本研究論文的目的是探討二氧化鈦(TiO2)應用在薄膜電晶體(TFT)之閘極氧化層的生長機制與其特性。以基板種類可區分為非晶矽(a-Si)與多晶矽(poly-Si)基板。以TiO2生長的方式可區分為有機金屬化學氣相沉積法(MOCVD)與液相沉積法(LPD)。其中液相沉積法在鈦(Ti)原料上又可區分為六氟鈦銨((NH)2TiF6)與六氟鈦酸(H2TiF6)兩種原料。在內容討論上可區分為兩個部分，第一部分是探討TiO2薄膜之生長機制、物性、化性與MOS結構的電性。第二部分則是探討元件的製程步驟與電特性。
在第一部分，我們將探討同一種生長方式在不同基板上的特性與行為。以MOCVD成長方式的TiO2薄膜比較偏向多晶結構，多晶結構具有較好的介電常數，然而其晶界具有較多的缺陷與懸鍵，因此漏電流比較大。以LPD成長方式的TiO2薄膜比較偏向非晶結構，非晶結構雖然有較低的介電常數，但是卻有較低的漏電流特性。此外，在LPD製程中，(NH)2TiF6將生成TiO2薄膜，而H2TiF6將生成TixSi(1-x)Oy薄膜。溶液中過多的F離子與OH離子會嵌入至薄膜而影響電特性，但藉由低溫回火可使得OH與部分的F離子脫離薄膜，不過適當的F離子將有助於鈍化缺陷與懸鍵。而低溫回火的方式則採用氮氣(N2)，氧氣(O2)以及金屬化後之退火處理(PMA)方式來改善其特性。
第二部分則是製作以共平面為主體的mesa結構元件，並探討TFT元件之電特性曲線行為。共平面結構具有簡易製程的優點但有較高的漏電流，可藉由mesa結構，並在過蝕刻的條件下，降低元件的漏電流。此外，此結構在離子佈植(ion implantation)的過程中更可在閘極區域使用自我校準(self-align)的方式摻雜源極與汲極，藉由減少Cgd的電容值進而降低回踢電壓。TFT的操作原理與金氧半場效電晶體(MOSFET)有些許的差異，因此在製作與量測上時的參數皆不同於MOSFET。由於a-Si與poly-Si是未摻雜且具有許多缺陷的基板，在操作上必須先將a-Si與poly-Si完全空乏(full depletion)才能進行反轉，此時通道才會發生。因此在製程上，其關鍵步驟在於a-Si與poly-Si必須維持的適當的厚度。太厚則不利於通道反轉，太薄則不利於蝕刻製程。在離子佈植部份，由於所設計的主動層厚度較薄，因此需要使用較低能量的離子能量來進行。離子活化的溫度與時間都需要適當的調配。初步的結果已經製作出以MOCVD-TiO2為閘極氧化層應用在多晶矽基板上。TFT元件特性曲線說明了為摻雜的多晶矽是屬於n型半導體。通道長度太短時亦可發現“Kink effect”存在。另外Ion/Ioff比率較小是後續能需努力的地方。

The purpose of this study is using titanium dioxide (TiO2) as gate oxide on thin film transistor (TFT) and discussed with their physical, chemical and electrical properties. Amorphous silicon (a-Si) and polycrystalline silicon (poly-Si) are used as substrates. The metal-organic chemical vapor deposition (MOCVD) and the liquid phase deposition (LPD) are used as the TiO2 growth methods. About the LPD growth method, ammonium hexafluoro-titanate ((NH4)2TiF6) and hexafluorotitanic acid (H2TiF6) are used as Ti sources. We are interested in two parts: (1) the growth mechanisms, physics properties, chemical properties and electrical properties of MOS structure; (2) the fabrication processes and electrical properties of devices.
In the first part, we discuss the thin films characteristics on a-Si and poly-Si substrates. For the MOCVD growth method, the MOCVD-TiO2 film tends to form the poly structure. Poly structure has a higher dielectric constant, however, higher traps and dangling bonds also exist at the grain boundaries. Thus, poly structure of TiO2 film has a higher leakage current. For the LPD growth method, the film tends to form the amorphous structure. Amorphous structure has lower leakage current but also has lower dielectric constant. The film that grown from the (NH)2TiF6 source is called LPD-TiO2 film. The film that grown from the (NH)2TiF6 source is called LPD-TixSi(1-x)Oy film. Both films are incorporated with OH and F ions during the growth, the OH and F ions can be outgassed during the low temperature annealing process. In addition, appropriate F ions in the film can passivate the traps and dangling bonds. The low temperature treatments in N2 or O2 ambient and post-metallization annealing (PMA) are adopted to improve the film characteristics. On the other hand, the substrate is not a prefect structure (not a single structure). Thus the film may be influenced by substrate during the annealing treatment.
In the second part, the electrical properties of TFT devices were discussed under the coplanar structure. There are several differences of the operation principle in TFT and MOSFET. A-Si and poly-Si are the un-doped substrates with many traps in the bulk. The channel should be occurred through the full depletion mode. The full depletion region is the substrate that under the gate electrode. Thus, the key point is kept the suitable thickness. Too thick, the channel can not appear. Too thin, the substrate may be over-etched. For ion implantation, due to the thinner active layer, the ion implantation energy should be lowed. In addition, the activation temperature and activation time should be adjusted suitable. We have fabricated the TFT devices with the MOCVD-TiO2 as gate oxide on poly-Si substrate. From the I-V characteristics, the Kink effect can be observed. However, the Ion/Ioff ratio is still low. We must further study how to increase the Ion/Ioff ratio.

CONTENTS

ACKNOWLEDGMENTS I
中文摘要 II
英文摘要 III
CONTENTS V
LIST OF FIGURES IX
LIST OF TABLES XIV

Chapter 1
1. Introduction 1
1.1 Introduction of Flat Panel Displays 1
1.1.1 Category of Flat Panel Displays 1
1.1.2 Structure of TFTLCD 1
1.1.3 Structure of TFT 3
1.1.4 Development of TFTLCD 4
1.2 Motivation of High k Material as Gate Oxide 5
1.2.1 Development of Large Size of Panel 5
1.2.2 Integration of Peripheral Circuits 6
1.2.3 Properties of High k Materials of TiO2 and TixSi(1-x)Oy 6
1.3 Growth Methods 7
1.3.1 Advantages of MOCVD 7
1.3.2 Advantages of LPD 8

Chapter 2
2. Experiments 15
2.1 Equipmental of Growth 15
2.1.1 MOCVD System 15
2.1.1.1 Characteristics of Ti Metalorganic Precursor 15
2.1.1.2 N2O Decomposition 16
2.1.2 LPD System 17
2.1.3 Other Instruments 17
2.2 Experiment Procedures 20
2.2.1 Preparation of Solutions 20
2.2.2 Flowchart of TiO2 21
2.2.3 Thermal Treatment of TiO2 22
2.2.4 Characterization and Analysis 22
2.3 TFT Fabrication 24
2.3.1 Mesa Structure 24
2.3.2 Gate Definition 24
2.3.3 Ion Implantation 25
2.3.4 Source-Drain Contact Fabrication 25

Chapter 3
3. Results and Discussion 37
3.1 Characteristics of MOCVD-TiO2 Films on a-Si and poly-Si Substrates 37
3.1.1 Source-Drain Contact Fabrication 37
3.1.2 AFM RMS (nm) of MOCVD-TiO2 Films 40
3.1.3 X-ray Diffraction Spectra of MOCVD-TiO2 Films 40
3.1.4 SIMS Depth Profiles of MOCVD-TiO2 Films 40
3.1.5 J-E Characteristics of MOCVD-TiO2 Films on a-Si 41
3.1.6 J-E Characteristics of MOCVD-TiO2 Films on poly-Si 42
3.1.6.1 The Improvement of J-E Characteristics of MOCVD-TiO2 Films on poly-Si by PMA 43
3.1.7 C-V Characteristics of MOCVD-TiO2 Films on a-Si 44
3.1.8 C-V Characteristics of MOCVD-TiO2 Films on poly-Si 45
3.1.9 Tentative Summary 46
3.2 Characteristics of LPD-TiO2 Films on a-Si and poly-Si Substrates ((NH4)2TiF6 as source) 69
3.2.1 Chemical Reaction of LPD-TiO2 Films 69
3.2.2 Growth Rate of LPD-TiO2 Films 69
3.2.3 SEM Cross-section and SIMS Depth Profile of LPD-TiO2 Films 70
3.2.4 ESCA Spectra of Ti 2p and O 1s Bonds 72
3.2.5 J-E Characteristics of LPD-TiO2 Films on a-Si 73
3.2.6 J-E Characteristics of LPD-TiO2 Films on poly-Si 74
3.2.7 C-V Characteristics of LPD-TiO2 Films on a-Si 76
3.2.8 C-V Characteristics of LPD-TiO2 Films on poly-Si 77
3.2.9 Tentative Summary 77
3.3 Characteristics of LPD-TixSi(1-x)Oy Films on a-Si and poly-Si Substrates (H2TiF6 as Source) 95
3.3.1 Chemical Reaction of LPD-TixSi(1-x)Oy Films 95
3.3.2 Growth Rate of LPD-TixSi(1-x)Oy Films 95
3.3.3 SEM Cross-section of LPD-TiO2 Films 96
3.3.4 J-E Characteristics of LPD-TixSi(1-x)Oy Films with and without NH4OH Incorporation 96
3.3.5 XPS Spectra of LPD-TixSi(1-x)Oy Films on a-Si and poly-Si as a function of Sputtering Time 96
3.3.6 FTIR Spectra of LPD-TixSi(1-x)Oy Films on a-Si and poly-Si as a function of Sputtering Time 98
3.3.7 J-E Characteristics of LPD-TixSi(1-x)Oy Films on a-Si 99
3.3.8 J-E Characteristics of LPD-TixSi(1-x)Oy Films on poly-Si 100
3.1.9 C-V Characteristics of LPD-TixSi(1-x)Oy Films on a-Si 101
3.1.10 C-V Characteristics of LPD-TixSi(1-x)Oy Films on poly-Si 101
3.2.11 Tentative Summary 101
3.4 Characteristics of TFT devices 120
3.4.1 Detail Discussion of Fabrication Processes of TFT 120
3.4.1.1 Full Depletion 121
3.4.1.2 Kickback Voltage 121
3.4.1.3 Low Ion Implantation Energy 122
3.4.2 Electrical Characteristics of TFT 123

Chapter 4
Conclusions 135
4.1 MOCVD-TiO2 on a-Si and poly-Si Substrates 135
4.2 LPD-TiO2 on a-Si and poly-Si Substrates 136
4.3 LPD-TixSi(1-x)Oy on a-Si and poly-Si Substrates 137
4.4 TFT Devices 138
4.5 Future Work 138

REFERENCES 140

Vita 148

Publication List 149

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