- •ACKNOWLEDGMENTS
- •TABLE OF CONTENTS
- •LIST OF TABLES
- •LIST OF FIGURES
- •INTRODUCTION
- •2.1.1 Structural Properties
- •2.1.2 Physical Properties
- •2.1.3 Electrical Properties of InN
- •2.1.3.1 Background Defects
- •2.1.4 Optical Properties of InN
- •2.2.1 Thermodynamic Models in Solid Solution
- •2.2.1.1 Regular Solution Model
- •2.2.1.2 Bonding in Semiconductor Solid Solutions Model
- •2.2.1.4 Strain Energy Model
- •2.2.1.5 First-Principal Models
- •2.2.2 Thermodynamic Analysis of InN
- •2.2.3 Phase Separation in InxGa1-xN
- •2.3.1 Growth Temperature and V/III Ratio
- •2.3.2 Nitrogen Source
- •2.4 Indium Nitride (InN) Growth Techniques
- •2.4.1 Chemical Vapor Deposition (CVD)
- •2.4.1.1 Metal-Organic Vapor Phase Epitaxy (MOVPE)
- •2.4.1.2 Hydride Vapor Phase Epitaxy (HVPE)
- •2.4.1.3 Plasma Enhanced Chemical Vapor Deposition (PECVD)
- •2.4.3 Atomic Layer Deposition (ALD)
- •2.5 Substrate Materials
- •2.5.1 Sapphire Substrate (Al2O3) (0001)
- •2.5.2 Silicon (Si) Substrate
- •2.5.4 Other Substrates
- •2.5.5 Buffer Layer
- •2.6 Summary for Growth of InN on Different Substrate
- •2.6.2 Growth on Silicon (Si) Substrate
- •2.6.3 Growth on Gallium Arsenide (GaAs) Substrate
- •2.6.4 Growth on Gallium Phosphorus (GaP) Substrate
- •2.7 Overview
- •THERMODYNAMIC ANALYSIS OF InN AND InXGa1-XN MOVPE GROWTH
- •3.1 Thermodynamic Analysis of InN and InxGa1-xN
- •3.1.1 Reaction Mechanism and Kinetics of InN MOVPE
- •3.2.1 Boundary Passivation Method with Hydrogen
- •5.1. Indium Nitride (InN) Growth Optimization
- •5.1.1. Substrate Selection
- •5.1.1.1. Sapphire (c-Al2O3 (0001))
- •5.1.1.2. Gallium Nitride (GaN/c-Al2O3 (0001))
- •5.1.1.3. Silicon (Si (111))
- •5.1.2. Substrate Preparation Procedure
- •5.1.3. Metal-Organic Vapor Phase Epitaxy (MOVPE) Reactor
- •5.1.4. Growth Chemistry and Conditions for InN Growth
- •5.1.5. Indium Nitride (InN) Growth and Optimization
- •5.1.5.1. Influence of Growth Temperature
- •5.1.5.2. Influence of Substrate Nitridation
- •5.1.5.3. Influence of N/In Ratio
- •5.1.5.4. Influence of Buffer Layer and Morphological Study
- •5.1.5.5. Influence of Pressure
- •5.1.5.6. Optical and Electrical Properties
- •5.1.5.7. Summary
- •5.1.6. Indium Nitride (InN) Droplet Formation
- •5.1.7. Annealing Effect
- •5.3. Inlet Tube Modification and Growth Results
- •CONCLUSIONS
- •LIST OF REFERENCES
- •BIOGRAPHICAL SKETCH
INDIUM NITRIDE GROWTH BY METAL-ORGANIC VAPOR PHASE EPITAXY
By
TAEWOONG KIM
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
2006
Copyright 2006
by
Taewoong Kim
ACKNOWLEDGMENTS
The author wishes first to thank his advisor, Dr. Timothy J. Anderson, for providing five years of valuable advice and guidance. Dr. Anderson always encouraged the author to approach his research from the highest scientific level. He is deeply thankful to his co-advisor, Dr. Olga Kryliouk, for her valuable guidance, sincere advice, and consistent support for the past five years.
Secondly, the author wishes to thank the remaining committee members of Dr. Steve Pearton and Dr. Fan Ren for their advice and guidance
The author is grateful to Scott Gapinski, the staff at Microfabritech, and Eric Lambers, the staff at the Major Analytical Instrumentation Center, especially for Auger characterization.
Acknowledgement needs to be given to Sangwon Kang who worked with the author for the past year and provided valuable assistance.
Thanks go to Youngsun Won for his useful discussion of quantum calculation and SEM characterization, and to Dr. Jianyun Shen for her assistance about how to use the ThermoCalc.
The author wishes to thank Hyunjong Park for useful discussion and Youngseok Kim for his kindness and friendship.
Most importantly, the author is grateful to Moonhee Choi, his beloved wife, for her endless support, trust, love, sacrifice and encouragement. Without her help, he would have not finished the Ph.D. course.
iii
The author is grateful to his mother, father, mother-in-law, father-in-law, sisters, and brother for providing love, support and guidance throughout his life.
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TABLE OF CONTENTS |
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page |
ACKNOWLEDGMENTS ................................................................................................. |
iii |
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LIST OF TABLES........................................................................................................... |
viii |
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LIST OF FIGURES ............................................................................................................. |
x |
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ABSTRACT.................................................................................................................... |
xvii |
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CHAPTER |
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1 |
INTRODUCTION ........................................................................................................ |
1 |
2 |
LITERATURE REVIEW ............................................................................................. |
3 |
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2.1 Indium Nitride (InN) and Indium Gallium Nitride (InxGa1-xN) Properties ............ |
4 |
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2.1.1 Structural Properties ..................................................................................... |
4 |
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2.1.2 Physical Properties ....................................................................................... |
7 |
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2.1.3 Electrical Properties of InN .......................................................................... |
9 |
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2.1.3.1 Background Defects ........................................................................... |
9 |
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2.1.3.2 Hall mobility and Electron Concentration in Undoped InN ............ |
10 |
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2.1.4 Optical Properties of InN............................................................................ |
14 |
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2.1.5. Indium Nitride (InN) andIindium Gallium Nitride (InxGa1-xN) |
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Applications ............................................................................................... |
16 |
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2.2 Thermodynamic Analysis and Phase Separation in the InxGa1-xN System .......... |
18 |
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2.2.1 Thermodynamic Models in Solid Solution................................................. |
19 |
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2.2.1.1 Regular Solution Model ................................................................... |
19 |
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2.2.1.2 Bonding in Semiconductor Solid Solutions Model.......................... |
19 |
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2.2.1.3 Delta Lattice Parameter (DLP) Model for Enthalpy of Mixing ....... |
21 |
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2.2.1.4 Strain Energy Model ........................................................................ |
22 |
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2.2.1.5 First-Principal Models...................................................................... |
23 |
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2.2.2 Thermodynamic Analysis of InN ............................................................... |
24 |
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2.2.3 Phase Separation in InxGa1-xN.................................................................... |
26 |
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2.3 Indium Nitride (InN) and Indium Gallium Nitride (InxGa1-xN) Growth |
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Challenges............................................................................................................. |
32 |
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2.3.1 Growth Temperature and V/III Ratio ......................................................... |
32 |
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2.3.2 Nitrogen Source.......................................................................................... |
34 |
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2.3.3 Carrier Gas.................................................................................................. |
36 |
v
2.4 |
Indium Nitride (InN) Growth Techniques............................................................ |
37 |
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2.4.1 Chemical Vapor Deposition (CVD) ........................................................... |
37 |
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2.4.1.1 Metal-Organic Vapor Phase Epitaxy (MOVPE).............................. |
38 |
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2.4.1.2 Hydride Vapor Phase Epitaxy (HVPE)............................................ |
41 |
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2.4.1.3 Plasma Enhanced Chemical Vapor Deposition (PECVD)............... |
42 |
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2.4.2 Molecular Beam Epitaxy (MBE) and Metalorganic Molecular Beam |
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Epitaxy (MOMBE) .................................................................................... |
44 |
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2.4.3 Atomic Layer Deposition (ALD) ............................................................... |
45 |
2.5 |
Substrate Materials ............................................................................................... |
46 |
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2.5.1 Sapphire Substrate (Al2O3) (0001) ............................................................. |
47 |
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2.5.2 Silicon (Si) Substrate.................................................................................. |
49 |
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2.5.3 Gallium Nitride (GaN) and Aluminium Nitride (AlN) Substrate .............. |
50 |
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2.5.4 Other Substrates.......................................................................................... |
51 |
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2.5.5 Buffer Layer ............................................................................................... |
52 |
2.6 |
Summary for Growth of InN on Different Substrate............................................ |
53 |
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2.6.1 Growth on Sapphire (Al2O3) Substrate....................................................... |
53 |
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2.6.2 Growth on Silicon (Si) Substrate................................................................ |
55 |
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2.6.3 Growth on Gallium Arsenide (GaAs) Substrate......................................... |
56 |
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2.6.4 Growth on Gallium Phosphorus (GaP) Substrate....................................... |
57 |
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2.6.5 Growth on Gallium Nitride (GaN) and Alumimum Nitride (AlN) |
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Substrate..................................................................................................... |
58 |
2.7 |
Overview............................................................................................................... |
59 |
3 THERMODYNAMIC ANALYSIS OF InN AND InxGa1-xN MOVPE GROWTH ..60 |
||
3.1 |
Thermodynamic Analysis of InN and InxGa1-xN.................................................. |
60 |
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3.1.1 Reaction Mechanism and Kinetics of InN MOVPE................................... |
60 |
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3.1.2 Pressur-Temperature (P-T) Phase Diagram of InxGa1-xN and Phase |
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Separation in InxGa1-xN.............................................................................. |
65 |
3.2 |
Quantum Calculation of Phase Separation in InxGa1-xN ...................................... |
70 |
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3.2.1 Boundary Passivation Method with Hydrogen........................................... |
70 |
4 CALCULATION OF THE CRITICAL THICKNESS OF InN ON GaN, AlN, Si, |
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AND Al2O3 ................................................................................................................. |
76 |
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4.1 |
Calculation of Critical Thickness of InN by Matthews’ Method. ........................ |
77 |
4.2 |
Calculation of Critical Thickness of InN by van der Merwe’s Method. .............. |
80 |
4.3 |
Calculation of Critical Thickness of InN by the Methods of Shen, Jesser, and |
|
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Wilsdorf. ............................................................................................................... |
86 |
5 Indium Nitride (InN) GROWTH BY METAL-ORGANIC VAPOR PHASE |
|
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EPITAXY (MOVPE).................................................................................................. |
93 |
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5.1. Indium Nitride (InN) Growth Optimization ........................................................ |
93 |
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5.1.1. Substrate Selection .................................................................................... |
94 |
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5.1.1.1. Sapphire (c-Al2O3 (0001))............................................................... |
96 |
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5.1.1.2. Gallium Nitride (GaN/c-Al2O3 (0001))........................................... |
97 |
vi
5.1.1.3. Silicon (Si (111))............................................................................. |
97 |
5.1.2. Substrate Preparation Procedure................................................................ |
98 |
5.1.3. Metal-Organic Vapor Phase Epitaxy (MOVPE) Reactor.......................... |
98 |
5.1.4. Growth Chemistry and Conditions for InN Growth.................................. |
99 |
5.1.5. Indium Nitride (InN) Growth and Optimization ..................................... |
102 |
5.1.5.1. Influence of Growth Temperature................................................. |
102 |
5.1.5.2. Influence of Substrate Nitridation ................................................. |
110 |
5.1.5.3. Influence of N/In Ratio ................................................................. |
115 |
5.1.5.4. Influence of Buffer Layer and Morphological Study.................... |
118 |
5.1.5.5. Influence of Pressure..................................................................... |
125 |
5.1.5.6. Optical and Electrical Properties................................................... |
127 |
5.1.5.7. Summary ....................................................................................... |
129 |
5.1.6. Indium Nitride (InN) Droplet Formation ................................................ |
130 |
5.1.7. Annealing Effect...................................................................................... |
136 |
5.2. Computational Fluid Dynamic Analysis of the Flow of NH3 and Proposed |
|
Inlet Tube Modification to Improve Flow Pattern of NH3................................ |
138 |
5.3. Inlet Tube Modification and Growth Results .................................................... |
145 |
6 CONCLUSIONS ...................................................................................................... |
154 |
LIST OF REFERENCES................................................................................................. |
158 |
BIOGRAPHICAL SKETCH ........................................................................................... |
179 |
vii