异质复合结构纳米纤维SnO2/ZnO的制备及其气敏特性研究

doi:10.15541/jim20170218

无机材料学报 ›› 2018, Vol. 33 ›› Issue (4): 453-461.DOI: 10.15541/jim20170218 CSTR: 32189.14.10.15541/jim20170218

异质复合结构纳米纤维SnO₂/ZnO的制备及其气敏特性研究

杜海英^1,2, 姚朋军³, 王兢⁴, 孙炎辉^4,5, 于乃森⁶, 张涛¹, 董良²

1. 大连民族大学机电工程学院, 大连116600;
2. 爱荷华州立大学工程学院, 电气与计算机工程系, 阿姆斯 50010, 美国;
3. 沈阳师范大学教育技术学院, 沈阳 110034;
4. 大连理工大学电子科学与技术学院, 大连 116023;
5. 大连民族大学信息与通信学院, 大连 116600;
6. 大连民族大学物理与材料学院, 大连 116600

收稿日期:2017-05-03 修回日期:2017-06-16 出版日期:2018-04-30 网络出版日期:2018-03-27
作者简介:杜海英(1978-), 女, 博士, 副教授. E-mail: duhaiying@dlnu.edu.cn
基金资助:
国家自然科学基金(61501081, 61574025);辽宁省自然科学基金(2015020096)

Preparation and Gas Sensing Property of SnO₂/ZnO Composite Hetero-nanofibers Using Two-step Method

DU Hai-Ying^1,2, YAO Peng-Jun³, WANG Jing⁴, SUN Yan-Hui^4,5, YU Nai-Sen⁶, ZHANG Tao¹, DONG Liang²

1. College of Mechanical and Electronic Engineering, Dalian Minzu University, Dalian 116600, China;
2. Department of Electrical and Computer Engineering, College of Engineering, Iowa State University, Ames 50011, U.S.;
3. School of Educational Technology, Shenyang Normal University, Shenyang 110034, China;
4. School of Electronic Science and Technology, Dalian University of Technology, Dalian 116023, China;
5. College of Information & Communication Engineering, Dalian Minzu University, Dalian 116600, China;
6. School of Physics and Materials Engineering, Dalian Minzu University, Dalian 116600, China

Received:2017-05-03 Revised:2017-06-16 Published:2018-04-30 Online:2018-03-27
About author:DU Hai-Ying. E-mail: duhaiying@dlnu.edu.cn
Supported by:
National Natural Science Foundation of China(61501081, 61574025);Liaoning Natural Science Foundation (2015020096)

摘要/Abstract

摘要：

采用静电纺丝法制备了多级中空结构的SnO₂纳米纤维, 然后将SnO₂纳米纤维置于90℃乙酸锌溶液中, 恒温水浴条件下, 在SnO₂纳米纤维上生长了ZnO纳米球, 形成了异质结构的SnO₂/ZnO复合纳米纤维。分别通过XRD、SEM、EDX和XPS等表征手段对异质复合纳米纤维SnO₂/ZnO材料的结构、形貌及元素含量进行了表征分析。异质结构的SnO₂/ZnO复合纳米纤维保持了SnO₂纳米纤维多级中空的纤维结构, SnO₂纳米纤维长度约为300 nm, 依附于SnO₂纤维表面的SnO₂纳米颗粒生长的ZnO纳米球直径为250~300 nm。采用静态气体测试系统对异质复合纳米纤维SnO₂/ZnO气敏元件的气敏性能进行了测试。测试结果表明: 异质复合纳米纤维SnO₂/ZnO气敏元件在最佳工作温度350℃下, 对(0.5~100)×10^-6丙酮具有优异的响应灵敏度、较好的选择性和长期稳定性。异质复合纳米纤维SnO₂/ZnO中存在于ZnO纳米球与SnO₂纳米颗粒间的N-N同型异质结导致复合材料晶界势垒高度的降低, 改善了电子与空穴的输运特性, 促使SnO₂/ZnO异质复合纳米纤维的吸附能力大大增强, 从而改善了SnO₂/ZnO元件的丙酮敏感特性。

关键词: 静电纺丝, 异质复合纳米纤维, N-N同型异质结, 气敏特性, 气敏机理

Abstract:

A two-step route was used to prepare SnO₂/ZnO composite hetero-nanofibers. In the first step, hierarchical SnO₂ nanofibers were synthesized by electrospinning; in the second step, ZnO nanospheres were fabricated in zinc acetate solution using water bath at 90℃. The morphology, structure and composition of SnO₂/ZnO composite hetero-nanofibers were characterized and analyzed by XRD, SEM, EDX, and XPS. SnO₂ nanofibers in the composite materials keep hollow and hierarchical structure with 300 nm in diameter. The diameters of ZnO nanospheres grown on SnO₂ nanofibers are 250-300 nm. Gas sensing properties of SnO₂/ZnO composite hetero-nanofibers were tested using a static gas testing system. Gas sensing properties of pure SnO₂ nanofibers and ZnO nanospheres were also studied to compare their gas sensing properties. The results show that SnO₂/ZnO composite hetero-nanofiber gas sensors exhibit excellent sensing sensitivity, selectivity and long-tern stability for (0.5-100)×10^-6 acetone at 350℃. N-N homotype heterojunctions, existed in the joint between ZnO nanospheres and SnO₂ particles in the SnO₂/ZnO composite materials, change the potential barrier height. The absorption capacity of SnO₂/ZnO composite materials increases greatly due to changes of the transport characteristics of electrons and holes, which results in the improvement of acetone sensing properties of SnO₂/ZnO composite materials.

Key words: electrospinning, composite hetero-nanofibers, N-N homotype heterojunction, gas sensing properties, gas sensing mechanism

中图分类号:

O641
O649

杜海英, 姚朋军, 王兢, 孙炎辉, 于乃森, 张涛, 董良. 异质复合结构纳米纤维SnO₂/ZnO的制备及其气敏特性研究[J]. 无机材料学报, 2018, 33(4): 453-461.

DU Hai-Ying, YAO Peng-Jun, WANG Jing, SUN Yan-Hui, YU Nai-Sen, ZHANG Tao, DONG Liang. Preparation and Gas Sensing Property of SnO₂/ZnO Composite Hetero-nanofibers Using Two-step Method[J]. Journal of Inorganic Materials, 2018, 33(4): 453-461.

图/表 12

图1 旁热式气敏元件结构图(a)和实物照片(b)

Fig. 1 Structure schematic (a) and photo (b) of the indirect- heat gas sensor

图2 (a) SnO2纳米纤维、(b) ZnO纳米球和(c) SnO2/ZnO异质复合纳米纤维的XRD图谱

Fig. 2 XRD patterns of (a) SnO2 nanofibers, (b) ZnO nanoballs and (c) SnO2/ZnO composite nanofibers

图3 (a)和(b) SnO2纳米纤维; (c)和(d) SnO2/ZnO异质复合纳米纤维的SEM照片

Fig. 3 SEM images of ((a) and (b)) SnO2, ((c) and (d)) SnO2/ZnO composite hetero-nanofibers

表1 异质复合纳米纤维SnO2/ZnO的元素含量百分比

Table 1 Element contents of SnO2/ZnO composite hetero-nanofibers

Elements	wt%	at%
O K	16.6	55.4
Zn K	18.9	15.7
Sn L	64.5	28.9

图4 异质复合纳米纤维SnO2/ZnO的XPS图谱

Fig. 4 XPS spectra of SnO2/ZnO homotypehetero-nanofibers

表2 异质复合纳米纤维SnO2/ZnO的主要特征峰的结合能及强度表

Table 2 Binding energy and intensity of main peaks of SnO2/ZnO composite hetero-nanofibers

XPS peaks	Zn2p_1/2	Zn2p_3/2	Sn3p_1/2	Sn3p_3/2	O1s	Sn3d_3/2	Sn3d_5/2
Binding energy /eV	1044.97	1021.97	756.97	714.97	529.97	493.97	485.97
Intensity of SnO₂/ZnO	785851	786074	610554	699586	776614	1169640	1396770

图5 SnO2/ZnO气敏元件响应与工作温度关系曲线

Fig. 5 Responses of SnO2/ZnO gas sensors as a function of operating temperature

图6 SnO2/ZnO气敏元件对(0.5~100)×10-6丙酮的动态响应曲线

Fig. 6 Transient response curve of gas sensor based on SnO2/ZnO to acetone at concentration of (0.5-100)×10-6 Inset: response and recovery curve of gas sensor to 10×10-6 acetone

图7 SnO2、ZnO和SnO2/ZnO气敏元件的响应值与丙酮浓度之间关系

Fig. 7 Response of the gas sensors based on the SnO2, ZnO and SnO2/ZnO vs acetone concentration

图8 异质复合纳米纤维SnO2/ZnO气敏元件对10×10-6丙酮、氨气、甲醛、乙醇、甲苯和苯的交叉响应

Fig. 8 Cross-responses of the SnO2/ZnO sensor to 10×10-6 acetone, ammonia, formaldehyde, alcohol, toluene, and benzene

图9 异质复合纳米纤维SnO2/ZnO气敏元件的长期稳定性

Fig. 9 Long-term stability of the SnO2/ZnO sensor

图10 异质复合纳米纤维SnO2/ZnO能带平衡前后电子转移过程的示意图

Fig. 10 Energy-band diagram of the SnO2/ZnO homotype hetero-nanofibers system (a) Before equilibrium; (b) At equilibrium

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异质复合结构纳米纤维SnO₂/ZnO的制备及其气敏特性研究

Preparation and Gas Sensing Property of SnO₂/ZnO Composite Hetero-nanofibers Using Two-step Method

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