臺灣博碩士論文加值系統

本論文係利用金屬誘發再結晶(Metal-Induced Crystallization, MIC)法製作多晶矽鍺(poly-Si1-xGex)薄膜，因此，本研究使用奈米金(Au)薄膜誘發非晶矽鍺(a-Si1-xGex:H)薄膜，探討不同退火時間及退火溫度對誘發之多晶矽鍺(poly-Si1-xGex)薄膜其微結構與電性之影響。首先在矽基板上以超高真空化學氣相沈積系統(UHVCVD)系統沉積300nm膜厚之非晶矽鍺薄膜(a-Si1-xGex)，然後將50nm膜厚之奈米金薄膜鍍覆到試片上，最後施以不同的退火條件處理，製作出多晶矽鍺薄膜。
場發射式電子顯微鏡（Field Emission Scanning Electron Microscope）乃用以觀察多晶矽鍺薄膜之表面結構，並利用能量散佈光譜儀(Energy Dispersive Spectrometer)分析確認表面各種形貌之成分。原子力顯微鏡(Atomic Force Microscope)用以分析多晶矽鍺薄膜之表面粗糙度。X光繞射分析儀(X-Ray Thin Film Diffractometer)用以分析多晶矽鍺薄膜之結晶性，並確認多晶矽鍺薄膜的結晶面，微拉曼光譜分析儀(Micro Raman Spectrometer)與傅利葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer)用以驗證多晶矽鍺之鍵結，而多晶矽鍺薄膜之載子移動率則由霍爾（Hall Measuremnet）量測儀測得。
本研究發現，藉由SEM與拉曼的結果互相比對得知，該多晶矽鍺薄膜在退火溫度提高且退火時間增加時，矽-鍺鍵之間的形成熱較低，使鍺原子會析出於薄膜表面，並於薄膜內部進行矽-矽鍵結。其中，析出於薄膜表面上之鍺原子將形成鍺-鍺鍵結並形成結晶型態。該矽-鍺鍵於不同的退火溫度與時間的製程下，將形成鍵結分離與再結合的情形。由AFM分析可知該多晶矽鍺薄膜在退火溫度為500℃時，表面粗糙度最大，其原因為結晶形成的晶介面所造成。利用X-Ray分析多晶矽鍺薄膜可得知該矽鍺薄膜結晶方向大部分為矽鍺(311)、矽鍺(111)與(220)結晶面。然而，隨著退火溫度與時間的提高，結晶方向只剩下矽鍺(311)結晶面，其原因為鍺原子析出於薄膜表面形成結晶。雖然，該矽鍺結晶變弱，但藉由調整退火溫度與時間的參數，可以使鍺結晶變好。藉由X-Ray的分析可估算出其結晶大小，因此，當退火溫度為400℃退火時間為5小時之多晶矽鍺薄膜則具有最大的結晶尺寸。由電性實驗可得知利用奈米金薄膜誘發非晶矽鍺薄膜形成多晶矽鍺薄膜之載子移動率最高可達到554cm2/V-s，為多晶矽薄膜的7.9倍。

In this thesis, poly-Si1-xGex films are fabricated by metal-induced crystallization (MIC) process for the application of optoelectronic device. MIC process means that a-Si1-xGex:H films are induced and crystallized by nano gold thin film in different processes. The electrical, structural, and crystallinity composition characterization were investigated by using Profile meter, Raman spectroscopy (TRIAX550), Scanning electron microscopy (HITACHI S-4800) and Hall measurement (ACC-HL5500PC) measurements. Ultra high vacuum chemical vapor deposit system is used to deposit a-Si1-xGex:H of 300nm-thick on silicon wafer first, and then the nano gold film of 50nm-thick is plated on the sample. Finally, the poly-Si1-xGex films with various crystalline sizes are obtained in different annealing processes.
The surface observations of the fabricated samples are observed by the Field emission scanning electron microscope (FE-SEM), and the samples surfaces components are confirmed by Energy dispersive spectrometer (EDS). The roughness and surface morphology of film surface are obtained by Atomic force microscope (AFM). The crystallization of samples are analyzed by X-Ray. The bonds of poly-Si1-xGex are verified by Micro Raman Spectrometer and Fourier Transform Infrared Spectrometer. Finally, the carrier mobility of Poly-Si1-xGex:H films can be measured by Hall measurement .
In this study, due to the lower heat of formation between Si and Ge, the Ge atoms are separated out of the Si-Ge thin films as the annealing time and temperature increased. The Si-Si bonds are also formed in the inside of thin films, which are discussed by the results of SEM images and Raman Shift. Then, the Ge atoms are formed bonds between Ge and Ge and crystallized on the surface of films. From the results of experiments, the Si-Ge bonds separated and combined together at different process are discussed clearly. The biggest roughness of film surface is analyzed by AFM and discovered at the annealing temperature of 500℃, which is caused by the grain boundary of crystallized thin films. X-Ray analysis is performed on these samples in order to confirm that the samples after annealing and etching are crystallized Si-Ge thin films. It is found the peaks correspond to Si-Ge(111), Si-Ge(311) and Si-Ge(220), which proves the crystallization of a-Si-Ge:H. However, it is left over one peak of Si-Ge(311) as the annealing time and temperature increased, which is caused by the Ge atoms are separated out of the Si-Ge thin films and crystallized at the surface. Though the Si-Ge bonds are weak, we can get the stronger Ge-Ge bonds by tunable parameters of annealing time and temperature. When the annealing time is 5 hours, the crystallization size attained to the biggest value is calculated by Scherrer equation. It is mentioning that the best value of mobility is almost reached to the 554 cm2/V-s which is eight times of poly-Si film.

目錄
中文摘要 I
Abstract III
誌謝 Ⅴ
目錄 Ⅶ
表目錄 XI
圖目錄 XI
第一章 序論 1
1-1 研究背景 1
1-2 研究動機 4
1-3 論文架構 5
第二章 基本理論 6
2-1 多晶矽薄膜製作技術 6
2-2-1 直接沉積型 6
2-2-2 再結晶型 8
2-2 金屬誘發結晶之原理 12
第三章 實驗步驟與儀器 15
3-1 實驗步驟 15
3-2 製程設備與製程參數 19
3-2-1 濕式蝕刻清洗系統 19
3-2-2 矽鍺超高真空化學氣相沈積系統 19
3-2-3 金屬濺鍍系統 20
3-2-4 退火爐管系統 20
3-3分析儀器 21
3-3-1 場放射型掃瞄式電子顯微鏡 21
3-2-2 X光繞射分析 22
3-2-3 原子力顯微鏡 23
3-2-4 拉曼光譜分析儀 23
3-2-5 傅利葉轉換紅外線光譜儀 24
3-2-6 霍爾量測 24
第四章 實驗結果與討論 25
4-1奈米金薄膜誘發多晶矽鍺薄膜之分析探討 26
4-1-1 製程參數 26
4-1-2 FE-SEM對矽鍺薄膜表面分析 26
4-1-3 EDS對矽鍺薄膜表面元素分析 37
4-1-4 AFM原子力顯微鏡 39
4-1-5 X-Ray繞射分析儀 48
4-1-6 Raman spectra結晶分析 52
4-1-7 FTIR 鍵結分析 56
4-1-8 電性之分析 59
第五章 結論 60
參考文獻 62
自傳 67
附錄一 68
表目錄
表 3- 1 RCA Cleaning準製程 16
表 3- 2 高溫爐管退火參數 17
表 3- 3 金蝕刻液參數表 17
圖目錄
圖 2- 1準分子雷射再結晶機制示意圖 10
圖 2- 2金與矽成長機制示意圖 14
圖 3- 1本實驗製程流程圖 15
圖 3- 2本實驗分析流程圖 18
圖 3- 3製程時間設定示意圖 21
圖 4- 1退火溫度400℃，退火溫度1小時之SEM圖 28
圖 4- 2退火溫度400℃，退火溫度3小時之SEM圖 28
圖 4- 3退火溫度400℃，退火溫度5小時之SEM圖 29
圖 4- 4退火溫度400℃，退火溫度8小時之SEM圖 29
圖 4- 5退火溫度400℃，退火溫度10小時之SEM圖 30
圖 4- 6非退火溫度500℃，退火溫度1小時之SEM圖 31
圖 4- 7退火溫度500℃，退火溫度3小時之SEM圖 32
圖 4- 8退火溫度500℃，退火溫度5小時之SEM圖 32
圖 4- 9退火溫度500℃，退火溫度8小時之SEM圖 33
圖 4- 10退火溫度500℃，退火溫度10小時之SEM圖 33
圖 4- 11退火溫度600℃，退火溫度1小時之SEM圖 35
圖 4- 12退火溫度600℃，退火溫度3小時之SEM圖 35
圖 4- 13退火溫度600℃，退火溫度5小時之SEM圖 36
圖 4- 14退火溫度600℃，退火溫度8小時之SEM圖 36
圖 4- 15退火溫度600℃，退火溫度10小時之SEM圖 37
圖 4- 16矽鍺薄膜重量百分比之關係圖 39
圖 4- 17退火溫度400℃，退火溫度1小時之AFM圖 40
圖 4- 18退火溫度400℃，退火溫度3小時之AFM圖 40
圖 4- 19退火溫度400℃，退火溫度5小時之AFM圖 41
圖 4- 20退火溫度400℃，退火溫度8小時之AFM圖 41
圖 4- 21退火溫度400℃，退火溫度10小時之AFM圖 42
圖 4- 22退火溫度500℃，退火溫度1小時之AFM圖 42
圖 4- 23退火溫度500℃，退火溫度3小時之AFM圖 43
圖 4- 24退火溫度500℃，退火溫度5小時之AFM圖 43
圖 4- 25退火溫度500℃，退火溫度8小時之AFM圖 44
圖 4- 26退火溫度500℃，退火溫度10小時之AFM圖 44
圖 4- 27退火溫度600℃，退火溫度1小時之AFM圖 45
圖 4- 28退火溫度600℃，退火溫度3小時之AFM圖 45
圖 4- 29退火溫度600℃，退火溫度5小時之AFM圖 46
圖 4- 30退火溫度600℃，退火溫度8小時之AFM圖 46
圖 4- 31退火溫度600℃，退火溫度10小時之AFM圖 47
圖 4- 32 AFM之表面粗糙度表示圖 48
圖 4- 33退火溫度400℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之X-Ray繞射圖 49
圖 4- 34退火溫度500℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之X-Ray繞射圖 50
圖 4- 35退火溫度600℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之X-Ray繞射圖 50
圖 4- 36矽鍺薄膜之晶粒結晶分析圖 51
圖 4- 37退火溫度400℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之拉曼圖 53
圖 4- 38退火溫度500℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之拉曼圖 54
圖 4- 39退火溫度600℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之拉曼圖 54
圖 4- 40多晶矽鍺薄膜於Si-Ge鍵之拉曼位移 55
圖 4- 41多晶矽鍺薄膜於Ge-Ge鍵之拉曼位移 56
圖 4- 42退火溫度400℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之FTIR分析圖 57

圖 4- 43退火溫度500℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之FTIR分析圖 58
圖 4- 44退火溫度600℃，退火時間分別為1小時、3小時、5小時、8小時、10小時之FTIR分析圖 58
圖 4- 45多晶矽鍺薄膜於400℃、500℃和600℃分別為1小時、3小時、5小時、8小時、10小時之載子移動率 59

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