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研究生： 巫雨諼
Wu, Yu-Hsuan
論文名稱： 貴金屬摻雜氧化錫奈米材料之醛類氣體選擇性表面增強拉曼散射感測
Selective Surface-Enhanced Raman Scattering Detection of Aldehyde Gases by Noble Metal-Doped Tin Oxide Nanostructure
指導教授： 黃志嘉
Huang, Chih-Chia
學位類別： 碩士
Master
系所名稱： 理學院 - 光電科學與工程學系
Department of Photonics
論文出版年： 2025
畢業學年度： 113
語文別： 英文
論文頁數： 102
中文關鍵詞： 表面增強拉曼散射 、氧化錫 、氣體感測 、選擇性檢測
外文關鍵詞： Surface-Enhanced Raman Scattering, SnO₂, Gas Sensing, Selective Detection
相關次數： 點閱：22  下載：0 
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    • 本研究旨在開發具高靈敏度之表面增強拉曼散射（Surface-Enhanced Raman Scattering, SERS）感測平台。SnO₂具備良好的電子傳輸特性與化學穩定性，是常見的感測材料，但單一SnO₂在訊號增強方面的表現仍有限。因此，我們嘗試以貴金屬摻雜來提升其SERS活性。實驗中，將摻雜Pd、Pt或Au的SnO₂膠體溶液與金鹽共同沉積在紙張基材上，並經紫外光照射還原金鹽，生成金奈米粒子，形成具SERS活性的金/半導體異質結構。SERS測量結果顯示，經Au摻雜的SnO₂基板，其SERS訊號強度較未摻雜基板提升約2.6倍，我們利用XPS、TEM及UV-vis等分析技術闡明了其中的基本機制與原理。
    另外，進一步在基板表面修飾4-胺基苯硫酚（4-ATP）分子後，成功建立針對醛類揮發性有機化合物（VOCs）的選擇性偵測系統。感測平台對甲醛與戊二醛的偵測極限分別為40 ppm及4 ppb，且呈現良好線性關係（R² > 0.95）。此優異偵測性能主要歸因於4-ATP分子胺基與醛基間的專一性化學交互作用。
    綜合而言，本研究成功整合金奈米結構、SnO₂基材與具官能基分子的表面設計，不僅有效提升SERS訊號與醛類氣體的選擇性，更建立具實用潛力之量化偵測策略，未來可望應用於環境污染監測與生物氣體感測等領域。

    This study establish a sensitive SERS sensing platform. SnO₂ is a standard sensing material with favorable electron transport, yet its undoped form shows limited Raman signal enhancement. Therefore, noble metal doping was employed to improve its SERS performance. In the experiments, Pd-, Pt-, or Au-doped SnO₂ colloidal solutions were co-deposited with gold salts onto paper substrates, followed by UV irradiation to reduce the gold salts and generate gold nanoparticles, forming SERS-active metal/semiconductor heterostructures. SERS measurements revealed that the Au-doped SnO₂ substrates exhibited approximately 2.6-fold higher Raman signal intensity compared to undoped substrates. The fundamental mechanisms were clarified through XPS, TEM, and UV-vis analyses.
    Furthermore, a selective detection system for aldehyde VOCs was established by functionalizing the substrate with 4-ATP. The platform demonstrated detection limits of 40 ppm for formaldehyde and 4 ppb for glutaraldehyde, with excellent linearity (R² > 0.95). The outstanding detection performance is primarily attributed to the specific chemical interactions between the amino groups of 4-ATP and the aldehyde groups.
    In summary, this work successfully integrates gold nanostructures, SnO₂ substrates, and functional molecules for surface modification, effectively enhancing SERS signals and aldehyde gas selectivity. The proposed quantitative sensing strategy demonstrates considerable potential for environmental pollution monitoring and biomedical gas detection applications.

    中文摘要 II Abstract III 致謝 IV Contents V Table Contents VIII Figure Contents IX Chapter 1 Conclusion 1 1.1 Volatile Organic Compounds (VOCs) 1 1.1.1 Hazards of VOCs and Their Impact on Health 1 1.1.2 Regulatory Standards for the Health Impacts of VOCs on Humans 4 1.2 Raman Spectroscopy 6 1.2.1 Raman Scattering 6 1.2.2 Surface-Enhanced Raman Scattering (SERS) 8 1.2.3 Electromagnetic Enhancement (EM) 9 1.2.4 Chemical Enhancement (CM) 12 1.3 Factors Affecting the SERS Enhancement Effect 14 1.3.1 Enhancement Mechanism of Heterostructures 14 1.3.2 Influence of Hotspot Effect 15 1.4 Types and Applications of SERS Substrates 17 1.4.1 Rigid Substrate 17 1.4.2 Flexible Substrate 18 1.4.3 Metal-Organic Framework Substrate 20 1.4.4 Applications of SERS Substrates 23 Chapter 2 Conclusion 28 Chapter 3 Conclusion and Materials 31 3.1 Materials 31 3.2 Instruments 33 3.3 Synthesis and preparations Methods 34 3.3.1 Synthesis of PVP Ink 34 3.3.2 Preparation of 5 mM HAuCl4 Solution. 34 3.3.3 Synthesis of 0.5% Au-doped SnO₂ Colloidal Solution 34 3.3.4 Synthesis of 0.5% Au-doped SnO₂ SERS Substrate 35 3.3.5 4-ATP-modified 0.5% Au-doped SnO2/Au substrate 36 3.3.6 SERS Measurement 37 3.3.7 Aldehyde Gas Sensing 37 Chapter 4 Conclusion and Discussion 39 4.1 Synthesis and Characterization of 0.5% Au-doped SnO2 nanoparticles 39 4.1.1 The Structure of 0.5% Au-doped SnO2 nanoparticles 40 4.1.2 The Morphology of 0.5% Au-doped SnO2 nanoparticles 42 4.1.3 Atomic-Scale Characterization of 0.5% Au-doped SnO2 nanoparticles by HR-TEM 44 4.1.4 X-ray photoelectron spectrum of 0.5% Au-doped SnO2 nanoparticles 47 4.2 0.5%Au-doped SnO2 nanoparticles on a SERS Substrate. 53 4.2.1 Mechanism of 0.5% Au-doped SnO2/Au Substrate. 53 4.2.2 Effects of Different Doped Metals on the Properties of SnO2/Au Substrates. 54 4.2.3 Optimization of 0.5% Au-doped SnO₂/Au Substrate. 57 4.2.4 SERS Performance Comparison of UV-Irradiated Metal Oxide Substrates. 59 4.2.5 Characterization of 0.5% Au-doped SnO₂/Au Substrate. 60 4.2.6 Effect of Different Excitation Wavelengths on the Reduction Behavior of Filter Paper 64 4.3 Detection and Comparison on 0.5% Au-doped SnO₂/Au substrate 67 4.3.1 Enhancement Mechanisms of Functional Group Molecules on SERS Substrates 67 4.3.2 SERS Enhancement Effect and Mechanism of Au-doped SnO₂/Au Substrate for Aldehyde Gases 69 4.3.3 The SERS Mechanism Verification of the Interaction Between 4-ATP and Aldehyde Molecules 72 4.3.4 Impact of Thiol Molecules on the Performance of Au-doped SnO₂/Au Substrate for Aldehyde Gases 76 4.3.5 Functional Group Gas Effects on the SERS Response of 4-ATP-Modified Au-doped SnO₂/Au Substrate. 78 4.3.6 Comparison of Detection Limits and Sensitivities for Aldehyde Gases Using Different Substrates 79 Chapter 5 Conclusion 81 Reference 83

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