Polymorphic Metastability in Colloidal Semiconductor Nanocrystals

Tappan, Bryce A.; Brutchey, Richard L.

doi:10.1002/cnma.202000406

Polymorphic Metastability in Colloidal Semiconductor Nanocrystals

Journal Article · Mon Aug 24 00:00:00 EDT 2020 · ChemNanoMat

DOI:https://doi.org/10.1002/cnma.202000406· OSTI ID:1780901

Tappan, Bryce A. ^[1]; ^[2]

Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
Univ. of Southern California, Los Angeles, CA (United States)

Metastable polymorphs of inorganic solids often possess material properties not present in the corresponding thermodynamic polymorphs, making them targets for the development of new functional materials. In contrast with isolating metastable bulk materials, syntheses of metastable polymorphs on the nanoscale are aided by fast non-equilibrium reaction kinetics and the favorable thermodynamic influence of surface energies, giving rise to greater ease of access to metastable high-temperature polymorphs and, in some cases, new polymorphs that do not exist in the bulk. The syntheses of metastable semiconductor nanocrystals are of interest for their potentially unique optoelectronic and physicochemical properties. However, in many material systems, synthesizing nanocrystalline products away from thermodynamic equilibrium in a predictable manner remains an outstanding challenge. This review outlines direct synthetic methodologies that have been developed to enable control over the nucleation and growth of metastable polymorphs of semiconductor nanocrystals by tailoring reaction conditions, precursor kinetics, ligand and surface effects, and other synthetic levers. The case studies reviewed herein expound on the direct syntheses of metastable ZnSe, Cu₂SnSe₃, CuInSe₂, Ag₂Se, and AgInSe₂ nanocrystals, and although there remain numerous examples of metastable nanocrystal syntheses outside of these metal chalcogenide systems, the concepts discussed are of general utility to the field of metastable nanocrystal syntheses as a whole. Explicit examples in which new functional properties are afforded by metastable polymorphs of the aforementioned material systems are presented within the context of applications for solar cells, photonics, and optical sensing. Finally, the factors that affect the kinetic persistence of metastable nanocrystalline polymorphs are discussed at length for these material systems.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0006812

OSTI ID:: 1780901

Journal Information:: ChemNanoMat, Journal Name: ChemNanoMat Journal Issue: 11 Vol. 6; ISSN 2199-692X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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