本研究利用掃描探針顯微鏡及掃描熱探針微影技術來探討均聚物及嵌段共聚物薄膜之結晶行為和形貌特性。掃描熱探針微影技術利用微米及奈米尺度熱探針在同排聚苯乙烯均聚物薄膜上進行定點熱處理。檢視原始及施加掃描熱探針微影技術處理的同排聚苯乙烯薄膜觀察其成核誘導時間及結晶成長行為。掃描熱探針微影技術提供熱植種所需的能量有效地加速同排聚苯乙烯成核誘導時間。和同排聚苯乙烯自結晶相比，經掃描熱探針微影處理之同排聚苯乙烯薄膜在140度恆溫結晶下其成核誘導時間快了20分鐘。另外，對所有試片來說同排聚苯乙烯的結晶成長速度保持相同。
嵌段共聚物，P4VP-b-PMMA,用來製備具有兩性表面結構的薄膜。逐層分子自組裝經由交替吸附帶負電的PAA及帶正電的P4VP在P4VP-b-PMMA薄膜上形成多層自組裝層，特別只在富含P4VP的區域上。這些有著不同多層自組裝層厚度及回火處理的試片利用掃描探針顯微鏡得到其表面形貌並經由快速傅立葉轉換分析。 快速傅立葉轉換分析可以使表面疏水的PMMA及親水的PAA/P4VP相分離現象加以量化。結果亦指出靜電形成之多層自組裝層可以使原本在熱處理之後會消失的P4VP區域留在原地不動。
本實驗示範了無論是在均聚物或是嵌段共聚物薄膜上分子級的重新排列。定點熱植種加速了成核誘導時間並可使高分子在所需的圖形下進行結晶。嵌段共聚物的相分離行為可被附著在其上的奈米結構多層自組裝層改變。

In this research work, the crystallization behavior and the morphological features of homopolymer and block copolymer thin films were investigated using the scanning thermal lithography (SThL) and the scanning probe microscopy (SPM). SThL technique was equipped with micro- or nano-scaled thermal probes providing the in-situ thermal treatment to the homopolymer thin films made of the isotactic polystyrene (i-PS). The induction period and the crystal growth of the i-PS thin films were examined with or without the desired SThL processes. SThL provided the energy to the thermal seeding which significantly accelerated the induction time of the i-PS nucleation. In comparison with the self-nucleation behavior, SThL-treated i-PS thin films revealed the induction period as fast as 20 minutes at the isothermal crystallization of 140 oC. Alternatively, the rates of the i-PS crystal growth remained the same for all samples.
Block copolymer, P4VP-b-PMMA, was employed to prepare the thin film samples containing amphiphilic surface structures. Self-assembly layer-by-layer multilayers based on the alternating adsorptions of anionic PAA and cationic P4VP were introduced to the P4VP-b-PMMA thin films where the multilayers were established exclusively to the P4VP-enriched domains. Surface morphologies of these samples with various multilayer thicknesses and annealing treatments were extracted by SPM, followed by the analysis of the fast Fourier transform (FFT). FFT analysis quantified the surface phase separations constructed by the hydrophobic PMMA and hydrophilic PAA/P4VP. Results also indicated the electrostatic multilayers immobilized the P4VP domains originally submerged upon the thermal treatment.
This work demonstrates the molecular-level rearrangements achieved in either homopolymer or block copolymer thin film samples. In-situ thermal seeding accelerates the induction period and directs the polymer crystallization with desired patterns. Phase separations of block copolymers can be altered by the nanostructured multilayers attached to the surfaces.

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