Mg和V<sub>2</sub>O<sub>5</sub>共溅射制备+4价钒的氧化物薄膜

付学成; 乌李瑛; 权雪玲; 瞿敏妮; 王英

Mg和V₂O₅共溅射制备+4价钒的氧化物薄膜

上海交通大学先进电子材料与器件校级平台，上海 200240

详细信息

作者简介:
付学成（1978-），男，河南人，实验师，研究方向为薄膜沉积和薄膜工艺开发。E-mail: xuecheng.f@sjt.edu.cn

通讯作者:
王英（1970-），女，辽宁人，博士，副教授，研究方向为微纳加工与测试。E-mail: wangying@sjt.edu.cn

中图分类号: TB43
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出版历程
- 收稿日期: 2020-05-05
- 修回日期: 2020-12-03
- 刊出日期: 2022-01-19

Preparation of +4-Valent Vanadium Oxide Films via the Co-Sputtering of Mg and V₂O₅

Advanced Electronics Materials and Devices, Shanghai Jiao Tong University, Shanghai 200240, China

摘要

摘要: 在常温、高真空条件下，采用高纯金属镁靶和V₂O₅靶进行共溅射，利用镁原子的还原性，将+5价的钒还原为+4价，在硅衬底上制备钒的氧化物薄膜。当Mg和V的原子比为1:2时，XPS测试表明薄膜中有V⁴⁺和V²⁺存在。X射线衍射结果显示，制备的薄膜主要成分是MgV₂O₅，且结晶状况良好。温度-电阻率测试结果显示，薄膜在20℃附近有相变行为，电阻温度系数高达－8.6%/K，回线弛豫温度约为0.3℃，负温度系数热敏电阻材料常数高达6700。这一发现为制备非制冷焦平面探测用的热敏薄膜材料提供了新的思路。
- 共溅射 /
- MgV₂O₅ /
- 电阻温度系数 /
- 热敏薄膜
Abstract: Vanadium oxide films were deposited on a silicon substrate via co-sputtering a high-purity magnesium and vanadium pentoxide target under high vacuum at room temperature. Owing to the reducibility of the magnesium atom, the valency of vanadium was reduced from +5 to +4. When the atomic ratio of Mg to V was 1:2, X-ray diffraction (XRD) results showed that the main component in the film was MgV₂O₅. X-ray photoelectron spectroscopy (XPS) results showed that both V⁴⁺ and V²⁺ were present in the fabricated films. The crystallization of the MgV₂O₅ film was in adequate condition, as observed in the SEM profiles. The results of the temperature resistivity test showed that the film experienced a phase transition near room temperature. The hysteresis loop occurred at a temperature of approximately 0.3℃ with a temperature coefficient of resistance of −8.6%/K. The material constant of the negative temperature coefficient thermistor was approximately 6700. This discovery provides a novel method for the preparation of thermal film materials for application in uncooled focal plane detectors.
- co-sputtering /
- MgV₂O₅ /
- TCR /
- thermal sensitive film

HTML全文

致谢: 感谢上海交通大学先进电子材料与器件平台程秀兰主任对实验工艺开发的大力支持！

图 1 丹顿explore-14磁控溅射沉积系统示意图

Figure 1. Schematic diagram of dent on vacuum sputter deposition system

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图 2 共溅射制备的钒的氧化物XRD图谱

Figure 2. XRD patterns of vanadium oxides prepared by Co-sputtering

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图 3 钒的氧化物薄膜中V2p的窄程扫描图谱

Figure 3. XPS spectra of V2p of vanadium oxide film

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图 4 MgV₂O₅薄膜的SEM图像

Figure 4. SEM images of MgV₂O₅ thin films

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图 5 共溅射制备的薄膜中V2p、Mg1S的窄程扫描图谱

Figure 5. XPS spectrum of V2p、Mg1S of the film prepared by co-sputtering

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图 6 MgV₂O₅和V₂O₅薄膜的电阻温度曲线

Figure 6. Resistance-temperature curves of MgV₂O₅ and V₂O₅

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参考文献(23)

[1]	Wood R A. High performance infrared thermal imaging with monolithic silicon focal planes operating at room temperature[J]. IEEE on IEDM, 1993: 175-177.
[2]	Tanaka A, Matsumoto S, Tsukamoto N, et al. Infrared focal plane array incorporation silicon IC process compatible bolometer[J]. IEEE Trans. Electron. Devices, 1996, 46(11): 1844-1848.
[3]	王宏臣, 易建新, 黄光, 等. 一种制备氧化钒薄膜的新工艺[J]. 半导体光电, 2003, 24(4): 280-281. DOI: 10.3969/j.issn.1001-5868.2003.04.019 WANG Hongchen, YI Jianxin, HUANG Guang, et al. A new method for preparation of vanadium oxide thin film[J]. Semiconductor Optoelectronics, 2003, 24(4): 280-281. DOI: 10.3969/j.issn.1001-5868.2003.04.019
[4]	尚东, 林理彬, 何捷, 等. 特型二氧化钒薄膜的制备及电阻温度系数的研究[J]. 四川大学学报: 自然科学版, 2005, 42(3): 523-527. DOI: 10.3969/j.issn.0490-6756.2005.03.018 SHANG Dong, LIN Libin, HE Jie, et al. Preparation and TCR characterization of VO₂(B) thin films[J]. Journal of Sichuan University: Natural Science Edition, 2005, 42(3): 523-527. DOI: 10.3969/j.issn.0490-6756.2005.03.018
[5]	Mohsen Fallah Vostakola, Seyed Mohammad Mirkazemi, Bijan Eftekhari Yekta. Structural, morphological and optical properties of W-doped VO₂ thin films prepared bysol-gel spin coating method[J]. International Journal of Applied Ceramic Technology, 2019, 16: 943-950. DOI: 10.1111/ijac.13170
[6]	TUAN Duc Vu, ZHANG Chen, ZENG Xianting, et al. Physical vapour deposition of vanadium dioxide for thermochromics smart window applications[J]. Journal of Materials Chemistry C, 2019(7): 2121-2145
[7]	邱家稳, 赵印中. VO₂薄膜制备工艺及电阻开关特性研究[J]. 中国空间科学技术, 2001, 21(6): 62-67. DOI: 10.3321/j.issn:1000-758X.2001.06.010 QIU Jiawen, ZHAO Yinzhong. Vanadium dioxide films technique and electrical switching property[J]. Chinese Space Science and Technology, 2001, 21(6): 62-67. DOI: 10.3321/j.issn:1000-758X.2001.06.010
[8]	PAN M, ZHONG H, WANG S, et al. Properties of VO₂ thin film prepared with precursor VO(acac)₂[J]. Journal of Crystal Growth, 2004, 265(1-2): 121-126. DOI: 10.1016/j.jcrysgro.2003.12.065
[9]	许旻, 邱家稳, 赵印中, 等. VO₂薄膜制备及电学性能[J]. 真空与低温, 2001, 7(4): 207-214. DOI: 10.3969/j.issn.1006-7086.2001.04.005 XU Min, QIU Jiawen, ZHAO Yinzhong, et al. Vanadium dioxide films with electrical property[J]. Vacuum and Cryogenics, 2001, 7(4): 207-214. DOI: 10.3969/j.issn.1006-7086.2001.04.005
[10]	尹大川, 许念坎, 刘正堂, 等. VO₂薄膜的主要制备工艺参数研究[J]. 功能材料, 1997(1): 52-55. DOI: 10.3321/j.issn:1001-9731.1997.01.015 YIN Dachuan, XU Niankan, LIU Zhengtang, et al. Preparation conditions of VO₂ thin films by sol gel method[J]. Journal of Functional Materials, 1997(1): 52-55. DOI: 10.3321/j.issn:1001-9731.1997.01.015
[11]	赵康, 魏建锋, 孙军, 等. 溶胶凝胶法制备VO₂薄膜的组织与性能研究[J]. 功能材料, 2002, 33(1): 84-85. DOI: 10.3321/j.issn:1001-9731.2002.01.029 ZHAO Kang, WEI Jianfeng, SUN Jun, et al. Property and microstructure of VO₂ film by inorganic sol-gel method[J]. Journal of Functional Materials, 2002, 33(1): 84-85. DOI: 10.3321/j.issn:1001-9731.2002.01.029
[12]	WU Jing, HUANG Wanxiag, Iwi Shi, et al. Effect of annealing temperature on thermochromic properties of vanadium dioxide thin films deposited by organic sol–gel method[J]. Applied Surface science, 2013, 268(1): 556-560.
[13]	易静, 颜文斌, 张晓君, 等. 水热法制备纳米二氧化钒粉体[J]. 精细化工, 2016, 33(4): 5-9. DOI: 10.3969/j.issn.1008-1100.2016.04.002 YI Jing, YAN Wenbin, ZHANG Xiaojun, et al. Hydrothermal synthesis of nano vanadium oxide powder[J]. Fine Chemicals, 2016, 33(4): 5-9. DOI: 10.3969/j.issn.1008-1100.2016.04.002
[14]	唐振方, 赵健, 卫红, 等. 射频磁控溅射工艺制备二氧化钒薄膜[J]. 人工晶体学报, 2008, 37(1): 88-92. https://www.cnki.com.cn/Article/CJFDTOTAL-RGJT200801020.htm TANG Zhenfang, ZHAO Jian, WEI Hong, et al. Preparation of vanadium dioxide thin film by RF magnetron sputtering method[J]. Journal of Synthetic Crystals, 2008, 37(1): 88-92. https://www.cnki.com.cn/Article/CJFDTOTAL-RGJT200801020.htm
[15]	陈冬丽. 掺杂对二氧化钒电学性能的影响[J]. 科技资讯, 2015(31): 236-236. https://www.cnki.com.cn/Article/CJFDTOTAL-ZXLJ201531140.htm CHEN Dongli. Effect of doping on electrical properties of vanadium dioxide[J]. Science & Technology Information, 2015(31): 236-236. https://www.cnki.com.cn/Article/CJFDTOTAL-ZXLJ201531140.htm
[16]	Burkhardt W, Christmann T, Franke S, et al. Tungsten and fluorine co-doping of VO₂ films[J]. Thin Solid Films, 2002, 402: 226-231. DOI: 10.1016/S0040-6090(01)01603-0
[17]	XU S Q, MA H P, DAI J, et al. Study on optical and electrical switching properties and phase transition mechanism of Mo⁶⁺-doped vanadium dioxide thin films[J]. Journal of Materials Science, 2004, 39(2): 489-493. DOI: 10.1023/B:JMSC.0000011503.22893.f4
[18]	付学成, 李金华, 谢建生, 等. 钽掺杂对二氧化钒多晶薄膜相变特性的影响[J]. 红外技术, 2010, 32(3): 173-176. DOI: 10.3969/j.issn.1001-8891.2010.03.013 FU Xuecheng, LI Jinhua, XIE Jiansheng, et al. The influence of tantalum doping on the phase transition of IBED VO₂ polycrystalline film[J]. Infrared Technology, 2010, 32(3): 173-176. DOI: 10.3969/j.issn.1001-8891.2010.03.013
[19]	覃源, 李毅, 方宝英, 等. 钨钒共溅掺杂二氧化钒薄膜的制备及其光学特性[J]. 光学学报, 2013(12): 351-356. https://www.cnki.com.cn/Article/CJFDTOTAL-GXXB201312053.htm TAN Yuan, LI Yi, FANG Baoying, et al. Fabrication and optical properties of vanadium dioxide thin films doped by tungsten-vanadium co-sputtering[J]. Acta Optica Sinica, 2013(12): 351-356. https://www.cnki.com.cn/Article/CJFDTOTAL-GXXB201312053.htm
[20]	陈长琦, 朱武, 干蜀毅, 等. 二氧化钒薄膜制备及其相变机理研究分析[J]. 真空科学与技术, 2001(6): 32-36. https://www.cnki.com.cn/Article/CJFDTOTAL-ZKKX200106008.htm CHEN Changqi, ZHU Wu, WANG Shuyi, et al. Growth and phase transition studies of VO₂ thin film[J]. Vacuum Science and Technology, 2001(6): 32-36. https://www.cnki.com.cn/Article/CJFDTOTAL-ZKKX200106008.htm
[21]	Spitaler Jürgen, Sherman E, Ambroschdraxl C. First-principles study of phonons, optical properties, and Raman spectra in MgV₂O₅[J]. Phys. Rev. B, 2008, 78(6): 064304.1-9
[22]	Goodenough J B. The two components of the crystallographic transition in VO₂[J]. Journal of Solid State Chemistry, 1971, 3(4): 490-500.
[23]	Anisimov V I, Dasgupta I, Korotin M A, et al. Electronic structure and exchange interactions of the ladder vanadates CaV₂O₅ and MgV₂O₅[J]. Journal of Physics Condensed Matter, 1999, 12(2): 113-124.