臺灣博碩士論文加值系統

為減少環境汙染，可再生之潔淨能源的利用成為重要因應策略，開發各種潔淨可再生能源如生質能、地熱能、海洋能、水力發電、風能及太陽能等等，太陽光熱是太陽能主要應用形式之一，其中太陽能選擇性吸收膜為太陽光熱系統中重要的組件，彩色的太陽能選擇性吸收膜可提供太陽光熱系統更多樣的設計性及增加其使用性。
本研究利用反應式磁控濺鍍製備多層堆疊結構之太陽能選擇性吸收膜，於銅基板上沉積CrAlN/Cr2O3/Al2O3之疊層結構吸收膜，分別改變Cr2O3及Al2O3厚度，製備不同顏色之彩色吸收膜，探討Cr2O3/Al2O3厚度組合對CrAlN/Cr2O3/Al2O3選擇性吸收膜顏色與光學性質之影響以及Cu/CrAlN/Cr2O3/Al2O3之熱穩定性能。使用場發射掃描電子顯微鏡 (FE-SEM)，能量散射光譜儀 (EDS) 及低掠角X光繞射儀 (GIXRD) 觀察各組成膜層之表面、結構及化學組成。使用橢圓偏光儀量測各單層薄膜CrAlN、Cr2O3及Al2O3的折射率及消光係數。使用紫外線/可見光/近紅外光分光光譜儀(UV/VIS/NIR) 及傅立葉轉換紅外光譜儀 (FTIR) 裝置積分球量測吸收率(α)及熱輻射率(ε)。
研究結果顯示Cu/CrAlN/Cr2O3/Al2O3能夠藉由改變Cr2O3/Al2O3厚度組合，影響入射光的干涉行為，造成反射光譜形貌改變而呈現不同顏色，分別改變Cr2O3厚度由80 nm、100 nm至120 nm；Al2O3厚度由50 nm、70 nm至90 nm，吸收膜顏色分別呈現出黃、青藍、藍、藍綠及紫等不同顏色，並以CIE色度座標標示；本實驗之彩色太陽能吸收膜之吸收率表現介於0.86至0.95，熱輻射率則介於0.17至0.19。藉由真空與大氣環境下退火持溫2小時，探討吸收膜之熱穩定性能，透過量測退火前後光學性質變化，結果顯示大氣熱穩定達300 ℃，真空熱穩定達500 ℃。

In order to reduce environment pollution, various renewable energies such as biomass energy, geothermal energy, tidal energy, hydro-electric power, wind energy, and solar energy, have been used. The solar photo-thermal system is one main application of solar energy. The solar selective absorber plays an important role in solar thermal system. The colored solar selective absorbers can increase the diversity and application of solar photo-thermal system.
In this study, a multi-layer spectrally selective absorber films were deposited by reactive magnetron sputtering. The structure of CrAlN/Cr2O3/Al2O3 absorbers were deposited on Cu substrates. The effect of thickness of Cr2O3 and Al2O3 on the optical properties and colors of absorbers were be studied.
The structure of the studied films was characterized by Field Emission Scanning Electron Microscopy(FE-SEM) and Grazing Incident X-Ray Diffraction(GIXRD). The chemical composition of the coatings was measured by Energy Dispersive Spectrometer(EDS). The refractive indexes and extinction coefficient of CrAlN, Cr2O3 and Al2O3 films were obtained by ellipsometer. The coatings of solar absorbance(α) and thermal emittance(ε) were calculated from the data of measured relative reflectance obtained by UV/VIS/NIR Spectrophotometer and a Fourier Transform Infrared Spectroscopy(FTIR).
Experimental results show that the solar selective absorbing coatings with multilayer structure can display different colors by changing the layer thickness. We adjusted the thickness of the Cr2O3 layer (80 nm, 100 nm and 120 nm) and the Al2O3 layer (50 nm,70 nm and 90 nm). The color of the samples contains yellow, greenish-blue, blue, lightsea-green and purple. This can be further demonstrated by the CIE chromaticity diagram. In this work, the solar absorbance of these absorbers was between 0.86 and 0.95, the thermal emittance was between 0.17 and 0.19.
The thermal stability of the absorbing coatings is studied by annealing for 2 hours at high temperature in vacuum and in air. The optical properties were used to characterize properties of the coatings. The results showed that absorbing coatings were thermally stable at 300 ℃ in air and 500 ℃ in vacuum.

摘要.....i
Abstract.....ii
誌謝.....iv
目錄.....v
表目錄.....vii
圖目錄.....ix
第一章、緒論.....1
1.1 前言.....1
1.2 研究動機.....2
第二章、文獻探討.....3
2.1 太陽能選擇性吸收膜.....3
2.1.1太陽光與熱輻射之特性.....3
2.1.2理想太陽能選擇性吸收膜之性質.....4
2.1.3太陽能選擇性吸收膜之種類.....4
2.1.3.1本質吸收型吸收膜.....4
2.1.3.2陶瓷-金屬堆疊型選擇性吸收膜.....5
2.1.3.3表面結構型吸收膜.....5
2.1.3.4多層堆疊型吸收膜.....5
2.2 鍍層材料.....5
2.2.1氮化鋁鉻(CrAlN).....5
2.2.2氧化鉻(Cr2O3).....6
2.2.3氧化鋁(Al2O3).....6
2.3 物理氣相沉積(Physical Vapor Deposition,PVD).....7
2.3.1 濺鍍.....7
2.3.2 濺鍍系統 .....7
2.3.2.1 直流濺鍍系統 (DC Sputtering System).....7
2.3.2.2 射頻濺鍍系統 (RF Sputtering System).....7
2.3.2.3 磁控濺鍍系統 (Magnetron Sputtering System).....8
2.3.2.4 反應式濺鍍系統 (Reactive Sputtering System).....8
2.4光學能隙計算.....9
2.5 CIE色度座標.....10
第三章、實驗步驟及儀器介紹.....15
3.1 實驗材料.....15
3.1.1 靶材.....15
3.1.2 化學藥品 15
3.1.3 氣體.....15
3.1.4 基板.....15
3.2 製程設備與分析儀器.....16
3.2.1 反應式磁控濺鍍系統 (Reactive Magnetron Sputter System).....16
3.2.2 紫外光/可見光/近紅外光光譜儀 (UV/Vis/NIR Spectrophotometer).....16
3.2.3 X光繞射分析儀(X-ray Diffraction).....17
3.2.4 場發射掃描式電子顯微鏡 (Field Emission Gun Scanning Electron Microscopy).....17
3.2.5 能量散射光譜儀(Energy Dispersive Spectroscope).....17
3.2.6 傅立葉轉換紅外光譜儀 (Fourier-transform infrared spectroscopy).....18
3.2.7 四點探針 (Four-Point Probe).....18
3.2.8 橢圓測厚儀 (Eillipsometer).....18
3.3 實驗製程.....19
3.3.1 基材前處理.....19
3.3.2單層與多層堆疊薄膜之製備.....19
3.3.3 熱穩定測試.....20
3.4 實驗流程.....21
第四章、結果與討論.....24
4.1 單層Cr1-XAlXN鍍膜之製備及性質探討.....24
4.1.1 Cr1-XAlXN之元素鑑定、形貌及微結構影響.....24
4.1.2 Cr1-XAlXN之光學性質與電性影響.....28
4.2 單層Cr1-XAlXN鍍膜之熱穩定性能探討.....32
4.2.1 Cr1-XAlXN鍍膜經真空熱穩定測試後之形貌及結構影響.....32
4.2.2 Cr1-XAlXN鍍膜經大氣熱穩定測試後之形貌及結構影響.....40
4.3 單層Cr2O3及Al2O3之性質探討.....47
4.4多層堆疊吸收膜之製備及性質探討.....51
4.4.1疊層參數選定.....51
4.4.2逐層堆疊吸收膜之膜層結構與光學性質.....54
4.4.3 Cr2O3/Al2O3厚度組合對堆疊吸收膜顏色與光學性質的影響.....57
4.5 Cu/CrAlN/Cr2O3/Al2O3之熱穩定性能探討.....66
4.5.1真空熱穩定測試.....66
4.5.2大氣熱穩定測試.....73
4.5.3疊層吸收膜大氣熱穩定失效原因探討.....80
第五章、結論.....83
參考文獻.....84

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