range can be described in different four ways (i) A positive MR at lower field range which arises in a two-band model from the action of the Lorentz force on the mobile carriers. For carriers in closed orbits, this term is of the form % MR =
aH 2 b 2 + cH 2
. This
74
Chapter3
saturates MR at higher fields, (ii) the open orbits terms, for which the magnetoresistance is quadratic and nonsaturating, is % MR = dH 2 , (iii) A negative term arises due to spin-flip scattering from singly occupied localized states with s =1/2 which
H % MR = cosh f
1
is given by
1 ,
(iv) A negative term due to scattering from a paramagnetic or
ferromagnetic moment is given by % MR = hM 2 where h is the dimensionless coefficient which depends on the strength of the s-d scattering in the system. The parameters a, b, c, d, f and h are the constants depend on the free carrier concentrations, magnetic properties of the films etc.
6
% MR at 8 T
3 2 1 0 -1 -2 0 20 40 60 80 Temperature (K) 100

7%
4
%MR at 8 T
(a)
2 0 -2
5%
0.9
%MR at 8 T
(b)
10%
-4 -6 0
Zn(FeO) Zn(Fe,Al)O
0.0
-0.9
20
40 60 80 Temperature (K)
100
Fig.3.18. The plot of %MR measured at 8 T magnetic field with temperatures of Zn(Fe)O and Zn(Fe,Al)O thin films with 5% Fe. Inset (a) and (b) are the same plot for 7% and 10% Fe doped films, respectively. The %MR is strongly temperature as well as free carrier concentration dependent. The semiconducting transition metal doped ZnO films show low field positive %MR at 1.6 K as shown in Fig. 3.17(a) and (b). Increasing of carrier concentration by incorporating 1% Al causes decrease of low field positive MR and increase of high field negative MR in the films. MR is positive at 10 K as shown in Fig. 3.17(c) and (d). The enhanced positive MR in the Al incorporated systems is caused by enhanced spin splitting of conduction band due to s-d exchange interactions. At 20 K the MR is negative at lower field and positive at higher field as shown in Fig. 3.17(e) and (f). MR shows oscillatory behavior at that temperature. The negative MR decreases in the Al incorporated films due to enhancement of spin splitting conduction band. The films show
75
20 40 60 80 Temperature (K)
100
negligible negative MR over 50 K as the insulating type DMS films shows. The temperature dependent %MR has been shown in Fig. 3.18 for Zn(Fe)O and Zn(Fe,Al)O films with 5% Fe. The insets (a) and (b) of Fig. 3.18 are the same plot for 7 and 10% Fe. As temperature increases the resistivity due to spin disorder scattering increases and it becomes larger than the resistivities due to impurity and thermal scattering. So, the MR increases with increasing temperature. At higher temperature the MR starts decreasing because of the both ionized impurity scattering and phonon scattering become independent of sub-band spin spilt energy (), whereas spin-disordered scattering decreases with . So, the MR vs. temperature curve shows the hump giving a peak of MR at a certain temperature. 3.4. Summary The high crystalline quality epitaxial Zn(Fe)O thin film doped with iron deposited on sapphire substrate at a substrate temperature of 450 C shows room temperature ferromagnetic behavior. Increasing of Fe doping concentration in the ZnO films decreases the magnetic moment of the systems. The incorporation of 1% Al enhances the saturation moment up to three times for 5% Fe doped samples. This result concludes that there is the effect of free carrier density on magnetism. A clear correlation between the magnetization per transition metal ion and the ratio of the number of carriers and number of donors have been found in these films and establishes the theory of carrier induced ferromagnetism. From the detailed low temperature magnetization investigation of all our (Fe,Al) doped films it has been confirmed that the ferromagnetic moment along with a huge paramagnetic components are present in each film. The steep exponential rise of ferromagnetic moment and paramagnetic susceptibility of the films in the lower temperature regimes do not follow the standard Curie law but it behaves more like to a insulating type DMS. We have also attempted to establish the carrier induced effect in our DMS films using defect model. The magnetic and transport properties of the Zn(Fe)O and Zn(Fe,Al)O films with 5, 7 and 10% Fe concentration grown by a PLD technique are investigated. Temperaturedependent Hall effect measurements have been performed on Zn(Fe)O and Zn(Fe,Al)O highly crystalline epitaxial thin films. We have extracted the free carrier concentration
76
Chapter3
and Hall mobility using the ordinary Hall coefficient. The Hall data analysis revealed that the dominant donor has an activation energy ranging from 33 to 41 meV. The temperature dependent Hall mobility data has can be explained by several type of scattering mechanism viz. ionized impurity, acoustic deformation, piezoelectric potential, polar optical scattering and as well as grain boundary scattering. The high field saturating nature of Hall resistivity in Zn(Fe,Al)O thin film also confirms the presence of ferromagnetism in the film. The behavior of anomalous Hall co-efficient with linear film resistivity confirms the presence of both scattering mechanisms (skew scattering and side jump mechanism) in the Zn(Fe,Al)O epitaxial thin film. We have observed the positive MR at low magnetic field and negative MR at higher magnetic field for all the doped DMS fims. The s-d exchange-induced spin splitting of the conduction band could account for positive MR while suppression of electron at weak localization of impurity centers could account for the negative MR of the iron doped ZnO. Negative magnetoresistance at higher magnetic field has been observed in transition-metal-doped ZnO DMS films at lower temperature. References [1] T. Dietl, H. Ohno, F. Matsukura, J. Cibert, and D. Ferrand, Zener Model Description of Ferromagnetism in Zinc-Blende Magnetic Semiconductors, Science 287, 1019 (2000). [2] T. Story, R. R. Galazka, R. B. Frankel, and P. A. Wolff, Carrier-ConcentrationInduced Ferromagnetism in PbSnMnTe, Phys. Rev. Lett. 56, 777 (1986). [3] P. azarczyk, T. Story, M. Arciszewska, and R. R. Gazka, Magnetic phase diagram of Pb1xySnyMnxTe semimagnetic semiconductors J. Magn. Magn. Mater. 169, 151 (1997). [4] F. Matskura, H. Ohno, A. Shen, and Y. Sugawara, Transport properties and origin of ferromagnetism in GaMnAs, Phys. Rev. B 57, R2037 (1998). [5] H. Ohno, Making Nonmagnetic Semiconductors Ferromagnetic, Science 281, 951 (1998). [6] M. Oestreich, J. Hubner, D. Hagele, P. J. Klar, W. Heimbrodt, W. W. Ruhle, D. E. Ashenford, and B. Lunn, Spin injection into semiconductors, Appl. Phys. Lett. 74, 1251 (1999). [7] Y. Ohno, D. K. Young, B. Beschoten, F. Matskura, H. Ohno, and D. D. Awschalom, Electrical spin injection in a ferromagnetic semiconductor heterostructure, Nature 402, 790 (1999). [8] A. Kaminski, S. Das Sarma, Polaron Percolation in Diluted Magnetic Semiconductors, Phys. Rev. Lett. 88, 247202 (2002). [9] S. J. Pearton, C. R. Abernathy, M. E. Overberg, G. T. Thalei, D. P. Norton, N. Theodoropoulou, A. F. Hebard, Y. D. Park, F. Ren, J. Kim, and L. A. Boatner, Wide band gap ferromagnetic semiconductors and oxides, J. Appl. Phys. 93, 1 (2003).
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[42] Qingyu Xu, Lars Hartmann, Heidemarie Schmidt, Holger Hochmuth, Michael Lorenz, Rdiger Schmidt-Grund, Chris Sturm, Daniel Spemann, and Marius Grundmann, Metal-insulator transition in Co-doped ZnO: Magnetotransport properties, Phys. Rev. B 73, 205342 (2006). [43] S. S. P. Parkin, N. More, and K. P. Roche, Oscillations in exchange coupling and magnetoresistance in metallic superlattice structures: Co/Ru, Co/Cr, and Fe/Cr, Phys. Rev. Lett. 64, 2304 (1990). [44] Jagadeesh S. Moodera, Janusz Nowak, and Rene J. M. van de Veerdonk, Interface Magnetism and Spin Wave Scattering in Ferromagnet-Insulator-Ferromagnet Tunnel Junction, Phys. Rev. Lett. 80, 2941 (1998). [45] T. Ditel, J. Spalek, Effect of thermodynamic fluctuations of magnetization on the bound magnetic polaron in dilute magnetic semiconductors, Phys. Rev. Lett. 28, 1548 (1983). [46] Jing Wang, Zhengbin Gu, Minghui Lu, Di Wu, Changsheng Yuan, Shantao Zhang, Yanfeng Chen, Shining Zhu, and Yongyuan Zhu, Giant magnetoresistance in transitionmetal-doped ZnO films, Appl. Phys. Lett. 88, 252110 (2006). [47] K T Roro, G H Kassier, J K Dangbegnon, S Sivaraya, J E Westraadt, J H Neethling, A W R Leitch and J R Botha, Temperature-dependent Hall effect studies of ZnO thin films grown by metalorganic chemical vapour deposition, Semicond. Sci. Technol. 23, 055021 (2008). [48] P. P. Debye and E. M. Conwell, Electrical Properties of N-Type Germanium, Phys. Rev. 93, 693(1954). [49] J. M. Dorkel, P. Leturcq, Carrier mobilities in silicon semi-empirically related to temperature, doping and injection level, Solid State Electronics 24, 821 (1981). [50] Seong-Il Kim, Chang-Sik Son, Min-Suk Lee, Yong Kim, Moo-Sung Kim, and SukKi Min, Temperature dependent electrical properties of heavily carbon-doped GaAs grown by low-pressure metalorganic chemical vapor deposition, Solid State Comm. 93, 939 (1995). [51] Y. Z. Peng, T. Liew, T. C. Chong, C. W. An, and W. D. Song, Anomalous Hall effect and origin of magnetism in Zn1xCoxO thin films at low Co content, Appl. Phys. Lett. 88, 192110 (2006). [52] Qingyu Xu, Lars Hartmann, Heidemarie Schmidt, Holger Hochmuth, Michael Lorenz, Rdiger Schmidt-Grund, Daniel Spemann, and Marius Grundmann, Magnetoresistance effects in Zn0.90Co0.10O films, J. Appl. Phys. 100, 013904 (2006). [53] P. Khatua, T. K. Nath, and A. K. Majumdar, Extraordinary Hall effect in selfassembled epitaxial Ni nanocrystallites embedded in a TiN matrix, Phys. Rev. B 73, 064408 (2006). [54] Z. Yang, W. P. Beyermann, M. B. Katz, O. K. Ezekoye, Z. Zuo, Y. Pu, J. Shi, X. Q. Pan, and J. L. Liu, Microstructure and transport properties of ZnO:Mn diluted magnetic semiconductor thin films, J. Appl. Phys. 105, 053708 (2009). [55] P. Stamenov, M. Venkatesan, and L. S. Dorneles, D. Maude, and J. M. D. Coey, Magnetoresistance of Co-doped ZnO thin films, J. Appl. Phys. 99, 08M124 (2006).
80
Chapter 4
Junction magnetoresistance of Pt/Zn(Fe)O and Pt/Zn(Fe,Al)O metal-dilute magnetic semiconductor junction
Thischapterisbasedon Internationaljournal 1. Room temperature enhanced positive magnetoresistance in Pt and carrier induced Zn(Fe)O and Zn(Fe,Al)O dilute magnetic semiconductor junction) by S. Chattopadhyay, T. K. Nath Journal of Applied Physics vol. 108, pp.083904(2010).SelectedforVirtualJournalofNanoscaleScience&TechnologyfortheOctober25,(2010) Conference/Symposia 2. Room temperature magnetic sensors with Zn(FeAl)O by Pt Schottky contact by S. Chattopadhyay, T. K. Nath 54thDAESolidStatePhysicsSymposium(2009)
JunctionmagnetoresistanceofPt/Zn(Fe)Oand Chapter4 Pt/Zn(Fe,Al)Ometaldilutemagneticsemiconductorjunction
4.1. Introduction Spin-polarized electron injection into semiconductors has been a field of growing interest in present microelectronics era. The injection and detection of a spin-polarized current in a semiconducting material could combine magnetic storage of information with electronic readout in a single semiconductor device [1]. Spin injection across a ferromagnet-nonmagnetic metal interface provided a cornerstone for the field of spin dependent transport in metals. The spin degree of freedom holds promise for the realization of enhanced or novel device concepts and applications in microelectronics. Most of the existing spintronic applications are based on metallic devices such as spin valves [2], magnetic tunnel junctions [3], spin torque effects [4], domain wall devices [5], etc. An important hurdle in this context is the inefficient injection of spin-polarized currents from metallic ferromagnets into semiconductors due to the large mismatch in conductivities [6]. Another research direction is the study of spin injection and transport in more traditional devices aimed at room-temperature operation [7]. Zinc oxide based materials have many interesting and useful properties in the field of optoelectronics and sensing devices [8,9]. Applications of such materials are especially attractive on consideration of the low cost and lack of toxicity of zinc oxide. The investigation on diluted magnetic semiconductors (DMS) [10-13] demonstrated an application of ZnO as a host material for spintronic devices, which make use of electron spin for data reading and writing. To integrate the DMS into present electronics, lowdimensional structures are required for exploiting the advantages offered by the spin [14]. The basic DMS property of ZnO is that it shows ferromagnetism at room temperature. In this chapter, the room temperature J-V properties of the junction between paramagnetic novel metal, Pt and dilute magnetic semiconductor with 5, 7 and 10% iron doped ZnO have been studied. In this work we have showed that the reasonably high value of positive magnetoresistances persists at the junction at room temperature and it depends on the magnitude of the magnetic moment of the dilute magnetic semiconducting (DMS) ZnO films. 4.2. Experimental procedure The detailed preparation method of the pulsed laser deposited iron doped epitaxial ZnO thin films [Zn(Fe)O] and 1% Aluminum incorporated iron doped ZnO films 81
Chapter4 JunctionmagnetoresistanceinPtandcarrier inducedZn(Fe)OandZn(Fe,Al)Ojunction
[Zn(Fe,Al)O] with iron concentrations 5, 7, 10% have been discussed in chapter-3 section-3.2. The point contact Pt metal has been used with the film to make a non-ohmic (Schottky) type contact. Undoped ZnO thin film has also been grown on c-plane (0001) sapphire substrate using the same PLD technique employing KrF excimer laser ( = 248 nm) as discussed in chapter-3 for comparative study. The I-V characterizations have been carried out using Keithley 2612 source meter with 1 microvolt resolution. The magnetic field was applied in the direction of current parallel to the film plane geometry using a high precision electromagnet (polytronic, model HEM 100). 4.3. Results and discussion 4.3.1. Structural properties The cross sectional high resolution transmission electron microscope (HRTEM) image, shown in Fig. 4.1(a) clearly establishes that the ZnO films grown on (0001) sapphire substrate are highly epitaxial and well crystalline in nature. The film - substrate interface is very sharp having extremely good lattice matching between substrate and film as discussed detailed in chapter-3.
(a)
(b)
(c)
(d)
Fig.4.1. (a) Cross sectional HRTEM image of Zn(Fe)O on sapphire substrate confirms that the films are epitaxial and well crystalline in nature. (b) Room temperature near edges EXAFS spectra for both Zn(Fe)O and Zn(Fe,Al)O epitaxial films compared to some standards. The valence looks to be Fe2+ for both the ZnO films. (c) and (d) are the AFM image of Zn(Fe)O for the scan area of 5 m 5 m and 1 m 1 m, respectively.
82
The room temperature near edge EXAFS spectra for both the Fe and Fe with Al doped epitaxial films along with some standards (FeO, Fe2O3 maghemite and Fe2O3 hematite) have been shown in Fig. 4.1(b). The valence of Fe in both the DMS films appears to be Fe2+ as the band edge positions are similar to FeO spectra. The small pre-edge peak of the films is likely due to the less symmetric environment in the Zn site compared to the octahedral coordination in FeO. The AFM image of the films recorded for 5 m 5 m and 1 m 1 m scan area have been shown in Fig. 4.1(c) and Fig. 4.1(d), respectively. The measured r.m.s. roughness of the films have been obtained to be ~ 1 nm. The thicknesses of the films are about 0.3 to 0.4 m. As discussed in earlier chapter all the Zn(Fe)O and Zn(Fe,Al)O are epitaxial and highly crystalline in nature. 4.3.2. Magnetic properties The room temperature ferromagnetic M(H) behavior of the Zn(Fe)O and Zn(Fe,Al)O films grown on sapphire substrate at optimum deposition condition in the magnetic field range of 0 to 1 T using a SQUID magnetometer have been shown in Fig. 4.2.
0.4
0.15 0.10
M (B/Fe2+) (a)
M (B/Fe2+)
0.3 0.2 0.1 0.0 -0.1 -0.2 -0.3 -0.4 -10000 -5000 0
Zn(FeAl)O
(b)
Zn(Fe)O
0.05 0.00
5% Fe doped 7% Fe doped 10% Fe doped
-0.05 -0.10 -0.15 -10000 -5000 0 H (Oe)
5000
10000
5000
10000
H (Oe)
0.03
0.08 M (B/Fe2+) 0.04
Zn(Fe)O Zn(FeAl)O
Zn(FeAl)O
(c)
0.02 M (B/Fe2+) 0.01 0.00 -0.01 -0.02 -0.03 -0.04 -10000
(d)
Zn(Fe)O
0.00
-0.04 -0.08 -10000 -5000 0 H (Oe) 5000
10000
-5000
0
H (Oe)
5000
10000
Fig.4.2. Ferromagnetic M-H loop for all the Zn(Fe)O and Zn(Fe,Al)O films at room temperature. (a) M-H loop of Zn(Fe)O films with different Fe doping concentrations. (b), (c) and (d) are the comparative magnetization behavior between Zn(Fe)O and Zn(Fe,Al)O films with 5, 7 and 10% Fe concentrations, respectively. Al content is 1% for all the films. 83
The diamagnetic contributions of sapphire substrate have been subtracted carefully at each magnetic field from the net magnetization (uncorrected raw data) to estimate the actual ferromagnetic contribution of such ferromagnetic films at 300 K [Detailed work on this is discussed in chapter-3]. Figure 4.2(a) shows the M-H loop of Zn(Fe)O samples with different doping concentrations of iron. Figure 4.2(b), (c) and (d) show comparative study of Zn(Fe)O and Zn(Fe,Al)O films with 5, 7 and 10% Fe doped, respectively. After correcting the substrate contributions in SQUID raw data a ferromagnetic hysteretic M(H) behavior at room temperature is observed for both kind films. The coercive field and saturation magnetization for the Zn(Fe)O sample are found to be 135 Oe and 0.18 B/Fe2+. In the case of 1% Al incorporated film the coercive field is 69 Oe and the saturation magnetization is strikingly enhanced to 0.4 B/Fe2+. The 7% and 10% Fe doped Zn(Fe)O samples show magnetic moment 0.04 B/Fe2+ and 0.02 B/Fe2+ respectively. The decrease of ferromagnetic moment with increasing concentration of iron may be due to the increase of antiferromagnetic coupling between Fe pairs in the matrix. With increase in the Fe doping in ZnO, the average distance between adjacent Fe2+ ions reduces. As the antiferromagnetic energy is less than ferromagnetic energy, the antiferromagnetic coupling between Fe2+Fe2+ ions dominates at higher Fe concentrations and act as a ferromagnetic moment killer reducing average magnetic moment per Fe ion. Similar results are obtained for Mn doped and Ni doped ZnO films [15,16]. 1% Al incorporation for those higher doping (7% and 10% Fe doping) cases also enhances the magnetic moment mainly due to enhanced carrier induced ferromagnetism [12]. 4.3.3 Current-voltage characteristics without applied magnetic field The current density-voltage (J-V) characteristics of Zn(Fe)O and Zn(Fe,Al)O with Pt non-ohmic point contact with 0.280.01 mm2 contact area has been shown in Fig. 4.3. Figure 4.3(a) shows the J-V behavior of Zn(Fe)O films with different Fe doping percentages. Figure 4.3(b), (c) and (d) are the comparative J-V behavior of ZnO, Zn(Fe)O and Zn(Fe,Al)O for 5%, 7% and 10% iron doping, respectively. The junction J-V characteristics are denoted as [17],
e (V IR s ) J = J 0 exp kT
(4.1)
84
where, J0 is the reverse saturation current density. and Rs are, ideality factor and junction series resistance, respectively. The parameters evaluated from the forward J-V curves of all the films shown in Fig. 4.3 have been summarized in Table 4.1. The ideality factor of all Zn(Fe,Al)O samples lies between 1 and 2 and the values are near to 1 implies that the thermionic emission dominates in Zn(Fe,Al)O samples whereas for Zn(Fe)O films recombination degeneration transport process along with other defect induced transport mechanism dominates.
10
Current density(A/cm2)
1
Current density(A/cm )
10 10 10 10 10
10 10 10 10 10
-1
-1
-2
-2
ZnO
-3
-4
Zn(Fe)O 5% Fe Zn(Fe)O 7% Fe Zn(Fe)O 10% Fe
(a)
4 6 8
-3
ZnO Zn(FeAl)O Zn(Fe)O
5% Fe doped
-4
(b)
4 6 8
-8
10
2 1
-6
-4
-2 0 2 Voltage (V)
-8
-6
-4
-2 0 2 Voltage (V)
10
2
10 10 10 10
10 10 10 10
-1
-1
-2
-3
ZnO Zn(Fe)O Zn(FeAl)O
7% Fe doped
-2
(c)
4 6 8
-3
ZnO Zn(Fe)O Zn(FeAl)O
10% Fe doped
(d)
6 8
10
-4
10
-4
-8
-6
-4
-2 0 2 Voltage (V)
-8
-6
-4
-2 0 2 4 Voltage (V)
Fig. 4.3. Junction J-V characteristics for all the Zn(Fe)O and Zn(Fe,Al)O films at room temperature. (a) J-V characteristics of Zn(Fe)O films with different Fe doping concentrations. (b), (c) and (d) are the comparative J-V study between Zn(Fe)O and Zn(Fe,Al)O films with 5, 7 and 10% Fe concentrations, respectively. Al content is 1% for all films. 4.3.4. Current-voltage characteristics with applied magnetic field Figure 4.4 shows the forward J-V characteristics of such magnetic semiconducting thin film junctions with Pt point contact and the J-V behaviors show reasonably high sensitivity under magnetic field according to their magnetic moments. Figure 4.4(a), (b) and (c) are the J-V plot of Zn(Fe)O films with 5, 7 and 10% iron 85
doping, respectively, and Fig. 4.4(d), (e) and (f) are the same plots of Zn(Fe,Al)O samples. The change of junction magneto-resistances (JMR) at a fixed bias voltage (7 V) with applied magnetic field up to 0.6 T of different Zn(Fe)O and Zn(Fe,Al)O have been shown in corresponding insets of Fig. 4.4. The J-V characteristics under magnetic field have been fitted by the Eq. (4.1) and the parameters have been summarized in Table 4.1. The series resistance increases with applied magnetic field and it shows the positive junction magneto-resistance behavior of the films.
% JMR
3.5
Current density (A/cm2)
10
12
0T 0.6 T
-0.6 -0.3 0.0 0.3 Magnetic field(T) 0.6
20 15 10 5
% JMR
3.0 2.5 2.0 1.5 1.0 0.5 0.0

3.5
8 6 4 2 0
10 8 6 4 2
0T 0.6 T
-0.6 -0.3 0.0 0.3 0.6 M agnetic field(T)
(a)
Zn(Fe)O with 5% Fe
(d)
Zn(FeA l)Owith 5%Fe and 1%A l
0
8 6
4 6 Voltage (V)
8
0T
10
0 0
12
10 8
4 6 V oltage (V )
0T 0.6 T
% JMR
Current density (A/cm )
4 2 0 -0.6 -0.3 0.0 0.3 0.6
0.6 T
% JMR
3.0 2.5 2.0 1.5 1.0 0.5 0.0
10 8 6 4 2 0 0
6 4 2 0 -0.6 -0.3 0.0 0.3 Magnetic field (T) 0.6
Magnetic field (T)
(b)
Zn(Fe)O with 7% Fe
(e)
Zn(FeAl)O with 7% Fe and 1% Al 2 3 4 5 6 7 8 Voltage (V)
0T 0.6 T
-0.6 -0.3 0.0 0.3 Magnetic field (T) 0.6
0
3
3.5
% JMR
6 8 Voltage (V)
0T
10
1
8 % JMR 6 4 2 0
12
2.5 2.0 1.5 1.0 0.5 0.0 0
1 0 -0.6 -0.3 0.0 0.3 Magnetic field (T) 0.6
0.6 T
3.0
10 8 6 4 2 0
(c)
(f)
Zn(Fe)O with 10% Fe
Zn(FeAl)O with 10% Fe and 1% Al
4 6 Voltage (V)
10
3 4 5 Voltage (V)
Fig. 4.4. Junction J-V characteristics with and without applied magnetic field at room temperature; (a), (b) and (c) are the J-V properties of Zn(Fe)O film with Fe concentration 5, 7 and 10%, respectively. (d), (e) and (f) are the same of Zn(Fe,Al)O with Fe concentration 5, 7 and 10%, respectively. Insets of all the figures of Fig.4 are the plot of %JMR with different applied magnetic field of the corresponding junctions. The blue lines are the corresponding fitted curves.
86
Table 4.1. Parameters extracted from the fitting of J-V characteristics Applied magnetic field 0T Zn(Fe)O with 5% Fe Zn(FeAl)O with 5% Fe Zn(Fe)O with 7% Fe Zn(FeAl)O with 7% Fe Zn(Fe)O with 10% Fe Zn(FeAl)O with 10% Fe 0.6 T Zn(Fe)O with 5% Fe Zn(FeAl)O with 5% Fe Zn(Fe)O with 7% Fe Zn(FeAl)O with 7% Fe Zn(Fe)O with 10% Fe Zn(FeAl)O with 10% Fe 0.03571 0.64 2.67733 0.04286 11.23 2.85482 0.02143 2.51 0.68197 0.05714 12.54 2.7769 0.325 9.47 0.66514 0.03929 10.72 2.81462 0.01429 1.13 0.66354 0.04643 9.19 2.82621 0.01786 1.13 0.63501 0.04643 9.19 2.74142 0.01429 1.12 0.61597 Samples Reverse saturation current density (A/cm2) 0.025 6.89 Ideality factor Series resistance (-cm) 2.67733
87
4.3.5. Junction magneto-resistance properties The increase of junction series resistance can be explained by the theoretical model of spin tunneling in ferromagnetic to non-magnetic junctions [18]. The spin injection process alters the potential drop across the F/N interface because differences of spin dependent electrochemical potentials on either side of the interface generate an effective resistance R . It follows that R J J = n (0) F (0) + PF sF (0) / 2 . R is the junction series resistance, n(0) and F(0) are the electrochemical potentials for nonmagnetic and ferromagnetic sides of the junctions, J is the junction current density. PF is related to the conductivity polarization at the ferromagnetic interface and sF(0) is the spin accumulation at ferromagnetic side. Under magnetic field the junction series resistance can be modified by R Jm = R J + R where R is the change of junction series resistance and it can be expressed by,
2 2 rN rF P2 F + rc P + rF rc (P F P ) rFN
R =
(4.2)
where, rF, rN and rc are the ferromagnetic, non-ferromagnetic and contact resistance respectively. P is the contact conductivity polarization. rFN is the effective equilibrium resistance of the Ferromagnetic/Non-ferromagnetic junction. From Eq. (4.2) it can be clearly seen that the R is always positive i.e. R > 0 at higher applied potentials. The positive junction MR and rectifying behavior has also been observed in ZnO heterostructures with other ferromagnetic systems. Similar spin injection theory has been evoked to explain their observed positive junction MR at the ferromagnet/semiconductor interface [19,20]. The plot of % of junction MR (JMR) with applied magnetic field at a bias voltage of 7 V has been shown in the insets of Fig. 4.4. It shows that the JMR behavior follows a simple empirical relation with magnetic field as [21],
JMR= H
(4.3)
where, and are coefficients and are evaluated employing a non-linear least square fitting using 2 minimization technique. The coefficients thus obtained are listed in
88
Table- 4.2 for all the samples. The coefficient is lower than one at room temperature showing nonlinear magnetic field dependence of positive MR of the junction. Table 4.2. Fit parameters and from junction magnetoresistance plot Sample Zn(Fe)O with 5% Fe Zn(Fe)O with 7% Fe Zn(Fe)O with 10% Fe Zn(FeAl)O with 5% Fe Zn(FeAl)O with 7% Fe Zn(FeAl)O with 10% Fe (T- ) 0.13 10.31 4.21 30.39 12.90 10.81 0.56 0.70 0.63 0.83 0.63 0.51
The % of JMR is found to be strongly dependent on the magnetic moments of the respective magnetic semiconducting films. From the magnetization as a function of the carrier density (nc) obtained from room temperature Hall voltage measurements of all the Zn(Fe)O and Zn(Fe,Al)O films with 5% iron, the maximum saturation magnetization (Ms) at 300 K is observed for the films with optimized carrier density of nc/ni 0.4 as shown in Fig. 4.5(a). The film growth conditions were changed systematically (varing oxygen pressure, laser energy, and target to substrate distance etc.) optimizing the best DMS film property. The localized spins of the Fe ions are interacting with band electrons and the standard theory of DMS can be applied. The % of JMR of those films is observed to follow interestingly the same trend as the magnetic moment of the films follows [shown in Fig. 4.5(b)]. With increasing doping percentage of iron the magnetic moment decreases. Fig. 4.5(c) shows the plot of magnetic moment as a function of doping concentration. The drop of moment with increasing iron concentration may be due to the increasing of antiferromagnetic coupling between Fe pairs which occurs at shorter separation distances. The % of JMR also decreases with increasing doping concentration mimicking the same trend as the magnetic moments of the DMS films demonstrate. 89

20 18
0.40 0.35 0.30
(a)
% JMR
M (mB/Fe2+)
16 14 12 10 8 0.0
(b)
0.25 0.20 0.15 0.10 0.05 0.00 0 1x10

21
2x10
21
5.0x10
20
1.0x10
21
1.5x10
21
2.0x10
21
2.5x10
21
M (B/Fe2+)
0.20 0.15 0.10 0.05 0.00 5 Zn(Fe)O 6
% JMR
0.40 0.35 0.30 0.25
Carrier concentration (cm-3)
Carrier concentration (cm-3)
(c)
Zn(Fe,Al)O
10
20 18 16 14 12 10 8 6 4 2
(d)
Zn(Fe,Al)O
Zn(Fe)O 5 6 7 8 9 Fe doping percentage 10
Fig. 4.5. (a) Room temperature carrier induced ferromagnetism in Zn(Fe)O and Zn(Fe,Al)O films with Fe concentration 5%. (b) % JMR of the corresponding films. (c) Plot of magnetic moment with different doping concentrations of iron. (d) Corresponding JMR of those films at room temperature. 4.4. Summary The room temperature ferromagnetic iron doped ZnO with Pt metal point contact shows non-ohmic J-V behavior at room temperature and shows reasonably high sensitivity under magnetic field. The Pt/Zn(Fe)O junction shows positive junction magnetoresistance at room temperature and the phenomenon can be best explained using usual ferromagnetic to paramagnetic spin injection theory. Incorporation of 1% Al shows higher junction magnetoresistance compared to without Al doped films. The junction magnetoresistances are found to strictly depend on the magnitude of magnetic moments of the DMS films. The magnetic moment depends on the carrier density and also the JMR depends on magnetic moment. As magnetic moment decreases due to higher concentration of Fe, JMR also mimics the same behavior. References [1] P. R. Hammar, B. R. Bennett, M. J. Yang, and M. Johnson, Observation of Spin Injection at a Ferromagnet-Semiconductor Interface, Phys. Rev. Lett. 83, 203 (1999). [2] I. Appelbaum, D. J. Monsma, K. J. Russell, V. Narayanamurti, and C. M. Marcus, Spin-valve photodiode, Appl. Phys. Lett. 83, 3737 (2003). 90
Fe doping percentage
[3] A. Kalitsov, M. Chshiev, I. Theodonis, N. Kioussis, and W. H. Butler, Spin-transfer torque in magnetic tunnel junctions, Phys. Rev. B 79, 174416 (2009). [4] F. Junginger, M. Klui, D. Backes, U. Rdiger, T. Kasama, R. E. DuninBorkowski, L. J. Heyderman, C. A. F. Vaz, and J. A. C. Bland, Spin torque and heating effects in current-induced domain wall motion probed by transmission electron microscopy, Appl. Phys. Lett. 90, 132506 (2007). [5] D. A. Allwood, G. Xiong, C. C. Faulkner, D. Atkinson, D. Petit, and R. P. Cowburn, Magnetic Domain-Wall Logic, Science 309, 1688 (2005). [6] S. H. Chun, S. J. Potashnik, K. C. Ku, P. Schiffer, and N. Samarth, Spin-polarized tunneling in hybrid metal-semiconductor magnetic tunnel junctions, Phys. Rev. B 66, 100408 (2002). [7] W. Van Roy, P. Van Dorpe, R. Vanheertum, P. J. Vandormael, and G. Borgh, Spin Injection and Detection in SemiconductorsElectrical Issues and Device Aspect, IEEE Trans. Electron Devices 54, 933 (2007). [8] X. J. Zheng, B. Yang, T. Zhang, C. B. Jiang, S. X. Mao, Y. Q. Chen, and B. Yuan, Enhancement in ultraviolet optoelectronic performance of photoconductive semiconductor switch based on ZnO nanobelts lm, Appl. Phys. Lett. 95, 221106 (2009) [9] S. W. Fan , A. K. Srivastava and V. P. Dravid, Nanopatterned polycrystalline ZnO for room temperature gas sensing, Sens. Act. B: Chem. 144, 159 (2010). [10] T. Dietl, H. Ohno, F. Matsukura, J. Cibert, and D. Ferrand , Zener Model Description of Ferromagnetism in Zinc-Blende Magnetic Semiconductors, Science 287, 1019 (2000). [11] X. J. Liu, X. Y. Zhu, C. Song, F. Zeng and F. Pan, Intrinsic and extrinsic origins of room temperature ferromagnetism in Ni-doped ZnO films, J. Phys. D: Appl. Phys. 42, 035004 (2009). [12] A. J. Behan, A. Mokhtari, H. J. Blythe, D. Score, X-H. Xu, J. R. Neal, A. M. Fox, and G. A. Gehring, Two Magnetic Regimes in Doped ZnO Corresponding to a Dilute Magnetic Semiconductor and a Dilute Magnetic Insulator, Phys. Rev. Lett. 100, 047206 (2008). [13] S. J. Pearton, C. R. Abernathy, M. E. Overberg, G. T. Thaler, D. P. Norton, N. Theodoropoulou, A. F. Hebard, Y. D. Park, F. Ren, J. Kim, and L. A. Boatner, Wide band gap ferromagnetic semiconductors and oxide, J. Appl. Phys. 93, 1 (2003) [14] C. Ronning, P. X. Gao, Y. Ding, Z. L. Wang, and D. Schwen, Manganese-doped ZnO nanobelts for spintronics, Appl. Phys. Lett. 84, 78 (2004). [15] D. L. Hou, R. B. Zhao, Y. Y. Wei, C. M. Zhen, C. F. Pan, G. D. Tang, Room temperature ferromagnetism in Ni-doped ZnO films, Curr. Appl. Phys. 10, 124 (2010) [16] W. B. Mi, H. L. Bai, Hui Liu, and C. Q. Sun, Microstructure, magnetic, and optical properties of sputtered Mn-doped ZnO lms with high-temperature ferromagnetism, J. Appl. Phys. 101, 023904 (2007). [17] A. Singh, A Datta, S. K. Das, and V. A. Singh, Generalized RKKY interaction and spin-wave excitations Ferromagnetism in a dilute magnetic semiconductor, Phys. Rev. B 68, 235208 (2003). [18] S. J. May and B. W. Wessels, High-eld magnetoresistance in p-InMnAs/n-InAs heterojunctions, Appl. Phys. Lett. 88, 072105 (2006).
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[19] K. X. Jin, S. G. Zhao, C. L. Chen, J. Y. Wang, and B. C. Luo, Positive colossal magnetoresistance effect in ZnO/La0.7Sr0.3MnO3 heterostructure, Appl. Phys. Lett. 92, 112512 (2008). [20] S. Y. Park, Hyung Woo Lee, Young Soo Lee, D. F. Wang, Y. P. Lee and J. Y. Rhee, Magneto-transport properties of ZnO/La0.7Sr0.3MnO3 bilayer on p-Si(100), Phys. Stat. Sol. (c) 4, 4471 (2007). [21] T. Edahiro, N. Fujimura, and T. Ito, Formation of two-dimensional electron gas and the magnetotransport behavior of ZnMnO/ZnO heterostructure, J. Appl. Phys. 93,7673 (2003). [22] C. Song, X. J. Liu, F. Zeng, and F. Pan, Fully epitaxial ZnCoO/ZnO/ ZnCoO junction and its tunnel magnetoresistance, Appl. Phys. Lett. 91, 042106 (2007). [23] S. Honda, T. Ishikawa, K. Takai, Y. Mitarai, and H. Harad, New type magnetoresistance in Co/Si system, J. Magn. Magn. Mater. 290-291, 1063 (2005). [24] S. S. P. Parkin, C. Kaiser, A. Panchula, P. M. Rice, B. Hughes, M. Samant, and S. H. Yang, Giant tunnelling magnetoresistance at room temperature with MgO (100) tunnel barriers, Nature Mater. 3, 862 (2004). [25] J. Moser, M. Zenger, C. Gerl, D. Schuh, R. Meier, P. Chen, G. Bayreuther, W. Wegscheider, D. Weiss, C. H. Lai, R. T. Huang, M. Kosuth and H. Ebert, Bias dependent inversion of tunneling magnetoresistance in Fe/GaAs/Fe tunnel junctions, Appl. Phys. Lett. 89, 162106 (2006). [26] J. H. Hsua, S. Y Chen, W. M. Chang, C. R. Chang, Temperature dependence of magnetoresistance effect in Ag-Fe3O4 composites lm, J. Magn. Magn. Mater. 272276, 1772 (2004). [27] I. uti, J. Fabian and S. Das Sarma, Spintronics: Fundamentals and applications, Rev. Mod. Phys. 76, 323 (2004). [28] Z. G. Sheng, W. H. Song, Y. P. Sun, J. R. Sun, and B. G. Shen, Crossover from negative to positive magnetoresistance in La0.7Ce0.3MnO3-SrTiO3-Nb heterojunctions, Appl. Phys. Lett. 87, 032501 (2005).
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Chapter 5
Structural, magnetic and electrical properties of La0.7Sr0.3MnO3 thin films on p-Si
Thischapterisbasedon Internationaljournals 1. Lowtemperature resistivity minima in colossal magnetoresistive La0.7Sr0.3MnO3 thin film: A quantum interferenceeffectbyS.ChattopadhyayandT.K.Nath,Solidstatecommunications(Communicated)
Structural,magneticandelectricalpropertiesofLa0.7Sr0.3MnO3 thinfilmsonpSi Chapter5
5.1. Introduction The perovskite manganites of the form R1-xAxMnO3 (R: rare earth elements, A: alkaline earth elements) thin films have attracted much attention of the researchers due to its exceptional electrical properties and the negative colossal magnetoresistance (CMR) effect [1-3]. The CMR thin films have potential application in the field of the spintronics devices like magnetic field sensor, hard disk read head and infrared bolometer. The large magnetoresistance (MR) ratio in low magnetic field and at room temperature from the CMR materials have attracted much attention in the area of research in manganites. There have been several reports on the La1xSrxMnO3
(LSMO) thin films [4-6] which attributes a high potential in application field.
The CMR effect and the correlated degrees of freedom of magnetic structure, crystallographic structure and electrical resistivity in CMR materials, in addition to being of fundamental scientific interest, appears to provide some scope for engineering in more sensitive magnetoresistive response. The colossal magnetoresistive (CMR) rare earth manganites display a fascinating diversity of behaviors including several forms of magnetic, orbital and charge ordering [7-9]. The materials also exhibit dramatic variations of physical properties with frequency, temperature, chemical composition and applied strain, as well as the magnetoresistive properties, which give them their colloquial name. The particular MR phenomena to be described here are the massive decrease of resistance by application of a magnetic field [10-12]. The electronic inhomogeneities in the hole-doped La1-xSrxMnO3 have attracted considerable attention with phase separation into conducting magnetic and insulating nonmagnetic domains [13]. Among the La1-xSrxMnO3 families La0.7Sr0.3MnO3 shows the ferromagnetic behavior over the room temperatures and a high value of magnetoresistance. Both the epitaxial and nonepitaxial thin films of manganites show huge strain effects on their magnetic, electronic and magneto-transport properties [14]. For device applications, it is necessary to find out the properties of LSMO films on Si, as Si is widely used material in semiconductor industries. So, it is necessary to find out the electrical and magnetic properties of the LSMO films with strain effects. The defects in the crystal also affect the electrical and magneto-electrical properties and hence it should be explored. In this chapter, a detailed study of structural, magnetic, electrical, and magneto-electronic properties of LSMO thin films have been explicitly studied. The effects of thickness and oxygen
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Structural,magneticandelectricalpropertiesofLa0.7Sr0.3MnO3 thinfilmsonpSi
vacancy defects in the crystal have been elaborated and the dominating scattering process in the conduction electron has been estimated. 5.2. Experimental procedure 5.2.1. Preparation of targets The La0.7Sr0.3MnO3 powder have been synthesized through chemical pyrophoric reaction process where we have employed stoichiometric mixtures of high purity La2O3 (99.99 %), SrCO3 (99.9+ %) and Mn(CH3COO)2 (99.0 %) [3]. After final grinding and pelletization of La0.7Sr0.3MnO3 powders, the pelletized sample have been first heated at 800 C for 12 h, then at 1000 C for 12 h and at 1200 C for another 12 h, with intermediate grinding. Final sintering of the La0.7Sr0.3MnO3 target has been carried out at 1200 C for 24 h. 5.2.2. Cleaning of substrates La0.7Sr0.3MnO3 films on (100) p-Si substrate have been grown by Pulsed Laser Deposition process using chemically synthesized single phase LSMO target. The substrates have been cleaned in ultrasonic bath followed by chemical cleaning as mentioned below: 1. The p-Si (100) substrates have been first cleaned by de-ionized (DI) water in ultrasonic chamber for 5 to 10 minutes to remove the dust particles. 2. Then the substrates have been cleaned ultrasonically for 5 to 10 minutes by acetone to remove oils and greases over them. 3. Acetone has been cleaned using a high flow of DI water. 4. The mixture of NH4(OH), H2O2 and H2O with ratio 5:1:1 has been employed for substrate cleaning to remove the acidic radicals and organic compounds. The substrates have been kept in the solution till the end of reaction. 5. The substrates have been pulled out from the solution and cleaned using a high flow of DI water. 6. Then the substrates have been kept in the mixture of H2O2 and H2SO4 (1:1) and boiled till the boiling stops. It removes the basic radicals from the substrates and formed a SiO2 layer over Si. 7. The substrates again cleaned using a high flow of DI water after removing it from the solution. 8. Finally the oxide layers have been etched by dipping the substrate in 10 % HF solution.
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Table 5.1: Condition for depositing different LSMO thin films on p-Si (100) substrates Sample Name T (C) O2 pressure (mbar) 10-5 0.5 0.5 0.5 0.5 0.5 0.5 Substrate treatment condition Oxidation time (min) Final substrate Film growth condition Temp (C) O2 pressure (mbar) 0.5 0.5 0.5 510-3 510-5 0.5 0.5 Deposition time (min) 20 20 20 20 20 15 10 Sintering condition Temp (C) O2 pressure (mbar) 0.5 0.5 0.5 510-3 510-5 0.5 0.5 Sintering time (min) 45 45 45 45 45 45 45
Sample1 Sample2 Sample3 Sample4 Sample5 Sample6 Sample7
800 800 800 800 800 800 800
No 30 45 45 45 45 45
p-Si/SiO2 with native oxide p-Si/SiO2 with thin oxide layer p-Si/SiO2 with thick oxide layer p-Si/SiO2 with thick oxide layer p-Si/SiO2 with thick oxide layer p-Si/SiO2 with thick oxide layer p-Si/SiO2 with thick oxide layer
800 800 800 800 800 800 800
800 800 800 800 800 800 800
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5.2.3. Deposition of La0.7Sr0.3MnO3 film The films have been deposited on (100) p-Si substrates employing the pulsed laser deposition technique using 248 nm KrF excimer pulsed mode laser. The different substrate treatment conditions and film growth conditions for different LSMO thin films has been summarized in Table 5.1. The substrate to target distance has been kept at 4 cm and the repetition rate of pulsed laser (~ 10 pulses/second) has been used for all the films. The electrical contacts have been made with high purity Ag-paste on LSMO film. The temperature dependent electronic- and magneto-transport measurements have been carried out using a source meter (Keithley, model - 2612), current source (Keithley, model-6221), PID temperature controller (Lakeshore, model-331). A cryogen free 8 T superconducting magnet with VTI system down to temperature 2 K (Cryogenics, U.K.) has been employed for high field and low temperature transport measurements of these LSMO thin films. 5.3. Results and discussion 5.3.1. Structural study The high resolution x-ray diffraction pattern (HRXRD) of LSMO film deposited on (100) p-Si substrate using Cu-K radiation has been shown in Fig. 5.1. The multipeaks of LSMO sample reveal the non-epitaxial nature of the LSMO film on SiO2/Si layer. Figure 5.1 (a) shows the HRXRD pattern of LSMO film on Si/SiO2 substrate for different thickness (different pulse duration at 0.5 mbar O2 and 800 C). Figure 5.1 (b) shows the HRXRD patterns of LSMO thin films deposited in different O2 pressure.
(a)
(110) (100)
(111) (200)
(b) Intensity (a.u.)
Sample-7
(210) (211)
(100)
(110)
(111)
(200)
Sample-5
(210) (211)
Intensity (a.u.)
Sample-4
Sample-6
Sample-3
Sample-3
20
30
40 50 2 (degree)
60
20
30
40 2 (degree)
50
60
Fig. 5.1. XRD pattern of LSMO thin film on Si/SiO2 up to 60 2 scan (a) for different pulse duration, (b) different O2 atmosphere
96
All the films show crystalline growth in (100), (110), (111), (210) and (211) planes and have little shift in 2 towards higher angle than a bulk one implying that the strain affects the crystal structure of non-epitaxial films. The shift in 2 and full width half maximum (FWHM) for different films have been summarized in Table 5.2. Table 5.2: Peak position in 2 and FWHM for different LSMO thin films Sam ple Sam Sam Sam Sam Sam 100 0.15 0.13 0.17 0.20 0.20 110 0.21 043 0.19 281 0.25 515 0.31 499 0.26 553 FWHM 111 0.30 978 0.30 41 0.29 465 0.46 937 0.31 6 200 0.27 78 0.25 256 0.31 115 0.37 259 0.30 433 210 0.25 898 0.24 628 0.38 229 0.23 701 0.20 203 211 0.43 56 0.45 302 0.39 15 0.45 42 0.44 257 100 566 546 937 389 26 110 6 883 348 751 681 111 781 427 412 835 589 2 200 067 527 569 32 358 210 644 312 857 304 188 211 877 161 025 88 022 23.02 32.78 40.49 46.96 52.95 58.50 23.02 32.78 40.50 46.95 52.94 58.50 23.12 32.92 40.62 47.08 53.09 58.67 23.26 33.04 40.72 47.32 53.25 58.84 22.89 32.67 40.33 46.83 52.72 58.38
ple-3 47 ple-6 493 ple-7 711 ple-4 44 ple-5 26
The thin films grown on lower O2 atmosphere shows greater FWHM. The oxygen vacancy in the films grown in O2 atmosphere causes a crystal deformation and can be a cause of higher strain in the crystals. Due to increase of strain the FWHM also increases. The preferred crystalline orientation of the nickel films has been evaluated by the texture coefficients (TC) given by [15],
TC =
0 I hkl / I hkl hkl 0 / I hkl
1 n
(I
(5.1)
Where, Ihkl and Iohkl are the diffraction intensity of the crystal plane (hkl) of the deposited and bulk standard samples, respectively. n is the number of diffraction peak appeared in the HRXRD
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pattern. If the texture coefficient is greater than 1.0, it indicates the existence of a preferred orientation. The TCs found for different planes in different samples are summarized in Table 5.3. Table 5.3. Texture coefficients of different planes in LSMO thin films Sample (100) Sample-7 Sample-6 Sample-3 Sample-4 Sample-5 3.32868 3.45816 3.91091 3.29052 3.4024 (110) (111) 0.31607 0.23579 0.26569 0.17807 0.18001 0.12874 0.33756 0.12235 0.466 0.57652 TC (200) 1.57143 1.65635 1.46965 2.08297 0.75415 (210) 0.34877 0.24201 0.17831 0.08709 0.32213 (211) 0.19925 0.19972 0.13239 0.0795 0.4788
The texture coefficient is greater than 1.0 for the plane (100) for all the films implies that the preferred orientation of LSMO thin films on (100) p-Si is crystallographic (100) plane. The texture coefficient of (100) plane is higher for the film with higher thickness. The deficiency in oxygen pressure causes a lower texture co-efficient of the films towards (100) plane.
(a) (b)
(c)
(d)
Fig.5.2. FESEM image of the surface of LSMO films (a) Sample-3, (b) Sample-6, (c) Sample-4 and (d) Sample-5
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5.3.2. Surface morphology The surface morphology obtained from field emission scanning electron microscopy images of different LSMO films have been shown in Fig. 5.2. Figure 5.2 (a), (b), (c) and (d) are the FESEM micrograph of Sample-3, Sample-6, Sample-4 and Sample-5, respectively. The images show the granular growth of the grains of the films. Figure 5.3 shows the cross sectional FESEM micrograph of LSMO films deposited in 0.5 mbar O2 pressure and 800 C substrate temperatures for different pulse duration (growth time).
(a) (a)
(b)
(b)
642 nm
538 nm
(c) (c)
Thickness (nm)
650
448 nm
(d)
600 550 500 450 10 12 14 16 18 Pulesed duration (min) 20
Fig. 5.3. Cross sectional FESEM micrograph of LSMO films; (a) Sample-3, (b) Sample-6 and (c) Sample-7. (d) Plot of thickness with pulse duration (growth time). Figure 5.3 (a), (b) and (c) are the cross sectional FESEM image of Sample-3, Sample-6 and Sample-7, respectively. All the films show rod like structure with nano dimensions. The plot of thickness of LSMO films with pulse duration (growth time) have been shown in Fig. 5.3 (d). The plot shows almost linear nature of thickness with pulse duration in this growth time range confirming uniform growth of the films.
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5.3.3. Magnetic properties The magnetic properties of the films have been characterized using Quantum Design ever-cool SQUID - VSM magnetometer. The temperature dependent magnetic M-H hysteresis loops have been shown in Fig. 5.4 after correcting the substrate contribution as discussed in chapter-3. The saturation fields are found to be ~ 0.07 T which is little greater than the bulk sample [16]. This may due to the strain effect of non-epitaxial LSMO films. The clear hysteresis at all temperatures up to 300 K shows the ferromagnetic behavior.
Magnetic moment (emu/gm) 100 50 0 -50 -100 -4000 -2000 0 2000 Magnetic Field (Oe) 4000
Sample-3
5K 50 K 100 K 300 K
Magnetic moment (emu/gm)
60 40 20 0 -20 -40 -60 -4000
(a)
5K 100 K 200 K 300 K
Sample-5
(b)
-2000 0 2000 4000 Magnetic Field (Oe)
Fig. 5.4. Corrected temperature dependent M-H loop of the LSMO thin films on p-Si substrate (a) for sample-3 and (b) for sample-5 The temperature dependent field-cool (FC) and zero field cool (ZFC) magnetization measurements have been carried out for those LSMO films to investigate the enhanced grain surface effect of non-epitaxial thin films. The FC and ZFC properties at a constant magnetic field
1.8 moment (emu) 1.6 1.4 1.2 1.0 0.8 0.6 0.4
ZFC FC
0.1 T
Sample-3
50
100 150 200 250 300 Temperature (T)
Fig. 5.5. Temperature dependence of FC and ZFC magnetic measurement at 100 Oe for LSMO films
100
of 100 Oe has been shown in Fig. 5.5. The curves show strong irreversibility between FC and ZFC curves exhibiting prominent maxima at Tmax (~ 130 K). The strong decrease of low field ZFC and the increase of irreversibility with decreasing temperature can be attributed to the passage from a ferromagnetic state to a low temperature disordered regime surface [17]. With reducing temperature local anisotropy at the grain surface increases more sharply than the exchange stiffness parameter due to lack of symmetry at grain surface. Consequently, opposing magnetic interaction stabilized a spin glass like state at the grain surface, yielding freezing of surface spin in random direction. This inhibits the exchange interaction to transmit across the interface. But, they are expected to interact through dipolar interaction. The strength of interaction depends on the assembly of grains which either can show superparamagnetic blocking or cooperative freezing of moment at Tmax. 5.3.4. Electrical transport properties The electrical characterization of all LSMO films having different thickness and different oxygen deficiency has been carried out using a source meter (Keithley, model - 2612), current source (Keithley, model -6221), PID temperature controller (Lakeshore, model-331). A cryogen free 8 T superconducting magnet with VTI system using closed cycle helium refrigeration technique down to temperature 2 K (Cryogenics, U.K.) has been employed for high field and low temperature transport measurements. 5.3.4.1. -T behavior without applied magnetic field Figure 5.6 shows the temperature dependent resistivity measurements for different LSMO thin films. Figure 5.6 (a) shows the -T plot under 0 T applied magnetic field for LSMO films with different thickness grown on SiO2/p-Si at a substrate temperature of 800 oC in 0.5 mbar O2 atmosphere. The absolute value of resistivity increases little with decreasing of thickness of the films but the overall -T behavior looks almost identical for all films. The films show resistivity minima (TM) at low temperatures (<50 K). The double exchange interaction model of Zener associated with the Jahn-Teller splitting of Mn d-levels and a strong electronphonon interaction explain most of the electrical and magnetic properties of these manganites [18]. All the films show a metal-insulator transition temperature (Tp) at higher temperature.
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Chapter5
According to the established phase diagram, a phase transition occurs from metal to insulator phase giving a peak temperature (TP). The TM and TP does not change much with the variation of thickness of the LSMO films.
(a)
Resistivity (k-cm)
1.4 1.2 H=0 1.0 0.8 0 50
Sample-6
Resistivity (k-cm)
1.6
Sample-7
1.3 1.2 1.1 1.0 0.9 0.8 0.7

(b)
Sample-3 Sample-4 Sample-5
Sample-3
100 150 200 250 300 Temperature (T)
50
100 150 200 250 300 Temperature (K)
Fig. 5.6. Temperature dependent resistivity plot of LSMO thin film (a) with different thickness, (b) with different oxygen vacancies Figure 5.6 (b) shows the -T plot under 0 T applied magnetic field for LSMO films grown on different oxygen ambient. The -T behavior shows distorted nature with deficiency of oxygen. The low temperature resistivity is much higher which may be due to the higher impurity scattering in high oxygen deficient films. The curvature near TM and TP are much broader than the well crystalline films. This may be due to creation of trap charges in disordered high oxygen vacancy films. 5.3.4.2. -T behavior under applied magnetic field The temperature dependent resistivity plots with applied magnetic field up to 8 T for the LSMO films with different thicknesses have been shown in Fig. 5.7. Figure 5.7 (a), (b) and (c) are the -T plots with different magnetic field for sample-3, sample-6 and sample-7, respectively. Figure 5.7 (d), (e) and (f) are the magnetic field dependent magnetoresistance (MR) plots for the corresponding films. Resistivity decreases drastically under applied magnetic field mainly due to the spin polarized tunneling of mobile eg electrons across the ferromagnetic manganite grain boundaries. The peak temperature shifts towards higher temperature with applied magnetic field. The films shows negative magnetoresistance under applied magnetic field and it does not
102
changes much with the film thickness. Hwang et al. [19] has described a model for spin polarized tunneling MR across the ferromagnetic manganite grain boundaries as,
H
MR = A f (k )dk JH KH 3
0
(5.2)
1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0 T(K)
1.6
1.6 Resistivity (k-cm)
1T 2T 3T 4T 5T 6T 7T 8T
Resistance (kcm)
1.4 1.2 1.0 0.8 0.6 0.4 0 Sample-6
Resistivity (k-cm)
0T
1.4 1.2 1.0 0.8 0.6 0.4 0 50 100 150 200 250 300 Temperature (K)
2.8 K 5K 10 K 50 K 100 K 150 K 200 K 250 K 300 K
Sample-3
Sample-7
50 100 150 200 250 300
50 100 150 200 250 300 Temperature (K)

2.8 K 5K 10 K 50 K 100 K 150 K 200 K 250 K 300 K
0 -10 % MR -20 -30 -40 -50

0 2 4 6 Magnetic Field (T)
% MR
% MR
2.8 K 5K 10 K 50 K 100 K 150 K 200 K 250 K 300 K
0 -10 -20 -30 -40
0 -10 -20 -30 -40 -50
-50 0 2 4 6 Magnetic field (T) 8
2 4 6 Magnetic field (T)
Fig. 5.7. Temperature dependent resistivity under applied magnetic field for (a) sample-3, (b) sample-6 and (c) sample-7; (d), (e) and (f) are corresponding % MR plot of the films with applied magnetic field. In zero field the domain boundaries are pinned at the grain boundary pinning centre with pinning strength k. The grain boundaries have a distribution of pinning strength f(k) defined as the minimum field needed to overcome a particular pinning barrier [20],
f ( k ) = A exp( Bk 2 ) + Ck 2 exp( Dk 2 )
(5.3)
A, B, C, D, J and K are the parameters. The best fit values of the parameters have been listed in Table 5.4 for all the LSMO films. The spin polarized tunneling MR ( MR
spt
= f (k )dk )
0
and
intrinsic MR (MRint) contributions have be evaluated using all the fit parameters keeping H = 8 T for each LSMO films as listed in Table 5.4.
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Table 5.4. Evaluated fitting parameter using Eq. (5.2) and Eq. (5.3) Sample Sample-3 T (K) 2.8 5 10 50 100 150 200 250 300 Sample-6 2.8 5 10 50 100 150 200 250 300 Sample-7 2.8 5 10 50 100 150 200 250 300 A -32.02 -33.15 -35.81 -30.92 -23.80 -18.99 -13.47 -7.93 -2.27 -38.13 -32.09 -34.03 -29.15 -21.95 -16.95 -11.55 -5.99 -2.63 -39.70 -32.53 -33.15 -29.71 -22.7 -18.19 -12.65 -7.06 -1.52 B 0.10 0.15 0.19 0.19 0.21 0.21 0.21 0.21 0.21 0.22 0.21 0.21 0.21 0.22 0.22 0.23 0.22 0.22 0.23 0.22 0.22 0.23 0.23 0.22 0.22 0.22 0.21 C 21.16 21.86 29.67 24.63 19.56 14.80 10.97 5.80 0.49 24.5 23.28 28.21 22.67 16.66 11.86 8.33 3.04 0.47 25.41 23.63 26.05 23.36 18.25 13.75 9.71 4.46 -0.34 D 0.34 0.39 0.47 0.47 0.49 0.49 0.48 0.48 0.49 0.48 0.49 0.49 0.48 0.49 0.49 0.46 0.5 0.49 0.49 0.49 0.50 0.49 0.5 0.49 0.49 0.50 0.49
104
MRspt(%) -42.3 -36.1 -32.0 -28.9 -20.7 -17.6 -11.4 -7.6 -3.7 -39.3 -31.9 -29.3 -26.1 -19.9 -16.7 -9.5 -7.5 -4.3 -40.5 -30.9 -29.9 -24.7 -19.1 -16.6 -11.3 -7.7 -2.5
MRint(%) -2.1 -9.1 -12.9 -13.8 -19.1 -20.1 -23.3 -22.8 -19.7 -4.1 -12.6 -14.4 -15.6 -18.7 -19.8 -24.1 -21.6 -17.8 -5.4 -16.1 -16.2 -19.5 -22.3 -22.7 -25.1 -24.4 -22.9
-4.21 -0.042 -0.50 -0.011 -1.32 -0.006 -1.45 -0.006 -2.39 -0.002 -2.37 -0.002 -3.07 0.0027 -2.93 0.0012 -5.20 0.0262 -1.43 -0.004 -1.34 -0.005 -1.77 -0.001 -1.70 -0.003 -2.43 0.0003 -2.47 -0.0005 -3.08 0.004 -2.85 0.0018 -2.85 0.0031 -2.18 0.0005 -1.96 -0.0014 -2.17 3E-5 -2.37 0.001 -3.06 0.004 -2.87 0.001 -3.44 0.005 -3.32 0.004 -3.4 0.006
The % of MRspt drops sharply, where as the % of MRint increases with increasing temperature. The temperature dependent % of MRspt can be explained using an empirical expression ( MRspt = (a + b) /(c + T ) [19].
5.3.4.2.1. -T behavior below TM Focusing on the resistivity plot again, it is necessary to study the appearance of low temperature minima and peak temperature and their dependence on magnetic field. To explore the fact we have chosen the -T behavior of the sample-3. The low temperature -T behavior below resistivity minimum (TM) showing resistivity upturn in all LSMO thin films can have various source of origin. At low temperatures, low resistive dilute alloys with very small magnetic impurity generally show Kondo resistivity minima and the (T) relation is given by [21] (5.4) where 0 is the residual resistivity. The Kondo resistivity minima are attributed to the localized magnetic impurities that are far apart and interact by polarizing electrons. The Kondo minima disappear with the application of external magnetic field. Moreover, in the disordered highly resistive systems the mean free path of conduction electrons become small and they involve in multiple elastic scattering [22]. It causes a higher resistivity in the system. Any inelastic process or electron-electron interaction or applied magnetic field can reduce the resistivity. A resistivity minimum occurs at TM because there is ultimately an increase of resistivity with temperature due to inelastic high temperature electronphonon scattering. Below the resistivity minima due to the electron-electron interaction the (T) relation is given by [23],
(T ) = 0 BT 1 / 2
(T ) = 0 C ln(T )
(5.5)
On the other hand, the resistivity due to the temperature dependent other scatterings like electron-phonon, electron-magnon can be expressed as,
(T ) = AT n
(5.6)
Figure 5.8 shows the low temperature minima of sample-3 with different applied magnetic fields up to 8 T. The resistivity curves lower than TM (T < TM) have been fitted considering both Kondo effect and electron-electron correlation effect as described in Eq. (5.4)
105
Chapter5
and Eq. (5.5). The temperature dependent inelastic term (Eq. 5.6) has been added with these equations and hence we can write,
(T ) = 0 C ln(T ) + AT n
(5.7)
(T ) = 0 BT 1 / 2 + AT n (5.8) All the (T) curves measured at different magnetic fields below TM have been fitted with
both Eq. (5.7) and Eq. (5.8) as shown in Fig. 5.8. Figure 5.8(a) is the low temperature (T) curves fitted with Eq. (5.8) (red lines) and Fig. 5.8(b) is the same fitted with Eq. (5.7) (green lines). The best fit 2 values for both the fits have been examined and it is found that the Eq. (5.8) fits much better as compared to Eq. (5.7). Comparative % of deviation of fit with Kondo effect and e-e interaction effect for the (T) curves with 0 T and 8 T applied magnetic field have been shown in Fig 5.8(c) and (d), respectively. It clearly shows that the e-e interaction model fits much better thereby explaining best possible electronic transport mechanism at very low temperature in these LSMO thin films. The evaluated parameters fitting with Eq. (5.8) have been summarized in Table 5.5. From the Table 5.5 it is clear that the coefficient B (e-e interaction term) in Eq. (5.8) remains unaltered with the application of magnetic field. However, the coefficient A changes noticeably with the magnetic field keeping the value of the exponent n ~ 2 ( ~ AT2). So the origin of this additional term in Eq.(5.8) possibly arises due to the electronmagnon scattering process these films.
0.9
Resistivity (kcm)
Resistivity (k-cm)
0.8 0.7
0T
0T
(a)
e-e interation
0.8 0.7
(b)
Kondo minima
0.6 0.5 0.4
0T 0T 0T 0T 0T 0T
0.6 0.5 0.4 0 10 20 30 40 50
10
20
30
40
50
Temperature (K)
Temperature (K)
0.2
% of Deviation
0.8 0.4 0.0 -0.4 -0.8 10
e-e interaction
H=0
% of deviation
Kondo Effect
0.1 0.0 -0.1
e-e interaction
H=8 T
(c)
Temperature (K)
20 30 40 50
Kondo Effect
-0.2 10 20 30 40
(d)
50
Fig. 5.8. Low temperature (T) curves fitted with (a) electron-electron interaction model, (b) Kondo Effect model; (c) and (d) are % of deviation of fit values at 0 and 8 T. The deviation clearly shows the good fit with e-e interaction model.
106
Temperature (K)
Table 5.5: Fit parameters evaluated using Eq. (5.8). Magnetic field (T) 0 1 2 3 4 5 6 7 8 0.912 0.675 0.639 0.613 0.589 0.567 0.547 0.529 0.510 0.0385 0.0314 0.0282 0.0277 0.0272 0.0268 0.0259 0.0266 0.0256 0 (k-cm) B (k-cmK-1/2) A ((k-cmK-n) 10-3 0.742 2.143 1.343 1.612 2.061 2.393 2.396 3.672 3.589 1.82 1.57 1.66 1.61 1.55 1.51 1.50 1.41 1.41 n
0.140
Depth of minima
0.135 0.130 0.125 0.120 0.115 0 2 4 6 8
Magnetic field (T)
Fig. 5.9. Magnetic field dependent The depth of minima { [ (1.6 K ) (TM )] / (1.6 K ) } has been plotted with magnetic field as shown in Fig. 5.9. The depth of minima initially decreases slightly with the magnetic field till 2 T beyond which it becomes almost field independent. 5.3.4.2.2. -T behavior above TM The temperature dependent resistivity above TM and below TP (metal-insulator transition temperature) as shown in Fig. 5.7(a) has been best described with the help of Matthiessens law as described below [24]:
107
Chapter5
(T ) = 0 + l + m
(5.9)
where, 0 is residual resistivity. The two other resistivity terms (l and m) originate from the scattering of lattice phonon and spin wave at finite temperatures, respectively. For both lattice and magnetic scatterings conduction electrons might undergo s-s and s-d transitions. The scattering due to lattice have been given by [25],
T l = A D
n
x n dx (e x 1)(1 e x )
(5.10)
where, the D is the Debye temperature; n is a constant generally it is 3 for magnetic metal and alloys with large d-band density of state. The resistivity due to exchange interaction between the conduction electrons (s) and the localized magnetic electrons (3d) is m. This interaction is generally called the s-d interaction. This spin disorder resistivity goes with the 2nd power of temperature ( (T ) = DT 2 ) where, D shows the strength of s-d interaction. Eq.(5.9) fits well with the all (T) curves in this
temperature regimes and describes well the electron transport mechanism in these LSMO films.
5.4. Summary
The LSMO thin films with different thicknesses and different oxygen vacancies have been grown on SiO2/p-Si substrates where the SiO2 layer have been created by oxidation of Si. All the films show nano rod like growth with high texturing towards (100) direction. The growth of the film is almost linear with deposition time implying good uniformity of the films. The magnetization measurement of the film shows good ferromagnetic nature at all temperatures with saturation field near 0.07 T. The FC and ZFC curves show strong irreversibility exhibiting prominent maximum at Tmax (~ 130 K). The sharp decrease of low field ZFC curve at low temperature and the increase of irreversibility with decreasing temperature generally are attributed to the passage from a ferromagnetic state to a low temperature disordered surface regime.
108
The temperature dependent resistivity shows the metal-insulator transition giving a peak temperature near 250 K. The peak temperature does not change, though the resistivity increases slightly with decreasing thickness. The distortion in -T curves for oxygen deficient films may be due to the oxygen vacancy and lattice defects. The low temperature resistivity is much higher which may be due to the higher impurity scattering in high oxygen deficient films. The curvature near TM and TP are much broader than the well crystalline film possibly due to the creation of trap charges in disordered high oxygen vacancy films. All the films show negative MR behavior for temperatures up to 300 K and there is not much effect of film thickness in that thickness range. Resistivity decreases sharply with the application of magnetic field in the low magnetic field region mainly due to the spin polarized tunneling of mobile eg electrons across the ferromagnetic manganite grain boundaries. The MR contribution due to extrinsic spin polarized tunneling across the grain boundaries as well intrinsic CMR inside grains has also been separated out for the films. The resistivity behavior in the temperature range lower than TM has been well described through the electron-electron interaction model rather than the Kondo effect. The dependency of parameter A with applied magnetic field and the depth of minima indicate the electron-magnon scattering process in the films. The resistivity behavior in the higher temperature regime (> TM) has been described through the lattice and magnetic scattering using the Matthiessens law.
References
[1] P. Dey, T. K. Nath and A. Banerjee, Enhanced grain surface effect on magnetic properties of La0.5Gd0.2Sr0.3MnO3 nanoparticles: A comparison with bulk counterpart, Appl. Phys. Lett. 91, 012504 (2007). [2] P. Dey and T. K. Nath, Tunable room temperature low-field spin polarized tunneling magnetoresistance of La0.7Sr0.3MnO3 nanoparticles, Appl. Phys. Lett. 89, 163102 (2006). [3] P. Dey and T. K. Nath, Effect of grain size modulation on the magneto- and electronictransport properties of La0.7Ca0.3MnO3 nanoparticles: The role of spin-polarized tunneling at the enhanced grain surface, Phys Rev. B 73, 214425 (2006). [4] J. Fontcuberta, M. Bibes, and B. Martnez, V. Trtik, C. Ferrater, F. Sanchez, and M. Varela, Tunable epitaxial growth of magnetoresistive La2/3Sr1/3MnO3 thin films, J. Appl. Phys. 85, 4800 (1999). [5] V. Moshnyaga, I. Khoroshun, A. Sidorenko, P. Petrenko, A. Weidinger, M. Zeitler, B. Rauschenbach, R. Tidecks, and K. Samwer, Preparation of rare-earth manganite-oxide thin films by metalorganic aerosol deposition technique, Appl. Phys. Lett. 74, 2842 (1999).
109
Chapter5
[6] A. Goyal, M. Rajeswari, R. Shreekala, S. E. Lofland, S. M. Bhagat, T. Boettcher, C. Kwon, R. Ramesh, and T. Venkatesan, Material characteristics of perovskite manganese oxide thin films for bolometric applications, Appl. Phys. Lett. 71, 2535 (1997). [7] A. Urushibara, Y. Moritomo, T. Arima, A. Asamitsu, G. Kido and Y. Tokura, Insulator-metal transition and giant magnetoresistance in La1-xSrxMnO3, Phys. Rev. B 51, 14103 (1995). [8] P. Schiffer, A. P. Ramirez, W. Bao, and S. W. Cheong, Low Temperature Magnetoresistance and the Magnetic Phase Diagram of La1-xCaxMnO3, Phys. Rev. Lett. 75, 3336 (1995). [9] Y. Tokura, Y. Tomioka, H. Kuwahara, A. Asamitsu, Y. Moritomo, and M. Kasai, Origins of colossal magnetoresistance in perovskite-type manganese Oxides, J. Appl. Phys. 79, 5288 (1996). [10] S. Jin, T. H. Tiefel, M. McCormack, R. A. Fastnacht, R. Ramesh and L. H. Chen, Thousand fold Change in Resistivity in Magnetoresistive La-Ca-Mn-O Films, Science 264, 413 (1994). [11] J. D. Boeck, Switching with Hot Spins, Science 281, 357 (1998). [12] G. A. Prinz, Magnetoelectronics, Science 282, 1660 (1998). [13] U. R. Singh, A. K. Gupta, G. Sheet, V. Chandrasekhar, H. W. Jang, and C. B. Eom, Pseudogap formation in the metallic state of La0.7Sr0.3MnO3 thin films, Appl. Phys. Lett. 93, 212503 (2008). [14] P. Dey, T. K. Nath, and A. Taraphder, Effect of substrate-induced strain on transport and magnetic properties of epitaxial La0.66Sr0.33MnO3 thin films, Appl. Phys. Lett. 91, 012511 (2007). [15] S. H. Kim, H. J. Sohn, Y. C. Joo, Y. W. Kim, T. H. Yim, H. Y. Lee, T. Kang, Effect of saccharin addition on the microstructure of electrodeposited Fe36 wt.% Ni alloy, Surf. Coat. Tech. 199, 43 (2005). [16] P. Dey and T. K. Nath, Tunable room temperature low-field spin polarized tunneling magnetoresistance of La0.7Sr0.3MnO3 nanoparticles, Appl. Phys. Lett. 89, 163102 (2006). [17] D. Fiorani, Surface effect in magnetic nanoparticles, Springer (2005). [18] A. P. Ramirez, Colossal magnetoresistance, J. Phys. Conds. Mat. 9, 8171 (1997). [19] H. Y. Hwang, S. W. Cheong, N. P. Ong, and B. Batlogg, Spin-Polarized Intergrain Tunneling in La2/3Sr1/3MnO3, Phys. Rev. Lett. 77, 2041 (1996). [20] P. Raychaudhuri, T. K. Nath, A. K. Nigam and R. Pinto, A phenomenological model for magnetoresistance in granular polycrystalline colossal magnetoresistive materials: The role of spin polarized tunneling at the grain boundaries, J. Appl. Phys. 84, 2048 (1998). [21] J. Kondo, Resistance Minimum in Dilute Magnetic Alloys, Prog. Theo. Phys. 32, 37 (1964). [22] G. Bergmann, Weak localization in thin films: a time-of-flight experiment with conduction electrons, Phys. Rep. 107, 1 (1984). [23] P. A. Lee and T. V. Ramakrishnan, Disordered electronic systems, Rev. Mod. Phy. 57, 287 (1985). [24] P. Khatua, T. K. Nath, Mitali Banerjee, and A. K. Majumdar, Quantum interference effects and magnetic scattering in the electrical resistivity of Ni nanocrystallites in TiN matrix, Appl. Phys. Lett. 92, 193106 (2008). [25] A. H. Wilson, The Electrical Conductivity of the Transition Metal, Prog. R. Soc. London A 167, 580 (1938).
110
Chapter 6
Junction magnetoresistance study in La0.7Sr0.3MnO3/SiO2/p-Si heterostructures
Thischapterisbasedon Internationaljournals 1. Electrical and magnetoelectronic properties of La0.7Sr0.3MnO3/SiO2/pSi heterostructure for spintronics application, S.Chattopadhyay,P.DeyandT.K.Nath,CurrentAppliedPhysics(Inpress) doi:10.1016/j.cap.2011.02.009 2. On investigation of origin of junction magnetoresistance in La0.7Sr0.3MnO3/SiO2/pSi heterostructures, S. ChattopadhyayandT.K.Nath,JournalofPhysicsD:AppliedPhysics(Communicated) Conferences/Symposia 1. Investigation on La0.7Ca0.3MnO3/SiO2/nSi and La0.7Sr0.3MnO3/SiO2/pSi MOS like heterostructures for Spintronics by S.Chattopadhyay,S.K.GiriandT.K.Nath,InternationalConferenceonFundamental&ApplicationsofNanoscience andTechnology(ICFANT)(2010). 2. Electrical properties of La0.7Sr0.3MnO3/SiO2/Si MOS structure by S. Chattopadhyay, P. Dey, T. K. Nath 53rd DAE Solid StatePhysicsSymposium(2008) 3. IV characteristics of La0.7Sr0.3MnO3/SiO2/Si MOS structure by S. Chattopadhyay, P. Dey, T. K. Nath National Seminar onAdvancedNanomaterialsanditsApplications(2008)
Junctionmagnetoresistancein Chapter6 La0.7Sr0.3MnO3/SiO2/pSiheterostructures
6.1. Introduction After Datta-Das transistor [1], there is an enormous development of spintronic devices in the area of microelectronics. Spintronics is a multidisciplinary field whose central theme is the active manipulation of spin degrees of freedom in solid-state systems. Generation of spin polarization usually means creating a non-equilibrium spin population which can be achieved in several ways. For device applications electrical spin injection is more desirable. In electrical spin injection a magnetic electrode is connected to the sample. When the current drives spin-polarized electrons from the electrode to the sample, non-equilibrium spin accumulates there. The rate of spin accumulation depends on spin relaxation, the process of bringing the accumulated spin population back to equilibrium. These properties of spin lead to open up new area of spintronic devices such as magnetic sensors, magnetic devices, photosensitive devices etc [2-4]. Typical time scales for spin relaxation in electronic systems are measured in nanoseconds, while the range is from picoseconds to microseconds for electrons, which can be very useful for high speed magneto-optic devices [5]. Spin detection, also a part of a generic spintronic scheme, typically relies on sensing the changes in the signals caused by the presence of non-equilibrium spin in the system. The common goal in many spintronic devices is to maximize the spin detection sensitivity to the point that it detects not the spin itself, but changes in the spin states. Manganite-based heterojunctions such as half-metalic colossal magnetorsistance, materials with extremely high degree of spin polarization [ S =
N (E F ) N (E F ) N (E F ) + N (E F )
] have
recently attracted lot of attention for their various fields of applications. Recently, a lot of research studies have been focused on perovskite based oxide semiconductors or semimetals heterojunctions with different semiconductors [6-8]. Generally the currentvoltage characteristic is guided by tunneling of conduction electrons between the junctions though the presence of edge leakage makes the transport mechanism complicated. As a result there is difficulty in the extraction of actual barrier height. Lanthanum Strontium Manganese Oxide with composition La0.7Sr0.3MnO3 (LSMO), a colossal magneto-resistive (CMR) ferromagnetic metal at room temperature belongs to 111
Chapter6 Junctionmagnetoresistancestudyin La0.7Sr0.3MnO3/SiO2/pSiheterostructures
one of the perovskite type i.e., half-metallic highly spin-polarized ferromagnetic oxides, hole doped manganites. The resistivity of the LSMO films can be tuned easily during deposition and is highly stable under further thermal treatment. Moreover, the resistivity of the materials can also be tuned by applying external magnetic field [9]. So using LSMO as an electrode in Si/ SiO2/ LSMO heterostructure the I-V and C-V characteristics can be modulated by applying magnetic field externally and it may open up possibilities in various technological applications, e.g., magnetic sensors, magnetic memories or other spin electronic applications. However, the origin of appearing positive junction MR of these perovskite based heterojunctions is still not understood clearly. Some reports have concluded that the increase of barrier height due to Zeeman splitting of bands causes the positive MR at the junction. But, the exact reason is still far from well established. In this chapter, the junction current density-voltage (J-V) characteristics of La0.7Sr0.3MnO3 (LSMO)/SiO2/Si junction with and without external magnetic field have been studied explicitly. The applied external magnetic fields up to 1 T and 8 T have been exerted on all the heterojunctions using a high precision electromagnet. The constant parameters of J-V characteristics at room temperature and all other temperature have been estimated by non-linear least square (2- minimization) curve fitting method. The estimated parameters conclusively show that the series resistance of the junction plays dominant role to make junction MR positive rather than the effective barrier height. The effect of leakage currents on junction MR for such heterostructures has also been established. 6.2. Experimental procedure The details of sample preparations have been discussed in details in chapter 5 section 5.2. The three best films which show higher value of negative magnetoresistance, (Film magnetoresistance) have been chosen for heterojunction study. The heterojunctions and its growth structures and conditions have been summarized in Table 6.1. The variation of the oxidation time at oxidation temperature 800 C under oxygen atmosphere of cleaned high conducting p-Si substrate forms different thermal oxide layer over p-Si with different thicknesses. The insulating layer between p-Si and La0.7Sr0.3MnO3 (LSMO) controls the current transport through the heterojunctions. 112
Table 6.1. The heterojunction structures and its growth conditions Heterojunct ion name
Sample-1
Structure of heterojunction
p-Si/SiO2 (native oxide)/ La0.7Sr0.3MnO3
Growth conditions for heterojunction

Substrate p-Si; No oxidation ((thickness of SiO2 ~9 ) La0.7Sr0.3MnO3 have been grown at 800 C substrate temperature under 0.5 mbar O2 atmosphere
Film properties
La0.7Sr0.3MnO3 shows rod like structure with ve magnetoresistance of film
Sample-2
p-Si/SiO2(thermal oxide)/ La0.7Sr0.3MnO3
Sample-3
p-Si/SiO2(thermal oxide)/ La0.7Sr0.3MnO3
Substrate p-Si; Oxidation has been carried out for 30 min at 800 C under oxygen pressure 0.5 mbar (thickness of SiO2 ~40 ). Then the La0.7Sr0.3MnO3 film have been grown at 800C substrate temperature under 0.5 mbar O2 atmosphere Substrate p-Si; Oxidation has been carried out for 45 min at 800 C under oxygen pressure 0.5 mbar (thickness of SiO2 ~45 ). Then the La0.7Sr0.3MnO3 film have been grown at 800 C substrate temperature under 0.5 mbar O2 atmosphere
La0.7Sr0.3MnO3 shows rod like structure with ve magnetoresistance film
La0.7Sr0.3MnO3 shows rod like structure with ve magnetoresistance in the form of thin film.
Electrical contacts were made with high purity Ag on LSMO film and pure Al contact with p-Si as ohmic contacts. The temperature and magnetic field dependence I-V characteristics were measured using a source meter (Keithley 2612), current source (Keithley 6221), temperature controller (Lakeshore, model-331), high precision electromagnet (Polytronic, Model HEM 100) and a variable temperature cryostat (Janis, USA). A cryogen free 8 T superconducting magnet with VTI system down to temperature 113
2 K (Cryogenics, U.K.) has been employed for high field and low temperature transport measurements. 6.3 Results and discussion 6.3.1 Structural properties The x-ray diffraction pattern of LSMO film (sample-3) deposited on (100) p-Si substrate using Cu-K radiation has been shown in Fig. 6.1. The multipeaks from different crystallographic planes of LSMO sample reveal the non-epitaxial nature of the LSMO film on SiO2/Si layer as discussed in chaper-5. In Fig. 6.1(b) and 6.1(c) the FESEM micrograph of the LSMO film (sample-3) and the cross sectional FESEM image of the heterojunction have been shown. The FESEM micrograph clearly shows the uniformly grown smooth LSMO film with good coverage on Si/SiO2 layer. The crosssectional FESEM picture reveals the nano-rod like growth of the film with film thickness ~ 600 nm.
(b) (a)
(a)
(c) (c)
Fig. 6.1. (a) XRD pattern of LSMO/SiO2/p-Si hereostructure. Inset shows the XRD pattern of LSMO film. (b) and (c) FESEM micrograph of LSMO film and crosssectional view of the heterostructure.
6.3.2. Electrical properties of LSMO/SiO2/p-Si hereostructure without applied magnetic

field
6.3.2.1. Current-Voltage study using diode characteristics Figure 6.2(a) shows the non-linear current density-voltage (J-V) characteristics of a typical LSMO/SiO2/Si structured heterojunction measured at room temperature. It can 114
be seen that the junctions exhibit diode-like behavior. The J-V characteristics of the films are found to depend strongly on the interfacial oxides layer. The ideality factor is much greater than 2 at room temperature. At low forward voltage the current increased exponentially which has been usually observed in diodes and attributed to recombination, tunneling mechanism. At moderate junction voltage the J-V deviated from ideal thermionic emission and behaves as J~V2 relation which is attributed to space charge limited current (SCLC) conduction. Applied voltage lower than the turn on voltage shows ohmic behavior. All the regions have been distinctly shown in log J - log V plot of Fig. 6.2(b). The junction J-V characteristics are described as [10],
e (V V 0 IR s ) J = J 0 exp kT
(6.1)
where, J0 is the reverse saturation current density. V0, , and Rs are turn on voltage, ideality factor and junction series resistance respectively. The fitted values of the parameters for different samples have been plotted in Fig. 6.2(c) and Fig. 6.2(d), respectively. The decrease of ideality factor and reverse saturation current density [in Fig. 6.2(c)] and increase of turn on voltage and series resistance [in Fig. 6.2(d)] with increasing the oxidation time illustrates that the leakage current and defect induced tunneling through the junction decreases effectively with the enhancement of oxidation time (thickness of the intermediate SiO2 oxide layer). As the native oxide layer contains inherently high density of oxide defect states in it, the leakage current becomes large at room temperature that enhances the junction forward current and causes lower series resistance through the junction. When the oxide layer is grown over the Si substrate thermally in O2 atmosphere the oxide defects decreases as well as the thickness of the oxide layer increases. So, both the leakage current and tunneling probability through the oxide interface decreases. It causes enhancement of series resistance from sample-1 to sample-3.
115
Current density (mA/cm2)
0.15 0.10 0.05 0.00 -0.05 -0.10 -0.15 -6
(a)
300 K
0.20
100
Sample-2
SCLC region
(b)
10
Tunneling region
Ohmic region
sample-1 sample-2 sample-3
300 K
-4
-2
1
Voltage (V)
10
Series ResistanceRS(kcm2)
Voltage (V)
32 28 24
300 K
80 70 60 50 40 30 20 10 0
0.62
Turn on voltage V0 (V)
(c)
4.0 3.5
J0 (A/cm2)
RS V0
(d)
300 K
0.60 0.58 0.56 0.54 0.52
3.0 2.5
20 16 12 8 0 10 20 30 40 Oxidation time (min)
2.0 1.5 1.0 50
J0
10 20 30 Oxidation time (min)
40
0.50 50
Fig.6.2: (a) J-V characteristics of LSMO/SiO2/p-Si heterojunction for three different samples at room temperature. (b) log J-log V plot of sample-2 to understand the current transport process at room temperature. (c) and (d) are evaluated fit parameters at room temperature. The ideality factors, reverse saturation current density plot for three different samples have been shown in (c), and series resistance and turn-on voltage have been shown in (d). The J-V characteristics for sample-3 at several temperatures down to 77 K have been shown in Fig. 6.3(a). It shows that the current decreases with decreasing temperature. The best fit parameters (, J0, Rs and V0) for all three samples have been evaluated for all six temperatures down to 77 K using Eq. (6.1) employing a 2 minimization technique. All these temperature dependent fit parameters are shown in Fig. 6.3(b) and 6.3(c). The strong dependency of current density and all four parameters with temperature indicates that not only the thermionic emission is occurring at the junction but other types of transport mechanisms are also present for all the heterojunctions. The strong dependency of ideality factor with temperature implies that the tunneling mechanism is one of the dominating current transport mechanisms through the junction.
116
The ln(J0/T2) vs. 1000/T plot shown in Fig. 6.3(d) provides the information about the effective barrier height and Richardson constant for all the three samples.
80
60
Sample-3
40
(a)
77 K 120 K 150 K 200 K 250 K 300 K
70
e-1 pl m e-2 pl sa m
(b)
J0
sample-2
60 50
3
sample-1
J0 (A/cm2)
40 sample-3 30 20
sa
sample-3
20
0
0 2 4 6 8 10
10
0 100 150 200 250 300
Voltage (V)
Series resistance (k-cm2)
500 400 300 200 100
sample-1 sample-3 sample-2
Temperature (K)
ln(J0/T2)
RS V0
sample-3
-16.4 -16.8 -17.2 -17.6 -18.0 -18.4 -18.8 -19.2 -19.6
Turn on voltage (V0) (V)
(d) Sample-2
sample-2
4
sample-1
Sample-3
Sample-1
(c)
0 50
0
100
150
200
250
300
Temperature (K)
Fig. 6.3. (a) Temperature dependent J-V characteristics of sample-3 without applied magnetic field. (b) and (c) are the plot of evaluated parameters with temperature. The ideality factor and reverse saturation current density plot with temperature for three different samples have been shown in (b), and series resistance and turn-on voltage with temperature have been shown in (c). (d) ln(I0/T2) vs. 1000/T plot to determine the effective barrier height. Table 6.2. Effective barrier height and Richardson constants for different samples Sample name Sample-1 Sample-2 Sample-3 Effective barrier height (eV) 0.021 0.027 0.030 Richardson constant (AK-2cm-2) 7.05 10-9 1.7 10-8 7.62 10-9
6 1000/T (K-1)
10
The evaluated values have been summarized in the Table 6.2. The slight difference in the value of Richardson constants may be due to different effective masses in the films. The
117
barrier height is much lower than expected because of high leakage current through the junction. 6.3.2.2. Tunneling Characteristics The I-V properties reveal that tunneling is occurring at all temperatures along with other mechanisms through our heterojunction as discussed earlier. Now it is necessary to find out the possible tunneling mechanism through the heterojunctions. The observed field stimulated emission and capture have been discussed in terms of FowlerNordheim tunneling [11], Poole-Frenkel effect [1214], phonon assisted tunneling [15], and a combination of both phenomena [16-20]. Fowler-Nordheim tunneling is the process whereby electrons tunnel through a barrier in the presence of a high electric field. This quantum mechanical tunneling process is an important mechanism for thin barriers similar to those in metal-semiconduictor junctions on highly-doped semiconductors. Fowler-Nordheim (F-N) tunneling current into the SiO2 conduction-band through a triangular barrier at high field is given by,
J FN = AV 2 exp( B / V )
where, A =
q3 8h B
(6.2) . Here q is the electronic charge,
and B =
3/ 2 8 (2m FN )1 / 2 B 3qh
and mFN
are the effective tunneling barrier height and effective mass of electron for F-N tunneling. V is the applied electric field across the thin oxide layer. The high field Fowler-Nordheim (F-N) plot [ln(JFN/V2) vs 1/V] of the heterojunction with native (sample-1) and thermal oxide intermediate layer (sample-3) at different temperatures have been shown in Fig. 6.4(a) and 6.4(b). The high field Fowler-Nordheim tunneling should be temperature independent. But our observed [ln(JFN/V2) vs 1/V] is strongly temperature dependent and hence we can conclude that the field dependent tunneling is mainly temperature dependent Frenkel-Poole type emission. The well-known Frenkel-Poole effect describes the increase of the thermal emission rate of carriers in an external electric field due to the lowering of the barrier associated with their Coulomb potential. It is a classical mechanism in which the electron is thermally emitted over the top of a potential barrier which has been lowered by the presence of an electric field. 118
-4 -6
ln(JFN/V2) 300 K
ln(JFN/V2)
-6
300 K 250 K
-8 -10 -12
Sample-1
250 K 200 K
-8 -10 -12 -14 0.1

Sample-3 200 K
(a)
150 K
(b)
150 K
-14 0.1 0.2 0.3 0.4 1/V (V-1)
0.5
0.2
0.3 0.4 1/V (V-1)
0.5
Fig.6.4. ln(JFN/V2) vs 1/V plot at different temperatures for (a) sample-1 and (b) sample-3. Frenkel-Poole emission refers to electric-field-enhanced thermal emission from a trap state into a band of electronic states of insulator conduction band. The current density associated with Frenkel-Poole emission is given by [21],
q ( B qV / 0 s J FP = CV exp kT
(6.3)
Where, B is the barrier height for electron emission from the trap state, s is the relative dielectric permittivity at high frequency, T is temperature, 0 is the permittivity of free space. As the electrons emitted from the trap states and can not polarize the surrounding atoms, the relevant dielectric constant is that at high frequency, rather than the static dielectric constant [15]. The high field ln(JFP/V) vs. V plot shown in Fig. 6.5(a) and Fig. 6.5(b) are linear for all temperatures and it implies that the temperature dependent Frenkel-Poole emission is the dominating current transport mechanism in non-epitaxial LSMO/SiO2/p-Si heterostructures.
119
-4 -6
ln(JFP/V) 300 K 250 K 200 K 150 K
(a)
ln(JFP/V)
-4 -6 -8 -10 -12 -14
300 K 250 K 200 K 150 K
(b)
-8 -10 -12 -14 0.5
Sample-1
Sample-3
1.0
1.5
Fig. 6.5. ln(JFP/V) vs. plot for V1/2 at different temperatures for (a) sample-1 and (b) sample-3 These plots show linear nature in higher field range confirms the presence of temperature dependent Frenkel-Poole emission through the heterostructures. 6.3.3. Electrical properties of LSMO/SiO2/p-Si hereostructure with applied magnetic field The J-V behaviors of sample-3 under very high magnetic field up to 8 T have been shown in Fig. 6.6(a) and Fig. 6.6(b) at 300 K and 120 K, respectively.
Current density (mA/cm )
2.0 2.5 1/2) V (V
3.0
3.5
0.5
1.0
1.5
2.0 1/2) V (V
2.5
3.0
0.07 0.06 0.05 0.04 0.03 0.02 0.01 0.00 0 1
0T 1T 2T 4T 6T 8T
(a)
20
% JMR
(c)
16 12 8
Sample-3 T = 300 K
4 0
Sample-3 300 K
3 4 Voltage (V)
5
(b)
6
60 50
%JMR
-8 -6 -4 -2 0 2 4 6 Magnetic field (T)
Current density (mA/cm2)
0.010 0.008 0.006 0.004 0.002 0.000 0 2 Voltage 4 (V) 6 0T 1T 2T 4T 6T 8T
(d)
40 30 20 10 0 -8 -6 -4 -2 0 2 4 Magnetic field (T) 6 8

Sample-3 120 K
Sample-3 T =120 K
10
Fig. 6.6. The J-V characteristics at 300 K and 120 K in (a) and (b), respectively at different applied magnetic field; the %JMR at 300 K and 120 K in (c) and (d), respectively.
120
Corresponding junction magnetoresistance have also been shown in Figs. 6.6(c) and (d), respectively. The change is almost linear up to 1 T magnetic field. After applying higher magnetic field beyond 1 T, the junction magnetoresistance starts saturating and applying very high magnetic field (> 4 T), junction magnetoresistance starts to decrease slightly. 6.3.3.1. Current-Voltage properties under magnetic field using diode characteristics Figure 6.7 (a) shows the room temperature J-V nature with and without external magnetic field of 1 T for all three samples.
current density (mA/cm2)
0.18
0.12
sample-1 at 0T sample-1 at 1T sample-2 at 0T sample-2 at 1T sample-3 at 0T sample-3 at 1T
(a)
m
0.06
0.00
100
RSm (k-cm2)
2 3 4 Voltage (V)
30 28 26 24 22 20 18 16 14 12 0
T=300 K
0.020 0.018 0.016

J0m(mA/cm2)
m
J0m
(b)
50
0.014
10 20 30 40 Oxidation time (min)

1.5 80 60 40 20 0 0 10 20 30 40 Oxidation time (min)
RSm V0m
1.4 1.3
% JMR
(c)
T =300 K
1.2 1.1
1.0 50
16 14 12 10 8 6 4 2 0
T=300 K
Fig. 6.7(a) J-V characteristics of LSMO/SiO2/p-Si heterojunction for three different samples at room temperature with and without applied 1 T magnetic field. (b) and (c) are evaluated parameters at room temperature. The ideality factor and reverse saturation current density plot for three different samples under 1 T magnetic field have been shown in (b), and series resistance and turn-on voltage have been shown in (c) at room temperature. (d) The measured %junction MR plot with applied magnetic field for all three samples at room temperature. The J-V curve shows reasonably good sensitivity under magnetic field at room temperature as shown in Fig. 6.7(a). The four parameters in Eq. (6.1) are modified under 121
V0m (V)
(d)
-0.8 -0.4 0.0 0.4 0.8 Applied magnetic field (T)
magnetic field (J0, , Rs and V0 are now replaced by J0m, m, Rsm and V0m, respectively) and the current density is found to decrease with magnetic field at higher bias potential. The reverse saturation current density (J0m) and ideality factor (m) evaluated from fitting to room temperature J-V curve under magnetic field for different oxide thickness have been plotted in Fig. 6.7(b) and series resistance (Rsm) and turn-on voltage (V0m) have been shown in Fig. 6.7(c). The current has been measured by keeping fixed forward junction voltage at 4.8 V for varying magnetic field up to 1 T at room temperature. It shows the change in junction MR is about 7, 9 and 16% at 4.8 V for sample-1, sample-2 and sample-3, respectively.

The
definition
used
here
for
the
junction
V applied V applied MR = I J ( H =1T ) I J ( H = 0T )
V applied I J ( H = 0T )
100% ,
where IJ(H=1T) is the current at 1 T applied
magnetic field. The plots of % of junction MR with applied magnetic field at a bias voltage of 4.8 V for all three samples have been shown in Fig. 6.7(d). The temperature dependent J-V properties without and with 1 T magnetic field of sample-3 have been shown in Fig. 6.8(a) for three different temperatures. It shows the positive junction MR properties for all the temperatures and the magnitude of junction MR is also temperature dependent. The fit parameters under magnetic field for different samples have been plotted in Fig. 6.8(b) and Fig. 6.8(c) respectively. The dependency of all four parameters with temperature show the same trend as the parameters evaluated from J-V without magnetic field shows. The ln(J0m/T2) vs. 1000/T plot shown in Fig. 6.8(d) provides the information about the effective barrier height and Richardson constant for all the three heterojunctions under magnetic field. The estimated parameters have also been listed in the Table 6.3. The evaluated effective barrier heights are not much increased under magnetic field. But the other parameters, mainly the series resistances are increased significantly under magnetic field and it cause the positive MR at the heterojunctions at all operating temperatures.
122
current densty (mA/cm2)
0.06 0.05 0.04 0.03 0.02 0.01 0.00 0
Sample-3
80
m
J0m Sample-3
Sa mp le1
0.07
(a)
120 K at 0T 120 K at 1T 250 K at 0T 250 K at 1T 300 K at 0T 300 K at 1T
100
Sample-1
0.020 0.016 0.012 0.008 0.004 0.000

J0m (mA/cm-2)
60 40 20
(b)
120 160 200 240 280 Temperature (K)
4 6 Voltage (V)
10
-15.0
RSm
600 500 Rsm (Kcm )

2
Sample -3
V0m
e-3 pl m Sa
-15.5 -16.0
ln(J0m/T2)
400 Sample-2 Sa mp le300 1 200 100 0 120

Sample-1 Sample-2
-16.5 -17.0 -17.5 -18.0 -18.5 -19.0 3 4 5
(c)
2 320
(d)
sam ple1 s am sam ple ple -2 -3
160 200 240 280 Temperature (K)
7 -1 1000/T (K )
Sa m pl e3
8
2 epl m Sa
320
Fig. 6.8. (a) Temperature dependent J-V characteristics of sample-3 with and without 1 T applied magnetic field. (b) and (c) are the plot of evaluated parameters with temperature. The ideality factor and reverse saturation current density plot with temperature for three different samples under 1 T magnetic field have been shown in (b), and series resistance and turn-on voltage with temperature under 1 T magnetic field have been shown in (c). (d) ln(I0/T2) vs. 1000/T plot to determine the effective barrier height under magnetic field. Table 6.3. Effective barrier height and Richardson constants for three different samples under 1 T magnetic field Sample name Sample-1 Sample-2 Sample-3 Effective barrier height (eV) 0.020 0.029 0.046 Richardson constant AK-2cm-2 2.73 10-8 4.22 10-8 9.21 10-8
The comparative study of barrier height and series resistance with and without magnetic field has been listed in Table 6.4.
123
V0m (V)
Table 6.4. Comparative study of effective barrier height and room temperature series resistance with and without applied 1 T magnetic field. Applied Magnetic Sample name Effective barrier height Series resistance field 0T Sample-1 Sample-2 Sample-3 1T Sample-1 Sample-2 Sample-3 (eV) 0.021 0.027 0.030 0.020 0.029 0.046 (k-cm2) 7.2 35.42 74.86 7.8 39.34 89.03
It is clear that the evaluated effective barrier heights are not much increased under magnetic field. But the other parameters, mainly the series resistances are increased much under magnetic field and cause the positive MR at the heterojunctions at all operating temperatures. 6.3.3.2. Tunneling Characteristics under1 T applied magnetic field As discussed earlier, the dominating tunneling mechanism through the heretojunctions fits very well with temperature dependent Frenkel-Poole emission. The ln(JFP/V) vs. V plot for J-V under 1 T applied magnetic field has also been shown in Fig 6.9(a) and Fig. 6.9(b) for both sample-1 and sample-3, respectively.
-4 -6
ln(JFP/V)
300 K 250 K
-8
200 K 150 K
(a)
-10 -12 -14 0.5 1.0 1.5
Sample-1 H= 1T
2.0
V (V )
1/2
2.5
3.0
3.5
-5 -6 -7 -8 -9 -10 -11 -12 -13 -14 -15 0.5
300 K 250 K 150 K 200 K Sample-3 H=1T (b)
ln(JFP/V)
1.0
1.5
2.0
V (V )
1/2
2.5
3.0
3.5
Fig.6.9. (a) ln(JFP/V) vs. plot for V1/2 at different temperatures for (a) sample-1 and (b) sample-3 under 1 T applied magnetic field. In the high biasing field region ln(JFP/V) vs. V graphs have been fitted linearly for both the sample-1 and sample-3. The intercept at y-axis have been plotted with 1000/T in Fig.
124
6.10 (a) and (b) for sample-1 and sample-3 without and with 1 T applied magnetic field, respectively. The slope of the plots gives the effective tunneling barrier height.
-6
Intercept at y-axis (a)
Intercept at y-axis
-8 -10 -12 -14
Sa mp le3 Sa mp le1
-6 -8 -10 -12 -14
Sa mp leSa 3 mp le1
(b)
H=0T
H=1T
-16 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 -1 1000/T (K )
-16 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 -1 1000/T (K )
Fig. 6.10. The intercept at y-axis evaluated from Fig. 6.5 and Fig. 6.9 with 1000/T plot for sample-1 and sample-3 under (a) 0 T and (b) 1 T applied magnetic field to determine the effective tunneling barrier height The evaluated effective tunneling barrier height with and without magnetic field for three samples have been listed in Table 6.5. Table 6.5: Evaluated effective tunneling barrier height with and without 1 T applied magnetic field for different samples Sample Sample-1 Sample-2 Sample-3 Applied magnetic field (Tesla) 0 1 0 1 0 1 6.3.4. Junction magnetoresistance properties study The % of JMR for the LSMO/SiO2/p-Si heterojunction has been calculated from the relation, JMR =
R sm R s 100% . Rs
Effective tunneling barrier height (meV) 179.72 180.37 193.54 194.11 211.21 212.70
The room temperature magnetic field dependent
125
junction magnetoresistance (JMR) behavior in the low magnetic field region (up to 1 T) of sample-3 have been analyzed using a simple empirical relation as [22], % JMR = H (6.4)
where, and are coefficients. The best fit values of and are and are found to be 0.31 and 0.73, respectively, employing a non-linear least square fitting 2 minimization technique. The coefficient is found to be smaller than one at room temperature showing non-linear magnetic field dependence of positive MR of the junction. The high dependency of JMR with interfacial oxide layer implies that the leakage current also plays an important role in JMR property of such p-i-p type heterojunctions. As discussed earlier, the increase of oxidation time causes the increase of crystalline SiO2 oxide layers and thereby causes decrease of oxide defects. The less oxide defect causes less leakage current through the junction. As defect related leakage currents decreases for sample-3, the value of the parameters (coefficients) enhances (modifies) and causes higher % of junction MR at room temperature [Fig. 6.7(d)]. Table 6.6. Evaluated and parameters Heterojunctions Sample-1 Sample-2 Sample-3 8.42 9.89 16.32 (T-) 0.85 0.85 0.80
The increase of junction series resistance can be explained by the theoretical model of spin tunneling in ferromagnetic to paramagnetic junctions [23]. It is interesting that the existence of JMR is positive when the dominating current transports mechanism is tunneling. So, it can be concluded that the appearance of positive JMR is due to tunneling of electron through the heterojunction. Considering eg electron tunnels from ferromagnetic LSMO to paramagnetic p-Si through insulating SiO2 layer, it can be
126
considered that there exist two channels (spin up I and spin down I) at conduction band for eg electrons to tunnel as shown in Fig. 6.11.
Fig. 6.11. Schematic diagram of spin tunneling from magnetic LSMO to non magnetic Si with and without applied magnetic field. The ratio I/I is proportional to the spin polarization of LSMO (Fig. 6.11). At room temperature the ratio is approximately 1 due to the lower spin polarization of LSMO. The both channels have allowed states at Fermi energy level and the both channels act in tunneling mechanism at room temperature in absence of magnetic field. If the external magnetic field is applied, the disordered spins are suppressed and the I/I ratio increases. One channel becomes inactive due to applied magnetic field and at Fermi energy level only the other channel will have allowed states for tunneling at room temperature and low temperatures. This reduces the current at a particular biasing field in presence of 1 T magnetic field as observed in the J-V characteristics of the heterojunction. It most likely causes enhancement of junction resistance under applied magnetic field. The slight decrease of turn-on voltage with applied magnetic field shown in Fig. 6.3 and Fig. 6.8 implies that there is a certain voltage region in which the junction MR is negative. This voltage region lies between the turn-on voltage and saturation voltage for corresponding temperatures. The % of JMR plot with temperature has been shown in Fig. 6.12. The % JMR for all three samples decreases sharply with increasing the temperature.
127
50 45 40 35 30 25 20 15 10 5
% JMR
120
160 200 240 Temperature (K)
280
320
Fig. 6.12. The temperature dependent junction MR plots for all three samples; the JMR has been calculated from the values of series resistances with and without 1 T magnetic field which are evaluated from the fitting of J-V curves. With increasing of thermal energy it is more likely that the spin polarization decreases and hence the change of junction resistance decreases. It causes the decrease of % JMR with increasing temperature. The change of junction MR with different forward bias voltages for all the three samples at room temperature and for different temperatures for sample-3 have been shown in Fig. 6.13(a) and Fig. 6.13(b), respectively.
24
50
20
% JMR
T = 300 K
40
% JMR
Sample 3
16 12 8 4 0 2 Sample-1 Sample-2 Sample-3 3 4 5 Applied voltage (V) 6
30 20 10
120 K 250 K 300 K
1 10 Applied Voltage (V)
Fig. 6.13. (a) The % of junction MR plot with applied bias voltage for all three samples. (b) The same plot for different temperature for sample-3. The positive junction MR occurs at higher voltages and increases almost exponentially with increasing forward bias voltages for all samples at all temperatures. In lower bias
128
voltage regions (voltage lies between turn-on voltage and saturation voltage) the junction shows either no such significant change in junction MR or negative junction MR for different samples. The negative junction MR in this region becomes prominent at low temperatures rather than room temperatures. It may be due to the effect of leakage current through the junction. The leakage current is higher at room temperatures and there is no such significant effect of magnetic field on leakage current which has been found through this study. The little change of junction current may be compensated with leakage current and overall current change can vanish at room temperature. When temperature decreases the leakage current also decreases. The current change through the junction becomes prominent at low temperatures. 6.4. Summary In summary, we have successfully grown the LSMO/SiO2/p-Si heterostructure by pulsed laser deposition technique and investigated its junction properties in details. We have varied the SiO2 barrier layers thickness by varying oxidation times on cleaned Si substrates. The various oxidation conditions are responsible for generating defects in oxide layer which most likely play important role in carrier transport through the junction. The dominating current transport mechanism through the junction is temperature dependent Frenkel-Poole type emission. We have thoroughly investigated the dependency of positive junction MR with applied biasing potentials and temperatures. We have also found that the junction MR also depends on the defects induced leakage current through the junction. The junction MR increases with increasing the thickness of the SiO2 interfacial layer. It can be concluded that the leakage current can damage the magnetic sensitivity (decrease of junction MR) of such devices. We have also estimated the junction parameters such as ideality factor, turn-on voltages, barrier heights, series resistances etc. It is found that the ideality factor, barrier height and series resistance increase and turn-on voltages slightly decreases with the increase of external applied magnetic field at all operating temperatures for all three samples. These results reveal that the junction MR is positive at higher potentials and shows little negative value at lower biasing voltage regions. Highest junction MR for the sample-3 has been found to be ~56% at 120 K and ~17% at 300 K at an applied bias voltage of 2 T. The thorough 129
analysis of junction J-V characteristics also leads to conclude that the arising of positive MR at the junction is mainly due to the change of series resistances under magnetic field rather than the change of effective barrier heights. We have also tried to establish possible mechanism of the observed experimental results from our oxide thickness layer dependent heterojunction employing the possible model of FM semiconductor/NM semiconductor tunneling junction. References [1] S. Datta and B. Das, Electronic analog of the electrooptic modulator, Appl. Phys. Lett. 56, 665 (1990). [2] J. Fontcuberta, L. Balcells, M. Bibes, J. Navarro, C. Frontera, J. Santiso, J. Fraxedas, B. Martnez, S. Nadolski, M. Wojcik, E. Jedryka and M J, Casanove, Magnetoresistive oxides: new developments and applications, J. Magn. Magn. Mat. 242, 98 (2002). [3] Y. Ishii, H. Yamada, H. Sato, H. Akoh, M. Kawasaki, Y. Tokura and Y. Tokura, Perovskite manganite magnetic tunnel junctions with enhanced coercivity contrast, Appl. Phys. Lett. 87, 022509 (2005). [4] R. S. Popovic, Not-plate-like Hall magnetic sensors and their applications, Sens. Act. A 85, 9 (2000). [5] M. Johnson, Magnetoelectronics, Academic Press, Elsevier, London,(2004). [6] J. Xing, K. Zhao , G. Z. Liu, M. He, K. J. Jin and H. B. Lu, Enhancement of photovoltaic effect in La0.9Sr0.1MnO3/Si heterojunction by side illumination, J. Phys. D: Appl. Phys. 40 5892 (2007). [7] K. Zhao, K. J. Jin, H. Lu, Y. Huang, Q. Zhou, M. He, Z. Chen, Y. Zhou and G. Yang, Transient lateral photovoltaic effect in p-n heterojunctions of La0.7Sr0.3MnO3 and Si, Appl. Phys. Lett. 88, 141914 (2006). [8] Lord K, Hunter D, Williams T M and Pradhan A K, Photocarrier injection effect and p-n junction characteristics of La0.7Sr0.3MnO3/ZnO and Si heterostructures, Appl. Phys. Lett. 89, 052116 (2006). [9] R. L. Zhang, W. H. Song, Y. Q. Ma, J. Yang, B. C. Zhao, G. H. Zheng, Z. G. Sheng, W. J. Lu and Y. P. Sun, The response for magnetic field, current and photo irradiation of charge-ordering LaSr2Mn2O7 thin film, J. Phys. D: Appl. Phys. 39 621 (2006). [10] S. J. May and B. W. Wessels, High-field magnetoresistance in p-(In,Mn)As/n-InAs heterojunctions, Appl. Phys. Lett. 88, 072105 (2006). [11] G. Chakraborty, S. Chattopadhyay, C. K. Sarkar, and C. Pramanik, Tunneling current at the interface of silicon and silicon dioxide partly embedded with silicon nanocrystals in metal oxide semiconductor structures, J. Appl. Phys. 101, 024315 (2007). [12] S. D. Ganichev, E. Ziemann, W. Prettl, I. N. Yassievich, A. A. Istratov and E. R. Weber, Distinction between the Poole-Frenkel and tunneling models of electric-fieldstimulated carrier emission from deep levels in semiconductors, Phys. Rev. B 61, 10361 (2000). [13] G. Vincent, A. Chantre, and D. Bois, Electric field effect on the thermal emission of traps in semiconductor junctions, J. Appl. Phys. 50, 5484 (1979).
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[14] W. R. Buchwald, N. M. Johnson, Revised role for the Poole-frenkel effect in deeplevel characterization, J. Appl. Phys. 64, 958 (1988). [15] L.Tsybeskov, G. F. Grom, P. M. Fauchet, J. P. McCaffrey, J. M. Baribeau, G. I. Sproule, and D. J. Lockwood , Phonon-assisted tunneling and interface quality in nanocrystalline Si/amorphous SiO2 superlattices, Appl. Phys. Lett. 75, 2265 (1999). [16] G. Vincent, A. Chantre, and D. Bois, Electric field effect on the thermal emission of traps in semiconductor junctions, J. Appl. Phys. 50, 5484 (1979). [17] F. D. Auret, S. A. Goodman, and W. E. Meyer, Electric-field-enhanced emission from radiation-induced hole traps in p-GaAs, Semicond. Sci. Technol. 10, 1376 (1995). [18] A. Ilie and B. Equer, Field-enhanced generation in hydrogenated amorphous silicon, Phys. Rev. B 57, 15349 (1998). [19] W. R. Buchwald and N. M. Johnson, Revised role for the Poole-frenkel effect in deep-level characterization, J. Appl. Phys. 64, 958 (1988). [20] P. A. Martin, B. G. Streetman and K. Hess, Electric field enhanced emission from non-Coulombic traps in Semiconductors, J. Appl. Phys. 52, 7409 (1981). [21] H. Zhang, E. J. Miller and E. T. Yua, Analysis of leakage current mechanisms in Schottky contacts to GaN and Al0.25Ga0.75N/GaN grown by molecular-beam epitaxy, J. Appl. Phys. 99, 023703 (2006). [22] Z. G. Sheng, W. H. Song, Y. P. Sun, J. R. Sun and B. G. Shen, Crossover from negative to positive magnetoresistance in La0.7Ce0.3MnO3-SrTiO3-Nb heterojunctions, Appl. Phys. Lett. 87, 032501 (2005). [23] I. uti, J. Fabian, and S. Das Sarma, Spintronics: Fundamentals and applications, Rev. Mod. Phys. 76, 323 (2004).
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Chapter 7
Electronic-and magneto transport of La0.7Sr0.3MnO3/ZnO, La0.7Sr0.3MnO3/Zn(Fe)O and La0.7Sr0.3MnO3/Zn(Fe,Al)O heterostructures
Thischapterisbasedon Internationaljournals 1. Enhanced temperature dependent junction magnetoresistance in the heterojunctions with La0.7Sr0.3MnO3 and iron doped ZnO carrier induced dilute magnetic semiconductors by S. Chattopadhyay, J. Panda, T. K. Nath, Journal of AppliedPhysics.(Communicated) Conferences/Symposia 1. Temperature dependent junction magnetoresistance behavior of LSMO/Zn(Fe,Al)O heterojunction for spintronics by J.Panda,S.ChattopadhyayandT.K.Nath,55thDAESolidStatePhysicsSymposium2010(2010).
ElectronicandmagnetotransportofLa0.7Sr0.3MnO3/ZnO, Chapter7 La0.7Sr0.3MnO3/Zn(Fe)OandLa0.7Sr0.3MnO3/Zn(Fe,Al)Oheterostructures
7.1. Introduction In recent time, a great interest in the field of spintronics devices widely deals with several kind of Schottky and heterojunctions of ferromagnetic materials/semiconductors with other non magnetic semiconductors. Since the rediscovery of colossal magnetoresistance (CMR) effect in manganite thin films, much attention has been focused on the fabrication of artificially designed structures [1-3], such as magnetic tunnel junctions, and pn junctions [4-7] to verify device concepts based on oxide materials. The doped manganite La1xAxMnO3 (A=Ca, Sr, and Ba) is a strongly correlated-electron system with charge, orbital, spin, and lattice degrees of freedom, possessing diverse physical phenomena. The heterostructures based on p-type perovskite oxides show some special characteristics such as high magnetic sensitivity, ultraviolet photo voltage, current field modulations, and the photo carrier injection effect [8-9]. The La0.7Sr0.3MnO3 (LSMO) is a typical double exchange highly spin-polarized system with a high Curie temperature of about 360 K due to its large one-electron bandwidth. Therefore, it is one of the best choices as a ferromagnetic electrode. On the other hand, ZnO is an n-type semiconductor with a wide band gap and large exciton binding energy. However, there have been only a few reports on the effect of magnetic fields on transport properties in LSMO/ZnO p-n heterostructures [10,11]. On the other hand ZnO doped with transition metals shows room temperature ferromagnetic properties, which is also called the dilute magnetic semiconductor (DMS). With carrier concentration much smaller than the magnetic impurity concentration, the DMS system provides a complimentary limit to Kondo system. The coupling between localized impurity spin (S) and mobile valence band holes or conduction band electron can be represented by the exchange interaction J S., where is the fermion spin operator. The Fe doped ZnO shows room temperature ferromagnetic behavior and incorporating 1% Al shows enhanced carrier induced ferromagnetism mainly due to the increase of charge carrier concentrations [12]. A few research work have been carried out with heterojunction of carrier induced ferromagnetic n-type ZnO DMS with ferromagnetic half metallic p-type LSMO [13]. But a detail study (thorough investigation) of spin injection through such p-n heterojunction is necessary for complete understanding to use it in proper spintronics device applications. In this chapter, we have demonstrated a detail junction magnetoresistive properties of LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O with different Fe concentrations (5, 7, and 132
Chapter7 ElectronicandmagnetotransportofLa0.7Sr0.3MnO3/ZnO, La0.7Sr0.3MnO3/Zn(Fe)OandLa0.7Sr0.3MnO3/Zn(Fe,Al)Oheterostructures
10%) and established the temperature dependent spin injection and spin extraction process through the junction. 7.2. Experimental Procedure 7.2.1. Preparation of target The LSMO powder was synthesized through chemical pyrophoric reaction process where we have employed stoichiometric mixtures of high purity La2O3 (99.99 %), SrCO3 (99.9+ %) and Mn(CH3COO)2 (99.0 %). After final grinding and pelletization of LSMO powders, the pelletized sample was first heated at 800 C for 12 h, then at 1000 C for 12 h and at 1200 C for another 12 h, with intermediate grinding. Final sintering of the LSMO target was carried out at 1200 C for 24 h. The iron doped ZnO powder was first synthesized by solid state reaction process. Required amount of high purity ZnO, Fe2O3 powder were well mixed with hand grinder repeatedly and sintered at 450 C till the required phase appeared. Required amount of Al2O3 powder were mixed with the ZnO and Fe2O3 powder to dope 1% aluminum in Zinc iron oxide target. Finally, the Zn(Fe)O and Zn(Fe,Al)O powders were pelletized and sintered at 450 C to use it as the target for pulsed laser deposition (PLD). 7.2.2. Cleaning of substrate The c-plane (0001) sapphire substrate has been cleaned repeatedly with De-ionized water, Acetone and Propanol using ultrasonic vibrator. Each cleaning method has been carried out for 20 min. 7.2.3. Preparation of heterojunction At first the LSMO film was deposited on (0001) well cleaned sapphire substrate at 800
o
C and 0.5 mbar O2 pressure. The laser pulse (248 nm KrF laser) of energy density 4 J/cm2 was
applied on the LSMO target for 20 min at a frequency of 10 Hz. The substrate to target distance was kept at 4 cm in the chamber. After deposition, the film was sintered at the same physical condition for 1 hr to get well crystalline samples. Then a portion of the substrates were masked and the ZnO films were grown on the LSMO. The films were grown on LSMO at a substrate temperature at 450 oC and in ambient oxygen pressures at 10-5 Torr. The excimer laser was used
133
for 30 min at a laser pulse frequency (repetition rate) of 10 Hz. Electrical contacts were made with high purity Ag on LSMO film and highly pure In contact with ZnO as ohmic contacts. 7.2.4. Characterization of heterostructure The structural and surface morphological studies have been carried out using high resolution x-ray diffraction (Philips pan analytical x-pert), scanning electron microscope (Carl Zeiss) and atomic force microscope (Nanonics). The electrical properties have been studied out in details using Keithley 2612 source meter with 1 microvolt resolution and a DMM (Keithley2000) along with a temperature controller (Lakeshore-330). The magnetic field was applied in the current parallel to the plane (CPP) geometry with the magnetic field parallel to the film plane using a high precision electromagnet (polytronic, model HEM 100). 7.3. Results and Discussion
7.3.1. Structural and surface study

ZnO (1 0 1) LSMO (1 1 1) Al2O3 (0 0 6) ZnO (1 0 2)
LSMO (1 1 0)
Intensity (a.u)
LSMO (1 0 0)
ZnO (2 0 1)
Intansity (a.u)
(a)
Intensity (a.u)
(b)
64
66
68
70
72
74
76
20
30
40
50 60 2 (Degree)
70
80
30
31
32 33 2(Degree)
34
35
(c)
ZnO LSMO
(d)
100 nm
200 nm
Fig. 7.1.(a) High resolution XRD pattern of LSMO/ZnO heterojunction on sapphire substrate. (b) Zoomed view of HRXRD along with Gaussian fit of (110) plane of LSMO and(201) plane of ZnO(inset). (c) and (d) are the FESEM image of surface and cross sectional view, respectively. 134
The high resolution x-ray diffraction (HRXRD) pattern, shown in Fig. 7.1(a), has been carried out using Cu-K radiation. Both LSMO film and ZnO films show non-epitaxial behavior on (0001) c-plane sapphire substrate. The growth of LSMO is in the directions of (100), (110) and (111) plane and ZnO is in the direction of (101), (102) and (201) planes have been found. Figure 7.1(b) shows the zoomed view of LSMO (110) and ZnO (201) planes (inset of Fig. 7.1(b)) along with Gaussian fit. It gives the lattice parameters LSMO and ZnO (aLSMO ~ 3.83 and aZnO ~ 3.53 ). In Fig. 7.1(c) and 7.1(d), the FESEM micrograph of the top view of one of the LSMO/ZnO heterojunction and the cross sectional FESEM image of the heterojunction have been shown, respectively. The FESEM micrograph clearly shows the uniformly grown smooth LSMO and ZnO film with good coverage on sapphire substrate. The average thickness of the LSMO layer is around ~ 371 nm and ZnO layer is around ~ 124 nm.
0.03 Volts
(a
(b)
1.0m
-0.04 Volts 1.20 Volts
0.97 Volts
(c)
(d)
1.0m
Fig. 7.2. AFM image of LSMO surface morphology: (a) 2-d and (b) 3-d view. AFM image of LSMO/ZnO heterojunction: (c) 2-d and (d) 3-d view. Figures 7.2(a) and (b) show the atomic force microscopic (AFM) image of the surface of LSMO film on (0001) sapphire substrate and 3-d view of the LSMO film, respectively. The r.m.s. roughness of the LSMO film is found to be ~2 nm. The AFM scan at the junction has been taken and their 2-d and 3-d image of the junction has been shown in Fig. 7.2(c) and (d), 135
-0.47 Volts
-0.43 Volts
respectively. From the image contrast in Fig. 7.2(d) it is clear that the ZnO layer has been grown on LSMO film and it confirms the formation of heterojunction. 7.3.2. Electrical properties study The room temperature current density-voltage (J-V) properties of ZnO/LSMO, Zn(Fe)O/LSMO and Zn(Fe,Al)/LSMO heterojunctions with 5% Fe have been shown in Fig. 7.3. Insets (a) and (b) of Fig. 7.3 are the isothermal LSMO/Ag and ZnO/In ohmic contacts, respectively measured at several different temperatures. These metallic contacts are linear in all temperatures which confirm that the non linearity of J-V properties originates from ZnO/LSMO junctions only, not from metal - semiconductor contacts. Doping with 1% Al enhances the carrier concentration of ZnO films (~1022 /cm3) and causes a very thin depletion layer across the heterojunctions. So, the reverse saturation current becomes very high and does not show good rectifying behavior where as ZnO/LSMO, Zn(Fe)O/LSMO shows reasonably good rectifying behavior as the films have moderate carrier concentrations (~1019-1021/cm3). Large current flows through the Zn(Fe,Al)O/LSMO junction rather than the ZnO/LSMO or Zn(Fe)O/LSMO heterojunctions.
0.4
77 K 100 K 150 K 200 K 250 K 300 K
Current (mA)
100 Current(mA/cm ) 50 0 -50 -100

2
0.2 0.0 -0.2 -0.4
Zn(Fe,Al)O
LSMO/Ag Ohmic contact
(a)
-3 -2
ZnO
15 10
Current (mA)
Voltage (V)
-1
3
77 K 100 K 150 K 200 K 250 K 300 K
Zn(Fe)O
5 0 -5 -10 -15
ZnO/In Ohmic contact
(b)
-4 -3 -2 -1
Voltage (V)
-5 -4 -3 -2 -1 0
Voltage(V)
Fig. 7.3. Room temperature J-V properties of LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O heterojunction. Upper inset shows the ohmic nature of I-V behavior for LSMO-Ag electrical contact at several temperatures (77-300 K). Lower inset shows the same for ZnO-In electrical contact.
136
35 30 25 20 15 10 5 0 -5 -10 -8
0%
Current (mA/cm )
7% 10%
Current(mA/cm )
300 K LSMO/Zn(Fe)O H=0 T
5%
2
100 50 0 -50
300 K LSMO/Zn(Fe,Al)O
5%
7%
10%
H=0 T
(a)
-6 -4 -2 0 2 4 6 Voltage (V)
-100 -3 -2 -1 0 1
(b)
2 3 Voltage(V)
Fig. 7.4. Room temperature J-V properties of (a) LSMO/ZnO, LSMO/Zn(Fe)O and (b) LSMO/Zn(Fe,Al)O heterojunction with different Fe concentrations. Figure 7.4(a) shows the J-V behavior of Zn(Fe)O/LSMO junction with different Fe doping percentages ranging from 0 to 10%. Figure 7.4(b) is the J-V behavior of Zn(Fe,Al)O/LSMO junction with different percentages. The junction J-V characteristics can be described as [14],
e (V JAR s ) J = J 0 exp kT
(7.1)
where, J0 is the reverse saturation current density. and Rs are, the ideality factor and junction series resistance, respectively. A is the junction area. The parameters evaluated from the forward J-V curves of all those films have been summarized in Table 7.1. The little increase of junction series resistance with increasing doping concentration reveals the lowering of carrier concentration in Zn(Fe)O and Zn(Fe,Al)O films. Figure 7.5(a) shows the temperature dependent J-V characteristics of LSMO/ZnO heterojunction. Figures 7.5(b), (c) and (d) are the temperature dependent J-V characteristics of LSMO/Zn(Fe)O heterojunctions with 5, 7, 10% iron doping, respectively. Accordingly, Fig. 7.6(a), (b) and (c) are the junction J-V characteristics of LSMO/Zn(Fe,Al)O with 5, 7 and 10% Fe. All parameters evaluated from the fitting using Eq. (7.1) have been listed in Table 7.1. The temperature dependent series resistance for the LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O junctions with 5% Fe doping have been shown in Fig. 7.6(d). The junction series resistance is found to decrease with increasing temperature which is generally expected in p-n junction characteristics. 137
35 30 (a) 300 K 250 K 25 LSMO/ZnO 20 200 K 15 150 K H=0 T 10 5 100 K 77 K 0 -5 -10 -10 -5 0 5 Voltage (V) 25 300 K (c) 20
30 25 Current (mA/cm )
2
(b) LSMO/Zn(Fe)O with 5% Fe H=0 T
300 K 250 K 200 K 150 K 100 K 77 K
Current (mA/cm )
20 15 10 5 0 -5
-10 -10 -8
20 Current (mA/cm )
2
-6
-4 -2 0 2 Voltage (V)
300 K
Current (mA/cm )
15 10 5 0 -5
LSMO/Zn(Fe)O with 7% H=0 T
250 K
(d) LSMO/Zn(Fe)O with 10% Fe H=0 T
250 K 200 K 150 K
200 K 150 K 100 K 77 K
15 10 5 0 -5
100 K 77 K
-10 -10 -8
-6
-4
-2
-10 -8
-6
Voltage (V)
-4 -2 0 Voltage (V)
Fig.7.5. (a) J-V properties of LSMO/ZnO heterojunction at different isothermal temperatures, (b), (c) and (d) are the same plots for LSMO/Zn(Fe)O heterostructures with 5, 7 and 10% Fe concentrations, respectively.
100 LSMO/Zn(Fe,Al)O 5% Fe 50 H=0 T 0 -50 -100 -3
80 60 40 20 0 -20 -40 -60 -80
(a)
77 K 100 K 150 K 200 K 250 K 300 K
100 80 60 40 20 0 -20 -40 -60 -80 -100
Current(mA/cm )
Current(mA/cm )
Zn(Fe,Al)O 7% Fe H=0 T
77 K 100 K 150 K 200 K 250 K 300 K
(b)
-2
-1
3
3.0 2.5 Rs (-cm ) 2.0 1.5 1.0 0.5 0.0
3
-3
-2
-1
Voltage(V)
Zn(Fe,Al)O 10% Fe
2
Voltage(V)
With out field ZnO ZnFeO ZnFeAlO
Current(mA/cm )
H=0 T
77 K 100 K 150 K 200 K 250 K 300 K
(c)
(d)
100 150 200 250 300
-3
-2
-1
Voltage(V)
50
Temperature (K)
Fig. 7.6. (a) J-V properties of LSMO/ZnO heterojunction at different isothermal temperatures, (b), (c) and (d) are the same plots for LSMO/Zn(Fe)O heterostructures with 5, 7 and 10% Fe concentrations, respectively.
138
35 300 K (a) 250 K 30 200 K 25 150 K 100 K 20 77 K 15 10 LSMO/ZnO 5 0 H=0.7 T -5 -10 -9 -6 -3 0 3 6 Voltage(V)
30 Current(mA/cm2) 20
(b)
Current(mA/cm2)
10 LSMO/Zn(Fe)O 5% Fe 0
300 K 250 K 200 K 150 K 100 K 77 K
-10 -10 -8 -6 -4 -2 0
25 20 (d) Current(mA/cm2) 15 10
H=0.7 T 2 4 6 Voltage(V)
300 K 250 K 200 K 150 K 100 K 77 K
25 20 Current(mA/cm2) 15 10 (c)
300 K 250 K 200 K 150 K 100 K 77 K
5 LSMO/Zn(Fe)O 7%Fe 0 -5 -10 -10 -8 -6 -4 -2 0 Voltage(V) H=0.7 T 2 4 6
5 LSMO/Zn(Fe)O 10%Fe 0 -5 -10 -8 -6 -4 -2 0 Voltage(V) H=0.7 T 2 4 6
Fig. 7.7. (a) Isothermal J-V characteristics of LSMO/ZnO heterojunction at several different temperatures under 0.7 T applied magnetic field, (b), (c) and (d) are the same plots for LSMO/Zn(Fe)O heterostructures with 5, 7 and 10% Fe concentrations, respectively.
100 (a) 80 60 LSMO/Zn(Fe,Al)O 40 with 5% Fe 20 0 -20 -40 -60 H=0.7 T -80 -100 -3 -2 -1 0
100 Current(mA/cm2) 50 0 -50
(b)
Current(mA/cm )
Zn(Fe,Al)O 7%
300K 100K 200K 250K 150K 77K
300K 100K 200K 250K 150K 77K
-100 -3
2.8 2.4 2.0
H=0.7 T -2 -1 0 1 2
Voltage(V)
Voltage(V)
(d) With applied magnetic field ZnO ZnFeO ZnFeAlO H=0.7 T
100 Current(mA/cm2) 50 0 -50 -100 -3
(c)
Rsm(cm )
Zn(Fe,Al)O 10%
300K 100K 200K 250K 150K 77K
1.6 1.2 0.8 0.4 0.0 50 100 150 200
H=0.7 T -2 -1 0 1 2
250
300
Voltage(V)
Temperature (K)
Fig. 7.8. (a), (b) and (c) Isothermal J-V characteristics of LSMO/Zn(Fe,Al)O heterostructures at several different temperatures under 0.7 T applied magnetic field with 5, 7 and 10% Fe concentrations, respectively. (b) Temperature dependent series resistance plot for LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O with 5% Fe and 1% Al under 0.7 T applied magnetic field. 139
Table 7.1. Evaluated fit parameters from the J-V characteristics employing Eq. (1) with and without applied 0.7 T magnetic field.
B (T) 0 T (K) n Rs k -cm2 300 250 200 150 100 77 0.7 300 250 200 150 100 77 3.1 4.1 4.0 22 10 106 3.0 4.1 5.1 22 16 125 0.13 0.2 0.28 0.34 1.88 1.97 0.12 0.25 0.33 0.34 1.70 1.71 J10-6 mA/cm
2
ZnO/LSMO 5% n Rs kcm2 6.9 8.2 4.0 17 10 29 6.9 4.1 4.0 20 10 29 0.14 0.15 0.33 0.42 2.14 2.97 0.12 0.35 0.41 0.42 2.06 2.7 J 10-6 mA/cm
2
Zn(Fe)O/LSMO 7% n Rs kcm2 7.2 4.1 4.0 17 10 44 7.2 4.1 4.0 17 10 44 0.18 0.28 0.3 0.46 2.32 2.88 0.16 0.33 0.41 0.45 2.23 2.57 J 10-6 mA/c m2 9.6 8.8 7.8 7.4 6.7 6.57 9.7 7.9 7.1 5.8 6.9 5.3 7.2 4.1 4.0 17 10 59 7.2 4.1 4.0 17 10 59 n 10% Rs kcm2 0.2 0.29 0.39 0.5 2.42 2.72 0.17 0.33 0.44 0.49 2.28 2.47 J 10-6 mA/cm
2
Zn(Fe,Al)O/LSMO 5% n Rs kcm2 0.76 0.18 15.5 21.4 48.3 7.4 1.1 127 14.9 21.4 35.6 22.4 0.03 0.04 0.03 0.04 0.03 0.11 0.02 0.07 0.04 0.04 0.04 0.17 J10-6 mA/cm
2
7% n Rs kcm2 0.76 0.18 15.5 21.4 48.3 7.46 0.76 0.18 15.5 21.4 48.3 7.46 0.03 0.04 0.04 0.04 0.04 0.12 0.03 0.06 0.04 0.04 0.03 1.02 J10-6 mA/c m2 6.8 1.7 3.3 7.8 6.5 6.1 6.2 3.6 8.2 7.08 6.08 5.9 0.76 0.18 15.5 21.4 48.3 7.46 0.76 0.18 15.5 21.4 48.3 7.46 n
10% Rs kcm2 0.03 0.05 0.04 0.05 0.04 0.12 0.03 0.06 0.05 0.04 0.03 0.09 J10-6 mA/cm
2
7.52 3.96 3.92 3.7 3.5 7.8 7.7 3.7 3.4 3.7 3.1 2.7
5.7
3.7
8 7 5.8
4.9
7.5 3.7 3.3 2.9 2.1 2 7.8 3.5 3.2 3 2.6 2.2
4.6 3.19 2.9 2.4 1.9 1.8 4.7 2.9 2.59 2.58 2.3 1.6
1.8 1.6 1.2 1.1 5.8 2.9 1.62 1.61 1.4 1.2
4.7 2.8 8.5 6.9 5.5 4.9 4.5 3
140
Figure 7.7(a) shows the temperature dependent J-V characteristics of LSMO/ZnO heterojunction under 0.7 T applied magnetic field. Figures 7.7(b), (c) and (d) are the temperature dependent J-V characteristics of LSMO/Zn(Fe)O heterojunctions with 5, 7, 10% iron doping, respectively under 0.7 T applied magnetic field. Figures 7.8(a), (b) and (c) are the junction J-V characteristics of LSMO/Zn(Fe,Al)O with 5, 7 and 10% Fe doping under 0.7 T applied magnetic field. The parameters in Eq. (7.1) are modified under magnetic field (J0, and Rs are now replaced by J0m, m and Rsm, respectively). The modified value of parameters evaluated employing modified Eq. (7.1) has also been enlisted in Table 7.1. The temperature dependent series resistance under 0.7 T magnetic field for the LSMO/ZnO, LSMO/Zn(Fe)O and Zn(Fe,Al)O junctions with 5% Fe has been shown in Fig. 7.8(d). The junction series resistance under magnetic field also decreases with increasing temperature. 7.3.3. Junction Magnetoresistance properties
2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 1
1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0
0.7T
Current(mA/cm2)
Current(mA/cm2)
Current(mA/cm2)
Current(mA/cm2)
77 K ZnO/LSMO
0T
I
2 3 4 Voltage(V) 5 6
18 16 14 12 10 8 6 4 2 1
16
ZnO/LSMO at 200K 0T 0.7T
25 20 15 10 5 0 0
ZnO/LSMO at 250K 0T 0.7T
35 30 25 20 15 10 5 0 0
ZnO/LSMO at 300K 0.7T 0T
I
2 3 4 5 6 Voltage(V)
I
1 2 3 Voltage(V) 4 5 6
I
1 2 3 4 5 Voltage(V)
35
ZnFeo/LSMO at 200K 0T
2
ZnFeO/LSMO
0.7T
14 Current(mA/cm )
0T
20 Current(mA/cm )
0.7T
ZnFeO/LSMO at 250K
0T 0.7T
30 Current (mA/cm2) 25 20 15 10 5 0 0
ZnFeO/LSMO at 300K 0.7T 0T
Current(mA/cm2)
12 10 8 6 4 2 0
15 10 5 0
II
1 2 3 4 5 6 Voltage(V)
II
1 2 3 4 Voltage(V) 5 6
II
0 1 2 3 4 5 6 Voltage(V)
II
1 2 3 4 Voltage(V) 5
30 ZnFeAl/LSMOat 77K
Current(mA/cm2) 60 50 40 30 20 10 0 0.0 0.5 1.0 1.5 2.0 ZnFeAl/LSMO at 200K 0T
70 60 Current(mA)
0.7T
ZnFeAlO/LSMO at 250K 0T
100 Current(mA/cm2) 80 60 40 20 0 0.0
ZnFeAlO/LSMO at 300K 0T 0.7T
0.7T Current(mA/cm2) 20 0T
50 40 30 20 10 0 0.0 0.5 1.0
10
0.7T
III
0 0 1 2 Voltage(V) 3
III
2.5 3.0 Voltage(V)
III
1.5 2.0 Voltage(V) 2.5 3.0
III
0.5 1.0 1.5 2.0 2.5 Voltage(V) 3.0
(c) (b) (d) Fig. 7.9. Comparative J-V characteristics of LSMO/ZnO (I), LSMO/Zn(Fe)O (II) and LSMO/Zn(Fe,Al)O (III) heterostructures with and without applied 0.7 T magnetic field. The Fe and Al concentration are 5% and 1%, respectively. (a), (b), (c) and (d) are the same J-V characteristics measured at 77, 200, 250 and 300 K, respectively.
(a)
141
The detailed comparative study of J-V with and without applied 0.7 T magnetic field measured at different temperatures (77, 200, 250 and 300 K) for LSMO/ZnO, LSMO/Zn(Fe)O and Zn(Fe,Al)O heterojunctions with 5% Fe doping have been shown in Fig. 7.9. Figure 7.9(a IIII) are the J-V characteristics at 77 K, Fig. 7.9(b I-III) are for 200 K, Fig. 7.9(c I-III) are for 250 K and Fig. 7.9(d I-III) for 300 K. It clearly demonstrates that all the heterojunctions show the negative junction MR at 77 and 300 K and positive junction MR at 200 and 250 K.
(b)
Fig. 7.10. Plot of junction magnetoresistance with applied magnetic field at (a) 77 K, (b) 200 K, (c) 250 K and (d) 300 K of the LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O heterojunctions with 5% Fe concentration at a bias voltage of 3 V. The change of junction MR with applied magnetic fields up to 0.7 T for LSMO/ZnO, LSMO/Zn(Fe)O, LSMO/Zn(Fe,Al)O heterojunctions with 5% Fe doping at a bias voltage of 3 V has been shown in Fig. 7.10 (a), (b), (c) and (d) for 77, 200, 250 and 300 K, respectively. The magnetic field dependent junction magnetoresistance (JMR) behavior in the magnetic field region up to 0.7 T of LSMO/ZnO, LSMO/Zn(Fe)O and Zn(Fe,Al)O junctions with 5% Fe have been analyzed using a simple empirical relation as [15],
142
JMR = H
(7.2)
where, and are coefficients. The junction magnetoresistance behaviors of other doped samples have also been investigated employing Eq. (7.2). The obtained best fit values of and for LSMO/ZnO, LSMO/Zn(Fe)O and Zn(Fe,Al)O junctions with 5% Fe are listed in Table 7.2. The exponent is found to be high (~1) at 200 K and it becomes ~0.5 at higher temperatures for all these heterojunctions. Table 7.2. Fit parameters ( and ) evaluated from Eq. (2) for undoped LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe)O with 5% Fe doping. Sample ZnO Temperature (K) 77 200 250 300 Zn(Fe)O 77 200 250 300 Zn(Fe,Al)O 77 200 250 300 -7.5 3.1 8.4 -4.5 -4.7 4.2 13.4 -4.1 -3.8 5.4 31.1 -0.72 0.27 0.82 0.53 0.5 0.39 0.83 0.53 0.51 0.39 0.83 0.45 0.51
The origin of junction magnetoresistances in those heterostructures can be best explained by the spin injection theory of magnetic p-n junction. Spin injection generally occurs in n-side while spin extraction generally occurs in p-side. Both spin injection and spin extraction becomes large with applied magnetic field. The current through the magnetic p-n junction depends on magnetic field because of the spin orbit splitting of magnetic materials [16]. The spin splitting of conduction bands are created by doping with magnetic ions in non-magnetic semiconductors. Doping with iron causes a large non equilibrium population of polarized electrons in ZnO conduction band. This non equilibrium population at magnetic n-side enhances the spin injection
143
through the space-charge region [17]. It causes a high magnetoresistance according to standard spin injection theory [18].
Fig. 7.11. Temperature dependent junction magnetoresistance plot for (a) LSMO/ZnO, (b) LSMO/Zn(Fe)O and (c) LSMO/Zn(Fe,Al)O heterojunctions with 5% Fe concentration at three bias voltages 2.5, 3.5 and 4.5 V. (d) Plot of highest value of the % of junction magnetoresistance (left y-axis scale) at 250 K as well as magnetic moment change in B/Fe2+ (right y-axis scale) with increasing iron concentration in both LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O heterojunctions. The temperature dependent junction MR for LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O with 5% Fe for three different bias voltages have been shown in Fig. 7.11 (a), (b) and (c), respectively. For three different applied bias voltages the junction magnetoresistance shows a peak near 250 K. The both spin injection and spin extraction are sensitive to spin lattice relaxation time which is very much dependent on temperature. The high value of spin lattice relaxation constant near 250 K [19], causes the enhancement of spin injection (and spin extraction) through the junction and causes a high positive junction magnetoresistance. At the higher temperatures the spin lattice relaxation constant drops sharply and spin injection effect die down through the junctions. The properties of magnetic electrodes dominates and shows little negative junction magnetoresistance. The change of junction MR 144
calculated at 250 K at 2.5 V applied bias voltage for different iron concentrations have been shown in Fig. 7.11(d). The change of magnetic moment (MS) in Bohr magneton per Fe2+of both Zn(Fe)O and Zn(Fe,Al)O films with doping percentage have also been shown in the Fig. 7.11(d) [the dashed lines]. Both the magnetic moment per Fe2+ and junction MR decreases with increase of Fe concentration. The drop of moment with increasing iron concentrations may be due to the increasing of antiferromagnetic coupling between Fe pairs which occurs at shorter separation distances and decrease the spin up population in DMS systems. The decrease of junction MR with increasing iron concentrations in both Zn(Fe)O and Zn(Fe,Al)O system is most likely due to the decrease of spin up population caused by higher doping. 7.4. Summary LSMO/ZnO, LSMO/Zn(Fe)O and LSMO/Zn(Fe,Al)O heterojunctions with 5, 7 and 10% Fe have been fabricated using pulsed laser deposition technique. The junction J-V properties have been studied with and without applying magnetic field. The junction with ZnO and Zn(Fe)O shows good rectifying behavior at all temperatures but heterojunctions with Zn(Fe,Al)O shows a quick break down at reverse bias. Higher carrier concentration in Zn(Fe,Al)O most likely causes thin depletion region and hence causes high current transport through the junction. All the heterojunctions show high positive junction magnetoresistance at a certain temperature range (150 to 280 K) and low negative magnetoresistance at 77 K and 300 K. The junction magnetoresistance enhances due to incorporation of 1% Al. This has been best explained using spin injection theory through magnetic p-n junction. Increase of Fe doping concentration decreases the junction magnetoresistance as well as magnetic moment per Fe2+ for both Zn(Fe)O and Zn(Fe,Al)O systems. This is mainly due to the decrease of population of polarized electron in conduction band. The properties of junction magnetoresistance of such heterostructures can be extremely useful in the area of spintronic devices. References [1] C. Mitra, P. Raychaudhuri, K. Dorr, K. H. Muller, L. Schultz, P.M. Oppeneer, and S.Wirth, Observation of Minority Spin Character of the New Electron Doped Manganite La0.7Ce0.3MnO3 from Tunneling Magnetoresistance, Phys. Rev. Lett. 90, 017202 (2003). [2] C. Mitra, G. Kbernik, K. Drr, K. H. Mller, L. Schultz, P. Raychaudhuri, R. Pinto, and E. Wieser, Magnetotransport properties of a room temperature rectifying tunnel junction made of electron and hole doped manganites, J. Appl. Phys. 91, 7715 (2002). 145
[3] C. Mitra, P. Raychaudhuri, G. Kbernik, K. Drr, K.-H. Mller, L. Schultz and R. Pinto, p-n diode with hole- and electron-doped lanthanum manganites, Appl. Phys. Lett. 79, 2408 (2001). [4] H. Tanaka, J. Zhang, and T. Kawai, Giant Electric Field Modulation of Double Exchange Ferromagnetism at Room Temperature in the Perovskite Manganite/Titanate p-n Junction, Phys. Rev. Lett. 88, 027204 (2002). [5] A. Tiwari, C. Jin, D. Kumar, and J. Narayan, Rectifying electrical characteristics of La0.7Sr0.3MnO3/ZnO heterostructure, Appl. Phys. Lett. 83, 1773 (2003). [6] B. B. Nelson-Cheeseman, F. J. Wong, R. V. Chopdekar , E. Arenholz, and Y. Suzuki, Room temperature magnetic barrier layers in magnetic tunnel junctions, Phys. Rev. B 81,214421 (2010). [7] G. Li , De-bin Huang, Shao-wei Jin , Yong-qing Ma, Xiao-guang Li, Electrical transport properties of heteroepitaxial p_n junction of charge-ordered La7/16Ca9/16MnO3 and 0.5 wt% Nb doped SrTiO3, Solid State Comm. 150, 1737 (2010). [8] H. B. Lu, S. Y. Dai, Z. H. Chen, Y. L. Zhou, B. L. Cheng, K. J. Jin, L. F. Liu, G. Z. Yang and X. L. Ma, High sensitivity of positive magnetoresistance in low magnetic field in perovskites oxide pn junctions, Appl. Phys. Lett. 86, 032502 (2005). [9] K. Zhao, Y. Huang, Q. Zhou, K. J. Jin, H. Lu, M. He, B. Cheng, Y. Zhou, Z. Chen and G. Yang, Ultraviolet photovoltage characteristics of SrTiO3/Si heterojunction, Appl. Phys. Lett. 86, 221917 (2005). [10] C. Mitra, P. Raychaudhuri, K. Drr, K. H. Mller, L. Schultz, P. M. Oppeneer and S. Wirth, Observation of Minority Spin Character of the New Electron Doped Manganite La0.7Ce0.3MnO3 from Tunneling Magnetoresistance, Phys. Rev. Lett. 90, 1107202 (2003). [11] C. Mitra, P. Raychaudhuri, G. Kbernik, K. Drr, K.-H. Mller, L. Schultz and R. Pinto, p n diode with hole- and electron-doped lanthanum manganites, Appl. Phys. Lett. 79, 2408 (2001) [12] S. Chattopadhyay, T.K. Nath, A.J. Behan, J.R. Neal, D. Score, Q. Feng, A.M. Fox, G.A. Gehring, Temperature dependent carrier induced ferromagnetism in Zn(Fe)O and Zn(FeAl)O thin films, Appl. Surf. Sc. 257, 381 (2010). [13] L. Yan, W. C. Goh, and C. K. Ong, Magnetic and electrical properties of La0.7Sr0.3MnO3 Zn0.8Co0.2Al0.01O junctions on silicon substrates, J. Appl. Phys. 97, 103903 (2005). [14] S. J. May and B. W. Wessels, High field magnetoresistance in p-(In,Mn)As/n-InAs heterojunctions, Appl. Phys. Lett. 88, 072105 (2006). [15] Z. G. Sheng, W. H. Song, Y. P. Sun, J. R. Sun, and B. G. Shen, Crossover from negative to positive magnetoresistance in La0.7Ce0.3MnO3-SrTiO3-Nb heterojunctions, Appl. Phys. Lett. 87, 032501 (2005). [16] J. Fabian, I. uti and S. Das Sarma , Theory of spin-polarized bipolar transport in magnetic p-n junctions, Phys. Rev. B 66, 165301 (2002). [17] Mark Johnson, Magnetoelectronics, academic press, Elsevier (2005). [18] S. Chattopadhyay and T. K. Nath, Room temperature enhanced positive magnetoresistance in Pt and carrier induced Zn(Fe)O and Zn(Fe,Al)O dilute magnetic semiconductors junction, J. Appl. Phys. 108, 083904 (2010). [19] A. I. Lobad, R. D. Averitt, C. Kwon, and A. J. Taylor, Spinlattice interaction in colossal magnetoresistance manganites, Appl. Phys. Lett. 77, 4025 (2000).
146
Chapter 8
Conclusions
Conclusions Chapter8
8.1. Conclusions of thesis The temperature dependent spin injection or extraction phenomena in magnetic semiconductors and semimetals have been widely studied in this thesis for possible active spintronics device applications. The Zn(Fe)O and Zn(Fe,Al)O thin films have been selected as a room temperature Dilute Magnetic Semiconductor (DMS). It shows n-type semiconducting behavior with wide band gap. La0.7Sr0.3MnO3 has been chosen as a hole doped half-metallic manganites as a p-type ferromagnetic electrode. The Zn(Fe)O and Zn(Fe,Al)O highly crystalline epitaxial thin films show room temperature ferromagnetic ordering with carrier mediated ferromagnetism. Doping with 1 % Al in ZnFeO film, the magnetic moment per Fe2+ ion is found to enhance by 3 times as compared to the ZnFeO film without Al doping. The magnetic moments die down due to higher doping of Fe in ZnO. The -T behavior shows that the films are semiconducting in nature and the electronic transport mechanisms in these films have been identified as Variable Range Hopping in lower temperature range, Efross Variable Range Hopping in the intermediate temperature range and thermally activated transport in higher temperature range. Analyzing Ordinary Hall Effect data, it is found that the dominant donor has an activation energy ranging from 33 to 41 meV and several type of scattering mechanisms are present. Anomalous or Extra-ordinary Hall Effect results show intrinsic ferromagnetic behavior in these DMS films and both skew scattering and side jump mechanisms are responsible for the origin of Anomalous Hall voltage in these DMS films. The spin injection from Zn(Fe)O and Zn(Fe,Al)O Dilute Magnetic Semiconductor to non-magnetic Pt has been demonstrated explicitly. The spin injection in Pt/Zn(Fe)O and Pt/Zn(Fe,Al)O shows positive JMR at room temperature and the JMR strictly depends on the magnetic moment of the films. La0.7Sr0.3MnO3 also shows good ferromagnetic behavior at all temperatures up to room temperature. The -T behavior of LSMO shows resistivity minima at ~50 K and a metal-insulator transition peak at ~250 K. The low temperature minima and the rising of resistivity with the decrease of temperature below 50 K can be best explained through electron-electron interaction as predicted by quantum interference effect (QIE). Electron tunneling phenomena through different SiO2 layer in La0.7Sr0.3MnO3/SiO2/p-Si has also been demonstrated, and, the temperature and oxide defect dependency in positive JMR is presented. The observed JMR behavior has been explained using tunneling model 147
Chapter8 Conclusions
where the Frenkel-Poole type tunneling mechanism dominates. The temperature dependent spin injection and spin extraction in La0.7Sr0.3MnO3/ZnO, La0.7Sr0.3MnO3/Zn(Fe)O and La0.7Sr0.3MnO3/Zn(Fe,Al)O heterostructures have also been investigated and it shows that the highest spin injection (i.e. maximum JMR) appears at a temperature ~ 250 K which is the temperature where La0.7Sr0.3MnO3 shows highest spin relaxation. The junction magnetoresistive properties of these heterostructures have been best explained using the standard spin injection mechanism through the magnetic p-n junction. Junction magnetoresistance dies out with the increase of doping concentrations of Fe in ZnFeO or Zn(Fe,Al)O films for all the three type of heterojunctions due to the less non equilibrium population of polarized electrons. The positive JMR for these cases also drastically enhances with enhancing the magnetic moments of Zn(Fe)O films with incorporating Al. 8.2. Scope of future work To propose the scope of future work based upon our present dissertation work, first we would like to consider the study on dilute magnetic semiconductors using other II-VI and III-V semiconductors. We would like to study the DMS materials using the magneto-optical methods and would like to search the origin of ferromagnetism in these dilute magnetic semiconductors. We would also like to fabricate different kind of homo, hetero and Schottky junctions using different magnetic metals, semiconductors and half-metals to study the spin injection properties through them as they have potentials in active spintronic device applications. 8.3. Contribution of thesis The temperature dependent spin injection or extraction phenomena involving the magnetic semiconductors, semimetals, other non-magnetic semiconductor or metals have been widely investigated for possible active spintronics device applications. As the semiconductor spintronic devices are still questionable in the area of both basic science and technology, this thesis can lead to various possible ideas to design different spintronics heterojunctions for industrial applications.
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THIN FILM OXIDES AND HETEROSTRUCTURES FOR SPINTRONICS

THIN FILM OXIDES AND HETEROSTRUCTURES FOR SPINTRONICS

APPROVAL OF THE VIVA-VOCE BOARD

(Member of the DSC)

(Member of the DSC)

(Member of the DSC)

Signature of the Student

A* A B D Ec Eg Ev H Ihkl Iohkl j j J J0 k m* M MRint MRspt n

n NA nc ND ni P PjF(0) q RFM RFM R0 RAP

rc rF rFN rN RP Rs RS S T* T TM TP V V0 vd 0 s D F(0) n(0) B dia para

SCLC SQUID TC 2DEG TM TMR UV-Vis VRH VTI XAS ZFC

93 94 94 94 96 96 96 99 100 101 101 102 105 107 108 109

111 112 114 114

114 114 118 120 121 124 125 129 130

, which is called the magnetoresistance ratio (or MR

(1.1) ; = 1 and 2. (1.2)

Here P is the spin polarization of a ferromagnetic electrode, and D ( E F ) and

energy for the majority-spin and minority-spin bands.

Resistance of MTJ (R)

AF layer Seed layer

FM electrode (pinned layer)

MR ratio = (RAP -RP) /

S= (x2-y2, 3z2-r2) Conduction Electron spin

Cubic crystal field splitting EJT

Jahn Teller distortion

Mn3+ tij Mn4+ ij

Overlapping BMPs Antiferromagnetic pair

while the spin density is, s = n n

is the spin current density and is the electron spin

assumed to be in equilibrium, i.e. sF () = 0 . The emf is sN () sF () . One of our 20

The above equation gives, sN (0) =

This allows writing the spin current at the contact as,

by direct electrical spin injection from a metallic ferromagnet into a 21

Fig. 2.1. The experimental set-up of PLD chamber

1 (2 1.540 + 1.554) = 1.541 3

and accuracy of 2 value is 0.03o.

Consequently, for R = V/2I, the resistivity for a thin sheet is,

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

Actual Fe concentration 2.85% 3.28% 6.12% 6.24% 8.56% 8.51%

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

10 K 50 K 100 K 150 K 200 K 250 K 300 K 350 K 400 K

Band gap (eV)

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

-0.05 -0.10 -0.15 -10000 -5000

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

6 Moment (x10 emu) 4 2 0 -2 -4 -6 5K 50 K 100 K 300 K

Ferromagnetic moment -4 (x 10 emu)

1.0 0.5 0.0 -0.5 -1.0

Magnetic field (x 10 Oe)

-2000 -1000 0 1000 Magnetic field (Oe)

600 400 200 0

-40000-20000 0 20000 40000 Magnetic field (Oe)

-1.5 -60000 -40000 -20000

100 150 200 250 300

dia + para = dia + para

para depends on temperature with simple Curie law,

T dia + para = C + T dia

2J + 1 2J + 1 1 1 x) x and coth( coth 2J 2J 2J 2J

Propertiesofroomtemperatureferromagnetic Chapter3 Zn(Fe)OandZn(Fe,Al)Oepitaxialthinfilm

Paramagnetic -5 moment (x10 emu)

Moment (x10-4 emu)