Hot-injection synthesis of monodispersed Cu2ZnSn(SxSe1−x)4 nanocrystals: tunable composition and optical properties

Keng-Liang Ou; Jian-Cin Fan; Jem-Kun Chen; Chih-Ching Huang; Liang-Yih Chen; Jinn-Hsuan Ho; Jia-Yaw Chang

doi:10.1039/C2JM31901B

Hot-injection synthesis of monodispersed Cu₂ZnSn(S_xSe_1−x)₄nanocrystals: tunable composition and optical properties†

Keng-Liang Ou,‡^abcd Jian-Cin Fan,‡^a Jem-Kun Chen,^e Chih-Ching Huang,^f Liang-Yih Chen,^a Jinn-Hsuan Ho^a and Jia-Yaw Chang*^a

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* Corresponding authors

^a Department of Chemical Engineering, National Taiwan University of Science and Technology, Section 4, #43, Keelung Road, Taipei 106, Taiwan, ROC
E-mail: jychang@mail.ntust.eu.tw
Fax: +886-2-27376644
Tel: +886-2-27303636

^b Research Center for Biomedical Devices, Taipei Medical University, 250 Wu Hsing Street, Taipei 110, Taiwan, ROC

^c Research Center for Biomedical Implants and Microsurgery Devices, Taipei Medical University, 250 Wu Hsing Street, Taipei 110, Taiwan, ROC

^d Department of Biomedical Materials and Tissue Engineering, College of Oral Medicine, Taipei Medical University, 250 Wu Hsing Street, Taipei 110, Taiwan, ROC

^e Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan, ROC

^f Institute of Bioscience and Biotechnology and Center for Marine Bioenvironment and Biotechnology, National Taiwan Ocean University, Keelung, Taiwan, ROC

Abstract

In this study, we demonstrate that Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals with a tunable bandgap could be synthesized by a “hot-injection” protocol. In this protocol, metal stearates dissolved in oleylamine were injected into a hot solution of anion precursors in 1-octadecene (ODE) at a given reaction temperature. ODE, which is a low-cost, low-hazard, and air-stable liquid, was used as the solvent. Oleylamine was chosen as both the reagent to activate the precursors and as the capping agent for the nanocrystals. The composition of the Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals could be adjusted across the x range from 0 to 1 by varying the S/Se reactant ratio. The lattice parameters (a and c) measured from X-ray diffraction patterns decreased linearly with increasing Se content. This trend was consistent with Vegard's law, which confirmed the formation of homogeneous Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals. The A₁ symmetry modes of the Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals seen by Raman spectroscopy gradually shifted with decreasing x (S content) to the lower frequency side and completely disappeared when x = 0. The absorption spectra of the Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals revealed that the bandgaps of the nanocrystals could be adjusted over the range 1.0–1.5 eV by decreasing the S content. The relatively small value for the bowing parameter indicated that the synthesized Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals had good miscibility.

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Article information

DOI: https://doi.org/10.1039/C2JM31901B
Article type: Paper
Submitted: 27 Mar 2012
Accepted: 28 May 2012
First published: 28 May 2012

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J. Mater. Chem., 2012,22, 14667-14673

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Hot-injection synthesis of monodispersed Cu₂ZnSn(S_xSe_1−x)₄ nanocrystals: tunable composition and optical properties

K. Ou, J. Fan, J. Chen, C. Huang, L. Chen, J. Ho and J. Chang, J. Mater. Chem., 2012, 22, 14667 DOI: 10.1039/C2JM31901B

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