Browsing by Subject "semiconductor nanocrystals"

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    Size-Dependent Optical and Electrochemical Energy Gaps Comparison of CdSe Nanolusters
    (Office of the Vice Chancellor for Research, 2013-04-05) Teunis, Meghan B.; Lawrence, Katie N.; Dolai, Sukanta
    The size-dependent optical and electronic properties of semiconductor nanocrystals have made them the focus of much research including the designing of photovoltaic devices and photocatalysts. These properties occur as a result of the phenomenon called quantum confinement. To improve the device efficiency it is important to have a better understanding of their size dependent electrochemical properties. Herein we demonstrate for the first time, a comparison of the size dependent optical properties and electrochemical energy gaps of poly(ethylene glycol) thiolate-protected ultra-small CdSe nanoclusters. The electrochemical energy gaps for various sized nanoclusters were determined from cyclic and differential pulse voltammetry in organic solvent/electrolyte medium, where large, moleculelike HOMO-LUMO energy gaps were observed. It was also found that a significant amount of charging energy is involved in the electrochemical energy gap. The effect of the thickness of the surface-pasivating ligands on the HOMO-LUMO energy gap is demonstrated and a quantized double layer (QDL) charging model presented.
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    Solvent-like ligand-coated ultrasmall cadmium selenide nanocrystals: Strong electronic coupling in a self-organized assembly
    (RSC, 2015-07) Lawrence, Katie N.; Johnson, Merrell A.; Dolai, Sukanta; Kumbhar, Amar; Sardar, Rajesh; Department of Chemistry & Chemical Biology, School of Science
    Strong inter-nanocrystal electronic coupling is a prerequisite for delocalization of exciton wave functions and high conductivity. We report 170 meV electronic coupling energy of short chain poly(ethylene glycol) thiolate-coated ultrasmall (<2.5 nm in diameter) CdSe semiconductor nanocrystals (SNCs) in solution. Cryo-transmission electron microscopy analysis showed the formation of a pearl-necklace assembly of nanocrystals in solution with regular inter-nanocrystal spacing. The electronic coupling was studied as a function of CdSe nanocrystal size where the smallest nanocrystals exhibited the largest coupling energy. The electronic coupling in spin-cast thin-film (<200 nm in thickness) of poly(ethylene glycol) thiolate-coated CdSe SNCs was studied as a function of annealing temperature, where an unprecedentedly large, ∼400 meV coupling energy was observed for 1.6 nm diameter SNCs, which were coated with a thin layer of poly(ethylene glycol) thiolates. Small-angle X-ray scattering measurements showed that CdSe SNCs maintained an order array inside the films. The strong electronic coupling of SNCs in a self-organized film could facilitate the large-scale production of highly efficient electronic materials for advanced optoelectronic device application.