掠射角溅射沉积纳米结构氧化钨薄膜

doi:10.15541/jim20180130

摘要/Abstract

摘要：

采用掠射角反应磁控溅射法在室温下沉积了纳米结构氧化钨(WO₃)薄膜, 并对薄膜进行热处理。利用场发射扫描电镜(FE-SEM)和X射线衍射仪(XRD)对氧化钨薄膜的形貌和结构进行了表征。当掠射角度为80°时, 采用直流电源沉积的氧化钨薄膜具有纳米斜柱状结构, 而采用脉冲直流电源沉积的薄膜呈现纳米孔结构。纳米薄膜经450℃热处理3 h后, 纳米斜柱彼此连接, 失去规整结构, 而纳米孔结构的孔尺寸变大。XRD分析表明室温沉积的氧化钨薄膜具有无定形结构, 经450℃热处理1 h后, 转变为单斜晶相。具有纳米斜柱状或纳米孔结构氧化钨薄膜的光学调制幅度在波长600 nm时达到60%, 且电致变色性能可逆。

关键词: 氧化钨薄膜, 纳米结构, 掠射角, 磁控溅射

Abstract:

Nano-structured tungsten oxide (WO₃) thin films were deposited at room temperature by glancing angle reactive magnetron sputtering and then annealed at 450℃ in air. The films were characterized by field-emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD). The WO₃ thin film deposited by DC magnetron sputtering at 80° glancing angle exhibited oblique nano-column structure, while deposited by pulsed DC magnetron sputtering at the same angle exhibits nano-pore structure. After annealing at 450℃ for 3 h, the oblique nanocolums are conjunct with each other but the nano-pore structured remains with bigger pore size. XRD analysis reveals that WO₃thin films deposited at room temperature demonstrate amorphous structure. The amorphous structure will transfers to monoclinic phase after annealing at 450℃ for 1 h. Transmittance difference between colorization and bleaching of nano-structured WO₃ thin film reaches 60% at wavelength of 600 nm. Electrochromic properties of nano-structured WO₃thin films are highly reversible.

Key words: WO₃ thin films, nano-structured, glancing angle, magnetron sputtering

中图分类号:

TB34

王美涵, 温佳星, 陈昀, 雷浩. 掠射角溅射沉积纳米结构氧化钨薄膜[J]. 无机材料学报, 2018, 33(12): 1303-1308.

WANG Mei-Han, WEN Jia-Xing, CHEN Yun, LEI Hao. Nano-structured WO₃ Thin Films Deposited by Glancing Angle Magnetron Sputtering[J]. Journal of Inorganic Materials, 2018, 33(12): 1303-1308.

图/表 8

图1 掠射角磁控溅射沉积WO3薄膜示意图[22]

Fig. 1 Schematic diagram of glancing angle magnetron sputtering of WO3 thin films[22]

图2 0和80°掠射角直流磁控溅射沉积WO3薄膜的表面和断面形貌

Fig. 2 Surface and cross-section images of WO3 thin films deposited by DC magnetron sputtering at 0 and 80° glancing angles Surface (a) and cross-section(b) images, deposited at 0 glancing angle; Surface (c) and cross-section (d) images, deposited at 80° glancing angle

图3 80°掠射角直流磁控溅射沉积WO3薄膜的XRD图谱

Fig. 3 XRD patterns of WO3 film deposited by DC magnetron sputtering at 80° glancing angle(a) As-deposited; (b) After annealing at 450℃ for 1 h; (c) After annealing at 450℃ for 3 h

图4 80°掠射角直流磁控溅射沉积WO3薄膜经450℃热处理3 h后的表面(a)和断面(b)形貌

Fig. 4 Surface (a) and cross-section (b) images of WO3 films deposited by DC magnetron sputtering at 80° glancing angles after annealing at 450℃ for 3 h

图5 不同掠射角度脉冲直流磁控溅射沉积WO3薄膜的表面形貌

Fig. 5 Surface morphologies of WO3 films deposited by pulsed DC magnetron sputtering at different glancing angles

图6 80°掠射角脉冲直流磁控溅射沉积WO3薄膜的表面和断面形貌

Fig. 6 Surface and cross-section images of WO3 films deposited by pulsed DC magnetron sputtering at 80o glancing angles(a,b) as-deposited; (c,d) after annealing at 450℃ for 1 h; (e,f) after annealing at 450℃ for 3 h

图7 0和80°掠射角直流磁控溅射沉积WO3薄膜的着色/褪色态透射光谱图

Fig. 7 Transmittance spectra of colorization/bleaching states of WO3 film deposited by DC magnetron sputtering at 0 and 80° glancing angles

图8 80°掠射角脉冲直流磁控溅射沉积WO3薄膜的着色/褪色态透射光谱图

Fig. 8 Transmittance spectra of colorization/bleaching states of WO3 film deposited by pulsed DC magnetron sputtering at 80° glancing angle

参考文献 28

[1]	DEB S K.Opportunities and challenges in science and technology of WO3 for electrochromic and related applications.Solar Energy Materials and Solar Cells, 2008, 92: 245-258.
[2]	PENG MING-DONG, ZHANG YUZHI, SONG LI-XIN,et al. Structured and electrochromic properties of titanium-doped WO3 thin film by sputtering. Journal of Inorganic Materials, 2017, 32(3): 287-292.
[3]	ZHOU J C, LIN S W, CHEN Y J,et al. Facile morphology control of WO3 nanostructure arrays with enhanced photoelectrochemical performance. Appl. Surf. Sci., 2017, 403: 274-281.
[4]	BUCH V R, CHAWLA A K, RAWAL S K.Review on electrochromic property for WO3 thin films using different deposition techniques.Materials Today, 2016, 3(6): 1429-1437.
[5]	MAN W K, LU H, JU L C,et al. Effect of substrate pre-treatment on microstructure and enhanced electrochromic properties of WO3 nanorod arrays. RSC Adv., 2015, 5: 106182-106190.
[6]	CAI G F, TU J P, ZHOU D,et al. Growth of vertically aligned hierarchical WO3 nano-architecture arrays on transparent conducting substrates with outstanding electrochromic performance. Sol. Energy Mater. Sol. Cells, 2014, 124: 103-110.
[7]	KONDALKAR V V, KHARADE R R, MALI S S,et al. Nanobrick- like WO3 thin films: hydrothermal synthesis and electrochromic application. Superlattices Microstruct., 2014, 73: 290-295.
[8]	PATIL J M, PATIL S B, BARI R H,et al. Influence of film thickness on structural, surface morphology and electrical properties of spray pyrolise nanostructured WO3 thin films. Journal of Advanced Physics, 2016, 5(4): 359-363.
[9]	HILLIARD S, BALDINOZZI G, FRIEDRICH D,et al. Mesoporous thin film WO3 photoanode for photoelectrochemical water spitting: a Sol-Gel dip coating approach. Sustainable Energy Fuels, 2017, 1: 145-153.
[10]	LU SHU-JUAN, WANG CHANG, ZHAO BO-WEN,et al. Electrochromic properties of PEG-modified tungsten oxide thin films. Journal of Inorganic Materials, 2017, 32(2): 185-190.
[11]	CHAI Y N, KHAIRUNISAK A R, ZAINOVIAL L.WO3 nanoporous-nanorod film formed by hydrothermal growth of nanorods on anodized nanoporous substrate.J. Electrochem. Soc., 2015, 162: E148-E153.
[12]	WHITE C M, GILLAPIE D T, WHITNEY E,et al. Flexible electrochromic devices based on crystalline WO3 nanostructures produced with hot-wire chemical vapor deposition. Thin Solid Films, 2009, 517(12): 3596-3599.
[13]	LI Y B, BANDO Y, GOLBERG D,et al. WO3 nanorods/nanobelts synthesized via physical vapor deposition process. Chemical Physics Letters, 2003, 367(1/2): 214-218.
[14]	CASTRO-HURTADO I, TAVERA T, YURRITA P,et al. Structural and optical properties of WO3 sputtered thin films nanostructured by laser interference lithography. Applied Surface Science, 2013, 276: 229-235.
[15]	DEEPA M, SRIVASTAVA A K, SOOD K N,et al. Nanostructured mesoporous tungsten oxide films with fast kinetics for electrochromic smart windows. Nanotechnology, 2006, 17: 2625-2630.
[16]	ROBBOE K, SIT J C, BRETT M J.Advanced techniques for glancing angle deposition (GLAD).Journal of Vacuum Science and Technology B, 1998, 16(3): 1115-1122.
[17]	ZHAO Y P, YE D X, WANG G C,et al. Designing nanostructures by glancing angle deposition. Proceeding of SPIE, 2003, 5219: 59-73.
[18]	CHARLES C, MARTIN N, DEVEL M.Optical properties of nanostructured WO3 thin films by glancing angle deposition: comparison between experiment and simulation.Surface & Coatings Technology, 2015, 276(2): 136-140.
[19]	CHARLES C, MARTIN N, DEVEL M,et al. Correlation between structural and optical properties of WO3 thin films sputter deposited by glancing angle deposition. Thin Solid Films, 2013, 534: 275-281.
[20]	HORPRATHUM M, LIMWICHEAN K, WISITSORAAT A,et al. NO2-sensing properties of WO3 nanorods prepared by glancing angle DC magnetron sputtering. Sensor and Actuator B, 2013, 176: 685-691.
[21]	王美涵. 制备结构可控功能薄膜的装置. 中国, 专利号ZL201620235960.0. 2016.08.17.
[22]	WISITSORAAT A, AHMAD M Z, YAACOB M H,et al. Optical H2 sensing properties of vertically aligned Pd/WO3 nanorods thin films deposited via glancing angle rf magnetron sputtering. Sensors and Actuators B: Chemical, 2013, 182: 795-801.
[23]	TAIT R N, SMY T, BRETT M J.Structural anisotropy in oblique incidence thin metal films. J. Vac. Sci. Technol. A, 1992, 10: 1518-1521.
[24]	ROBBIE K, BRETT M J.Sculptured thin films and glancing angle deposition: growth mechanics and applications. J. Vac. Sci. Technol. A, 1997, 15: 1460-1465.
[25]	NIEUWENHUIZEN J M, HAANSTRA H B.Microfractography of thin films.Philips Technol. Rev., 1966, 27(3/4): 87-89.
[26]	BESNARD A, MARTIN N, CARPENTIER L,et al. A theoretical model for the electrical properties of chromium thin films sputter deposited at oblique incidence. J. Phys. D: Appl. Phys., 2011, 44: 215301.
[27]	TAIT R N, SMY T, BRETT M J.Modelling and characterization of columnar growth in evaporated films.Thin Solid Films, 1993, 226(2): 196-201.
[28]	ROBBIE K, BRETT M J.Sculptured thin ﬁlms and glancing angle deposition: growth mechanics and applications.Journal of Vacuum Science and Technology A, 1997, 15(3): 1460-1465.