SnO/SnO<sub>2</sub> heterojunction: an alternative candidate for sensing NO<sub>2</sub> with fast response at room temperature

doi:10.1007/s11706-022-0609-5

Front. Mater. Sci.

2022, Vol. 16

Issue (3) : 220609 https://doi.org/10.1007/s11706-022-0609-5

RESEARCH ARTICLE

SnO/SnO₂ heterojunction: an alternative candidate for sensing NO₂ with fast response at room temperature

Pengtao WANG¹, Wanyin GE¹(

), Xiaohua JIA¹, Jingtao HUANG², Xinmeng ZHANG¹, Jing LU¹

¹. School of Materials Science and Engineering, Shaanxi Key Laboratory of Green Preparation and Functionalization for Inorganic Materials, Shaanxi University of Science and Technology, Xi’an 710021, China
². School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China

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Abstract

The SnO₂-based family is a traditional but important gas-sensitive material. However, the requirement for high working temperature limits its practical application. Much work has been done to explore ways to improve its gas-sensing performance at room temperature (RT). For this report, SnO₂, SnO, and SnO/SnO₂ heterojunction was successfully synthesized by a facile hydrothermal combined with subsequent calcination. Pure SnO₂ requires a high operating temperature (145 °C), while SnO/SnO₂ heterojunction exhibits an excellent performance for sensing NO₂ at RT. Moreover, SnO/SnO₂ exhibits a fast response, of 32 s, to 50 ppm NO₂ at RT (27 °C), which is much faster than that of SnO (139 s). The superior sensing properties of SnO/SnO₂ heterojunction are attributed to the unique hierarchical structures, large number of adsorption sites, and enhanced electron transport. Our results show that SnO/SnO₂ heterojunction can be used as a promising high-performance NO₂ sensitive material at RT.

Keywords SnO SnO₂ heterostructure NO₂ room temperature

Corresponding Author(s): Wanyin GE

Issue Date: 28 July 2022

Cite this article:

Pengtao WANG,Wanyin GE,Xiaohua JIA, et al. SnO/SnO₂ heterojunction: an alternative candidate for sensing NO₂ with fast response at room temperature[J]. Front. Mater. Sci., 2022, 16(3): 220609.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-022-0609-5
https://academic.hep.com.cn/foms/EN/Y2022/V16/I3/220609

Fig.1 (a) Schematic illustration of the evolution process of precursors. (b) XRD patterns of synthesized SnO₂ (i), Sn₆O₄(OH)₄ (ii), SnO (iii), and SnO/SnO₂ (iv).

Fig.2 SEM images of (a) SnO₂, (b) Sn₆O₄(OH)₄, (c) SnO, and (d) SnO/SnO₂. (e) TEM and (f) HRTEM images of SnO/SnO₂.

Fig.3 High-resolution XPS spectrum of SnO/SnO₂ heterojunction. Insets: Sn 3d_5/2 (left); O 1s (right).

Fig.4 N₂ adsorption?desorption isotherms of (a) pure SnO₂, (b) pure SnO, and (c) SnO/SnO₂ heterojunction (insets show pore size distribution curves).

Fig.5 (a) Temperature-dependent responses of pure SnO₂ to 500 ppm NO₂ at different operating temperatures. (b) Transient resistance changes of pure SnO₂ to 50 ppm NO₂ at 145 and 230 °C. Dynamic response/recovery curves of pure SnO₂ at (c) 145 °C and (d) 230 °C to different concentrations of NO₂.

Tab.1 NO₂ sensing comparison of metal oxide-based sensors [9,12,17,21,26–30]

Fig.6 Dynamic response/recovery curves of (a) the SnO sensor and (c) the SnO/SnO₂ heterojunction sensor to NO₂ at RT (insets show responses to low concentrations of NO₂). Response/recovery curves of (b) the SnO sensor and (d) the SnO/SnO₂ heterojunction sensor to 50 ppm NO₂ at RT.

Fig.7 (a) The selectivity of SnO/SnO₂ heterojunction to various gases at 1000 ppm at RT. (b) The response curves of SnO/SnO₂ to 50 ppm NO₂ under different RH values from 41.3% to 91.3%. (c) Repeatability and (d) long-term stability tests of the SnO/SnO₂ sensor to 50 ppm NO₂ at RT.

Fig.8 (a)(b) Depletion layer responses to different gas environment (in air and in NO₂, respectively). (c) Schematic diagram of the band structure of SnO/SnO₂ heterostructure.

1	Y, Yan S, Krishnakumar H, Yu , et al.. Nickel(II) dithiocarbamate complexes containing sulforhodamine B as fluorescent probes for selective detection of nitrogen dioxide. Journal of the American Chemical Society, 2013, 135( 14): 5312– 5315 https://doi.org/10.1021/ja401555y pmid: 23530626
2	C, Yan H, Lu J, Gao , et al.. Improved NO2 sensing properties at low temperature using reduced graphene oxide nanosheet–In2O3 heterojunction nanofibers. Journal of Alloys and Compounds, 2018, 741 : 908– 917 https://doi.org/10.1016/j.jallcom.2018.01.209
3	G, Martinelli M C, Carotta M, Ferroni , et al.. Screen-printed perovskite-type thick films as gas sensors for environmental monitoring. Sensors and Actuators B: Chemical, 1999, 55( 2–3): 99– 110 https://doi.org/10.1016/S0925-4005(99)00054-4
4	H S, Jeong M J, Park S H, Kwon , et al.. Low temperature NO2 sensing properties of RF-sputtered SnO–SnO2 heterojunction thin-film with p-type semiconducting behavior. Ceramics International, 2018, 44( 14): 17283– 17289 https://doi.org/10.1016/j.ceramint.2018.06.189
5	J Z, Ou W, Ge B, Carey , et al.. Physisorption-based charge transfer in two-dimensional SnS2 for selective and reversible NO2 gas sensing. ACS Nano, 2015, 9( 10): 10313– 10323 https://doi.org/10.1021/acsnano.5b04343 pmid: 26447741
6	M S, Choi A, Mirzaei H G, Na , et al.. Facile and fast decoration of SnO2 nanowires with Pd embedded SnO2−x nanoparticles for selective NO2 gas sensing. Sensors and Actuators B: Chemical, 2021, 340 : 129984 https://doi.org/10.1016/j.snb.2021.129984
7	Z, Yang L, Jiang J, Wang , et al.. Flexible resistive NO2 gas sensor of three-dimensional crumpled MXene Ti3C2Tx/ZnO spheres for room temperature application. Sensors and Actuators B: Chemical, 2021, 326 : 128828 https://doi.org/10.1016/j.snb.2020.128828
8	A, Umar H Y, Ammar R, Kumar , et al.. Square disks-based crossed architectures of SnO2 for ethanol gas sensing applications ― an experimental and theoretical investigation. Sensors and Actuators B: Chemical, 2020, 304 : 127352 https://doi.org/10.1016/j.snb.2019.127352
9	N A, Isaac M, Valenti A, Schmidt-Ott , et al.. Characterization of tungsten oxide thin films produced by spark ablation for NO2 gas sensing. ACS Applied Materials & Interfaces, 2016, 8( 6): 3933– 3939 https://doi.org/10.1021/acsami.5b11078 pmid: 26796099
10	V X, Hien Y W Heo . Effects of violet-, green-, and red-laser illumination on gas-sensing properties of SnO thin film. Sensors and Actuators B: Chemical, 2016, 228 : 185– 191 https://doi.org/10.1016/j.snb.2015.12.105
11	M, Hübner C E, Simion A, Tomescu-Stănoiu , et al.. Influence of humidity on CO sensing with p-type CuO thick film gas sensors. Sensors and Actuators B: Chemical, 2011, 153( 2): 347– 353 https://doi.org/10.1016/j.snb.2010.10.046
12	W, Du W, Si W, Du , et al.. Unraveling the promoted nitrogen dioxide detection performance of N-doped SnO2 microspheres at low temperature. Journal of Alloys and Compounds, 2020, 834 : 155209 https://doi.org/10.1016/j.jallcom.2020.155209
13	J Y, Liu C, Wang Q Y, Yang , et al.. Hydrothermal synthesis and gas-sensing properties of flower-like Sn3O4. Sensors and Actuators B: Chemical, 2016, 224 : 128– 133 https://doi.org/10.1016/j.snb.2015.09.089
14	P H, Suman A A, Felix H L, Tuller , et al.. Giant chemo-resistance of SnO disk-like structures. Sensors and Actuators B: Chemical, 2013, 186 : 103– 108 https://doi.org/10.1016/j.snb.2013.05.087
15	Q Q, Ren X P, Zhang Y N, Wang , et al.. Shape-controlled and stable hollow frame structures of SnO and their highly sensitive NO2 gas sensing. Sensors and Actuators B: Chemical, 2021, 340 : 129940 https://doi.org/10.1016/j.snb.2021.129940
16	S T, Rezalou T, Oznuluer U Demir . One-pot electrochemical fabrication of single-crystalline SnO nanostructures on Si and ITO substrates for catalytic, sensor and energy storage applications. Applied Surface Science, 2018, 448 : 510– 521 https://doi.org/10.1016/j.apsusc.2018.04.034
17	W T, Li X D, Zhang X Guo . Electrospun Ni-doped SnO2 nanofiber array for selective sensing of NO2. Sensors and Actuators B: Chemical, 2017, 244 : 509– 521 https://doi.org/10.1016/j.snb.2017.01.022
18	X F, Chu X H, Zhu Y P, Dong , et al.. Formaldehyde sensing properties of SnO–graphene composites prepared via hydrothermal method. Journal of Materials Science and Technology, 2015, 31( 9): 913– 917 https://doi.org/10.1016/j.jmst.2015.05.001
19	L L, Meng W Y, Bu Y, Li , et al.. Highly selective triethylamine sensing based on SnO/SnO2 nanocomposite synthesized by one-step solvothermal process and sintering. Sensors and Actuators B: Chemical, 2021, 342 : 130018 https://doi.org/10.1016/j.snb.2021.130018
20	L, Li C, Zhang W Chen . Fabrication of SnO2–SnO nanocomposites with p–n heterojunctions for the low-temperature sensing of NO2 gas. Nanoscale, 2015, 7( 28): 12133– 12142 https://doi.org/10.1039/C5NR02334C pmid: 26123121
21	H, Yu T Y, Yang Z Y, Wang , et al.. p-N heterostructural sensor with SnO–SnO2 for fast NO2 sensing response properties at room temperature. Sensors and Actuators B: Chemical, 2018, 258 : 517– 526 https://doi.org/10.1016/j.snb.2017.11.165
22	L, Zhang R B, Tong W Y, Ge , et al.. Facile one-step hydrothermal synthesis of SnO2 microspheres with oxygen vacancies for superior ethanol sensor. Journal of Alloys and Compounds, 2020, 814 : 152266 https://doi.org/10.1016/j.jallcom.2019.152266
23	W, Ge S, Jiao Z, Chang , et al.. Ultrafast response and high selectivity toward acetone vapor using hierarchical structured TiO2 nanosheets. ACS Applied Materials & Interfaces, 2020, 12( 11): 13200– 13207 https://doi.org/10.1021/acsami.9b23181 pmid: 32096401
24	B J, Wang S Y, Ma S T, Pei , et al.. High specific surface area SnO2 prepared by calcining Sn-MOFs and their formaldehyde-sensing characteristics. Sensors and Actuators B: Chemical, 2020, 321 : 128560 https://doi.org/10.1016/j.snb.2020.128560
25	C, Liu H B, Lu J N, Zhang , et al.. Crystal facet-dependent p-type and n-type sensing responses of TiO2 nanocrystals. Sensors and Actuators B: Chemical, 2018, 263 : 557– 567 https://doi.org/10.1016/j.snb.2018.02.145
26	S, Deng V, Tjoa H M, Fan , et al.. Reduced graphene oxide conjugated Cu2O nanowire mesocrystals for high-performance NO2 gas sensor. Journal of the American Chemical Society, 2012, 134( 10): 4905– 4917 https://doi.org/10.1021/ja211683m pmid: 22332949
27	Y J, Kwon S Y, Kang P, Wu , et al.. Selective improvement of NO2 gas sensing behavior in SnO2 nanowires by ion-beam irradiation. ACS Applied Materials & Interfaces, 2016, 8( 21): 13646– 13658 https://doi.org/10.1021/acsami.6b01619 pmid: 27167241
28	M Z, Xu R W, Yu Y X, Guo , et al.. New strategy towards the assembly of hierarchical heterostructures of SnO2/ZnO for NO2 detection at a ppb level. Inorganic Chemistry Frontiers, 2019, 6( 10): 2801– 2809 https://doi.org/10.1039/C9QI00788A
29	D, Gu X G, Li Y Y, Zhao , et al.. Enhanced NO2 sensing of SnO2/SnS2 heterojunction based sensor. Sensors and Actuators B: Chemical, 2017, 244 : 67– 76 https://doi.org/10.1016/j.snb.2016.12.125
30	H W, Kim H G, Na Y J, Kwon , et al.. Microwave-assisted synthesis of graphene–SnO2 nanocomposites and their applications in gas sensors. ACS Applied Materials & Interfaces, 2017, 9( 37): 31667– 31682 https://doi.org/10.1021/acsami.7b02533 pmid: 28846844
31	B X, Yang N V, Myung T T Tran . 1D metal oxide semiconductor materials for chemiresistive gas sensors: a review. Advanced Electronic Materials, 2021, 7( 9): 2100271 https://doi.org/10.1002/aelm.202100271
32	L, Zhou Z, Hu H Y, Li , et al.. Template-free construction of tin oxide porous hollow microspheres for room-temperature gas sensors. ACS Applied Materials & Interfaces, 2021, 13( 21): 25111– 25120 https://doi.org/10.1021/acsami.1c04651 pmid: 34003629
33	M S, Choi H G, Na J H, Bang , et al.. SnO2 nanowires decorated by insulating amorphous carbon layers for improved room-temperature NO2 sensing. Sensors and Actuators B: Chemical, 2021, 326 : 128801 https://doi.org/10.1016/j.snb.2020.128801
34	S K, Zhao Y B, Shen P F, Zhou , et al.. Enhanced NO2 sensing performance of ZnO nanowires functionalized with ultra-fine In2O3 nanoparticles. Sensors and Actuators B: Chemical, 2020, 308 : 127729 https://doi.org/10.1016/j.snb.2020.127729
35	P H, Suman A A, Felix H L, Tuller , et al.. Comparative gas sensor response of SnO2, SnO and Sn3O4 nanobelts to NO2 and potential interferents. Sensors and Actuators B: Chemical, 2015, 208 : 122– 127 https://doi.org/10.1016/j.snb.2014.10.119
36	K, Tôel S, Motomizu S Kuse . Naphthoquinonedioxime derivatives as analytical reagents for the spectrophotometric determination of nickel. Analytica Chimica Acta, 1975, 75( 2): 323– 334 https://doi.org/10.1016/S0003-2670(01)85357-5
37	B M Arghiropoulos . Electrical conductivity of pure and doped zinc oxides, catalysts of the hydrogenation of ethylene: I. Activation of the catalyst and adsorption of oxygen on pure zinc oxide. Journal of Catalysis, 1964, 3( 6): 477– 487 https://doi.org/10.1016/0021-9517(64)90048-X
38	S C Chang . Oxygen chemisorption on tin oxide: correlation between electrical conductivity and EPR measurements. Journal of Vacuum Science and Technology, 1980, 17( 1): 366– 369 https://doi.org/10.1116/1.570389

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