Engineering topics
Dennis, Allison M
Publications and source records attributed to Dennis, Allison M.
Synthesis of Non-blinking Semiconductor Quantum Dots Emitting in the Near-Infrared
Our previous work demonstrates that Quasi-Type II CdSe/CdS core-shell quantum dots with thick shells (3-5 nm) exhibit unique photophysical characteristics, including improved chemical robustness over typical thin-shelled core/shell systems and the elimination of blinking through suppression of nonradiative Auger recombination. Here we describe a new thick-shelled heterostructure, InP/CdS, which exhibits a Type II bandgap alignment producing near-infrared (NIR) emission. Samples with a range of shell thicknesses were synthesized, enabling shell-thickness-dependent study of the absorbance and emission spectra, fluorescence lifetimes, and quantum yields. InP/CdS/ZnS core/shell/shell structures were also synthesized to reduce cadmium exposure for applications in the biological environment. Single particle spectroscopy indicates reduced blinking and improved photostability with increasing shell thickness, resulting in thick-shelled dots that are appropriate for single-particle tracking measurements with NIR emission.
Bandgap Engineering of InP QDs Through Shell Thickness and Composition
Fields as diverse as biological imaging and telecommunications utilize the unique photophysical and electronic properties of nanocrystal quantum dots (NQDs). The development of new NQD compositions promises material properties optimized for specific applications, while addressing material toxicity. Indium phosphide (InP) offers a 'green' alternative to the traditional cadmium-based NQDs, but suffers from extreme susceptibility to oxidation. Coating InP cores with more stable shell materials significantly improves nanocrystal resistance to oxidation and photostability. We have investigated several new InP-based core-shell compositions, correlating our results with theoretical predictions of their optical and electronic properties. Specifically, we can tailor the InP core-shell QDs to a type-I, quasi-type-II, or type-II bandgap structure with emission wavelengths ranging from 500-1300 nm depending on the shell material used (ZnS, ZnSe, CdS, or CdSe) and the thickness of the shell. Single molecule microscopy assessments of photobleaching and blinking are used to correlate NQD properties with shell thickness.
Process-Dependent Properties in Colloidally Synthesized “Giant” Core/Shell Nanocrystal Quantum Dots
Due to their characteristic bright and stable photoluminescence, semiconductor nanocrystal quantum dots (NQDs) have attracted much interest as efficient light emitters for applications from single-particle tracking to solid-state lighting. Despite their numerous enabling traits, however, NQD optical properties are frustratingly sensitive to their chemical environment, exhibit fluorescence intermittency ('blinking'), and are susceptible to Auger recombination, an efficient nonradiative decay process. Previously, we showed for the first time that colloidal CdSe/CdS core/shell nanocrystal quantum dots (NQDs) comprising ultrathick shells (number of shell monolayers, n, > 10) grown by protracted successive ionic layer adsorption and reaction (SILAR) leads to remarkable photostability and significantly suppressed blinking behavior as a function of increasing shell thickness. We have also shown that these so-called 'giant' NQDs (g-NQDs) afford nearly complete suppression of non-radiative Auger recombination, revealed in our studies as long biexciton lifetimes and efficient multiexciton emission. The unique behavior of this core/shell system prompted us to assess correlations between specific physicochemical properties - beyond shell thickness - and functionality. Here, we demonstrate the ability of particle shape/faceting, crystalline phase, and core size to determine ensemble and single-particle optical properties (quantum yield/brightness, blinking, radiative lifetimes). Significantly, we show how reaction process parameters (surface-stabilizing ligands, ligand:NQD ratio, choice of 'inert' solvent, and modifications to the SILAR method itself) can be tuned to modify these function-dictating NQD physical properties, ultimately leading to an optimized synthetic approach that results in the complete suppression of blinking. We find that the resulting 'guiding principles' can be applied to other NQD compositions, allowing us to achieve non-blinking behavior in the near-infrared. Lastly, in addition to realizing novel light-emission properties by refining nanoscale architectures at the single-NQD level, we also investigate collective properties by assembling our core/shell NQDs into larger scale arrays.