Topological polarons in halide perovskites.

Halide perovskites emerged as a revolutionary family of high-quality semiconductors for solar energy harvesting and energy-efficient lighting. There is mounting evidence that the exceptional optoelectronic properties of these materials could stem from unconventional electron-phonon couplings, and it has been suggested that the formation of polarons and self-trapped excitons could be key to understanding such properties. By performing first-principles simulations across the length scales, here we show that halide perovskites harbor a uniquely rich variety of polaronic species, including small polarons, large polarons, and charge density waves, and we explain a variety of experimental observations. We find that these emergent quasiparticles support topologically nontrivial phonon fields with quantized topological charge, making them nonmagnetic analog of the helical Bloch points found in magnetic skyrmion lattices.

Halide perovskite dynamics at work: Large cations at 2D-on-3D interfaces are mobile.

SignificanceSurface engineering of halide perovskites (HaPs), semiconductors with amazing optoelectronic properties, is critical to improve the performance and ambient stability of HaP-based solar cells and light emitting diodes (LEDs). Ultrathin layers of two-dimensional (2D) analogs of the three-dimensional (3D) HaPs are particularly attractive for this because of their chemical similarities but higher ambient stability. But do such 2D/3D interfaces actually last, given that ions in HaPs move readily-i.e., what happens at those interfaces on the atomic scale? A special electron microscopy, which as a bonus also reveals the true conditions for nondestructive analysis, shows that the large ions that are a necessary part of the 2D films can move into the 3D HaP, a fascinating illustration of panta rei in HaPs.

Inhibiting the Appearance of Green Emission in Mixed Lead Halide Perovskite Nanocrystals for Pure Red Emission.

Mixed halide perovskites exhibit promising optoelectronic properties for next-generation light-emitting diodes due to their tunable emission wavelength that covers the entire visible light spectrum. However, these materials suffer from severe phase segregation under continuous illumination, making long-term stability for pure red emission a significant challenge. In this study, we present a comprehensive analysis of the role of halide oxidation in unbalanced ion migration (I/Br) within CsPbI2Br nanocrystals and thin films. We also introduce a new approach using cyclic olefin copolymer (COC) to encapsulate CsPbI2Br perovskite nanocrystals (PNCs), effectively suppressing ion migration by increasing the corresponding activation energy. Compared with that of unencapsulated samples, we observe a substantial reduction in phase separation under intense illumination in PNCs with a COC coating. Our findings show that COC enhances phase stability by passivating uncoordinated surface defects (Pb2+ and I-), increasing the formation energy of halide vacancies, improving the charge carrier lifetime, and reducing the nonradiative recombination density.

Room-Temperature Ferroelectric Epitaxial Nanowire Arrays with Photoluminescence.

The development of large-scale, high-quality ferroelectric semiconductor nanowire arrays with interesting light-emitting properties can address limitations in traditional wide-bandgap ferroelectrics, thus serving as building blocks for innovative device architectures and next-generation high-density optoelectronics. Here, we investigate the optical properties of ferroelectric CsGeX3 (X = Br, I) halide perovskite nanowires that are epitaxially grown on muscovite mica substrates by vapor phase deposition. Detailed structural characterizations reveal an incommensurate heteroepitaxial relationship with the mica substrate. Furthermore, photoluminescence that can be tuned from yellow-green to red emissions by varying the halide composition demonstrates that these nanowire networks can serve as platforms for future optoelectronic applications. In addition, the room-temperature ferroelectricity and ferroelectric domain structures of these nanowires are characterized using second harmonic generation (SHG) polarimetry. The combination of room-temperature ferroelectricity with photoluminescence in these nanowire arrays unlocks new avenues for the design of novel multifunctional materials.

Multiscale Supercrystal Meta-atoms.

Meta-atoms are the building blocks of metamaterials, which are employed to control both generation and propagation of light as well as provide novel functionalities of localization and directivity of electromagnetic radiation. In many cases, simple dielectric or metallic resonators are employed as meta-atoms to create different types of electromagnetic metamaterials. Here, we fabricate and study supercrystal meta-atoms composed of coupled perovskite quantum dots. We reveal that these multiscale structures exhibit specific emission properties, such as spectrum splitting and polaritonic effects. We believe that such multiscale supercrystal meta-atoms will provide novel functionalities in the design of many novel types of active metamaterials and metasurfaces.

Observation of Ferromagnetism in Dilute Magnetic Halide Perovskite Semiconductors.

Dilute magnetic semiconductors (DMSs) have attracted much attention because of their potential use in spintronic devices. Here, we demonstrate the observation of robust ferromagnetism in a solution-processable halide perovskite semiconductor with dilute magnetic ions. By codoping of magnetic (Fe2+) and aliovalent (Bi3+) metal ions into CH3NH3PbCl3 (MAPbCl3) perovskite, ferromagnetism with well-saturated magnetic hysteresis loops and a maximum coercivity field of 1280 Oe was observed below 12 K. The ferromagnetic resonance measurements revealed that the incorporation of aliovalent ions modulates the carrier concentration and plays an essential role in realizing the ferromagnetism in dilute magnetic halide perovskites. Magnetic ions are proposed to interact through itinerant charge carriers to achieve ferromagnetic coupling. Our work provides a new avenue for the development of solution-processable magnetic semiconductors.

Ultracompact and Uniform Nanoemitter Array Based on Periodic Scattering.

As emerging gain materials, lead halide perovskites have drawn considerable attention in coherent light sources. With the development of patterning and integration techniques, a perovskite laser array has been realized by distributing perovskite microcrystals periodically. Nevertheless, the packing density is limited by the crystal size and the channel gap distance. More importantly, the lasing performance for individual laser units is quite random due to variation of size and crystal quality. Herein an ultracompact perovskite nanoemitter array with uniform emission has been demonstrated. Individual emitters are formed via scattering evanescent components from a shared Fabry-Perot laser, ensuring uniform lasing emission in a unit cell with a side length of 160 nm and lattice constant of 400 nm. And the periodic silicon scatterers do not deteriorate the lasing threshold dramatically. In addition, the surface emitting efficiency increased significantly. The direct integration of a densely packed nanoemitter array with a silicon platform promises high-throughput sensing and high-capacity optical interconnects.

Influence of Material Properties on Surface Chemistry Induced Circular Dichroism in Halide Perovskite: Computational Insights.

The chirality transfer phenomenon is attractive for enhancing the optical functionality of nanomaterials by inducing sensitivity to the circular polarization states of photons. An underexplored aspect is how material properties of the achiral semiconductor impact the induced chiroptical signatures. Here we apply atomistic time-dependent density functional theory simulations to investigate the material properties that influence the chiroptical signatures of a lead halide perovskite nanocrystal with a chiral molecule bound to the surface. First, we find that both lattice disorder created by surface strain and halide substitution can increase the chiroptical response of the perovskite quantum dots by an order of magnitude. Both phenomena are attributed to a broadening of the density of the electronically excited states. Second, the intensity of the anisotropy spectra decreases with increasing dot size with a power law decay. Overall, these insights can be used to help guide experimental realization of highly resolvable polarized optical features in semiconducting nanomaterials.

Ferroelectricity in Ultrathin Halide Perovskites.

Ferroelectricity has recently been demonstrated in germanium-based halide perovskites. We use first-principles-based simulations to study 4-18 nm CsGeBr3 films and develop a theory for ferroelectric ultrathin films. The theory introduces (i) a local order parameter, which identifies phase transitions into both monodomain and polydomain phases, and (ii) a dipole pattern classifier, which allows efficient and reliable identification of dipole patterns. Application of the theory to both halides CsGeBr3 and CsGeI3 and oxide BiFeO3 ultrathin ferroelectrics reveals two distinct scenarios. First, the films transition into a monodomain phase below the critical value of the residual depolarizing field. Above this critical value, the second scenario occurs, and the film undergoes a transition into a nanodomain phase. The two scenarios exhibit opposite responses of Curie temperature to thickness reduction. Application of a dipole pattern classifier reveals rich nanodomain phases in halide films: nanostripes, labyrinths, zig-zags, pillars, and lego domains.

Spatially Resolved Anion Diffusion and Tunable Waveguides in Bismuth Halide Perovskites.

Bismuth halide perovskites are widely regarded as nontoxic alternatives to lead halide perovskites for optoelectronics and solar energy harvesting applications. With a tailorable composition and intriguing optical properties, bismuth halide perovskites are also promising candidates for tunable photonic devices. However, robust control of the anion composition in bismuth halide perovskites remains elusive. Here, we established chemical vapor deposition and anion exchange protocols to synthesize bismuth halide perovskite nanoflakes with controlled dimensions and variable compositions. In particular, we demonstrated the gradient bromide distribution by controlling the anion exchange and diffusion processes, which is spatially resolved by time-of-flight secondary ion mass spectrometry. Moreover, the optical waveguiding properties of bismuth halide perovskites can be modulated by flake thicknesses and anion compositions. With a unique gradient anion distribution and controllable optical properties, bismuth halide perovskites provide new possibilities for applications in optoelectronic devices and integrated photonics.

Scintillation Properties of CsPbBr3 Nanocrystals Prepared by Ligand-Assisted Reprecipitation and Dual Effect of Polyacrylate Encapsulation toward Scalable Ultrafast Radiation Detectors.

Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymeric hosts are gaining attention as scalable and low-cost scintillation detectors for technologically relevant applications. Despite rapid progress, little is currently known about the scintillation properties and stability of LHP-NCs prepared by the ligand assisted reprecipitation (LARP) method, which allows mass scalability at room temperature unmatched by any other type of nanostructure, and the implications of incorporating LHP-NCs into polyacrylate hosts are still largely debated. Here, we show that LARP-synthesized CsPbBr3 NCs are comparable to particles from hot-injection routes and unravel the dual effect of polyacrylate incorporation, where the partial degradation of LHP-NCs luminescence is counterbalanced by the passivation of electron-poor defects by the host acrylic groups. Experiments on NCs with tailored surface defects show that the balance between such antithetical effects of polymer embedding is determined by the surface defect density of the NCs and provide guidelines for further material optimization.

Diffusion-Dominated Luminescence Dynamics of CsPbBr3 Studied Using Cathodoluminescence and Microphotoluminescence Spectroscopy.

Time-resolved or time-correlation measurements using cathodoluminescence (CL) reveal the electronic and optical properties of semiconductors, such as their carrier lifetimes, at the nanoscale. However, halide perovskites, which are promising optoelectronic materials, exhibit significantly different decay dynamics in their CL and photoluminescence (PL). We conducted time-correlation CL measurements of CsPbBr3 using Hanbury Brown-Twiss interferometry and compared them with time-resolved PL. The measured CL decay time was on the order of subnanoseconds and was faster than PL decay at an excited carrier density of 2.1 × 1018 cm-3. Our experiment and analytical model revealed the CL dynamics induced by individual electron incidences, which are characterized by highly localized carrier generation followed by a rapid decrease in carrier density due to diffusion. This carrier diffusion can play a dominant role in the CL decay time for undoped semiconductors, in general, when the diffusion dynamics are faster than the carrier recombination.

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.

Oriented Assembly of Lead Halide Perovskite Nanocrystals.

Cesium lead halide nanostructures have highly tunable optical and optoelectronic properties. Establishing precise control in forming perovskite single-crystal nanostructures is key to unlocking the full potential of these materials. However, studying the growth kinetics of colloidal cesium lead halides is challenging due to their sensitivity to light, electron beam, and environmental factors like humidity. In this study, in situ observations of CsPbBr3-particle dynamics were made possible through extremely low dose liquid cell transmission electron microscopy, showing that oriented attachment is the dominant pathway for the growth of single-crystal CsPbBr3 architectures from primary nanocubes. In addition, oriented assembly and fusion of ligand-stabilized cubic CsPbBr3 nanocrystals are promoted by electron beam irradiation or introduction of polar additives that both induce partial desorption of the original ligands and polarize the nanocube surfaces. These findings advance our understanding of cesium lead halide growth mechanisms, aiding the controlled synthesis of other perovskite nanostructures.

Floquet Engineering of Excitons in Two-Dimensional Halide Perovskites via Biexciton States.

Layered two-dimensional halide perovskites (2DHPs) exhibit exciting non-equilibrium properties that allow the manipulation of energy levels through coherent light-matter interactions. Under the Floquet picture, novel quantum states manifest through the optical Stark effect (OSE) following intense subresonant photoexcitation. Nevertheless, a detailed understanding of the influence of strong many-body interactions between excitons on the OSE in 2DHPs remains unclear. Herein, we uncover the crucial role of biexcitons in photon-dressed states and demonstrate precise optical control of the excitonic states via the biexcitonic OSE in 2DHPs. With fine step tuning of the driven energy, we fully parametrize the evolution of exciton resonance modulation. The biexcitonic OSE enables Floquet engineering of the exciton resonance with either a blue-shift or a red-shift of the energy levels. Our findings shed new light on the intricate nature of coherent light-matter interactions in 2DHPs and extend the degree of freedom for ultrafast coherent optical control over excitonic states.

Synchronously Polishing the Lead-Rich Surface and Passivating Surface Defects of CsPb(Br/I)3 Quantum Dots for High-Performance Pure-Red PeLEDs.

Mixed-halide CsPb(Br/I)3 perovskite quantum dots (QDs) are regarded as one of the most promising candidates for pure-red perovskite light-emitting diodes (PeLEDs) due to their precise spectral tuning property. However, the lead-rich surface of these QDs usually results in halide ion migration and nonradiative recombination loss, which remains a great challenge for high-performance PeLEDs. To solve the above issues, we employ a chelating agent of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid hydrate (DOTA) to polish the lead-rich surface of the QDs and meanwhile introduce a new ligand of 2,3-dimercaptosuccinic acid (DMSA) to passivate surface defects of the QDs. This synchronous post-treatment strategy results in high-quality CsPb(Br/I)3 QDs with suppressed halide ion migration and an improved photoluminescence quantum yield, which enables us to fabricate spectrally stable pure-red PeLEDs with a peak external quantum efficiency of 23.2%, representing one of the best performance pure-red PeLEDs based on mixed-halide CsPb(Br/I)3 QDs reported to date.

Tailoring Auger Recombination Dynamics in CsPbI3 Perovskite Nanocrystals via Transition Metal Doping.

Auger recombination is a pivotal process for semiconductor nanocrystals (NCs), significantly affecting charge carrier generation and collection in optoelectronic devices. This process depends mainly on the NCs' electronic structures. In our study, we investigated Auger recombination dynamics in manganese (Mn2+)-doped CsPbI3 NCs using transient absorption (TA) spectroscopy combined with theoretical and experimental structural characterization. Our results show that Mn2+ doping accelerates Auger recombination, reducing the biexciton lifetime from 146 to 74 ps with increasing Mn doping concentration up to 10%. This accelerated Auger recombination in Mn-doped NCs is attributed to increased band edge wave function overlap of excitons and a larger density of final states of Auger recombination due to Mn orbital involvement. Moreover, Mn doping reduces the dielectric screening of the excitons, which also contributes to the accelerated Auger recombination. Our study demonstrates the potential of element doping to regulate Auger recombination rates by modifying the materials' electronic structure.

Ultrafast Dynamics of Self-Trapped Excitons in Cs2AgInCl6:Al3+ Double Perovskite Nanocrystals.

It is a huge challenge to increase the photoluminescence (PL) of lead-free halide perovskites, and understanding the mechanism behind exciton dynamics can provide a valuable solution. Herein, we achieved enhanced broad-band emission at ambient conditions in Cs2AgInCl6 by tuning self-trapped excitons (STEs) through Al3+ doping. Cryogenic measurements showed an inhomogeneous nature of STE emission due to the presence of defect states and is subject to thermal quenching. An increased Huang-Rhys factor (S-factor) resulted in better electron-phonon coupling and high-density STE states post Al3+ doping. Femtosecond transient absorption (fs-TA) results provided insights into the distribution dynamics of excitons, which occurs through gradient energy levels from free excitons (FE) to STEs, where each STE state potentially possesses higher quantized energy states. Overall, this study aims to comprehend the origins of self-trapping and decay of STEs in Cs2AgInCl6:Al3+ and emphasizes the potential of compositional engineering to mitigate self-trapping in this material.

Glass Disorder Modulated Luminescence in Zero-Dimensional Antimony-Chloride Coplanar Dimers for Optical Anti-counterfeiting.

Zero-dimensional metal halides have received wide attention due to their structural diversity, strong quantum confinement, and associated excellent photoluminescence properties. A reversible and tunable luminescence would be desirable for applications such as anti-counterfeiting, information encryption, and artificial intelligence. Yet, these materials are underexplored, with little known about their luminescence tuning mechanisms. Here we report a pyramidal coplanar dimer, (TBA)Sb2Cl7 (TBA = tetrabutylammonium), showing broadband emission wavelength tuning (585-650 nm) by simple thermal treatment. We attribute the broad color change to structural disorder induced by varying the heat treatment temperatures. Increasing the heating temperature transitions the material from long-range ordered crystalline phase to highly disordered glassy phase. The latter exhibits stronger electron-phonon coupling, enhancing the self-trapped exciton emission efficiency. The work provides a new material platform for manifold optical anti-counterfeiting applications and sheds light on the emission color tuning mechanisms for further design of stimuli-responsive materials.

Solution Synthesis and Light-Emitting Applications of One-Dimensional Lead-Free Cerium(III) Metal Halides.

Combining rare earth elements with the halide perovskite structure offers valuable insights into designing nonlead (Pb) luminescent materials. However, most of these compositions tend to form zero-dimensional (0D) networks of metal-halide polyhedra, with higher-dimensional (1D, 2D, and 3D) structures receiving relatively less exploration. Herein, we present synthesis and optical properties of Cs3CeCl6·3H2O, characterized by its unique 1D crystal structure. The conduction band minimum of Cs3CeCl6·3H2O becomes less localized as a result of the increased structural dimension, making it possible for the materials to achieve an efficient electrical injection. For both Cs3CeCl6·3H2O single crystals and nanocrystals, we also observed remarkable luminescence with near-unity photoluminescence quantum yield and exceptional phase stability. Cs3CeCl6·3H2O single crystals demonstrate an X-ray scintillation light yield of 31900 photons/MeV, higher than that of commercial LuAG:Ce (22000 photons/MeV); electrically driven light-emitting diodes fabricated with Cs3CeCl6·3H2O nanocrystals yield the characteristic emission of Ce3+, indicating their potential use in next-generation violet-light-emitting devices.