本研究旨在探討透過混摻不同分子量的均聚物聚苯乙烯 (hPS) 來調控團鏈共聚物聚苯乙烯－聚4乙烯吡啶 (PS-b-P4VP) 微胞在四氫呋喃 (THF) 蒸氣中進行溶劑退火的側向有序性及微胞大小。我們發現短鏈長的hPS可以有效緩解PS-b-P4VP微胞－微胞間以及微胞－基材間受拉伸造成的自由能上升，且使PS-b-P4VP更趨向於球狀微胞結構，而此效果隨著鏈長的增加而降低，在長鏈長的hPS混摻下，由於長鏈上更喜好自糾纏而不喜參與微胞的組成，無法潤濕的乾毛刷將與PS-b-P4VP形成巨觀相分離，造成微胞由差排造成的有序性下降。而尾端皆有羫基的聚苯乙烯 (hPS-OH) 因其在矽基材 (SiOx/Si) 上具有更好的潤濕性能有效緩解基材與PS-b-P4VP鏈間拉伸所造成的自由能上升，因此在混摻相近分子量下的hPS-OH皆較混摻hPS有更低的缺陷密度和更高的有序性。 混摻均聚物對微胞結構重組的效應可分為三個階段： (1) 膨潤初期均聚物僅影響微胞的擴散速率造成有序性的變化，微胞大小影響並不明顯； (2) 膨潤充足後，均聚物才逐漸改變微胞的的大小； (3) 當退火結束的快速乾燥過程中，均聚物影響鏈的收縮亦影響到乾燥誘導微胞的有序性。透過KTHNY理論及GI-SAXS的量測可得混摻小分子量的HPs下長程方位有序以及近長程的平移有序，大範圍掃描所呈現的摩爾紋則發現在1個小時的THF退火下便可達到8*8 μm2的有序陣列。 ;In this study, we aim to blend polystyrene homopolymerss (hPS) of various molar masses with PS-b-P4VP block copolymers (BCPs) to control the spatial ordering of spherical micelles on top of bare (SiOx/Si) during solvent vapour annealing (SVA) processes in THF vapour. Small amounts of hPS added into the PS-b-P4VP block copolymer easily induce the formation of spherical nanodomains with long-range spatial order and, on the other hand, added hPS and its derivatives with hydroxylic chain ends (hPS-OH) could interact with the substrate to relax the packing frustration of the PS-b-P4VP spherical micelles at planar interfaces, which further destroyed the packing order via a two-stage melting process. We find that blending shorter chains of hPS can more effectively bring about long-range orientational order and quasi-long range translational order of PS-b-P4VP micellar films. Also we find that the hydroxyl chain ends of hPS-OH preferentially reside at the substrate-film interface so as to improve wettability of the micelle films on the bare and PS-grafted substrates. As result, an 8 * 8 μm2 long-range order of arrays of PS-b-P4VP/PS micelles could be achieved by SVA under THF vapor.
