由本實驗室黃于哲學長最近的研究[1]，將高熵的想法導入高分子中，提出「高熵高分子」的概念。研究中發現：當混摻多種高分子時，高熵效應與分子鏈的空間阻隔效應，可抑制高分子的相分離。基於此一結果，本論文進一步探討高熵高分子的殘留應力、相分離的行為，並由動力學與熱力學兩個面向去探討高熵高分子薄膜中，不同種類高分子鏈彼此間的交互作用，最後藉由機械拉伸來觀察高熵高分子的機械穩定度。
使用旋轉塗佈法(spin coating)可快速且方便的製備出高分子薄膜，但其過程中溶劑快速揮發，分子鏈在極短的時間內被拘束在極小的空間中，分子鏈受到拉扯產生殘留應變並re-entanglement在一起，因此產生殘留應力，使固態薄膜中的分子鏈處於非平衡態。由於高熵高分子薄膜表面並不平整，我們無法以傳統藉由計算除潤孔洞成長的方式計算殘留應力，需另尋他法。
而我們將0.1% MEH-PPV加入不同厚度的PS薄膜後，發現其發光強度正比於殘留應力，因此我們由PL強度可方便量測高熵高分子的殘留應力；但MEH-PPV混摻在各種高分子後，其發光波長會有些微的差異，尤其是在聚異戊二烯(PIP)中，其光譜紅移嚴重。本實驗則假設PL只受殘留應力影響，不受光譜紅移、藍移或溶解度參數影響，在此前提下以PL強度來量測殘留應力。
而我們藉由PL強度來量測多成分高分子薄膜後發現：隨著混摻的高分子數量增加，殘留應力也隨之下降，表示高熵高分子在旋轉塗佈成膜時，其分子鏈狀態比單成分高分子薄膜更接近平衡態，而我們將藉由動力學與熱力學兩個角度來探討此現象。
在動力學上，高熵高分子在旋轉塗佈成膜時，分子鏈re-entanglement的狀況和單成分高分子薄膜有很大的差異，在多成分的情形下，種類相異的高分子鏈彼此會相互排斥，會抵消掉部分溶劑快速揮發時拉扯高分子鏈的力量，因此多成分高分子薄膜的entanglement的程度較低；殘留應力也較單成分高分子薄膜低，高分子鏈較接近平衡態。而從熱力學的觀點來看，我們可以計算多成分高熵高分子在混摻時的自由能、混和熵變化；當高分子成分數量增加時，混和熵的絕對值也隨之增加，而混和熵的增加會造成自由能的降低，表示自由能隨高分子成分數量增加而下降，高熵高分子薄膜的分子鏈更接近穩定態。
最後我們將藉由溶劑退火，讓高熵高分子薄膜加入0.1% MEH-PPV後進行除潤來觀察其在橡膠態時分子鏈的運動。由於其交纏密度較低，分子鏈結構較鬆散，除潤過後分子鏈的拉扯遠小於單成分PS薄膜，作為標記物的MEH-PPV分子鏈未受強烈拉扯，因此其發光強度並沒有提升，分子鏈無法進行大規模的運動，留下大量殘留薄膜。為了近一步了解高熵高分子的鬆散結構是否會對機械性質造成影響，我們比較高分子濃度大於和小於高分子鏈交纏密度(c*)時，其高分子薄膜受拉伸後的機械強度差異。當c<c*時，高熵高分子薄膜非常脆，拉伸1%薄膜便產生破裂，但當c>c*時，高分子薄膜可以拉伸到6%才破裂，且不會產生craze，表示若我們同時增加高分子成分數量和高分子鏈交纏密度，應可得到一分子鏈穩定且機械強度強的高分子薄膜，應有其應用上的未來性與發展性。

From recently study by our laboratory, we put the idea of “high entropy” in to polymer. Study found that: if we increase the number of polymer species in blend, the de-mixing can be suppressed by high mixing entropy and a kinetic steric effect blocking. Base on this result, this thesis investigate the residual stress and phase separation behavior from high entropy polymer by kinetic and thermodynamics. At last, we observed the mechanical stability by dewetting and mechanical stretching.
Spin coating can be quickly and easily prepared in a polymer film, however, large residual stress was created in the rapid evaporation of the solvent, so the polymer chain is not at the equilibrium state. In order to measure residual stress more conveniently, we use PL to measure residual stress. After callibrition, we found the residual stress is proportional to PL intensity. Then we detected residual stress by PL intensity, we found that if we blend more species of polymer, the residual stress will decrease, it means molecular chain state of high entropy polymer is closer to equilibrium than a single component polymer film, and we will explore this phenomenon by kinetics and thermodynamics.
On kinetics view, the polymer chain re-entanglement of high entropy polymer and single component polymer are very different during the spin coating process. The different species molecular chain in high entropy polymer will repel each other, it will decrease the pulling force from the rapid solvent elapse, so the entanglement of high entropy polymer is much lower. If we mixing more species of polymer, the same polymer chain will block by different polymer chain, they can not form strong entanglement, so the residual stress will decrease with increasing polymer.
From thermodynamic perspective, we can calculate the free energy, mixing entropy of high entropy polymer. We found that when the number of polymer component increase, the mixing entropy is also increased, and the increase of mixing entropy will result free energy decrease, indicates the number of polymer component increase, the free energy decrease, polymer chain will closer to the steady state.
At last, we observed the high entropy polymer molecular chain movement by dewetting. Because of its weak entanglement, molecular chain structure is loose, molecular chain cannot be mass movement, leaving a large amount of residual film. In order to research the relationship between loose molecular chain and mechanical properties, we compare the mechanical strength from c>c* and c<c* by stretching. When c<c*, the polymer chain is lack of entanglement, the high entropy polymer film can only be stretched 1% and the film raptured. However, when c>c*, the polymer chain entangles together, the high entropy polymer film will not rapture until stretched to 6%. So, if we increase number of component and molecular chain entanglement, we will find a steady polymer chain and nice mechanical strength high entropy polymer film.

摘要 I
Abstract IV
致謝 VI
目錄 VIII
圖目錄 XI
第一章　簡介 1
第二章　文獻回顧 2
2-1 高熵高分子 2
2-2 高分子薄膜殘留應力與除潤現象 3
2-2-1 高分子薄膜的殘留應力 3
2-2-2 高分子薄膜的除潤機制 7
2-2-3 高分子薄膜吸收溶劑 Case II diffusion 10
2-2-4 高分子薄膜的溶劑退火除潤 11
2-3 共軛高分子光電特性 13
2-3-1 MEH-PPV分子組態及其特性 13
2-3-2 Exciton、Excimer、Exciplexes和Polaron pair 16
2-3-3 共軛高分子的溶劑退火除潤 17
第三章 實驗方法 21
3-1 實驗材料 21
3-1-1 非共軛高分子材料 21
3-1-2 共軛高分子 22
3-2 實驗流程 23
3-2-1 除水 23
3-2-2 薄膜製備 23
3-2-3 溶劑退火處理 24
3-2-4 高分子薄膜拉伸 25
3-3 實驗儀器 27
3-3-1 真空烘箱(vacuum drying oven) 27
3-3-2 光學顯微鏡(optical microscopy) 28
3-3-3 原子力顯微鏡(atomic force microscopy, AFM) 29
3-3-4 螢光光譜儀 32
第四章 結果與討論 34
4-1 以PL強度量測薄膜殘留應力 34
4-2 單成分與多成分高分子薄膜殘留應力 37
4-2-1 單成分高分子薄膜殘留應力 37
4-2-2 多成分高分子薄膜殘留應力 38
4-2-3 相分離與殘留應力之關係 42
4-3 高熵高分子薄膜熱力學上的穩定度 46
4-3-1 高熵高分子熱力學上的混和熵與自由能 46
4-4 高熵高分子薄膜除潤 49
4-4-1 單成分PS薄膜除潤 50
4-4-2 雙成分PS/PC薄膜除潤 54
4-4-3 三元PS/PMMA/PIP薄膜除潤 57
4-4-4 四元PS/PMMA/PC/PIP薄膜除潤 60
4-4-5 四元PS/PMMA/PVP/PIP薄膜除潤 63
4-4-6 五元PS/PMMA/PC/PVP/PIP薄膜除潤 66
4-4-7 殘留應力與殘留薄膜的關係 70
4-5 高熵高分子薄膜拉伸 73
第五章　結論 78
第六章　參考文獻 80
附錄 84

1. Yu-Jr Huang, Jien-Wei Yeh, Arnold Chang-Mou Yang, Materialia 2020, in revision
2. Reiter, G.; de Gennes, P. G., The European Physical Journal E 2001, 6, 25-28.
3. Reiter, G., Macromolecules 1994, 27, 3046-3052.
4. Reiter, G.; Hamieh, M,; Damman, P.; Sclavons, S.; Gabriele, S.; Vilmin, T.; Raphaël, A. E., Nature Materials 2005, 4, 754-758.
5. Reiter, G.; de Gennes, P. G., The European Physical Journal E 2001, 6, 25-28.
6. 張昱崙, 清華大學材料系碩士論文 2008, 拘束於旋塗奈米超薄膜內高分子團之分子力、堆積、和形變之量測與分析研究.
7. Seemann, R.; Herminghaus, S.; Jacobs, K., Physical Review Letters 2001, 86, 5534-5537.
8. Sharma, A., Langmuir 1993, 9, 861-869.
9. Sharma, A., Langmuir 1993, 9, 3580-3586.
10. Sharma, A.; Khanna, R., Physical Review Letters 1998, 81, 3463-3466.
11. Sharma, A.; Khanna, R., Journal of Chemical Physics 1999, 110, 4929.
12. Seemann. R.; Hermnghaus, S.; Jacobs, K., Journal of Physics: Condensed Matter 2001, 13, 4925.
13. Rayleigh, L., Proceeding of the London Mathematical Society 1878, 10, 4-13.
14. Reiter, G., Physical Review Letters 1992, 68, 75-78.
15. Reiter, G., Langmuir 1993, 9, 1344-1351.
16. Stange, T. G.; Evans, D. F.; Hendrickson, W. A., Langmuir 1997, 13, 4459-4465.
17. Xie, R.; Karim, A.; Douglas, J. F.; Han, C. C.; Weiss, R. A., Physical Review Letters 1998, 81, 1251-1254.
18. Alfrey Jr., T.; Gurnee, E. F.; Lloyd, W. G., Journal of Polymer Science Part C: Polymer Symposia 1966, 12, 249-261.
19. Brandrup, J.; Immergut, E. H., Polymer handbook. John Wiley& Sons, Inc. 3rd, 1989.
20. Lee, S. H.; Yoo, P. J.; Kwon, S. J.; Lee, H. H., Journal of Chemical Physics 2004, 121, 4346.
21. Nguyen, T. Q.; Doan, V.; Schwartz, B. J., Journal of Chemical Physics 1999, 110, 4068
22. Collini, E.; Scholes, G. D., Science 2009, 323, 369-373.
23. Nguyen, T. Q.; Wu, J.; Doan, V.; Schwartz, B. J.; Tolbert, S. H., Science 2000, 288, 652-656.
24. Tung, K. P.; Chen, C. C.; Lee, P. W.; Liu, Y. W.; Hong, T. M.; Hwang, K. C.; Hsu, J. H.; White, J. D.; Yang, A. C.-M., ACS Nano 2011, 5, 7296-7302.
25. Reiter, G.; Hamieh, M,; Damman, P.; Sclavons, S.; Gabriele, S.; Vilmin, T.; Raphaël, A. E., Nature Materials 2005, 4, 754-758.
26. Yang, M. H.; Hou, S. Y.; Chang, Y. L.; Yang, A. C.-M., Physical Review Letters 2006, 96, 066105.
27. Reiter, G., Physical Review Letters 1992, 68, 75-78.
28. Vogelsang, J.; Adachi, T.; Brazard, J.; Vanden Bout, D. A. Barbara, P. F., Nature Materials 2011, 10, 942-946.
29. Vogelsang, J.; Brazard, J.; Adachi, T.; Bolinger, J. C.; Barbara, P. F., Angewandte Chemie International Editon 2011, 50, 2257-2261.
30. Barbara, P. F.; Gesquiere, A. J.; Park, S. J.; Lee, Y. J., Accounts of Chemical Research 2005, 38, 602-610.
31. Yu, J.; Hu, D.; Barbara, P. F., Science 2000, 289, 1327-1330.
32. Brédas, J. L.; Silbey, R., Science 2009, 323, 348-349.
33. Schwartz, B. J., Annual Review of Physical Chemistry 2003, 54, 141-172.
34. Nguyen, T. Q.; Martini, I. B.; Liu, J.; Schwartz, B. J., Journal of Physical Chemistry B 2000, 104, 237-255.
35. Schwartz, B. J., Nature Materials 2008, 7, 427-428.
36. Collini, E.; Scholes, G. D., Science 2009, 323, 369-373
37. Schwartz, B. J., Annual Review of Physical Chemistry 2003, 54, 141-172.
38. Brédas, J. L.; Silbey, R., Science 2009, 323, 348-349.
39. Jenekhe, S. A.; Osaheni, J. A., Science 1994, 265, 765-768.
40. Jenekhe, S. A.; Osaheni, J. A., Chemistry of Materials 1994, 6, 1906-1909.
41. Shinar, J.; Partee, J., Synthetic Metals 1997, 84, 525-528
42. 楊志偉, 清華大學材料系碩士論文 2006, 利用除潤與薄膜拉伸測試研究分子鏈運動對共軛高分子發光之影響
43. 陳炳志, 清華大學材料系碩士論文 2010, 表面除潤摩擦形變引起之共軛高分子巨大之光電增益.
44. 李培煒, 清華大學材料系碩士論文 2011, 共軛高分子薄膜之分子堆積、除潤運動與拉伸的發光增益研究.
45. 賴韋呈, 清華大學材料系碩士論文 2018, 奈米薄膜高分子殘留應力等於凍結型變成以楊氏係數？