Bulk and Thin Films of ZnCoO by PLD

S. Karamat, R.S. Rawat and Paul Lee

NIE/NTU
 Introduction
• Dilute Magnetic Semiconductors (DMSs)
The semiconductors in which the lattice is made up in part of substitution magnetic
ions.
Applications
Spintronics: Spin LEDs, Spin Transistors, Spin Valves, Magnetic recorders ----------
Challenge
Synthesis of a material exhibiting both semiconducting as well as magnetic
properties, a prerequiste for spin- electronic devices. The incompatibility between
non-magnetic semiconductors and magnetic materials is a big hinderance to combine
them in the form of one material having both properties.
One of the approaches to combine the spin and charge of the carriers in a material
having both semiconducting as well as magnetic properties is to introduce magnetic
ions like Mn, Cr, Co and Fe into non-magnetic semiconductors.
Synthesis Methods
Solid state reaction, Ball-milling, Sol-gel, RF magnetron sputtering, Chemical vapor
deposition (CVD), Metalorganic chemical vapor deposition (MOCVD), Molecular beam
epitaxy (MBE), Pulsed laser deposition (PLD), etc.
 Motivation
Dietl. predicted on a theoretical basis that ZnO
and GaN would exhibit ferromagnetism above
room temperature on doping with Mn.
According to the theory, ferromagnetism
between magnetic dopant ions is mediated by
holes in the valence band through indirect
exchange. Dietl's theory has proven useful in
understanding the experimental results for
GaMnAs but it appears to be inconsistent for
the experimental results of transition metal
doped wide bandgap semiconductors, such as
ZnO and GaN. It is based on many reasons,
including the difficulty in experimentally
preparing p-type ZnO material and the
observations of ferromagnetism in n-type ZnO
DMS.

T. Dietl, H. Ohno, F. Matsukura, J. Cibert and D. Ferrand, Science, 287 1019 (2000)
 Coey’s Model
Acoording to coey, donor defects which could arise from oxygen vacancies or zinc interstitials
in the case of ZnO, overlapped and form an impurity band. This impurity band can interact
with local magnetic moments through the formation of bound magnetic polarons (BMP).
Within each BMP, the bound carrier interacts with the magnetic dopants inside its radius and
can align the spins of the magnetic dopants parallel to one another. Ferromagnetism is
achieved when the BMPs start to overlap to form a continuous chain throughout the material,
thus percolating ferromagnetism in the DMS.

 Kittilstved confirmation
Kittilstved spectroscopic experiment of cobalt-doped ZnO showed that the singly ionized
Co + state lies close to the conduction band having almost the same energy as in a shallow
donor state. It showed if the energies are similar, charge transfer can take place between the
cobalt atoms and the donor impurities which lead towards the hybridization necessary for
ferromagnetism. It showed an inherent polarity difference for ferromagnetism in cobalt doped
ZnO.

 Ueda Experiments
Ueda showed promising results and it was found that the ZnCoO become FM above 280 K
with 5–25% Co doping.
 Experimental Setup

Pulsed Laser
Deposition
System

Nd:YAG
Laser
 Characterization Techniques

 SIEMENS D5000 X-ray Diffractometer

 Kratos Axis Ultra X-ray Photoelectron Spectroscopy

(XPS) system

 Cary 50 UV-VIS Spectrophotometer

 SHIMADZU UV-VIS 2501 Spectrophotometer

 Lakeshore 7400 Vibrating Sample Magnetometer

 Results for Bulk Samples

 XRD Results of bulk samples

 Quantitative analysis

 Rietveld Method

Material a c Volume

Å Å Å3

(ZnO)0.99(Co3O4)0.01 3.2510 5.2019 47.61526

(ZnO)0.98(Co3O4)0.02 3.2513 5.2015 47.62114

(ZnO)0.97(Co3O4)0.03 3.2517 5.2014 47.63133

(ZnO)0.95(Co3O4)0.05 3.2517 5.2014 47.63133

XPS Survey Scans for Bulk Samples
 Zn 2p and Co 2p core peaks

The Co 2p doublet, Co 2p3/2 and Co 2p1/2 is observed at 779.9 and 795.8 eV, respectively. The Co
2p core peaks showed only the presence of Co+2 valance ions with their shaking satellites. The
energy splitting between the doublets is almost around 15.9 eV which indicates that the Co2+ ion is
in high spin state. The information about spin state helps us to know the coordination of Co+2 ions
with other ions. High spin state of Co+2 ions has the probability to acquire tetrahedral coordination
as well as octahedral coordination.
Band gap measurements in bulk sample

The optical band gap

measurements has been done
using the Kubelka–Munk
function F(R) = (1 − R)2/2R
where R is the diffuse
reflectance of the pellets. To
measure the band gap we
plotted data.

1/ n =
( F ( R)) h
M-H curves for (ZnO)1-x(Co3O4)x≤0.05 bulk samples

Hysteretic behavior observed in VSM signals of samples showed mixing of

paramagnetic (indicated by non-saturation of magnetization) and ferromagnetic
(indicated by finited coercivity) behavior. The magnified spectra reveal the weak
ferromagnetic nature (finite coercivity) of samples.
 A weak ferromagnetic behaviour indicates that the presence of cobalt
ions in the ZnO lattice is not enough to overcome paramagnetic signal
of ZnO which is essentially due to low doping concentration of Co
used in the present experiment. However, if we increase the Co
doping concentration to increase the Co+2 ion substitution in ZnO
lattice to increase the ferromagnetic component we might end up
having Co clusters and spinel phases which will also contribute to
ferromagnetic component and then it that case the origin of
ferromagnetism in samples cannot be singly attributed to ZnCoO
phase.
 In the present study less doping % of Co was preferred to avoid Co
clusters and spinel phase formation and their contribution to
ferromagnetic component. Our XRD and XPS results also confirm the
formation of homogeneous ZnCoO phase and hence the observation
of ferromagnetism, though albeit on the weaker side, is only due to
Co+2 ion substitution in ZnO lattice in ZnCoO phase.
 Results for Thin films
XRD for films XRD for films
grown in Vacuum grown in Ar-O2

The θ–2θ XRD patterns for a series of films grown at 350 °C in vacuum (base pressure
~ 7×10–5 mbar) using pellets with varying cobalt doping concentration. The peaks
correspond to the wurtzite ZnO (002) indicating good texture with the c-plane of the
sapphire substrate.
 Particle Size in thin films

Scherer’s equation
t=0.9λ/β cos θ

where λ is the X-ray

wavelength, β is the full-
width at half-maximum of
the (002) diffraction line,
and θ is the diffraction angle
of the XRD spectra.
XPS core peak spectrum for Zn, Co and O elements

XPS survey scans were done for all Co doped

ZnO thin film samples which show the presence
of zinc, cobalt and oxygen clearly.
Zn 2p core peaks showed quiet symmetrical
behaviour in BE for different samples. Here
shows for Zn 2p spectrum only for
(ZnO)0.98(Co3O4)0.02 thin film sample. Zn 2p3/2
and Zn 2p1/2 core peaks have BE peaks at
1021.08 and 1044.1 eV, respectively which is in
agreement with the previous reports.

The O1s core peak exhibits a slight

asymmetrical behaviour. This profile can be fit
by two symmetrical peaks, having binding
energy at 530.0 and 531.2 eV.
Co 2p doublet was observed for all
samples. The Co 2p3/2 peak occurs at
780.6, 780.4, 780.1 and 780.1 eV,
while the Co 2p1/2 peak is located at
796.2 , 796.1, 796.0 and 796.0eV for
1,2,3 and 5% Co doped ZnO thin film
samples respectively, showing
chemical shifts compared to that of
pure Co metal.
The difference between Co 2p1/2 and
Co 2p3/2 is 15.5 eV which indicate that
Co ions have a valance of 2+ in a
rather high probability.
Satellite peaks appeared at about
786.0 and 802.4 eV for Co 2p3/2 and
Co 2p1/2, respectively, for almost all
samples. The very intense satellite
structure results from the charge-
transfer band structure characteristic
of the late 3d transition metal
monoxides.
The differences between the main
peaks and the corresponding
satellites further prove that Co ions
are surrounded by oxygen atoms and
have a chemical valence of 2+.
 M-H curves for (ZnO)1-x(Co3O4)x≤0.05 thin films
deposited in vacuum

Magnetization measurements display a distinct ferromagnetic behaviour. It is useful to mention here that the
magnetic background of the substrate has been subtracted from all of the magnetization data. All the loops show
the features of ferromagnetism at room temperature (∼300 K). The ferromagnetic ordering is indeed intrinsic to
Co:ZnO films based on the substitutional behaviour of Co in the wurtzite lattice of ZnO, and the donor defects as
well as the electrons are important to the enhancement of FM. Magnetization data taken at 300 K for a series of
films grown under vacuum with different amounts of cobalt show smaller magnetization due to very small doping
percentage.
Deposition of thin film on Si substrate
 Reasons
 PLD plasma consists of two fraction of species: high energetic
ions of up to several 100 eV energy and lower energetic atoms
and ions (10–50 eV).

penetration in the
(growing film)
surface

activation of
surface reactions High activation of
with e.g.
physiosorbed Energetic surface mobility
(reactive gas) Plasma (diffusion)
atoms or molecules

re-sputtering of
both impinging and
loosely bonded
species from the
surface.
 The total energy in any film deposited on a substrate is the sum of
three components: surface energy of the film, the film–substrate
interface energy, and the strain energy in the film. Films grow in
such a way that the total energy is minimized.

 However, surface, interface, and strain energy minimization do not

necessarily favour the same orientation. Therefore, one could
expect different textures depending on whether surface, interface,
or strain energy minimization is the dominant factor.

 ZnO has tetragonal coordination formed by the sp3 hybridized orbit.

As it has a wurtzite hexagonal structure, the direction of each apex
is parallel to the c-axis. According to the calculation of Fujimara et
al, the (002) lattice plane has the lowest density of surface energy.
Therefore, surface energy minimization favours (002) texture in ZnO
films. Thus, in most cases, films grow with the (002) plane parallel
to the surface of the substrate, thus, minimizing the surface free
energy of the film. In the case of polycrystalline films grown on
single crystalline substrates, interface energy minimization can lead
to the dominance of epitaxial orientations.
Deposition of thin films at different temperatures
M-H curves for Zn0.97Co0.03O thin films
 Conclusions

 Co doped ZnO films showed only the (002) peak in the XRD patterns,
indicating that all of them had preferential orientation along the (002)
reflection plane of ZnO.
 The films grown in vacuum are highly crystalline as compare to films grown in
Ar-O2 environment.
 The crystallite size of the films grown in vacuum showed a consistent
increase with the increase in doping % of cobalt while the particle size of films
grown in Ar-O2 showed inconsistency.
 M-H curves showed the ferromagnetic behaviour for the films grown in
vacuum and for the films grown in Ar-O2, M-H curves are not very developed.
 Compositional analysis of thin films done by XPS showed the presence of
Co+2 ions which is the source of ferromagnetism in our thin film samples.
Thank You