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研究生： 蘇晟銘
Su, Cheng-Ming
論文名稱： 基於蝕刻矽孔洞中奈米銀團簇表面增強拉曼散射核鹼基感測器
Nucleobase Sensors Based on Surface Enhanced Raman Scattering of Silver Nanoclusters in Etched Silicon Holes
指導教授： 曾永華
Tzeng, Yon-Hua
學位類別： 碩士
Master
系所名稱： 電機資訊學院 - 微電子工程研究所
Institute of Microelectronics Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 70
中文關鍵詞： 表面增強拉曼散射 、核鹼基 、DNA感測器 、奈米銀粒子
外文關鍵詞： surface-enhanced Raman scattering, nucleobases, DNA sensors, silver nanoparticles
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    • 脫氧核糖核酸（DNA）是存在於生命體中重要且具有遺傳訊息的生物分子，其中DNA分子由四個不同的核鹼基所構成，分別為腺嘌呤（縮寫為A）、胸腺嘧啶（T）、胞嘧啶（C）、鳥嘌呤（G），而無標記且未修飾的DNA檢測及定序是DNA分析的一個挑戰，倘若能夠藉由表面增強拉曼光譜（Surface-Enhanced Raman Scattering,SERS）放大吸附分子信號的能力，則可提供具有高靈敏度的化學訊息，是適合用於DNA分析的工具之一，也能在生物學及醫學研究給予助益。
    本文提出了一具備高增強效應、穩定性及可再現性的表面增強拉曼光譜感測器，透過實驗，嘗試在蝕刻後的金字塔結構矽基板上濺鍍一層銅薄膜，經高溫退火後，即會沉積些許分散的銅塊於金字塔側壁及孔洞中，為使感測器產生更多的熱點，於是將基板浸置於硝酸銀水溶液中，使較多的銀沉積在退火後的銅結構上，形成堆疊緊湊且具備高局部電場的三維奈米級銀顆粒團簇，經過雷射光激發下顆粒間電場相互耦合，電磁效應增強拉曼訊號隨之增加。
    藉由我們實驗所製備的感測器，量測四種不同單分子核鹼基的檢測極限，以及將兩種相異的核鹼基進行雜化測量極限，由上述實驗結果得出DNA分子間的吸附性差異，對於腺嘌呤水溶液最低檢測極限為10^(-14) M，胞嘧啶(檢測限10^(-12) M）、鳥嘌呤(檢測限10^(-11) M）、胸腺嘧啶(檢測限10^(-8) M）也能檢測出較低的濃度。

    Deoxyribonucleic acid (DNA) is an important biological molecule with genetic information in the human body. The DNA molecule is composed of four different nucleobases, namely adenine (abbreviated as A), thymine (T), cytosine (C), and guanine (G). The detection and sequencing of unlabeled and unmodified DNA is a challenge for DNA analysis. If the ability of Surface-Enhanced Raman Scattering (SERS) to amplify the signal of adsorbed molecules can provide highly sensitive chemical information, it is one of the tools suitable for DNA analysis, and it can also be used in biology.
    Our team proposed a surface-enhanced Raman spectrum sensor with high enhancement effect, stability and reproducibility. In the experiment, the three-dimensional copper structure in the etched pyramid structure silicon substrate is immersed in a silver nitrate aqueous solution to form a compact stack of three-dimensional nano-scale silver particle clusters with a high local electric field. The electric field between particles is coupled with each other under the excitation of laser light, and the electromagnetic effect enhances the Raman signal.
    We use the prepared sensor to measure four different single-molecule nucleobases. From the experimental results, we can conclude that the adsorption capacity of DNA molecules is different. The lowest detection limit for adenine aqueous solution is 10^(-14) M, and lower concentrations can be detected for cytosine(Detection limit 10^(-12) M), guanine(Detection limit 10^(-11) M), and thymine(Detection limit 10^(-8) M).

    第一章 緒論 1 第二章 文獻回顧 2 2.1 矽奈米結構蝕刻及製造介紹 2 2.1.1 氣液固生長（VLS） 2 2.1.2 金屬輔助化學蝕刻 4 2.1.3 硫酸銅蝕刻機制 5 2.1.4 反應性離子蝕刻（Reactive ion etching, RIE） 7 2.1.5 電化學蝕刻（Electrochmeical etching） 9 2.2 三維微結構基板介紹 10 2.2.1金字塔結構 (Pyramid structure) 10 2.3 表面增強拉曼散射（Surface-Enhanced Raman Scattering, SERS） 13 2.3.1 拉曼光譜介紹 13 2.3.2 表面增強拉曼散射（Surface-Enhanced Raman Scattering,SERS） 16 2.3.3 單分子核鹼基吸附性差異 24 第三章 實驗方法 26 3.1 實驗流程介紹 26 3.2 實驗製程設備 28 3.2.1 濕蝕刻化學反應槽設計 28 3.2.2 射頻磁控電漿濺鍍系統（RF magnetron Sputtering system） 28 3.2.3 熱化學氣相沉積機台（Thermal CVD） 33 3.2.4 化學反應槽設置 37 3.3 實驗分析量測儀器 38 3.3.1 光學顯微鏡（Optical Microscople,OM） 38 3.3.2 掃描式電子顯微鏡（Scanning electron microscopy,SEM） 38 3.3.3 原子力顯微鏡（Atomic force microscope） 40 3.3.4 拉曼光譜儀（Raman spectroscopy） 40 第四章 結果與討論 42 4.1 三維蝕刻孔矽基板的製備探討 42 4.2 濺鍍銅薄膜及退火製程探討 45 4.2.1 銅薄膜製程量測分析 45 4.2.2 蝕刻孔洞上覆蓋銅薄膜退火製程量測分析 47 4-3 蝕刻孔洞中三維銅結構複合銀奈米團簇對於表面拉曼散射基板 50 4.4 SERS基板量測 51 4.4.1 浸置於硝酸銀溶液反應時間探討 51 4.4.2 二維結構基板與三維結構基板比較 54 4.4.3 單分子核鹼基SERS量測 55 4.4.4混和核鹼基SERS量測 62 第五章 結論與未來展望 65 第六章 參考資料 66

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