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標題: | 具熱可交聯性、彈性與高疏水性之PEDOT:PSS導電複合薄膜:製備、性質分析及應用 Thermally Curable, Elastic, and Hydrophobic PEDOT:PSS Conductive Composite Films: Preparation, Characterization, and Application |
作者: | Hui-En Yin 鄞暉恩 |
指導教授: | 邱文英(Wen-Yen Chiu) |
關鍵字: | PEDOT:PSS導電薄膜,乳化聚合,溶膠−,凝膠聚合,熱可交聯,彈性,可撓性,親水性,疏水性,耐候性,接觸角模擬, PEDOT:PSS conductive film,emulsion polymerization,sol-gel,thermally curable,elasticity,flexibility,hydrophilic and hydrophobic property,weather stability,contact angle simulation, |
出版年 : | 2012 |
學位: | 博士 |
摘要: | Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)導電薄膜具有高導電度和高透明性,並在抗靜電薄膜、光電顯示器、太陽能電池等領域被廣泛應用,但是此薄膜仍然具有耐水、耐候性不佳且無韌性等缺點。本研究利用引進熱可交聯單體、低玻璃轉移溫度(Tg)高分子、及無機矽奈米顆粒等方法改質PEDOT:PSS導電分散液性質,並製備出一系列具熱可交聯性、彈性、可撓性、高疏水性及耐候性之PEDOT:PSS導電複合薄膜。
在第一部分(Chapter 2),使用熱可交聯性單體N-(methylol acrylamide) (NMA) 與4-styrenesulfonate (SSNa) 在水中進行溶液聚合,合成具熱可交聯性P(SS-NMA)共聚物,並以交聯程度(Gel content)、吸水率(Moisture absorptivity) 與膨潤程度(Swelling index)來比較含不同NMA比例之P(SS-NMA)共聚物性質。接著,使用具有較高交聯程度的P(SS-NMA)共聚物為分散劑,在水中氧化聚合成PEDOT:P(SS-NMA) 導電分散液,並使用旋轉塗佈機製備導電薄膜,探討引入熱可交聯性單體對其光電性質的影響。同時,使用掃描式電子顯微鏡(SEM)與原子力顯微鏡(AFM)觀察薄膜表面型態,在耐水性測試上,具熱可交聯性PEDOT:P(SS-NMA)導電薄膜可保持薄膜完整性。 第二部分採用兩種方式引入低Tg高分子來提高PEDOT:PSS導電薄膜之韌性: 在Chapter 3中,使用陰離子型乳化劑Dodecylbenzenesulfonic acid (DBSA)、非離子型乳化劑TweenR 20與陽離子型乳化劑Cetyltrimethylammoniumbromide (CTAB),分別在水中乳化聚合Poly(butyl acrylate-styrene) (P(BA-St))乳液,另一方面使用PSS與EDOT合成PEDOT:PSS導電分散液。將此P(BA-St) 乳液與PEDOT:PSS導電分散液進行混摻並塗佈成膜,製備出一系列PEDOT:PSS/P(BA-St)導電薄膜,探討不同離子型態乳化劑所合成之P(BA-St) 與不同混摻比例對導電複合薄膜光電性質的影響。將PEDOT:PSS/P(BA-St) 利用載具製備成80μm厚度之彈性導電厚膜,使用拉力機(Tensile testing machine)來測量延伸率,結果顯示此導電厚膜具有高達97% 的延伸率與30 S/cm之導電度。 在Chapter 4中,使用PSS當作高分子型介面劑,在水中乳化聚合Butyl acrylate (BA),製備出低Tg之核殼形PSS-PBA乳液,其粒徑大小與型態使用穿透式電子顯微鏡 (TEM) 與粒徑分析儀 (Zeta-sizer) 進行分析。並以PSS-PBA為穩定劑,在水中氧化聚合PEDOT:PSS-PBA導電分散液,探討引入不同PBA比例對導電複合薄膜光電性質的影響,在耐候性測試與撓曲測試中,PEDOT:PSS-PBA導電薄膜具有比PEDOT:PSS導電薄膜較佳之可撓性(R/R0 < 1.2) 與疏水性(接觸角=75°)。 第三部分藉由引入無機矽奈米顆粒來提高導電薄膜的疏水性。在Chapter 5中,先以溶膠-凝膠(Sol-gel)合成方法在酸與鹼中分別製備不同粒徑大小之二氧化矽奈米顆粒,並進行表面氟改質,再分別以直接混摻與塗佈等方法來製備PEDOT:PSS-PBA/fluorine-modified silica疏水導電薄膜,探討引入不同比例與不同大小之無機矽奈米顆粒對導電複合薄膜光電性質與接觸角的影響,同時使用SEM與AFM觀察薄膜表面型態,並進行高溫高濕度下之耐候性測試。此PEDOT:PSS-PBA/fluorine-modified silica導電複合薄膜其具有高疏水性(接觸角> 90°)與優良耐候性等優點。 在Chapter 6中,利用能量計算模型建立程式,估算平面之條紋、格子點與對角點等三種圖紋之親疏水複合薄膜平衡接觸角,並進一步修正程式以估算粗糙親疏水複合薄膜接觸角。最小收斂體積 (Minimum Convergent Curve (MCV)) 可以用來估算量測接觸角時固定誤差範圍內所需的水體積。更進一步,使用程式計算疏水導電薄膜PEDOT:PSS/fluorine-modified silica之接觸角並與量測值討論比較。 最後一個章節中(Chapter 7),將PEDOT:PSS應用在電致發光(Electroluminescent)元件上,使用水相高分子Poly(vinyl pyrrolidone) (PVP) 與PEDOT:PSS導電分散液以不同比例進行混摻,可大幅提高導電分散液黏度及改善導電分散液與樹脂接著性,同時也增加成膜後之透明性與可撓性,將介電樹脂、發光層與改質後之PEDOT:PSS/PVP導電分散液依序塗佈在平板與線材上,並通以110V交流電,可獲得發光平板與發光線材。 Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) conductive film exhibits excellent conductivity and transparency so that it could be applied in various fields, such as antistatic coatings, optoelectronic displays, and solar cells. However, the water resistivity, weather stability, and fragile property of PEDOT:PSS film limit its development. In this research, a series of approaches by introducing thermally curable monomer, soft latex, and inorganic silica nanoparticles were employed to effectively improve the weather stability, elasticity, flexibility and hydrophobic property of PEDOT:PSS conductive film. In the first part (Chapter 2), P(SS-NMA) was copolymerized by thermally curable monomer N-(methylol acrylamide) (NMA) and 4-styrenesulfonate (SSNa) in water. The gel content, moisture absorptivity, and swelling index were used to evaluate the properties of P(SS-NMA) copolymer. Then, P(SS-NMA) copolymer was regarded as a template to prepare PEDOT:P(SS-NMA) dispersion. The optoelectronic properties and surface morphology of the PEDOT:P(SS-NMA) thin film were investigated. The thermally curable PEDOT:P(SS-NMA) conductive film possessed better weather stability and water resistivity than PEDOT:P(SS) conductive film did. In the second part, two approaches were adopted to enhance the film’s elasticity and flexibility. In Chapter 3, poly(butyl acrylate-styrene) (P(BA-St)) soft latex with low glass transition temperature (Tg) was synthesized by using different ionic charge types of surfactant. The P(BA-St) soft latex was blended with PEDOT:PSS dispersion to prepare a series of PEDOT:PSS/P(BA-St) conductive thin films and elastic conductive thick films. The PEDOT:PSS/P(BA-St) conductive thick film exhibited 97 % of elongation and 30 S/cm of conductivity with good weather stability. In Chapter 4, the core-shell PSS-PBA soft latex was also carried out by using PSS as a polymeric surfactant in the polymerization of butyl acrylate (BA). Transmission electron microscopy (TEM) and zeta-sizer were employed to investigate the size and morphology of PSS-PBA soft latex. Then, the PSS-PBA soft latex was used as a template in the oxidative polymerization of EDOT. The optoelectronic properties and surface morphology of the resulting PEDOT:PSS-PBA conductive thin films were characterized. During the bending and weather stability test, the PEDOT:PSS-PBA conductive thin film exhibited better flexibility (R/R0 < 1.2) and hydrophobic property (contact angle = 75°) than PEDOT:PSS film did (R/R0 = 1.5, contact angle = 40°). In the third part (Chapter 5), the hydrophobic property of the PEDOT:PSS film was improved by introducing fluorine-modified silica nanoparticles. The fluorine-modified silica with various particle sizes was prepared via sol-gel process. By either blending or coating approach, PEDOT:PSS/fluorine-modified silica conductive film exhibited high water contact angle (contact angle > 90°) and good weather stability. Also, the optoelectronic properties and surface morphology of the conductive thin films were characterized. In Chapter 6, a modeling program was developed to calculate the contact angle in the stripe, grid point, and diagonal point patterns as well as a composite film with roughness. Minimum convergent volume (MCV) was specified to obtain an appropriate water drop volume to measure the contact angle. Furthermore, the contact angle of hydrophobic PEDOT:PSS/fluorine-modified silica conductive film was calculated by the program to compare with the experimental measurement. For bending method, a particle restriction supposition was presented. For coating method, different wetting states resulted from the different particle sizes on the surface. Finally, in Chapter 7, PEDOT:PSS was applied as the anode material in the field of electroluminescent devices. Via introducing water soluble polymer poly(vinyl pyrrolidone) (PVP), the PEDOT:PSS/PVP conductive dispersion could effectively increase its viscosity and wetting property on the resin. After coating the dielectric resin, fluorescent layer and PEDOT:PSS/PVP dispersion on the template orderly, the electroluminescent devices could be demonstrated. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/63789 |
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