Epitaxial Heterostructures of CsPbBr3 Perovskite Nanocrystals with Post-transition Metal Bismuth.

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 CsPbBr3 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 CsPbBr3 and octahedral Bi(0). A high reaction temperature and the presence of alkylamine kept Bi(III) in reduced form and helped in sustaining these CsPbBr3-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 CsPbBr3 are discussed.

CsPbBr3 Perovskite Crack Platelet Nanocrystals and Their Biexciton Generation.

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 CsPbBr3 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.

Pt-CsPbBr3 Perovskite Nanocrystal Heterostructures: All Epitaxial.

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 CsPbBr3 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) CsPbBr3 with {020} of cubic Pt and again (011) of CsPbBr3 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.

Vertex-Oriented Cube-Connected Pattern in CsPbBr3 Perovskite Nanorods and Their Optical Properties: An Ensemble to Single-Particle Study.

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 CsCdBr3 and product orthorhombic CsPbBr3 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.

Transformation of Metal Halides to Facet-Modulated Lead Halide Perovskite Platelet Nanostructures on A-Site Cs-Sublattice Platform.

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 Cs7Cd3Br13 platelets as the parent material, herein, a slower diffusion of Pb(II) leading to facet-modulated CsPbBr3 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 CsPbBr3 platelet nanostructures. These platelets having different facets were also explored for catalytic CO2 reduction, and their catalytic rates were compared.

Facet Engineering for Amplified Spontaneous Emission in Metal Halide Perovskite Nanocrystals.

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 CsPbBr3 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.

Halide Perovskite Single Crystals and Nanocrystal Films as Electron Donor-Acceptor Heterojunctions.

Halide perovskites are materials for future optical displays and solar cells. Electron donor-acceptor perovskite heterostructures with distinguishing halide compositions are promising for transporting and harvesting photogenerated charge carriers. Combined e-beam lithography and anion exchange are promising to develop such heterostructures but challenging to prepare multiple heterojunctions at desired locations in single crystals. We demonstrate swift laser trapping-assisted band gap engineering at the desired locations in MAPbBr3 microrods, microplates, or nanocrystal thin films. The built-in donor-acceptor double and multi-heterojunction structures let us transport and trap photogenerated charge carriers from wide-band gap bromide to narrow-band gap iodide domains. We discuss the charge carrier transport and trapping mechanisms from the viewpoints of engineered bands and band continuity. This work offers a convenient method for designing single-, double- and multi-heterojunction donor-acceptor halide perovskites for photovoltaic, photonic, and electronic applications.

Tuning Crystal Plane Orientation in Multijunction and Hexagonal Single Crystalline CsPbBr3 Perovskite Disc Nanocrystals.

Two-dimensional-shaped CsPbBr3 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 CsPbBr3 are reported to have all their vertical axes [100]. These are obtained by using the perovskite derivative of tetragonal Cs3MnBr5 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 Cs3MnBr5 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 CsPbBr3 discs remain unique among 2D perovskites nanostructures, and their formation mechanism indeed introduced new fundamentals of the crystallization process of these emerging energy materials.

Facets-Directed Epitaxially Grown Lead Halide Perovskite-Sulfobromide Nanocrystal Heterostructures and Their Improved Photocatalytic Activity.

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 CsPbBr3 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 CsPbBr3. 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 CO2 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.

Alkylammonium Halides for Facet Reconstruction and Shape Modulation in Lead Halide Perovskite Nanocrystals.

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 CsPbBr3 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.

Introducing B-Site Cations by Ion Exchange and Shape Anisotropy in CsPbBr3 Perovskite Nanostructures.

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 Cs2ZnBr4 with the complete replacement of Zn tetrahedra by Pb octahedra, dimension-tunable anisotropic nanocrystals of CsPbBr3 are reported. This B-site ion introduction led to CsPbBr3 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 Cs2ZnBr4 and also the facets of transformed CsPbBr3. While similar experiments are extended to orthorhombic Cs2HgBr4, 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.

Chemically Spiraling CsPbBr3 Perovskite Nanorods.

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 CsPbBr3, the 1D shaped nanostructures reported are linear and along either of the axial directions ⟨100⟩. In contrast, herein, spiral CsPbBr3 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 Cs2CdBr4 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 CO2 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.

Light-Emitting Metal-Organic Halide 1D and 2D Structures: Near-Unity Quantum Efficiency, Low-Loss Optical Waveguide and Highly Polarized Emission.

Organic-inorganic metal-halide materials (OIMMs) with zero-dimensional (0D) structures offer useful optical properties with a wide range of applications. However, successful examples of 0D structural OIMMs with well-defined optical performance at the micro-/nanometer scale are limited. We prepared one-dimensional (1D) (DTA)2 SbCl5 ⋅DTAC (DTAC=dodecyl trimethyl ammonium chloride) single-crystal microrods and 2D microplates with a 0D structure in which individual (SbCl5 )2- quadrangular units are completely isolated and surrounded by the organic cation DTA+ . The organic molecular unit with a long alkyl chain (C12 ) and three methyl groups enables microrod and -plate formation. The single-crystal microrods/-plates exhibit a broadband orange emission peak at 610 nm with a photoluminescence quantum yield (PLQY) of ca. 90 % and a large Stokes shift of 260 nm under photoexcitation. The broad emission originates from self-trapping excitons. Spatially resolved PL spectra confirm that these microrods exhibit an optical waveguide effect with a low loss coefficient (0.0019 dB µm-1 ) during propagation, and linear polarized photoemission with a polarization contrast (0.57).

α-Halo Ketone for Polyhedral Perovskite Nanocrystals: Evolutions, Shape Conversions, Ligand Chemistry, and Self-Assembly.

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 CsPbBr3, 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 CsPbBr3 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.

Facets Directed Connecting Perovskite Nanocrystals.

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 CsPbBr3 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.

Color Tunable Self-Trapped Emissions from Lead-Free All Inorganic IA-IB Bimetallic Halides Cs-Ag-X (X = Cl, Br, I).

Multi-metallic halides of group IA and IB metals are emerged as a new class of color tunable emitters. While chalcogenides and perovskites are extensively studied, these families of materials are little explored. In comparison, herein, lead and cadmium free bimetallic Cs-Ag-X (X = Cl, Br, I) halides are reported where the larger ion Ag+ helped in incorporating all the halide ions which in turn tune their emission color in spanning from 397 nm (violet) to 820 nm (near infrared) as a function of their composition. The synthesis method adopted here is the solvent free ball milling of respective halides of Cs and Ag and took the record shortest time and in bulk scale. From decay lifetimes, emissions from these bimetallic halides are found as a result of fast recombination of self-trapped excitons, which exhibited not only reasonably high quantum yield in the range of 17-68% but also excellent stability to air and moisture under ambient conditions. These also show wide Stokes shift with relatively longer decay lifetimes ranging above the exciton and below the surface trap or dopant induced emissions of inorganic semiconductors, indicating a new class of materials having unique identity of their optical behaviors.

Arm Growth and Facet Modulation in Perovskite Nanocrystals.

Highly emissive isotropic CsPbX3 (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 CsPbBr3 and then extended to CsPbCl3; however, for CsPbI3 nanocrystals, Sr(II) dopant was used for obtaining stable emission. Arm lengths could also be tuned with a function of reaction temperature for CsPbBr3. 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.

Near-Unity Photoluminescence Quantum Efficiency for All CsPbX3 (X=Cl, Br, and I) Perovskite Nanocrystals: A Generic Synthesis Approach.

In a generic synthesis approach, all three CsPbX3 (X=Cl, Br and I) perovskite nanocrystals having near unity quantum yields is reported. This has been achieved by injecting the desired amount of preformed alkylammonium halide salts which acted as a dual source providing halide ions and the capping agent to an equimolar amount of non-halide Pb and Cs precursors in a reaction flask at an optimized reaction temperature. The composition sensitivity of Pb to Cs ratio, high temperature reaction, and injection of ammonium halide remained the key parameters for obtaining the high quantum yields. Details of the reaction process, use of different reagents and setting up the reaction parameters are reported.

Modulated Triple-Material Nano-Heterostructures: Where Gold Influenced the Chemical Activity of Silver in Nanocrystals.

For efficient charge separations, multimaterial hetero-nanostructures are being extensively studied as photocatalysts. While materials with one heterojunction are widely established, the chemistry of formation of multijunction heterostructures is not explored. This needs a more sophisticated approach and modulations. To achieve these, a generic multistep seed mediated growth following controlled ion diffusion and ion exchange is reported which successfully leads to triple-material hetero-nanostructures with bimetallic-binary alloy-binary/ternary semiconductors arrangements. Ag2 S nanocrystals are used as primary seeds for obtaining AuAg-AuAgS bimetallic-binary alloyed metal-semiconductor heterostructures via partial reduction of Ag(I) using Au(III) ions. These are again explored as secondary seeds for obtaining a series of triple-materials heterostructures, AuAg-AuAgS-CdS (or ZnS or AgInS2 ), with introduction of different divalent and trivalent ions. Chemistry of each step of the gold ion-induced changes in the rate of diffusion and/or ion exchanges are investigated and the formation mechanism for these nearly monodisperse triple material heterostructures are proposed. Reactions without gold are also performed, and the change in the reaction chemistry and growth mechanism in presence of Au is also discussed.

Phase-Stable CsPbI3 Nanocrystals: The Reaction Temperature Matters.

High temperature colloidal synthesis for obtaining thermal, colloidal and phase-stable CsPbI3 nanocrystals with near-unity quantum yield is reported. While standard perovskite synthesis reactions were carried out at 160 °C (below 200 °C), increase of another ≈100 °C enabled the alkylammonium ions to passivate the surface firmly and prevented the nanocrystals from phase transformation. This did not require any inert atmosphere storage, use of heteroatoms, specially designed ligands, or the ice cooling protocol. Either at high temperature in reaction flask or in the crude mixture or purified dispersed solution; these nanocrystals were observed stable and retained the original emission. Different spectroscopic analyses were carried out and details of the surface binding of alkyl ammonium ligands in place of surface Cs in the crystal lattice were investigated. As CsPbI3 is one of the most demanding optical materials, bringing stability by proper surface functionalization without use of secondary additives would indeed help in wide spreading of their applications.