超材料是一種新穎的跨領域技術，透過材料與奈米結構設計達成常態不可見的特殊性質，並廣泛應用於光電子學、電子工程、聲學與熱學等領域。在光電領域中，透過奈米尺度的結構設計，在金屬與介電質的交界面發生電子震盪形成的表面電漿子共振，由於其引發的局域電場增強與環境靈敏特性，可發展高靈敏生物元件、動態無標定檢測、奈米解析度光學顯微鏡等。
常見的表面電漿子共振激發是利用稜鏡的全反射或光柵的繞射特性，精準補償光的水平動量使與表面電漿子產生耦合。我們透過精確的模擬與製程，製作奈米尺度之光柵耦合表面電漿子共振感測晶片，用於樣品的折射率與拉曼指紋量測，並設計表面電漿子共振波長坐落在綠光雷射波長範圍，使得綠光拉曼量測時得到很強的表面增強拉曼散射效果，兼具定性與定量的雙重檢測能力。實驗結果顯示最佳的線性靈敏度337nm/RIU與解析度達4.4x10-5 RIU、拉曼增強因子高於106。我們也比較了不同偏振角度的量測，驗證入射光電場方向垂直奈米光柵時，始有表面電漿子共振效應，與預期吻合。此外，此晶片可適用於波長變化和強度變化兩種折射率量測方法，提供了系統簡化的可行性。
相較於常見的一階繞射模態光柵耦合，我們利用高階繞射激發表面電漿子共振，放寬製程的線寬要求，以應用於光罩微影製程，減少成本並提高產量。我們也使用相同的製程技術製備金屬-介電質-金屬光柵耦合表面電漿子共振感測晶片，和純銀的光柵晶片量測結果做比較，透過模擬進一步分析兩者共振模態的差異，以證實我們的模擬可信度。
最後，我們實際使用老鼠之白血球介素-六作為生物檢測對象置於光柵晶片，實驗得最佳線性檢測極限值可達1.2pg/mL，證實其奇佳的檢測能力，相較於現有常規檢測方式，我們的光柵晶片提供了即時、無標定、定量定性的多重檢測能力。

Metamaterials represent a cutting-edge technology that utilizes nano-scaled design to achieve extraordinary properties not found in traditional materials, and finds diverse applications in the fields of electronics, acoustics, thermal, and optics science. In the realm of photonic metamaterials, one fascinating phenomenon involves the excitation of surface plasmon resonance (SPR) through precisely designed nanostructures at the interface between metal and dielectric. The most commonly employed ways to excite surface plasmons (SPs) entail total internal reflection from prism or the diffraction of a grating. These approaches could compensate the horizontal momentum of light to achieve optimal coupling with surface plasmons.
SPR could generates localized field enhancements and exhibits remarkable sensitivity to the surrounding environment. Consequently, it has enabled the development of high-sensitivity biochemical devices, dynamic label-free detection techniques, and nano-scaled analysis. In this work, we aim to design a unique grating-coupled SPR sensing chips capable of measuring both refractive index and Raman fingerprints of analyte. Our design specifically targets the resonance wavelength to align with the green light spectrum, thereby benefiting from the strong surface enhanced Raman scattering effect during green laser excitation. Besides, our chips utilize the high-order diffraction mode SPR and could be applied on not only wavelength interrogation but also intensity interrogation of normal incident light, delivering the cost-efficient fabrication processes and compact system.
From the experimental results, we found that the grating chip exhibits impressive performance in both SPR sensing and Raman measurement, including the best linear sensitivity of 337nm/RIU, resolution of 4.4x10-5 RIU, and Raman enhancement factors surpassing 106. To further evaluate the performance of our chip, we used Interleukin-6 extracted from mice as the target for biochemical detection. The experiment results showcased an impressive limit of detection (LOD) value of 1.2 pg/mL, validating the exceptional detection capabilities.
In conclusion, our nano-grating sensing chip offers label-free and multiplex detection ability, thereby providing a powerful tool for dual-functional quantitative and qualitative analysis in various applications.

摘要………………………………………………………………………………………………………………………………………………………………… I
Abstract………………………………………………………………………………………………………………………………………………………II
致謝……………………………………………………………………………………………………………………………………………………………… IV
Contents…………………………………………………………………………………………………………………………………………………………V
List of Figures……………………………………………………………………………………………………………………………… IX
Chapter 1 Introduction…………………………………………………………………………………………………………………1
Chapter 2 Theory and Literature Review…………………………………………………………………………3
2.1 Surface Plasmon…………………………………………………………………………………………………………………………3
2.1.1 Surface Plasmon Resonance …………………………………………………………………………………………3
2.1.1.1 Excitation of surface plasmons ………………………………………………………………………3
2.1.1.2 Total internal reflection configuration ……………………………………………6
2.1.1.3 Grating configuration………………………………………………………………………………………………7
2.1.2 Interrogations of SPR systems………………………………………………………………………………9
2.1.2.1 Wavelength interrogation…………………………………………………………………………………………9
2.1.2.2 Angle interrogation……………………………………………………………………………………………………11
2.1.2.3 Intensity interrogation…………………………………………………………………………………………13
2.1.2.4 Phase interrogation……………………………………………………………………………………………………14
2.1.3 Localized Surface Plasmon Resonance…………………………………………………………………15
2.1.3.1 Extinction cross-section of LSPR……………………………………………………………………15
2.1.3.2 Morphology dependency…………………………………………………………………………………………………16
2.2 Plasmon Resonance-based Sensors………………………………………………………………………………18
2.2.1 Dynamic and label-free detection………………………………………………………………………18
2.2.2 Surface-Enhanced Raman Scattering (SERS) ……………………………………………21
2.3 Introduction of Interleukin-6……………………………………………………………………………………24
Chapter 3 Motivation……………………………………………………………………………………………………………………25
Chapter 4 Simulation………………………………………………………………………………………………………………………27
4.1 Simulation Setup………………………………………………………………………………………………………………………27
4.1.1 Environment setting…………………………………………………………………………………………………………27
4.1.2 Diffraction order of grating-coupled SPR…………………………………………………28
4.2 Optimization…………………………………………………………………………………………………………………………………29
4.2.1 Parametric sweep…………………………………………………………………………………………………………………29
4.2.1.1 Grating period (P) sweeping…………………………………………………………………………………30
4.2.1.2 Duty cycle (D) and refractive index (na) sweeping……………………31
4.2.2 Field distribution…………………………………………………………………………………………………………32
4.2.3 Metal-insulator-metal (MIM) grating…………………………………………………………………33
Chapter 5 Experimental Section…………………………….……………………………………………………………36
5.1 Experimental Procedure…………………………………………………………………………………………………………36
5.2 Fabrication equipment……………………………………………………………………………………………………………37
5.2.1 Physical Vapor Evaporation (E-gun Evaporator) ……………………………………37
5.2.2 Auto Spin Coater/Developer (TRACK) …………………………………………………………………38
5.2.3 Photolithography Stepper System (I-line Stepper) ……………………………39
5.3 Analysis equipment and Optical Setup……………………………………………………………………40
5.3.1 Scanning Electron Microscope (SEM) …………………………………………………………………40
5.3.2 Atomic Force Microscopy (AFM) ………………………………………………………………………………41
5.3.3 Fourier Transform Infrared Spectroscopy (FTIR) ………………………………41
5.3.4 Ultraviolet-Visible Spectroscopy (UV-vis) ……………………………………………42
5.3.5 Confocal Raman Microscopy………………………………………………………………………………………43
Chapter 6 Results and Discussion………………………………………………………………………………………44
6.1 Morphology……………………………………………………………………………………………………………………………………44
6.1.1SEM results…………………………………………………………………………………………………………………………………44
6.1.2AFM results…………………………………………………………………………………………………………………………………45
6.2 SPR Sensing Performance……………………………………………………………………………………………………46
6.2.1 Wavelength interrogation……………………………………………………………………………………………46
6.2.2 Intensity interrogation…………………………………………………………………………………………………52
6.2.3 MIM grating sensing performance…………………………………………………………………………53
6.3 SERS Sensing Performance…………………………………………………………………………………………………56
6.3.1Enhancement Factor calculation…………………………………………………………………………………56
6.3.2 Polarization dependency………………………………………………………………………………………………58
6.4 Detection of Interleukin-6……………………………………………………………………………………………59
6.4.1 SPR sensing results………………………………………………………………………………………………………59
6.4.2 SERS sensing results……………………………………………………………………………………………………60
6.5 Comparison and Improvement………………………………………………………………………………………………62
Chapter 7 Conclusion………………………………………………………………………………………………………………………64
Chapter 8 Appendix……………………………………………………………………………………………………………………………65
Chapter 9 Reference………………………………………………………………………………………………………………………68

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