導電高分子材料因其可撓性、輕量特性及優異的導電性能，在電子元件中展現出廣泛的應用潛力，特別是作為半導體傳導層的核心材料。然而高分子薄膜機械強度較低，導致在承受應力時難以維持穩定且可靠的電學性能。此外高分子薄膜傾向以無序的非結晶相沉積，將進一步降低元件中載子的傳導效率。因此提高導電高分子薄膜的有序性為問題的關鍵。
本研究旨在通過統一矽基板表面分子組成，定量調控表面親水基的密度，以系統性地調節自組裝單分子層的嫁接密度。這種方法能有效控制導電高分子與自組裝單分子層之間的分子間作用力，進而優化導電高分子的沉積過程，提升薄膜內的電子結構。該研究為未來埃米級分子間作用力設計、分子磊晶及有機半導體電子結構的精確控制提供了理論支持和技術基礎。本研究優化了偏極化微拉曼散射頻譜儀的光學準直性。並自主搭建了液氦極低溫系統，將其整合進偏極化微拉曼散射頻譜儀中。根據變溫拉曼頻譜藍移，結合基礎熱力學參數進行模型推導，分析高分子晶格振盪與溫度變化之間的關係。通過對實驗結果進行線性擬合，獲得高分子晶格的熱膨脹係數。將微觀的分子間振盪頻率轉換為宏觀材料受溫度變化的形變程度，從而提供固態薄膜內軟性分子的定量化溫度膨脹參數。此研究為有機電子學領域提供了系統化的實驗與分析方法，能夠系統性地控制並分析高分子排列，為定量控制有機半導體埃米級電子結構開創了可靠的方向。

Conductive polymers have tunable band gaps and good conductivity, making them suitable semiconducting materials for electronic devices. However, the flexible backbone of conductive polymers tends to become entangled during the film formation process, leading to the formation of amorphous phases that can act as defects that impede carrier transport. To improve carrier transport efficiency in conductive polymer films, it is necessary to control the orientation of the polymer backbones through process. This study focuses on the systematic control of the solute-solvent-substrate interactions during the liquid phase process to achieve an ordered alignment of the polymer backbones in the film. Building on the optimized conditions for solute-solvent molecular interactions, the research will modify the surface of silicon substrates with nanogrooves of different self-assembled monolayers (SAMs) densities to create conditions favorable for the ordered polymer precipitation. Polarized Raman scattering spectrometer is used to analyses the Raman vibrational response of backbones with different alignment under low temperature conditions. By using self-derived thermodynamic parameters model, the relationship between lattice vibrations and temperature variations was analyzed. A linear fit of the experimental results yielded the thermal expansion coefficient (CTE) of the polymer film, which increases with the order of the polymer alignment. This approach provides a quantitative thermal expansion parameter for flexible polymer within solid films. This method provides a new perspective on the study of flexible organic electronic devices.

1.Panzer, F., et al., The impact of polydispersity and molecular weight on the order–disorder transition in poly (3-hexylthiophene). The journal of physical chemistry letters, 2014. 5(15): p. 2742-2747.
2.Kumar, D. and R. Sharma, Advances in conductive polymers. European polymer journal, 1998. 34(8): p. 1053-1060.
3.Abrahamsson, T., Synthetic Functionalities for Ion and Electron Conductive Polymers: Applications in Organic Electronics and Biological Interfaces. 2021, Linköping University Electronic Press.
4.Hu, H., et al., Entanglements in marginal solutions: a means of tuning pre-aggregation of conjugated polymers with positive implications for charge transport. Journal of Materials Chemistry C, 2015. 3(28): p. 7394-7404.
5.Wietzke, S., et al., Thermomorphological study of the terahertz lattice modes in polyvinylidene fluoride and high-density polyethylene. Applied Physics Letters, 2010. 97(2).
6.Osaka, I. and K. Takimiya, Backbone orientation in semiconducting polymers. Polymer, 2015. 59: p. A1-A15.
7.Esseni, D. and F. Driussi, A quantitative error analysis of the mobility extraction according to the Matthiessen rule in advanced MOS transistors. IEEE Transactions on Electron Devices, 2011. 58(8): p. 2415-2422.
8.Zaumseil, J., P3HT and other polythiophene field-effect transistors. P3HT Revisited–From Molecular Scale to Solar Cell Devices, 2014: p. 107-137.
9.Panzer, F., H. Bässler, and A. Köhler, Temperature induced order–disorder transition in solutions of conjugated polymers probed by optical spectroscopy. The journal of physical chemistry letters, 2017. 8(1): p. 114-125.
10.Na, J.Y., et al., Understanding solidification of polythiophene thin films during spin-coating: effects of spin-coating time and processing additives. Scientific reports, 2015. 5(1): p. 13288.
11.Pascual-San-José, E., et al., Blade coated P3HT: non-fullerene acceptor solar cells: a high-throughput parameter study with a focus on up-scalability. Journal of materials chemistry A, 2019. 7(35): p. 20369-20382.
12.Xue, L., et al., The formation of different structures of poly (3-hexylthiophene) film on a patterned substrate by dip coating from aged solution. Nanotechnology, 2010. 21(14): p. 145303.
13.O'Connor, B., et al., Anisotropic Structure and Charge Transport in Highly Strain‐Aligned Regioregular Poly (3‐hexylthiophene). Advanced Functional Materials, 2011. 21(19): p. 3697-3705.
14.Kim, D.H., et al., Surface-induced conformational changes in poly (3-hexylthiophene) monolayer films. Langmuir, 2005. 21(8): p. 3203-3206.
15.Heimel, G., et al., The interface energetics of self-assembled monolayers on metals. Accounts of Chemical Researchc, 2008. 41(6): p. 721-729.
16.Faucheux, N., et al., Self-assembled monolayers with different terminating groups as model substrates for cell adhesion studies. Biomaterials, 2004. 25(14): p. 2721-2730.
17.Miozzo, L., A. Yassar, and G. Horowitz, Surface engineering for high performance organic electronic devices: the chemical approach. Journal of Materials Chemistry, 2010. 20(13): p. 2513-2538.
18.Skountzos, E.N., F. von Wrochem, and V.G. Mavrantzas, Structure and Conformation of a Crystalline P3HT Film Adsorbed on an Alkanethiol Self‐Assembled Monolayer Deposited on Gold. Macromolecular Theory and Simulations, 2020. 29(3): p. 2000010.
19.Kirschner, J., et al., Driving forces for the self-assembly of graphene oxide on organic monolayers. Nanoscale, 2014. 6(19): p. 11344-11350.
20.Jang, M., Y.-I. Huh, and M. Chang, Effects of solvent vapor annealing on morphology and charge transport of poly (3-hexylthiophene)(P3HT) films incorporated with preformed P3HT nanowires. Polymers, 2020. 12(5): p. 1188.
21.Cooper, E. and G.J. Leggett, Influence of tail-group hydrogen bonding on the stabilities of self-assembled monolayers of alkylthiols on gold. Langmuir, 1999. 15(4): p. 1024-1032.
22.Choi, D., et al., Effects of side-chain interdigitation on stability: an environmentally, electrically, and thermally stable semiconducting polymer. ACS applied materials & interfaces, 2012. 4(2): p. 702-706.
23.Lepikko, S., et al., Droplet slipperiness despite surface heterogeneity at molecular scale. Nature chemistry, 2024. 16(4): p. 506-513.
24.Ito, Y., et al., Crystalline ultrasmooth self-assembled monolayers of alkylsilanes for organic field-effect transistors. Journal of the American Chemical Society, 2009. 131(26): p. 9396-9404.
25.Chen, J.-Y., et al., Manipulation on the morphology and electrical properties of aligned electrospun nanofibers of poly (3-hexylthiophene) for field-effect transistor applications. Macromolecules, 2011. 44(8): p. 2883-2892.
26.Xiao, G., et al., Controlled evaporative self-assembly of poly (3-hexylthiophene) monitored with confocal polarized Raman spectroscopy. Physical Chemistry Chemical Physics, 2012. 14(47): p. 16286-16293.
27.El-Desawy, M., Characterization and application of aromatic self-assembled monolayers. 2007.
28.Zhuravlev, L., The surface chemistry of amorphous silica. Zhuravlev model. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000. 173(1-3): p. 1-38.
29.Israelachvili, J.N. and M.L. Gee, Contact angles on chemically heterogeneous surfaces. Langmuir, 1989. 5(1): p. 288-289.
30.Schrader, A.M., et al., Surface chemical heterogeneity modulates silica surface hydration. Proceedings of the National Academy of Sciences, 2018. 115(12): p. 2890-2895.
31.Cao, Y., A. Salvini, and M. Camaiti, Current status and future prospects of applying bioinspired superhydrophobic materials for conservation of stone artworks. Coatings, 2020. 10(4): p. 353.
32.Bredas, J.-L., Relationship between band gap and bond length alternation in organic conjugated polymers. The Journal of chemical physics, 1985. 82(8): p. 3808-3811.
33.Veerender, P., et al., Probing the annealing induced molecular ordering in bulk heterojunction polymer solar cells using in-situ Raman spectroscopy. Solar energy materials and solar cells, 2014. 120: p. 526-535.
34.Chaudhary, V., et al., Self-assembled H-aggregation induced high performance poly (3-hexylthiophene) Schottky diode. Journal of Applied Physics, 2017. 122(22).
35.Lin, R., et al., Spontaneous dissociation of a conjugated molecule on the Si (100) surface. The Journal of chemical physics, 2002. 117(1): p. 321-330.
36.Dantanarayana, V., et al., Multi–scale Modeling of Bulk Heterojunctions for Photovoltaic Applications.
37.Ma, B.S., et al., Thermomechanical Behavior of Poly (3-hexylthiophene) Thin Films on the Water Surface. ACS omega, 2022. 7(23): p. 19706-19713.
38.Rahimi, K., et al., Light absorption of poly (3-hexylthiophene) single crystals. Rsc Advances, 2014. 4(22): p. 11121-11123.