Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Jayaweera, Nuwanthaka P.; Havenridge, Shana; Bielinski, Ashley R.; Kim, Kihoon; Thompson, Niklas B.; Hoffman, Justin M.; Wheaton, Amelia M.; Sarkar, Prasenjit; Pathak, Rajesh; Elam, Jeffrey W.; Liu, Cong; Mulfort, Karen L.; Martinson, Alex B. F.

doi:10.1002/ange.202421259

Title: Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Journal Article · 13 January 2025 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202421259 · OSTI ID:2499825

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Material Science Division Argonne National Laboratory 9700 South Cass Avenue Lemont Illinois 60439 United States
Chemical Science and Engineering Division Argonne National Laboratory 9700 South Cass Avenue Lemont Illinois 60439 United States
X-ray Science Division Argonne National Laboratory 9700 South Cass Avenue Lemont Illinois 60439 United States
Applied Materials Division Argonne National Laboratory 9700 South Cass Avenue Lemont Illinois 60439 United States

Abstract Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd ₄ S ₄ core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.

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Sponsoring Organization:: USDOE

OSTI ID:: 2499825

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 10 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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