本研究討論聚苯乙烯聚氧化乙烯(poly(styrene-block-ethylene oxide, P(S-b-EO))團鏈共聚合物在矽基材上之薄膜，藉由混合溶劑退火(甲苯/丁醇)與退火時間的關係，誘導其薄膜產生梯田狀結構和微觀相分離結構。受溶劑退火期間，薄膜為了滿足膜厚相稱性而產生梯田狀結構。在短時間內 (溶劑退火12小時)，薄膜表面之梯田狀結構是由三種不同大小之圓球以兩類型的六角陣列依磊晶方式所構成。個別的六角陣列有其對應之相對薄膜厚度。在長時間中 (溶劑退火16和 20小時)，圓球狀微觀相分離結構經由融合成長為平行基材方向之圓柱狀結構。也因為非潤濕現象讓薄膜產生擾動，而梯田狀結構則會進一步形成以圓柱狀微觀相分離結構所構成之多層薄膜厚度，並且探討P(S-b-EO)薄膜受混合溶劑退火誘導之相轉變機制。最後，本論文進一步探討膜厚效應、基材界面受PS鏈段改質以及混合溶劑種類對P(S-b-EO)的薄膜奈米微結構之影響。In this study, we have investigated the temporal evolution of relief terraces and microphase-separated nanodomains in poly(styrene-block-ethylene oxide) P(S-b-EO) on silicon substrates (SiOx/Si) annealed under toluene/butanol vapors. For thin films, solvent annealing causes the formation of relief terraces. With solvent annealing for 12 h, hexagonal arrays of nanospheres of three sizes are dominant over the surface morphology of relief-terraced microstructures with epitaxial packing. The coexistence of nanospheres of three sizes is ascribed to a morphology triggered by the constraint of the film thickness. Upon exposure to toluene/butanol vapors for 16 and 20 h, these nanospheres become metastable and grow further into nanocylinders lying on the surface. During dewetting, the undulations of the local thickness and the nanodomain transitions are inseparable, consequently forming relief terraces comprising multiple layers of lying nanocylinders. The mechanisms and causes of nanodomain transitions of varied routes in solvent-annealed P(S-b-EO) films are analyzed and discussed. Finally, the influences of film thickness, PS-grafted substrates and binary mixed vapors of nonpolar (toluene) and polar solvents (water, methanol, ethanol or propanol) on the nanodomains of P(S-b-EO) were investigated.
