Revealing Cation-Exchange-Induced Phase Transformations in Multielemental Chalcogenide Nanoparticles

Joel M.R. Tan; Mary C. Scott; Wei Hao; Tom Baikie; Christopher T. Nelson; Srikanth Pedireddy; Runzhe Tao; Xingyi Ling; Shlomo Magdassi; Timothy White; Shuzhou Li; Andrew M. Minor; Haimei Zheng; Lydia H. Wong

doi:10.1021/acs.chemmater.7b03029

Revealing Cation-Exchange-Induced Phase Transformations in Multielemental Chalcogenide Nanoparticles

Joel M.R. Tan, Mary C. Scott, Wei Hao, Tom Baikie, Christopher T. Nelson, Srikanth Pedireddy, Runzhe Tao, Xingyi Ling, Shlomo Magdassi, Timothy White, Shuzhou Li, Andrew M. Minor, Haimei Zheng, Lydia H. Wong

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

To control the process of cation exchange (CE) in a multielemental system, a detailed understanding of structural changes at the microscopic level is imperative. However, the synthesis of a multielemental system has so far relied on the CE phenomenon of a binary system, which does not necessarily extend to the higher-order systems. Here, direct experimental evidence supported by theoretical calculations reveals a growth model of binary Cu-S to ternary Cu-Sn-S to quaternary Cu-Zn-Sn-S, which shows that cations preferentially diffuse along a specific lattice plane with the preservation of sulfuric anionic framework. In addition, we also discover that, unlike the commonly accepted structure (P6₃mc), the metastable crystal structure of Cu-Zn-Sn-S phase possesses fixed Sn occupancy sites. By revealing the preferential nature of cations diffusion and growth mechanism, our work provides insight into controlling the stoichiometry and phase purity of novel multielemental materials.

Original language	English
Pages (from-to)	9192-9199
Number of pages	8
Journal	Chemistry of Materials
Volume	29
Issue number	21
DOIs	https://doi.org/10.1021/acs.chemmater.7b03029
State	Published - Nov 14 2017
Externally published	Yes

Funding

We acknowledge financial support from National Research Foundation (NRF), Singapore, through the Singapore-Berkeley Research Initiative for Sustainable Energy (SinBeRISE) and Nanomaterials for Energy and Water Management (SHARE NEW) CREATE program. L.H.W. thanks the funding support from Singapore Ministry of Education, Tier 2 (2016-T2-1-030). S.L. acknowledges the funding support from Singapore Ministry of Education Tier 1 (107/15). H.Z. thanks the funding support from U.S. DOE BES Materials Sciences and Engineering Division Under Contract No. KC22ZH. X.Y.L. thanks the funding support from Singapore Ministry of Education, Tier 1 (RG21/16) and Tier 2 (MOE2016-T2-1-043) grants.. The work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. We thank Fiona Doyle for lending us her synthetic laboratory in University of California Berkeley (UCB), Song Chengyu and Karen Bustilo for their help and assistance on TEM, and Matthew P. Sherburne for nanoparticle growth discussion.

Funders	Funder number
Nanomaterials for Energy and Water Management
U.S. Department of Energy	DE-AC02-05CH11231
Office of Science
Basic Energy Sciences	MOE2016-T2-1-043, KC22ZH, RG21/16
National Research Foundation Singapore
Ministry of Education - Singapore	107/15, 2016-T2-1-030

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title = "Revealing Cation-Exchange-Induced Phase Transformations in Multielemental Chalcogenide Nanoparticles",

abstract = "To control the process of cation exchange (CE) in a multielemental system, a detailed understanding of structural changes at the microscopic level is imperative. However, the synthesis of a multielemental system has so far relied on the CE phenomenon of a binary system, which does not necessarily extend to the higher-order systems. Here, direct experimental evidence supported by theoretical calculations reveals a growth model of binary Cu-S to ternary Cu-Sn-S to quaternary Cu-Zn-Sn-S, which shows that cations preferentially diffuse along a specific lattice plane with the preservation of sulfuric anionic framework. In addition, we also discover that, unlike the commonly accepted structure (P63mc), the metastable crystal structure of Cu-Zn-Sn-S phase possesses fixed Sn occupancy sites. By revealing the preferential nature of cations diffusion and growth mechanism, our work provides insight into controlling the stoichiometry and phase purity of novel multielemental materials.",

author = "Tan, {Joel M.R.} and Scott, {Mary C.} and Wei Hao and Tom Baikie and Nelson, {Christopher T.} and Srikanth Pedireddy and Runzhe Tao and Xingyi Ling and Shlomo Magdassi and Timothy White and Shuzhou Li and Minor, {Andrew M.} and Haimei Zheng and Wong, {Lydia H.}",

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AU - Baikie, Tom

AU - Nelson, Christopher T.

AU - Pedireddy, Srikanth

AU - Tao, Runzhe

AU - Ling, Xingyi

AU - Magdassi, Shlomo

AU - White, Timothy

AU - Li, Shuzhou

AU - Minor, Andrew M.

AU - Zheng, Haimei

AU - Wong, Lydia H.

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AB - To control the process of cation exchange (CE) in a multielemental system, a detailed understanding of structural changes at the microscopic level is imperative. However, the synthesis of a multielemental system has so far relied on the CE phenomenon of a binary system, which does not necessarily extend to the higher-order systems. Here, direct experimental evidence supported by theoretical calculations reveals a growth model of binary Cu-S to ternary Cu-Sn-S to quaternary Cu-Zn-Sn-S, which shows that cations preferentially diffuse along a specific lattice plane with the preservation of sulfuric anionic framework. In addition, we also discover that, unlike the commonly accepted structure (P63mc), the metastable crystal structure of Cu-Zn-Sn-S phase possesses fixed Sn occupancy sites. By revealing the preferential nature of cations diffusion and growth mechanism, our work provides insight into controlling the stoichiometry and phase purity of novel multielemental materials.

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Revealing Cation-Exchange-Induced Phase Transformations in Multielemental Chalcogenide Nanoparticles

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