119Sn MAS NMR to Assess the Cationic Disorder and the Anionic Distribution in Sulfoselenide Cu2ZnSn(SxSe1鈥搙)4 Compounds Prepared from Colloidal and Ceramic Routes

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• 作者：Micha毛l Paris ; Gerardo Larramona ; Pierre Bais ; St茅phane Bourdais ; Alain Lafond ; Christophe Chon茅 ; Catherine Guillot-Deudon ; Bruno Delatouche ; Camille Moisan ; Gilles Dennler
• 刊名：Journal of Physical Chemistry C
• 出版年：2015
• 出版时间：December 3, 2015
• 年：2015
• 卷：119
• 期：48
• 页码：26849-26857
• 全文大小：407K
• ISSN：1932-7455

文摘

Crystalline powders of the photovoltaic material candidate copper zinc tin sulfoselenide Cu₂ZnSn(S_xSe_1鈥?i>x)₄ (CZTSSe) with x = S/(S + Se) from 0 to 1 were characterized by ¹¹⁹Sn solid state nuclear magnetic resonance (NMR) and by powder X-ray diffraction (PXRD). Two series of powders were characterized: one synthesized by a ceramic route and having cationic stoichiometry 2:1:1 and another one synthesized by a colloidal route, having a cationic Cu-poor Zn-rich composition and used as precursors for photovoltaic active films. The homogeneous anionic composition of the samples, which is a feature needed for the NMR analysis of the anionic distribution, has been proved by PXRD. The x values determined from the quantitative analysis of the ¹¹⁹Sn spectra are in very good agreement with those deduced by PXRD. In addition, the ¹¹⁹Sn spectra reveal, for the first time, the random distribution of the chalcogen atoms, which seems to be a general process. Finally, a qualitative, but thorough, analysis of the line width of the ¹¹⁹Sn NMR spectra was undertaken to investigate the Cu/Zn cationic disorder, a feature which can seriously affect the optoelectronic properties of CZTSSe. The cationic disorder turns out to be dependent on the type of cationic composition. Indeed, regardless of x ratios and the synthesis methods, our samples containing A-type defect complexes [V_Cu + Zn_Cu] are less prone to Cu/Zn disorder.