系統識別號 U0026-3008202002095600
論文名稱(中文) 應用於高溫之高熵氧化物太陽能吸收膜
論文名稱(英文) High Entropy Oxide Thin Films as High Temperature Solar Selective Absorber
校院名稱 成功大學
系所名稱(中) 材料科學及工程學系
系所名稱(英) Department of Materials Science and Engineering
學年度 108
學期 2
出版年 109
研究生(中文) 林易成
研究生(英文) Yi-Cheng Lin
學號 N56061488
學位類別 碩士
語文別 中文
論文頁數 83頁
口試委員 指導教授-丁志明
中文關鍵字 高熵氧化物  太陽能選擇性吸收膜 
英文關鍵字 High entropy oxide  reactive magnetron sputter  solar selective coatings 
中文摘要 本研究利用反應式磁控濺鍍將高熵合金和高熵氧化物薄膜沉積於不鏽鋼基板上進行太陽能選擇性吸收膜之應用,在本實驗中,我們將探討不同參數對於薄膜所造成的影響,像是靶材功率、氧氣和氬氣比例以及沉積時間,沉積後的薄膜將進行空氣退火熱處理分析薄膜之熱穩定性以及退火前後變化,將著重於晶體結構、組成元素比例、厚度和光學性質的探討,使用的儀器像是X光繞射儀、場發射掃描式電子顯微鏡、橢圓偏光儀、UV-Vis-NIR分光光譜儀以及放射率計等,用於薄膜的性質探討以及用於太陽能選擇性吸收膜之表現。
英文摘要 High entropy alloy (HEA) and high entropy oxide (HEO) coatings were deposited using RF reactive magnetron co-sputtering techniques. Stainless steel (SS) was used as substrates for solar absorber coatings. In this works, various deposition parameters including sputtering power, O2 flow rate, and deposited time were investigated. The as-deposited coatings were post annealing at different temperatures in air to investigate its thermal stability. The resulting coatings therefore exhibit various compositions, crystal structures, grain sizes, and thicknesses. The obtained coatings were examined using, field emission scanning electron microscopes (FE-SEM), transmission electron microscopes (TEM), glazing angle X-Ray diffraction (GIXRD), Energy-dispersive X-ray spectroscopy (EDS), UV/vis/NIR spectrometer, emissionmeter, and ellipsometer. Effects of the material characteristics on the coating performance are discussed.
論文目次 摘要 II
英文摘要 III
總目錄 IX
圖目錄 XII
表目錄 XV
第1章 緒論 1
1.1 背景 1
1.2 研究動機與目標 2
第2章 理論背景與文獻回顧 4
2.1 熱輻射與光學的吸收性質 4
2.1.1 熱輻射與黑體輻射 4
2.1.2 太陽光輻射光譜 6
2.1.3 光學吸收性質 8
2.2 太陽能吸收概要與原理 9
2.2.1 太陽能選擇性吸收模概要 9
2.2.2 太陽能吸收器 13
2.3 太陽能選擇性吸收膜種類與其文獻回顧 17
2.3.1 選擇性吸收膜種類 17
2.3.2 各類型選擇性吸收膜以及高溫環境使用狀況 18
2.4 材料之基本性質與文獻回顧 21
2.4.1 紅外光反射層 21
2.4.2 高熵材料之概念與高熵合金 21
2.4.3 高熵氧化物 22
2.5 物理氣象沉積之濺鍍及薄膜沉積機制 24
2.5.1 濺鍍機制 24
2.5.2 薄膜沉積機制 27
2.6 實驗重要性 29
第3章 研究方法與分析原理 31
3.1 實驗材料 31
3.2 實驗架構及流程圖 32
3.2.1 實驗流程 32
3.2.2 基板清洗與裁切 32
3.2.3 單層膜的製程參數 33
3.2.4 多層膜製程參數 36
3.3 材料分析與儀器設備 37
3.3.1 X光繞射儀 (X-ray Diffractometer, XRD) 37
3.3.2 場發射掃描式電子顯微鏡 (FE-SEM) 38
3.3.3 穿透式電子顯微鏡(TEM) 39
3.3.4 橢圓偏光儀 (Ellipsometer) 39
3.3.5 UV-vis-NIR分光光譜儀 (Spectrometer) 40
3.3.6 放射率計 (Emissionmeter) 41
第4章 結果與討論 42
4.1 單層紅外光反射之高熵合金 CrFeCoNiAl 42
4.2 中熵氧化物 44
4.2.1 鍍膜速率與微觀結構 44
4.2.2 結晶結構 46
4.2.3 光學性質 48
4.3 高熵氧化物(CrMnFeCoNi)O 49
4.3.1 鍍膜速率與微觀結構 49
4.3.2 結晶結構和元素比例 52
4.3.3 光學性質 57
4.4 高熵氧化物(CrFeCoNiAl)O 61
4.4.1 鍍膜速率和微觀結構 61
4.4.2 結晶結構 63
4.4.3 光學性質 64
4.5 多層膜太陽能選擇性吸收膜 66
4.5.1 折射率 66
4.5.2 高熵合金高溫(600°C)退火測試 67
4.5.3 A2c和A2f之比較 69
4.5.4 IR/A1d/A2f/A3b 退火測試 74
4.5.5 IR/A1d/A2f/A3b/AR 75
第5章 結論 77
第6章 參考文獻 78
參考文獻 [1] IEA, "Concentrating Solar Power (CSP)," IEA, vol. Paris, no. https://www.iea.org/reports/concentrating-solar-power-csp, 2020.
[2] H. Tabor, "Solar collectors, selective surfaces, and heat engines," Proceedings of the National Academy of Sciences of the United States of America, vol. 47, no. 8, p. 1271, 1961.
[3] F. Cao, K. McEnaney, G. Chen, and Z. Ren, "A review of cermet-based spectrally selective solar absorbers," Energy & Environmental Science, vol. 7, no. 5, pp. 1615-1627, 2014.
[4] J. Wang, B. Wei, Q. Wei, and D. Li, "Optical property and thermal stability of Mo/Mo–SiO2/SiO2 solar‐selective coating prepared by magnetron sputtering," physica status solidi (a), vol. 208, no. 3, pp. 664-667, 2011.
[5] Y. Zhang et al., "Microstructures and properties of high-entropy alloys," Progress in Materials Science, vol. 61, pp. 1-93, 2014.
[6] J. Zhu, H. Fu, H. Zhang, A. Wang, H. Li, and Z. Hu, "Synthesis and properties of multiprincipal component AlCoCrFeNiSix alloys," Materials Science and Engineering: A, vol. 527, no. 27-28, pp. 7210-7214, 2010.
[7] C.-Y. Hsu, C.-C. Juan, W.-R. Wang, T.-S. Sheu, J.-W. Yeh, and S.-K. Chen, "On the superior hot hardness and softening resistance of AlCoCrxFeMo0. 5Ni high-entropy alloys," Materials Science and Engineering: A, vol. 528, no. 10-11, pp. 3581-3588, 2011.
[8] M.-H. Tsai et al., "Thermal stability and performance of NbSiTaTiZr high-entropy alloy barrier for copper metallization," Journal of the Electrochemical Society, vol. 158, no. 11, p. H1161, 2011.
[9] Y.-x. Liu, C.-q. Cheng, J.-l. Shang, W. Rui, L. Peng, and Z. Jie, "Oxidation behavior of high-entropy alloys AlxCoCrFeNi (x= 0.15, 0.4) in supercritical water and comparison with HR3C steel," Transactions of Nonferrous Metals Society of China, vol. 25, no. 4, pp. 1341-1351, 2015.
[10] C. M. Rost et al., "Entropy-stabilized oxides," Nature communications, vol. 6, p. 8485, 2015.
[11] A. Mao, F. Quan, H.-Z. Xiang, Z.-G. Zhang, K. Kuramoto, and A.-L. Xia, "Facile synthesis and ferrimagnetic property of spinel (CoCrFeMnNi) 3O4 high-entropy oxide nanocrystalline powder," Journal of Molecular Structure, vol. 1194, pp. 11-18, 2019.
[12] D. Bérardan, S. Franger, D. Dragoe, A. K. Meena, and N. Dragoe, "Colossal dielectric constant in high entropy oxides," physica status solidi (RRL)–Rapid Research Letters, vol. 10, no. 4, pp. 328-333, 2016.
[13] 張志純, "太陽能之理論及應用, 徐氏基金會, 台北市," 1982.
[14] A. G-173-03, "Standard Tables for Reference Solar Spectral Irradiances: Direct Normal and Hemispherical on 37° Tilted Surface," 2012.
[15] M. Fox, "Optical properties of solids," ed: American Association of Physics Teachers, 2002.
[16] K. Zhang, L. Hao, M. Du, J. Mi, J.-N. Wang, and J.-p. Meng, "A review on thermal stability and high temperature induced ageing mechanisms of solar absorber coatings," Renewable and Sustainable Energy Reviews, vol. 67, pp. 1282-1299, 2017.
[17] J. Moon et al., "High performance multi-scaled nanostructured spectrally selective coating for concentrating solar power," Nano Energy, vol. 8, pp. 238-246, 2014.
[18] M. Blanco and L. R. Santigosa, Advances in concentrating solar thermal research and technology. Woodhead Publishing, 2016.
[19] C. E. Kennedy, "Review of mid-to high-temperature solar selective absorber materials," National Renewable Energy Lab., Golden, CO.(US)2002.
[20] Y. Yin, Y. Pan, L. Hang, D. McKenzie, and M. Bilek, "Direct current reactive sputtering Cr–Cr2O3 cermet solar selective surfaces for solar hot water applications," Thin Solid Films, vol. 517, no. 5, pp. 1601-1606, 2009.
[21] D. Xinkang, W. Cong, W. Tianmin, Z. Long, C. Buliang, and R. Ning, "Microstructure and spectral selectivity of Mo–Al2O3 solar selective absorbing coatings after annealing," Thin Solid Films, vol. 516, no. 12, pp. 3971-3977, 2008.
[22] A. Antonaia, A. Castaldo, M. Addonizio, and S. Esposito, "Stability of W-Al2O3 cermet based solar coating for receiver tube operating at high temperature," Solar Energy Materials and Solar Cells, vol. 94, no. 10, pp. 1604-1611, 2010.
[23] F. Cao, D. Kraemer, T. Sun, Y. Lan, G. Chen, and Z. Ren, "Enhanced Thermal Stability of W‐Ni‐Al2O3 Cermet‐Based Spectrally Selective Solar Absorbers with Tungsten Infrared Reflectors," Advanced Energy Materials, vol. 5, no. 2, p. 1401042, 2015.
[24] C.-Y. Li, F. N. I. Sari, and J.-M. Ting, "Reactive magnetron sputter-deposited TiNxOy multilayered solar selective coatings," Solar Energy, vol. 181, pp. 178-186, 2019.
[25] N. Selvakumar, H. C. Barshilia, K. Rajam, and A. Biswas, "Structure, optical properties and thermal stability of pulsed sputter deposited high temperature HfOx/Mo/HfO2 solar selective absorbers," Solar Energy Materials and Solar Cells, vol. 94, no. 8, pp. 1412-1420, 2010.
[26] 薛春木, "HfO2-x 薄膜之結構與光學性質暨其應用於高溫 HfO2-x/W/HfO2-x/W 多層太陽能選擇性吸收膜之研究," 成功大學材料科學及工程學系學位論文, no. 2017 年, pp. 1-131, 2017.
[27] H. Liu et al., "The spectral properties and thermal stability of CrAlO-based solar selective absorbing nanocomposite coating," Solar energy materials and solar cells, vol. 122, pp. 226-232, 2014.
[28] H. Liu et al., "Enhanced thermal stability of solar selective absorber based on nano-multilayered TiAlON films deposited by cathodic arc evaporation," Applied Surface Science, vol. 501, p. 144025, 2020.
[29] M. Lira-Cantu, A. M. Sabio, A. Brustenga, and P. Gomez-Romero, "Electrochemical deposition of black nickel solar absorber coatings on stainless steel AISI316L for thermal solar cells," Solar energy materials and solar cells, vol. 87, no. 1-4, pp. 685-694, 2005.
[30] M. Hasegawa, "Ellingham diagram," in Treatise on Process Metallurgy: Elsevier, 2014, pp. 507-516.
[31] R. Wild, "High temperature oxidation of austenitic stainless steel in low oxygen pressure," Corrosion Science, vol. 17, no. 2, pp. 87-104, 1977.
[32] J. D. Rancourt, Optical thin films: user handbook. SPIE Press, 1996.
[33] D. R. Lide, CRC handbook of chemistry and physics. CRC press, 2004.
[34] F. Cverna, ASM Ready Reference: Thermal properties of metals. ASM International, 2002.
[35] K. Sibin, S. John, and H. C. Barshilia, "Control of thermal emittance of stainless steel using sputtered tungsten thin films for solar thermal power applications," Solar Energy Materials and Solar Cells, vol. 133, pp. 1-7, 2015.
[36] J. R. Davis, ASM specialty handbook: heat-resistant materials. Asm International, 1997.
[37] J. H. Westbrook, "Intermetallic compounds: Their past and promise," Metallurgical Transactions A, vol. 8, no. 9, pp. 1327-1360, 1977.
[38] J. W. Yeh et al., "Nanostructured high‐entropy alloys with multiple principal elements: novel alloy design concepts and outcomes," Advanced Engineering Materials, vol. 6, no. 5, pp. 299-303, 2004.
[39] K.-Y. Tsai, M.-H. Tsai, and J.-W. Yeh, "Sluggish diffusion in Co–Cr–Fe–Mn–Ni high-entropy alloys," Acta Materialia, vol. 61, no. 13, pp. 4887-4897, 2013.
[40] M.-H. Tsai, J.-W. Yeh, and J.-Y. Gan, "Diffusion barrier properties of AlMoNbSiTaTiVZr high-entropy alloy layer between copper and silicon," Thin Solid Films, vol. 516, no. 16, pp. 5527-5530, 2008.
[41] Q. Wang et al., "Multi-anionic and-cationic compounds: new high entropy materials for advanced Li-ion batteries," Energy & Environmental Science, vol. 12, no. 8, pp. 2433-2442, 2019.
[42] D. Bérardan, S. Franger, A. Meena, and N. Dragoe, "Room temperature lithium superionic conductivity in high entropy oxides," Journal of Materials Chemistry A, vol. 4, no. 24, pp. 9536-9541, 2016.
[43] A. Sarkar et al., "Rare earth and transition metal based entropy stabilised perovskite type oxides," Journal of the European Ceramic Society, vol. 38, no. 5, pp. 2318-2327, 2018.
[44] A. Sarkar et al., "Multicomponent equiatomic rare earth oxides with a narrow band gap and associated praseodymium multivalency," Dalton transactions, vol. 46, no. 36, pp. 12167-12176, 2017.
[45] J. Dąbrowa et al., "Synthesis and microstructure of the (Co, Cr, Fe, Mn, Ni) 3O4 high entropy oxide characterized by spinel structure," Materials Letters, vol. 216, pp. 32-36, 2018.
[46] A. Mao, H.-Z. Xiang, Z.-G. Zhang, K. Kuramoto, H. Zhang, and Y. Jia, "A new class of spinel high-entropy oxides with controllable magnetic properties," Journal of Magnetism and Magnetic Materials, vol. 497, p. 165884, 2020.
[47] H. Chen, N. Qiu, B. Wu, Z. Yang, S. Sun, and Y. Wang, "A new spinel high-entropy oxide (Mg 0.2 Ti 0.2 Zn 0.2 Cu 0.2 Fe 0.2) 3 O 4 with fast reaction kinetics and excellent stability as an anode material for lithium ion batteries," RSC Advances, vol. 10, no. 16, pp. 9736-9744, 2020.
[48] "http://www.semicore.com/what-is-sputtering."
[49] "https://www.sputtertargets.net/blog/an-overview-of-magnetron-sputtering.html."
[50] G. L. Hornyak, J. J. Moore, H. F. Tibbals, and J. Dutta, Fundamentals of nanotechnology. CRC press, 2018.
[51] J. Vossen, "Glow discharge phenomena in plasma etching and plasma deposition," Journal of the Electrochemical Society, vol. 126, no. 2, p. 319, 1979.
[52] J. A. Thornton, "Influence of apparatus geometry and deposition conditions on the structure and topography of thick sputtered coatings," Journal of Vacuum Science and Technology, vol. 11, no. 4, pp. 666-670, 1974.
[53] W. D. Chemelewski, O. Mabayoje, D. Tang, A. J. Rettie, and C. B. Mullins, "Bandgap engineering of Fe 2 O 3 with Cr–application to photoelectrochemical oxidation," Physical Chemistry Chemical Physics, vol. 18, no. 3, pp. 1644-1648, 2016.
[54] R. Cheng et al., "Characterization of the native Cr 2 O 3 oxide surface of CrO 2," Applied Physics Letters, vol. 79, no. 19, pp. 3122-3124, 2001.
[55] J. Chen, X. Wu, and A. Selloni, "Electronic structure and bonding properties of cobalt oxide in the spinel structure," Physical Review B, vol. 83, no. 24, p. 245204, 2011.
[56] A. Dirks, R. Wolters, and A. De Veirman, "Columnar microstructures in magnetron-sputtered refractory metal thin films of tungsten, molybdenum and W-Ti-(N)," Thin Solid Films, vol. 208, no. 2, pp. 181-188, 1992.
[57] J. Sure, D. S. M. Vishnu, and C. Schwandt, "Electrochemical conversion of oxide spinels into high-entropy alloy," Journal of Alloys and Compounds, vol. 776, pp. 133-141, 2019.
[58] "http://www.semicore.com/reference/sputtering-yields-reference."
[59] Z. Y. Nuru, C. Arendse, S. Khamlich, and M. Maaza, "Optimization of AlxOy/Pt/AlxOy multilayer spectrally selective coatings for solar–thermal applications," Vacuum, vol. 86, no. 12, pp. 2129-2135, 2012.
[60] M. Waite and S. I. Shah, "Target poisoning during reactive sputtering of silicon with oxygen and nitrogen," Materials Science and Engineering: B, vol. 140, no. 1-2, pp. 64-68, 2007.
[61] M. Stygar et al., "Formation and properties of high entropy oxides in Co-Cr-Fe-Mg-Mn-Ni-O system: Novel (Cr, Fe, Mg, Mn, Ni) 3O4 and (Co, Cr, Fe, Mg, Mn) 3O4 high entropy spinels," Journal of the European Ceramic Society, vol. 40, no. 4, pp. 1644-1650, 2020.
[62] R. Hong, H. Qi, J. Huang, H. He, Z. Fan, and J. Shao, "Influence of oxygen partial pressure on the structure and photoluminescence of direct current reactive magnetron sputtering ZnO thin films," Thin Solid Films, vol. 473, no. 1, pp. 58-62, 2005.
[63] H. Seel and R. Brendel, "Optical absorption in crystalline Si films containing spherical voids for internal light scattering," Thin Solid Films, vol. 451, pp. 608-611, 2004.
[64] C. Wang, J. Shi, Z. Geng, and X. Ling, "Polychromic Al–AlN cermet solar absorber coating with high absorption efficiency and excellent durability," Solar Energy Materials and Solar Cells, vol. 144, pp. 14-22, 2016.
[65] A. Mao, H.-X. Xie, H.-Z. Xiang, Z.-G. Zhang, H. Zhang, and S. Ran, "A novel six-component spinel-structure high-entropy oxide with ferrimagnetic property," Journal of Magnetism and Magnetic Materials, vol. 503, p. 166594, 2020.
[66] A. Venter and J. R. Botha, "Optical and electrical properties of NiO for possible dielectric applications," South African Journal of Science, vol. 107, no. 1-2, pp. 1-6, 2011.
  • 同意授權校內瀏覽/列印電子全文服務,於2025-07-24起公開。
  • 同意授權校外瀏覽/列印電子全文服務,於2025-07-24起公開。

  • 如您有疑問,請聯絡圖書館