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.

Partial Chemicalization of Nanoscale Metals: An Intra-Material Transformative Approach for the Synthesis of Functional Colloidal Metal-Semiconductor Nanoheterostructures.

Heterostructuring colloidal nanocrystals into multicomponent modular constructs, where domains of distinct metal and semiconductor phases are interconnected through bonding interfaces, is a consolidated approach to advanced breeds of solution-processable hybrid nanomaterials capable of expressing richly tunable and even entirely novel physical-chemical properties and functionalities. To meet the challenges posed by the wet-chemical synthesis of metal-semiconductor nanoheterostructures and to overcome some intrinsic limitations of available protocols, innovative transformative routes, based on the paradigm of partial chemicalization, have recently been devised within the framework of the standard seeded-growth scheme. These techniques involve regiospecific replacement reactions on preformed nanocrystal substrates, thus holding great synthetic potential for programmable configurational diversification. This review article illustrates achievements so far made in the elaboration of metal-semiconductor nanoheterostructures with tailored arrangements of their component modules by means of conversion pathways that leverage on spatially controlled partial chemicalization of mono- and bi-metallic seeds. The advantages and limitations of these approaches are discussed within the context of the most plausible mechanisms underlying the evolution of the nanoheterostructures in liquid media. Representative physical-chemical properties and applications of chemicalization-derived metal-semiconductor nanoheterostructures are emphasized. Finally, prospects for developments in the field are outlined.

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.

Hexahedron Symmetry and Multidirectional Facet Coupling of Orthorhombic CsPbBr3 Nanocrystals.

The cube shape of orthorhombic phase CsPbBr3 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 CsPbBr3 nanostructures.

Chemically Sculpturing the Facets of CsPbBr3 Perovskite Platelet Nanocrystals.

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 CsPbBr3 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 CsPbBr3 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.

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.

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.

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.

Nucleophile-Controlled Halide Release from the Substitution Reaction of Haloketone for Facet Tuning and Manganese Doping in CsPbCl3 Nanocrystals.

Halide content of the reaction medium not only enhances the brightness of CsPbCl3 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 CsPbCl3 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.

Epitaxial Orientation Angle Tuned Disk-on-Rod Nanoheterostructures for Boosting Charge Transfer.

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 Sb2SexTe3-x disks on orthorhombic Sb2Se3 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.

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.

Cs3Bi2I9 nanodiscs with phase and Bi(III) state stability under reductive potential or illumination for H2 generation from diluted aqueous HI.

The increasingly popular, lead-free perovskite, Cs3Bi2I9 has a vulnerable Bi3+ state under reductive potentials, due to the high standard reduction potential of Bi3+/Biδ+ (0 < δ < 3). Contrary to this fundamental understanding, herein, ligand-coated Cs3Bi2I9 nanodiscs (NDs) demonstrate outstanding electrochemical stability with up to -1 V versus a saturated calomel electrode in aqueous 0.63 M (5% v/v) and 6.34 M (50% v/v) hydroiodic acid (HI), with a minor BiI3 fraction due to the unavoidable partial aqueous disintegration of the perovskite phase after 8 and 16 h, respectively. A dynamic equilibrium of saturated 0.005 M NDs maintains the common ion effect of I-, and remarkably stabilizes ∼93% Bi3+ in 0.63 M HI under a strong reductive potential. In comparison, the hexagonal phase of bulk Cs3Bi2I9 disintegrates considerably in the semi-aqueous media. Lowering the concentration of synthetic HI from the commonly used ∼50% v/v by elevating the pH from -0.8 to 0.2 helps in reducing the cost per unit of H2 production. Our Cs3Bi2I9 NDs with a hexagonal lattice have 4-6 (002) planes stacked along the c-axis. With 0.005 M photostable NDs, 22.5 µmol h-1 H2 is photochemically obtained within 8 h in a 6.34 M HI solution. Electrocatalytic H2 evolution occurs with a turnover frequency of 11.7 H2 per s at -533 mV and outstanding operational stability for more than 20 h.

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.

Growth of Lead Halide Perovskite Nanocrystals: Still in Mystery.

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 CsPbBr3 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.

Equilibriums in Formation of Lead Halide Perovskite Nanocrystals.

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 CsPbX3 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 CsPbBr3, 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.

Au-Cu2-xTe Plasmonic Heteronanostructure Photoelectrocatalysts.

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 Cu2-xTe 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 Cu2-xTe disks on presynthesized Au nanoparticles under optimized reaction conditions. The resulting heterostructured nanocrystals acted as efficient photoelectrocatalysts for the H2 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.

Cs-Lattice Extension and Expansion for Inducing Secondary Growth of CsPbBr3 Perovskite Nanocrystals.

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 CsPbBr3 perovskite nanocrystals is reported. As direct layer growth by adding precursors was not successful, Cs-lattice extension to preformed CsPbBr3 nanocrystals was performed by coupling CsBr to these nanocrystals. Opening both {110}/{002} and {200} facets of parent CsPbBr3 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 CsPbBr3 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 CsPbBr3 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.

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.

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.