Colloidal CdSe nanocrystals from tri-n-octylphosphine: Part 1: growth and optical properties from polar and non-polar solvents.

This manuscript reports the ready synthesis of high-quality colloidal CdSe nanocrystals from tri-n-octylphosphine (TOP) and reports the optical properties of the resulting CdSe dispersed in nonpolar and polar environments. With cadmium oxide (CdO) as the Cd precursor and TOPSe as the Se source, the CdSe nanocrystals were synthesized in a reaction medium consisting of TOP. The synthetic approach is as simple as: the swift injection of a TOPSe/TOP solution into a CdO/TOP solution at one particular (high) temperature, with subsequent growth at a lower temperature. The temporal evolution of the optical properties, including absorption and luminescence, were monitored in detail. The photoluminescence (PL) properties of the TOP-capped CdSe investigated comprise the intensity, emission peak wavelength, full width at half maximum of the PL spectra, and stability; these PL properties are sensitive to the history of growth as well as the environment of dispersion. An appropriate parameter, termed "Sensitivity Index (SI)," is proposed to define the percent difference in the PL intensity that arises when the dots are dispersed in non-polar hexane (Hex) as compared to polar tetrahydrofuran (THF). The decrease in the PL efficiency on going from Hex to THF is attributed to changes in surface states rather than in the internal core as more ligands are removed in THF. Dilution experiments further confirm the suggestion of the ligand removal mechanism and provide a conceptual estimate of surface quality via the SI parameter. Due to a slow growth in size (the size of the nanocrystals is almost constant during early 20 min) and good PL stability (tested as PL changes after storage for days both in dispersed or solid states, as well as after UV-irradiation), we suggest that our synthetic approach is likely to be practical for large-scale CdSe nanocrystals with good PL stability.

Colloidal CdSe nanocrystals from tri-n-octylphosphine: Part II: control of growth rate for high quality and large-scale production by tuning Cd-to-Se stoichiometry.

Colloidal CdSe nanocrystals were synthesized in reaction media consisting of tri-n-octylphosphine (TOP) without addition of other species; the single-step approach used cadmium oxide (CdO) and TOPSe as Cd and Se sources, respectively. The temporal evolution of the optical properties of the growing TOP-capped CdSe nanocrystals was monitored for a couple of hours, showing that there are two distinguishable stages of growth: an early stage (less than 5 minutes) and a later stage; the growth kinetics of the two stages is a function of the Cd-to-Se precursor molar ratios. A rational choice of 2-6Cd-to-1Se molar ratio was found, based on the temporal evolution of the photoluminescent (PL) efficiency (studied as PL intensity and sensitivity to the media of dispersion, and non-resonant Stokes shifts). For a 2Cd-to-1Se synthesis, the growth in size was slow in the early stages and became fast in the later stages; this fast-later-stage feature could be suppressed by going to a synthesis with a 4-6Cd-to-1Se mole ratio: the nanocrystals between 0.5-60 min growth time exhibit very much similar optical properties, with less than 19 nm redshift of bandgap absorption and emission occurring. Thus, the synthetic route developed here, with a rational 4-6Cd-to-1Se molar ratio, enables us to produce high-quality CdSe nanocrystals on a large-scale with a high degree of synthetic reproducibility. The insights gained facilitate a deeper understanding of the concept of what constitutes high-quality nano-crystals: high PL efficiency resulting from a low growth rate, which can be thoroughly and readily investigated by the red-shift rate of the band-gap peak positions; in addition, the insights gained help us to define a proper synthetic approach for large-scale production with high-quality product.

Sequential synthesis of type II colloidal CdTe/CdSe core-shell nanocrystals.

Colloidal type II CdTe/CdSe nanocrystals were synthesized by sequential addition of a tri-n-octylphosphine telluride (TOPTe)/TOP solution and several shell-precursor solutions to a CdO/TOP solution; the shell-precursor solutions consisted of CdO and TOPSe in TOP. For the growth of the CdTe core, the TOPTe/TOP solution was swiftly added to the CdO/TOP solution at a higher temperature (300 degrees C) than the growth temperature (250 degrees C). For the growth of the CdSe shell, in contrast, the CdO/TOPSe/TOP solution was slowly added to the CdTe/TOP solution at a lower temperature than the growth temperature (200-240 degrees C). The temporal evolution of the optical properties of the growing core-shell nanocrystals was monitored in detail. During the growth of the CdSe shell, the core-shell nanocrystals exhibited interesting changes in photoluminescence (PL) properties. The highest PL efficiency (approximately 38 %) was detected from core-shell nanocrystals with a CdSe shell thickness of 0.4-0.5 nm (indicated by TEM); the formation of the first monolayer is proposed. Our synthetic approach is well suited to a practical realization of engineering materials with bandgaps in the near-IR and IR spectral ranges.