Recently, Ag incorporation into Cu(In,Ga)Se2 structure was found to benefit the solar cell performance. However, (Ag,Cu)2ZnSnS4 used as the solar cell absorber is not widely reported even though Ag2ZnSnS4 has shown much better photocatalysts activity for H2 evolution than Cu2ZnSnS4. In this paper, (Ag,Cu)2ZnSnS4 thin film solar cell was synthesized through sulfurization of Ag/Zn/Cu/Sn metallic stacked layers. In order to understand the actual role of Ag in the Cu2ZnSnS4 structure, the changing chemical environment, microstructure and intragrain defect due to the Ag incorporation, were studied by X-ray photoelectron spectroscopy and transmission electron microscopy. After sulfurization, Ag is uniformly distributed in the absorber and is incorporated into Cu2ZnSnS4 crystal structure but no obvious change of the Cu2ZnSnS4 chemical environment is detected. A large density of voids is formed at the Cu2ZnSnS4/Mo interface and some of these voids are found to be coated with CdS which is believed to be detrimental to Cu2ZnSnS4 device performance. In contrast, Ag incorporation reduces the size and amount of voids and thus effectively eliminates CdS deposited at back contact region. Moreover, fewer planar defects and Cu vacancies are formed in the (Ag,Cu)2ZnSnS4 sample than Cu2ZnSnS4 sample as suggested by electron diffraction patterns. Therefore, improved solar cell performance should result from the formation of (Ag,Cu)2ZnSnS4 structure.
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