Browsing by Subject "nanoclusters"

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    Design of Anisotropically Shaped Plasmonic Nanocrystals from Ultrasmall Sn-Decorated In2O3 Nanoclusters Used as Seed Materials
    (American Chemical Society, 2022-12-07) Davis, Gregory A., Jr.; Prusty, Gyanaranjan; Hati, Sumon; Lee, Jacob T.; Langlais, Sarah R.; Zhan , Xun; Sardar, Rajesh; Chemistry and Chemical Biology, School of Science
    Ultrasmall inorganic nanoclusters (<2.0 nm in diameter) bridge the gap between individual molecules and large nanocrystals (NCs) and provide the critical foundation to design and prepare new solid-state nanomaterials with previously unknown properties and functions. Herein, for the first time, we report the monodispersed colloidal synthesis and successful isolation of metastable, rhombohedral-phase, <2.0 nm indium oxide (In2O3) nanoclusters. Ultrasmall nanocluster formation is controlled by a kinetically driven growth process, as evaluated through the variation of metal-to-passivating ligand concentrations. Although <2.0 nm-diameter In2O3 nanoclusters are synthesized in the presence of tin (Sn) precursors, they do not display typical localized surface plasmon resonance (LSPR) properties, which are commonly observed in Sn-doped In2O3 (Sn:In2O3) NCs. Our Raman and X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy (HRTEM) analyses support the existence of Sn-decorated In2O3 nanoclusters, where Sn complexes reside on the surface of the nanocluster as Z-type ligands, as opposed to the formation of Sn:In2O3 nanoclusters, which behave as wide band gap (∼5.5 eV) nanomaterials. The experimentally determined band gap is in good agreement with the theoretical effective mass calculations. The newly synthesized Sn-decorated, 1.7 nm-diameter In2O3 nanoclusters are further used as reactive monomers for the seeded growth synthesis of bcc-phase, plasmonic Sn:In2O3 NCs via ex situ injection of In precursors without the addition of any Sn precursors. The LSPR peak of Sn:In2O3 NCs, which appear to form nanoflower assemblies, is tunable in the 1800–4000 nm region and possibly even the deep-IR region. In addition to altering the size and assembly of the spherical Sn:In2O3 NCs by introducing different amounts of indium acetylacetonate, injection of indium chloride precursors in the reaction mixture results in the formation of rod-shaped NCs. Surprisingly, Sn-decorated, <1.5 nm-diameter In2O3 nanoclusters do not grow into large plasmonic Sn:In2O3 NCs. Taken together, the results presented here contribute to the fundamental understanding of the surface free energy of ultrasmall metal oxide nanoclusters and further advance the knowledge on the phase transformation and growth of plasmonic NCs.
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    Synthesis of PEG-Thiolate Monolayer Protected CdSe Nanoclusters with Unique Solubility Properties
    (Office of the Vice Chancellor for Research, 2012-04-13) Lawrence, Katie N.; Dolai, Sukanta; Sardar, Rajesh
    Ligands protected metal chalcogenides have shown potential applications in bionanotechnology and device fabrication due to their unique optical properties. However, most metal chalcogenides suffer from solubility problems, which hinders their applications. To overcome the solubility issue of metal chalcogenide nanoclusters, we have demonstrated the aqueous phase synthesis of polyethylene glycol thiolate (PEG-S-) protected CdSe nanoclusters for the first time. The CdSe nanoclusters displayed a first absorption peak ~430 nm, which indicated formation of magic-sized nanoclusters with possible composition of (CdSe)33,34. The PEG-thiolate protected CdSe nanoclusters demonstrated unique solubility properties. The resulting nanoclusters can easily be transferred to organic solvents from an aqueous medium by a simple solvent extraction method. The organic-phase extracted CdSe nanoclusters can readily be redispersed in a wide array of organic solvents such as CH3CN, CH2Cl2, DMF, THF, and CH3Cl. Most importantly, the CdSe nanoclusters, soluble in organic solvents, can also be redispersed in aqueous medium as well. We investigated different chain length PEGn-thiols, e.g., PEG4-SH, PEG6-SH, PEG12-SH, and PEG18-SH and found that the PEG-chain length significantly influenced the aqueous to organic phase transfer properties. Successful transfers were accomplished for PEGn-SH (n = 6, 12, 18). Future studies will be performed on the synthesis of PEG-SH stabilized various metal chalcogenide nanoclusters (CdS, CdTe, ZnS, ZnSe, and CdSe/ZnS nanoclusters).