Successive ion layer adsorption and reaction (SILAR) originally developed for the deposition of thin films on solid substrates from solution baths is introduced as a technique for the growth of high-quality core/shell nanocrystals of compound semiconductors. The growth of the shell was designed to grow one monolayer at a time by alternating injections of air-stable and inexpensive cationic and anionic precursors into the reaction mixture with core nanocrystals. The principles of SILAR were demonstrated by the CdSe/CdS core/shell model system using its shell-thickness-dependent optical spectra as the probes with CdO and elemental S as the precursors. For this reaction system, a relatively high temperature, about 220-240 degrees C, was found to be essential for SILAR to fully occur. The synthesis can be readily performed on a multigram scale. The size distribution of the core/shell nanocrystals was maintained even after five monolayers of CdS shell (equivalent to about 10 times volume increase for a 3.5 nm CdSe nanocrystal) were grown onto the core nanocrystals. The epitaxial growth of the core/shell structures was verified by optical spectroscopy, TEM, XRD, and XPS. The photoluminescence quantum yield (PL QY) of the as-prepared CdSe/CdS core/shell nanocrystals ranged from 20% to 40%, and the PL full-width at half-maximum (fwhm) was maintained between 23 and 26 nm, even for those nanocrystals for which the UV-vis and PL peaks red-shifted by about 50 nm from that of the core nanocrystals. Several types of brightening phenomena were observed, some of which can further boost the PL QY of the core/shell nanocrystals. The CdSe/CdS core/shell nanocrystals were found to be superior in comparison to the highly luminescent CdSe plain core nanocrystals. The SILAR technique reported here can also be used for the growth of complex colloidal semiconductor nanostructures, such as quantum shells and colloidal quantum wells.

Type II CdSe/CdTe core/shell nanocrystals with a dot shape were synthesized using a modified SILAR technique that incorporates cycling of the reaction temperature (thermal cycling). Conversely, experimental results revealed that the standard SILAR alone produced type II core/shell nanocrystals in a peanut shape (1D). Despite their differences in shape, the optical properties observed for the type II dot- and peanut-shaped core/shell nanocrystals were similar. The dot-shaped nanocrystals were confirmed as core/shell structures with an abrupt type II heterojunction within the experimental accuracy, and the peanut-shaped ones were found to be consistent with CdSe and CdTe separated on the two ends of the rods. Similar techniques were used for the synthesis of CdS/CdSe/CdTe type II colloidal quantum well heterostructures with dot and peanut shapes. For these type II colloidal quantum well structures, the PL peak positions were shown to be readily tunable by varying the CdSe and CdTe shell thickness, something not typically seen for the quantum dots. The PL quantum yield of these nanocrystals were found to range between 30 and 60%.

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