Fabrication of In2O3/SnO2-coaxial-electrospinning fiber and investigation on its formaldehyde sensing properties
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摘要: 两种半导体材料合成的复合材料由于电子亲合能和带隙宽度差形成了同型异质或异型异质结，利用异质结界面形成的费米能级效应可以提高界面载流子迁移率，从而有效改善气体传感器的气敏性能。本文采用自行设计开发的多层同轴静电纺丝装置，构筑了同轴异质复合纳米纤维In2O3/SnO2。所构筑的同轴异质复合纤维In2O3/SnO2外层较大的In2O3纳米颗粒附着在内层较小SnO2纳米颗粒表面，形成中空的分级纤维结构。同轴异质复合纤维In2O3/SnO2中由于存在大量的N-N同型异质结界面，电子迁移率增强，表面活性增强，吸附氧含量增加，对甲醛表现出良好的气敏性能。在250℃环境下，同轴复合纤维In2O3/SnO2气敏元件对50×10-6的甲醛响应为14.12，分别是SnO2、In2O3和混合异质In2O3/SnO2气敏元件对甲醛响应的3.22倍、3.84倍和1.51倍。同轴异质复合纤维In2O3/SnO2气敏元件对甲醛、乙醇、丙酮、甲苯和甲醇表现出良好的交叉选择性。利用同轴静电纺丝法构筑同轴异质复合纤维中提高半导体功能器件性能具有巨大的应用潜力和发展前景。Abstract: Homo heterojunction or hetero heterojunction will form at the surface of two kinds of different semiconductor due to the difference of electronic affinity and band gap width. The interface carrier mobility can be improved by means of Fermi level effect at interface of heterojunction, which improves the gas sensitivity perfor-mance of gas sensor. The coaxial heterocomposite In2O3/SnO2 nanofibers were fabricated by a self-designed multilayer coaxial electrospinning device. The bigger In2O3 nanoparticles on the outer layer of In2O3/SnO2 fibers grow on the surface of the SnO2 nanoparticles on the inner layer of In2O3/SnO2 fiber, which forms the hollow hierarchical fiber structure. N-N homo-heterojunctions interface between of In2O3 and SnO2 nanoparticles will enhance electron mobility, surface activity and the content of adsorption oxygen, which will improve the adsorption capacity of In2O3/SnO2 sensor to formaldehyde. The response of coaxial hetero-nanofiber In2O3/SnO2 sensor is 14.12×10-6 to 50 ×10-6 formaldehyde, are 3.22 times, 3.84 times and 1.51 times of that of SnO2, In2O3 and mixed hetero-nanofiber In2O3/SnO2 sensor at 250℃. The coaxial hetero-nanofiber In2O3/SnO2 sensor also shows excellent cross-selectivity to formaldehyde, ethanol, acetone, ammonia, toluene and methanol. The coaxial hetero composite synthesized by coaxial electrospinning has application potential and development prospect to improve semiconductor function device.
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图 1 同轴异质In2O3/SnO2复合纳米纤维结构示意图
Figure 1. Schematic diagram of composite nano-In2O3/SnO2 fiber structure
图 4 SnO2、In2O3、In2O3/SnO2-T和In2O3/SnO2-H纳米纤维的XRD图谱
Figure 4. XRD spectra of SnO2, In2O3, In2O3/SnO2-T and In2O3/SnO2-H
图 5 SnO2 (a)、In2O3 (b)、In2O3/SnO2-T (c)和In2O3/SnO2-H (d) 的SEM图像
Figure 5. SEM images of SnO2 (a), In2O3 (b), In2O3/SnO2-T (c) and In2O3/SnO2-H (d)
图 7 SnO2 (a)、In2O3 (b)、In2O3/SnO2-T (c) 和In2O3/SnO2-H (d) 的O1s XPS图谱
Figure 7. XPS O1s spectrum of SnO2 (a), In2O3 (b), In2O3/SnO2-T (c) and In2O3/SnO2-H (d)
Olat—Lattice oxygen; Oads—Adsorbed oxygen; Ode—Oxygen defects
图 8 SnO2 (a)、In2O3 (b)、In2O3/SnO2-T (c) 和In2O3/SnO2-H (d) 的纳米纤维N2等温吸附-脱附曲线
Figure 8. N2 isotherms adsorption-desorption curves of SnO2 (a), In2O3 (b), In2O3/SnO2-T (c) and In2O3/SnO2-H (d) nanofibers
图 9 (a) In2O3/SnO2-T气敏元件对甲醛、乙醇、氨气、丙酮、甲苯和甲醇气体的交叉响应曲线；(b) SnO2、In2O3、In2O3/SnO2-T和In2O3/SnO2-H气敏元件工作温度曲线；(c) SnO2、In2O3、In2O3/SnO2-T和In2O3/SnO2-H气敏元件对甲醛的动态响应曲线；(d) SnO2、In2O3、In2O3/SnO2-T和In2O3/SnO2-H气敏元件的响应及恢复时间曲线
Figure 9. (a) Cross-response curves of In2O3/SnO2-T sensor to formaldehyde, ethanol, ammonia, acetone, toluene and methanol; (b) Sensitivities of SnO2, In2O3, In2O3/SnO2-T and In2O3/SnO2-H temperature curves; (c) Transient response curves of gas sensors based on the SnO2, In2O3, In2O3/SnO2-T and In2O3/SnO2-H to formaldehyde; (d) Response and recovery time of SnO2, In2O3, In2O3/SnO2-T and In2O3/SnO2-H sensors
图 10 (a) SnO2和In2O3的能带示意图；(b) SnO2/ In2O3异质结传感机制和能带示意图
Figure 10. (a) Schematic energy band diagram of SnO2 and In2O3; (b) Schematic energy band diagram and illustration of sensing mechanism for a SnO2/In2O3 heterojunction
EVAC—Vacuum level; EF—Fermi level; ECB—Conductive band; EVB—Valence band; Φ—Work function
表 1 同轴异质纳米纤维In2O3/SnO2-T的元素含量
Table 1. Elements content of In2O3/SnO2-T composite nanofibers
Element Mass fraction/wt% Atomic fraction/at% O 11.6 48.9 In 39.6 23.3 Sn 48.8 27.8 
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表 2 SnO2、In2O3、In2O3/SnO2-T和In2O3/SnO2-H的比表面积
Table 2. Specific surface areas of SnO2, In2O3, In2O3/SnO2-T and In2O3/SnO2-H nanofibers
Sample Specific surface areas/(m2·g−1) SnO2 37.9230 In2O3 33.4763 In2O3/SnO2−T 88.6171 In2O3/SnO2−H 63.8690
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