本研究成功將2,2’-bis(trifluoromethyl)-4,4’-bis(diethyl methylenephosphonate)biphenyl與9,9’-dioctylfluorene-2,7-dicarbaldehyde、thiophene-2,5-dicarbaldehyde以Horner-Emmons方法合成新型共軛高分子PFV-CF3、PTV-CF3。PFV-CF3和PTV-CF3的數目平均分子量(Mn)分別為34000、13000。PFV-CF3和PTV-CF3的5%熱裂解溫度(Td)分別為394℃和436℃，玻璃轉移溫度(Tg)則是125℃和190℃，顯示擁有好的熱穩定性。PTV-CF3因未接入長脂肪鏈，所以有較高的Tg、Td，但同時仍擁有極佳的溶解度，在室溫下即可溶於DMSO、NMP、DMAc、DMF、THF及1,2-dichlorobenzene。在UV-Visible吸收光譜中，PFV-CF3、PTV-CF3的最大吸收長分別為404和407nm，從光譜中可以看出並無ICT(intramolecular charge transfer)效應的產生。光激發螢光光譜(PL)顯示，最大放光波長則為420和448nm，螢光量子效率為92和42%，這與PFV及PTV homopolymer相比均有明顯提升。PFV-CF3、PTV-CF3的最高占有電子軌域能階(HOMO)分別為-5.80和-5.30 eV，最低未占有電子軌域能階(LUMO)則是-3.31和-3.27 eV。我們和各種不同的拉電子基團作為比較，可以發現我們所合成的PFV-CF3、PTV-CF3的HOMO能階均較低，顯示本實驗室所合成的新型含有三氟甲基之聯苯結構為一強拉電子基團，能有效降低HOMO能階，可以做為將來設計新型共軛高分子時拉電子基團的新選擇。將PFV-CF3、PTV-CF3當發光層並製成兩種不同元件結構的PLED，其PFV-CF3、PTV-CF3在元件結構為ITO/PEDOT:PSS/Emission layer /BCP/LiF/Ca/Al達到最大亮度及最大發光效率，分別為2571 cdm-2、4.79 cdA-1和618 cdm-2、2.03 cdA-1。利用OTFT測得PFV-CF3、PTV-CF3的電子及電洞mobility，分別為5.4 × 10-4、8.7 × 10-4 cm2/Vs及1.0 × 10-4、2.7 × 10-3 cm2/Vs。結果顯示導入含有三氟甲基之聯苯結構能有效平衡電荷傳輸能力。

New fluorescent fluorene vinylene and thiophene vinylene copolymers incorporating 2,2’-bis(trifluoromethyl)-4,4’-biphenylene were synthesized by Horner-Emmons reaction (PFV-CF3、PTV-CF3). The number average molecular weights (Mn) of PFV-CF3 and PTV-CF3 were 34000 and 13000, respectively. PFV-CF3 and PTV-CF3 had high glass transition temperatures (Tg = 125℃ and 190℃) and outstanding thermal stability (Td =394℃ and 436℃ ). Because PTV-CF3 didn’t have alkyl substituent on thiophene ring, the copolymer had higher glass transition temperatures and the temperature at 5% weight loss. PTV-CF3 also had good solubility that can dissolve in common organic solvent, such as DMSO, NMP, DMAc, DMF, THF and 1,2-dichlorobenzene. The UV-Visible absorption spectra exhibited the absorption maxima of PFV-CF3、PTV-CF3 at 404 and 407 nm, respectively. The PL emission spectra exhibited the emission maxima of PFV-CF3、PTV-CF3 at 420 and 448 nm, and the PL quantum yield were 92 and 42%, respectively. The PL quantum yield was higher than the homopolymer PFV and PTV. The HOMO levels of the PFV-CF3 and PTV-CF3 were -5.80 and -5.30 eV, and the LUMO levels were -3.31 and -3.27 eV。Campared with different electron with-drawing group, and we found that the PFV-CF3 and PTV-CF3 of the HOMO levels were the lowest. So we can consider that 2,2’-bis(trifluoromethyl)-4,4’-bis(diethyl methylenephosphonate)biphenyl was the strong with-drawing group. Polymer lightemitting diodes using PFV-CF3 or PTV-CF3 as the emission layer (ITO/PEDOT:PSS/Emission layer /BCP/LiF/Ca/Al) had the maximum luminance (2571 cdm-2、618 cdm-2) and the maximum luminance efficiency (4.79 cdA-1、2.03 cdA-1). Organic thin-film transistors made of PFV-CF3 and PTV-CF3 showed balance charge mobility, the electron mobility were 5.4 × 10-4 and1.0 × 10-4 cm2/Vs and hole mobility were 2.7 × 10-3 and 8.7 × 10-4cm2/Vs, respectively. The result incidered that 2,2’-bis(trifluoromethyl)-4,4’-biphenylene introduced the electron-donating conjugated polymer can efficiency balance the charge mobility.

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