Void and secondary phase formation mechanisms of CZTSSe using Sn/Cu/Zn/Mo stacked elemental precursors

• Published in: Nano energy 2019-05, Vol.59, p.399-411
• Main Authors: Kim, Se-Yun, Son, Dae-Ho, Kim, Young-Ill, Kim, Seung-Hyun, Kim, Sammi, Ahn, Kwangseok, Sung, Shi-Joon, Hwang, Dae-Kue, Yang, Kee-Jeong, Kang, Jin-Kyu, Kim, Dae-Hwan
• Format: Article
• Language: English
• Subjects: CZTSSe; Formation mechanism; Metal precursor; Secondary phase; Two-step process; Void
• ISSN: 2211-2855
• DOI: 10.1016/j.nanoen.2019.02.063

In recent years, Cu2ZnSn(S1-xSex)4 (CZTSSe) prepared by a two-step process using metal precursors has been reported to exhibit a relatively high power conversion efficiency, and a high efficiency of 12.5% by two-step process contained via sputtering method was recently confirmed by our group. In this study, we proposed formation mechanisms for the CZTSSe double layer, voids and ZnSSe layer, which were observed in the CZTSSe using metal precursor. Due to the persistent dezincification from the metal precursors and preferential reaction between the Zn and chalcogens such as S and Se, almost all Zn is consumed to form the ZnSSe layer; as a result, large voids are produced first under the ZnSSe layer. Cu2Se and SnSe are grown on the ZnSSe layer via migration of the Cu and Sn through the grain boundaries of the ZnSSe layer. Thus, additional small voids are expected to form due to the mass transfer of Cu and Sn. Because of the preferentially formed ZnSSe layer and the chalcogenation of Cu and Sn after the mass transfer, a CZTSSe double layer can be formed, and ZnSSe can exist between these CZTSSe layers. Finally, we propose a method based on the formation mechanism to control the voids and secondary phases, which affect the fill factor and output current. The new formation mechanisms of the voids, ZnSSe layer and CZTSSe double layer that were observed in the sister sample of 12.5% of CZTSSe cell. [Display omitted] •The new formation mechanisms of the voids, ZnSSe layer and CZTSSe double layer that were observed in the sister sample of 12.5% of CZTSSe cell.•Large voids are produced under the ZnSSe layer due to the persistent dezincification and preferential reaction between the Zn and chalcogens.•Additional small voids are expected to form due to the migration of Cu and Sn from under the ZnSSe layer to above ZnSSe layer.•Due to the preferentially formed ZnSSe layer and Cu and Sn migration, ZnSSe secondary phase exists between the CZTSSe double layers.