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Polymorphic Control of Solution-Processed Cu₂SnS₃ Films with Thiol-Amine Ink Formulation

Koskela, Kristopher M. and Mora Perez, Carlos and Eremin, Dmitry B. and Evans, Jake M. and Strumolo, Marissa J. and Lewis, Nathan S. and Prezhdo, Oleg V. and Brutchey, Richard L. (2022) Polymorphic Control of Solution-Processed Cu₂SnS₃ Films with Thiol-Amine Ink Formulation. Chemistry of Materials, 34 (19). pp. 8654-8663. ISSN 0897-4756. doi:10.1021/acs.chemmater.2c01612.

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There is increasing demand for tailored molecular inks that produce phase-pure solution-processed semiconductor films. Within the Cu–Sn–S phase space, Cu₂SnS₃ belongs to the I₂–IV–VI₃ class of semiconductors that crystallizes in several different polymorphs. We report the ability of thiol–amine solvent mixtures to dissolve inexpensive bulk Cu₂S and SnO precursors to generate free-flowing molecular inks. Upon mild annealing, polymorphic control over phase-pure tetragonal (I4̅2m) and orthorhombic (Cmc2₁) Cu₂SnS₃ films was realized simply by switching the identity of the thiol (i.e., 1,2-ethanedithiol vs 2-mercaptoethanol, respectively). Polymorph control is dictated by differences in the resulting molecular metal–thiolate complexes and their subsequent decomposition profiles, which likely seed distinct Cu₂₋ₓS phases that template the ternary sulfide sublattice. The p-type tetragonal and orthorhombic Cu₂SnS₃ films possess similar experimental direct optical band gaps of 0.94 and 0.88 eV, respectively, and strong photoelectrochemical current responses. Understanding how ink formulation dictates polymorph choice should inform the development of other thiol–amine inks for solution-processed films.

Item Type:Article
Related URLs:
URLURL TypeDescription
Koskela, Kristopher M.0000-0001-6002-6737
Mora Perez, Carlos0000-0001-8840-5093
Eremin, Dmitry B.0000-0003-2946-5293
Evans, Jake M.0000-0002-8721-5316
Lewis, Nathan S.0000-0001-5245-0538
Prezhdo, Oleg V.0000-0002-5140-7500
Brutchey, Richard L.0000-0002-7781-5596
Additional Information:This work was supported by the National Science Foundation under awards DMR-1904719 to R.L.B. and CHE-2154367 to O.V.P. XPS experiments were carried out at the Molecular Materials Resource Center (MMRC) of the Beckman Institute of the California Institute of Technology with financial support from Award No. DE-SC0022087 from the Basic Energy Sciences Office of the DOE to N.S.L. D.B.E. acknowledges the support of Agilent Technologies through an Agilent Fellowship.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0022087
Agilent TechnologiesUNSPECIFIED
Issue or Number:19
Record Number:CaltechAUTHORS:20221010-454096500.23
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:117307
Deposited By: Research Services Depository
Deposited On:14 Oct 2022 17:39
Last Modified:14 Oct 2022 17:39

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