本研究探討利用四氫呋喃(THF)溶劑退火方法調控聚苯乙烯聚4 乙烯吡啶(polystyrene-block-poly(4-vinylpyridine)，P(S-b-4VP)) 微胞在矽基材(SiOx/Si)和接有聚苯乙烯(polystyrene, PS)接枝鏈的基材(PS4k-SiOx/Si, PS19k-SiOx/Si)上之聚變與裂變過程。基材上PS接枝鏈的長短對於微胞形態從圓球轉變成圓柱狀的變化速率具有極大的影響力。當P(S-b-4VP)微胞旋鍍在PS4k-SiOx基材上且處於溶劑退火的初期與中期階段，薄膜結構主要為圓柱狀形態。然而，當微胞旋鍍在SiOx/Si和PS19k-SiOx/Si基材時，底層的蘑菇狀(mushroom)接枝鏈會和旋鍍在上的微胞產生糾結(entanglement)與穿透(penetration)效應，使得微胞間不易互相合併形成圓柱形態，仍然維持圓球狀形態。當薄膜經THF溶劑退火時間超過300分鐘而達到退火末期時，不管是在SiOx/Si或是接有PS接枝鏈的基材上，結構均為圓球狀形態為主。另一方面，本研究亦利用照射紫外光臭氧(UV/ozone)來控制PS4k-SiOx/Si基材的表面能。PS4k-SiOx/Si照射紫外光臭氧(UV/ozone)後的表面性質差異可依照射時間長短分成表面氧化丶表面劣化丶高分子毛刷完全移除等三階段。而微胞在這些不同表面性質的基材上經溶劑退火後，其結構形態的轉變也隨之不同。我們進一步結合紫外光臭氧選擇性調控基材表面能等方式，製備出在微米尺度有序下同時具有圓柱與圓球的P(S-b-4VP)單層薄膜。

This work focuses on the temporal evolution of micellar nanostructures in solvent-annealed P(S-b-4VP) monolayer films on bare and PS-grafted substrates (PS4k-SiOx/Si, PS19k-SiOx/Si) under tetrahydrofuran (THF) vapor. The size of end-grafted PS homopolymers on Si substrates plays an important role in controlling the rate of structural transitions between spherical and cylindrical micelles through fusion or fission. At the early and intermediate stages of solvent annealing, cylindrical micelles are dominant over spherical micelles on a grafted layer of short brushes (PS4k-SiOx/Si). On substrates having an attractive surface (SiOx/Si) or a grafted layer of long PS chains (PS19k-SiOx/Si), upon solvent annealing, the major domain within thin monolayered films is still spherical micelles due to the retardation of micellar fusion by which spherical micelles merege to form cylindrical micelles. We ascribe the retardation of micellar fusion to the presence of the entanglement and interpenetration of micelles with the underlying chains in a mushroom-like conformation. Then the spherical micelles become the only discernible species if monolayered films are exposed to THF for time periods longer than 300 min (final stage) regardless of bare or grafted substrates. Besides, we also controlled the interfacial interactions by imposing UV/ozone (UVO) exposure to substrates that were initially coated with end-grafting a layer of short PS chains, by which the grafted PS chains would be oxidized, degraded or totally removed with controls over the UVO treatment time. The dynamics of the transition between spherical and cylindrical micelles was found to depend on the interfacial potentials as thin films were annealed in vapors of THF. On combining the chemical micropatterning of the grafted layer of PS brushes with UV/ozone etching, we prepared P(S-b-4VP) films that have cylindrical and parallel cylinders coexisting with a micro-scale order within the same monolayer.

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