Identifying Short-Range Disorder in Crystalline Bulk Cu2SnS3 Phases: A Solid-State Nuclear Magnetic Resonance Spectroscopic Investigation

Cu2SnS3 has recently attracted attention as a low-cost, earth-abundant absorber material for thin-film solar cells. Unfortunately, multiple Cu2SnS3 structures exist and the conditions under which different structures form are poorly defined. The structures of tetragonal and monoclinic Cu2SnS3 phases are clarified by use of solid-state nuclear magnetic resonance spectroscopy (ssNMR). The monoclinic Cu2SnS3 phase is shown to form under Sn-rich, Cu-poor conditions and the tetragonal Cu2SnS3 phase forms under Cu-rich, Sn-poor conditions, indicating that there is a composition difference between the structures that has not previously been reported. Furthermore, the monoclinic phase is destabilized at temperatures between 200 and 345 °C, when the material becomes tetragonal.

[1]  A. Rockett,et al.  Oxygen-Induced Ordering in Bulk Polycrystalline Cu2ZnSnS4 by Sn Removal. , 2017, Inorganic chemistry.

[2]  D. Abou‐Ras,et al.  Secondary phase formation during monoclinic Cu2SnS3 growth for solar cell application , 2016 .

[3]  S. Lany,et al.  A review of defects and disorder in multinary tetrahedrally bonded semiconductors , 2016 .

[4]  C. Li,et al.  Eco-friendly p-type Cu2SnS3 thermoelectric material: crystal structure and transport properties , 2016, Scientific Reports.

[5]  Kunihiko Tanaka,et al.  Exciton luminescence from Cu2SnS3 bulk crystals , 2016 .

[6]  P. Patil,et al.  Fabrication of Cu2SnS3 thin film solar cells using pulsed laser deposition technique , 2015 .

[7]  D. Zahn,et al.  Raman Scattering Study of Cu3SnS4 Colloidal Nanocrystals , 2014 .

[8]  Lauryn L. Baranowski,et al.  Control of Doping in Cu2SnS3 through Defects and Alloying , 2014 .

[9]  Stéphane Jobic,et al.  Solid-state NMR and Raman spectroscopy to address the local structure of defects and the tricky issue of the Cu/Zn disorder in Cu-poor, Zn-rich CZTS materials. , 2014, Inorganic chemistry.

[10]  Ji-Hyun Cha,et al.  Electrophoretic deposition of Ga–Cu core–shell nanocomposites for CuGaS2 thin films , 2014 .

[11]  S. Uthanna,et al.  Effect of annealing temperature on the properties of spray deposited Cu2SnS3 thin films , 2013 .

[12]  Stéphane Jobic,et al.  Multinuclear (67Zn, 119Sn and 65Cu) NMR spectroscopy--an ideal technique to probe the cationic ordering in Cu2ZnSnS4 photovoltaic materials. , 2013, Physical chemistry chemical physics : PCCP.

[13]  A. Yamamoto,et al.  High-performance thermoelectric mineral Cu12−xNixSb4S13 tetrahedrite , 2013 .

[14]  A. Pérez‐Rodríguez,et al.  Raman analysis of monoclinic Cu2SnS3 thin films , 2012 .

[15]  A. D. Cunha,et al.  A study of ternary Cu2SnS3 and Cu3SnS4 thin films prepared by sulfurizing stacked metal precursors , 2010 .

[16]  Jinlong Yang,et al.  Hexagonal Cu2SnS3 with metallic character: Another category of conducting sulfides , 2007 .

[17]  G. Hoatson,et al.  Modelling one‐ and two‐dimensional solid‐state NMR spectra , 2002 .

[18]  A. Sato,et al.  Synthesis, Electrical Conductivity, and Crystal Structure of Cu4Sn7S16and Structure Refinement of Cu2SnS3 , 1998 .

[19]  G. V. Gibbs,et al.  Quadratic Elongation: A Quantitative Measure of Distortion in Coordination Polyhedra , 1971, Science.