Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Weston, Kimberly; Taylor, Richard A.; Kisslinger, Kim; Mantripragada, Shobha

doi:10.1039/d4dt02826k

Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Journal Article · Fri Jan 17 00:00:00 EST 2025 · Dalton Transactions

DOI:https://doi.org/10.1039/d4dt02826k· OSTI ID:2519656

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University of the West Indies (West Indies)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
North Carolina A & T State Univ., Greensboro, NC (United States)

Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu_3-aSb_1+bS_4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g^-1 obtained at a scan rate of 5 mV s^-1. Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2519656

Alternate ID(s):: OSTI ID: 2502110

Report Number(s):: BNL--227581-2025-JAAM

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 8 Vol. 54; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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