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J Am Chem Soc. 2016 May 4;138(17):5576-84. doi: 10.1021/jacs.5b13288. Epub 2016 Apr 21.

Polytypic Nanocrystals of Cu-Based Ternary Chalcogenides: Colloidal Synthesis and Photoelectrochemical Properties.

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Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemistry, Hefei Science Center, CAS, CAS Center for Excellence in Nanoscience, University of Science and Technology of China , Hefei, Anhui 230026, People's Republic of China.
Key Laboratory of Polar Materials and Devices (MOE), East China Normal University , Shanghai 200241, People's Republic of China.


Heterocrystalline polytype nanostructured semiconductors have been attracting more and more attention in recent years due to their novel structures and special interfaces. Up to now, controlled polytypic nanostructures are mostly realized in II-VI and III-V semiconductors. Herein, we report the synthesis and photoelectrochemical properties of Cu-based ternary I-III-VI2 chalcogenide polytypic nanocrystals, with a focus on polytypic CuInS2 (CIS), CuInSe2 (CISe), and CuIn(S0.5Se0.5)2 alloy nanocrystals. Each obtained polytypic nanocrystal is constructed with a wurtzite hexagonal column and a zinc blende/chalcopyrite cusp, regardless of the S/Se ratio. The growth mechanisms of polytypic CIS and CISe nanocrystals have been studied by time-dependent experiments. The polytypic nanocrystals are solution-deposited on indium-tin oxide glass substrate and used as a photoelectrode, thus showing stable photoelectrochemical activity in aqueous solution. Density functional theory calculation was used to study the electronic structure and the band gap alignment. This versatile synthetic method provides a new route for synthesis of novel polytypic nanostructured semiconductors with unique properties.


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