Semiconductor colloidal quantum dots (CQDs) have attracted vast scientific and technological interest throughout the past three decades, due to the unique tuneability of their optoelectronic properties by variation of size and composition. However, the nanoscale size brings about a large surface-to-bulk volume ratio, where exterior surfaces have a pronounced influence on the chemical stability and on the physical properties of the semiconductor. Therefore, numerous approaches have been developed to gain efficient surface passivation, including a coverage by organic or inorganic molecular surfactants as well as the formation of core/shell heterostructures (a semiconductor core epitaxially covered by another semiconductor shell). This review focuses on special designs of core/shell heterostructures from the IV-VI and II-VI semiconductor compounds, and on synthetic approaches and characterization of the optical properties. Experimental observations revealed the formation of core/shell structures with type-I or quasi-type-II band alignment between the core and shell constituents. Theoretical calculations of the electronic band structures, which were also confirmed by experimental work, exposed surplus electronic tuning (beyond the radial diameter) with adaptation of the composition and control of the interface properties. The studies also considered strain effects that are created between two different semiconductors. It was disclosed experimentally and theoretically that the strain can be released via the formation of alloys at the core-shell interface. Overall, the core/shell and core/alloyed-shell heterostructures showed enhancement in luminescence quantum efficiency with respect to that of pure cores, extended lifetime, uniformity in size and in many cases good chemical sustainability under ambient conditions.
Controlling the synthesis of narrow band gap semiconductor nanocrystals (NCs) with a high-quality surface is of prime importance for scientific and technological interests. This Letter presents facile solution-phase syntheses of SnTe NCs and their corresponding core/shell heterostructures. Here, we synthesized monodisperse and highly crystalline SnTe NCs by employing an inexpensive, nontoxic precursor, SnCl2, the reactivity of which was enhanced by adding a reducing agent, 1,2-hexadecanediol. Moreover, we developed a synthesis procedure for the formation of SnTe-based core/shell NCs by combining the cation exchange and the Kirkendall effect. The cation exchange of Sn(2+) by Cd(2+) at the surface allowed primarily the formation of SnTe/CdTe core/shell NCs. Further continuation of the reaction promoted an intensive diffusion of the Cd(2+) ions, which via the Kirkendall effect led to the formation of the inverted CdTe/SnTe core/shell NCs.
Above band-edge photoexcitation of PbSe nanocrystals induces strong below band gap absorption as well as a multiphased buildup of bleaching in the 1Se1Sh transition. The amplitudes and kinetics of these features deviate from expectations based on biexciton shifts and state filling, which are the mechanisms usually evoked to explain them. To clarify these discrepancies, the same transitions are investigated here by double-pump-probe spectroscopy. Re-exciting in the below band gap induced absorption characteristic of hot excitons is shown to produce additional excitons with high probability. In addition, pump-probe experiments on a sample saturated with single relaxed excitons prove that the resulting 1Se1Sh bleach is not linear with the number of excitons per nanocrystal. This finding holds for two samples differing significantly in size, demonstrating its generality. Analysis of the results suggests that below band edge induced absorption in hot exciton states is due to excited-state absorption and not to shifted absorption of cold carriers and that 1Se1Sh bleach signals are not an accurate counter of sample excitons when their distribution includes multiexciton states.
The achievement of tunable optical properties across a wide spectral range, along with an efficient surface passivation of lead chalcogenide (PbSe) colloidal quantum dots (CQDs), has significant importance for scientific research and for technological applications. This paper describes two comprehensive pathways to tune optical activities of PbSe CQDs in the near-infrared (NIR, 0.75−1.4 μm) and the short-wave infrared (SWIR, 1.4−3 μm) ranges. A one-pot procedure enabled the growth of relatively large PbSe CQDs (with average sizes up to 14 nm) exploiting programmable temperature control during the growth process. These CQDs showed optical activity up to 3.2 μm. In addition, PbSe/PbS core/shell CQDs prepared by an orderly injection rate led to an energy red-shift of the absorption edge with the increase of the shell thickness, whereas a postannealing treatment further extended the band-edge energy toward the SWIR regime. A better chemical stability of the CQDs with respect to that of PbSe core CQDs was attained by shelling of PbSe by epitaxial layers of PbS, but limited to a short duration (<1 day). However, air stability of the relatively large PbSe as well as the PbSe/PbS CQDs over a prolonged period of time (weeks) was achieved after a postsynthesis chlorination treatment.
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