SnS2/In2O3 based gas sensors and its high performance of detecting NO2 at room temperature

Chen Jin-Long; Tao Ran; Li Chong; Zhang Jian-Lei; Fu Chen; Luo Jing-Ting

doi:10.7498/aps.73.20231554

Abstract

NO₂ is a toxic gas that can react with other organic compounds in the air, causing air pollution and posing a significant harm to human health. Therefore, a gas sensor that can detect NO₂ is needed. However, conventional NO₂ gas sensors are difficult to operate at room temperature (25 ℃). In this work, NO₂ gas sensing based on SnS₂/In₂O₃, which can operate at room temperature (25 ℃), is reported. In₂O₃ quantum dots and SnS₂ nanosheets are prepared by the hot-injection method and hydrothermal method. By using the unique two-dimensional structure of SnS₂, In₂O₃ is decorated on it, and the composite enhances its sensing performance. The products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS). The results demonstrate that the composites prepared by 52% In₂O₃ exhibit the best sensing response. The fabricated sensor shows a response range from 26.6 to NO₂ of 1×10^–6 in volume fraction, fast response and short recovery time at room temperature (25 ℃). Moreover, this sensor demonstrates excellent reproducibility and selectivity. The heterojunction structure increases the number of active sites and accelerates the gas transport, which promotes charge transfer and gas desorption to improve NO₂ gas sensing performance. This excellent sensing performance has a great application prospect in NO₂ detection.

Keywords:

Authors and contacts

Shenzhen Key Laboratory of Advanced Thin Films and Applications, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China

Corresponding author: Tao Ran, ran.tao@szu.edu.cn ; Luo Jing-Ting, luojt@szu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 12104320), the National Key Research and Development Program of China (Grant No. 2021YFF0603704), the Research Project in Fundamental and Application Fields of Guangdong Province, China (Grant Nos. 2020A1515110561, 2019A1515111199), the Research and Development Program of Guangdong Province, China (Grant No. 2020B0101040002), the Key Research Program of Education Department for Guangdong Province, China (Grant No. 2020ZDZX2007), the Shenzhen Science & Technology Project, China (Grant Nos. RCBS20200714114918249, GJHZ20200731095803010, JCYJ20220818095611025, JSGG20201103090801005), and the Start-up Research Foundation of Shenzhen University, China (Grant No. QNJS0352).

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References

[1]	Copat C, Cristaldi A, Fiore M, Grasso A, Zuccarello P, Signorelli S S, Conti G O, Ferrante M 2020 Environ. Res. 191 110129 Google Scholar
[2]	Cibella F, Cuttitta G, Della Maggiore R, Ruggieri S, Panunzi S, De Gaetano A, Bucchieri S, Drago G, Melis M R, La Grutta S, Viegi G 2015 Environ Res. 138 8 Google Scholar
[3]	Wang J, Shen H, Xia Y, Komarneni S 2021 Ceram. Int. 47 7353 Google Scholar
[4]	Xu Y, Zheng L, Yang C, Zheng W, Liu X, Zhang J 2020 ACS Appl. Mater. Interfaces 12 20704 Google Scholar
[5]	Fang H R, Li S, Zhao H M, Deng J, Wang D, Li J 2022 Sens. Actuators, B 352 131068 Google Scholar
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[7]	Zhang B W, Fang D, Fang X, Zhao H B, Wang D K, Li J H, Wang X H, Wang D B 2021 Rare Met. 41 982 Google Scholar
[8]	Gao L, Cheng Z, Xiang Q, Zhang Y, Xu J 2015 Sens. Actuators, B 208 436 Google Scholar
[9]	Wang M S, Wang Y W, Li X J, Ge C X, Hussain S, Liu G W, Qiao G J 2020 Sens. Actuators, B 316 128050 Google Scholar
[10]	Maeng S, Kim S W, Lee D H, Moon S E, Kim K C, Maiti A 2014 ACS Appl. Mater. Interfaces 6 357 Google Scholar
[11]	Shah S, Han S, Hussain S, Liu G, Shi T, Shaheen A, Xu Z, Wang M, Qiao G 2022 Ceram. Int. 48 12291 Google Scholar
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[13]	Ahmad I, Zhou Z, Li H Y, Zang S Q 2020 Sens. Actuators, B 304 127379 Google Scholar
[14]	Liu Y L, Wang L L, Wang H R, Xiong M Y, Yang T Q, Zakharova G S 2016 Sens. Actuators, B 236 529 Google Scholar
[15]	Hou M, Gao J Y, Yang L, Guo S H, Hu T, Li Y X 2021 Appl. Surf. Sci. 535 147666 Google Scholar
[16]	Wu J, Zhang D, Cao Y 2018 J. Colloid Interface Sci. 529 556 Google Scholar
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图 1 (a) SnS₂, (b) In₂O₃量子点, (c) SnS₂/In₂O₃的SEM图. (d), (g) SnS₂, (e), (h) In₂O₃, (f), (i) SnS₂/In₂O₃的HR-TEM图和SAED图

Figure 1. SEM images of (a) SnS₂ nanoplates, (b) In₂O₃ QDs and (c) SnS₂/In₂O₃ composites. HR-TEM images and SAED patterns with a 5 nm scale of (d), (g) accordion-like SnS₂ nanoplates, (e), (h) In₂O₃ QDs and (f), (i) SnS₂/In₂O₃ composites.

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图 2 (a) In₂O₃, SnS₂和SnS₂/In₂O₃的XRD图谱; (b) SnS₂/In₂O₃, (c) O 1s, (d) In 3d, (e) Sn 3d, (f) S 2p的XPS能谱

Figure 2. (a) XRD patterns of In₂O₃, SnS₂ and SnS₂/In₂O₃; XPS spectra of (b) SnS₂/In₂O₃, (c) O 1s, (d) In 3d, (e) Sn 3d, (f) S 2p.

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图 3 SnS₂纳米片、In₂O₃量子点和SnS₂/In₂O₃复合材料的气敏性能　(a), (b) 不同SnS₂/In₂O₃比例的复合材料对体积分数为1×10^–6 NO₂ 的响应大小及变化情况; (b) 不同SnS₂/In₂O₃比例的复合材料对体积分数为1×10^–6 NO₂的响应变化情况; (c) 室温下不同SnS₂/In₂O₃比例的复合材料对体积分数为1×10^–6 NO₂ 响应和恢复时间的变化情况

Figure 3. Gas-sensing properties of SnS₂ nanoplates, In₂O₃ QDs and SnS₂/In₂O₃ composites: (a) Response sensitivity to 1×10^–6 NO₂ of volume fraction of all composites of different SnS₂/In₂O₃ concentration; (b) variation of response sensitivity to 1×10^–6 NO₂ of volume fraction of all composites of different SnS₂/In₂O₃ concentration; (c) variation of response and recovery time to 1×10^–6 NO₂ of volume fraction of all composites of different SnS₂/In₂O₃ concentration.

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图 4 (a) 52%传感器对不同NO₂浓度的电阻时间曲线; (b) 52%传感器对不同NO₂浓度的线性拟合曲线; (c) 传感器的选择性; (d) 52%传感器对体积分数为8×10^–7 NO₂的重复性曲线

Figure 4. (a) Resistance time curves of 52% sensor to different NO₂ concentrations; (b) the fitting curves of 52% sensor to different NO₂ concentrations; (c) selectivity of the sensor; (d) repeatability curves of 52% sensor toward NO₂ of volume fraction of 8×10^–7.

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图 5 (a), (b) SnS₂和In₂O₃接触前后的能带图; (c) SnS₂/In₂O₃异质结的NO₂气体传感机理示意图

Figure 5. (a), (b) Energy band structure diagram of SnS₂ and In₂O₃ before and after contact; (c) schematic diagram of NO₂ gas sensing mechanism of the sensor based on SnS₂/In₂O₃ heterostructure.

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表 1 不同传感材料的NO₂气敏性能比较

Table 1. Performance comparison of NO₂ sensors based on different composites.

Material	Temp./℃	NO₂ concentration/×10^–6	Response	Response/recovery time/s	Ref.
SnS₂-nanosheets	250	10	2.49	6/40	[20]
SnO₂/SnS₂	80	1	1.8	159/297	[12]
Monolayer MoS₂	25	1.2	1.06	>1800	[21]
In₂O₃ microspheres	250	20	37	5/20	[22]
In₂O₃ thin films	200	5	10	—/—	[23]
In₂O₃ nanocubes	50	3	10	21/522	[17]
SnS₂/In₂O₃	25	1	26.6	146/243	This work

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[1]	Copat C, Cristaldi A, Fiore M, Grasso A, Zuccarello P, Signorelli S S, Conti G O, Ferrante M 2020 Environ. Res. 191 110129 Google Scholar
[2]	Cibella F, Cuttitta G, Della Maggiore R, Ruggieri S, Panunzi S, De Gaetano A, Bucchieri S, Drago G, Melis M R, La Grutta S, Viegi G 2015 Environ Res. 138 8 Google Scholar
[3]	Wang J, Shen H, Xia Y, Komarneni S 2021 Ceram. Int. 47 7353 Google Scholar
[4]	Xu Y, Zheng L, Yang C, Zheng W, Liu X, Zhang J 2020 ACS Appl. Mater. Interfaces 12 20704 Google Scholar
[5]	Fang H R, Li S, Zhao H M, Deng J, Wang D, Li J 2022 Sens. Actuators, B 352 131068 Google Scholar
[6]	Mahajan S, Jagtap S 2020 Appl. Mater. Today 18 100483 Google Scholar
[7]	Zhang B W, Fang D, Fang X, Zhao H B, Wang D K, Li J H, Wang X H, Wang D B 2021 Rare Met. 41 982 Google Scholar
[8]	Gao L, Cheng Z, Xiang Q, Zhang Y, Xu J 2015 Sens. Actuators, B 208 436 Google Scholar
[9]	Wang M S, Wang Y W, Li X J, Ge C X, Hussain S, Liu G W, Qiao G J 2020 Sens. Actuators, B 316 128050 Google Scholar
[10]	Maeng S, Kim S W, Lee D H, Moon S E, Kim K C, Maiti A 2014 ACS Appl. Mater. Interfaces 6 357 Google Scholar
[11]	Shah S, Han S, Hussain S, Liu G, Shi T, Shaheen A, Xu Z, Wang M, Qiao G 2022 Ceram. Int. 48 12291 Google Scholar
[12]	Gu D, Li X, Zhao Y, Wang J 2017 Sens. Actuators, B 244 67 Google Scholar
[13]	Ahmad I, Zhou Z, Li H Y, Zang S Q 2020 Sens. Actuators, B 304 127379 Google Scholar
[14]	Liu Y L, Wang L L, Wang H R, Xiong M Y, Yang T Q, Zakharova G S 2016 Sens. Actuators, B 236 529 Google Scholar
[15]	Hou M, Gao J Y, Yang L, Guo S H, Hu T, Li Y X 2021 Appl. Surf. Sci. 535 147666 Google Scholar
[16]	Wu J, Zhang D, Cao Y 2018 J. Colloid Interface Sci. 529 556 Google Scholar
[17]	Patil S P, Patil V L, Vanalakar S A, Shendage S S, Pawar S A, Kim J H, Ryu J, Patil D R, Patil P S 2022 Mater. Lett. 306 130916 Google Scholar
[18]	Liu H, Su Y, Chen P, Wang Y 2013 J. Mol. Catal. A: Chem. 378 285 Google Scholar
[19]	Price L S, Parkin I P, Hardy A M E, Clark R J H, Hibbert T G, Molloy K C 1999 Chem. Mater. 11 1792 Google Scholar
[20]	Kim Y H, Phan D T, Ahn S, Nam K H, Park C M, Jeon K J 2018 Sens. Actuators, B 255 616 Google Scholar
[21]	He Q, Zeng Z, Yin Z, Li H, Wu S, Huang X, Zhang H 2012 Small 8 2994 Google Scholar
[22]	Vanalakar S A, Patil V L, Harale N S, Vhanalakar S A, Gang M G, Kim J Y, Patil P S, Kim J H 2015 Sens. Actuators, B 221 1195 Google Scholar
[23]	Patil S P, Patil V L, Shendage S S, Harale N S, Vanalakar S A, Kim J H, Patil P S 2016 Ceram. Int. 42 16160 Google Scholar
[24]	Fang H R, Li S, Jiang W J, Zhao H M, Han C S, Li J, Wang G, Zhang Y, Wang S, Deng J, Feng B, Wang D 2022 Sens. Actuators, B 368 132225 Google Scholar
[25]	Yang B X, Myung N V, Tran T T 2021 Adv. Electron. Mater. 7 2100271 Google Scholar
[26]	Cheng M, Wu Z, Liu G, Zhao L, Gao Y, Zhang B, Liu F, Yan X, Liang X, Sun P, Lu G 2019 Sens. Actuators, B 291 216 Google Scholar
[27]	Ferro R, Rodríguez J A, Bertrand P 2008 Thin Solid Films 516 2225 Google Scholar

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SnS₂/In₂O₃ based gas sensors and its high performance of detecting NO₂ at room temperature

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Authors and contacts

Corresponding author: Tao Ran, ran.tao@szu.edu.cn ; Luo Jing-Ting, luojt@szu.edu.cn

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