Optimization of the recipe for the synthesis of CuInS2/ZnS nanocrystals supported by mechanistic considerations

Abstract

CuInS2/ZnS (CIS/ZnS) quantum dots (QDs) with high photoluminescence (PL) were synthesized via a facile solvothermal approach. Gaussian deconvolution of PL spectra, transmission electron microscopy, and time-resolved PL spectroscopies were used to characterize the emission properties of the prepared CIS and CIS/ZnS QDs. It was found that the growth of ZnS can reduce the surface defect acting as traps to minimize donor-acceptor emissions, and the contribution of band to donor/acceptor transition becomes a dominating emission with the increase of shell growth time. The blue shift of PL emission wavelength of CIS/ZnS QDs underwent two steps: the dramatic blue shift originated from the decreased fraction donor-acceptor transition due to the reduction of surface defects at the beginning and the subsequently mild blue-shift with the time from the interdiffusion of CIS and ZnS. The effect of trioctylphosphine (TOP) and dodecanethiol (DDT) as ligands during shell growth on the optical properties of QDs were investigated and compared. The PL quantum yield (QY) of CIS core affects the final value of CIS/ZnS QDs, and the higher PL QY is achieved while using CIS core with higher PL QY. Based on the selected ligand DDT, the reaction parameters, such as CIS core reaction time, shell growth time, and Zn/Cu feed molar ratio, were further optimized. CIS/ZnS QDs with high PL QY can be obtained with a Zn/Cu feed molar ratio larger than 4, shell growth time of 30 to 90 min, and shell growth temperature 220°C–240°C, and the maximum value was up to about 80% by adjusting the above-mentioned parameters.

Keywords

• core/shell
• cuins2
• ligands
• process optimization
• quantum dots