VO2(B)/ZnO异质复合纳米棒结构的室温NH3敏感性能研究

doi:10.15541/jim20180162

摘要/Abstract

摘要：

以VO₂(B)纳米棒为内核, 利用液相生长法制备了VO₂(B)/ZnO异质复合纳米棒, 研究了ZnO生长溶液浓度对复合结构微观形貌和气敏性能的影响规律。采用扫描电子显微镜和X射线衍射仪对复合结构样品的微观形貌和结晶取向进行表征, 并测试了复合结构对NH₃的敏感性能。实验结果表明, 随着ZnO种子液浓度的增大, ZnO逐渐由纳米颗粒生长为纳米棒结构, 当ZnO种子液浓度为0.01 mol/L时, ZnO呈棒状沿径向发散生长在VO₂(B)纳米棒表面, 形成树枝状VO₂(B)/ZnO异质复合纳米棒结构, 这一结构在室温下表现出对NH₃的高灵敏度和突出的选择性, 其灵敏度最大可达5.6, 对NH₃的响应时间最短仅为2 s。在室温下表现出的优良NH₃敏感性能, 主要与高密度的VO₂(B)/ZnO异质结和树枝状结构有关。研究结果为低功耗高灵敏度NH₃气敏传感器的研制提供了重要依据。

关键词: VO₂(B)纳米棒, ZnO纳米棒, 金属氧化物异质结, 氨气传感器

Abstract:

VO₂(B)/ZnO nanorods hierarchical heterogeneous composite was synthesized by solution growth method on VO₂(B) nanorods surface. Effects of ZnO seeds’ solution concentration on microstructure and NH₃ gas sensing properties of composite structures were investigated. X-ray diffractometer and scanning electron microscopy were used to characterize the crystal structure and surface morphology of the samples. NH₃ gas sensing properties of the composite was measured by the gas testing system at different temperatures and gas concentrations. The results show that ZnO grows on VO₂(B) surface and changes its shape from nanoparticle to nanorod as the ZnO seeds’ solution concentration increasing from 0.002 mol/L to 0.03 mol/L. ZnO nanorods radially grows on the VO₂(B) nanorod surface and branch-shaped hierarchical heterogeneous VO₂(B)/ZnO composite structures are formed when the solution concentration is 0.01 mol/L. The composite exhibits high gas response and outstanding selectivity at room temperature. The response value reaches 5.6 while the response time is reduced to 2 s at room temperature. This excellent NH₃ gas sensing performance is related to the highly dense VO₂(B)/ZnO hetero-junction and hierarchical structure. The present results may provide more information for design and fabrication of low power and high sensitive NH₃ gas sensors at room temperature.

Key words: VO₂(B) nanorods, ZnO nanorods, metal oxide heterojunction, NH₃ Gas sensors

中图分类号:

O649

梁继然, 张叶, 杨然, 赵一瑞, 郭津榜. VO₂(B)/ZnO异质复合纳米棒结构的室温NH₃敏感性能研究[J]. 无机材料学报, 2018, 33(12): 1323-1329.

LIANG Ji-Ran, ZHANG Ye, YANG Ran, ZHAO Yi-Rui, GUO Jin-Bang. Room-temperature NH₃ Gas Sensing Property of VO₂(B)/ZnO Hierarchical Heterogeneous Composite with Nanorod Structure[J]. Journal of Inorganic Materials, 2018, 33(12): 1323-1329.

图/表 10

表1 ZnO纳米棒生长溶液中溶质用量、溶液浓度与样品编号对应关系

Table 1 Relationship of the amount of solute, the concentration of solution and the sample number

Sample	n(Zn(NO₃)₂•6H₂O)/ mmol	n(C₆H₁₂N₄)/ mmol	c(sol)/ (mol·L^-1)
VZ1	0.4	0.4	0.002
VZ2	1.0	1.0	0.005
VZ3	2.0	2.0	0.010
VZ4	6.0	6.0	0.030

图1 气敏传感器的结构示意图

Fig. 1 Schematic structure of the gas sensor

图2 气敏测试系统示意图

Fig. 2 Test system of gas sensitivity

图3 VO2(B)纳米棒以及VO2(B)/ZnO复合结构的XRD图谱

Fig. 3 XRD patterns of VO2(B) nanorods and VO2(B)/ZnO composite structures

图4 (a)水热产物VO2(B)纳米棒的SEM照片和(b)局部放大照片

Fig. 4 SEM image (a) and corresponding high magnified image (b) of hydrothermal product VO2 (B) nanorods

图5 不同ZnO生长溶液浓度条件下VO2(B)/ZnO复合结构的SEM照片

Fig. 5 SEM images of VO2(B)/ZnO composite structures with different concentrations of ZnO growth solution(a, b) VZ1; (c, d) VZ2; (e, f) VZ3; (g, h) VZ4

图6 VO2(B)/ZnO复合结构传感器在不同温度下对100× 10-6氨气的气体响应

Fig. 6 Gas responses of VO2(B)/ZnO composite structure sensors to 100×10-6 NH3 at different operating temperatures

图7 VO2(B)/ZnO复合结构传感器电阻随时间动态变化曲线

Fig. 7 Dynamic resistance-time curves of VO2(B)/ZnO composite structure sensors

图8 VO2/ZnO复合结构传感器响应值与气体浓度关系(a)以及圆圈中部分的放大图(b)

Fig. 8 Relationship of the response value of VO2/ZnO composite sensors and gas concentrations (a), and high magnification figure of circle parts (b)

图9 VO2(B)/ZnO复合结构传感器在室温下对不同气体的气敏响应

Fig. 9 Gas responses of VO2(B)/ZnO composite structure sensors to different gases at room temperature

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VO₂(B)/ZnO异质复合纳米棒结构的室温NH₃敏感性能研究

Room-temperature NH₃ Gas Sensing Property of VO₂(B)/ZnO Hierarchical Heterogeneous Composite with Nanorod Structure

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