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The metal halide perovskite nanocrystals exhibit a remarkable tolerance to midgap defect states, resulting in high photoluminescence quantum yields. However, the potential of these nanocrystals for applications in display devices is hindered by the suppression of biexcitonic emission due to various Auger recombination processes. By adopting single-particle photoluminescence spectroscopy, herein, we establish that the biexcitonic quantum efficiency increases with the increase in the number of facets on cesium lead bromide perovskite nanocrystals, progressing from cube to rhombic dodecahedron to rhombicuboctahedron nanostructures. The observed enhancement is attributed mainly to an increase in their surface polarity as the number of facets increases, which reduces the Coulomb interaction of charge carriers, thereby suppressing Auger recombination. Moreover, Auger recombination rate constants obtained from the time-gated photon correlation studies exhibited a discernible decrease as the number of facets increased. These findings underscore the significance of facet engineering in fine-tuning biexciton emission in metal halide perovskite nanocrystals.

The facet chemistry of halide perovskite nanocrystals plays a key role in designing nanoscale epitaxial heterostructures. However, despite significant successes achieved in designing these nanocrystals, their heterostructures with several leading transition metals could not be established yet. Herein, the possible heterostructures of metals beyond transition metals are explored and the epitaxial combinations of soft CsPbBr 3 nanocrystals with the post-transition metal Bi(0) are reported. These heterostructures are built with interfacing facets having hexagonal atomic configurations of both the rhombicuboctahedron CsPbBr 3 and octahedral Bi(0). A high reaction temperature and the presence of alkylamine kept Bi(III) in reduced form and helped in sustaining these CsPbBr 3 -Bi(0) heteronanocrystals. Since understanding of and synthesis optimization of metal-halide perovskite heterostructures are limited, this finding adds a new fundamental insight in designing ionic and nonionic materials heterojunctions. Furthermore, oxidation and sulfidation of Bi(0) are studied, and the possible oxide/sulfide heterostructures with CsPbBr 3 are discussed.

Designing heterostructures of soft ionic nanocrystals with metallic or covalent nanostructures having epitaxial junctions in solution poses several fundamental challenges. Hence, in spite of large successes in developing lead halide perovskite nanocrystals, the chemistry of formation of their facet-directive epitaxial growth of noble metals cannot be explored yet. To address this, herein, epitaxial heterostructures of orthorhombic CsPbBr 3 and cubic Pt in multiple directional approaches are reported. Appropriate facets of perovskite nanocrystals and high-temperature reaction are the key parameters for obtaining such nanocrystal heterostructures. Interfacial planes at the junctions having ideal lattice matching helped in establishing the epitaxial relations of (110) of orthorhombic (space group Pbnm ) CsPbBr 3 with {020} of cubic Pt and again (011) of CsPbBr 3 with {111} of Pt. These results provided strong fundamental insights that ionic halide perovskite nanostructures and materials having different crystal phases can be placed in a single building block with continuous sublattice structures.

Auger recombination and thermalization time are detrimental in reducing the gain threshold of optically pumped semiconductor nanocrystal (NC) lasers for future on-chip nanophotonic devices. Here, we report the design strategy of facet engineering to reduce the gain threshold of amplified spontaneous emission by manyfold in NCs of the same concentration and edge length. We achieved this hallmark result by controlling the Auger recombination rates dominated by processes involving NC volume and thermalization time to the emitting states by optimizing the number of facets from 6 (cube) to 12 (rhombic dodecahedron) and 26 (rhombicuboctahedrons) in CsPbBr 3 NCs. For instance, we demonstrate a 2-fold reduction in Auger recombination rates and thermalization time with increased number of facets. The gain threshold can be further reduced ∼50% by decreasing the sample temperature to 4 K. Our systematic studies offer a new method to reduce the gain threshold that ultimately forms the basis of nanolasers.

Magnetic field- and polarization-dependent measurements on bright and dark excitons in monolayer WSe 2 combined with time-dependent density functional theory calculations reveal intriguing phenomena. Magnetic fields up to 25 T parallel to the WSe 2 plane lead to a partial brightening of the energetically lower lying exciton, leading to an increase of the dephasing time. Using a broadband femtosecond pulse excitation, the bright and partially allowed excitonic state can be excited simultaneously, resulting in coherent quantum beating between these states. The magnetic fields perpendicular to the WSe 2 plane energetically shift the bright and dark excitons relative to each other, resulting in the hybridization of the states at the K and K' valleys. Our experimental results are well captured by time-dependent density functional theory calculations. These observations show that magnetic fields can be used to control the coherent dephasing and coupling of the optical excitations in atomically thin semiconductors.

The conversion of metal halides to lead halide perovskites with B-site metal ion diffusion has remained a convenient approach for obtaining shape-modulated perovskite nanocrystals. These transformations are typically observed for materials having a common A-site Cs-sublattice platform. However, due to the fast reactions, trapping the interconversion process has been difficult. In an exploration of the tetragonal phase of Cs 7 Cd 3 Br 13 platelets as the parent material, herein, a slower diffusion of Pb(II) leading to facet-modulated CsPbBr 3 platelets is reported. This was expected due to the presence of Cd(II) halide octahedra along with Cd(II) halide tetrahedra in the parent material. This helped in microscopically monitoring their phase transformation via an epitaxially related core/shell intermediate heterostructure. The transformation was also derived and predicted by density functional theory calculations. Further, when the reaction chemistry was tuned, core/shell platelets were transformed to different facet-modulated and hollow CsPbBr 3 platelet nanostructures. These platelets having different facets were also explored for catalytic CO 2 reduction, and their catalytic rates were compared.

Lead halide perovskite nanocrystals, whether formed by their own nucleation and growth or by ion diffusion into the lattice of others, are still under investigation. Moreover, beyond isotropic nanocrystals, fabricating anisotropic perovskite nanocrystals by design has remained difficult. Exploring the lattice of orthorhombic-phase Cs 2 ZnBr 4 with the complete replacement of Zn tetrahedra by Pb octahedra, dimension-tunable anisotropic nanocrystals of CsPbBr 3 are reported. This B-site ion introduction led to CsPbBr 3 nanorods having [100] as major axis, in contrast with all reports on rods/wires where the lengths were along the [001] direction. This was possible by using derivatives of α-bromo ketones, which helped in tuning the shape of Cs 2 ZnBr 4 and also the facets of transformed CsPbBr 3 . While similar experiments are extended to orthorhombic Cs 2 HgBr 4 , standard nanorods with [001] as the major axis were observed. From these results, it is further concluded that anisotropic perovskite nanocrystals might not follow any specific rules for directional growth and instead might depend on the structure of the parent lattice.

Mn2+-doped ZnSe quantum dots (Mn:ZnSe d-dots) with a tunable photoluminescence (PL) peak position were made to be water soluble by coating them with a monolayer of mercaptopropionic acid, a very short hydrophilic thiol. If the dopant centers were located close to the surface, thiol-coating partially quenched the PL. With about 2-3 monolayers of pure ZnSe on the surface, the PL of d-dots was actually enhanced upon thiol coating. When the doping centers were placed reasonably inside a d-dot, with about four monolayers of pure ZnSe between the doping centers and the surface ligands, the thiol ligands did not quench the PL of the d-dots, even though they did completely quench the PL of intrinsic ZnSe quantum dots. The overall size of such d-dots/ligand complex is only about 7-8 nm, implying an excellent permeability in biological issues. These d-dots were found to be exceptionally stable against continuous UV radiation in air for at least 25 days. They were also stable in boiling water with air bubbling under room light for hours. Recognition of a biotin pattern by d-dots conjugated with avidine was carried to illustrate the suitability of these efficient (about 40% PL quantum yield), stable, small, and water-soluble d-dots as biomedical labeling reagents.

We report here a relatively low temperature (100-180 degrees C) synthetic route to high-quality and single-crystalline CdSe nanowires using air-stable and generic chemicals. The diameter of nanowires was controlled and varied in an exceptionally small size regime, between 1.5 and 6 nm. This was achieved by using alkylamines, a single type or a mixture of two different types of amines, with different chain lengths and varying the reaction temperature. The experimental results suggest the coexistence of two types of fragments in the prewire aggregates, known as "pearl-necklace" or "string-of-pearls" in the literature, which are loosely associated and chemically fused sections.