可撓性導電薄膜：聚苯乙烯磺酸-聚丙烯酸丁酯/聚3,4-乙烯基二氧噻吩之製備與性質研究

Abstract

本實驗的目的為製備聚苯乙烯磺酸-聚丙烯酸丁酯/聚-3,4-乙烯基二氧噻吩 (PSS-PBA/PEDOT) 之核殼型態複合導電分散液，再以旋轉塗佈的方式製成可撓性導電薄膜，並測量不同配方的核殼型態複合導電分散液對導電度、穿透度及可撓性的影響。 實驗主要分為兩個部份，第一部分利用高分子型界面劑聚苯乙烯磺酸鈉(PSSNa)及聚苯乙烯磺酸(PSSH)，在水中乳化聚合丙烯酸丁酯(BA)，合成PSSNa-PBA及PSSH-PBA乳膠溶液，分別討論此兩種高分子型界面劑在不同比例下與BA單體的反應及其影響，並以微差掃描熱卡計測定其玻璃轉移溫度；動態粒徑分析儀與穿透式電子顯微鏡觀察粒徑與形態。研究發現不論是PSSH-PBA或PSSNa-PBA乳膠溶液，玻璃轉移溫度(Tg)皆呈現以PBA為主體表現的Tg，約-42∼-46℃。此外，PSSNa-PBA的乳膠顆粒，粒徑隨BA比例提高而略微增大；而PSSH-PBA乳膠顆粒的粒徑則隨PSSH比例增多而上升。 第二部份將聚-3,4-乙烯基二氧噻吩單體EDOT氧化聚合並分散於前一部分所得乳膠溶液之殼層上，形成具有可撓性的PSSNa-PBA/PEDOT及PSSH-PBA/PEDOT核殼型態複合導電分散液，並用動態粒徑分析儀與穿透式電子顯微鏡觀察粒徑與形態。接著以旋轉塗佈法將此複合導電分散液製成薄膜，測量其導電度、穿透度及可撓性。研究顯示所製成的薄膜穿透度在100 nm的厚度下皆超過80%，為透明度良好的導電材料。此外，以PSSH為分散劑所製成的PSSH-PBA/PEDOT薄膜導電度明顯高於以PSSNa為分散劑所製成的PSSNa-PBA/PEDOT薄膜，而含有PBA之複合導電薄膜PSSNa-PBA/PEDOT或PSSH-PBA/PEDOT，其可撓性比PSS/PEDOT導電薄膜大為增加。

The aim of this study was to synthesize the Poly(styrenesulfonate)-Poly(butyl acrylate)/Poly(3,4-ethylenedioxythiophene) (PSS-PBA/PEDOT) core-shell complex conductive dispersion. In this study, the flexible conductive film was fabricated by spin coating the PSS-PBA/PEDOT complex dispersion on PET and glass substrate. The optoelectronic properties of the flexible conductive film such as transparency, conductivity, and flexibility were investigated to compare the relationship between the monomer content and polymeric surfactant.

This study included two parts. In first part, by using Poly(4-styrenesulfonic acid) (PSSH) and Poly(Sodium styrenesulfonate) (PSSNa) as the surfactant, PSSH-PBA and PSSNa-PBA core-shell latex were synthesized from Butyl Acrylate (BA) monomer via emulsion polymerization. Then, the effect of the two kinds of polymeric surfactants with BA monomer in different ratio was discussed. Furthermore, the glass transition temperature (Tg), particle size and morphology were characterized by Differential Scanning Calorimeter (DSC), Dynamic Light Scattering Analyzer (DLS) and Transmission Electron Microscope (TEM), respectively. It was found that the Tg of both PSSH-PBA and PSSNa-PBA are approximate to the Tg of pure PBA. In addition, the particle size of PSSNa-PBA latex increased slightly with the proportion of BA increased; on the other hand, the particle size of PSSH-PBA latex increased with the proportion of PSSH increased. In second part, the flexible core-shell complex conductive dispersion, PSSNa-PBA/PEDOT and PSSH-PBA/PEDOT, were carried out via oxidative polymerization of EDOT monomer. In which the shell of PSS-PBA core-shell latex was served as the template in water. Dynamic Light Scattering Analyzer (DLS) and Transmission Electron Microscope (TEM) were employed to detect the particle size and morphology, respectively. By spin coating the complex conductive dispersion to form the PSS-PBA/PEDOT thin film, the conductivity, transparency and flexibility could be measured. It showed that the PSS-PBA/PEDOT complex thin film owned superior transparency (transmittance > 80% at 100 nm film thickness). The conductivity of the PSSH-PBA/PEDOT thin film synthesized was obviously better than the PSSNa-PBA/PEDOT film. Furthermore, the flexibility of the PBA-PSS/PEDOT thin film effectively increased due to the introduction of PSS-PBA core-shell latex.