Insight into the crystal phase and shape evolution from monoclinic Cu1.94S to wurtzite Cu2ZnSnS4 nanocrystals

Phase pure wurtzite Cu2ZnSnS4 (CZTS) nanocrystals have been prepared by using monoclinic Cu1.94S nanoplates as starting materials via a hot-injection method. The rapid injection of Zn-thiols resulted in the symmetrical growth of CZTS onto both sides of Cu1.94S nanoplates, yielding sandwich-like CZTS-Cu1.94S heterostructures, which finally converted into CZTS nanocrystals. Interestingly, with 50% excess Sn precursor in the initial reaction system, the morphology of CZTS can retain the shape of nanoplates with increased thickness. The morphology and crystal phase evolution processes have been further investigated to understand the formation mechanism. These findings are meaningful for the controllable synthesis of copper chalcogenide nanocrystals as well as their photoelectrical applications.

[1]  Liming Shen,et al.  Synthesis of Wurtzite Cu2ZnSnS4 Nanosheets with Exposed High-Energy (002) Facets for Fabrication of Efficient Pt-Free Solar Cell Counter Electrodes , 2018, Scientific Reports.

[2]  Zhengguang Zou,et al.  Understanding the growth mechanism of wurtzite Cu2ZnSnS4 nanocrystals and the photodegradation properties , 2017 .

[3]  K. Ryan,et al.  Compound Copper Chalcogenide Nanocrystals. , 2017, Chemical reviews.

[4]  Fangyang Liu,et al.  Spatial Grain Growth and Composition Evolution during Sulfurizing Metastable Wurtzite Cu2ZnSnS4 Nanocrystal-Based Coatings , 2017 .

[5]  Q. Liang.  Phase-Controlled Synthesis of Cu2SnS3Nanocrystals: The Effect of Redox Conditions on the Initial Binary Cu2-xS Nucleation: Phase-Controlled Synthesis of Cu2SnS3Nanocrystals: The Effect of Redox Conditions on the Initial Binary Cu2-xS Nucleation , 2016 .

[6]  K. Ryan,et al.  Complete study of the composition and shape evolution in the synthesis of Cu2ZnSnS4 (CZTS) semiconductor nanocrystals , 2015 .

[7]  Nicola Doebelin,et al.  Profex: a graphical user interface for the Rietveld refinement program BGMN , 2015, Journal of applied crystallography.

[8]  Bin Zhou,et al.  Phase-selective synthesis and formation mechanism of CZTS nanocrystals , 2015 .

[9]  Shaoming Huang,et al.  Cu1.94S-Assisted Growth of Wurtzite CuInS2 Nanoleaves by In Situ Copper Sulfidation , 2015, Nanoscale Research Letters.

[10]  F. Huang,et al.  Reversible self-assembly of MxS (M = Cu, Ag) nanocrystals through ligand exchange , 2014 .

[11]  F. Teng,et al.  Synthesis of Cu2−xS nanocrystals induced by foreign metal ions: phase and morphology transformation and localized surface plasmon resonance , 2014 .

[12]  Hua Zhang,et al.  Copper-based ternary and quaternary semiconductor nanoplates: templated synthesis, characterization, and photoelectrochemical properties. , 2014, Angewandte Chemie.

[13]  Tae Whan Kim,et al.  Synthesis of wurtzite-zincblende Cu2ZnSnS4 and Cu2ZnSnSe4 nanocrystals: insight into the structural selection of quaternary and ternary compounds influenced by binary nuclei. , 2014, Nanoscale.

[14]  Fujun Zhang,et al.  Facile one-step synthesis and transformation of Cu(I)-doped zinc sulfide nanocrystals to Cu(1.94)S-ZnS heterostructured nanocrystals. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[15]  F. Huang,et al.  Cu1.94S–MnS dimeric nanoheterostructures with bifunctions: localized surface plasmon resonance and magnetism , 2013 .

[16]  W. Su,et al.  Facile synthesis of wurtzite copper–zinc–tin sulfide nanocrystals from plasmonic djurleite nuclei , 2013 .

[17]  Wenhui Zhou,et al.  Synthesis of Pure Metastable Wurtzite CZTS Nanocrystals by Facile One-Pot Method , 2012 .

[18]  Shuhong Yu,et al.  One-pot controlled synthesis of hexagonal-prismatic Cu1.94S-ZnS, Cu1.94S-ZnS-Cu1.94S, and Cu1.94S-ZnS-Cu1.94S-ZnS-Cu1.94S heteronanostructures. , 2012, Angewandte Chemie.

[19]  C. Grimes,et al.  Facile thermolysis synthesis of CuInS2 nanocrystals with tunable anisotropic shape and structure. , 2011, Chemical communications.

[20]  M. Gao,et al.  From Ultrathin Two-Dimensional Djurleite Nanosheets to One-Dimensional Nanorods Comprised of Djurleite Nanoplates: Synthesis, Characterization, and Formation Mechanism , 2011 .

[21]  Qinghua Xu,et al.  One-pot synthesis of Cu1.94S-CdS and Cu1.94S-Zn(x)Cd(1-x)S nanodisk heterostructures. , 2011, Journal of the American Chemical Society.

[22]  Xiaoming Li,et al.  Columnar self-assembly of Cu2S hexagonal nanoplates induced by tin(IV)-X complex as inorganic surface ligand. , 2010, Journal of the American Chemical Society.

[23]  Yi Cui,et al.  Phase transformation of biphasic Cu2S-CuInS2 to monophasic CuInS2 nanorods. , 2009, Journal of the American Chemical Society.

[24]  L. An,et al.  Synthesis of Cu-In-S ternary nanocrystals with tunable structure and composition. , 2008, Journal of the American Chemical Society.

[25]  H. T. Evans.  Djurleite (Cu1.94S) and Low Chalcocite (Cu2S): New Crystal Structure Studies , 1979, Science.

[26]  J. Tauc,et al.  Optical properties and electronic structure of amorphous Ge and Si , 1968 .