論文的第一部分，利用調配不同濃度的聚苯乙烯聚2乙烯吡啶(Polystyrene-block-poly(2-vinylpyridine), P(S-b-2VP))溶液以控制高分子模板之表面覆蓋率，進而含浸至硝酸銀的乙醇溶液，藉由紫外光還原而得到點狀的有序銀粒子陣列。隨著紫外光曝曬的時間增加，高分子模板的劣化使得聚集的銀粒子無法受模版侷限，因而造成聚集的銀粒子散佈於基材上。藉由控制粒子間距以及觀察粒子隨著紫外光照射的變化可得知當銀粒子間距較小時，吸附上Rhodamine 6G後能夠有較強的表面增強拉曼效應。本研究除了利用模板來控制粒子間距，在論文的第二部分使用聚苯乙烯聚４乙烯吡啶(Polystyrene-block-poly(4-vinylpyridine), P(S-b-4VP))經由溶劑退火的方式，製造圓球狀的微胞模版以及圓柱狀的微胞模版。形成圓球狀及圓柱狀的微胞模版含浸至乙醇，分別形成了具有奈米級孔洞的薄膜與指紋狀的奈米溝槽薄膜。進一步利用四種不同形狀的模板：圓球狀、圓柱狀、奈米孔洞與指紋狀的奈米溝槽，以氬氣電漿的方式還原銀離子得到不同形狀的奈米銀陣列。當增加氬氣電漿處理的時間，由圓球狀與圓柱狀模版所製成的奈米銀陣列較能維持模版給予的有序性。此外，當氬氣電漿處理三百秒後，藉由指紋狀的奈米溝槽模版製備的奈米銀陣列，吸附上Rhodamine 6G則具有較強的表面拉曼增強訊號。Tailor-made templates through self-assembly of block copolymers are capable of fabricating technologically nanostructured substrates. In this thesis, a sample but robust method is demonstrated to fabricate arrays of silver nanostructures with morphological diversity and a tunable adjacent gap for large area surface-enhanced Raman spectroscopy (SERS) substrates. First, nanostructured silver arrays of adjustable particulate size and inter-particle distance were fabricated by block copolymer templates for SERS substrates. The templates were formed by polystyrene-block-poly(2-vinylpyridine), P(S-b-2VP), micelles. The silver arrays with various surface coverage were prepared by spin-coating from o-xylene solution of varied polymer concentration (0.3 and 0.8 wt%). Photochemical reduction was applied to reduce silver ions after the P(S-b-2VP) micellar films were immersed in ethanol containing AgNO3. The interplay between the reduction of Ag+ and the removal of the P(S-b-2VP) template during UV-exposure for various time intervals affect the growth and spatial order of Ag nanoparticles, which in turn influences their SERS properties. Moreover, polystyrene-block-poly(4-vinylpyridine) was used to produce spherical micellar templates and cylindrical micellar templates through solvent annealing. Nanoporous and nanogrooves templates were made when spherical micellar templates and cylindrical micellar templates were immersed in ethanol. Spherical micelles, cylindrical micelles, nanoporous, and nanogrooves were utilized to fabricate silver arrays. Petal-like cluster, fingerprint clusters, network clusters and reverse fingerprint clusters were produced by reducing silver salts in BCP templates. Through long time of Ar plasma treatment, petal-like clusters and fingerprint clusters could maintain the order of spherical micellar templates and cylindrical micellar templates. Furthermore, reverse fingerprint clusters with R6G adsorption had the strongest SERS enhancement through Ar plasma treatment for 300 sec.
