本研究利用自行架設的紫外光輔助原子層沉積 (UVALD)系統以及使用Co(CO)3NO當作鈷前驅物成功合成厚度僅僅4奈米而且具有結晶性的金屬鈷薄膜。紫外光輔助的機制主要有： (1) 藉由提供足夠高的能量打斷前驅物的配位基 (ligands)，不僅能夠促使產生高活性的懸空鍵 (dangling bonds)以利於產生化學吸附的特性；(2) 可以避免前驅物龐大的體積而產生屏蔽效應 (screen effect)，以至於加速沉積速率緩慢的困境以及(3)具有降低製程溫度的優點。
結果顯示製程溫度落於190-200 °C時表現出ALD window行為以及沉積速率高達5.1 Å/cycle。在經過250度退火後，對於鈷薄膜結晶性之研究中得到XRD顯示於薄膜厚度為50 nm±5nm的樣品上觀察到二倍角 (2θ)位於44.6°處有一個主要的峰值 (111)，代表此薄膜符合面心立方 (空間群族為Fm3m (225))而且平均的結晶大小為36 nm，占了薄膜厚度的76 \%。另外，為了確定低溫合成以及退火後的鈷薄膜含量，XPS結果顯示鈷元素占了整個薄膜含量的98.2 \%、氧約為1\%，而碳以及氮含量皆小於1\%．由此可知在經過200度沉積以及250度退火後的金屬鈷薄膜具有純度相當高的鈷含量。此外，奈米薄膜表面粗糙度是對於原子從沉積的一項重要指標，由AFM結果得知鈷金屬膜的表面粗糙度於厚度十奈米時，表面粗糙是1.0 nm的表面粗糙度，而於厚度為4奈米時，表面粗糙是0.6 nm。最後對於電特性的量測結果，電阻率最佳可以優化至10 μΩ∙cm。
選擇氮化矽前驅物過程中，總共嘗試三種氮化矽前驅物，並通過UVALD沉積氮化矽薄膜。最好的前驅體是C$ _{8} $H$ _{20} $N$ _{2} $Si，它可以沉積無碳的超薄膜，並且它可以通過保形和無間隙填充沉積在溝槽結構上。

Ultrathin, flat, and high-purity Co films have been grown on TaN/Si substrates using UV-assisted atomic layer deposition with cobalt tricarbonyl nitrosyl [Co(CO)3NO] as the Co precursor. Under an optimized condition, the growth rate was determined to be 5.1 Å/cycle within a growth window of 190–200 °C. The root-mean-square roughness of the deposited films is ~0.6 nm, and the resistivity can be as low as 1×10-5 ohm-cm. The greatly reduced resistivity as compared with previously reported is attributed to the flatter surface and higher purity of the films, indicating that the UV light effectively reduces impurity contaminants stemming from the ligand residues.

Three kinds of silicon nitride precursors are used to deposit SiNx thin film by UVALD. The best precursor is C8H20N2 $Si, which can deposit the ultra-thin film with carbon-free. And it can deposit on trench structure with conformal and gap-fill.

中文摘要..........................................................I
英文摘要........................................................III
致謝............................................................IV
Publication List.............................................. ..V
目錄.............................................................IX
第一章 簡介...................................................... 1
1.1 薄膜沉積技術之發展 . . . . . . . . . . . . . . . . . . . . . . 1
1.2 吸附行為 . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 薄膜成長之模式 . . . . . . . . . . . .. . . . . . . . . . . . 13
1.4 氣體吸附法 (BET) . . . . . . . . . . . . . . . . . . . . . . 17
1.5 摩爾定律 . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.6 論文之動機與貢獻. . . . . . . . . . . . . . . . . . . . . . . 25
第二章 原子層沉積技術之工作原理................................... 30
2.1 原子層沉積技術的基本特徵與應用.. . . . . . . . . . . . . . . . 30
2.1.1 原子層沉積技術之機制........................................32
2.1.1.1 前驅物飽和以及自我限制之反應.................. . . . . . . 33
2.1.1.2 原子層沉積之操作範圍............... . . . . . . . . . . . 34
2.1.1.3 前驅物之計量 ......... . . . . . . . . . . . . . . . . . 36
2.1.2 原子層沉積的優勢與限制......................................38
2.2 原子層沉積之化學吸附機制......................................39
2.3 遮蔽效應 . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.4 前驅物化學 . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.4.1 圈物之介紹.......... . . . . . . . . . . . . . . . . . . . 43
2.4.2 原子層沉積反應物種類..... . . . . . . . . . . . . . . . . . 46
2.4.3 氫氣轉移...... . . . . . . . . . . . . . . . . . . . . . . 46
第三章 紫外光輔助原子層沉積系統之設計與架設......................... 49
3.1 自行架設之紫外光輔助原子層沉積系統 . . .... . . . . . . . . . . 49
3.1.1 系統總覽 . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.1.2 幫浦抽氣之計算..... . . . . . . . . . . . . . . . . . . . . 54
3.1.3 前驅物以及反應物之傳輸........ . . . . . . . . . . . . . . . 59
第四章 利用原子層沉積系統沉積鈷金屬薄膜............................. 65
4.1 銅金屬連線技術之瓶頸 . . . . . . . . . . . . . . . . . . . . . 65
4.2 鈷前驅物之介紹. . . . . . . . . . . . . . . . . . . . . . . . 66
4.2.1 Co(CO)3NO 前驅物之介紹 ...... . . . . . . . . . . . . . . . 67
4.2.2 Co(CO)3NO流量... . . . . . . . . . . . . . . . . . . . . . 68
4.3 利用原子層沉積技術沉積鈷薄膜之示意圖..... . . . . . . . . . . . 68
4.4 沉積鈷薄膜之行為分析 . . . . . . . . . . . . . . . . . . . . . 69
4.4.1 原子層沉積方法之操作範圍........ . . . . . . . . . . . . . . 71
4.5 X-射線光電子光譜之分析 . . . . . . . . . . . . . . . . . . . . 75
4.6 X-射線繞射之分析. . . . . . . . . . . . . . . . . . . . . . . 76
4.7 表面粗糙度之分析. . . . . . . . . . . . . . . . . . . . . . . 78
4.8 退火隊鈷薄膜之電阻率影響 . . . . . . . . . . . . . . . . . . . 79
4.9 由下而上之沉積 . . . . . . . . . . . . . . . . . . . . . . . 85
4.10 ่結論. . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
第五章 利用原子層沉積系統沉積氮化矽薄膜............................. 92
5.1 前言.. . . . . . . . . . . . . . . . . . . . . . . . . . ....92
5.2 前驅物介紹. . . . . . . . . . . . . . . . . . . . . . . . . .95
5.3 Si(C4H7)4 .. . . . . . . . . . . . . . . . . . . . . . . . .96
5.4 CH2=CHCH2NH[Si(CH3)3]2 . . . . . . . . . . . . . . . . . . 101
5.5 C8H20N2Si. . . . . . . . . . . . . . . . . . . . . . . . . 105
5.6 氮化矽薄膜之保形以及填洞能力..................................112
5.7 ่結論. . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
第六章 未來與展望................................................119
附錄一：紫外光的光子數之計算...................................... 121
附錄二：成核點之間之距離計算...................................... 122
附錄三：估計在表面處於紫外光照射之後，能夠產生多少懸空鍵............. 123
附錄四：固態表面沉積之行為....................................... 124
附錄五：利用 Scherrer 方程式計算晶格大小.......................... 126
附錄六：比較三種不同電阻率計算之模型.............................. 127
參考文獻....................................................... 129

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