Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide–copper sulfide heterostructured nanorods

Zheng, Haimei; Sadtler, Bryce; Habenicht, Carsten; Freitag, Bert; Alivisatos, A. Paul; Kisielowski, Christian

doi:10.1016/j.ultramic.2013.05.004

Title: Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide–copper sulfide heterostructured nanorods

Journal Article · Wed May 22 00:00:00 EDT 2013 · Ultramicroscopy

DOI:https://doi.org/10.1016/j.ultramic.2013.05.004· OSTI ID:1545123

Zheng, Haimei ^[1]; Sadtler, Bryce ^[2]; Habenicht, Carsten ^[3]; Freitag, Bert ^[4]; Alivisatos, A. Paul ^[5]; Kisielowski, Christian ^[6]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
FEI Company, Eindhoven (Netherlands)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Center for Electron Microscopy; California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)

The atomic structure and interfaces of CdS/Cu₂S heterostructured nanorods are explored with the aberration-corrected TEAM 0.5 electron microscope operated at 80 kV and 300 kV applying in-line holography and complementary techniques. Cu₂S exhibits a low-chalcocite structure in pristine CdS/Cu₂S nanorods. Under electron beam irradiation the Cu₂S phase transforms into a high-chalcocite phase while the CdS phase maintains its wurtzite structure. Time-resolved experiments reveal that Cu⁺-Cd²⁺ cation exchange at the CdS/Cu₂S interfaces is stimulated by the electron beam and proceeds within an undisturbed and coherent sulfur sub-lattice. A variation of the electron beam current provides an efficient way to control and exploit such irreversible solid-state chemical processes that provide unique information about system dynamics at the atomic scale. Particularly, we show that the electron beam-induced copper-cadmium exchange is site specific and anisotropic. A resulting displacement of the CdS/Cu₂S interfaces caused by beam-induced cation interdiffusion equals within a factor of 3-10 previously reported Cu diffusion length measurements in heterostructured CdS/Cu₂S thin film solar cells with an activation energy of 0.96 eV.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1545123

Journal Information:: Ultramicroscopy, Vol. 134, Issue C; ISSN 0304-3991

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

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Title: Controlling electron beam-induced structure modifications and cation exchange in cadmium sulfide–copper sulfide heterostructured nanorods

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