Low temperature synthesis of ZnS and CdZnS shells on CdSe quantum dots.

Methods for synthesizing quantum dots generally rely on very high temperatures to both nucleate and grow core and core-shell semiconductor nanocrystals. In this work, we generate highly monodisperse ZnS and CdZnS shells on CdSe semiconductor nanocrystals at temperatures as low as 65 degrees C by enhancing the precursor solubility. Relatively small amounts of trioctylphosphine and trioctylphosphine oxide have marked effects on the solubility of the metal salts used to form shells; their inclusion in the precursor solutions, which use thiourea as a sulfur source, can lead to homogeneous and fully dissolved solutions. Upon addition to suspensions of quantum dot cores, these precursors deposit as uniform shells; the lowest temperature for shell growth (65 degrees C) yields the thinnest shells (d < 1 nm) while the same process at higher temperatures (180 degrees C) forms thicker shells (d approximately 1-2 nm). The growth of the shell structures, average particle size, size distribution, and shape were examined using optical spectroscopy, transmission electron microscopy, x-ray diffraction, and transmittance small angle x-ray scattering. The photoluminescence quantum yield (QY) of the as-prepared CdSe/ZnS quantum dots ranged from 26% to 46% as compared to 10% for the CdSe cores. This method was further generalized to CdZnS shells by mixing cadmium and zinc acetate precursors. The CdSe/CdZnS nanocrystals have a thicker shell and higher QY (40% versus 36%) as compared to the CdSe/ZnS prepared under similar conditions. These low temperature methods for shell growth are readily amenable to scale-up and can provide a route for economical and less energy intensive production of quantum dots.