根據硝酸可增進鈦矽氧化膜的生長速率及使介電材料極化可提昇介電常數的概念，以液相沉積法發展等效氧化層厚度低於1奈米且具有高介電係數之鋇摻雜鈦矽氧化膜是本研究的主旨。在本研究中，原料之一的硝酸鋇溶液，其莫耳濃度對於鋇摻雜鈦矽氧化膜之沉積速率、折射率及介電係數的影響扮演著極重要的角色。薄膜電性可藉由熱退火處理而有效的改善。以液相沉積法所製備的鋇摻雜鈦矽氧化膜在實際光學厚度為7.4 奈米下具有最佳等效氧化層厚度0.9奈米。其介電係數可高達31.9且漏電流在電場強度5 MV/cm之下為5 × 10-6 A/cm2 。本研究所發展之等效厚度低於1奈米的鋇摻雜鈦矽氧化膜對於下一世代的應用有良好的發展性。

High dielectric constant barium doped titanium silicon oxide films with equivalent oxide thickness below 1 nm can be prepared by liquid phase deposition. We learn from this research that the deposition rate of titanium silicon oxide films can be much enhanced by nitric acid incorporation, and the dielectric constant of materials can be increased by the dipole polarization from barium. The key parameter for the deposition rate, refractive index, and the dielectric constant of barium doped titanium silicon oxide is the molarity of barium nitrate. The electrical properties can be improved effectively by thermal annealing treatments. The optimum equivalent oxide thickness of barium doped titanium silicon oxide thin film is 0.9 nm with the optical thickness of 7.4 nm. The high dielectric constant can reach 31.9 and the leakage current density is 5 × 10-6 A/cm2 at the electrical field intensity of 5 MV/cm, which has high potential application for the next generation MOSFET.

CONTENTS
CHAPTER 1 1
INTRODUCTION 1
1-1 Technology Requirements for MOSFET 1
1-2 High Dielectric Constant Materials 3
1-3 Various Techniques for TiO2 Preparation 5
1-4 Advantages of Amorphous Films 6
1-5 Binary System of TiO2-SiO2 6
1-6 Titanium Silicon Oxide (TixSi(1-x)Oy) 8
1-7 Advantages of Liquid Phase Deposition 9
1-8 Background of Liquid Phase Deposition Technique in Our Lab 10
1-8.1 LPD-SiO2 10
1-8.2 LPD-SiON and Biased-LPD-SiON 11
1-8.3 LPD-TiO2 12
1-8.4 LPD-Barium Titanate (BTO) 13
1-8.5 LPD-TixSi(1-x)Oy 17
1-9 Aims of this Study 19
1-9.1 Motivation 19
1-9.2 Mechanism of Chemically Etching Si by HNO3-HF Mixture 21
1-9.3 Function of Barium Incorporation in Dielectric Material 22
CHAPTER 2 23
EXPERIMENTS 23
2-1 Deposition System 23
2-2 Cleaning of Silicon Substrate 25
2-3 Preparation of Deposition Solutions 26
2-3.1 Preparation of the Precursor Solutions 26
2-3.2 Deposition Solution Process for LPD-TixSi(1-x)Oy Films 29
2-3.3 Deposition Solution Process for Ba doped LPD-TixSi(1-x)Oy Films 29
2-4 Films Depositions 30
2-5 Characteristics 31
2-5.1 Physical Properties 31
2-5.2 Chemical Properties 31
2-5.3 Electrical Properties 32
CHAPTER 3 36
RESULTS AND DISCUSSION 36
PART I: Preparation of LPD-TixSi(1-x)Oy Films with HNO3 Incorporation 37
3-1 Mechanism of LPD-TixSi(1-x)Oy Deposition 37
3-1.1 Structure and Morphology of LPD-TixSi(1-x)Oy Film 37
3-1.2 Preparation of LPD-TixSi(1-x)Oy Film 40
3-1.3 Proposed Chemical Equilibriums of LPD-TixSi(1-x)Oy Film 41
3-1.4 Growth Mechanism of LPD-TixSi(1-x)Oy Films 41
3-2 Physical Properties of As-deposited LPD-TixSi(1-x)Oy Films 44
3-2.1 Deposition Rate as a Function of HNO3 Molarity 44
3-2.2 Relationship between Refractive Index and Deposition Rate with HNO3 Molarity 46
3-3 Chemical Properties of As-deposited LPD-TixSi(1-x)Oy Films 48
3-3.1 ESCA Analysis of LPD-TixSi(1-x)Oy Film 48
3-3.2 SIMS Depth Profile of LPD-TixSi(1-x)Oy Film 52
3-3.3 Analysis of FTIR Spectra 53
3-4 Electrical Characteristics of As-deposited LPD-TixSi(1-x)Oy Films 57
3-4.1 C-V Characteristics 57
3-4.2 Relationship between Dielectric Constant and Deposition Rate with HNO3 Molarity 60
3-4.3 J-E Characteristics 62
3-5 Tentative Conclusions of LPD-TixSi(1-x)Oy Films Prepared with HNO3 Incorporation 64
PART II: Development of Ba doped LPD-TixSi(1-x)Oy Films 65
3-6 Mechanism of Ba doped LPD-TixSi(1-x)Oy Deposition 65
3-6.1 Structure and Morphology of Ba doped LPD-TixSi(1-x)Oy Film 65
3-6.2 Preparation of Ba doped LPD-TixSi(1-x)Oy Films 68
3-6.3 Proposed Chemical Equilibriums of Ba doped LPD-TixSi(1-x)Oy Film 69
3-6.4 Growth Mechanism of Ba doped LPD-TixSi(1-x)Oy Films 71
3-7 Physical Properties of As-deposited Ba doped LPD-TixSi(1-x)Oy Films 74
3-7.1 Relationship between Refractive Index and Deposition Rate with Ba(NO3)2 Molarity 74
3-8 Chemical Properties of As-deposited Ba doped LPD-TixSi(1-x)Oy Films 76
3-8.1 ICP-MS Analysis of the Deposition Solution for Ba doped LPD-TixSi(1-x)Oy Film 76
3-8.2 SIMS Depth Profile of Ba doped LPD-TixSi(1-x)Oy Film 78
3-8.3 AES Depth Profile of Ba doped LPD-TixSi(1-x)Oy Film 79
3-8.4 Analysis of FTIR Spectra 81
3-9 Electrical Characteristics of As-deposited Ba doped LPD-TixSi(1-x)Oy Films 87
3-9.1 C-V Characteristics 87
3-9.2 Relationship between Dielectric Constant and Ba(NO3)2 Molarity 89
3-9.3 J-E Characteristics 91
3-10 Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Film after Thermal Annealing 93
3-10.1 Structure of Ba Doped LPD-TixSi(1-x)Oy Films after Annealing in O2 Ambient 96
3-10.2 FTIR Spectra of Ba doped LPD-TixSi(1-x)Oy Films after Thermal Annealing 98
3-10.3 Thickness Variation of Ba doped LPD-TixSi(1-x)Oy Films after Thermal Annealing 100
3-10.4 Improvements of Electrical Properties by Thermal Annealing 102
3-11 Tentative Conclusions from Characteristics of Ba doped LPD-TixSi(1-x)Oy Films 117
PART III: Ba doped LPD-TixSi(1-x)Oy Thin Films with EOT Application 120
3-12 Equivalent Oxide Thickness (EOT) of Ba doped LPD-TixSi(1-x)Oy Film 121
3-13 Preparation of Ba doped LPD-TixSi(1-x)Oy Thin Film 124
3-14 Characteristics of Ba doped LPD-TixSi(1-x)Oy Thin Film 126
3-14.1 Deposition Rate of Ba doped LPD-TixSi(1-x)Oy Thin Films as a Function of Deposition Time 126
3-14.2 Analysis of Structure and Components of Ba doped LPD-TixSi(1-x)Oy Thin Films 128
3-14.3 Absorption Spectra of Ba doped LPD-TixSi(1-x)Oy Thin Films 131
3-14.4 Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Thin Films Annealed in N2 Ambient 133
3-14.5 Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Thin Films Annealed in N2O Ambient 138
3-14.6 Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Thin Films Annealed in O2 Ambient 142
3-14.7 Summarizing Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Thin Films by Thermal Annealing 146
3-15 Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Thin Film by Various Annealing Temperatures in O2 Ambient 151
3-15.1 Structural Analysis of Ba doped LPD-TixSi(1-x)Oy Thin Films Annealed at 500 ºC, 600 ºC, and 700 ºC 153
3-15.2 FTIR Spectra of Ba doped LPD-TixSi(1-x)Oy Thin Films Annealed at 500 ºC, 600 ºC, and 700 ºC 154
3-15.3 Absorption Spectra of Ba doped LPD-TixSi(1-x)Oy Thin Films after Thermal Annealing 156
3-15.4 Electrical Properties of Ba doped LPD-TixSi(1-x)Oy Thin Films Annealed at 500 ºC, 600 ºC, and 700 ºC 158
3-16 Tentative Conclusions of Ba doped LPD-TixSi(1-x)Oy Thin Films for EOT Application 169
CHAPTER 4 172
CONCLUSIONS 172
REFERENCES 175

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