Utilizing Diselenide Precursors toward Rationally Controlled Synthesis of Metastable CuInSe2 Nanocrystals

Tappan, Bryce A.; Barim, Gözde; Kwok, Jacky C.; Brutchey, Richard L.

doi:10.1021/acs.chemmater.8b02205

Utilizing Diselenide Precursors toward Rationally Controlled Synthesis of Metastable CuInSe₂ Nanocrystals

Journal Article · Mon Jul 30 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b02205· OSTI ID:1582646

Tappan, Bryce A. ^[1]; Barim, Gözde ^[2]; Kwok, Jacky C. ^[2]; ^[2]

Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
Univ. of Southern California, Los Angeles, CA (United States)

We present that within the past decade, there has been an emergence of reports regarding the synthetic isolation of multinary metal chalcogenide nano-crystals that persist under ambient conditions with metastable crystal structures; however, many of the direct syntheses remain largely serendipitous with respect to the conditions needed to achieve the metastable product. Towards the development of more rational design principles that enable the predictable isolation of metastable nanocrystals, we demonstrate a molecular programming approach for the synthesis of CuInSe₂ nanocrystals utilizing diorganyl diselenide precursors of the structure R-Se-Se-R. Specifically, we show that the kinetics of diselenide precursor conversion are dependent upon C–Se and Se–Se bond dissociation energies, and that the strength of the C–Se bond is the phase-directing variable. When employing dibenzyl and dimethyl selenide precursors with relatively weaker C–Se bonds, the resulting nanocrystals form in the thermodynamically stable chalcopyrite phase of CuInSe₂. However, precursors like diphenyl diselenide that possess stronger C–Se bonds alter the reaction kinetics so as to steer the reaction towards formation of the metastable wurtzite-like phase. These two phases form via distinct copper selenide intermediates, with chalcopyrite forming through Cu_2-xSe and the wurtzite-like phase forming through Cu₃Se₂ intermediates, and it was found that the ultimate wurtzite-like phase displays remarkable resistance to relaxation to the chalcopyrite phase. Lastly, this molecular programming approach should be applicable towards the isolation of other metastable phases of metal chalcogenide nanocrystals.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0006812

OSTI ID:: 1582646

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 16 Vol. 30; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited By (2)

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