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Exploring the role of film thickness and oxygen vacancies on the H2S gas-sensing performance of RF magnetron-sputtered NiO thin films

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Abstract

This work explores the thickness effect of RF magnetron-sputtered nickel oxide (NiO) thin films for evaluating their H2S gas-sensing characteristics. NiO thin films were prepared on alumina substrates by varying the deposition time, and the resulting film thicknesses were 25 nm, 52 nm, and 76 nm. X-ray diffraction results demonstrate the polycrystalline nature and cubic structure of NiO thin films. Photoluminescence spectroscopy measurements revealed increased defect content (Ni interstitials and O vacancies) in the 52-nm-thick NiO thin film. Furthermore, X-ray photoelectron spectroscopy results confirmed the thickness effect on NiO thin film stoichiometry. Conductivity measurements at working temperatures ranging from 200 to 450 °C were also used to investigate the gas-sensing tests. The NiO thin film with a thickness of 52 nm proved to be an excellent H2S gas sensor, with a remarkable sensor response of 260% and a response/recovery time of ~ 52 s/23 s for 50 ppm H2S at a relatively low operating temperature of 275 °C. Additionally, the film displays a low H2S detection limit of ~ 0.2 ppm. This study investigates the relationship between the thickness, structural, optical, and electrical properties of NiO thin film-based H2S gas sensors and their gas-sensing capabilities.

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References

  1. Liu W, Wu J, Yang Y et al (2018) Facile synthesis of three-dimensional hierarchical NiO microflowers for efficient room temperature H2S gas sensor. J Mater Sci Mater Electron 29:4624–4631. https://doi.org/10.1007/s10854-017-8413-1

    Article  CAS  Google Scholar 

  2. Ganapathi SK, Kaur M, Singh R et al (2019) Anomalous sensing response of NiO nanoparticulate films toward H2S. ACS Appl Nano Mater 2:6726–6737. https://doi.org/10.1021/acsanm.9b01637

    Article  CAS  Google Scholar 

  3. Pai SHS, Mondal A, Barathy TR et al (2023) Effect of calcination temperature on NiO for hydrogen gas sensor performance. Int J Hydrogen Energy 50:928–941. https://doi.org/10.1016/j.ijhydene.2023.07.345

    Article  CAS  Google Scholar 

  4. Godbole R, Godbole VP, Alegaonkar PS, Bhagwat S (2017) Effect of film thickness on gas sensing properties of sprayed WO3 thin films. New J Chem 41:11807–11816. https://doi.org/10.1039/c7nj00963a

    Article  CAS  Google Scholar 

  5. Bin JS, Kim HJ, Ahn JH et al (2020) Effects of thin-film thickness on sensing properties of SnO2 -based gas sensors for the detection of H2S gas at ppm levels. J Nanosci Nanotechnol 20:7169–7174. https://doi.org/10.1166/jnn.2020.18854

    Article  CAS  Google Scholar 

  6. Barsan N, Simion C, Heine T et al (2010) Modeling of sensing and transduction for p-type semiconducting metal oxide based gas sensors. J Electroceram 25:11–19. https://doi.org/10.1007/s10832-009-9583-x

    Article  CAS  Google Scholar 

  7. Liu Y, Liu F, Bai J et al (2019) Direct growth of NiO films on Al2O3 ceramics by electrochemical deposition and its excellent H2S sensing properties. Sens Actuators B Chem 296:126619. https://doi.org/10.1016/j.snb.2019.05.096

    Article  CAS  Google Scholar 

  8. Nakate UT, Bhuyan P, Yu YT, Park S (2022) Synthesis and characterizations of highly responsive H2S sensor using p-type Co3O4 nanoparticles/nanorods mixed nanostructures. Int J Hydrogen Energy 47:8145–8154. https://doi.org/10.1016/j.ijhydene.2021.12.115

    Article  CAS  Google Scholar 

  9. Li D, Tang Y, Ao D et al (2019) Ultra-highly sensitive and selective H2S gas sensor based on CuO with sub-ppb detection limit. Int J Hydrogen Energy 44:3985–3992. https://doi.org/10.1016/j.ijhydene.2018.12.083

    Article  CAS  Google Scholar 

  10. Liang YC, Chang YC (2020) The effect of Ni content on gas-sensing behaviors of ZnO–NiO p-n composite thin films grown through radio-frequency cosputtering of ceramic ZnO and NiO targets. CrystEngComm 22:2315–2326. https://doi.org/10.1039/d0ce00052c

    Article  CAS  Google Scholar 

  11. Srivastava S, Dwivedi C, Yadav A et al (2023) Enhanced H2S gas sensing of Pd functionalized NiO thin films deposited by the magnetron sputtering process. Mater Lett 351:135040. https://doi.org/10.1016/j.matlet.2023.135040

    Article  CAS  Google Scholar 

  12. Srivastava S, Gangwar AK, Kumar A et al (2023) Impact of O2/Ar gas ratio on the DC reactive magnetron sputtered NiO thin films for ultrafast detection with high sensitivity and selectivity towards H2S gas. Micro Nanostruct 184:207678. https://doi.org/10.1016/j.micrna.2023.207678

    Article  CAS  Google Scholar 

  13. Srivastava S, Gangwar AK, Kumar A et al (2023) Room temperature RF magnetron sputtered nanocrystalline NiO thin films for highly responsive and selective H2S gas sensing at low ppm concentrations. Mater Res Bull 165:112330. https://doi.org/10.1016/j.materresbull.2023.112330

    Article  CAS  Google Scholar 

  14. Ngoc Hoa TT, Hoa ND, Van Duy N et al (2019) An effective H2S sensor based on SnO2 nanowires decorated with NiO nanoparticles by electron beam evaporation. RSC Adv 9:13887–13895. https://doi.org/10.1039/c9ra01105f

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. Rajesh K, Pothukanuri N, Dasari SG, Reddy MR (2023) Investigations of spray-deposited NiO thin films for ultrasensitive formaldehyde detection. J Alloys Metall Syst 1(2):100009. https://doi.org/10.1016/j.jalmes.2023.100009

    Article  Google Scholar 

  16. Dastan D, Shan K, Jafari A et al (2023) Influence of heat treatment on H2S gas sensing features of NiO thin films deposited via thermal evaporation technique. Mater Sci Semicond Process 154:107232. https://doi.org/10.1016/j.mssp.2022.107232

    Article  CAS  Google Scholar 

  17. Soleimanpour AM, Jayatissa AH, Sumanasekera G (2013) Surface and gas sensing properties of nanocrystalline nickel oxide thin films. Appl Surf Sci 276:291–297. https://doi.org/10.1016/j.apsusc.2013.03.085

    Article  CAS  Google Scholar 

  18. Zhang J, Zeng D, Zhu Q et al (2015) Effect of grain-boundaries in NiO nanosheet layers room-temperature sensing mechanism under NO2. J Phys Chem C 119:17930–17939. https://doi.org/10.1021/acs.jpcc.5b04940

    Article  CAS  Google Scholar 

  19. Chou PC, Chen HI, Liu IP et al (2015) Hydrogen sensing performance of a nickel oxide (NiO) thin film-based device. Int J Hydrogen Energy 40:729–734. https://doi.org/10.1016/j.ijhydene.2014.10.142

    Article  CAS  Google Scholar 

  20. Souissi R, Bouguila N, Bouricha B et al (2020) Thickness effect on VOC sensing properties of sprayed In2S3films. RSC Adv 10:18841–18852. https://doi.org/10.1039/d0ra01573c

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Wilson RL, Simion CE, Blackman CS et al (2018) The effect of film thickness on the gas sensing properties of ultra-thin TiO2 films deposited by atomic layer deposition. Sensors 18(3):735. https://doi.org/10.3390/s18030735

    Article  CAS  Google Scholar 

  22. Ritala M, Leskela M, Niinisto L, Haussalo P (1993) Titanium isopropoxide as a precursor in atomic layer epitaxy of titanium dioxide thin films. Chem Mater 5:1174–1181. https://doi.org/10.1021/cm00032a023

    Article  CAS  Google Scholar 

  23. Balakarthikeyan R, Santhanam A, Anandhi R et al (2021) Fabrication of nanostructured NiO and NiO: Cu thin films for high-performance ultraviolet photodetector. Opt Mater 120:111387. https://doi.org/10.1016/j.optmat.2021.111387

    Article  CAS  Google Scholar 

  24. Musevi SJ, Aslani A, Motahari H, Salimi H (2016) Offer a novel method for size appraise of NiO nanoparticles by PL analysis: synthesis by sonochemical method. J Saudi Chem Soc 20:245–252. https://doi.org/10.1016/j.jscs.2012.06.009

    Article  CAS  Google Scholar 

  25. Hammad AH, Abdel-Wahab MS, Vattamkandathil S, Ansari AR (2019) Growth and correlation of the physical and structural properties of hexagonal nanocrystalline nickel oxide thin films with film thickness. Coatings 9:615. https://doi.org/10.3390/coatings9100615

    Article  CAS  Google Scholar 

  26. Kumari L, Li WZ, Vannoy CH et al (2009) Vertically aligned and interconnected nickel oxide nanowalls fabricated by hydrothermal route. Cryst Res Technol 44:495–499. https://doi.org/10.1002/crat.200800583

    Article  CAS  Google Scholar 

  27. Gandhi AC, Wu SY (2017) Strong deep-level-emission photoluminescence in NiO nanoparticles. Nanomaterials 7:231. https://doi.org/10.3390/nano7080231

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  28. Mochizuki S, Saito T (2009) Intrinsic and defect-related luminescence of NiO. Phys B Condens Matter 404:4850–4853. https://doi.org/10.1016/j.physb.2009.08.166

    Article  CAS  Google Scholar 

  29. Mauraya AK, Mahana D, Jhaa G et al (2022) Heterostructure nanoarchitectonics with ZnO/SnO2 for ultrafast and selective detection of CO gas at low ppm levels. Ceram Int 48:36556–36569. https://doi.org/10.1016/j.ceramint.2022.08.215

    Article  CAS  Google Scholar 

  30. Duan H, Chen Z, Xu N et al (2021) Non-stoichiometric NiOx nanocrystals for highly efficient electrocatalytic oxygen evolution reaction. J Electroanal Chem 885:114966. https://doi.org/10.1016/j.jelechem.2020.114966

    Article  CAS  Google Scholar 

  31. Salunkhe P, Muhammed MA, Kekuda D (2021) Structural, spectroscopic and electrical properties of dc magnetron sputtered NiO thin films and an insight into different defect states. Appl Phys A Mater Sci Process 127:390. https://doi.org/10.1007/s00339-021-04501-0

    Article  CAS  Google Scholar 

  32. Ai L, Fang G, Yuan L et al (2008) Influence of substrate temperature on electrical and optical properties of p-type semitransparent conductive nickel oxide thin films deposited by radio frequency sputtering. Appl Surf Sci 254:2401–2405. https://doi.org/10.1016/j.apsusc.2007.09.051

    Article  CAS  Google Scholar 

  33. Cheng M, Fan H, Song Y et al (2017) Interconnected hierarchical NiCo2O4 microspheres as high-performance electrode materials for supercapacitors. Dalton Trans 46:9201–9209. https://doi.org/10.1039/c7dt01289f

    Article  CAS  PubMed  Google Scholar 

  34. Ding C, Yan D, Zhao Y et al (2016) A bubble-template approach for assembling Ni–Co oxide hollow microspheres with an enhanced electrochemical performance as an anode for lithium ion batteries. Phys Chem Chem Phys 18:25879–25886. https://doi.org/10.1039/c6cp04097g

    Article  CAS  PubMed  Google Scholar 

  35. Singh P, Srivatsa KMK, Barvat A, Pal P (2016) X-ray photoelectron spectroscopic studies of CeO2 thin films deposited on Ni-W (100), c-Al2O3 (0001) and Si (100) substrates. Curr Appl Phys 16:1388–1394. https://doi.org/10.1016/j.cap.2016.07.013

    Article  Google Scholar 

  36. Ciftyurek E, Li Z, Schierbaum K (2023) Adsorbed oxygen ions and oxygen vacancies: their concentration and distribution in metal oxide chemical sensors and influencing role in sensitivity and sensing mechanisms. Sensors 23:29. https://doi.org/10.3390/s23010029

    Article  CAS  Google Scholar 

  37. Srivastava R (2012) Investigation on temperature sensing of nanostructured zinc oxide synthesized via oxalate route. J Sens Technol 02:8–12. https://doi.org/10.4236/jst.2012.21002

    Article  CAS  Google Scholar 

  38. Shankar P, Bosco J, Rayappan B (2015) Gas sensing mechanism of metal oxides: the role of ambient atmosphere type of semiconductor and gases—a review. Sci Lett J 4:126.

    Google Scholar 

  39. Hu J, Wang Y, Wang W et al (2017) Enhancement of the acetone sensing capabilities to ppb detection level by Fe-doped three-dimensional SnO2 hierarchical microstructures fabricated via a hydrothermal method. J Mater Sci 52:11554–11568. https://doi.org/10.1007/s10853-017-1319-8

    Article  CAS  Google Scholar 

  40. Shringi AK, Kumar A, Das M et al (2023) Ag catalysts boosted NO2 gas sensing performance of RF sputtered α-Fe2O3 films. Sens Actuators B Chem 393:134307. https://doi.org/10.1016/j.snb.2023.134307

    Article  CAS  Google Scholar 

  41. Dang TK, Cuong ND, Sinh VH et al (2023) Hexagonal annular-NiO nanoarchitecture with local p-n homojunctions: novel formation mechanism and H2S gas sensing properties. J Alloys Compd 933:167782. https://doi.org/10.1016/j.jallcom.2022.167782

    Article  CAS  Google Scholar 

  42. Mahana D, Mauraya AK, Kumaragurubaran S et al (2023) Synthesis of CuO thin films by a direct current reactive sputtering process for CO gas sensing application. Phys Scr 98:035709. https://doi.org/10.1088/1402-4896/acb866

    Article  Google Scholar 

  43. Mahana D, Mauraya AK, Pal P et al (2022) Comparative study on surface states and CO gas sensing characteristics of CuO thin films synthesised by vacuum evaporation and sputtering processes. Mater Res Bull 145:111567. https://doi.org/10.1016/j.materresbull.2021.111567

    Article  CAS  Google Scholar 

  44. Kaur M, Dadhich BK, Singh R et al (2017) RF sputtered SnO2: NiO thin films as sub-ppm H2S sensor operable at room temperature. Sens Actuators B Chem 242:389–403. https://doi.org/10.1016/j.snb.2016.11.054

    Article  CAS  Google Scholar 

  45. Mokoena TP, Tshabalala ZP, Hillie KT et al (2020) The blue luminescence of p-type NiO nanostructured material induced by defects: H2S gas sensing characteristics at a relatively low operating temperature. Appl Surf Sci 525:146002. https://doi.org/10.1016/j.apsusc.2020.146002

    Article  CAS  Google Scholar 

  46. Jiang H, Sui L, Zhao D et al (2023) In situ growth of hierarchical NiO microspheres via ionic liquid-assisted synthesis for ppb-level detection of H2S. Sens Actuators B Chem 378:133161. https://doi.org/10.1016/j.snb.2022.133161

    Article  CAS  Google Scholar 

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Acknowledgements

The authors are thankful to the Director, CSIR-NPL, India, for his continuous encouragement and financial support (Project No. OLP-220332). S.S. would like to gratefully acknowledge the University Grant Commission (UGC) for the Senior Research fellowship (SRF) award. C.D. is thankful to the Department of Science & Technology (DST), New Delhi, India, for support through Project (DST/WOS-A/PM-49/2021) Dr. K.K. Maurya from CSIR-NPL, and Prof. R. Chandra from IIT Roorkee, India, is highly acknowledged for their help in characterizations.

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Authors and Affiliations

  1. CSIR-National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi, 110012, India

    Stuti Srivastava, Charu Dwivedi, Govind Gupta & Preetam Singh

  2. Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India

    Stuti Srivastava, Govind Gupta & Preetam Singh

  3. Nanoscience Laboratory, Institute Instrumentation Centre, IIT Roorkee, Roorkee, 247667, India

    Ashwani Kumar

  4. Department of Physics, Graphic Era (Deemed to Be University), Dehradun, Uttarakhand, India

    Ashwani Kumar

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  1. Stuti Srivastava
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  4. Govind Gupta
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Contributions

SS contributed to conceptualization, methodology, validation, formal analysis, writing—original draft; CD contributed to investigation; AK contributed to investigation; GG contributed to investigation, writing—review and editing; PS contributed to supervision, visualization, writing—review and editing.

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Correspondence to Preetam Singh.

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Srivastava, S., Dwivedi, C., Kumar, A. et al. Exploring the role of film thickness and oxygen vacancies on the H2S gas-sensing performance of RF magnetron-sputtered NiO thin films. J Mater Sci (2024). https://doi.org/10.1007/s10853-024-10204-7

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