Hydrogen-enhanced carrier collection enabling wide-bandgap Cd-free Cu2ZnSnS4 solar cells with 11.4% certified efficiency

Ao Wang, Jialin Cong, Shujie Zhou, Jialiang Huang (), Jingwen Cao, Xin Cui, Xiaojie Yuan, Yin Yao, Zhou Xu, Guojun He, Jefferson Zhe Liu, Julie M. Cairney, Yi-sheng Chen, Martin A. Green, Su-Huai Wei, Kaiwen Sun () and Xiaojing Hao ()
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Ao Wang: University of New South Wales
Jialin Cong: University of New South Wales
Shujie Zhou: University of New South Wales
Jialiang Huang: University of New South Wales
Jingwen Cao: University of New South Wales
Xin Cui: University of New South Wales
Xiaojie Yuan: University of New South Wales
Yin Yao: University of New South Wales
Zhou Xu: Monash University
Guojun He: University of New South Wales
Jefferson Zhe Liu: The University of Melbourne
Julie M. Cairney: The University of Sydney
Yi-sheng Chen: The University of Sydney
Martin A. Green: University of New South Wales
Su-Huai Wei: Eastern Institute of Technology
Kaiwen Sun: University of New South Wales
Xiaojing Hao: University of New South Wales

Nature Energy, 2025, vol. 10, issue 2, 255-265

Abstract: Abstract Wide-bandgap kesterite Cu2ZnSnS4 offers an economically viable, sustainably sourced and environmentally friendly material for both single-junction and tandem photovoltaic applications. Nevertheless, since 2018 the record efficiency of such solar cells has stagnated at 11%, largely due to carriers recombining before they are collected. Here we demonstrate enhanced carrier collection in devices annealed in a hydrogen-containing atmosphere. We find that hydrogen is incorporated mainly in n-type layers and on the absorber surface. Furthermore, we show that the hydrogen treatment triggers the out-diffusion of oxygen and sodium from the absorber bulk to the surface, favourably diminishing the acceptor concentration at the surface and increasing the p-type doping in the bulk. Consequently, Fermi-level pinning is relieved and carrier transport in the absorber is facilitated. We achieve a certified efficiency of 11.4% in Cd-free devices. Although hydrogenation already plays a major role in silicon photovoltaics, our findings can further advance its application in emerging photovoltaic technologies.

Date: 2025
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DOI: 10.1038/s41560-024-01694-5

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