本研究是藉由原子轉移自由基聚合法 ( Atom Transfer Radical
Polymerization，ATRP ) ，聚合出末端帶有炔端的聚丙烯腈高分子
(Propargyl-PAN ) 及將矽晶片改質為疊氮層，再將Propargyl-PAN與晶
片表面上的疊氮層經由銅催化炔-疊氮環化加成反應( Copper-catalyzed
Azide-Alkyne Cycloaddition，CuAAC；點擊化學，Click Chemistry ) ，
將 Propargyl-PAN 高分子接枝於矽晶片表面上。PAN 高分子刷在氮氣
環境下經加熱使 PAN 環化交鏈。由 1H NMR 及FTIR光譜之鑑定，
證明本研究已成功合成出起始劑及 Propargyl-PAN；再經由ESCA 及
FTIR 光譜之鑑定，證實表面的自組裝層、疊氮層及Propargyl-PAN 高
分子已成功接枝於矽晶片表面上，以及更近一步證實PAN高分子刷因
加熱而環化交鏈。在接觸角方面因PAN高分子刷環化交鏈後有較疏水
的性質（119.2O）。在Propargyl-PAN聚合時間來到24小時，高分子刷
的厚度為144.08nm。使用SEM 與AFM，分析各製程的表面形貌及表
面粗糙度。電子束微影在矽晶片上製備出線寬比為1：2(400nm：800nm)
的正型光阻圖案，將光阻圖案之矽晶片進行自組裝後將光阻移除，即
可合成圖案化高分子刷。

In this work, functionalized polymer of Propargyl-PAN
(polyacrylonitrile) polymerized by Atom Transfer Radical Polymerization
(ATRP) was grafted to modified silicon wafer with azide group by Click
chemistry (Copper-catalyzed Azide-Alkyne Cycloaddition, CuAAC), and
utilized thermal curing with nitrogen flow to form cross-link PAN structure.
The so-called polymer brushes reached144.08nm in thickness after
polymerization time of 24 hour. 1H NMR and FTIR spectroscopy
demonstrated the initiator using in ATRP and Propargyl-PAN had
synthesized successfully. XPS and FTIR spectroscopy confirmed the
formation of self-assembly monolayer (SAM) on the silicon wafer and the
modification of silicon wafer with azide group and demonstrated
Propargyl-PAN had been grafted to silicon wafer by Click chemistry.
Furthermore, we demonstrated that PAN transformed from linear to
cross-link structure via thermal curing. Contact angle showed a more
hydrophobic characteristic (119.2°) refers to the cross-link structure. With
SEM and AFM images, we can determine the topography and roughness on
the surface between different parameters. We prepared a positive type
photoresist pattern with the width ratio 1:2 (400nm:800nm) on the silicon
wafer and then removing it after forming the self-assembly monolayer, and
went further polymerization to get the patterned polymer brushes on the
silicon wafer.

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