EXPLORING BISMUTH SULFIDE FOR PHOTOVOLTAICS

Jake Forsyth-Hughes^a

^aNorthumbria University, 302 Whynne Jones Building, Newcastle Upon Tyne, United Kingdom

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)

Emerging chalcogenide materials for thin film photovoltaic applications - #ChalcoPV

Sevilla, Spain, 2025 March 3rd - 7th

Organizers: Giulia Longo and Lucy Whalley

Oral, Jake Forsyth-Hughes, presentation 150
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.150
Publication date: 16th December 2024

Bismuth sulfide (Bi₂S₃) is a nontoxic and inexpensive semiconductor that has potential for use in low-cost thin film photovoltaics owing to its near optimal 1.2eV bandgap and high absorption coefficients greater than 1x10⁴cm^-1 within the IR to UV range [1][2]. Although Bi₂S₃ has potential in photovoltaics, devices have performed poorly with typical efficiencies not surpassing 2% [3][4][5]. One of the challenges of creating high performance cells is from the bulk defects that can exist due to stoichiometric imbalances acting as effective recombination centres [6]. These defects such as the sulfur vacancy and interstitials act mostly as donors making p-type doping difficult [6][7]. The reported properties of Bi₂S₃ are also inconsistent and depend on how the film was prepared. Its lack of crystallinity for example can blue shift the band gap to as high as 1.8eV due to quantum confinement effects [9][4]. Carrier mobilities have varied greatly from 5 cm²V^-1s^-1 prepared by chemical bath to much higher values of 257 cm²V^-1s^-1 and 588 cm²V^-1s^-1 for rapid thermal evaporation and spray pyrolysis [9][4][10]. The latter tow is greater than the typical carrier mobilities reported of 21 cm²V^-1s^-1 to50cm²V^-1s^-1 for monocrystalline Bi₂S₃ grown via the Bridgman technique, suggesting the importance of purity [12][11]. The choice of substrate can influence the charge transfer efficiency in photovoltaic devices due how the bands bend at the interface. Bi₂S₃ deposited onto fluorine doped tin oxide (FTO) for example exhibited better photocurrent than those on tin doped indium oxide (ITO), Molybdenum or Gold [8]. This research has embarked on a systematic study of Bi₂S₃ thin films for photovoltaic devices. These thin films were synthesised via sulfurization of sputtered bismuth films on FTO substrates within a tube furnace. By varying the holding temperatures, ramp rates and holding times different optical and structural properties can be obtained. The effect of different film properties such as crystallite size, stichometry and thickness will be tested in a ITO/ZnO/CdS/Bi₂S₃/FTO cell architecture. By gaining control over the film properties, they can be tuned to improve the performance as an absorbing layer in photovoltaic devices.

References:

[1] P. Larson, V. A. Greanya, W. C. Tonjes, R. Liu, S. D. Mahanti, and C. G. Olson, “Electronic structure of Bi2X3 (X=S,Se, T) compounds: Comparison of theoretical calculations with photoemission studies,” Phys Rev B, vol. 65, no. 8, p. 085108, Feb. 2002

[2] J. Lukose and B. Pradeep, “Electrical and optical properties of bismuth sulphide [Bi2S3] thin films prepared by reactive evaporation,” Solid State Commun, vol. 78, no. 6, pp. 535–538, May 1991

[3] H. Song et al., “Rapid thermal evaporation of Bi2S3 layer for thin film photovoltaics,” Solar Energy Materials and Solar Cells, vol. 146, pp. 1–7, Mar. 2016

[4] E. Pineda, Ma. E. Nicho, P. K. Nair, and H. Hu, “Optoelectronic properties of chemically deposited Bi2S3 thin films and the photovoltaic performance of Bi2S3/P3OT solar cells,” Solar Energy, vol. 86, no. 4, pp. 1017–1022, Apr. 2012

[5] L. E. Ríos-Saldaña, V. D. Compeán-García, H. Moreno-García, and A. G. Rodríguez, “Improvement of the conversion efficiency of as-deposited Bi2S3/PbS solar cells using a CeO2 buffer layer,” Thin Solid Films, vol. 670, pp. 93–98, Jan. 2019

[6] D. Han, M.-H. Du, C.-M. Dai, D. Sun, and S. Chen, “Influence of defects and dopants on the photovoltaic performance of Bi 2 S 3 : first-principles insights,” J Mater Chem A Mater, vol. 5, no. 13, pp. 6200–6210, 2017

[7] A. C. Glatz and V. F. Meikleham, “The Preparation and Electrical Properties of Bismuth Trisulfide,” J Electrochem Soc, vol. 110, no. 12, p. 1231, 1963

[8] S. Khan, S. Daemi, M. Kanwal, C. Xiao, and F. E. Osterloh, “Substrate controls photovoltage, photocurrent and carrier separation in nanostructured Bi 2 S 3 films,” J Mater Chem A Mater, vol. 11, no. 43, pp. 23418–23429, 2023

[9] H. Moreno-García, M. T. S. Nair, and P. K. Nair, “Chemically deposited lead sulfide and bismuth sulfide thin films and Bi2S3/PbS solar cells,” Thin Solid Films, vol. 519, no. 7, pp. 2287–2295, Jan. 2011

[10] M. Bouachri et al., “Zinc doping effects on the microstructural, electrical and optical properties of nanostructured ZnxBi2-xS3 thin films grown by ultrasonic spray pyrolysis,” Current Applied Physics, vol. 54, pp. 16–25, Oct. 2023

[11] L. Gildart, J. M. Kline, and D. M. Mattox, “Some semiconducting properties of bismuth trisulfide,” Journal of Physics and Chemistry of Solids, vol. 18, no. 4, pp. 286–289, Mar. 1961

[12] A. Cantarero, J. Martinez-Pastor, A. Segura, and A. Chevy, “Transport properties of bismuth sulfide single crystals,” Phys Rev B, vol. 35, no. 18, pp. 9586–9590, Jun. 1987

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