高分子複合薄膜之物性探討及其於全拉伸電子元件之應用

Abstract

傳統元件由於其受限於變形能力、電拉伸性和生物相容性等因素，限制了應用於新興產業的可能性。因此，本論文旨在開發具有高度彈性和卓越功能性的薄膜，並應用於各種全拉伸元件，以滿足可穿戴電子、生物醫學感測器和軟體機器人等領域的需求。然而，目前全拉伸元件所面臨的問題主要有三點：其一，在拉伸過程中元件的電性效果通常表現不佳。其二，元件易於在反覆拉伸後出現損壞，耐久性不佳。其三，在高度或反覆拉伸時，元件的不同層常出現分層現象，進而導致易損壞。為了克服這些困難，本論文選擇了適合的高分子材料並採用特定的製程方法來製備可拉伸複合薄膜。同時，通過多種鑑定技術對這些薄膜的力學和電性進行了評估。最終，將所開發的複合薄膜應用到電子設備中，例如電晶體、光記憶體和充電電池，以確保其實用性。 本論文首先專注於開發可拉伸電極，以作為所有元件和電路的基礎單元。我們採用了導電高分子poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)和軟性高分子polyvinyl alcohol (PVA)的複合材料，以獲得具有高拉伸性和高導電性的電極。添加PVA可與PSS之間形成氫鍵，提升薄膜的拉伸耐久性，同時增加電極與其他層之間的附著力，進一步改善電晶體和其他元件在高應變環境下的耐久性和電氣性能。 接著，本論文將所開發的電極應用於光記憶體和充電電池。然而，拉伸光記憶體和電池面臨的另一個挑戰是元件結構過於複雜，導致分層問題嚴重，進而影響元件在高應變環境下的耐久性和電氣性能。因此，本論文同樣利用高分子易於加工和複合的優勢，開發出結構簡單的光記憶體和充電電池，以克服上述問題。 在光記憶體方面，本研究使用了poly(3-hexylthiophene)-nano fiber (P3HT-NF)、pervoskite-quantum dot (PVSK-QD)和styrene ethylene butylene styrene (SEBS)的複合薄膜。該複合薄膜將傳統記憶體中的半導體層、鈍器層和光敏感層合併為一層，以解決分層的問題。同時，透過材料間的自發相分離形貌，這種複合薄膜能夠讓光記憶體在高拉伸狀態下依然保持高記憶體特性。 在充電電池方面，本研究設計了僅有三層結構的電池。陰極由PEDOT:PSS/PVA/poly(TEMPO-substituted acrylamide) (PTAm)複合製備，陽極則由single-walled carbon nanotubes (SWCNTs)/zinc製備，固態電解質則使用合成的poly(ethylene glycol) dimethacrylates (PEGDMA)水膠。這種簡單的元件結構和抗水氧的電極賦予該電池優異的拉伸性和耐久性。同時，具有優異的氧化還原能力的活性物質，使得該電池能夠提供高且穩定的輸出電壓，並具有良好的充放電循環性能。 總結而言，本研究利用高分子複合薄膜成功開發出多種具有優異元件特性的全拉伸元件。這些策略奠定了獨立式全拉伸元件的基礎，為拉伸式元件提供了明確的指引，使其更上層樓。

Tranditional rigid electronics are limited by the lack of deformability, stretchability, and biocompatibility, which hampers their potential in emerging industries. Therefore, the objective of this thesis is to create highly stretchable and functional composite films for a range of stretchable devices, catering to the needs of wearable electronics, biomedical sensors, and soft robotics. However, current stretchable devices face three primary challenges. Firstly, the electrical performance of these devices often deteriorates during stretching. Secondly, they are prone to damage and lack durability after repeated stretching. Lastly, frequent delamination between layers occurs during various deformation, resulting in device failure. To overcome these issues, this thesis focuses on selecting suitable polymers and employing specific processing techniques to fabricate stretchable composite films. The mechanical and electrical properties of these films are evaluated using various characterization techniques. Finally, the developed composite films are integrated into electronics such as transistors, photomemory, and rechargeable batteries to ensure their practicality. This thesis initially concentrates on the development of stretchable electrodes, which serve as fundamental components for all electronics and circuits. I employ a composite comprising the conductive polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and the soft polymer polyvinyl alcohol (PVA) to achieve electrodes with high stretchability and conductivity. The addition of PVA facilitates the formation of hydrogen bonds with PSS, thereby improving the film's stretchability. Furthermore, the inclusion of PVA enhances the adhesion between the electrode and other layers, thereby improving the durability and electrical performance of transistors and other devices under high tension. Next, the developed electrodes are utilized in photomemory and rechargeable batteries. However, stretchable photomemory and batteries also face the challenge of complex device configurations, leading to severe delamination that affects their durability and electrical performance under high tension. Therefore, this thesis also designs simplified configurations for photomemory and rechargeable batteries to overcome the aforementioned issues. For the photomemory, a composite film comprising poly(3-hexylthiophene)-nanofiber (P3HT-NF), perovskite-quantum dot (PVSK-QD), and styrene ethylene butylene styrene (SEBS) is employed. This composite film combines the semiconductor, passivation, and photosensitive layers into a single layer to minimize the risk of delamination. Moreover, the spontaneous phase separation morphology between the materials allows the photomemory to maintain high memory characteristics even under severe deformation. In the case of the rechargeable battery, a sandwich configuration is designed. The cathode consists of a PEDOT:PSS/PVA/poly(TEMPO-substituted acrylamide) (PTAm) composite, while the anode is composed of single-walled carbon nanotubes (SWCNTs)/zinc. The solid-state electrolyte comprises a synthesized poly(ethylene glycol) dimethacrylates (PEGDMA) hydrogel. The simple configuration and water-and-air-stable electrodes impart excellent stretchability and durability to the battery. Additionally, the active material, with its outstanding redox capability, allows the battery to provide a high and stable output voltage and exhibit good charge-discharge cycling performance. In conclusion, this thesis successfully develops various stretchable devices with exceptional electrical stretchability by utilizing polymer composite films. These strategies lay the foundation for self-sufficient electronics and provide clear guidelines for advancing stretchable devices to new heights.