雙炔基分子在特定結晶結構下可經由紫外光照射進行拓樸化學聚合反應(Topochemical reaction)，形成具有共軛聚(烯-炔)骨架結構的聚雙炔高分子，此材料具有良好的光電特性，是為導電高分子，可應用在場效電晶體中。本實驗研究了三個系列含有雙炔基線性羧酸的有向性薄膜的製備，實驗主要包含了三種分子，第一個分子為：C12H25(C≡C)2(CH2)nCOOH，n=7-10，其中改變了雙炔基官能基與末端酸基中間的碳鏈長度；第二個分子為：C12H25(C≡C)2(CH2)n-CONHPh-COOH，n=7-10，不僅改變了雙炔基官能基與末端酸基的碳鏈長度，並在碳鏈後接上氨基苯甲酸官能基，最後一項為：PhC9H18(C≡C)2(CH2)8COOH，此材料為苯環官能基接在碳鏈末端的雙炔基線性羧酸。以溶液剪切製程將配置於溶液中的各類雙炔基分子製備成薄膜，利用單一方向之剪切力影響薄膜中分子排列方向與形貌。以偏振拉曼光譜、原子力顯微鏡、掠入射廣角X光散射等工具，研究薄膜在照光前後的詳細結構。最後將高分子薄膜運用於場效電晶體中的主動層，分析不同分子膜中電極平行與垂直共軛方向的電性差異。

Diacetylenic compounds, when packed in specific crystalline structure, are known to undergo topochemical polymerization to yield poly(eny-yne) conjugate polymers, which are useful in electronic applications such as transistors. In this work, three series of linear carboxylic acids containing diacetylenic unit, including C12H25(C≡C)2(CH2)nCOOH with n=7-10; C12H25(C≡C)2(CH2)n-CONHPh-COOH with n=7-10; and PhC9H18(C≡C)2(CH2)8COOH, were used to prepare oriented molecular films on silicon surface by solution-shearing method. The shearing force can influence the molecular packing and orientation of the molecules in the films and their UV-polymerization behavior. The detailed structures of the films before and after UV-irradiation were investigated as a function of the spacer chain length between the diacetylene unit and the carboxyl group, by using polarization Raman spectroscopy, AFM, and grazing-incidence wide-angle X-ray scattering. Potential of these films as the conducting channel in field-effect transistor is evaluated.

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1. 維基百科編者. “電晶體”.
2. 維基百科編者. “有機場效應電晶體”.
3. Jackson, T.N., et al., Organic thin-film transistors for organic light-emitting flat-panel display backplanes. IEEE Journal of selected topics in quantum electronics, 1998. 4(1): p. 100-104.
4. Steudel, S., et al., Comparison of organic diode structures regarding high-frequency rectification behavior in radio-frequency identification tags. Journal of applied physics, 2006. 99(11): p. 114519.
5. Ebisawa, F., T. Kurokawa, and S. Nara, Electrical properties of polyacetylene/polysiloxane interface. Journal of applied physics, 1983. 54(6): p. 3255-3259.
6. Tsumura, A., H. Koezuka, and T. Ando, Macromolecular electronic device: Field‐effect transistor with a polythiophene thin film. Applied Physics Letters, 1986. 49(18): p. 1210-1212.
7. Assadi, A., et al., Field‐effect mobility of poly (3‐hexylthiophene). Applied Physics Letters, 1988. 53(3): p. 195-197.
8. Garnier, F., et al., An all‐organic" soft" thin film transistor with very high carrier mobility. Advanced Materials, 1990. 2(12): p. 592-594.
9. Lee, J., et al., Field-effect mobility anisotropy in PDA-PTS single crystals. Synthetic metals, 2005. 152(1-3): p. 169-172.
10. Dhawan, S., et al., Organic field effect transistors based on self-assembling core-modified peptidic polymers. Molecular Systems Design & Engineering, 2020. 5(4): p. 847-855.
11. Guo, Y.-l., High Performance Ambipolar Polymer Semiconductors and Transistors. ACTA POLYMERICA SINICA, 2020. 51(5): p. 448-456.
12. Alakhras, F., In situ UV/VIS Spectroscopy of Electrochemically Synthesized Selenophene Thiophene Copolymers. Helvetica Chimica Acta, 2015. 98(6): p. 851-862.
13. Gajdos, F., et al., On the inapplicability of electron-hopping models for the organic semiconductor phenyl-C61-butyric acid methyl ester (PCBM). The journal of physical chemistry letters, 2013. 4(6): p. 1012-1017.
14. Watson, P.K., The transport and trapping of electrons in polymers. IEEE transactions on Dielectrics and Electrical Insulation, 1995. 2(5): p. 915-924.
15. Shirakawa, H., et al., Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene,(CH) x. Journal of the Chemical Society, Chemical Communications, 1977(16): p. 578-580.
16. Turkoglu, G., M.E. Cinar, and T. Ozturk, Thiophene-based organic semiconductors. Sulfur Chemistry, 2019: p. 79-123.
17. Panzer, M.J., C.R. Newman, and C.D. Frisbie, Low-voltage operation of a pentacene field-effect transistor with a polymer electrolyte gate dielectric. Applied Physics Letters, 2005. 86(10): p. 103503.
18. Ahmed, R., et al., Air stability of C60 based n-type OFETs. Synthetic metals, 2014. 188: p. 136-139.
19. Li, R., et al., Synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris (phthalocyaninato) europium (III) complexes with hydrophilic poly (oxyethylene) substituents. Inorganic chemistry, 2007. 46(26): p. 11397-11404.
20. Yi, H., et al., Vacuum Lamination Approach to Fabrication of High‐Performance Single‐Crystal Organic Field‐Effect Transistors. Advanced materials, 2011. 23(48): p. 5807-5811.
21. Burroughes, J., C. Jones, and R. Friend, New semiconductor device physics in polymer diodes and transistors. Nature, 1988. 335(6186): p. 137-141.
22. Wegner, G., Topochemische Reaktionen von Monomeren mit konjugierten Dreifachbindungen/Tochemical Reactions of Monomers with conjugated triple Bonds: I. Mitt.: Polymerisation von Derivaten des 2.4-Hexadiin-1.6-diols im kristallinen Zustand. Zeitschrift für Naturforschung B, 1969. 24(7): p. 824-832.
23. Baughman, R., Solid‐state polymerization of diacetylenes. Journal of Applied Physics, 1972. 43(11): p. 4362-4370.
24. Schermann, W. and G. Wegner, Topochemische Reaktionen von Monomeren mit konjugierten Dreifachbindungen, 10. Elektrische Leitfähigkeit von Einkristallen aus Polydiacetylenen. Die Makromolekulare Chemie: Macromolecular Chemistry and Physics, 1974. 175(2): p. 667-674.
25. Kim, Y., et al., Pressure-Induced Transition of Bisamide-Substituted Diacetylene Crystals from Nonphotopolymerizable to Photopolymerizable State. ACS applied materials & interfaces, 2018. 10(42): p. 36407-36414.
26. Enkelmann, V., Structural aspects of the topochemical polymerization of diacetylenes. Polydiacetylenes, 1984: p. 91-136.
27. Mortazavian, S. and A. Fatemi, Effects of fiber orientation and anisotropy on tensile strength and elastic modulus of short fiber reinforced polymer composites. Composites part B: engineering, 2015. 72: p. 116-129.
28. Luo, Z., et al., Anisotropic in-plane thermal conductivity observed in few-layer black phosphorus. Nature communications, 2015. 6(1): p. 1-8.
29. Li, Z. and R. Bradt, Thermal expansion and thermal expansion anisotropy of SiC polytypes. Journal of the American Ceramic Society, 1987. 70(7): p. 445-448.
30. Poe, B.T., et al., Electrical conductivity anisotropy of dry and hydrous olivine at 8 GPa. Physics of the Earth and Planetary Interiors, 2010. 181(3-4): p. 103-111.
31. Borradaile, G. and B. Henry, Tectonic applications of magnetic susceptibility and its anisotropy. Earth-Science Reviews, 1997. 42(1-2): p. 49-93.
32. Samoc, A., et al., Refractive‐index anisotropy and optical dispersion in films of deoxyribonucleic acid. Journal of applied polymer science, 2007. 105(1): p. 236-245.
33. Hoofman, R.J., et al., Anisotropy of the charge-carrier mobility in polydiacetylene crystals. The Journal of chemical physics, 1998. 109(5): p. 1885-1893.
34. Lochner, K., B. Reimer, and H. Bässler, Anisotropy of electrical properties of a polydiacetylene single crystal. Chemical Physics Letters, 1976. 41(2): p. 388-390.
35. Bleier, H., et al., Photoconductivity in trans-polyacetylene: Transport and recombination of photogenerated charged excitations. Physical Review B, 1988. 38(9): p. 6031.
36. Mergu, N., et al., A simple and fast responsive colorimetric moisture sensor based on symmetrical conjugated polymer. Sensors and Actuators B: Chemical, 2020. 311: p. 127906.
37. Kim, M.J., et al., Tuning of the topochemical polymerization of diacetylenes based on an odd/even effect of the peripheral alkyl chain: thermochromic reversibility in a thin film and a single-component ink for a fountain pen. ACS applied materials & interfaces, 2018. 10(29): p. 24767-24775.
38. Burns, A., et al., Shear-induced mechanochromism in polydiacetylene monolayers. Tribology Letters, 2001. 10(1): p. 89-96.
39. Wenz, G., et al., Structure of poly (diacetylenes) in solution. Macromolecules, 1984. 17(4): p. 837-850.
40. Tseng, C.W., et al., Self‐Assembly Behavior of Diacetylenic Acid Molecules upon Vapor Deposition: Odd–Even Effect on the Film Morphology. Chemistry–A European Journal, 2020. 26(61): p. 13948-13956.
41. Lee, J.-H., et al., Solvent-dependent performance of solution-processed small-molecule organic field-effect transistors. Organic Electronics, 2018. 52: p. 184-189.
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