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.

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.

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.

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.

Comprehensive Neurotoxicity of Lead Halide Perovskite Nanocrystals in Nematode Caenorhabditis elegans.

To date, all-inorganic lead halide perovskite quantum dots have emerged as promising materials for photonic, optoelectronic devices, and biological applications, especially in solar cells, raising numerous concerns about their biosafety. Most of the studies related to the toxicity of perovskite quantum dots (PeQDs) have focused on the potential risks of hybrid perovskites by using zebrafish or human cells. So far, the neurotoxic effects and fundamental mechanisms of PeQDs remain unknown. Herein, a comprehensive methodology is designed to investigate the neurotoxicity of PeQDs by using Caenorhabditis elegans as a model organism. The results show that the accumulation of PeQDs mainly focuses on the alimentary system and head region. Acute exposure to PeQDs results in a decrease in locomotor behaviors and pharyngeal pumping, whereas chronic exposure to PeQDs causes brood decline and shortens lifespan. In addition, some abnormal issues occur in the uterus during reproduction assays, such as vulva protrusion, impaired eggs left in the vulva, and egg hatching inside the mother. Excessive reactive oxygen species formation is also observed. The neurotoxicity of PeQDs is explained by gene expression. This study provides a complete insight into the neurotoxicity of PeQD and encourages the development of novel nontoxic PeQDs.

Dynamic Local Structure in Caesium Lead Iodide: Spatial Correlation and Transient Domains.

Metal halide perovskites are multifunctional semiconductors with tunable structures and properties. They are highly dynamic crystals with complex octahedral tilting patterns and strongly anharmonic atomic behavior. In the higher temperature, higher symmetry phases of these materials, several complex structural features are observed. The local structure can differ greatly from the average structure and there is evidence that dynamic 2D structures of correlated octahedral motion form. An understanding of the underlying complex atomistic dynamics is, however, still lacking. In this work, the local structure of the inorganic perovskite CsPbI3 is investigated using a new machine learning force field based on the atomic cluster expansion framework. Through analysis of the temporal and spatial correlation observed during large-scale simulations, it is revealed that the low frequency motion of octahedral tilts implies a double-well effective potential landscape, even well into the cubic phase. Moreover, dynamic local regions of lower symmetry are present within both higher symmetry phases. These regions are planar and the length and timescales of the motion are reported. Finally, the spatial arrangement of these features and their interactions are investigated and visualized, providing a comprehensive picture of local structure in the higher symmetry phases.

Composition-Property Relations for GAx FAy MA1- x - y PbI3 Perovskites.

Halide perovskites are materials for diverse optoelectronic applications owing to a combination of factors, including their compositional flexibility. A major source of this diversity of compositions comes from the use of mixed organic cations in the A-site of such compounds to form solid solutions. Many organic cations are possible for this purpose. Although significant progress is made over years of intensive research, the determination of systematic relationships between the compositions and properties of halide perovskites is not exploited accordingly. Using the MAPbI3 prototype, a wide range of compositions substituted by formamidinium (FA+ ) and guanidinium (GA+ ) cations are studied. From a detailed collection of experimental data and results reported in the literature, heat maps correlating the composition of GAx FAy MA1- x - y PbI3 solid solutions with phase transition temperatures, dielectric permittivity, and activation energies are constructed. Considering the characteristics of organic cations, namely their sizes, dipole moments, and the number of N─H bonds, it is possible to interpret the heat maps as consequences of these characteristics. This work brings a systematization of how obtaining specific properties of halide perovskites might be possible by customizing the characteristics of the A-site organic cations.

Combining Trivalent Ion-Doping with Halide Alloying to Increase the Efficiency of Tin Perovskites.

Tin-halide perovskites (THP) are emerging materials for photovoltaics with optoelectronic properties potentially rivaling lead-based analoges. Their efficiencies in solar cells are, however, severely limited by the high sensitivity of tin to oxygen and the heavy p-doping natively present in the material. While the effects of oxygen can be mitigated by using reducing agents upon the synthesis and by encapsulating the device, the native p-doping caused by the high density of acceptor defects remains a challenge to be further addressed for prolonging carrier lifetimes and, consequently, device efficiency. In this work, potential compositional engineering strategies aimed at reducing the p-doping of this class of materials and increasing their efficiency in solar cells are investigated. Based on density functional theory simulations it is demonstrated that THP doping with d1s2 trivalent ions effectively decreases the hole background density and the density of the deep defects responsible for the non-radiative recombination in these materials. This effect is enhanced by alloying iodide with small fractions of bromide, up to 33%. Higher bromide fractions, instead, are detrimental due to the increased non-radiative recombination. These results may provide useful guidelines to experimentalists for improving the optoelectronic quality of THPs and consequently of the ensuing devices.

Atomic Imaging of Multi-Dimensional Ruddlesden-Popper Interfaces in Lead-Halide Perovskites.

Ruddlesden-Popper (RP) interface with defined stacking structure will fundamentally influence the optoelectronic performances of lead-halide perovskite (LHP) materials and devices. However, it remains challenging to observe the atomic local structures in LHPs, especially for multi-dimensional RP interface hidden inside the nanocrystal. In this work, the advantages of two imaging modes in scanning transmission electron microscopy (STEM), including high-angle annular dark field (HAADF) and integrated differential phase contrast (iDPC) STEM, are successfully combined to study the bulk and local structures of inorganic and organic/inorganic hybrid LHP nanocrystals. Then, the multi-dimensional RP interfaces in these LHPs are atomically resolved with clear gap and blurred transition region, respectively. In particular, the complex interface by the RP stacking in 3D directions can be analyzed in 2D projected image. Finally, the phase transition, ion missing, and electronic structures related to this interface are investigated. These results provide real-space evidence for observing and analyzing atomic multi-dimensional RP interfaces, which may help to better understand the structure-property relation of LHPs, especially their complex local structures.

Weak Dispersion of Exciton Landé Factor with Band Gap Energy in Lead Halide Perovskites: Approximate Compensation of the Electron and Hole Dependences.

The optical properties of lead halide perovskite semiconductors in vicinity of the bandgap are controlled by excitons, so that investigation of their fundamental properties is of critical importance. The exciton Landé or g-factor gX is the key parameter, determining the exciton Zeeman spin splitting in magnetic fields. The exciton, electron, and hole carrier g-factors provide information on the band structure, including its anisotropy, and the parameters contributing to the electron and hole effective masses. Here, gX is measured by reflectivity in magnetic fields up to 60 T for lead halide perovskite crystals. The materials band gap energies at a liquid helium temperature vary widely across the visible spectral range from 1.520 up to 3.213 eV in hybrid organic-inorganic and fully inorganic perovskites with different cations and halogens: FA0.9Cs0.1PbI2.8Br0.2, MAPbI3, FAPbBr3, CsPbBr3, and MAPb(Br0.05Cl0.95)3. The exciton g-factors are found to be nearly constant, ranging from +2.3 to +2.7. Thus, the strong dependences of the electron and hole g-factors on the bandgap roughly compensate each other when combining to the exciton g-factor. The same is true for the anisotropies of the carrier g-factors, resulting in a nearly isotropic exciton g-factor. The experimental data are compared favorably with model calculation results.

Tuning Electronic and Structural Properties of Lead-Free Metal Halide Perovskites: A Comparative Study of 2D Ruddlesden-Popper and 3D Compositions.

In recent decades, two-dimensional (2D) perovskites have emerged as promising semiconductors for next-generation photovoltaics, showing notable advancements in solar energy conversion. Herein, we explore the impact of alternative inorganic lattice BX-based compositions (B=Ge or Sn, X=Br or I) on the energy gap and stability. Our investigation encompasses BA2Man-1BnX3n+1 2D Ruddlesden-Popper perovskites (for n=1-5 layers) and 3D bulk (MA)BX3 systems, employing first-principles calculations with spin-orbit coupling (SOC), DFT-1/2 quasiparticle, and D3 dispersion corrections. The study unveils how atoms with smaller ionic radii induce anisotropic internal and external distortions within the inorganic and organic lattices. Introducing the spacers in the low-layer regime reduces local distortions but widens band gaps. Our calculation protocol provides deeper insights into the physics and chemistry underlying 2D perovskite materials, paving the way for optimizing environmentally friendly alternatives that can efficiently replace with sustainable materials.

A Comprehensive Review on Perovskite Solar Cells Integrated Photo-supercapacitors and Perovskites-Based Electrochemical Supercapacitors.

Perovskite solar cells (PSCs) have rapidly become a prevalent photovoltaic technology owing to their simple structure, low processing cost, and remarkable increase in solar-to-electric power conversion efficiency (PCE). However, the intermittent nature of solar radiation induces some technical and financial challenges for its practical applications as a reliable power source. To address this issue, the integration of PSCs with supercapacitors (SCs) in the form of integrated photo-supercapacitors (IPSs) has gathered significant attention. This integration can balance energy availability and demand, reduce energy wastage, and stabilize power output for portable and wearable electronics. Meanwhile, the excellent optoelectronic properties with mixed electronic and ionic conductivity of metal halide perovskites (MHPs) have expanded their application as electrode and electrolyte materials for SCs and photo-supercapacitors (PSs) applications. This review provides an all-inclusive summary of the current state-of-the-art research progress of PSCs-IPSs and MHPs-based SCs and PSs by highlighting their basics and integration approaches. It also discusses the challenges and prospects of these materials and technologies.

Exploring Highly Efficient Broadband Self-Trapped-Exciton Luminophors: from 0D to 3D Materials.

The review summarizes our recent reports on brightly-emitting materials with varied dimensionality (3D, 2D, 0D) synthesized using "green" chemistry and exhibiting highly efficient photoluminescence (PL) originating from self-trapped exciton (STE) states. The discussion starts with 0D emitters, in particular, ternary indium-based colloidal quantum dots, continues with 2D materials, focusing on single-layer polyheptazine carbon nitride, and further evolves to 3D luminophores, the latter exemplified by lead-free double halide perovskites. The review shows the broadband STE PL to be an inherent feature of many materials produced in mild conditions by "green" chemistry, outlining PL features general for these STE emitters and differences in their photophysical properties. The review is concluded with an outlook on the challenges in the field of STE PL emission and the most promising venues for future research.

Decoding ultrafast polarization responses in lead halide perovskites by the two-dimensional optical Kerr effect.

The ultrafast polarization response to incident light and ensuing exciton/carrier generation are essential to outstanding optoelectronic properties of lead halide perovskites (LHPs). A large number of mechanistic studies in the LHP field to date have focused on contributions to polarizability from organic cations and the highly polarizable inorganic lattice. For a comprehensive understanding of the ultrafast polarization response, we must additionally account for the nearly instantaneous hyperpolarizability response to the propagating light field itself. While light propagation is pivotal to optoelectronics and photonics, little is known about this in LHPs in the vicinity of the bandgap where stimulated emission, polariton condensation, superfluorescence, and photon recycling may take place. Here we develop two-dimensional optical Kerr effect (2D-OKE) spectroscopy to energetically dissect broadband light propagation and dispersive nonlinear polarization responses in LHPs. In contrast to earlier interpretations, the below-bandgap OKE responses in both hybrid CH3NH3PbBr3 and all-inorganic CsPbBr3 perovskites are found to originate from strong hyperpolarizability and highly anisotropic dispersions. In both materials, the nonlinear mixing of anisotropically propagating light fields results in convoluted oscillatory polarization dynamics. Based on a four-wave mixing model, we quantitatively derive dispersion anisotropies, reproduce 2D-OKE frequency correlations, and establish polarization-dressed light propagation in single-crystal LHPs. Moreover, our findings highlight the importance of distinguishing the often-neglected anisotropic light propagation from underlying coherent quasiparticle responses in various forms of ultrafast spectroscopy.

Giant and Tunable Excitonic Optical Anisotropy in Single-Crystal Halide Perovskites.

During the last years, giant optical anisotropy has demonstrated its paramount importance for light manipulation. In spite of recent advances in the field, the achievement of continuous tunability of optical anisotropy remains an outstanding challenge. Here, we present a solution to the problem through the chemical alteration of halogen atoms in single-crystal halide perovskites. As a result, we manage to continually modify the optical anisotropy by 0.14. We also discover that the halide perovskite can demonstrate optical anisotropy up to 0.6 in the visible range─the largest value among non-van der Waals materials. Moreover, our results reveal that this anisotropy could be in-plane and out-of-plane depending on perovskite shape─rectangular and square. As a practical demonstration, we have created perovskite anisotropic nanowaveguides and shown a significant impact of anisotropy on high-order guiding modes. These findings pave the way for halide perovskites as a next-generation platform for tunable anisotropic photonics.

Lead Halide Perovskite Nanocrystals with Low Inhomogeneous Broadening and High Coherent Fraction through Dicationic Ligand Engineering.

Lead halide perovskite nanocrystals (LHP NCs) are an emerging materials system with broad potential applications, including as emitters of quantum light. We apply design principles aimed at the structural optimization of surface ligand species for CsPbBr3 NCs, leading us to the study of LHP NCs with dicationic quaternary ammonium bromide ligands. Through the selection of linking groups and aliphatic backbones guided by experiments and computational support, we demonstrate consistently narrow photoluminescence line shapes with a full-width-at-half-maximum below 70 meV. We observe bulk-like Stokes shifts throughout our range of particle sizes, from 7 to 16 nm. At cryogenic temperatures, we find sub-200 ps lifetimes, significant photon coherence, and the fraction of photons emitted into the coherent channel increasing markedly to 86%. A 4-fold reduction in inhomogeneous broadening from previous work paves the way for the integration of LHP NC emitters into nanophotonic architectures to enable advanced quantum optical investigation.

Chemical Mapping of Excitons in Halide Double Perovskites.

Halide double perovskites comprise an emerging class of semiconductors with tremendous chemical and electronic diversity. While their band structure features can be understood from frontier-orbital models, chemical intuition for optical excitations remains incomplete. Here, we use ab initio many-body perturbation theory within the GW and the Bethe-Salpeter equation approach to calculate excited-state properties of a representative range of Cs2BB'Cl6 double perovskites. Our calculations reveal that double perovskites with different combinations of B and B' cations display a broad variety of electronic band structures and dielectric properties and form excitons with binding energies ranging over several orders of magnitude. We correlate these properties with the orbital-induced anisotropy of charge-carrier effective masses and the long-range behavior of the dielectric function by comparing them with the canonical conditions of the Wannier-Mott model. Furthermore, we derive chemically intuitive rules for predicting the nature of excitons in halide double perovskites using computationally inexpensive density functional theory calculations.

Elastic Phonon Scattering Dominates Dephasing in Weakly Confined Cesium Lead Bromide Nanocrystals at Cryogenic Temperatures.

Cesium lead halide perovskite nanocrystals (PNCs) have emerged as a potential next-generation single quantum emitter (QE) material for quantum optics and quantum information science. Optical dephasing processes at cryogenic temperatures are critical to the quality of a QE, making a mechanistic understanding of coherence losses of fundamental interest. We use photon-correlation Fourier spectroscopy (PCFS) to obtain a lower bound to the optical coherence times of single PNCs as a function of temperature. We find that 20 nm CsPbBr3 PNCs emit nearly exclusively into a narrow zero-phonon line from 4 to 13 K. Remarkably, no spectral diffusion is observed at time scales of 10 µs to 5 ms. Our results suggest that exciton dephasing in this temperature range is dominated by elastic scattering from phonon modes with characteristic frequencies of 1-3 meV, while inelastic scattering is minimal due to weak exciton-phonon coupling.