本論文主要經由對奈米薄膜不穩除潤過程的精細觀察，量測共軛高分子薄膜內部的分子鏈反彈應力(molecular recoiling stress)，並據以探究高分子從溶液旋塗成固態薄膜的演變與分子堆積情形。本研究
所使用的共軛高分子為(poly[2-methoxy-5-((2’-ethylhexyl)oxy)-1,4-phenylenevinylene]) MEH-PPV，並輔以非共軛結構之高分子聚苯乙烯(polystyrene，PS)。我們經由量測奈米薄膜除潤時，在初期孔洞邊緣的應力釋放，以及在複層結構時對彈性基材的彈性形變，發現共軛高分子薄膜有較小的分子應力，此可能與硬桿型分子結構所具有較長的分子堅持長度（Persistence length）和較小的分子亂度有關。此外，在旋塗形成薄膜時，共軛高分子由於硬桿結構，較不易形成阻礙溶劑逸散的表皮層(skin layer)，因此，其分子應力對薄膜厚度，呈現單一的指數下降現象，而非一般非共軛高分子的雙指數下降行為。同時，共軛高分子奈米薄膜在旋塗基材寬約2nm的介面層，也有遠較非共軛高分子為小的堆積密度(約為十分之一)，此應與旋塗成形時，溶劑揮發造成的分子反彈力較小有關。最後，由於高分子強大的聲子-電子交互作用(electron-phonon coupling)，共軛高分子的光電發光效率其實與分子鏈段應力(Segmental stress)密切相關，此薄膜成形時所產生的殘留應力，與高分子光電元件的性能密切相關。

The thesis aims to measure the molecular stresses operative in conjugated polymer molecules and explore their packing in the ultrathin films prepared by spin coating. The conjugated polymer MEH-PPV (poly[2-methoxy-5-((2’-ethylhexyl)oxy)-1,4-phenylenevinylene]) was used as the model polymer in comparison to the non-conjugated polymer polystyrene (PS). The molecular stresses were determined from the thin film instability of dewetting, by measuring the stress release at the edge of an incipient hole or the depression in the soft elastic substrate underneath a dewetting hole. The molecular stresses of the conjugated polymer confined in thin films were found substantially smaller than those of PS. The observation is attributed to the rigid-rod molecular structure that exhibits a longer persistence length and hence a smaller entropy variation for the transition of the molecules from solute to solid film. In addition, the local mass density in the thin (~2nm) interfacial layer next to the substrate was found to be only one tenth of that of PS, believably resulted from the smaller molecular recoiling forces during solvent evaporation. Moreover, in contrast to the double-exponential behavior of flexible-chain polymers such as PS, the molecular stress demonstrated a single exponential decay with film thickness, indicating the absence of skin layer during the rapid solidification of spin coating, which is also attributed to the rigid-rod structure that allows easier passing of the solvent molecules. Since the optoelectronic quantum efficiencies are highly dependent on the segmental stress due to the robust electron-phonon interactions of the linear chains, good control over the residual stress of thin conjugated polymer films plays a fundamental role for the development of polymer-based devices.

第一章 簡介 16
第二章 文獻回顧 18
2-1 高分子之相關物理性質介紹 18
2-1.1 高分子鏈的分子組態 18
2-1.2 高分子溶液的交纏濃度(C*) 19
2-2 旋轉塗佈過程中分子鏈受形變過程 21
2-3 高分子薄膜除潤現象 23
2-3.1除潤現象的發生機制 24
2-3.2 Nucleation dewetting 26
2-3.3 Spinodal dewetting 27
2-4 高分子超薄膜的殘留應力 28
2-5 MEH-PPV共軛高分子 32
2-5.1 MEH-PPV分子組態及其特性 33
2-5.2 MEH-PPV共軛高分子的光電效率 35
2-5.3 MEH-PPV共軛高分子的熱退火 37
2-5.4 MEH-PPV共軛高分子的除潤現象 39
第三章 實驗方法 41
3-1 實驗材料 41
3-1.1 高分子材料 41
3-1.2 基材 42
3-2 實驗流程 44
3-2.1 薄膜製備 44
3-2.2 基材製備 45
3-2.3 熱除潤退火實驗 46
3-3 實驗儀器 47
3-3.1 光學顯微鏡 (Optical microscopy) 47
3-3.2 原子力顯微鏡 (Atomic force microscopy) 48
3-3.3 螢光光譜儀 (Photoluminescence spectrometer) 50
3-3.4 低掠角X-ray反射率(X-Ray reflectivity) 51
第四章 結果與討論 57
4-1 矽晶片上的分子鏈反應力量測方式 57
4-2 矽膠(Silicon rubber)上雙層膜除潤 63
4-2.1 柔軟高分子PS薄膜熱退火除潤實驗 63
4-2.2 共軛高分子MEH-PPV薄膜 69
4-3 Spinodal Dewetting 74
4-3.1 分子鏈反彈應力計算方式 74
4-3.2 分子量效應 79
4-4 MEH-PPV與PS之分子鏈反彈應力 82
4-4.1 高分子鏈受形變的過程對分子鏈反彈應力的影響 83
4-4.2 高分子鏈結構對分子鏈反彈應力的影響 90
4-4.3 分子鏈反彈應力對Persistence length的關係 96
4-5 共軛高分子MEH-PPV光致發光 98
4-5.1 稀釋效應 98
4-5.2 基材效應 99
4-5.3 分子鏈反彈應力對共軛高分子光致發光的影響 102
第五章 結論 107
參考文獻 109
附錄 114

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