Journal of Crystal Growth 192 (1998) 423429

Liquid injection metal organic chemical vapour deposition of nickel zinc ferrite thin lms
P.A. Lane *, P.J. Wright , M.J. Crosbie , A.D. Pitt , C.L. Reeves , B. Cockayne , A.C. Jones , T.J. Leedham
DRA Malvern, St. Andrews Road, Malvern, Worcestershire WR14 3PS, UK School of Metallurgy and Materials, University of Birmingham, P.O. Box 363, Birmingham B15 2TT, UK Inorgtech, 25 James Carter Road, Mildenhall, Suolk, UK Received 14 March 1998; accepted 6 May 1998

Abstract Liquid injection metal organic chemical vapour deposition has been used to grow thin lms of the single metal oxides of nickel, zinc and iron, the binary ferrites of nickel ferrite and zinc ferrite and the ternary nickel zinc ferrite. The precursor chemicals used for the deposition of the metal oxide layers were solutions of the metal thd compounds (thd"2,2,6,6tetramethyl-3,5-heptanedionato) dissolved in tetrahydrofuran. The growth rates of the single metal oxide layers have been systematically determined as a function of substrate temperature in the temperature range 300650C and the ferrite layers were deposited at a substrate temperature of 500C. The ferrite layers were polycrystalline with well-dened spinel crystal structures. Crown Copyright 1998 Published by Elsevier Science B.V. All rights reserved.

1. Introduction The aim of this study is the deposition of the thin lm ferrite materials nickel ferrite, zinc ferrite and the ternary nickel zinc ferrite. Polycrystalline ferrite thin lms exhibit properties such as large resistivities and permeabilities which make them attractive for use in high-frequency microwave devices [1]. The growth of thin ferrite lms oers the potential for integration of microwave devices in place of bulk ferrite components.

* Corresponding author. 0022-0248/98/$19.00 Crown Copyright PII: S 0 0 2 2 - 0 2 4 8 ( 9 8 ) 0 0 4 7 7 - 1

The production of ferrite thin lms has been reported by several deposition techniques which include sputtering [2], ferrite plating [3], laser ablation [4,5] and chemical vapour deposition [6]. In the present work, the technique of chemical vapour deposition has been chosen because it is well suited to growth onto large areas, has good conformal coverage on complex structures and has the versatility to deposit metals, oxides and semiconductors. The technique of chemical vapour deposition requires the transport of suitable precursor chemicals in the gaseous phase into the growth reactor. Thermal decomposition of the precursor takes place to deposit the required material in thin lm form onto the heated substrate. The precursors available for

1998 Published by Elsevier Science B.V. All rights reserved.

424

P.A. Lane et al. / Journal of Crystal Growth 192 (1998) 423429

the deposition of oxide materials, however, are in general solids with vapour pressures too low to achieve viable precursor transport rates using conventional bubbler technology. To overcome these problems, the technique of liquid injection metal organic chemical vapour deposition (MOCVD) [7,8] has been used in which the precursors are dissolved in suitable solvents and the liquid is injected directly into a hot vaporiser before entering the growth reactor. This technique has the advantage that the precursors are maintained at room temperature and the precursor inputs are dependent only on the injection rates of the liquids and the concentration of the solution. The precursors used in this study are solutions of Ni(thd) , Zn(thd) and Fe(thd) , (thd"2,2,6,6-tet   ramethyl-3,5-heptanedionato) dissolved in tetrahydrofuran (THF). The THF acts as a solvent and also eectively reduces the intermolecular association through potential coordination with the metal atom. The use of a common ligand for all the precursors is benecial in overcoming potential problems with ligand exchange, either in the liquid or gaseous phases; both of which would lead to irreproducible growth results.

operating conditions in the evaporator. The TGA was performed in Polymer Laboratories STA 1500 instrument with 10 mg samples of the metal thd precursors being contained in an open alumina crucible. The temperature was increased from room temperature to 300C at a rate of 10C/min in an atmosphere of nitrogen owing at 20 ml/min. The TGA results are summarised in Fig. 1. The precursors evaporate predominantly over the temperature range 190260C with 50% weight loss occurring at ca. 220C for Zn(thd) and 240C for  the Fe(thd) and Ni(thd) precursors under the ex  perimental conditions of the TGA experiment. In addition to the major weight loss between 190 and 260C, the TGA results for the Ni(thd) also re vealed two smaller weight losses in the temperature ranges (i) 3073C and (ii) 148174C. These additional reactions for the Ni(thd) are attributed to  the evaporation of hexane at 3073C and free thd at 148174C. Both the Fe(thd) and Ni(thd) pre  cursors evaporated cleanly leaving less than 1% residue. However, approximately 8% residue remained after the evaporation of Zn(thd) , which on  holding at 300C exhibited a small weight loss. The

2. Experimental procedure 2.1. Manufacture and characterisation of precursors The Ni(thd) , Zn(thd) and Fe(thd) precursors    were manufactured by Inorgtech Limited, from the anhydrous acetates or chlorides by salt elimination. The synthesis routes all employed rigorously anhydrous hydrocarbon or alcohol solvents in order to exclude trace water which would otherwise coordinate with, or become entrained in the precursors, leading to instability of the resulting precursor solution. Analysis for trace metal impurities using inductively coupled mass spectrometry (ICP-MS) indicated that all precursors had a purity of at least 99.99%. The vapour-phase transport characteristics of the Ni, Zn and Fe precursors were investigated by thermogravimetric analysis (TGA) in order to assess the evaporating characteristics of the precursors and to provide a guide to the optimum

Fig. 1. Thermogravimetric analysis of the metal oxide precursors Ni(thd) , Zn(thd) and Fe(thd) .   

P.A. Lane et al. / Journal of Crystal Growth 192 (1998) 423429

425

residue was most likely to be predominantly zinc oxide. Using the TGA results as a guide to the optimum evaporating conditions for use of the thd precursors in MOCVD, the growth conditions employed were an evaporator temperature of 200C with a ow of 4 slm of high-purity argon gas. Under these growth conditions, however, there was no formation of a residue from the Zn(thd) pre cursor. 2.2. Growth and characterisation of metal oxide layers The liquid injection MOCVD apparatus is shown schematically in Fig. 2. The solutions of the metal (thd) precursors in THF are contained in a high-integrity syringe which meters the precursors into the vapourisation chamber. Standard experimental conditions of 4 slm of high-purity argon carrier gas and 800 sccm of oxygen were maintained throughout all growth experiments, and the vapouriser and inlet line temperatures were set at 200C. All oxide layers were grown on (1 0 0) silicon substrates, and for each metal oxide, a constant precursor injection rate was maintained and the substrate temperature was varied systematically. The thickness of the deposited layers was calculated by measuring the mass of material deposited ($2 g). X-ray diraction was used to assess the phase and orientation of the layers and the

ratios of the metal components were measured by energy dispersive X-ray (EDX) analysis.

3. Results 3.1. Growth rate characterisation of metal oxide layers as a function of substate temperature To assess the growth characteristics of the individual precursors the growth rates of the metal oxide layers of nickel, zinc and iron as a function of substrate temperature were measured and are plotted in Fig. 3. The onset of metal oxide deposition occurred at substrate temperatures above 350C for both the iron and zinc precursors, but a higher temperature of 400C was required for the deposition of nickel oxide. In addition, the general shape of the growth rate curves of the three oxides also diered. The nickel oxide data showed a systematic increase in growth rate with increasing substrate temperature from 400 to 475C, but no signicant change in growth rate from 475 to 550C, suggesting that the nickel oxide deposition is kinetically controlled by the thermal decomposition of the Ni(thd) up to 475C and in the range 475550C  the growth rate is mass transport controlled. The zinc oxide growth rate increased systematically with increasing substrate temperature to a maximum growth rate at 550C. Above 550C however, the growth rate decreased and this is

Fig. 2. Schematic diagram of the liquid injection MOCVD apparatus used for metal oxide deposition.

426

P.A. Lane et al. / Journal of Crystal Growth 192 (1998) 423429

Fig. 3. The growth rate of nickel oxide, zinc oxide and iron oxide by MOCVD from the metal (thd) precursors.

attributed mainly to the desorption of zinc oxide due to its high vapour pressure. The iron oxide growth increased systematically from 350 to 425C however, a decrease in growth rate is observed at higher temperatures; this has been attributed to the increased reactor wall deposition observed in the iron oxide growth experiments at the higher temperatures. Unlike zinc oxide, the iron oxide has a much lower vapour pressure and desorption of iron oxide from the growth surface at the higher substrate temperatures is not expected to be a signicant factor. There was no signicant evidence for homogeneous nucleation in the gas phase for any of the metal oxides investigated, which is consistent with the relatively low gas-phase concentration of the precursors in the growth reactor. The present growth rates of the single metal oxides are low for the process to be viable on a commercial basis, however, there is scope for increasing the growth rate by up to an order of magnitude by increasing both the concentrations of the solutions and the precursor injection rates. 3.2. Deposition of nickel ferrite, zinc ferrite and nickel zinc ferrite The growth environment for deposition of alloys is more complex than for the deposition of single

metal oxides, both in terms of the gas-phase reactions and the growth interface chemistry. However, using the growth characterisation results of the single metal oxides presented in Fig. 3 as a general guide, a growth temperature of 500C was chosen for the deposition of the ferrite thin lms. This temperature is in a range in which all the precursors individually have usable and similar growth rates, and from an applications viewpoint 500C is compatible with deposition directly onto pre-existing circuitry. A series of layers was grown in which the ratio of the Ni(thd) : Fe(thd) : Zn(thd) in THF    solution was systematically varied and the resulting compositions of the lms were determined by EDX. The results of this study are presented in Fig. 4 and show data for binary and ternary ferrite lms. Results for deposition of nickel ferrite showed that the mole fraction of the nickel/iron thd precursor was approximately equal to the mole fraction of nickel/iron in the deposited layer. Ferrite layers containing zinc, however, showed that the mole fraction of zinc incorporated in the layer was greater than the mole fraction of zinc in the precursor solution.

Fig. 4. Mole fraction of metal in precursor as a function of mole fraction of metal ion in deposited layer.

P.A. Lane et al. / Journal of Crystal Growth 192 (1998) 423429

427

3.3. Characterisation of the metal oxide thin lms X-ray diraction was performed on the nickel, zinc and iron oxide layers to determine the phase and orientation of the layers. The experimental results, together with the data from the JCPDS for comparison, are plotted in Fig. 5. The nickel oxide results (Fig. 5a) were a good match to the NiO rhombohedral structure with no strongly preferred orientation. The ZnO layers had the hexagonal wurtzite crystal structure. At a growth temperature of 450C, a strong (0 0 2) preferred orientation was observed (Fig. 5b), but increasing the growth temperature to 550C, resulted in a less well-oriented layer (Fig. 5c). The iron oxide deposited was identied as Fe O (hematite) rhombodedral structure   with no strongly preferred orientation (Fig. 5d). X-ray diraction results of nickel ferrite, zinc ferrite and nickel zinc ferrite grown at 500C are plotted in Fig. 6, together with the data from the JCPDS, and

conrm that the layers are spinel in structure and do not have a strongly preferred orientation. The morphology of the metal oxide lms was examined by scanning electron microscopy. All the metal oxide layers, with the exception of ZnO, had a regular equiaxed morphology with grain sizes of approximately 0.1 m. However, the morphology of the ZnO layers varied considerably with deposition temperature. Deposition at 450C resulted in an unusual morphology (Fig. 7a), with relatively few nuclei growing anisotropically. This suggests that the initial steps of precursor decomposition and nucleation onto the substrate were rate limiting, but once nuclei had formed, they provided an autocatalytic role, and growth onto the pre-existing nuclei proceeded readily. Signicant areas of the substrate had no deposition of zinc oxide. Examination of the morphology of the zinc oxide layer grown at 500C (Fig. 7b) showed a greater substrate coverage than the deposition at 450C, but

Fig. 5. X-ray diraction traces of (a) nickel oxide, (b) zinc oxide grown at 450C, (c) zinc oxide grown at 550C and (d) iron oxide. Experimental results are shown as hatched bars and the JCPDS as solid lines.

428

P.A. Lane et al. / Journal of Crystal Growth 192 (1998) 423429

Fig. 6. X-ray diraction traces of (a) nickel ferrite, (b) zinc ferrite and (c) nickel zinc ferrite. Experimental results are shown as hatched bars and the JCPDS as solid lines.

the grains also had an anisotropic morphology. However, a higher growth temperature of 550C (Fig. 7c), resulted in a more equiaxed morphology and good coverage of the substrate. The X-ray diffraction results of the ZnO layers were consistent with the morphologies and showed the samples grown at 450C to be highly oriented and the samples grown at 550C to have no preferred orientation (Fig. 5b and Fig. 5c). The ferrite layers containing zinc however, were uniform and equiaxed as shown in Fig. 7d for zinc ferrite grown at 500C.

4. Conclusions The growth technique of liquid injection MOCVD has demonstrated successfully the depos-

ition of thin metal oxide lms of nickel oxide, zinc oxide and iron oxide from the metal(thd) precursors. Initial growth studies of the individual precursors were performed and the growth rates of the metal oxides nickel oxide, zinc oxide and iron oxide were determined as a function of substrate temperature. The binary ferrites, nickel ferrite and zinc ferrite and the ternary alloy nickel zinc ferrite were deposited at 500C, and the layers were analysed by X-ray diraction and shown to be crystalline with no strongly preferred orientation. The diraction results correlated closely with the standard X-ray diraction les. From a future application point of view the growth temperatures used are compatible with deposition onto pre-existing circuitry and the small uniform equiaxed grains are a suitable microstructure for device processing.

P.A. Lane et al. / Journal of Crystal Growth 192 (1998) 423429

429

Fig. 7. SEM micrographs showing the surface morphologies of ZnO grown at (a) 450C, (b) 500C, (c) 550C and (d) zinc ferrite grown at 500C.

References
[1] J.D. Adam, S.V. Krishnaswamy, S.H. Talisu, K.C. Yoo, J. Magn. Magn. Mater. 83 (1990) 419. [2] L. Strichauer, G. Gavoille, Z. Simsu, J. Appl. Phys. 79 (1996) 3645. [3] M. Abe, Y. Tamaura, J. Appl. Phys. 55 (1984) 2614. [4] P. Samarasekara, R. Rani, F.J. Cadieu, S.A. Shaheen, J. Appl. Phys. 79 (1996) 5425.

[5] Y. Suzuki, R.B. van Dover, E.M. Gyorgy, J.M. Phillips, V. Korenivski, D.J. Werder, C.H. Chen, R.J. Felder, R.J. Cava, J.J. Krajewski, W.F. Peck Jr., J. Appl. Phys. 79 (1996) 5923. [6] E. Fujii, H. Torii, R. Takayama, T. Hirao, Jpn. J. Appl. Phys. 34 (1995) 130. [7] C. Roger, T.S. Corbitt, M.J. Hampden-Smith, Appl. Phys. Lett. 65 (1994) 1021. [8] W. Tao, S.B. Desu, T.K. Li, Mater. Lett. 23 (1995) 177.