The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO<sub>2</sub> thin film

Yu ZHANG; Haozhe WANG; Tao HE; Yan LI; Ying GUO; Jianjun SHI; Yu XU; Jing ZHANG

doi:10.1088/2058-6272/acb24e

Plasma Science and Technology > 2023 > 25(6): 065504. > DOI: 10.1088/2058-6272/acb24e

Yu ZHANG, Haozhe WANG, Tao HE, Yan LI, Ying GUO, Jianjun SHI, Yu XU, Jing ZHANG. The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO₂ thin film[J]. Plasma Science and Technology, 2023, 25(6): 065504. DOI: 10.1088/2058-6272/acb24e

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The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO₂ thin film

1.
New Energy Materials and Devices, College of Science, Donghua University, Shanghai 201620, People's Republic of China
2.
Textile Key Laboratory for Advanced Plasma Technology and Application, China National Textile and Apparel Council, Shanghai 201620, People's Republic of China
3.
Magnetic Confinement Fusion Research Center, Ministry of Education, Shanghai 201620, People's Republic of China

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Corresponding author:
Yu XU, E-mail: yuxu@dhu.edu.cn

Jing ZHANG, E-mail: jingzh@dhu.edu.cn
Received Date: November 01, 2022
Revised Date: January 08, 2023
Accepted Date: January 10, 2023
Available Online: December 05, 2023
Published Date: March 13, 2023

Graphical Abstract

Abstract

Abstract

The effects of radio frequency (RF) atmospheric pressure (AP) He/H₂ plasma and thermal treatment on the hydrogenation of TiO₂ thin films were investigated and compared in this work. The color of the original TiO₂ film changes from white to black after being hydrogenated in He/H₂ plasma at 160 W (gas temperature ~381 ℃) within 5 min, while the color of the thermally treated TiO₂ film did not change significantly even in pure H₂ or He/H₂ atmosphere with higher temperature (470 ℃) and longer time (30 min). This indicated that a more effective hydrogenation reaction happened through RF AP He/H₂ plasma treatment than through pure H₂ or He/H₂ thermal treatment. The color change of TiO₂ film was measured based on the Commission Internationale d'Eclairage L^*a^*b^* color space system. Hydrogenated TiO₂ film displayed improved visible light absorption with increased plasma power. The morphology of the cauliflower-like nanoparticles of the TiO₂ film surface remained unchanged after plasma processing. X-ray photoelectron spectroscopy results showed that the contents of Ti³⁺ species and Ti–OH bonds in the plasma-hydrogenated black TiO₂ increased compared with those in the thermally treated TiO₂. X-ray diffraction (XRD) patterns and Raman spectra indicated that plasma would destroy the crystal structure of the TiO₂ surface layer, while thermal annealing would increase the overall crystallinity. The different trends of XRD and Raman spectra results suggested that plasma modification on the TiO₂ surface layer is more drastic than on its inner layer, which was also consistent with transmission electron microscopy results. Optical emission spectra results suggest that numerous active species were generated during RF AP He/H₂ plasma processing, while there were no peaks detected from thermal processing. A possible mechanism for the TiO₂ hydrogenation process by plasma has been proposed. Numerous active species were generated in the bulk plasma region, accelerated in the sheath region, and bumped toward the TiO₂ film, which will react with the TiO₂ surface to form OVs and disordered layers. This leads to the tailoring of the band gap of black TiO₂ and causes its light absorption to extend into the visible region.
- black TiO₂ thin film,
- atmospheric pressure plasma,
- thermal treatment,
- visible light response,
- hydrogenation

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Acknowledgments

This research was financially supported by National Natural Science Foundation of China (Nos. 12075054, 12205040, 12175036 and 11875104).

References (60)

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The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO₂ thin film

Abstract