On-Demand Sonochemical Synthesis of Ultrasmall and Magic-Size CdSe Quantum Dots in Single-Phase and Emulsion Systems.

The sonochemical synthesis of CdSe quantum dots (QDs) in a single-liquid bulk phase and in an emulsion-based system is presented. Reactions utilized cadmium oleate and trioctylphosphine selenide precursors and were monitored as a function of sonication time under controlled temperature conditions to isolate the effects of cavitation from those of bulk temperature changes. QD synthesis was found to be slow in the single-phase liquid system (i.e., 1-octadecene) but greatly accelerated in the dispersed system (i.e., emulsions of 1-octadecene in ethylene glycol). It is hypothesized that the emulsion system increases the cavitation efficiency while also delivering acoustic energy in closer proximity to the precursor molecules. The capacity of CdSe production in the emulsion system was found to be 3.8 g/(L h), which is comparable to the typical hot-injection synthesis of CdSe QDs and can likely be further optimized. While the single-phase solvent system was found to produce ultrasmall QDs that exhibit broadband white-light emission, the emulsion system was found to produce well-defined magic-size clusters (MSCs) with photoluminescence quantum yield as high as 34%. Differences in synthesis rate and product properties from the emulsion and single-phase systems were probed by X-ray diffraction, electron microscopy, UV-visible (vis) and photoluminescence spectroscopy, and small-angle X-ray scattering (SAXS). Finally, precise temporal control of the QD synthesis was demonstrated via on-off cycling of the ultrasound waves.