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Hyperpolarization derived from water protons enhances the NMR signal of 15 N nuclei in a small molecule, enabling the sensitive detection of a protein-ligand interaction. The water hyperpolarized by dissolution dynamic nuclear polarization (D-DNP) acts as a universal signal enhancement agent. The 15 N signal of benzamidine was increased by 1480-fold through continuous polarization transfer by J -coupling-mediated cross-polarization ( J -CP) via the exchangeable protons. The signal enhancement factor favorably compares to factors of 110- or 17-fold using non-CP-based polarization transfer mechanisms. The hyperpolarization enabled detection of the binding of benzamidine to the target protein trypsin with a single-scan measurement of 15 N R 2 relaxation. J N or other low-frequency nuclei near an exchangeable proton. The hyperpolarization transfer sustained within the relaxation time limit of water protons additionally can be applied for the study of macromolecular structure and biological processes.15 N or other low-frequency nuclei near an exchangeable proton. The hyperpolarization transfer sustained within the relaxation time limit of water protons additionally can be applied for the study of macromolecular structure and biological processes.

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.

Lead halide perovskite nanocrystals have been extensively studied in recent years as efficient optical materials for their bright and color-tunable emissions. However, these are mostly confined to their 3D nanocrystals and limited to the anisotropic nanostructures. By exploring the Cs-sublattice-induced metal(II) ion exchange with Pb(II), crack CsPbBr 3 perovskite platelet nanocrystals having polar surfaces in all three directions are reported here, which remained different than reported standard square platelets. The crack platelets are also passivated with halides to enhance their brightness. Further, as these crack and passivated crack platelets have defects and polar surfaces, the exciton and biexciton generation in these platelets is investigated using femtosecond photoluminescence and transient absorption measurement at ambient as well as cryogenic temperatures, correlated with time-resolved single-particle photoluminescence spectroscopy, and compared with standard square platelets having nonpolar facets. These investigations revealed that the crack platelets and passivated crack platelets possess enhanced biexciton emission compared to square platelets due to the presence of polar surfaces in all three directions. These results provide insights into not only the design of the anisotropic nanostructures of ionic nanocrystals but also the possibility of tuning the single exciton to biexciton generation efficiency, which has potential applications in optoelectronic systems.

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.

The design of cube-connected nanorods is accomplished by connecting seed nanocrystals of a defined shape in a particular orientation or by etching selective facets of preformed nanorods. In lead halide perovskite nanostructures, which retain mostly a hexahedron cube shape, such patterned nanorods can be designed with the anisotropic direction along the edge, vertex, or facet of seed cubes. Combining the Cs-sublattice platform for transforming metal halides to halide perovskites with facet-specific ligand binding chemistry, herein, vertex-oriented patterning of nanocubes in one-dimensional (1D) rod structures is reported. By tuning the length of host metal halides, their lengths could also be tuned from 100 nm to nearly 1000 nm. The symmetry of the hexagonal phase of host halide CsCdBr 3 and product orthorhombic CsPbBr 3 helped in maintaining the vertex [201] as the anisotropic direction. Neutral exciton recombination rates, extracted from photoluminescence blinking traces, showed a systematic increase from isolated cubes to cube-connected nanorods of various lengths. Efficient coupling of wave functions in vertex-oriented cube assemblies permits exciton delocalization. Our findings on carrier delocalization in cube-connected nanorods along their vertex direction having minimum interfacial contacts provide valuable insights into the fundamental chemistry of assembling anisotropic halide perovskite nanostructures as conducting wires.

Homogeneous and pinhole-free large-area perovskite films are required to realize the commercialization of perovskite modules and panels. Various large-area perovskite coatings were developed; however, at their film coating and drying stages, many defects were formed on the perovskite surface. Consequently, not only the devices lost substantial performance but also their long-term stability deteriorated. Here, we fabricated a compact and uniform large-area MAPbI 3 -perovskite film by a slot-die coater at room temperature ( T ) and at high relative humidity (RH) up to 40%. The control slot-die-coated perovskite solar cell (PSC) produced 1.082 V open-circuit voltage ( V oc ), 24.09 mA cm -2 short current density ( J sc ), 71.13% fill factor (FF), and a maximum power conversion efficiency (PCE) of 18.54%. We systematically employed a multi-functional artificial amino acid (F-LYS-S) to modify the perovskite defects. Such amino acids are more inclined to bind and adhere to the perovskite defects. The amino, carbonyl, and carboxy functional groups of F-LYS-S interacted with MAPbI 3 through Lewis acid-base interaction and modified iodine vacancies significantly. Fourier transform infrared spectroscopy revealed that the C═O group of F-LYS-S interacted with the uncoordinated Pb 2+ ions, and X-ray photoelectron spectroscopy revealed that the lone pair of -NH 2 coordinated with the uncoordinated Pb 2+ and consequently modified the I - vacancies remarkably. As a result, the F-LYS-S-modified device demonstrated more than three-fold charge recombination resistance, which is one of the primary requirements to fabricate high-performance PSCs. Therefore, the device fabricated employing F-LYS-S demonstrated remarkable PCE of 21.08% with superior photovoltaic parameters of 1.104 V V oc , 24.80 mA cm -2 J sc , and 77.00%. FF. Concurrently, the long-term stability of the PSCs was improved by the F-LYS-S post-treatment, where the modified device retained ca. 89.6% of its initial efficiency after storing for 720 h in air ( T ∼ 27 °C and RH ∼ 50-60%).

Designing high energy density dielectric capacitors for advanced energy storage systems needs nanocomposite-based dielectric materials, which can utilize the properties of both inorganic and polymeric materials. Polymer-grafted nanoparticle (PGNP)-based nanocomposites alleviate the problems of poor nanocomposite properties by providing synergistic control over nanoparticle and polymer properties. Here, we synthesize "core-shell" barium titanate-poly(methyl methacrylate) (BaTiO 3 -PMMA) grafted PGNPs using surface-initiated atom transfer polymerization (SI-ATRP) with variable grafting densities of (0.303 to 0.929) chains/nm 2 and high molecular masses (97700 g/mL to 130000 g/mol) and observe that low grafted density and high molecular mass based PGNP show high permittivity, high dielectric strength, and hence higher energy densities (≈ 5.2 J/cm 3 ) as compared to the higher grafted density PGNPs, presumably due to their "star-polymer"-like conformations with higher chain-end densities that are known to enhance breakdown. Nonetheless, these energy densities are an order of magnitude higher than their nanocomposite blend counterparts. We expect that these PGNPs can be readily used as commercial dielectric capacitors, and these findings can serve as guiding principles for developing tunable high energy density energy storage devices using PGNP systems., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The cube shape of orthorhombic phase CsPbBr 3 nanocrystals possesses the ability of selective facet packing that leads to 1D, 2D, and 3D nanostructures. In solution, their transformation with linear one-dimensional packing to nanorods/nanowires is extensively studied. Here, multifacet coupling in two directions of the truncated cube nanocrystals to rod couples and then to single-crystalline rectangular rods is reported. With extensive high-resolution transmission electron microscopy image analysis, length and width directions of these nanorods are derived. For the seed cube structures, finding {110} and {002} facets has remained difficult as these possess the hexahedron symmetry and their size remains smaller; however, for nanorods, these planes and the ⟨110⟩ and ⟨001⟩ directions are clearly identified. From nanocrystal to nanorod formation, the alignment directions are observed as random (as shown in the abstract graphic), and this could vary from one to the other rods obtained in the same batch of samples. Moreover, seed nanocrystal connections are derived here as not random and are rather induced by addition of the calculated amount of additional Pb(II). The same has also been extended to nanocubes obtained from different literature methods. It is predicted that a Pb-bromide buffer octahedra layer was created to connect two cubes, and this can connect along one, two, or even more facets of cubes simultaneously to connect other cubes and form different nanostructures. Hence, these results here provide some basic fundamentals of seed cube connections, the driving force to connect those, trapping the intermediate to visualize their alignments for attachments, and identifying and establishing the orthorhombic ⟨110⟩ and ⟨001⟩ directions of the length and width of CsPbBr 3 nanostructures.

The facet chemistry of lead halide perovskite nanocrystals is critically important for determining their shape and interface ligand binding. In colloidal nanocrystals, these are mostly controlled by adopting specific synthetic strategies with a selection of the appropriate reactants. However, using selected ligands, the surface of preformed nanocrystals can be reconstructed without altering the crystal phase and lattice structure of their core. This has been shown here for hexagonal-shaped orthorhombic CsPbBr 3 platelet nanocrystals. When oleylammonium bromide was added to these postsynthesized platelets, all six edges and two planar facets are transformed from flat to wavy structures. With a variation in concentration, the crest-to-crest distance of these wavy platelets are also tuned. These became possible because of the oleylammonium ions, which changed the {200}, {012} and {020} facets of orthorhombic phase of CsPbBr 3 to the more compatible {110} and {002} facets simply by surface atom dissolution. This was also observed for multisegmented platelets having multiple junctions and even for platelets having a size of more than 200 nm. While shape modulations in ionic halide perovskite nanocrystals still face synthetic challenges, these results of surface reconstruction provide strong evidence of the possibility of sculpturing surface facets and shape changes in these nanostructures.

The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has increased and levels with silicon solar cells; however, their commercialization has not yet been realized because of their poor long-term stability. One of the primary causes of the instability of PSC devices is the large concentration of defects in the polycrystalline perovskite film. Such defects limit the device performance besides triggering hysteresis and device instability. In this study, tetradodecylammonium bromide (TDDAB) was used as a postsurface modifier to suppress the density of defects from the mixed perovskite film (CsFAMA). X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analyses validated that TDDAB binds to the mixed perovskite through hydrogen bonding. The X-ray diffraction (XRD) and two-dimensional grazing incidence wide-angle X-ray scattering (2D GIWAXS) study uncovered that the TDDAB modification formed a capping layer of (TDDA) 2 PbI 1.66 Br 2.34 on the surface of the three-dimensional (3D) perovskite. The single charge transport device prepared from the TDDAB-modified perovskite film revealed that both the electron and hole defects were considerably repressed due to the modification. Consequently, the modified device displayed a champion PCE of 21.33%. The TDDAB surface treatment not only enhances the PCE but the bulky cation of the TDDAB also forms a hydrophobic capping surface (water contact angle of 93.39°) and safeguards the underlayer perovskite from moisture. As a result, the modified PSC has exhibited almost no performance loss after 30 days in air (RH ≈ 40%).

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.

Lead halide perovskite nanocrystal heterostructures have been extensively studied in the recent past for improving their photogenerated charge carriers mobility. However, most of such heterostructures are formed with random connections without having strong evidence of epitaxial relation. Perovskite-chalcohalides are the first in this category, where all-inorganic heterostructures are formed with epitaxial growth. Going beyond one facet, herein, different polyhedral nanocrystals of CsPbBr 3 are explored for facet-selective secondary epitaxial sulfobromide growths. Following a decoupled synthesis process, the heterojunctions are selectively established along {110} as well as {200} facets of 26-faceted rhombicuboctahedrons, the {110} facets of armed hexapods, and the {002} facets of 12-faceted dodecahedron nanocrystals of orthorhombic CsPbBr 3 . Lattice matching induced these epitaxial growths, and their heterojunctions have been extensively studied with electron microscopic imaging. Unfortunately, these heterostructures did not retain the intense host emission because of their indirect band structures, but such combinations are found to be ideal for promoting photocatalytic CO 2 reduction. The pseudo-Type-II combination helped here in the successful movement of charge carriers and also improved the rate of catalysis. These results suggest that facet-selective all-inorganic perovskite heterostructures can be epitaxially grown and this could help in improving their catalytic activities.

The maximum capacitive energy stored in polymeric dielectric capacitors, which are ubiquitous in high-power-density devices, is dictated by the dielectric breakdown strength of the dielectric polymer. The fundamental mechanisms of the dielectric breakdown, however, remain unclear. Based on a simple free-volume model of the polymer fluid state, we hypothesized that the free ends of linear polymer chains might act as "defect" sites, at which the dielectric breakdown can initiate. Thus, the dielectric breakdown strength of cyclic polymers should exhibit enhanced stability in comparison to that of their linear counterparts having the same composition and similar molar mass. This hypothesis is supported by the ∼50% enhancement in the dielectric breakdown strength and ∼80% enhancement in capacitive energy density of cyclic polystyrene melt films in comparison to corresponding linear polystyrene control films. Furthermore, we observed that cyclic polymers exhibit a denser packing density than the linear chain melts, an effect that is consistent with and could account for the observed property changes. Our work demonstrates that polymer topology can significantly influence the capacitive properties of polymer films, and correspondingly, we can expect polymer topology to influence the gas permeability, shear modulus, and other properties of thin films dependent on film density., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The power conversion efficiency (PCE) of perovskite solar cells has been showing rapid improvement in the last decade. However, still, there is an unarguable performance deficit compared with the Schockley-Queisser (SQ) limit. One of the major causes for such performance discrepancy is surface and grain boundary defects. They are a source of nonradiative recombination in the devices that not only causes performance loss but also instability of the solar cells. In this study, we employed a direct postsurface passivation strategy at mild temperatures to modify perovskite layer defects using tetraoctylammonium chloride (TOAC). The passivated perovskite layers have demonstrated extraordinary improvement in photoluminescence and charge carrier lifetimes compared to their control counterparts in both Cs 0.05 (FAPbI 3 ) 0.83 (MAPbBr 3 ) 0.17 and MAPbI 3 -type perovskite layers. The investigation on electron-only and hole-only devices after TOAC treatment revealed suppressed electron and hole trap density of states. The electrochemical study demonstrated that TOAC treatment improved the charge recombination resistance of the perovskite layers and reduced the charge accumulation on the surface of perovskite films. As a result, perovskite solar cells prepared by TOAC treatment showed a champion PCE of 21.24% for the Cs 0.05 (FAPbI 3 ) 0.83 (MAPbBr 3 ) 0.17 -based device compared to 19.58% without passivation. Likewise, the PCE of MAPbI 3 improved from 18.09 to 19.27% with TOAC treatment. The long-term stability of TOAC-passivated perovskite Cs 0.05 (FAPbI 3 ) 0.83 (MAPbBr 3 ) 0.17 devices has retained over 97% of its initial performance after 720 h in air.

Halide content of the reaction medium not only enhances the brightness of CsPbCl 3 nanocrystals but also, control the shape modulations as well as doping Mn(II) in these host nanocrystals. Correlating both the shape effect and doping, herein, an in situ reaction of nucleophile-controlled halide release was explored for monitoring facets modulations and doping in CsPbCl 3 nanocrystals. This was performed using alkyl amine as nucleophile which reacted with α-halo ketone, phenacyl chloride, to release chloride ions. Increase in amine concentration which released more Cl ions, reduced the possibility of shape transformation from perfect to truncated cubes during annealing. Similarly, for Mn(II) doping, the dopant photoluminescence intensity remained directly proportional to the amount of introduced amine nucleophiles. Quality of both doped and undoped nanocrystals obtained in this procedure remained unparallel and the method provided a strong correlation of rate of halide release with both facet modulations and doping in these nanocrystals.

Controlling the compositions of Se(VI) and Te(VI) ions in a 2D disk on 1D structures of Sb(V) chalcogenides, disk-on-rod heterostructures having three different epitaxial angles with different surface facets are reported. Te injection temperature determined the composition, ensuring heterostructure formation with trigonal Sb 2 Se x Te 3- x disks on orthorhombic Sb 2 Se 3 rods having orientation angles 180°, 135°, and 90°. The growth kinetics of disks connected at one/two heads of parent rods is manipulated using an Se precursor as a limiting reagent. Theoretical calculations established the energy minimization of different orientations, their possible formation, and suitability in energy transfer applications. Electrochemical measurements were also in agreement with theoretical calculations. Hence, this is a case study of advanced modular synthesis of disk-on-rod nanostructures, leading a step further in nanocrystal engineering for more desirable complex structures and their charge transfer property.

Two-dimensional-shaped CsPbBr 3 platelet nanocrystals are widely studied for their bright high energy emission and self-assembly. These nanostructures are in orthorhombic phase, have a square shape, and have the vertical axis [001] perpendicular to the basal plane. Moreover, these are mostly single-crystalline structures with a continuous lattice and appear like slices of cube nanocrystals. In contrast, herein, multijunction and hexagonal single crystalline 2D discs of CsPbBr 3 are reported to have all their vertical axes [100]. These are obtained by using the perovskite derivative of tetragonal Cs 3 MnBr 5 as the parent material and subsequent B-site Pb(II) introduction in the presence of phenacyl bromide at different reaction temperatures. At low temperature, multijunction discs having random orientations of two horizontal axes [010] and [001] from one to another segment are observed. Orientations of planes remained random as both coherent and incoherent twin planes were observed at their boundaries. However, the number of junctions/segments was reduced at higher temperature, and finally hexagonal single crystalline discs remained as the ultimate product. Analysis suggested that the crystal nature of parent Cs 3 MnBr 5 and temperature-dependent variation in the rate of Pb(II) insertions determined the nature of discs having randomly oriented or static planes in the entire nanostructure. Not only in 2D discs but also, 3D nanocrystals having similar segments with different orientations are formed upon Pb(II) exchange with Mn(II) alloyed cubic CsBr. Hexagonal single crystalline and segmented multijunction CsPbBr 3 discs remain unique among 2D perovskites nanostructures, and their formation mechanism indeed introduced new fundamentals of the crystallization process of these emerging energy materials.

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 with different halide ions can lead to color-tunable emissions in visible window with near-unity photoluminescence quantum yields. Extensive research has been carried out for optimizing the synthesis of these nanocrystals for the last 6 years, and thousands of research papers have been reported. However, due to the ionic nature, these nanocrystals formed instantaneously and hence, their growth kinetics could not be established yet. In most of the reactions, the formation mechanism typically followed one reaction for one size or shape principle, and their dimension tuning was achieved predominantly with thermodynamic control. There is no clear evidence yet on the decoupling growth from nucleations and monitoring their growth kinetics. Hence, the progress of understanding the fundamentals of crystal growth faced road blocks for these halide perovskite nanocrystals. Keeping eyes on all such reports on one reaction for one size and one reaction for tunable size of the most widely studied CsPbBr 3 nanocrystals, in this perspective, details of their size tunability are analyzed and reported. In addition, comparison of the classical mechanism, obstacles for establishing secondary growth, and possible road maps for controlling the kinetic parameters of formation of these nanocrystals are also discussed., Competing Interests: The author declares no competing financial interest., (© 2022 The Author. Published by American Chemical Society.)

Physical insights related to ion equilibrium involved in the synthesis of lead halide perovskite nanocrystals remain key parameters for regulating the phase stability and luminescence intensity of these emerging materials. These have been extensively studied since the development of these nanocrystals, and different reaction processes controlling the formation of CsPbX 3 nanocrystals are largely understood. However, growth kinetics related to the formation of these nanocrystals have not been established yet. Hence, more fundamental understanding of the formation processes of these nanocrystals is urgently required. Keeping these in mind and emphasizing the most widely studied nanocrystals of CsPbBr 3 , different equilibrium processes involved in their synthesis for phase and composition variations are summarized and discussed in this Perspective. In addition, implementations of these findings for shape modulations by growth are discussed, and several new directions of research for understanding more fundamental insights are also presented.

Semiconductor nanocrystals coupled with plasmonic Au nanoparticles have been widely studied as photoelectrocatalysts for solar water splitting. Among these, heterostructures of copper chalcogenides with Au remained a unique category for their dual plasmon character. However, while sulfides and selenides of copper have been extensively reported, heterostructures of copper tellurides with Au have not been explored. Herein, the plasmonic semiconductor Cu 2- x Te disks grown on Au nanoparticles (disk-on-dot) were explored as efficient photoelectrocatalysts for hydrogen evolution reactions (HER). This has been successfully designed by growing Cu 2- x Te disks on presynthesized Au nanoparticles under optimized reaction conditions. The resulting heterostructured nanocrystals acted as efficient photoelectrocatalysts for the H 2 evolution reaction with a low Tafel slope and less cathodic overpotential in the presence of light. Details of their synthesis, characterization, optical properties, and electrocatalytic activities are studied and reported in this letter.

The increase of the stability of perovskite nanocrystals with respect to exposure to polar media, layers growth, or shelling with different materials is in demand. While these are widely studied for metal chalcogenide nanocrystals, it has yet to be explored for perovskite nanocrystals. Even growth of a single monolayer on any facet or on the entire surface of these nanocrystals could not be established yet. To address this, herein, a secondary growth approach leading to creation of a secondary lattice with subsequent expansion on preformed CsPbBr 3 perovskite nanocrystals is reported. As direct layer growth by adding precursors was not successful, Cs-lattice extension to preformed CsPbBr 3 nanocrystals was performed by coupling CsBr to these nanocrystals. Opening both {110}/{002} and {200} facets of parent CsPbBr 3 nanocrystals, CsBr was observed to be connected with lattice matching to the {200} facets. Further with Pb(II) incorporation, the Cs-sublattices of CsBr were expanded to CsPbBr 3 and led to cube-couple nanocrystals. However, as cubes in these nanostructures were differently oriented, these showed lattice mismatch at their junctions. This lattice mismatch though restricted complete shelling but successfully favored the secondary growth on specific facets of parent CsPbBr 3 nanocrystals. Details of this secondary growth via lattice extension and expansion are microscopically analyzed and reported. These results further suggest that lead halide perovskite nanocrystals can be epitaxially grown under proper reaction design and more complex as well as heterostructures of these materials can be fabricated to meet the current demands.

Light emitting lead halide perovskite nanocrystals are currently emerging as the workhorse in quantum dot research. Most of these reported nanocrystals are isotropic cubes or polyhedral; but anisotropic nanostructures with controlled anisotropic directions still remain a major challenge. For orthorhombic CsPbBr 3 , the 1D shaped nanostructures reported are linear and along either of the axial directions ⟨100⟩. In contrast, herein, spiral CsPbBr 3 perovskite nanorods in the orthorhombic phase are reported with unusual anisotropy having (101) planes remaining perpendicular to the major axis [201]. While these nanorods are synthesized using the prelattice of orthorhombic Cs 2 CdBr 4 with Pb(II) diffusion, the spirality is controlled by manipulation of the compositions of alkylammonium ions in the reaction system which selectively dissolve some spiral facets of the nanorods. Further, as spirality varied with facet creation and elimination, these nanorods were explored as photocatalysts for CO 2 reduction, and the evolution of methane was also found to be dependent on the depth of the spiral nanorods. The entire study demonstrates facet manipulation of complex nanorods, and these results suggest that even if perovskites are ionic in nature, their shape could be constructed by design with proper reaction manipulation.

Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

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.

Recently, halide perovskites have emerged as a promising material for device applications. Lead-based perovskites have been widely explored, while investigation of the optical properties of lead-free perovskites remains limited. Lead-halide perovskite single crystals have shown light-induced positive photoconductivity, and as lead-free perovskites are optically active, they are expected to demonstrate similar properties. However, we report here light-induced negative photoconductivity with slow recovery in lead-free Cs 3 Bi 2 Cl 9 perovskite. Femtosecond transient reflectance (fs-TR) spectroscopy studies further reveal that these electronic transport properties are due to the formation of light-activated metastable trap states within the perovskite crystal. The figure of merits were calculated for Cs 3 Bi 2 Cl 9 single-crystal detectors, including responsivity (17 mA/W), detectivity (6.23 × 10 11 Jones), and the ratio of current in dark to light (∼7160). These observations for Cs 3 Bi 2 Cl 9 single crystals, which were optically active but showed retroactive photocurrent on irradiation, remain unique for such materials.

ConspectusThe interactions of halides and ammonium ions with lead halide perovskite nanocrystals have been extensively studied for improving their phase stability, controlling size, and enhancing their photoluminescence quantum yields. However, all these nanocrystals, which showed intense and color tunable emissions, mostly retained the six faceted cube or platelet shapes. Shape tuning needs the creation of new facets, and instead of composition variations by foreign ions interactions/substitutions, these require facet stabilizations with suitable ligands. Among most of the reported cases of lead halide perovskites, alkyl ammonium ions are used as a capping agent, which substituted in the surface Cs(I) sites of these nanocrystals. Hence, new surface ligands having a specific binding ability with different facets other than those in cube/platelet shapes are required for bringing stability to new facets and, hence, for tuning their shapes.In this Account, interactions of alkyl ammonium ions on the surface of perovskite nanocrystals and their impact on surface reconstructions are reviewed. Emphasizing the most widely studied CsPbBr 3 nanocrystals, the usefulness and impact of alkyl ammonium ions on the phase stability, high-temperature annealing, enhancement of the brightness and doping in these nanocrystals are first discussed. Then, nanocrystals formed under limited primary alkyl ammonium ions and also with specific tertiary ammonium ions having new facets are elaborated. Further, the treatment of excess alkyl ammonium halides to these newly formed multifaceted polyhedron nanocrystals under different conditions, which led to armed and step-armed structures, are discussed. The change in optical properties during these shape transformations is also presented. Finally, the shape-change mechanism with alkyl ammonium halide-induced dissolutions of {200} and {112} facets and formation of {110} and {002} facets are discussed. Further, in summary, future prospects of new ligand designing for stabilizing new facets of perovskite nanocrystals and obtaining new shapes and properties are proposed.

Bright lead halide perovskite nanocrystals, which have been extensively studied in the past 5 years, are mostly confined to a six faceted hexahedron (cube/platelet) shape. With variations of ligand, precursor, reaction temperature, and surface modification, their brightness has been enhanced and phase became stable, but ultimate nanocrystals still retained the hexahedron cube or platelet shape in most of the hot injection reactions. In contrast, by exploration of α-halo ketone in amine as a halide precursor, different shaped nanocrystals without compromising the photoluminescence quantum yield (PLQY) are reported. Confining to orthorhombic CsPbBr 3 , the obtained nanocrystals are stabilized by 12 facets ({200}, {020}, {112}) and led to 12 faceted rhombic dodecahedrons. These facets are absolutely different from six ({110}, {002}) equivalent facets of widely reported orthorhombic cube shaped CsPbBr 3 nanocrystals. These also retained the colloidal and phase stability, as well as showed near unity PLQY. With further annealing, these are transformed to 26 faceted rhombicuboctahedrons by dissolving all their vertices. Importantly, these 12 faceted nanocrystals showed wide area self-assembly in most of the reactions. It has also been concluded that primary ammonium ions led to six faceted nanocrystals, but tertiary ammonium ions obtained in this case stabilized different group of facets. While perovskite nanocrystals were broadly confined to only nanocubes, these new nanocrystals with intense emission would certainly provide a new avenue for continuing their further research.

In current research, halide perovskite nanocrystals have emerged as one of the potential materials for light-harvesting and photovoltaic applications. However, because of phase sensitivity, their exploration as photocatalysts in polar mediums is limited. It has been recently reported that these nanocrystals are capable of driving solar-to-chemical production through CO 2 reduction. Using bare nanocrystals and also coupling in different supports, several reports on CO 2 reduction in low polar mediums were reported, and the mechanism of involved redox processes was also proposed. Considering the importance of this upcoming catalytic activity of perovskites, in this Perspective, details of the developments in the field established to date and supported by several established facts are reported. In addition, some unestablished stories or unsolved pathways surrounding the redox process and the importance of using a polar solvent which confused the understanding of the exclusive roles of perovskite nanocrystals in catalysis are also discussed. Further, the future prospects of these materials that face challenges in dispersing in polar solvents, a key process in redox catalysis for CO 2 reduction, are also discussed.

Synthetic ion transporters have attracted tremendous attention for their therapeutic potential against various ion-transport-related diseases, including cancer. Inspired by the structure and biological activities of natural products, we synthesized a small series of squaramide and thiourea derivatives of quinine and investigated their ion transport activities. The involvement of a quinuclidine moiety for the cooperative interactions of Cl - and H + ions with the thiourea or squaramide moiety resulted in an effectual transport of these ions across membranes. The interference of ionic equilibrium by the potent Cl - ion carrier selectively induced cancer cell death by endorsing caspase-arbitrated apoptosis. In vivo assessment of the potent ionophore showed an efficient reduction in tumor growth with negligible immunotoxicity to other organs.

Light-emitting lead halide perovskite nanocrystals are typically obtained in a six-faceted cube shape. However, for applications such as catalysis, more active facets for the adsorption/desorption of reactants/products and the suppression of carrier recombination are essentially required. To meet these challenges, herein CsPbBr 3 perovskite nanocrystals in cube and faceted noncube shapes were explored for photocatalytic reductions of CO 2 . Importantly, halide-deficient dim multifaceted noncube emitters having less than 1% photoluminescence quantum yields showed superior catalytic activity compared to that of bright halide-rich cube nanocrystals. Beyond these, hexapod-shaped nanocrystals were also explored, and these remained in an intermediate state. With the support of density functional theory, the adsorption and desorption probabilities of reactants/products on different facets were also calculated and correlated with experimental findings. These results indicated that facets and defects of perovskite nanocrystals are equally important for carrying out catalytic reactions.

Connecting nanocrystals with removal of interface ligand barriers is one of the key steps for efficient carrier transportation in optoelectronic device fabrication. Typically, ion migration for crystal deformation or connection with other nanocrystals needs a solvent as medium. However, on the contrary, this has been observed for CsPbBr 3 perovskite nanocrystals in film where nanocrystals were swollen to get wider and fused with adjacent nanocrystals in self-assembly on film during solvent evaporation. Depending on precursor composition and exposed facets, again these connections could be programmed for tuning their connecting directions leading to different shapes. Aging further on solid substrate, these were also turned to continuous film of nanostructures eliminating all interparticle gaps on the film. This transformation could be ceased at any point of time, simply by heating or adding sufficient ligands. Analysis suggested that these unique and controlled connections were only observed with polyhedron shaped nanostructures with certain compositions and not with traditionally cubes. Details of this solid-surface transformation during solvent evaporation were analyzed, and an interparticle material transfer type mechanism was proposed. As these observations were not seen in chalcogenide and oxide nanocrystals and exclusively observed in perovskite nanocrystals, this would add new fundamentals to the insights of crystal growths of nanocrystals and would also help in obtaining films of connecting nanocrystals.

Red emitting α-CsPbI 3 nanocrystals are highly phase sensitive to ambient exposure, and B-site doping with suitable cations is adopted as one of the most feasible approaches for their phase stability. There are several reports herein: Ni(II) ions having the smallest transition metal Shannon radii were explored for doping in these nanocrystals. This successfully stabilized the cubic phase and retained the intense emission of nanocrystals for nearly 2 months. Being the smallest ion, the halide octahedra in the perovskite lattice were expected to provide high restraint ability toward δ-CsPbI 3 . Comparing with postsynthesis iodide treatments, the importance of doping in high temperature reaction was discussed. Finally, these doped nanocrystals were explored for photovoltaic devices and showed comparable efficiency (9.1%) to different other similar doped nanocrystals. Hence, the finding reported here is a step forward for understanding the insights of phase stability of α-CsPbI 3 perovskite nanocrystals.

Lead halide perovskite nanocrystals have recently emerged as an efficient optical material for light harvesting. While these have been extensively studied for obtaining bright emissions, their use as catalysts for enhancing the rate of chemical reactions has been explored little. Considering their importance in catalysis, herein, Fe(II)-doped CsPbBr 3 perovskite nanocrystals have been explored for photocatalytic reduction of CO 2 . In comparison to undoped CsPbBr 3 , doped nanocrystals showed enhanced catalytic activity and also predominantly led to evolution of CH 4 instead of CO. The observation of a reverse trend of predominated CH 4 evolution in doped nanocrystals rather than CO observed for undoped nanocrystals was correlated to the adsorption/desorption energy of respective products established theoretically earlier. This selective evolution of major products on doping remained unique and also a step forward for understanding more regarding light to chemical energy conversions using perovskite nanocrystals.

Insights of Mn(II) doping in CsPbCl 3 -armed hexapod nanostructures is reported. These complex structures were typically formed in halide concentration tuned modulated reactions. Cores were first formed under halide deficient condition and with enriching halides; these were transformed to armed structures. Doping of Mn(II) was observed facilitated during the arm growth in the second stage of the reaction. These observations were supported with decoupled reactions with minimized and maximized halide concentrations carried out in separate reactions. However, less interference for the exciton to dopant energy transfer was noticed for the defect states created in halide-deficient medium, and the intensity of the dopant emission remained proportional to the amount of dopant inserted in the nanocrystals. Being this is an in situ observation in the coupled reactions of both poor and rich halide reaction systems, the finding would strengthen the understanding of doping in perovskite host nanocrystals.

Highly emissive isotropic CsPbX 3 (X = Cl, Br, and I) perovskite nanocrystals are typically observed in a six-faceted cube shape. When a unique approach is adopted and the reaction medium is enriched with halides, arm growth on all six facets was carried out and reported. Analysis suggested that these armed nanostructures were obtained from intermediate polyhedron shaped structures having 26 facets, and these were formed under halide-deficient conditions. Surface energy calculations further supported the possible existence of all facets for both of these structures under different halide composition environments. The entire study was first explored for CsPbBr 3 and then extended to CsPbCl 3 ; however, for CsPbI 3 nanocrystals, Sr(II) dopant was used for obtaining stable emission. Arm lengths could also be tuned with a function of reaction temperature for CsPbBr 3 . Formation of stable facets in polyhedron shaped nanostructures and their transformation to respective hexapods under halide-deficient and halide-rich conditions add new fundamental concepts for these nanostructures and their shape evolutions.

Understanding physical insights of making different lead halide perovskite nanocrystals remains in limelight of current research because of their strong emission that is tunable in the entire visible spectrum. Optimizing reaction parameters, intensifying the emission, modulating A, B, and X sites to bring optical and phase stability, understanding the interface and ligand chemistry, investigating the growth kinetics, tuning the dimension, making heterostructures, etc. were intensively studied. In addition, several aspects of colloidal nanocrystals such as time-dependent growth and obtaining size-tunable nanocrystals as a function of time from one reaction, controlling anisotropic growth or stabilizing other than the six facets of cubes, formation of various heterostructures with epitaxial growths, etc. could not be established largely. Hence, while the field is emerging among efficient optically active materials, addressing these issues by summarizing different directions of research became important. Under these prospects, this Perspective focuses on top developments in the field of synthesis modulations where success has been achieved and also summarizes several directions of research where physical insights still could not be understood broadly.

Doping Mn 2+ in semiconductor nanocrystals is widely known for its long-lifetime Mn d-d orange emission. While this had been extensively studied for chalcogenide nanostructures, recently this was also extended to perovskite nanocrystals. Being that CsPbCl 3 has a wide bandgap, the exciton energy transfer was found to be more efficient, but the dopant-induced photoluminescence was also obtained for layered perovskites and quantum-confined CsPbBr 3 nanocrystals. In recent years significant advances have been achieved in understanding the physical insights of doping following various approaches and optimizing the conditions for obtaining intense dopant emission. In addition, several new properties associated with these doped nanocrystals were also reported, and by modulating the compositions, the host bandgap and the dopant emission positions were also tuned. Keeping all of these developments in mind, this Perspective focuses on the insights of doping and the photoluminescence properties of Mn 2+ -doped perovskite nanocrystals. In addition, it also proposes possible future prospects of both synthesis and optical properties of these nanomaterials.

Doping Mn(II) in inorganic Ruddlesden-Popper phase Cs 2 PbCl 2 I 2 perovskite nanoplatelets is reported. The host nanostructures were prepared with a calculative protocol taking the exact required composition of Cs(I) and Pb(II) and injecting the preformed mixed oleylammonium chlorides and iodides at optimized reaction temperature. Reactions were optimized with various halides and their mixtures, but the stable phase of the Cs 2 PbX 4 system was obtained only for the chloride-iodide mixed-halide system. Introduction of Mn(II) along with Pb(II), resulted in successful light-emitting doped nanocrystals. Measuring the photoluminescence and the decay lifetimes at room and liquid nitrogen temperatures, the variations in the excitonic, self-trapped, and Mn dopant emission properties were compared with those of the chalcogenide and perovskite nanocrystals.

Pretreatment using metal chlorides during the formation of halide deficient free perovskite nanocrystals is reported. Among several metal chlorides, Cu(II)Cl 2 was observed to be ideal for the synthesis of highly emitting CsPbCl 3 nanocrystals at high reaction temperature. Because high temperature remained more favorable for the dopant insertion, doping of Mn(II) was carried out under this halide-rich system, and nearly 68% photoluminescence quantum yield was recorded. Analysis could not provide strong evidence of insertion of Cu(II) inside the nanocrystals; rather, it was established that Cu(II)Cl 2 in the system helped to stabilize the reaction even at and above 260 °C and provided an adequate chloride source for obtaining the highly emitting host as well as doped nanocrystals. Details of the physical process involved for this metal ion-induced uplifting of the reaction temperature and the consequent impacts on the nanocrystal formation are studied in detail and reported in this Letter.

Impact of acid-amine equilibrium for triggering the formation of CsPbBr 3 platelets and subsequent long-range self-assembly as a function of acid concentration is reported. The study was performed by treating Cs precursor followed by oleic acid to the ongoing process of L 2 PbBr 4 layered perovskites formation at room temperature, and this led to the thinnest possible platelets of CsPbBr 3 with one atomic layer of Cs insertion. These platelets form self-assembly in the micrometer range, and this ordering was tuned as a function of oleic acid concentration and reaction time. With evidence obtained from in situ live monitoring by optical microscopy of these assemblies during the ongoing reaction in solution and analyzing the collected samples ex situ by electron microscopy, it was established that these long-range 1D organizations of platelets took place in solution. Details of the insights of the formation, self-assembly, and impact of different reaction parameters in the formation of these platelets are investigated and reported in this Letter.

Insights into the formation mechanism of a dual-layered and doped heterostructure material Sn II S-Sn IV :Sb 2 S 3 are reported. In the presence of mixed alkyl thiols, first nanotubes of Sb 2 S 3 were formed, and upon introduction of Sn(IV), Sn II S was deposited onto the surface of these tubular structures. Upon further annealing at a constant temperature, sluggish transformation resulted in a Sn(II)S-Sn(IV) doped Sb 2 S 3 heterostructure, which finally turned to flake-like layered doped Sb 2 S 3 nanostructures. SnS and Sb 2 S 3 , both being layered materials, were explored for the study of Na-ion storage, and these heterostructures were observed to be superior in comparison to the individual materials as well as the final doped nanostructures. The mechanism of formation of the heterostructures, the epitaxy at the junction, the diffusion doping, and the dopant-induced axial exfoliations leading to the final doped structures were studied. The electrochemical conversions in the presence of Na ions were also investigated, and insights into the mechanisms of both are reported in this Letter.

High-energy-emitting CsPbCl 3 nanocrystals have shown significant loss and enhancement of their emission intensity (∼40-50 folds) during purification and surface treatments, respectively. This confirms that the surfaces of these nanocrystals are very sensitive. In this Letter, physical insights of the interface bindings on the surface of these blue-emitting CsPbCl 3 nanocrystals with different passivating agents and their consequential impact on purification are investigated. Using various metal chlorides irrespective of the charge and size of the metal ions, metal acetates, and nonmetal chloride, the predominant influence of chloride ions in helping retrieve/intensify the blue emission is established. The purification processes are observed to be very delicate, and successive purifications with introduction of polar nonsolvents led to the transformation of an emitting cubic CsPbCl 3 phase to nonemitting tetragonal CsPb 2 Cl 5 phase nanocrystals irreversibly. The impact of various salt additions only temporarily helped in enhancing the emission, but the phase change remained inevitable upon successive purification. However, as a remedy, by in situ use of alkylammonium chloride salt in high-temperature reactions, the surface binding was improved, and significant emission as well as the phase could be retained with successive purifications.

Annealing perovskite nanocrystals at high reaction temperature changes their crystal phase, shape, and optical properties. Carrying out reactions between 180 and 250 °C, the impact of thermal annealing for CsPbCl 3 and CsPbBr 3 nanocrystals in a reaction flask was investigated here. At higher temperature, a phase change was observed instantly, which could not be trapped even with ice-bath cooling. Interestingly, using a calculated amount of preformed alkylammonium halides as dual passivating agents, the nanocrystals of both CsPbCl 3 and CsPbBr 3 could even be stabilized for hours of annealing at 250 °C. CsPbCl 3 , which was reported to be a poor emissive nanocrystal in comparison to CsPbBr 3 , could sustain even more than 5 h of annealing at 250 °C and recorded ∼51% absolutely quantum yield. Details of the interface chemistry and the role of the used dual passivating agent for providing thermal stability are studied and reported in this Letter.

Synthetic anion transporters have been recognized as one of the potential therapeutic agents for the treatment of diseases including cystic fibrosis, myotonia, and epilepsy that originate due to the malfunctioning of natural Cl - ion transport systems. Recent studies showed that the synthetic Cl - ion transporters can also disrupt cellular ion-homeostasis and induce apoptosis in cancer cell lines, leading to a revived attention for synthetic Cl - ion transporters. Herein, we report the development of conformationally controlled 1,2-diphenylethylenediamine-based bis(thiourea) derivatives as a new class of selective Cl - ion carrier. The strong Cl - ion binding properties ( K d = 3.87-6.66 mM) of the bis(thiourea) derivatives of diamine-based compounds correlate well with their transmembrane anion transport activities (EC 50 = 2.09-4.15 nM). The transport of Cl - ions via Cl - /NO 3 - antiport mechanism was confirmed for the most active molecule. Perturbation of Cl - ion homeostasis by this anion carrier induces cell death by promoting the caspase-mediated intrinsic pathway of apoptosis.