Recent advances of ethanol detection materials based on metal oxides

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

Abstract

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

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

CLC Number:

O643.3

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.

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.

Figures/Tables 10

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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]