CHEMICAL VAPOR DEPOSITION OF THIN FILM MATERIALS FOR ...

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which can contaminate the thin film growth if the purging/pumping time is not long enough. The surface Si-H bonds subtraction has been found for adsorption above 150˚C and it is closely related to the TDMAH decomposition behavior. Hafnium nitride thin film deposition by PEALD using TDMAH and hydrogen plasma has been investigated. Uniform and moderately conductive HfNxCy thin films were deposited on Si(100) and SiO2 substrates. A thin surface layer (2~3 nm) containing both hafnium nitride and organic complexes of TDMAH decomposition has been found by in vacuo XPS analysis. Depth profile analysis by XPS indicated the existence of hafnium carbide phase in the bulk. Thin film resistivity is greatly affected by the level of hydrogen plasma power, in which higher plasma power results in lower thin film resistivity. In spite of this tunability of resistivity by plasma power, carbon incorporation is still an issue for this PEALD method. 6.1.2 DLI-CVD of nickel ferrite and lithium ferrite films We have used DLI-CVD technique for the growth of high quality epitaxial NiFe2O4 films on MgAl2O4 (100), MgO (100), MgO (111) and few piezoelectric substrates. Anhydrous Ni(acac)2 and Fe(acac)3 precursor sources are dissolved in DMF and vaporized under optimum conditions to generate stoichiometric concentration of the cations in the gas phase for the CVD reaction. Appropriate oxygen flow with the precursors is important both for improving the film morphology and also to obtain stoichiometric deposition. Under our experimental conditions, film growth rate has been found in the range of 0.6-1.1 um/hr and can be further increased by increasing the solution concentration or liquid flow rate. However, the vaporizer process condition and the oxygen flow rate also need to be adjusted to maintain the desired film morphology and stoichiometry. Under optimized vaporization conditions, the film morphology is dependent on the deposition temperature because of changes in the surface diffusion behavior. In 115
the temperature range of 600˚C to 700˚C, relatively thick epitaxial NiFe2O4 films, which are extremely smooth and exhibit excellent magnetic properties, have been deposited on both MgAl2O4 (100) and MgO (100) substrates. However, macroscopic cracks develop on MgO after deposition and cool down, likely because of high residual tensile stress. The increased saturation magnetization with increasing deposition temperature can be attributed to improved crystalline quality, which is verified from X-ray diffraction and polarized Raman measurements. The difference between in plane and out-of-plane FMR line width measured at 9.5 GHz indicates the presence of two magnon scattering effect which is related to crystal defects or chemical inhomogeneities in the films. FMR line width as low as ~160 Oe has been achieved for out-of- plane measurement of nickel ferrite films deposited at 600˚C, which is quite close to the value of bulk crystal. DLI-CVD growth of lithium ferrite is investigated by using Li(acac) and Fe(acac)3 as the metal organic precursors. Different from the deposition of nickel ferrite, lithium ferrite films grown on MgAl2O4(100) are much rougher and do not show any crystalline features for deposition at 500˚C and 600˚C. Spinel crystalline phases have been found for the deposition at 700˚C and 800˚C. However, more than one orientation are present for deposition at 800˚C. Comparatively, lithium ferrite films deposited on MgO(100) exhibits single crystal quality and much smoother surface for the deposition temperature range of 500˚C to 800˚C. The smaller lattice mismatch between MgO and Nickel ferrite can be the principal reason. The narrowest in plane FMR line width ~368 Oe has been found for the films deposited at 600˚C. With suitable optimization of the vaporization and film deposition conditions, excellent quality ferrite films can be grown at a relatively high rate using DLI-CVD. 116
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CHEMICAL VAPOR DEPOSITION OF THIN F
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ABSTRACT Chemical vapor deposition
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DEDICATION This dissertation is ded
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φ In-plane tilt angle of X-ray dif
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ACKNOWLEDGMENTS It is my pleasure t
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CONTENTS ABSTRACT .................
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3.2.1 Introduction ................
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LIST OF TABLES Table 1. Hafnium ami
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indicated by the complex FMR curve.
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Fig. 49. Ferromagnetic resonance cu
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growth rate, good step coverage and
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growth of thin film oxides due to t
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one can uniformly deliver precursor
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for the next reaction step as shown
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Fig. 3. Schematic of a typical dire
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is predominantly dependent on syste
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J r J A -D n b-n 0 δ n or for the
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surface passivation with certain in
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ay spectroscopy (EDS), Wavelength d
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incidence angle is larger than cert
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epresenting those characteristic ph
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1.2.3.3 X-ray Diffraction (XRD) X-r
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exhibit diffraction peaks in the no
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(nanometers to tens of nanometers),
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strongest absorption of microwave s
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pinch-off to indicate the lack of a
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coupling is from unbound ferrite-fe
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diffusion barrier material in micro
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Fig. 14. A cross sectional scanning
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In spite of the same spinel structu
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ferrites has been investigated exte
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systems is showed in Fig.18.[83] As
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precursor vaporization process, e.g
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CHAPTER 3. PLASMA ENHANCED ATOMIC L
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the initial surface chemistry for t
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delay time of 2 seconds between spe
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Kcal/mol respectively. The stronger
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negative slope) behavior in the pum
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the existence of both physisorbed a
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decomposition products (Hf-H) and g
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dried by ultra high purity N2 gas.
Page 83 and 84: pressure for XPS analysis is around
Page 85 and 86: Hf and N elements, incorporation of
Page 87 and 88: [150,151] This is a unique feature
Page 89 and 90: software. The thickness results are
Page 91 and 92: CHAPTER 4. DIRECT LIQUID INJECTION
Page 93 and 94: film growth region. The properties
Page 95 and 96: solution was accurately controlled
Page 97 and 98: size). For the rocking curve analys
Page 99 and 100: oxygen does not participate in the
Page 101 and 102: ecause vapor velocity cannot be cha
Page 103 and 104: Fig. 40. Cross-sectional view by fi
Page 105 and 106: the MgAl2O4 substrate confirms cube
Page 107 and 108: pattern. Fig.44(b) has diffraction
Page 109 and 110: We have used an AGM (Alternating Gr
Page 111 and 112: as derived equations for different
Page 113 and 114: deposited at 600˚C is the lowest.
Page 115 and 116: wave states degenerate with the FMR
Page 117 and 118: Fig. 53. ϕ-scan of nickel ferrite
Page 119 and 120: Surface roughness characterized by
Page 121 and 122: Fig. 56. X-ray diffraction θ-2θ c
Page 123 and 124: 4.4 Conclusion In summary, we have
Page 125 and 126: CHAPTER 5. DIRECT LIQUID INJECTION
Page 127 and 128: eaction zone of the tube furnace is
Page 129 and 130: Fig. 58. X-ray diffraction characte
Page 131 and 132: interface. This phenomenon probably
Page 133: 6.1 Conclusion CHAPTER 6. CONCLUSIO
Page 137 and 138: such as PMN-PT and PZN-PT. CVD proc
Page 139 and 140: [18]. L. S.-J. Peng, X. X. Xi, B. H
Page 141 and 142: [54]. B. O. Johansson, J. -E. Sundg
Page 143 and 144: [96]. J. D. Adam, S. V. Krishnaswam
Page 145 and 146: [136]. J. Zhao, V. Fuflyigin, F. Wa
Page 147 and 148: APPENDIX A: LabVIEW PROGRAM FOR PEA
Page 149 and 150: APPENDIX B: TDMAH MOLECULAR STRUCTU
Page 151 and 152: H 18 B19 2 A18 1 D17 H 18 B20 2 A19
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