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.

The work focuses on the synthesis of smallsized PbSe/PbS core/shell colloidal quantum dots with the core diameter of 2−2.5 nm and the shell thickness of 0.5−1.0 nm. The PbSe/PbS core/shell CQDs are chemically stable under time-limited air exposure and have emission quantum efficiency of 60% at room temperature. The PbSe/PbS core/ shell CQDs have a tunable absorption edge around 1 μm, large exciton emission Stokes shift (∼150 meV), and small exchange interaction (∼1.5 meV). Theoretical calculations associate the mentioned parameters to the small-size regime as well as to a lift of band-edge degeneracy due to slight shape anisotropy. The specific parameters are of special interest in photovoltaic applications.

The electronic properties of colloidal quantum dots (CQDs) have shown intriguing potential in recent years for implementation in various optoelectronic applications. However, their chemical and photochemical stabilities, mainly derived from surface properties, have remained a major concern. This paper reports a new strategic route for the synthesis of surface-treated CQDs, the CdSe/CdS core/shell heterostructures, based on low-temperature coating of a shell constituent, followed by a programmed annealing process. A comprehensive follow-up of the stability and the optical properties through the various synthesis stages is reported, suggesting that the low-temperature coating is responsible for the formation of a sharp interface between the core and the shell, whereas a postcoating annealing process leads to the generation of a thin alloy interfacial layer. At the end of the process, the CdSe/CdS CQDs show a significant improvement of the photoluminescence quantum yield, as well as an exceptional photostability. Consequently, the work reported here provides a convenient generic route to the formation of core/shell CQDs to be employed as a procedure for achieving various other heterostructures.

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.