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To control the process of cation exchange (CE) in a multielemental system, a detailed understanding of structural changes at the microscopic level is imperative. However, the synthesis of a multielemental system has so far relied on the CE phenomenon of a binary system, which does not necessarily extend to the higher-order systems. Here, direct experimental evidence supported by theoretical calculations reveals a growth model of binary Cu–S to ternary Cu–Sn–S to quaternary Cu–Zn–Sn–S, which shows that cations preferentially diffuse along a specific lattice plane with the preservation of sulfuric anionic framework. In addition, we also discover that, unlike the commonly accepted structure (P63mc), the metastable crystal structure of Cu–Zn–Sn–S phase possesses fixed Sn occupancy sites. By revealing the preferential nature of cations diffusion and growth mechanism, our work provides insight into controlling the stoichiometry and phase purity of novel multielemental materials. Ministry of Education (MOE) National Research Foundation (NRF) Accepted version We acknowledge financial support from National Research Foundation (NRF), Singapore, through the Singapore-Berkeley Research Initiative for Sustainable Energy (SinBeRISE) and Nanomaterials for Energy and Water Management (SHARE NEW) CREATE program. L.H.W. thanks the funding support from Singapore Ministry of Education, Tier 2 (2016-T2-1-030). S.L. acknowledges the funding support from Singapore Ministry of Education Tier 1 (107/15). H.Z. thanks the funding support from U.S. DOE BES Materials Sciences and Engineering Division Under Contract No. KC22ZH. X.Y.L. thanks the funding support from Singapore Ministry of Education, Tier 1 (RG21/16) and Tier 2 (MOE2016-T2-1- 043) grants.. The work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. We thank Fiona Doyle for lending us her synthetic laboratory in University of California Berkeley (UCB), Song Chengyu and Karen Bustilo for their help and assistance on TEM, and Matthew P. Sherburne for nanoparticle growth discussion.

Potassium (K) post-treatment on CIGSSe has been shown to yield the highest efficiency reported to date. However, very little is known on the effect of K doping in CZTSSe and the mechanism behind the efficiency improvement. Here we reveal the mechanism by which K enhances the charge separation in CZTSSe. We show that K accumulates at the CdS/CZTSSe, passivating the recombination at the front interface and improving carrier collection. K is also found to accumulate at the CZTSSe/Mo interface and facilitates the diffusion of Cd into the absorber which affects the morphology and grain growth of CZTSSe. As revealed by the C–V, external quantum efficiency, and color J–V test, K doping significantly increases the carrier density, improves carrier collection, and passivates the front interface and grain boundaries, leading to the enhancement of Voc and Jsc. The average power conversion efficiency has been promoted from 5% to above 7%, and the best 7.78% efficiency has been achieved for the 1.5 mol % K-doped CZTSS...

Recently, considerable attention in the development of Cu2ZnSnS4 (CZTS)-based thin-film solar cells has been given to the reduction of antisite defects via cation substitution. In this Letter, we report the substitution of copper atoms by silver, incorporated into the crystal lattice through a solution processable method. We observe an increase in open-circuit voltage (VOC) by 50 mV and an accompanying rise in device efficiency from 4.9% to 7.2%. The incorporation of Ag is found to improve the grain size, enhance the depletion width of the pn-junction, and reduce the concentration of antisite defect states. This work demonstrates the promising role of Ag in reducing the VOC deficit of Cu-kesterite thin-film solar cells.