基于金属氧化物的乙醇检测气敏材料的研究进展

doi:10.16085/j.issn.1000-6613.2018-1858

摘要/Abstract

摘要：

金属氧化物型半导体气体传感器是目前常用的乙醇检测手段，深入研究和改进金属氧化物型半导体材料是提升传感器性能的重要方式。本文首先论述了气敏检测的机理和影响因素，并综述了近年来发展的主要金属氧化物型半导体气敏材料，重点介绍了不同微观结构的Co₃O₄、ZnO、SnO₂及掺杂金属氧化物材料、氧化物异质结等的研究和发展情况，对它们的合成方法、结构特点以及结构与乙醇气敏性能之间的关系进行了探讨。分析表明，减小材料颗粒尺寸、构建大比表面积多孔结构、掺杂和复合改性，是提升金属氧化物材料气敏性能的有效措施。此外，基于传感器微小化的趋势，以微机电系统（MEMS）工艺为基础的微型传感器成为气体传感器的发展趋势。然而，目前针对金属氧化物气敏材料的制备依然缺乏一定的理论指导，气体检测缺乏相应的机理研究，亟需物理、化学、材料等多学科的相互结合，促进乙醇等半导体气体传感器的进一步发展。

关键词: 金属氧化物型半导体材料, 乙醇, 气体, 氧化, 微电子学

Abstract:

At present, metal oxide semiconductor gas sensor is the most widely studied sensor for ethanol detection. It is an important way to improve the performance of gas sensor by enhancing the response and selectivity of metal oxide. In this paper, the mechanism and influence factors of gas sensing are discussed. The development of main metal oxides for gas sensor in recent years is also reviewed. The investigation and development of different structural Co₃O₄, ZnO, SnO₂ and their metal doped oxide materials, oxide heterojunction are introduced. Especially, the synthesis, structural characteristics and the relationship between the structure and performance are emphasized. The results show that the performance of gas sensor can be greatly improved by decreasing particle size, increasing large specific surface area, constructing multi-dimensional materials, doping materials and forming heterojunctions. In addition, micro-hot-plate sensors based on MEMS process have become the development trend of gas sensors due to the advantages of sensor miniaturization. However, the insufficiency of theoretical guidance limits the development of metal oxides. The integration of the developments from multiple-disciplies of materials, physics, and chemistry will greatly promote the development of gas sensing materials.

Key words: metal oxide semiconductor materials, ethanol, gas, oxidation, microelectronics

中图分类号:

O643.3

张晓, 徐瑶华, 刘皓, 魏峰, 苑鹏. 基于金属氧化物的乙醇检测气敏材料的研究进展[J]. 化工进展, 2019, 38(07): 3207-3226.

Xiao ZHANG, Yaohua XU, Hao LIU, Feng WEI, Peng YUAN. Recent advances of ethanol detection materials based on metal oxides[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3207-3226.

图/表 10

参考文献 115

1	MANGAS J J , RODRÍGUEZ R , SUÁREZ B . Validation of a gas chromatography-flame ionization method for quality control and spoilage detection in wine and cider[J]. Acta Alimentaria, 2018, 47(1): 17-25.
2	RONG Q , ZHANG Y , LV T , et al . Highly selective and sensitive methanol gas sensor based on molecular imprinted silver-doped LaFeO₃ core-shell and cage structures[J]. Nanotechnology, 2018, 29(14): 145503.
3	DOLAI S , BHUNIA S K , BEGLARYAN S S , et al . Colorimetric polydiacetylene-aerogel detector for volatile organic compounds (VOCs)[J]. ACS Applied Materials & Interfaces, 2017, 9(3): 2891-2898.
4	LIU X , CHENG S , LIU H , et al . A survey on gas sensing technology[J]. Sensors, 2012, 12(7): 9635-9665.
5	HÜBERT T , BOON-BRETT L , BLACK G , et al . Hydrogen sensors-a review[J]. Sensors and Actuators B: Chemical, 2011, 157(2): 329-352.
6	YAMAZOE N , SHIMANOE K . New perspectives of gas sensor technology[J]. Sensors and Actuators B: Chemical, 2009, 138(1): 100-107.
7	ZHU Z , KAO C T, WU R J . A highly sensitive ethanol sensor based on Ag@TiO₂ nanoparticles at room temperature[J]. Applied Surface Science, 2014, 320: 348-355.
8	RAUT B T , GODSE P R , PAWAR S G , et al . Novel method for fabrication of polyaniline-CdS sensor for H₂S gas detection[J]. Measurement, 2012, 45(1): 94-100.
9	KARMAOUI M , LEONARDI S G , LATINO M , et al . Pt-decorated In₂O₃ nanoparticles and their ability as a highly sensitive (<10ppb) acetone sensor for biomedical applications[J]. Sensors and Actuators B: Chemical, 2016, 230: 697-705.
10	JIN C , PARK S , KIM H, et al . Ultrasensitive multiple networked Ga₂O₃-core/ZnO-shell nanorod gas sensors[J]. Sensors and Actuators B: Chemical, 2012, 161(1): 223-228.
11	WANG C , YIN L , ZHANG L , et al . Metal oxide gas sensors: sensitivity and influencing factors[J]. Sensors, 2010, 10(3): 2088-2106.
12	MIRZAEI A , JANGHORBAN K , HASHEMI B , et al . Highly stable and selective ethanol sensor based on α-Fe₂O₃ nanoparticles prepared by pechini sol-gel method[J]. Ceramics International, 2016, 42(5): 6136-6144.
13	SUN Y F , LIU S B , MENG F L , et al . Metal oxide nanostructures and their gas sensing properties: a review[J]. Sensors, 2012, 12(3): 2610-2631.
14	YAMAZOE N , SHIMANOE K . Basic approach to the transducer function of oxide semiconductor gas sensors[J]. Sensors & Actuators B: Chemical, 2011, 160(1):1352-1362.
15	ZHANG J , LIU X , NERI G , et al . Nanostructured materials for room-temperature gas sensors[J]. Advanced Materials, 2016, 28(5): 795-831.
16	JIN C , GE C , XU G , et al . Influence of nanoparticle size on ethanol gas sensing performance of mesoporous α-Fe₂O₃ hollow spheres[J]. Materials Science and Engineering B, 2017, 224: 158-162.
17	AMBARDEKAR V , BANDYOPADHYAY P P , MAJUMDER S B . Atmospheric plasma sprayed SnO₂ coating for ethanol detection[J]. Journal of Alloys and Compounds, 2018, 752: 440-447.
18	TANG W , WANG J , QIAO Q , et al . Mechanism for acetone sensing property of Pd-loaded SnO₂ nanofibers prepared by electrospinning: Fermi-level effects[J]. Journal of Materials Science, 2015, 50(6): 2605-2615.
19	ZHANG J , LIANG Y , MAO J , et al . 3D microporous Co₃O₄-carbon hybrids biotemplated from butterfly wings as high performance VOCs gas sensor[J]. Sensors and Actuators B: Chemical, 2016, 235: 420-431.
20	CHUNG J S , HUR S H . A highly sensitive enzyme-free glucose sensor based on Co₃O₄ nanoflowers and 3D graphene oxide hydrogel fabricated via hydrothermal synthesis[J]. Sensors and Actuators B: Chemical, 2016, 223: 76-82.
21	ZHANG M L , SONG J P , YUAN Z H , et al . Response improvement for In₂O₃-TiO₂ thick film gas sensors[J]. Current Applied Physics, 2012, 12(3): 678-683.
22	MONTAZERI A , JAMALI-SHEINI F . Enhanced ethanol gas-sensing performance of Pb-doped In₂O₃ nanostructures prepared by sonochemical method[J]. Sensors and Actuators B: Chemical, 2017, 242: 778-791.
23	XU J J , LI S J , LI L , et al . Facile fabrication and superior gas sensing properties of spongelike Co-doped ZnO microspheres for ethanol sensors[J]. Ceramics International, 2018, 44(14): 16773-16780.
24	XING L L , YUAN S , CHEN Z H , et al . Enhanced gas sensing performance of SnO₂/α -MoO₃ heterostructure nanobelts[J]. Nanotechnology, 2011, 22(22): 225502.
25	唐伟, 王兢 . 金属氧化物异质结气体传感器气敏增强机理[J]. 物理化学学报, 2016, 32(5): 1087-1104.
	TANG W , WANG J . Enhanced gas sensing mechanisms of metal oxide heterojunction gas sensors[J]. Acta Physico-Chimica Sinica, 2016, 32(5): 1087-1104.
26	PARK S , KIM S, SUN G J , et al . Ethanol sensing properties of networked In₂O₃, nanorods decorated with Cr₂O₃-nanoparticles[J]. Ceramics International, 2015, 41(8):9823-9827.
27	KATOCH A , CHOI S W , KIM J H, et al . Importance of the nanograin size on the H₂S-sensing properties of ZnO-CuO composite nanofibers[J]. Sensors and Actuators B: Chemical, 2015, 214: 111-116.
28	NAYAK A K , GHOSH R , SANTRA S , et al . Hierarchical nanostructured WO₃-SnO₂ for selective sensing of volatile organic compounds[J]. Nanoscale, 2015, 7(29): 12460-12473.
29	KUMAR M , BHATI V S , RANWA S , et al . Pd/ZnO nanorods based sensor for highly selective detection of extremely low concentration hydrogen[J]. Scientific Reports, 2017, 7(1): 236.
30	PRADES J D , JIMENEZ-DIAZ R , HERNANDEZ-RAMIREZ F , et al . Ultralow power consumption gas sensors based on self-heated individual nanowires[J]. Applied Physics Letters, 2008, 93(12): 123110.
31	LUPAN O , POSTICA V , LABAT F , et al . Ultra-sensitive and selective hydrogen nanosensor with fast response at room temperature based on a single Pd/ZnO nanowire[J]. Sensors and Actuators B: Chemical, 2018, 254: 1259-1270.
32	GANESH R S , DURGADEVI E , NAVANEETHAN M , et al . Low temperature ammonia gas sensor based on Mn-doped ZnO nanoparticle decorated microspheres[J]. Journal of Alloys and Compounds, 2017, 721: 182-190.
33	KIM H J, LEE J H . Highly sensitive and selective gas sensors using p-type oxide semiconductors: overview[J]. Sensors and Actuators B: Chemical, 2014, 192: 607-627.
34	SAN X, WANG G , LIANG B , et al . Flower-like NiO hierarchical microspheres self-assembled with nanosheets: surfactant-free solvothermal synthesis and their gas sensing properties[J]. Journal of Alloys and Compounds, 2015, 636: 357-362.
35	YOON J W , KIM H J, JEONG H M , et al . Gas sensing characteristics of p-type Cr₂O₃ and Co₃O₄ nanofibers depending on inter-particle connectivity[J]. Sensors and Actuators B: Chemical, 2014, 202: 263-271.
36	SUN C , SU X , XIAO F , et al . Synthesis of nearly monodisperse Co₃O₄ nanocubes via a microwave-assisted solvothermal process and their gas sensing properties[J]. Sensors and Actuators B: Chemical, 2011, 157(2): 681-685.
37	ZHOU X , QU F , ZHANG B , et al . Facile synthesis of In₂O₃ microcubes with exposed {100} facets as gas sensing material for selective detection of ethanol vapor[J]. Materials Letters, 2017, 209: 618-621.
38	ZHANG Y , HE X , LI J , et al . Fabrication and ethanol-sensing properties of micro gas sensor based on electrospun SnO₂ nanofibers[J]. Sensors and Actuators B: Chemical, 2008, 132(1): 67-73.
39	LI R , CHEN S , LOU Z , et al . Fabrication of porous SnO₂ nanowires gas sensors with enhanced sensitivity[J]. Sensors and Actuators B: Chemical, 2017, 252: 79-85.
40	ZHANG L , YIN Y . Large-scale synthesis of flower-like ZnO nanorods via a wet-chemical route and the defect-enhanced ethanol-sensing properties[J]. Sensors and Actuators B: Chemical, 2013, 183: 110-116.
41	MA M X, PAN Z Y , GUO L , et al . Porous cobalt oxide nanowires: notable improved gas sensing performances[J]. Chinese Science Bulletin, 2012, 57(31): 4019-4023.
42	WEN Z , ZHU L , MEI W , et al . Rhombus-shaped Co₃O₄ nanorod arrays for high-performance gas sensor[J]. Sensors and Actuators B: Chemical, 2013, 186: 172-179.
43	LIU L , ZHANG T , WANG Z J , et al . High performance micro-structure sensor based on TiO₂ nanofibers for ethanol detection[J]. Chinese Physics Letters, 2009, 26(9): 77-80.
44	ZHU L , LI Y , ZENG W . Hydrothermal synthesis of hierarchical flower-like ZnO nanostructure and its enhanced ethanol gas-sensing properties[J]. Applied Surface Science, 2018, 427: 281-287.
45	DENG S , LIU X , CHEN N , et al . A highly sensitive VOC gas sensor using p-type mesoporous Co₃O₄ nanosheets prepared by a facile chemical coprecipitation method[J]. Sensors and Actuators B: Chemical, 2016, 233: 615-623.
46	CHOI K I , KIM H R, KIM K M, et al . C₂H₅OH sensing characteristics of various Co₃O₄ nanostructures prepared by solvothermal reaction[J]. Sensors and Actuators B: Chemical, 2010, 146(1): 183-189.
47	DENG H , LI H , WANG F , et al . A high sensitive and low detection limit of formaldehyde gas sensor based on hierarchical flower-like CuO nanostructure fabricated by sol-gel method[J]. Journal of Materials Science: Materials in Electronics, 2016, 27(7): 6766-6772.
48	WANG B , SUN L , WANG Y . Template-free synthesis of nanosheets-assembled SnO₂ hollow spheres for enhanced ethanol gas sensing[J]. Materials Letters, 2018, 218: 290-294.
49	LI W , WU X , HAN N , et al . MOF-derived hierarchical hollow ZnO nanocages with enhanced low-concentration VOCs gas-sensing performance[J]. Sensors and Actuators B: Chemical, 2016, 225: 158-166.
50	CHITRA M , UTHAYARANI K , RAJASEKARAN N , et al . Rice husk templated mesoporous ZnO nanostructures for ethanol sensing at room temperature[J]. Chinese Physics Letters, 2015, 32(7): 078101.
51	LI L , LIU M , HE S , et al . Freestanding 3D mesoporous Co₃O₄@carbon foam nanostructures for ethanol gas sensing[J]. Analytical Chemistry, 2014, 86(15): 7996-8002.
52	LI L , ZHANG C , ZHANG R , et al . 2D ultrathin Co₃O₄ nanosheet array deposited on 3D carbon foam for enhanced ethanol gas sensing application[J]. Sensors and Actuators B: Chemical, 2017, 244: 664-672.
53	WANG Y , LIU C , WANG L , et al . Horseshoe-shaped SnO₂ with annulus-like mesoporous for ethanol gas sensing application[J]. Sensors and Actuators B: Chemical, 2017, 240: 1321-1329.
54	ZHANG B , FU W , LI H , et al . Synthesis and characterization of hierarchical porous SnO₂ for enhancing ethanol sensing properties[J]. Applied Surface Science, 2016, 363: 560-565.
55	FAN F , TANG P , WANG Y , et al . Facile synthesis and gas sensing properties of tubular hierarchical ZnO self-assembled by porous nanosheets[J]. Sensors and Actuators B: Chemical, 2015, 215: 231-240.
56	MENG F , HOU N , GE S , et al . Flower-like hierarchical structures consisting of porous single-crystalline ZnO nanosheets and their gas sensing properties to volatile organic compounds (VOCs)[J]. Journal of Alloys and Compounds, 2015, 626: 124-130.
57	JIN Z , ZHANG Y X , MENG F L , et al . Facile synthesis of porous single crystalline ZnO nanoplates and their application in photocatalytic reduction of Cr(Ⅵ) in the presence of phenol[J]. Journal of Hazardous Materials, 2014, 276: 400-407.
58	MENG F , GE S , JIA Y , et al . Interlaced nanoflake-assembled flower-like hierarchical ZnO microspheres prepared by bisolvents and their sensing properties to ethanol[J]. Journal of Alloys and Compounds, 2015, 632: 645-650.
59	XIE X , WANG X , TIAN J , et al . Growth of porous ZnO single crystal hierarchical architectures with ultrahigh sensing performances to ethanol and acetone gases[J]. Ceramics International, 2017, 43(1): 1121-1128.
60	SONG L , YUE H , LI H , et al . Hierarchical porous ZnO microflowers with ultra-high ethanol gas-sensing at low concentration[J]. Chemical Physics Letters, 2018, 699: 1-7.
61	CHENG X L , ZHAO H , HUO L H , et al . ZnO nanoparticulate thin film: preparation, characterization and gas-sensing property[J]. Sensors and Actuators B: Chemical, 2004, 102(2): 248-252.
62	TAMVAKOS A , CALESTANI D , TAMVAKOS D , et al . Effect of grain-size on the ethanol vapor sensing properties of room-temperature sputtered ZnO thin films[J]. Microchimica Acta, 2015, 182(11/12): 1991-1999.
63	WEN Z , ZHU L , LI Y , et al . Mesoporous Co₃O₄ nanoneedle arrays for high-performance gas sensor[J]. Sensors and Actuators B: Chemical, 2014, 203: 873-879.
64	GOPALAKRISHNA D , VIJAYALAKSHMI K , RAVIDHAS C . Effect of pyrolytic temperature on the properties of nano-structured CuO optimized for ethanol sensing applications[J]. Journal of Materials Science: Materials in Electronics, 2013, 24(3): 1004-1011.
65	KIM B Y, CHO J S, YOON J W , et al . Extremely sensitive ethanol sensor using Pt-doped SnO₂ hollow nanospheres prepared by Kirkendall diffusion[J]. Sensors and Actuators B: Chemical, 2016, 234: 353-360.
66	LIU Y , HUANG J , YANG J , et al . Pt nanoparticles functionalized 3D SnO₂ nanoflowers for gas sensor application[J]. Solid-State Electronics, 2017, 130: 20-27.
67	SHAIKH F I , CHIKHALE L P , MULLA I S , et al . Facile Co-precipitation synthesis and ethanol sensing performance of Pd loaded Sr doped SnO₂ nanoparticles[J]. Powder Technology, 2018, 326: 479-487.
68	XIAO L , XU S , YU G , et al . Efficient hierarchical mixed Pd/SnO₂ porous architecture deposited microheater for low power ethanol gas sensor[J]. Sensors and Actuators B: Chemical, 2018, 255: 2002-2010.
69	GUO J , ZHANG J , GONG H , et al . Au nanoparticle-functionalized 3D SnO₂ microstructures for high performance gas sensor[J]. Sensors and Actuators B: Chemical, 2016, 226: 266-272.
70	KIM S Y, KIM J, CHEONG W H , et al . Alcohol gas sensors capable of wireless detection using In₂O₃/Pt nanoparticles and Ag nanowires[J]. Sensors and Actuators B: Chemical, 2018, 259: 825-832.
71	DAI E , WU S , YE Y , et al . Highly dispersed Au nanoparticles decorated WO₃ nanoplatelets: laser-assisted synthesis and superior performance for detecting ethanol vapor[J]. Journal of Colloid and Interface Science, 2018, 514: 165-171.
72	ZHANG W , YANG B , LIU J , et al . Highly sensitive and low operating temperature SnO₂ gas sensor doped by Cu and Zn two elements[J]. Sensors and Actuators B: Chemical, 2017, 243: 982-989.
73	INDERAN V , ARAFAT M M , KUMAR S , et al . Study of structural properties and defects of Ni-doped SnO₂ nanorods as ethanol gas sensors[J]. Nanotechnology, 2017, 28(26): 265702.
74	LI Z , YI J . Enhanced ethanol sensing of Ni-doped SnO₂ hollow spheres synthesized by a one-pot hydrothermal method[J]. Sensors and Actuators B: Chemical, 2017, 243: 96-103.
75	KUMAR M , BHATT V , ABHYANKAR A C , et al . New insights towards strikingly improved room temperature ethanol sensing properties of p-type Ce-doped SnO₂ sensors[J]. Scientific Reports, 2018, 8(1): 8079.
76	ZHOU T , ZHANG T , ZHANG R , et al . Highly sensitive sensing platform based on ZnSnO₃ hollow cubes for detection of ethanol[J]. Applied Surface Science, 2017, 400:262-268.
77	ZHU L , LI Y , ZENG W . Enhanced ethanol sensing and mechanism of Cr-doped ZnO nanorods: experimental and computational study[J]. Ceramics International, 2017, 43(17): 14873-14879.
78	ZHANG P , WANG J , LV X , et al . Facile synthesis of Cr-decorated hexagonal Co₃O₄ nanosheets for ultrasensitive ethanol detection[J]. Nanotechnology, 2015, 26(27): 275501.
79	GONG Y , WANG Y , SUN G , et al . Carbon nitride decorated ball-flower like Co₃O₄ hybrid composite: hydrothermal synthesis and ethanol gas sensing application[J]. Nanomaterials, 2018, 8(3): 132.
80	LIU J , WANG T , WANG B , et al . Highly sensitive and low detection limit of ethanol gas sensor based on hollow ZnO/SnO₂ spheres composite material[J]. Sensors and Actuators B: Chemical, 2017, 245: 551-559.
81	FANG J , ZHU Y , WU D , et al . Gas sensing properties of NiO/SnO₂ heterojunction thin film[J]. Sensors & Actuators B: Chemical, 2017, 252: 1163-1168.
82	CHOI K S , PARK S , CHANG S P . Enhanced ethanol sensing properties based on SnO₂ nanowires coated with Fe₂O₃ nanoparticles[J]. Sensors and Actuators B: Chemical, 2017, 238: 871-879.
83	WANG Q , KOU X , LIU C , et al . Hydrothermal synthesis of hierarchical CoO/SnO₂ nanostructures for ethanol gas sensor[J]. Journal of Colloid and Interface Science, 2018, 513: 760-766.
84	GONG H M , ZHAO C H , WANG F . On-chip growth of SnO₂/ZnO core-shell nanosheet arrays for ethanol detection[J]. IEEE Electron Device Letters, 2018,39(7): 1065-1068.
85	WANG H , WEI S , ZHANG F , et al . Sea urchin-like SnO₂/Fe₂O₃ microspheres for an ethanol gas sensor with high sensitivity and fast response/recovery[J]. Journal of Materials Science Materials in Electronics, 2017, 28(13):9969-9973.
86	LIU L , SONG P , YANG Z , et al . Ultra-fast responding C₂H₅OH sensors based on hierarchical assembly of SnO₂ nanorods on cube-like α-Fe₂O₃ [J]. Journal of Materials Science Materials in Electronics, 2018, 29(7):1-8.
87	BEHERA B , CHANDRA S . An innovative gas sensor incorporating ZnO-CuO nanoflakes in planar MEMS technology[J]. Sensors and Actuators B: Chemical, 2016, 229: 414-424.
88	XIONG Y , XU W , ZHU Z , et al . ZIF-derived porous ZnO-Co₃O₄ hollow polyhedrons heterostructure with highly enhanced ethanol detection performance[J]. Sensors & Actuators B: Chemical, 2017, 253:523-532.
89	ZHANG H , YI J . Enhanced ethanol gas sensing performance of ZnO nanoflowers decorated with LaMnO₃ perovskite nanoparticles[J]. Materials Letters, 2018, 216: 196-198.
90	LIU X , SUN Y , YU M , et al . Enhanced ethanol sensing properties of ultrathin ZnO nanosheets decorated with CuO nanoparticles[J]. Sensors and Actuators B: Chemical, 2018, 255: 3384-3390.
91	WANG T , KOU X , ZHAO L , et al . Flower-like ZnO hollow microspheres loaded with CdO nanoparticles as high performance sensing material for gas sensors[J]. Sensors and Actuators B: Chemical, 2017, 250: 692-702.
92	WANG J , YANG J , HAN N , et al . Highly sensitive and selective ethanol and acetone gas sensors based on modified ZnO nanomaterials[J]. Materials & Design, 2017, 121: 69-76.
93	CHEN Y , LI H , MA Q, et al . ZIF-8 derived hexagonal-like α-Fe₂O₃/ZnO/Au nanoplates with tunable surface heterostructures for superior ethanol gas-sensing performance[J]. Applied Surface Science, 2018, 439: 649-659.
94	SUN Y , CHEN L , WANG Y , et al . Synthesis of MoO₃/WO₃ composite nanostructures for highly sensitive ethanol and acetone detection[J]. Journal of Materials Science, 2017, 52(3):1561-1572.
95	CHOI S , BONYANI M , SUN G J , et al . Cr₂O₃ nanoparticle-functionalized WO₃ nanorods for ethanol gas sensors[J]. Applied Surface Science, 2018, 432: 241-249.
96	HU J , WANG X , ZHANG M , et al . Synthesis and characterization of flower-like MoO₃/In₂O₃ microstructures for highly sensitive ethanol detection[J]. RSC Advances, 2017, 7(38):23478-23485.
97	GENG L , WANG S , ZHAO Y , et al . Study of the primary sensitivity of polypyrrole/γ-Fe₂O₃ to toxic gases[J]. Materials Chemistry and Physics, 2006, 99(1): 15-19.
98	HAYNES A , GOUMA P I . Sensors for environment, health and security[M]. Dordrecht: Springer, 2009: 451-459.
99	DAS M, SARKAR D . Development of room temperature ethanol sensor from polypyrrole (PPy) embedded in polyvinyl alcohol (PVA) matrix[J]. Polymer Bulletin, 2018, 75(7): 3109-3125.
100	CUI S , YANG L , WANG J , et al . Fabrication of a sensitive gas sensor based on PPy/TiO₂ nanocomposites films by layer-by-layer self-assembly and its application in food storage[J]. Sensors and Actuators B: Chemical, 2016, 233: 337-346.
101	GAWRI I , RIDHI R , SINGH K P , et al . Chemically synthesized TiO₂ and PANI/TiO₂ thin films for ethanol sensing applications[J]. Materials Research Express, 2018, 5(2): 025303.
102	KANNAPIRAN N , MUTHUSAMY A , RENGANATHAN B , et al . Investigation of magnetic, dielectric and ethanol sensing properties of poly(o-phenylenediamine)/NiFe₂O₄ nanocomposites[J]. Journal of Materials Science Materials in Electronics, 2017, 29(4):1-11.
103	CHATTERJEE S G , CHATTERJEE S , RAY A K, et al . Graphene-metal oxide nanohybrids for toxic gas sensor: a review[J]. Sensors and Actuators B: Chemical, 2015, 221: 1170-1181.
104	LI Y , LUO N , SUN G , et al . In situ decoration of Zn₂SnO₄ nanoparticles on reduced graphene oxide for high performance ethanol sensor[J]. Ceramics International, 2018, 44(6): 6836-6842.
105	ZITO C A , PERFECTO T M , VOLANTI D P . Impact of reduced graphene oxide on the ethanol sensing performance of hollow SnO₂ nanoparticles under humid atmosphere[J]. Sensors and Actuators B: Chemical, 2017, 244: 466-474.
106	THU N T A, CUONG N D , KHIEU D Q , et al . Fe₃O₄ nanoporous network fabricated from Fe₃O₄/reduced graphene oxide for high-performance ethanol gas sensor[J]. Sensors and Actuators B: Chemical, 2018, 255: 3275-3283.
107	DWIVEDI P , CHAUHAN N , VIVEKANANDAN P , et al . Scalable fabrication of prototype sensor for selective and sub-ppm level ethanol sensing based on TiO₂ nanotubes decorated porous silicon[J]. Sensors and Actuators B: Chemical, 2017, 249: 602-610.
108	SEMANCIK S , CAVICCHI R E , GAITAN M , et al . Temperature-controlled, micromachined arrays for chemical sensor fabrication and operation: US 5345213[P]. 1994-09-06.
109	朱斌, 殷晨波, 陶春曼,等 . 气体传感器叉指电极结构设计及电极间分布电阻计算[J]. 仪表技术与传感器, 2011(8):14-16.
	ZHU B , YIN C B , TAO C M , et al . Structural design and calculation of distributed film resistance of gas sensor’s interdigital electrodes[J]. Instrument Technique and Sensor, 2011(8): 14-16.
110	JOHNSON C L , WISE K D , SCHWANK J W . A thin-film gas detector for semiconductor process gases[C]// San Francisco, CA, USA：Electron Devices Meeting, 1988. 1988: 662-665.
111	SUEHLE J S , CAVICCHI R E , GAITAN M , et al . Tin oxide gas sensor fabricated using CMOS micro-hotplates and in-situ processing[J]. IEEE Electron Device Letters, 1993, 14(3): 118-120.
112	张子立, 殷晨波, 朱斌,等 . 基于MEMS工艺微气体传感器结构与工艺设计[J]. 南京工业大学学报(自然科学版), 2012, 34(3):31-35.
	ZHANG Z L , YIN C B , ZHU B , et al . Design of structure and process for micro-gas sensor based on MEMS technology[J]. Journal of Nanjing University of Technology(Natural Science Edition), 2012, 34(3): 31-35.
113	TAO C M , HE M X , TU S . Thermal analysis and design of a micro-hotplate for Si-substrated micro-structural gas sensor[C]//Sanya, China：Nano/Micro Engineered and Molecular Systems, 2008. 2008: 284-287.
114	KIM I, CHOI W Y . Hybrid gas sensor having TiO₂ nanotube arrays and SnO₂ nanoparticles[J]. International Journal of Nanotechnology, 2017, 14(1/2/3/4/5/6): 155-165.
115	XU J M , CHENG J P . The advances of Co₃O₄ as gas sensing materials: a review[J]. Journal of Alloys and Compounds, 2016, 686: 753-768.

材料	形貌	材料	温度/℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	选择性（响应度）				参考文献
材料	形貌	材料	温度/℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	甲醇	甲醛	丙酮	氢气	参考文献
零维材料	立方颗粒	Co₃O₄	200	100	5.0	无			3.0		[36]
	团聚颗粒	Co₃O₄	300	100	5.5	150/55				5.1	[46]
	纳米颗粒	ZnO	350	400	20.3	12/14	无				[44]
	立方颗粒	In₂O₃	200	100	17.0	无			5.0		[37]
一维材料	纳米纤维	SnO₂	330	10	4.5	13/13.9	无				[38]
	纳米线	SnO₂	380	100	17.0	22/18	无				[39]
	纳米棒	ZnO	400	100	149.2	9/15	无				[40]
	纳米线	Co₃O₄	350	300	5.1	无	无				[41]
	纳米棒	Co₃O₄	160	500	71.0	90/60	38.8		20.1		[42]
	纳米棒	Co₃O₄	300	100	25.7	29/13				20.1	[46]
	纳米管	Co₃O₄	300	100	24.7	49/13				26.3	[46]
	纳米纤维	TiO₂	300	100	14.0	3/5		3.5			[43]
二维材料	纳米片	ZnO	350	400	23.3	12/5	无				[44]
	纳米片	Co₃O₄	100	300	419.0	44/328	94.0	36.4	234.0		[45]
	纳米片	Co₃O₄	300	100	57.5	66/10				56.0	[46]
	层状结构	CuO	250	5	3.1	11.9/8.4	3.0	1.6	2.5		[47]
三维材料	分级结构	SnO₂	350	100	10.5	5	无				[48]
	介孔材料	SnO₂	225	100	17.3	8/780	2.5	2.5	3.0		[53]
	分级多孔	SnO₂	240	500	72.0	10/15	12.0	9.0	7.0		[54]
	分级多孔	SnO₂	240	500	72.0	(20μg?g^-1)	12.0	9.0	7.0		[54]
	空心笼状	ZnO	300	1	8.0	无			14.8		[49]
	介孔材料	ZnO	室温	300	1.4	42/40	无				[50]
	分级多孔	ZnO	250	50	36.6	14/8	3.0				[55]
	分级多孔	ZnO	220	100	8.5	10/80			5.0		[56]
	分级结构	ZnO	370	100	340.0	12/约50			362.0		[59]
	分级结构	ZnO	260	50	110.0	4/12	12.0	40.0	2.0		[60]
	纳米花	ZnO	350	400	30.4	10/4	无				[44]
	三维微孔	Co₃O₄@C	170	100	14.7	无	11.0		7.8		[19]
	三维介孔	Co₃O₄@CF	320	100	4.2	44/31	无				[51]
	介孔纳米片	Co₃O₄/NCF	100	100	10.4	45/140	1.7	1.6	1.3		[52]
薄膜	薄膜	SnO₂	300	300	1.84	8/340			70.0		[17]
	薄膜	ZnO	室温	30	6.0	28/49	5.1 (10μg?g^-1)				[61]
	薄膜	ZnO	400	50	55.0	362/147	无				[62]
	阵列	Co₃O₄	130	100	89.6	无	25.8		55.2		[63]
	薄膜	CuO	室温	200	1.24	15/15	无				[64]

材料	形貌	材料	温度/℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	选择性（响应度）				参考文献
材料	形貌	材料	温度/℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	甲醇	甲醛	丙酮	氢气	参考文献
零维材料	立方颗粒	Co₃O₄	200	100	5.0	无			3.0		[36]
	团聚颗粒	Co₃O₄	300	100	5.5	150/55				5.1	[46]
	纳米颗粒	ZnO	350	400	20.3	12/14	无				[44]
	立方颗粒	In₂O₃	200	100	17.0	无			5.0		[37]
一维材料	纳米纤维	SnO₂	330	10	4.5	13/13.9	无				[38]
	纳米线	SnO₂	380	100	17.0	22/18	无				[39]
	纳米棒	ZnO	400	100	149.2	9/15	无				[40]
	纳米线	Co₃O₄	350	300	5.1	无	无				[41]
	纳米棒	Co₃O₄	160	500	71.0	90/60	38.8		20.1		[42]
	纳米棒	Co₃O₄	300	100	25.7	29/13				20.1	[46]
	纳米管	Co₃O₄	300	100	24.7	49/13				26.3	[46]
	纳米纤维	TiO₂	300	100	14.0	3/5		3.5			[43]
二维材料	纳米片	ZnO	350	400	23.3	12/5	无				[44]
	纳米片	Co₃O₄	100	300	419.0	44/328	94.0	36.4	234.0		[45]
	纳米片	Co₃O₄	300	100	57.5	66/10				56.0	[46]
	层状结构	CuO	250	5	3.1	11.9/8.4	3.0	1.6	2.5		[47]
三维材料	分级结构	SnO₂	350	100	10.5	5	无				[48]
	介孔材料	SnO₂	225	100	17.3	8/780	2.5	2.5	3.0		[53]
	分级多孔	SnO₂	240	500	72.0	10/15	12.0	9.0	7.0		[54]
	分级多孔	SnO₂	240	500	72.0	(20μg?g^-1)	12.0	9.0	7.0		[54]
	空心笼状	ZnO	300	1	8.0	无			14.8		[49]
	介孔材料	ZnO	室温	300	1.4	42/40	无				[50]
	分级多孔	ZnO	250	50	36.6	14/8	3.0				[55]
	分级多孔	ZnO	220	100	8.5	10/80			5.0		[56]
	分级结构	ZnO	370	100	340.0	12/约50			362.0		[59]
	分级结构	ZnO	260	50	110.0	4/12	12.0	40.0	2.0		[60]
	纳米花	ZnO	350	400	30.4	10/4	无				[44]
	三维微孔	Co₃O₄@C	170	100	14.7	无	11.0		7.8		[19]
	三维介孔	Co₃O₄@CF	320	100	4.2	44/31	无				[51]
	介孔纳米片	Co₃O₄/NCF	100	100	10.4	45/140	1.7	1.6	1.3		[52]
薄膜	薄膜	SnO₂	300	300	1.84	8/340			70.0		[17]
	薄膜	ZnO	室温	30	6.0	28/49	5.1 (10μg?g^-1)				[61]
	薄膜	ZnO	400	50	55.0	362/147	无				[62]
	阵列	Co₃O₄	130	100	89.6	无	25.8		55.2		[63]
	薄膜	CuO	室温	200	1.24	15/15	无				[64]

掺杂物	形貌	材料	温度 /℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	选择性(响应度)				参考文献
掺杂物	形貌	材料	温度 /℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	甲醇	甲醛	丙酮	氨气	参考文献
贵金属	中空纳米球	Pt-SnO₂	325	5	1399.9	1/525		600.0	700.0	200	[65]
	纳米棒	Pt-SnO₂	320	200	8.3	3~5/5~15	无				[66]
	纳米颗粒	Pt-SnO₂	275	100	1.9	1/5	无				[67]
	空心材料	Pd-SnO₂	300	50	2.0	1.5/18	0.9	0.9	1.0		[68]
	纳米花	Au-SnO₂	340	150	29.3	5/10	13.3		20.3		[69]
	纳米花	Au-SnO₂	340	150	29.3	(100μg·g^-1)	13.3		20.3		[69]
	薄膜	Pt-In₂O₃	室温	0.095	12.2	1/2	无				[70]
	纳米颗粒	Pt-In₂O₃	250	100	32.6	2.2/0.7			4.0		[22]
	纳米片	Au-WO₃	320	100	97.2	无	8.0	3.0	11.0		[71]
非贵金属	纳米颗粒	CuZn-SnO₂	110	50	210.0	无			10.0		[72]
	纳米棒	Ni-SnO₂	450	50	2000.0	30/600	无				[73]
	纳米微球	Ni-SnO₂	260	100	28.9	11/54	6.0		4.0		[74]
	纳米颗粒	Ce-SnO₂	室温	400	4.8	2~25/30~60	无				[75]
	立方中空	ZnSnO₃	260	100	34.1	2/276			11.0	3	[76]
	纳米棒	Cr-ZnO	300	400	45.0	无	无				[77]
	海绵状	Co-ZnO	220	100	120.0	10/5		18.0	24.0		[23]
	六边形	Cr-Co₃O₄	300	100	28.9	1/7	4.0		3.0		[78]
	纳米球	Co₃O₄/pCNH	210	500	30.2	无	2.0		7.0		[79]

掺杂物	形貌	材料	温度 /℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	选择性(响应度)				参考文献
掺杂物	形貌	材料	温度 /℃	检测浓度 /μg?g^-1	响应度	响应/恢复(时间)/s	甲醇	甲醛	丙酮	氨气	参考文献
贵金属	中空纳米球	Pt-SnO₂	325	5	1399.9	1/525		600.0	700.0	200	[65]
	纳米棒	Pt-SnO₂	320	200	8.3	3~5/5~15	无				[66]
	纳米颗粒	Pt-SnO₂	275	100	1.9	1/5	无				[67]
	空心材料	Pd-SnO₂	300	50	2.0	1.5/18	0.9	0.9	1.0		[68]
	纳米花	Au-SnO₂	340	150	29.3	5/10	13.3		20.3		[69]
	纳米花	Au-SnO₂	340	150	29.3	(100μg·g^-1)	13.3		20.3		[69]
	薄膜	Pt-In₂O₃	室温	0.095	12.2	1/2	无				[70]
	纳米颗粒	Pt-In₂O₃	250	100	32.6	2.2/0.7			4.0		[22]
	纳米片	Au-WO₃	320	100	97.2	无	8.0	3.0	11.0		[71]
非贵金属	纳米颗粒	CuZn-SnO₂	110	50	210.0	无			10.0		[72]
	纳米棒	Ni-SnO₂	450	50	2000.0	30/600	无				[73]
	纳米微球	Ni-SnO₂	260	100	28.9	11/54	6.0		4.0		[74]
	纳米颗粒	Ce-SnO₂	室温	400	4.8	2~25/30~60	无				[75]
	立方中空	ZnSnO₃	260	100	34.1	2/276			11.0	3	[76]
	纳米棒	Cr-ZnO	300	400	45.0	无	无				[77]
	海绵状	Co-ZnO	220	100	120.0	10/5		18.0	24.0		[23]
	六边形	Cr-Co₃O₄	300	100	28.9	1/7	4.0		3.0		[78]
	纳米球	Co₃O₄/pCNH	210	500	30.2	无	2.0		7.0		[79]

异质结	材料	温度/℃	检测浓度/μg?g^-1	响应度	响应/恢复时间/s	选择性(响应度)				参考文献
异质结	材料	温度/℃	检测浓度/μg?g^-1	响应度	响应/恢复时间/s	甲醇	甲醛	丙酮	氨气	参考文献
MO _x -MO _x	ZnO/SnO₂	225	30	34.8	1/120	53.7	8.9	52.1		[80]
	ZnO/SnO₂	225	30	34.8	1/120	(100μg?g^-1，此时乙醇响应度为78.2）				[80]
	NiO/SnO₂	250	100	7.9	15/100	无				[81]
	Fe₂O_3/SnO₂	300	200	57.6	无	20.0	15.0	35.0		[82]
	CoO/SnO₂	250	100	145.0	无	56.0	15.0	54.0		[83]
	SnO₂/ZnO	350	100	13.3	无	4.0		4.0	1.4	[84]
	SnO₂/Fe₂O₃	260	100	41.7	3/4		9.0		5.0	[85]
	SnO₂/Fe₂O₃	240	100	5.9	1/5		1.0	2.5	1.5	[86]
	ZnO/CuO	300	10	2.2	22/26			1.2	0.7	[87]
	ZnO/Co₃O₄	200	1000	106.0	7/236	无				[88]
	LaMnO₃/ZnO	300	50	6.0	8/17	无				[89]
	CuO/ZnO	320	200	97.0	5/25	57.0			20.0	[90]
	CdO/ZnO	250	100	65.5	2/136	10.0	9.0	15.0		[91]
	CdO/Mn-ZnO	340	20	11.4	11.4/12.4		2.0	1.2		[92]
	α-Fe₂O₃/ZnO/Au	280	100	170.0	4/5	无				[93]
	MoO₃/WO₃	320	100	28.5	13/10			18.2		[94]
	Cr₂O₃/WO₃	300	200	5.6	约46/57			4.1		[95]
	MoO₃/In₂O₃	185	100	7.0	11/94	2.5				[96]
有机材料&石墨烯/MO _x	PANI/TiO₂	室温	200	约47.0	115/340	无				[101]
	Zn₂SnO₄/rGO	275	100	38.0	11/18	15.0	3.5	16		[104]
	rGO-SnO₂	300	100	70.4	11/	42.0		13		[105]
	Fe₃O₄/rGO	400	100	9.0	3/138				1.100	[106]
	TiO₂[/多孔硅	150	100	1.4	无			1.03		[107]