Efficient Control of Atom Arrangement in Ternary Metal Chalcogenide Nanoparticles Using Precursor Oxidation State

Journal Article · Fri Jan 31 00:00:00 EST 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b05261· OSTI ID:1688787

Eikey, Emily A. ^[1]; Gan, Xing Yee ^[1]; Kaseman, Derrick C. ^[1]; Murphey, Corban E. ^[1]; Crawford, Scott E. ^[1]; Johnston, Kathryn A. ^[1]; Yazdi, Sadegh ^[2]; Millstone, Jill E. ^[3]

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1. Univ. of Pittsburgh, PA (United States). Dept. of Chemistry
2. Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Inst.
3. Univ. of Pittsburgh, PA (United States). Dept. of Chemistry, Dept. of Chemical and Petroleum Engineering, and Dept. of Mechanical Engineering and Materials Science

Controlling both the concentration and the distribution of elements in a given material is often crucial to extracting and optimizing synergistic properties of the various constituents. An interesting class of such multielement materials is metal chalcogenide nanoparticles, which exhibit a wide range of composition-dependent optoelectronic properties including both bandgap-mediated processes and localized surface plasmon resonance properties, each of which is useful in applications ranging from energy conversion to sensing. Because metal chalcogenide nanoparticles can support several different metal elements in a variety of chalcogen lattices, this material class has particularly benefited from the ability to control both atom concentration and atom arrangement to tailor final particle properties. The primary method to access complex, multimetallic chalcogenide particles is via a postsynthetic cation exchange strategy. One-pot syntheses have been less explored to access these complex particles, although this route is desirable for economy and scalability. In this work, we compare the composition and morphology outcomes from cation exchange and one-pot preparation approaches using a Cu/Ag/Se system, which is already known to exhibit both binary and ternary metal chalcogenide phases. We show that at similar concentrations of the two metal cations, initial reaction conditions for the one-pot method yield multicomponent nanoparticles, whereas cation exchange yields homogeneous ternary metal chalcogenide structures. We then show that by tuning the precursor oxidation state for the one-pot method, this approach can be used to access homogeneous ternary metal chalcogenide particles that are similar in atom arrangement to the particles obtained using cation exchange. Taken together, our results demonstrate reliable synthetic methods that yield a variety of controlled compositions and composition morphologies in the Cu/Ag/Se system. Importantly, we demonstrate that this entire collection of architectures can all be accessed via a one-pot method simply by modifying metal precursor chemistry. The mechanistic insights gained and the resulting streamlined syntheses outlined indicate pathways to easily scaled, highly tailorable syntheses for rapid translation into downstream technologies.

• Research Organization: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
• Sponsoring Organization: National Science Foundation (NSF); USDOD Defense Threat Reduction Agency (DTRA); USDOE
• Grant/Contract Number: 89233218CNA000001
• OSTI ID: 1688787
• Report Number(s): LA-UR--19-31921
• Journal Information: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 3 Vol. 32; ISSN 0897-4756
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

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