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 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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Layered semiconductors have attracted significant attention due to their diverse physical properties controlled by composition and the number of stacked layers. Herein, large crystals of the ternary layered semiconductor chromium thiophosphate (CrPS4) are prepared by a vapor transport synthesis. Optical properties are determined using photoconduction, absorption, photoreflectance, and photoacoustic spectroscopy exposing the semiconducting properties of the material. A simple, one‐step protocol for mechanical exfoliation onto a transmission electron microscope grid is developed, and multiple layers are characterized by advanced electron microscopy methods, including atomic resolution elemental mapping confirming the structure by directly showing the positions of the columns of different elements' atoms. CrPS4 is also liquid exfoliated, and in combination with colloidal graphene, an ink‐jet‐printed photodetector is created. This all‐printed graphene/CrPS4/graphene heterostructure detector demonstrates a specific detectivity of 8.3 × 108 (D*). This study shows a potential application of both bulk crystal and individual flakes of CrPS4 as active components in light detection, when introduced as ink‐printable moieties with a large benefit for manufacturing.