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钒掺杂W18O49纳米线的室温p型电导与NO2敏感性能

秦玉香 刘凯轩 刘长雨 孙学斌

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钒掺杂W18O49纳米线的室温p型电导与NO2敏感性能

秦玉香, 刘凯轩, 刘长雨, 孙学斌

P-type conductivity and NO2 sensing properties for V-doped W18O49 nanowires at room temperature

Qin Yu-Xiang, Liu Kai-Xuan, Liu Chang-Yu, Sun Xue-Bin
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  • 钨氧化物纳米线在高灵敏度低功耗气体传感器中极具应用潜力, 且通过掺杂改性可进一步显著改善其敏感性能. 本文以WCl6为钨源, NH4VO3为掺杂剂, 采用溶剂热法合成了钒掺杂的W18O49纳米线. 利用扫描电镜、透射电镜、X射线衍射、X射线光电子能谱仪表征了纳米线的微结构, 并利用静态气敏性能测试系统评价了掺杂纳米线的NO2敏感性能. 研究结果表明: 五价钒离子受主掺杂进入氧化钨晶格结构, 抑制了纳米线沿轴向的生长并导致了纳米线束的二次集聚; 室温下, 钒掺杂W18O49纳米线接触NO2气体后表现出反常的p型响应特性; 随工作温度逐渐升高至约110 ℃时, 发生从p型到n型的电导特性转变; 该掺杂纳米线气敏元件对浓度低至80 ppb (1 ppb=10-9) 的NO2气体具有明显的室温敏感响应和良好的响应稳定性. 分析并探讨了钒掺杂W18O49纳米线的高室温敏感特性及其p-n电导转型机理, 认为钒掺杂W18O49纳米线在室温下的良好敏感响应及反常p型导电性与掺杂纳米线表面高密度非稳表面态诱导的低温气体强吸附有关.
    Tungsten oxide nanowire has a great potential application to gas sensor with high sensitivity and low power consumption. Its gas-sensing properties can be greatly improved after doping the nanowires. In this paper, vanadium (V)-doped W18O49 nanowires are synthesized by solvothermal method, with WCl6 serving as precursor and NH4VO3 as dopant. The microstructures of the pure and the doped nanowires are characterized by using SEM, TEM, XRD, and XPS techniques, and the NO2-sensing properties are evaluated in a static gas-sensing measurement system. The obtained results indicate that the introduction of V dopant suppresses the growth of one-dimensional nanowires along their axis direction and causes the secondary assembly of nanowires bundles. At room temperature, the V-doped W18O49 nanowires show an abnormal p-type response characteristic upon being exposed to NO2 gas, and a conductivity transition from p-to n-type occurs when operating temperature is raised to about 110 ℃. The doped nanowires-based sensor exhibits obvious sensitivity and good response stability to dilute NO2 gas of 80 ppb at room temperature. The origin for the p-n conductivity transition and the high sensitivity at room temperature for the V-doped W18O49 nanowires are analyzed, and they can be attributed to the strong surface adsorption of oxygen and NO2 molecules due to the large density of unstable surface states.
    • 基金项目: 国家自然科学基金 (批准号: 61274074, 61271070)和天津市自然科学基金(批准号: 11JCZDJC15300) 资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61274074, 61271070) and the Tianjin Natural Science Foundation, China (Grant No. 11JCZDJC15300).
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    Liu Y L, Yang H F, Yang Y, Liu Z M, Shen G L, Yu R Q 2006 Thin Solid Films 497 355

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    Li M Y, Yu M L, Su Q, Liu X Q, Xie E Q, Zhang X Q 2012 Acta Phys. Sin. 61 236101 (in Chinese) [李明阳, 于明朗, 苏庆, 刘雪芹, 谢二庆, 张晓倩 2012 物理学报 61 236101]

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    Safonova O V, Delabouglise G, Chenevier B, Gaskov A M, Labeau M 2002 Mater. Sci. Eng. C 21 105

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    Sayago I, Gutiérrez J, Arés L, Robla J I, Horrillo M C, Getino J, Agapito J A 1995 Sens. Actuators B 25 512

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    Lee Y C, Chueh Y L, Hsieh C H, Chang M T, Chou L J, Wang Z L, Lan Y W, Chen C D, Kurata H, Isoda S 2007 Small 3 1356

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    Licznerski B W, Nitsh K, Teterycz H, Wisniewski K 2001 Sens. Actuators B 79 157

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    Shieh J, Feng H M, Hon M H, Juang H Y 2002 Sens. Actuators B 86 75

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  • [1]

    Hu M, Liu Q L, Jia D L, Li M D 2013 Acta Phys. Sin. 62 057102 (in Chinese) [胡明, 刘青林, 贾丁立, 李明达 2013 物理学报 62 057102]

    [2]

    Hieu N V, Vuong H V, Duy N V, Hoa N D 2012 Sens. Actuators B 171-172 760

    [3]

    Zhao Y M, Zhu Y Q 2009 Sens. Actuators B 137 27

    [4]

    Wei A, Wang Z, Pan L H, Li W W, Xiong L, Dong X C, Huang W 2011 Chin. Phys. Lett. 28 080702

    [5]

    Qin Y X, Shen W J, Li X, Hu M 2011 Sens. Actuators B 155 646

    [6]

    Kim Y S, Ha S C, Kim K, Yang H, Choi S Y, Kim Y T Park J T, Lee C H, Choi J, Paek J, Lee K 2005 Appl. Phys. Lett. 86 213105

    [7]

    Zhao Y M, Zhu Y Q 2009 Sens. Actuators B 137 27

    [8]

    Vaishampayan M V, Deshmukh R G, Walke P, Mulla I S 2008 Mater. Chem. Phys. 109 230

    [9]

    Shen Y B, Yamazaki T, Liu Z F, Meng D, Kikuta T, Nakatani N, Saito M, Mori M 2009 Sens. Actuators B 135 524

    [10]

    Qin Y X, Hu M, Zhang J 2010 Sens. Actuators B 150 339

    [11]

    Sun S B, Zou Z D, Min G H 2009 Mater. Charact. 60 437

    [12]

    Li Y H, Zhao Y M, Ma R Z, Zhu Y Q, Fisher N, Jin Y Z, Zhang X P 2006 J. Phys. Chem. B 110 18191

    [13]

    Yan J F, You T G, Zhang Z Y, Tian J X, Yun J N, Zhao W 2011 Chin. Phys. B 20 048102

    [14]

    P Siciliano 2000 Sens. Actuators B 70 153

    [15]

    Fardindoost S, Zad A I, Rahimi F, Ghasempour R 2010 Int. J. Hydrogen Energy 35 854

    [16]

    Cabot A, Diéguez A, Romano-Rodriguez A, Morante J R, Bârsan N 2001 Sens. Actuators B 79 98

    [17]

    Silversmit G, Depla D, Poelman Hilde, Marin G B, Gryse R D 2004 J. Electron. Spectrosc. Relat. Phenom. 135 167

    [18]

    Galatsis K, Cukrov L, Wlodarski W, McCormick P, Kalantar-zadeh K, Comini E, Sberveglieri G 2003 Sens. Actuators B 93 562

    [19]

    Zhang C, Debliquy M, Boudiba A, Liao H L, Coddet C 2010 Sens. Actuators B 144 280

    [20]

    Williams D E 1999 Sens. Actuators B 57 1

    [21]

    Liu Y L, Yang H F, Yang Y, Liu Z M, Shen G L, Yu R Q 2006 Thin Solid Films 497 355

    [22]

    Li M Y, Yu M L, Su Q, Liu X Q, Xie E Q, Zhang X Q 2012 Acta Phys. Sin. 61 236101 (in Chinese) [李明阳, 于明朗, 苏庆, 刘雪芹, 谢二庆, 张晓倩 2012 物理学报 61 236101]

    [23]

    Safonova O V, Delabouglise G, Chenevier B, Gaskov A M, Labeau M 2002 Mater. Sci. Eng. C 21 105

    [24]

    Sayago I, Gutiérrez J, Arés L, Robla J I, Horrillo M C, Getino J, Agapito J A 1995 Sens. Actuators B 25 512

    [25]

    Lee Y C, Chueh Y L, Hsieh C H, Chang M T, Chou L J, Wang Z L, Lan Y W, Chen C D, Kurata H, Isoda S 2007 Small 3 1356

    [26]

    Viswanathan K, Brandt K, Salje E 1981 J. Solid State Chem. 36 45

    [27]

    Licznerski B W, Nitsh K, Teterycz H, Wisniewski K 2001 Sens. Actuators B 79 157

    [28]

    Shieh J, Feng H M, Hon M H, Juang H Y 2002 Sens. Actuators B 86 75

    [29]

    Xu C N, Tamaki J, Miura N, Yamazoe N 1991 Sens. Actuators B 3 147

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出版历程
  • 收稿日期:  2013-05-31
  • 修回日期:  2013-07-03
  • 刊出日期:  2013-10-05

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