本研究探討高分子的自組裝(self-assembly)行為再配合微接觸式壓印(micro-contact imprinting)控制對稱性雙團鏈共聚物非潤濕過程，以製備出具有微米層級結構(hierarchical structure)之高分子。實驗程序是利用具有大範圍六角有序PS陣列之基材，再藉由控制不同選擇性溶劑退火以得到不同的階層性薄膜。本實驗研究聚苯乙烯聚4乙烯吡啶(polystyrene-block-poly(4-vinylpyridine), P(S-b-4VP))在不同選擇性溶劑蒸氣刺激下表面型態的改變，以及其奈米結構受到微米陣列形狀之影響情形。當P(S-b-4VP)在四氫呋喃(THF)溶劑退火下，將形成奈米圓柱所組成之半圓液滴狀(droplet)非潤濕結構；在丙酮(acetone)及三氯甲烷(chloroform)蒸氣下則形成平行層板組成之梯田狀結構，其層板每層皆為PS-P4VP/P4VP-PS排列之完整層。相較而言，在二甲基甲醯胺(DMF)溶劑之動態退火過程時，其液滴狀非潤濕結構演化成三種微米結構，包含奈米圓球組成之梯田狀結構、奈米圓柱組成之半圓液滴狀結構以及由奈米層板組成之梯田狀結構。在DMF蒸氣下所形成之梯田狀結構，其層板厚度為PS-P4VP/P4VP-PS排列完整層之一半，故其層板每層由PS-P4VP排列之半層結構。上述奈米尺度及微米尺度之差異主要是由於在模板限制下，外在環境對高分子之刺激而回應之結果。最後我們發現在傾斜模板下退火時，液滴狀非潤濕結構會由於重力而移動，其移動情形受到溶劑蒸氣之選擇性以及內部奈米結構影響。We studied the self-assembly of block copolymer thin films with a combination of micro-contact imprinting and solvent annealing. Patterned substrates were prepared by selectively grafting PS chains on SiOx/Si by micro-contact imprinting. The PS-grafted regions have a hexagonal array on SiOx/Si. After spin coating on the patterned substrates, the block copolymer would selectively wet the PS-grafted regions with solvent vapor exposure. Therefore, solvent annealing causes dewetting-induced microdroplets with a microscopic order defined by the pattern of PS-grafted substrates. In this thesis, we investigated how relief polystyrene-block-poly(4-vinylpyridine), (P(S-b-4VP)) microstructures effected the internal nanostructures and microscopic shape on PS-patterned substrates in response to the solvent vapor selectivity. Upon annealing in THF vapor, the droplets comprised of nanospheres and the shape of each droplet is hemispherical cap. Solvent annealing in chloroform and acetone vapors led to terraced stack of lamellae. Each lamellar layer has the thickness of an entire PS-P4VP/P4VP-PS layer. In a dynamic process of DMF vapor annealing, the droplets would transform into three types of microstructures. They are nanosphere-comprised terraces, nanolamella-comprised terraces and nanocylinder-comprised droplets. For DMF annealed terraces, lamellar layers comprise PS-P4VP layer indicated that the thickness of PS-P4VP layer is half of the thickness of an entire PS-P4VP/P4VP-PS layer. The changes in nanoscale and microscale structures are due to the adaption of stimuli-responsive polymer materials to the free surface under the confinement of the patterned substrates. Finally, the movement of relief microstructures on a 30°-inclined patterned substrate was found to depend on the solvent solubility and internal nanostructures.
