花状掺杂W-VO2/ZnO热致变色纳米复合薄膜研究

朱慧群; 李毅; 叶伟杰; 李春波

doi:10.7498/aps.63.238101

摘要

为解决掺杂引起的二氧化钒薄膜的红外调制幅度下降以及二氧化钒复合薄膜相变温度需要进一步降低等问题, 采用纳米结构、掺杂改性和复合结构等多种机理协同作用的方案, 利用共溅射氧化法, 先在石英玻璃上制备高(002)取向的ZnO薄膜, 再在ZnO层上室温共溅射沉积钒钨金属薄膜, 最后经热氧化处理获得双层钨掺杂W-VO2/ZnO纳米复合薄膜. 利用X射线衍射、X射线光电子能谱、扫描电镜和变温光谱分析等对薄膜的结构、组分、形貌和光学特性进行了分析. 结果显示, W-VO2/ZnO 纳米复合薄膜呈花状结构, 取向性提高, 在保持掺杂薄膜相变温度(约39 ℃)和热滞回线宽度(约6 ℃)较低的情况下, 其相变前后的红外透过率差量增加近2倍, 热致变色性能得到协同增强.

关键词:

VO2 /
ZnO /
W掺杂 /
热致变色

Abstract

Based on the nanocomposite structure and doping modification, we have studied the preparation technology of high performance nanocomposite thin film and its characterization methods. The W-doped VO2/ZnO nanocomposite thin films are prepared successfully on SiO2 substrates by the three-step method. The structure and morphology of the W-doped VO2/ZnO/SiO2 films are analyzed by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscope. Results show that the films are mainly composed of VO2 and high valence cation W6+ replacing the V ion in the W-doped VO2/ZnO/SiO2 films. It is found that the flake nanocrystallines resemble a flower in shape, and its size and orientational growth are reduced. The thermochromic properties of W-doped VO2/ZnO films are measured and compared with the single-layer W-doped VO2 films on SiO2 substrates with the same thickness. The variation of infrared transmittance of the W-doped VO2/ZnO/SiO2 nanocomposite film is increased nearly two times, the phase transition temperature reduced approximately to 39 °C, and the width of the thermal hysteresis loop is about 6 °C. The W-doped VO2/ZnO/SiO2 nanocomposite film has a high infrared modulation ability, a lower phase transition temperature, and a narrower thermal hysteresis loop. Thus the potential application of this nanocomposite film is significantly improved.

Keywords:

VO2 /
ZnO /
W-doped /
thermochromism

作者及机构信息

1.
五邑大学应用物理与材料学院, 江门 529020;

2.
上海理工大学光电信息与计算机工程学院, 上海 200093

基金项目: 国家高技术研究发展计划(批准号:2006AA03Z348)、广东省自然科学基金(批准号:10152902001000025)、广东高校省级重点平台和重大科研项目特色创新项目(批准号:2014)、广东省大学生创新创业训练计划(批准号:教发[2012]62)和江门市产业技术研究与开发项目(批准号:江财工[2012]156)资助的课题.

Authors and contacts

1.
School of Applied Physics and Material, Wuyi University, Jiangmen 529020, China;

2.
College of Optical-Electrical and Computer Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China

Funds: Project supported by the National High Technology Research and Development Program of China (Grant No. 2006AA03Z348), the Natural Science Foundation of Guangdong Province, China (Grant No. 10152902001000025), the Distinctive Innovations Project of Provincial Key Platform and Major Scientific Research Project of Universities in Guangdong Province, China (Grant No. 2014), the Innovation and Entrepreneurship Training Project for Undergraduate of Guangdong Province, China (Grant No. JF [2012]62), and the Industrial Technology Research and Development Project of Jiangmen City, China (Grant No. JCG [2012]156).

参考文献

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[4]	Zhu N W, Hu M, Xia X X, Wei X Y, Liang J R 2014 Chin. Phys. B 23 048108
[5]	Wang X J, Liu Y Y, Li D H, Feng B H, He Z W, Qi Z 2013 Chin. Phys. B 22 066803
[6]	Joyeeta N, Haglund Jr R F 2008 J. Phys.: Condens. Matter 20 264016
[7]	Saeli M, Binions R, Piccirillo C 2009 Appl. Surf. Sci. 255 7291
[8]	Kyoung J, Seo M, Park H, Koo S, Kim H, Park Y, Kim B J, Ahn K, Park N, Kim H, Kim D S 2010 Opt. Express 18 16452
[9]	Peng Z F, Wang Y, Du Y Y, Lu D, Sun D Z 2009 J. Alloys Compd. 480 537
[10]	Li J, Liu C Y, Mao L J 2009 J. Solid State Chem. 182 2835
[11]	Wang Y L, Chen X K, Li M C 2007 Surf. Coat. Technol. 201 5344
[12]	Zhou S, Li Y, Zhu H Q, Sun R X, Zhang Y M, Zheng Q X, Li L, Shen Y J, Fang B Y 2012 Surf. Coat. Technol. 206 2922
[13]	Shi J Q, Zhou S X, You B, Wu L M 2007 Sol. Energy Mater. Sol. Cells 91 1856
[14]	Zhu H Q, Li Y, Zhou S, Huang Y Z, Tong G X, Sun R X, Zhang Y M, Zheng Q X, Li L, Shen Y J, Fang B Y 2011 Acta Phys. Sin. 60 098104 (in Chinese) [朱慧群, 李毅, 周晟, 黄毅泽, 佟国香, 孙若曦, 张宇明, 郑秋心, 李榴, 沈雨剪, 方宝英 2011 60 098104]
[15]	Kiri P, Warwick M E A, Ridley I, Binions R 2011 Thin Solid Films 520 1363
[16]	Yan J Z, Zhang Y, Liu Y S, Zhang Y B, Huang W X, Tu M J 2008 Rare Metal Mater. Eng. 37 1648 (in Chinese) [颜家振, 张月, 刘阳思, 张玉波, 黄婉霞, 涂铭旌 2008 稀有金属材料与工程 37 1648]
[17]	Wang L X, Li J P, He X L, Gao X G 2006 Acta Phys. Sin. 55 2846 (in Chinese) [王利霞, 李建平, 何秀丽, 高晓光 2006 55 2846]
[18]	Xu X, Yin A Y, Du X L 2010 Appl. Surf. Sci. 256 2750
[19]	Zhu H Q, Li Y, Guo G X, Fang B Y, Wang X H 2013 Adv. Mater. -Rapid Commun. 7 1015
[20]	Case F C 1987 Appl. Opt. 26 1550
[21]	Yan J Z, Zhang Y, Huang W X, Tu M J 2008 Thin Solid Films 516 8554
[22]	He Q, Xu X D, Wen Y J, Jiang Y D, Ao T H, Fan T J, Huang L, Ma C Q, Sun Z Q 2013 Acta Phys. Sin. 62 056802 (in Chinese) [何琼, 许向东, 温粤江, 蒋亚东, 敖天宏, 樊泰君, 黄龙, 马春前, 孙自强 2013 62 056802]
[23]	Pauli S A, Herger R, Willmott P R, Donev E U, Suh J Y, Haglund Jr R F 2007 J. Appl. Phys. 102 073527
[24]	Lopez R, Feldman L C 2004 Phys. Rev. Lett. 93 177403

施引文献

[1]	Morin F J 1959 Phys. Rev. Lett. 3 34
[2]	Gao Y F, Luo H J, Zhang Z T 2012 Nano Energy 1 221
[3]	Granqvist C G, Lansaker P C, Mlyuka N R 2009 Sol. Energy Mater. Sol. Cells 93 2032
[4]	Zhu N W, Hu M, Xia X X, Wei X Y, Liang J R 2014 Chin. Phys. B 23 048108
[5]	Wang X J, Liu Y Y, Li D H, Feng B H, He Z W, Qi Z 2013 Chin. Phys. B 22 066803
[6]	Joyeeta N, Haglund Jr R F 2008 J. Phys.: Condens. Matter 20 264016
[7]	Saeli M, Binions R, Piccirillo C 2009 Appl. Surf. Sci. 255 7291
[8]	Kyoung J, Seo M, Park H, Koo S, Kim H, Park Y, Kim B J, Ahn K, Park N, Kim H, Kim D S 2010 Opt. Express 18 16452
[9]	Peng Z F, Wang Y, Du Y Y, Lu D, Sun D Z 2009 J. Alloys Compd. 480 537
[10]	Li J, Liu C Y, Mao L J 2009 J. Solid State Chem. 182 2835
[11]	Wang Y L, Chen X K, Li M C 2007 Surf. Coat. Technol. 201 5344
[12]	Zhou S, Li Y, Zhu H Q, Sun R X, Zhang Y M, Zheng Q X, Li L, Shen Y J, Fang B Y 2012 Surf. Coat. Technol. 206 2922
[13]	Shi J Q, Zhou S X, You B, Wu L M 2007 Sol. Energy Mater. Sol. Cells 91 1856
[14]	Zhu H Q, Li Y, Zhou S, Huang Y Z, Tong G X, Sun R X, Zhang Y M, Zheng Q X, Li L, Shen Y J, Fang B Y 2011 Acta Phys. Sin. 60 098104 (in Chinese) [朱慧群, 李毅, 周晟, 黄毅泽, 佟国香, 孙若曦, 张宇明, 郑秋心, 李榴, 沈雨剪, 方宝英 2011 60 098104]
[15]	Kiri P, Warwick M E A, Ridley I, Binions R 2011 Thin Solid Films 520 1363
[16]	Yan J Z, Zhang Y, Liu Y S, Zhang Y B, Huang W X, Tu M J 2008 Rare Metal Mater. Eng. 37 1648 (in Chinese) [颜家振, 张月, 刘阳思, 张玉波, 黄婉霞, 涂铭旌 2008 稀有金属材料与工程 37 1648]
[17]	Wang L X, Li J P, He X L, Gao X G 2006 Acta Phys. Sin. 55 2846 (in Chinese) [王利霞, 李建平, 何秀丽, 高晓光 2006 55 2846]
[18]	Xu X, Yin A Y, Du X L 2010 Appl. Surf. Sci. 256 2750
[19]	Zhu H Q, Li Y, Guo G X, Fang B Y, Wang X H 2013 Adv. Mater. -Rapid Commun. 7 1015
[20]	Case F C 1987 Appl. Opt. 26 1550
[21]	Yan J Z, Zhang Y, Huang W X, Tu M J 2008 Thin Solid Films 516 8554
[22]	He Q, Xu X D, Wen Y J, Jiang Y D, Ao T H, Fan T J, Huang L, Ma C Q, Sun Z Q 2013 Acta Phys. Sin. 62 056802 (in Chinese) [何琼, 许向东, 温粤江, 蒋亚东, 敖天宏, 樊泰君, 黄龙, 马春前, 孙自强 2013 62 056802]
[23]	Pauli S A, Herger R, Willmott P R, Donev E U, Suh J Y, Haglund Jr R F 2007 J. Appl. Phys. 102 073527
[24]	Lopez R, Feldman L C 2004 Phys. Rev. Lett. 93 177403

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