本文係以分子動力學模擬聚甲基丙烯酸甲酯(poly(methyl Methacrylate), PMMA）製成高分子薄膜，研究薄膜在金基板上之結構型態與特性。首先，由甲基丙烯酸薄膜建構於金基板之模型，可觀察到在其兩物質交界面處受到金基板影響，具有較緊密堆積之分子結構呈現。此外，並研究薄膜於不同溫度下之結構與材料特性。可觀察到溫度升高時，在交界面處之分子薄膜型態會較低溫時鬆散。此外，藉由應力計算、表面張力(surface tension)、平均勢能(average potential energy)、形成能(formation energy)與秩序參數(orientation parameter)等參數研究何為其影響之因素。本文為了解甲基丙烯酸薄膜在其兩物質交界面處之機械性質，進而建構奈米壓痕系統，對甲基丙烯酸甲酯薄膜於不同厚度具有的機械性質與其微結構變化進行分析探討。另外，為研究鏈長效應對於此高分子薄膜結構之影響，建構相同組態不同鏈長的高分子薄膜模型，可觀察到短鏈之高分子在兩物質之交界面處有較緊密堆積的結構，而長鏈則無此特性存在。在此藉由平均-平方迴旋半徑等參數對此差異做分析探討。

Molecular dynamics simulations is performed to investigate the structural properties of the PMMA (poly(methyl methacrylate)) thin film on an Au (111) surface. According to model the MMA (methyl methacrylate) thin film on an Au (111) surface, we found that there is a significant effect on the density profile near the interface between the thin film and Au substrate. Moreover, the density clearly decreases in this region as the temperature increases. Next, we calculated and examined the relationships among the stress, surface tension, average potential energy, orientation, and formation energy. In order to investigate the material properties of MMA nano-thin films of different thicknesses on the Au (111) surface, the simulation for the nano-indentation process is used to obtain the material properties of MMA nano-thin films. And the deformation mechan- ism of the MMA thin films during the course of the indentation is also discussed in this study, completely.
Furthermore, Molecular dynamics simulations were employed to investigate chain-length effect on conformations of methyl methacrylate (MMA)-oligomer thin films on an Au (111) substrate. For short chain films, there is a sharp peak in the density profile of the MMA monomers for the adsorption region and the thin films exhibit a flattened conformation in the adsorption and the surface regions. For long chain films, however, there is no sharp peak in the whole density profiles and a snake-like conformation appears in the adsorption region, which shrinks and convolutes gradually in the bulk region and even more in the surface region of the thin film.

第1 章 緒論 1
1.1 研究動機與目的 1
1.2 聚甲基丙烯酸甲酯簡介 5
1.3 文獻回顧. 8
1.4 本文架構 11
第2 章 分子動力學理論方法 12
2.1 運動方程式 13
2.2 積分法則 14
2.3 勢能函數 15
2.3.1 聚甲基丙烯酸甲酯分子之作用勢能 15
2.3.2 金原子間作用勢能 18
2.3.3 聚甲基丙烯酸甲酯與金原子間之作用勢能 20
2.4 時間步階選取 21
2.5 溫度修正 22
2.5.1 反正規化法(Rescaling method) 22
2.5.2 諾斯-胡佛恆溫法(Nosé-Hoover thermostat) 23
2.6 週期性邊界的處理 25
第3 章 分子動力學數值方法 26
3.1 鄰近原子表列數值方法 26
3.1.1 截斷半徑法(Cut-off method) 26
3.1.2 維理表列法(Verlet List) 27
3.1.3 巢室表列法(Cell Link) 29
3.1.4 維理表列結合巢室表列法 31
3.2 物理參數與無因次化 33
3.3 模擬流程圖 35
第4 章 結果分析與討論 36
4.1 溫度對於甲基丙烯酸甲酯分子於AU(111)基板上之影響 36
4.1.1 物理模型之建構 36
4.1.2 密度與自由能 40
4.1.3 應力與表面張力 41
4.1.4 平均勢能與形成能 43
4.1.5 秩序參數 44
4.2 不同鏈長之間規組態聚甲基丙烯酸甲酯於AU(111)基板上之型態分佈 53
4.2.1 物理模型之建構 53
4.2.2 不同鏈長之型態分析 56
4.3 甲基丙烯酸甲酯薄膜之機械性質分析 64
4.3.1 物理模型之建構 64
4.3.2 不同厚度之MMA 分子薄膜密度分佈型態 67
4.3.3 不同厚度之MMA 分子薄膜壓痕行為探討 67
第5 章 結論與建議 78
5.1 結論 78
5.2 建議與未來展望 81

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