Газочувствительные характеристики маломощных полупроводниковых газовых сенсоров при воздействии СО и H₂

В связи с жёсткими требованиями по определению концентрации газов в рабочей среде является актуальной разработка полупроводниковых сенсоров для обеспечения оперативного реагирования и безопасности персонала в промышленных и бытовых помещениях. Целью работы являлось исследование газочувствительных и динамических характеристик высокочувствительных маломощных сенсоров, изготовленных на тонких нанопористых подложках с газочувствительными слоями из полупроводниковых оксидов металлов. В этой связи разработана конструкция полупроводникового газового сенсора на подложке из анодного оксида алюминия. Изготовлены датчики с газочувствительными слоями из полупроводниковых оксидов металлов, полученных методом осаждения из водных растворов с последующим отжигом, на основе In₂O₃+Ga₂O₃, In₂O₃+SnO₂ и SnO₂+Pd, нанесённых на измерительные электроды сенсоров. Проведённые исследования газочувствительных характеристик показали, что максимальной чувствительностью, около 85 %, и высоким быстродействием к воздействию 10 ppm H₂ при 410 ºС обладают сенсоры с плёнками из SnO₂ с добавлением наночастиц Pd. Наибольшая чувствительность сенсора – 250 % при воздействии 10 ppm CO и температуре 220 ºС достигнута при использовании In₂O₃+SnO₂ , время срабатывания τ90 составило 5 с, тогда как  чувствительность  In₂O₃+Ga₂O₃  и  SnO₂+Pd  была  на  уровне  30–50 % при 410–420 ºС. Меньшую чувствительность к воздействию водорода показали полупроводниковые оксиды металлов In₂O₃+Ga₂O₃ (70 % при 420 ºС) и In₂O₃+SnO₂ (30 % при 250 ºС) при времени срабатывания τ₉₀ = 20 с. Подаваемая мощность на нагреватели сенсоров во всех режимах измерений составляла 28–60 мВт. Полупроводниковые газовые сенсоры с низким энергопотреблением могут быть использованы при разработке систем, обеспечивающих контроль концентрации оксида углерода в рабочей зоне, а также обнаружения ранних стадий возгорания.

1. Linlin Wang, Jun Gao, Baofeng Wu, Kan Kan, Shuang Xu, Yu Xie, Li Li, Keying Shi Designed synthesis of In2O3 Beads@TiO2-In2O3 composite nanofibers for high performance NO2 sensor at room temperature. ACS Appl. Mater. Interfaces.2015;7:27152-27159. DOI: 10.1021/acsami.5b09496

2. Zhang H, Feng J, Fei T, Liu S, Zhang T. SnO2 nanoparticles-reduced graphene oxide nanocomposites for NO2 sensing at low operating temperature. Sensors and Actuators. B Chem. 2014;190:472-478. DOI: 10.1016/j.snb.2013.08.067

3. Park S, Sun GJ, Jin C, Kim HW, Lee S, Lee C. Synergistic effects of a combination of Cr2O3-functionalization and UV-irradiation techniques on the ethanol gas sensing performance of ZnO nanorod gas sensors. ACS Appl. Mater. Interfaces. 2016;8:2805- DOI: 10.1021/acsami.5b11485

4. Kim H-J, Le J-H. Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview. Sensors and Actuators B: Chem. 2014;192:607-627.DOI: 10.1016/j.snb.2013.11.005

5. Védrine JC. Heterogeneous Catalysis on Metal Oxides. Catalysts. 2017;7:341. DOI: 10.3390/catal7110341

6. Liu XY, Wang A, Zhang T, Mou CY. Catalysis by gold: new insights into the support effect. Nano Today. 2013;8:403-416. DOI: 10.1016/j.nantod.2013.07.005

7. Comini E. Metal oxides nanowires chemical/gas sensors: recent advances. Materials Today Advances. 2020;7:100099. DOI: 10.1016/j.mtadv.2020.100099

8. Li G, Du K, Wang X, Qiu C, Xu J. Pd nanoparticles decorated SnO2 ultrathin nanosheets for highly sensitive H2 sensor: Experimental and theoretical studies 2024. International Journal of Hydrogen Energy. Part A. 2024;50:761-771. DOI: 10.1016/j.ijhydene.2023.06.263

9. Pineau NJ, Keller SD, Güntner AT, Pratsinis SE. Palladium embedded in SnO2 enhances the sensitivity of flame-made chemoresistive gas sensors. Microchim Acta. 2020;187:1-9. DOI: 10.1007/s00604-0194080-7

10. Sivaperuman K, Thomas A, Thangavel R, Thirumalaisamy L, Palanivel S, Pitchaimuthu S, Ahsan N, Okada Y. Binary and ternary metal oxide semiconductor thin films for effective gas sensing applications: A comprehensive review and future prospects. Progress in Materials Science. 2024;142:101222. DOI: 10.1016/j.pmatsci.2023.101222

11. Meng X, Bi M, Xiao O, Gao W. Ultrasensitive gas sensor based on Pd/SnS2/SnO2 nanocomposites for rapid detection of H2, Sensors and Actuators B: Chemical. 2022;359:131612. DOI: 10.1016/j.snb.2022.131612

12. Jeong HM, Kim JH, Jeong SY, Kwak CH, Lee JH. Co3O4-SnO2 hollow heteronanostructures: facile control of gas selectivity by compositional tuning of sensing materials via galvanic replacement. ACS Appl. Mater. Interfaces. 2016;8:7877-7883. DOI: 10.1021/acsami.6b00216

13. Kumpika T, Kantarak E, Sroila W, Panthawan A, Sanmuangmoon P, Thongsuwan W, Singjai P. Fabrication and composition control of porous ZnO-TiO2 binary oxide thin films via a sparking method. Optik. 2017;133:114121. DOI: 10.3390/ma11050841

14. Arfaoui А. [et al.] nvestigations into the physical properties of SnO2/MoO3 and SnO2/WO3 bi-layered structures along with photocatalytic and antibacterial applications. Thin Solid Films. 2018;648:12-20. DOI: 10.1016/j.tsf.2018.01.002

15. Eshmakov R, Filatova D, Konstantinova E, Rumyantseva M. Effect of Manganese Distribution on Sensor Properties of SnO2/MnOx Nanocomposites. Nanomaterials. 2023;13:1437. DOI: 10.3390/nano13091437

16. Gorokh G, Belahurau Y, Zakhlebaeva A, Taratyn I, Khatko V. Ring gyroscope sensitive element based on nanoporous alumina. Aircr. Eng. Aerosp. Technol. 2018;90:43-50. DOI: 10.1108/AEAT-01-2015-0026

17. Ali HO. Review of porous anodic aluminium oxide (AAO) applications for sensors, MEMS and biomedical devices. Transactions of the IMF. The International Journal of Surface Engineering and Coatings. 2017;95:290296. DOI: 10.1080/00202967.2017.1358514

18. Han J, Cheng P, Wang H, Zhang C, Zhang J, Wang Y, Duan L, Ding G. MEMS-based Pt film temperature sensor on an alumina substrate. Materials Letters. 2014;125:224-226. DOI: 10.1016/j.matlet.2014.03.170

19. Gorokh GG, Zakhlebayeva AI, Belahurau YA, Khatko VV, Taratyn IA. Chemical gas sensors on the nanoporous anodic alumina substrate. J. Nano Microsyst. Technol. 2014;9:45-51. DOI: 10.1108/AEAT-01-2015-0026

20. Ghasemi-Varnamkhastia M, Lozano J. Electronic nose as an innovative measurement system for the quality assurance and control of bakery products: A review. Engineering in Agriculture, Environment and Food. 2017;9:365-374. DOI: 10.1016/j.eaef.2016.06.001

21. Gorokh G, Zakhlebayeva A, Lazavenka A, Sobolev N, Zhylinski V, Bogomazova N, Yarmolich M, Kalanda N. Functional Multicomponent Metal Oxide Films Based on Sr, Sn, Fe and Mo in the Anodic Alumina Matrices. Phys. Status Solidi. 2020;257:1900283. DOI: 10.1002/pssb.201900283

22. Korotcenkov G. Current Trends in Nanomaterials for Metal Oxide-Based Conductometric Gas Sensors: Advantages and Limitations. Part 1: 1D and 2D Nanostructures. Nanomaterials. 2020;7(10):1392. DOI: 10.3390/nano10071392

23. Zakhlebayeva A, Lazavenka A, Gorokh G. Multicomponent Sn–Mo–O-Containing Films Formed in Anodic Alumina Matrixes by Ionic Layer Deposition. Mater. Today Proc. 2021;37:4064-4070. DOI: 10.1016/j.matpr.2020.09.252

24. Tolstoy VP. Successive ionic layer deposition. The use in nanotechnology. Russian Chemical Reviews. 2006;2(75):161-175. DOI: 10.1070/RC2006v075n02ABEH001197

25. Gorokh G, Bogomazova N, Taleb A, Zhylinski V, Galkovsky T, Zakhlebayeva A, Lozovenko A, Iji M, Fedosenko V, Tolstoy V. Spatially Ordered Matrix of Nanostructured Tin–Tungsten Oxides Nanocomposites Formed by Ionic Layer Deposition for Gas Sensing. Sensors. 2021;21:4169. DOI: 10.3390/s21124169

26. Kim JH, Jeong HM, Na ChW, Yoon JW, Abdel-Hady F, Wazzan AA, Lee JH. Highly selective and sensitive xylene sensors using Cr2O3-ZnCr2O4 heteronanostructures prepared by galvanic replacement. Sensor. Actuator. B Chem. 2016;235:498-506. DOI: 10.1016/j.snb.2016.05.104

27. Santos А, Kumeria T, Losic D. Nanoporous anodic aluminum oxide for chemical sensing and biosensors. Trends in Analytical Chemistry. 2013;44,:25-38. DOI: 10.1016/j.snb.2016.05.104

28. Mohd Ch SA, Hamidon MN, Mamat MS, Ertugrul M, Abdullah NH. A Hydrogen Gas Sensor Based on TiO2 Nanoparticles on Alumina Substrate. Sensors. 2018;18:2483. DOI: 10.3390/s18082483

29. Kumeria T, Santos A, Losic D. Nanoporous Anodic Alumina Platforms: Engineered Surface Chemistry and Structure for Optical Sensing Applications. Sensors. 2014;14:11878-11918. DOI: 10.3390/s140711878

30. Tsyntsaru N, Kavas B, Sort J, Urgen M, Celis J-P. Mechanical and frictional behavior of nano-porous anodized aluminum, Materials Chemistry and Physics. 2014;148:887-895. DOI: 10.1016/j.matchemphys.2014.08.066

31. Belahurau YA, Khatko VV, Gorokh GG, Zakhlebayeva AI, Reutskaya OG, Taratyn IA. Low-power gas sensor on nanostructured dielectric membrane. J. Nano Microsyst. Tech. 2015;6:34-42.

32. Gorokh G, Taratyn I, Fiadosenka U, Reutskaya O, Lozovenko A. Heater Topology Influence on the Functional Characteristics of Thin-Film Gas Sensors Made by MEMS-Silicon Technology. Chemosensors. 2023;11:443. DOI: 10.3390/chemosensors11080443

33. Gorokh G, Zakhlebayeva A, Taratyn I, Lozovenko A, Zhylinski V, Iji M, Fedosenko V, Taleb A. A Micropowered Chemoresistive Sensor Based on a Thin Alumina Nanoporous Membrane and SnxBikMoyOz Nanocomposite. Sensor. 2022;22:3640. DOI: 10.3390/s22103640

34. Kutukov P, Rumyantseva M, Krivetskiy V, Filatova D, Batuk M, Hadermann J, Khmelevsky N, Aksenenko A, Gaskov A. Influence of Monoand Bimetallic PtOx, PdOx, PtPdOx Clusters on CO Sensing by SnO2 Based Gas Sensors. Nanomaterials. 2018;8:917. DOI: 10.3390/nano8110917

35. Sui N, Zhang P, Zhou T, Zhang T. Selective ppb-level ozone gas sensor based on hierarchical branchlike In2O3 nanostructure. Sensors Actuators B Chem. 2021;336:129612. DOI: 10.1016/j.snb.2021.129612

36. Majhi SM, Navale S, Mirzaei A, Kim HW, Kim SS. Strategies to Boost Chemiresistive Sensing Performance of In2O3-based Gas Sensors: An Overview. Inorganic Chemistry Frontiers. 2023;10:3428-3467. DOI: 10.1039/D3QI00099K

37. Malik R, Tomer VK, Chaudhary V, Dahiya MS, Nehra SP, Duhan S, Kailasam K. A low temperature, highly sensitive and fast response toluene gas sensor based on In (III)-SnO2 loaded cubic mesoporous graphitic carbon nitride. Sensors Actuators B Chem. 2018;255:3564-3575. DOI: 10.1016/j.snb.2017.09.193

38. Cao J, Zhang N, Wang S, Zhang H. Electronic structure-dependent formaldehyde gas sensing perfor mance of the In2O3/Co3O4 core/shell hierarchical heterostructure sensors. Journal Colloid Interface Science. 2020;577:19-28. DOI: 10.1016/j.jcis.2020.05.028

39. Staerz A, Suzuki T, Weimar U, Barsan N. SnO2: The most important base material for semiconducting metal oxide-based materials. Tin Oxide Mater, Elsevier. 2020;345-377. DOI: 10.1016/B978-0-12-815924-8.00012-8

40. Masuda Y. Recent advances in SnO2 nanostructure-based gas sensors. Sensors Actuators B Chem. 2022;131876. DOI: 10.1016/j.snb.2022.131876

41. Cai Z, Park S. Synthesis of Pd nanoparticle-decorated SnO2 nanowires and determination of the optimum quantity of Pd nanoparticles for highly sensitive and selective hydrogen gas sensor. Sensors and Actuators B: Chemical. 2020;322:128651. DOI: 10.1016/j.snb.2020.128651

42. Yao Dong, Lingling Du, Yingnan Jiang, Yankai Wang, Jie Zhang, Xinyue Wang, Shuli Wei, Mengling Sun, Qing Lu, Guangchao Yin, In2O3-SnO2 HedgehogLike nanostructured heterojunction for acetone detection, Applied Surface Science. 2024;654:159543.

43. DOI: 10.1016/j.apsusc.2024.159543

44. Yang S, Jiang C, Wei S-H. Gas Sensing in 2D Materials. Applied Physics Reviews. 2017;4:021304. DOI: 10.1063/1.4983310

45. Reutskaya OG, Pleskachevsky YM. Measurement of CO and NO2 gas concentration's by multisensor microsystem in the mode of pulse heating. Devices and Methods of Measurements. 2017;8(2):160-167. (In Russ.). DOI: 10.21122/2220-9506-2017-8-2-160-167

46. Bubnov YuZ. Analysis of thermal regimes of semiconductor sensors. Messenger HEE. Iinstrument making. 2010;53(4):38-41. (In Russ.).