動態記憶體尺寸的縮減在一開始即為一持續的趨勢。傳統二氧化矽用在閘極氧化層上將達至物理極限，因此採用高介電係數材料已是刻不容緩的事。而二氧化鈦由於具有高介電常數、高折射率、高化學穩定性，故適合應用在動態記憶體中金氧半場效電晶體之閘極介電材料。
我們採用水平、低壓、冷壁式之有機金屬化學氣相沈積法來成長二氧化鈦薄膜，採用的原料為四異丙烷氧化鈦，並以笑氣作為氧化氣體。成長溫度從400℃到650℃。利用有機金屬化學氣相沈積在矽基板上生長二氧化鈦薄膜具有高的介電常數，但由於二氧化鈦薄膜是多晶結構，除本身缺陷外，其晶界具有很多缺陷及懸鍵，故其漏電流也非常大。成長溫度明顯地影響二氧化鈦薄膜的電性，在經由氧回火處理後漏電流也有顯著的改善。然而，在氧回火後經金屬化熱處理，可以再更進一步地改善電性。
金屬化熱處理是一種利用氧化層表面的氫氧根(OH-)和披覆金屬層(Al)反應而產生活性氫原子，此活性氫原子可擴散進入到氧化膜裡，進而鈍化氧化膜裡的缺陷及懸鍵，可用來降低金氧半(MOS)結構的氧化層電荷密度及介面能態密度。因此，將金屬化熱處理這種技術運用在有機金屬化學氣相沈積成長二氧化鈦薄膜的金氧半電容上，將可鈍化其氧化膜裡的缺陷及懸鍵，進而可在維持高介電常數的條件下降低漏電流。其漏電流在-5 MV/cm下可達至3.44×10^-6 A/cm^2，遲滯偏移電壓為5 mV，介面狀態密度可達至1.17 × 10^11 cm^−2 eV^−1。

Scaling down of DRAM’s dimensions is a continuous trend since its inception. Therefore, the high dielectric constant material is necessary because the application of conventional SiO2 will reach its physical limits. Due to TiO2 have high dielectric constant (ε// = 170, ε⊥ = 90), high refractive index (~2.5) and high chemical stability, it is a promising candidate for fabricating thin dielectrics in DRAM storage capacitors and as gate dielectrics of MOSFET without the problem of conventional SiO2 thickness scaling down in ULSI processes.
TiO2 thin films grown on p-type (100) Si substrate are investigated by a cold wall horizontal MOCVD system using Ti(i-OC3H7)4, N2O as precursors at the growth temperature which ranges from 400 oC to 650 oC. The dielectric constant of poly-crystalline titanium oxide (TiO2) films grown on silicon (Si) by metal organic chemical vapor deposition (MOCVD) is high. The leakage current is also high, which is dominated by the film defect and the grain boundary. The electrical characteristics are also strongly associated with growth temperature. After oxygen annealing, the leakage current is improved due to the reduction of the oxygen vacancy of TiO2 film. However, the electrical characteristics can be further improved by the postmetallization annealing treatment especially under the negative electric field.
Post-metallization annealing (PMA) is an effective method in MOS technology to reduce the effective charge density and the interface state density. The mechanism of PMA is to use the reaction between the aluminum contact and hydroxyl groups existed on oxide surface to form active hydrogen and diffuse through the oxide to passivate the oxide traps. Therefore, MOCVD-TiO2/Si films which treated by O2-annealing and PMA with high dielectric constant and low leakage current can be obtained. The leakage current can reach 3.44×10^-6 A/cm2 under a negative electric field of 5 MV/cm. The hysteresis loop shift voltage and the interface state densities are 5 mV and 1.17 × 10^11 cm−2 eV^−1, respectively.

Acknowledgment.....................................I
Contents...........................................V
List of Figures....................................VII
List of Tables.....................................IX
Abstract...........................................X

CHAPTER 1..........................................1
Introduction.......................................1
1-1 Developments in DRAM.........................1
1-2 Properties of TiO2...........................2
1-3 Comparison of deposition method of TiO2......3
1-4 Advantages of MOCVD..........................4
1-5 Our Previous study of MOCVD-TiO2 films.......4
1-5.1 Thickness of TiO2 films as a function of growth temperature........................................5
1-5.2 XRD spectra of TiO2 films as a function of growth temperature........................................6
1-5.3 SEM morphologies of TiO2 films as a function of growth temperature.................................6
1-5.4 ESCA stoichiometries of TiO2 films as a function of growth temperature..............................7
1-5.5 Electrical characteristics of TiO2 films...8
1-5.5.1 Leakage of TiO2 films as a function of growth temperature........................................8
1-5.5.2 C-V characteristics of as-grown and O2-annealed TiO2 films.........................................9
1-6 Motivation of TiO2/Si with PMA treatment.....11
References.........................................30

CHAPTER 2..........................................40
Experiments........................................40
2-1 CVD theorem..................................40
2-2 Growth system of MOCVD.......................41
2-3 Properties of source materials...............42
2-3.1 Ti metalorganic precursor..................42
2-3.2 N2O decomposed.............................42
2-4 Experimental details.........................43
2-4.1 Si wafer cleaning procedures...............43
2-4.2 Aluminum metal cleaning processes..........44
2-4.3 Preparations of TiO2 thin films............44
2-4.4 PMA procedure..............................44
2-5 Characterization.............................45
2-5.1 Physical characteristics...................45
2-5.2 Chemical characteristics...................45
2-5.3 Electrical characteristics.................46
References.........................................58

CHAPTER 3..........................................59
Results and Discussion.............................59
3-1 Improvement of electrical characteristics of TiO2 films by PMA.......................................59
3-2 Leakage current density of O2-annealed TiO2 films as a function of PMA temperature......................60
3-3 Mechanisms of leakage current................62
3-3.1 Frenkel-Poole plots for as-grown TiO2 films...62
3-3.2 Space-charge limited plots for O2-ammealed TiO2 films..............................................62
3-3.3 Schottky emission plots of TiO2 films with PMA treatment..........................................63
3-4 Hydrogen depth profiles by SIMS..............63
3-5 C-V characteristics of O2-annealed TiO2 films as a function of PMA temperature........................64
3-6 The effect of PMA treatment on as-grown TiO2 films ..........................................66
References.........................................90

CHAPTER 4..........................................92
Conclusions........................................92

List of Figures
Figure 1-1~1-13...............................14~26
Figure 2-1~2-6 ...............................51~56
Figure 3-1~3-14...............................69~89

List of Tables
Table 1-1~1-3.................................27~29

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