本研究主要是利用奈米壓痕的技術量測鎳/矽薄膜的機械性質並探討奈米壓痕深度及加熱溫度對鎳/矽薄膜其微觀機械性質與壓痕影響區之鎳矽化合物形成之影響。藉由一快速且有效率搜尋微小奈米壓痕之陣列定位技術，可準確確認壓痕之位置。實驗利用半導體製程於 (100) 方向之矽晶圓上製作一100 nm厚度之鎳薄膜，選取並切割實驗試片後，以奈米壓痕系統分別對試片進行500 nm及800 nm深度之奈米壓痕試驗，以瞭解壓痕深度對微觀機械性質之影響。再將經奈米壓痕試驗之試片分別加熱至200℃、300℃、500℃及800℃，並持溫二分鐘，藉以比較未加熱及不同加熱條件下，其微觀組織之變化及壓痕影響區之鎳矽化合物形成之特徵與機制。爾後，透過所發展之定位陣列技術定位出原有之奈米壓痕位置，並利用聚焦離子束顯微鏡切割出穿透式電子顯微鏡之觀測試片。
巨觀機械性質的量測結果顯示，硬度與楊氏模數曲線受壓痕尺寸效應與表面粗糙度 (壓痕深度小於10 nm) 及基材效應 (壓痕深度大於膜厚10%) 所影響，薄膜硬度值約為 GPa，楊氏模數約為 GPa。微觀結果顯示，鎳矽薄膜及壓痕影響區內鎳矽化合物之形成受奈米壓痕及加熱溫度之影響，在壓痕器正下方之高應力塑性變形區造成原子重新排列，矽基材由原本diamond cubic結構轉變為Si-III與Si-XII混合的結構，隨著加熱溫度的增加，鎳原子大量往壓痕區擴散並形成鎳矽化合物，在200℃、300℃及800℃下分別形成 、 及 ，此結果說明奈米壓痕改變了薄膜與基材間之表面能量、內應力及原子排列，經外加溫度之作用，加速鎳、矽界面原子擴散，整合出局部區域之低電阻的鎳矽化合物。

The study investigates the nano-mechanical properties of Ni/Si thin film using a nanoindentation technique. The effects of indentation depth and the annealing temperature on the microstructural evolution are also evaluated. The thin film is prepared by depositing a Ni layer with thickness of 100 nm on a Si(100) substrate using an evaporation deposition technique. The fabricated film is indented to maximum depths of 500 nm or 800 nm, and selected specimens are then annealed at temperatures of 200℃, 300℃, 500℃ or 800℃ for 2 min. The indented position is accurately identified using a proprietary position array system, and TEM specimens are extracted by the focused ion beam microscope technique.
The overall tendencies of the hardness and Young’s modulus curves are governed by the indentation size effect and surface roughness for indentation depths of less than 10 nm, and by the substrate effect for indentation depths greater than 10% of the thin film thickness. The hardness and Young’s modulus are measured as GPa and GPa respectively. The microstructural observations reveal that nanoindentation induces an atoms reorganization, and results in the formation of high-stress plastic deformation regions beneath the indenter. The microstructure of indentation affected zone of silicon substrate transfers from diamond cubic structure to a mixed structure of Si-III and Si-XII. However, the heating temperature has a significant effect on the formation of nickel silicides phase. The diffusion ability of Ni atoms is enhanced as the heating temperature is increased. The nickel silicides of , and are found at 200℃, 300℃ and 800℃, respectively. The results indicate that nanoindentation causes a significant change in the surface energy, internal stress state and atomic arrangements of the nickel thin film and silicon substrate. The annealing process activates atomic diffusion in the interface between the thin film and substrate, and this accelerates the formation of nickel silicides phase, and results in a low resistance zone.

中文摘要 I
ABSTRACT II
誌謝 IV
總目錄 V
圖目錄 VIII
第一章 前言 1
第二章 理論與文獻回顧 4
2-1金屬矽化物 4
2-1-1金屬矽化物的介紹 4
2-1-2金屬矽化合物特性與形成機制 4
2-1-3鎳矽化合物之應用 5
2-2 奈米壓痕理論 6
2-2-1薄膜機械性質之量測 6
2-2-2初始卸載勁度與接觸面積之量測 8
2-2-3連續勁度量測法 10
2-3 奈米壓痕實驗前的校正 11
2-3-1五點定位校正 12
2-3-3熱漂移校正 12
2-4 影響薄膜量測之因素 13
2-4-1壓痕尺寸效應 (Indentation Size Effect, ISE) 13
2-4-2表面粗糙效應 (Surface roughness) 13
2-4-3基材效應 (Substrate effect) 14
2-4-4擠出和沉陷效應 (Pile-up & sink-in effect) 14
2-5 聚焦離子束顯微技術 15
第三章 實驗方法與步驟 22
3-1實驗流程 22
3-2實驗儀器與設備 22
3-2-1熱蒸鍍機 (Thermal coater) 23
3-2-2電子束微影光罩製作系統 23
(Electron beamlithography system, EBL) 23
3-2-3奈米三維量測儀及奈米薄膜材料試驗機 (Nano-indenter XP) 24
3-2-4快速退火爐 (Rapid Thermal Annealing, RTA) 25
3-2-5聚焦離子束顯微鏡 25
(Focused Ion Beam, FIB/SEM) 25
3-2-6高解析穿透式電子顯微鏡 (High Resolution Transmission Electron Microscope, HR-TEM) 26
3-2-7拉曼光譜儀 (Raman Spectroscopy) 26
3-3試片製備 27
3-3-1 蒸鍍材料之性質與試片製備 27
3-3-2 微影蝕刻製程 28
3-4實驗方法與步驟 29
3-4-1奈米壓痕試驗 29
3-4-2對試片進行不同溫度的退火處理 29
3-4-3微觀結構的觀察 30
第四章 實驗結果與討論 39
4-1 薄膜機械性質之討論 39
4-1-2 壓痕深度與硬度曲線之分析 39
4-1-3 壓痕深度與楊氏模數曲線之分析 40
4-2 壓痕表面形貌之討論 40
4-2-1 壓痕深度500 nm退火處理前後之壓痕表面形貌分析 41
4-2-2 壓痕深度800 nm退火處理前後之壓痕表面形貌分析 41
4-2-3 不同壓痕深度下退火處理前後之壓痕表面形貌分析 42
4-3 壓痕剖面形貌之討論 43
4-3-1 壓痕深度500 nm退火處理前後之壓痕剖面形貌分析 43
4-3-2 壓痕深度800 nm退火處理前後之壓痕剖面形貌分析 45
4-3-3 不同壓痕深度下退火處理前後之壓痕剖面形貌分析 47
4-4 壓痕區拉曼光譜之討論 48
第五章 結論 76
參考文獻 78
自述 86

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