迄今為止，金屬表面電漿技術因其獨特的光學現象和各種應用而受到了廣泛的關注。目前較為常用的金屬表面電漿材料是：金和銀，在可見及近紅外光譜區域具有良好的電漿子共振性能；鋁和銅，具CMOS製程兼容性，亦有相關的電漿子應用研究。然而，上述金屬的熱穩定性和化學穩定性，因其熔點不高，導致在高溫以及高功率應用受限。氮化鈦其熔點為~3000 oC，具耐高溫、金色金屬光澤、並具高導電率；其帶間吸收於~450 nm相對金的~520 nm更短波長，因此可應用於可見光和近紅外光譜區域的電漿子共振元件，並且於~6 K具有超導的特性。基於上述優勢，氮化鈦過去已成功應用於Si-CMOS的製程所需的阻擋層，以及作為電晶的閘極金屬、氮化物發光二極體的n型電極，因此與現有的半導體技術製程相兼容。
藉由超高真空條件的電漿輔助分子束磊晶(PA-MBE)技術，成長氮化鈦(111)薄膜於c面藍寶石基板上。透過調控氮電漿通量與生長溫度，優化氮化鈦薄膜的化學劑量TiNx (x≤1)來控制其光學性質。通過反射高能電子繞射(RHEED)，可即時了解磊晶情況，並觀察不同氮電漿通量成長對氮化鈦薄膜表面形貌。此外，利用橢圓偏光技術並藉由Drude-Lorentz模型擬合TiNx之介電常數。對於，晶體結構上的分析，高解析X射線繞射(HRXRD)掃描結果顯示，其半高寬約~200 arcsec；而穿透式電子顯微鏡(TEM)亦可獲得單晶繞射圖，並可得高倍率原子解析影像。同時，採用XPS縱向分析，驗證無氧元素存在於氮化鈦薄膜，更加證實了超高真空條件對高純度的氮化鈦磊晶的重要性。利用優化之氮化鈦薄膜成長條件，成長不同厚度的單晶氮化鈦薄膜，分別是4 nm、6 nm、8 nm、20 nm及30 nm。利用電子束微影(EBL)及感應電漿耦合蝕刻(ICP etching)製程，製作不同週期之光柵，調控其表面電漿共振峰值，成功獲得1-4 μm頻率選擇面。此項成果，可應用於熱光伏電之熱吸收器或熱發射器、近紅外－中紅外光感元件設計，以及生物感測應用等。

Metal surface plasmonic has received extensive attention due to its unique optical phenomena and various applications. Au and Ag as surface plasmon materials are commonly used in the visible/NIR spectra due to good resonance performance. Al and Cu are also studied for plasmonic applications due to CMOS compatibility. However, these metals have a limitation of high temperature/power applications due to thermal and chemical instability caused by their low melting point. The advantages of titanium nitride (TiN) are high-temperature resistance (mp ~3000 oC), golden metallic color, and high conductivity. Its interband absorption is at ~450 nm shorter than gold (~520 nm). Therefore, it can be applied to the visible/NIR spectral regions plasmon devices. Besides, it has superconducting behavior at ~6 K. Based on these advantages, TiN has been successfully applied in several fields, such as blocking layer of Si-CMOS process, gate metal of transistors, and n-type electrode of nitride-LEDs, exhibiting superior compatible with existing semiconductor process.
Epitaxial TiN (111) thin films are grown on c-sapphire by ultra-high vacuum PA-MBE technique. The stoichiometric TiN as well its optical properties are optimized by adjusting the N2 plasma flux and growth temperature. In-situ RHEED patterns offer the real-time epitaxy situation and indicate TiN surface topological changed under different N2 plasma flux. Drude-Lorentz model is utilized to define the permittivity of TiNx via ellipsometry spectra. HRXRD rocking curves show FWHM are ~200 arcsec; high resolution atomic images and selected area diffraction are demonstrated epitaxial and high-quality single crystal properties by TEM. XPS depth-profile illustrates oxygen-free results to indicate importance of ultra-high vacuum growth conditions. The different thicknesses ultrathin TiN film under optimized growth conditions are presented from 4 nm to 30 nm. The tunable frequency selective surface (1-4 μm) have been achieved by varying surface plasmon resonance via EBL and ICP etching to provide different periods grating nanostructures. This achievement could be applied for thermal photovoltaics emitter/absorber, NIR/MIR photodetector, and biosensor.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VI
表目錄 X
第一章 簡介以及原理 1
1.1 簡介及動機 1
1.1.1 表面電漿效應及超薄膜效應之研究理論 1
1.1.2 氮化鈦材料晶體特性及光學特性文獻回顧 7
1.2 論文結構及簡介 15
第二章 儀器介紹及原理 16
2.1 電漿輔助分子束磊晶系統(Plasma-assisted molecular beam epitaxy，PA-MBE) 16
2.2 晶體品質及表面分析系統 21
2.2.1 反射式高能電子繞射儀(Reflection high-energy electron diffraction，RHEED) 21
2.2.2 高解析X光繞射儀(High resolution X-ray diffractometer，HRXRD) 25
2.2.3 原子力顯微鏡(Atomic Force Microscope，AFM) 27
2.2.4 掃描式電子顯微鏡(Scanning electron microscope，SEM) 30
2.2.5 高解析穿透式電子顯微鏡(High resolution transmission electron microscope，HRTEM) 31
2.2.6 高解析電子能譜儀(High resolution X-ray photoelectron spectrometer，HRXPS) 32
2.3 電性分析系統 33
2.3.1 霍爾量測(Hall measurement) 33
2.4 光學分析系統 34
2.4.1 傅立葉轉換紅外光譜儀(Fourier-transform infrared spectroscopy，FTIR) 34
2.5 結構製程系統 35
2.5.1 電子束微影系統(Electron beam lithography，EBL) 35
2.5.2 感應耦合式電漿蝕刻系統(Inductive couple plasma etcher，ICP-etcher) 36
第三章 不同氮流量之氮化鈦的薄膜磊晶材料特性之研究與討論 37
3.1 基板的選擇 37
3.2 基板清理方法 38
3.3 緩衝層的選擇 39
3.4 氮化鈦薄膜於不同氮氣流量下成長 41
3.5 氮化鈦薄膜於不同氮氣流量下成長之高解析X光繞射分析 46
3.6 氮化鈦薄膜於不同氮氣流量下成長之高解析電子能譜分析 47
3.7 氮化鈦薄膜於不同氮氣流量下成長之表面形貌分析 50
第四章 超薄氮化鈦薄膜調控表面電漿色散曲線 59
4.1 成長氮化鈦超薄膜 59
4.2 氮化鈦超薄膜X光繞射分析 59
4.3 氮化鈦超薄膜之表面形貌分析 64
4.4 氮化鈦超薄膜之霍爾電性分析 70
4.5 氮化鈦超薄膜之結構製程 72
4.6.1 設計結構 72
4.6.2 清洗樣品及旋塗光阻 73
4.6.3 電子束曝光(EBL)及顯影 74
4.6.4 感應式電漿耦合蝕刻 74
4.7 霍氏轉換紅外光譜量測結果與色散曲線分析 79
第五章 結論 85
參考文獻 86

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