W掺杂NiO_x薄膜的制备及全固态电致变色器件的性能
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摘要
采用直流反应磁控溅射技术,使用原子比4∶1的镍钨合金靶,在不同氩氧比条件下制备了W掺杂的NiO_x薄膜。利用X射线衍射仪(XRD),扫描电子显微镜(SEM),原子力显微镜(AFM),分光光度计和光谱椭圆偏振仪(SE)对薄膜进行分析和表征,研究溅射过程中氧分压对薄膜形貌、结构和光学性能的影响。研究结果表明:颗粒之间相互接触在薄膜表面形成片状结构;随着氧分压上升,薄膜中的颗粒尺寸减小,结晶程度下降,衍射峰的位置向小角度方向移动;光学透过率和光学带隙随氧分压上升而下降,而折射率和消光系数则随氧分压上升而增大。最优工艺条件下制备的电致变色器件结构为FTO/Li_yWO_3/电解质/W掺杂NiO_x/ITO。器件在波长550nm处的光调制幅度为56.3%,着色态透过率为3.9%,褪色态透过率为60.2%。
W doped NiO_x can be used as anodic electrochromic material. W doped NiO_x films were deposited by reactive DC magnetron sputtering from a Ni_4W_1(atomic ratio) alloy target and characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, spectrophotometry and spectroscopic ellipsometry. Effects of the Ar/O_2 ratios during depositing on morphology, structure, and optical properties were systematically studied. Results show that all samples have flake-like surface morphology. With the increasing of O_2 gas flow, the size of grains decrease, crystallinity of the films decrease, and the position of diffraction peaks shift to small diffraction angle. Transmittance and optical band gap decrease when adding more O_2 during depositing, but optical constants increase. Based on the above results, an optimized condition was used to fabricate an inorganic all-solid-state electrochromic device with layers stack of FTO/Li_yWO_3/electrolyte/W doped NiO_x/ITO. At wavelength 550 nm, the device has good optical modulation of 56.3% with T_(bleached)=60.2% and T_(colored)=3.9%.
W doped NiO_x can be used as anodic electrochromic material. W doped NiO_x films were deposited by reactive DC magnetron sputtering from a Ni_4W_1(atomic ratio) alloy target and characterized by scanning electron microscopy, atomic force microscopy, X-ray diffraction, spectrophotometry and spectroscopic ellipsometry. Effects of the Ar/O_2 ratios during depositing on morphology, structure, and optical properties were systematically studied. Results show that all samples have flake-like surface morphology. With the increasing of O_2 gas flow, the size of grains decrease, crystallinity of the films decrease, and the position of diffraction peaks shift to small diffraction angle. Transmittance and optical band gap decrease when adding more O_2 during depositing, but optical constants increase. Based on the above results, an optimized condition was used to fabricate an inorganic all-solid-state electrochromic device with layers stack of FTO/Li_yWO_3/electrolyte/W doped NiO_x/ITO. At wavelength 550 nm, the device has good optical modulation of 56.3% with T_(bleached)=60.2% and T_(colored)=3.9%.
引文
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[4] W.Li-ge,L.Jian-feng, L.Guo-qing. Electrochromic Performances of Nanosized Nickel Oxide Films Deposited by Mid-frequency Magnetron Sputtering[J]. Journal of Materials Science & Engineering. 2009, 27(2): 157～160.
[5] N.Penin, A.Rougier, L. Laffont, et al. Improved Cyclability by Tungsten Addition in Electrochromic NiO Thin Films[J]. Solar Energy Materials and Solar Cells, 2006, 90 (4): 422～433.
[6] J. Smulko, A. Azens, R. Marsal, et al. Application of 1/f Current Noise for Quality and Age Monitoring of Electrochromic Devices[J]. Solar Energy Materials and Solar Cells, 2008, 92 (8): 914～918.
[7] T. Chien-Jen, Y. Jia-Ming, Y. Yueh-Ting. Large-area Flexible Monolithic ITO/WO3/Nb2O5/NiVOx/ITO Electrochromic Devices Prepared by Using Magnetron Sputter Deposition[J]. Optical Materials, 2016, 55: 83～89.
[8] Z. Junling, L. Gui, W. Youxiu. Enhanced Electrochromic Performances and Cycle Stability of NiO-based Thin Films via Li-Ti Co-doping Prepared by Sol-gel Method[J]. Electrochimica Acta, 2015, 186: 182～191.
[9] Trang V. T., Alok K. R., Jihyeon G.. High Performance of Co-doped NiO Nanoparticle Anode Material for Rechargeable Lithium Ion Batteries[J]. Journal of Power Sources, 2015, 292: 23～30.
[10] I. Manouchehri, D. Mehrparvar, R. Moradian. Investigation of Structural and Optical Properties of Copper Doped NiO Thin Films Deposited by RF Magnetron Reactive Sputtering[J]. Optik, 2016, 127: 8124～8129.
[11] S.V. Green, A. Kuzmin, J. Purans. Structure and Composition of Sputter-deposited Nickel-tungsten Oxide films[J]. Thin Solid Films, 2011, 519: 2062～2066.
[12] S.V. Green, C.G.Granqvist, G.A.Niklasson. Structure and Optical Properties of Electrochromic Tungsten-containing Nickel Oxide Films[J]. Solar Energy Materials and Solar Cells, 2014, 126: 248～259.
[13] S.V. Green, E. Pehlivan, C.G. Granqvist. Electrochromism in Sputter Deposited Nickel-containing Tungsten Oxide Films[J]. Solar Energy Materials and Solar Cells, 2012, 99: 339～344.
[14] J. C. Hu, K.K. Zhu, L.F. Chen, et al. Preparation and Surface Activity of Single-Crystalline NiO(111) Nanosheets with Hexagonal Holes: A Semiconductor Nanospanner[J]. Advanced Material, 2008, 20 (2): 267～271.
[15] 杨海刚, 宋桂林, 王天兴, 等. 反应溅射制备NiOx薄膜及其电致变色响应时间性能研究[J]. 光学学报, 2011, 05: 275～279.
[16] V. Madhavi, P. Kondaiah, O.M. Hussain. Structural, Optical and Electrochromic Properties of RF Magnetron Sputtered WO3 Thin Films[J]. Physica B, 2014, 454: 141～147.
[17] I. Valyukh, S.V. Green b, C.G. Granqvist. Optical Properties of Thin Films of Mixed Ni-W Oxide Made by Reactive DC Magnetron Sputtering [J]. Thin Solid Films, 2011, 519: 2914～2918.