Understanding the Mechanisms of Methylammonium-Induced Thermal Instability in Mixed-FAMA Perovskites.

Despite a recent shift toward methylammonium (MA)-free lead-halide perovskites for perovskite solar cells, high-efficiency formamidinium lead iodide (FAPbI) devices still often require methylammonium chloride (MACl) as an additive, which evaporates away during the annealing process. In this article, it is shown that the residual MA, however, triggers thermal instability. To investigate the possibility of an optimal concentration of MA that may improve thermal stability, the intrinsic thermal stability of pure FA, FA-rich, MA-rich, and pure MA perovskite films (FAMAPbI, FAMA) is studied.

Stable and Highly Emissive Infrared Yb-Doped Perovskite Quantum Cutters Engineered by Machine Learning.

Quantum cutting (QC) allows the conversion of high-energy photons into lower-energy photons, exhibiting great potential for infrared communications. Yb-doped perovskite nanocrystals can achieve an efficient QC process with extremely high photoluminescence quantum yield (PLQY) thanks to the favorable Yb incorporation in the perovskite structure. However, conventionally used oleic acid-oleylamine-based ligand pairs cause instability issues due to highly dynamic binding to surface states that have curbed their potential applications.

Weakly Confined Organic-Inorganic Halide Perovskite Quantum Dots as High-Purity Room-Temperature Single Photon Sources.

Colloidal perovskite quantum dots (PQDs) have emerged as highly promising single photon emitters for quantum information applications. Presently, most strategies have focused on leveraging quantum confinement to increase the nonradiative Auger recombination (AR) rate to enhance single-photon (SP) purity in all-inorganic CsPbBr QDs. However, this also increases the fluorescence intermittency.

Molecular Locking with All-Organic Surface Modifiers Enables Stable and Efficient Slot-Die-Coated Methyl-Ammonium-Free Perovskite Solar Modules.

The power conversion efficiency (PCE) of the state-of-the-art large-area slot-die-coated perovskite solar cells (PSCs) is now over 19%, but issues with their stability persist owing to significant intrinsic point defects and a mass of surface imperfections introduced during the fabrication process. Herein, the utilization of a hydrophobic all-organic salt is reported to modify the top surface of large-area slot-die-coated methylammonium (MA)-free halide perovskite layers. Bearing two molecules, each of which is endowed with anchoring groups capable of exhibiting secondary interactions with the perovskite surfaces, the organic salt acts as a molecular lock by effectively binding to both anion and cation vacancies, substantially enhancing the materials' intrinsic stability against different stimuli.

Inorganic frameworks of low-dimensional perovskites dictate the performance and stability of mixed-dimensional perovskite solar cells.

Mixed-dimensional perovskites containing mixtures of organic cations hold great promise to deliver highly stable and efficient solar cells. However, although a plethora of relatively bulky organic cations have been reported for such purposes, a fundamental understanding of the materials' structure, composition, and phase, along with their correlated effects on the corresponding optoelectronic properties and degradation mechanism remains elusive. Herein, we systematically engineer the structures of bulky organic cations to template low-dimensional perovskites with contrasting inorganic framework dimensionality, connectivity, and coordination deformation.

Reversible Photochromism in ⟨110⟩ Oriented Layered Halide Perovskite.

Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr to a ⟨110⟩ oriented FAPbBr structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate phase in the FAPbBr structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented mono-halide/cation perovskite.

One-Pot Synthesis and Structural Evolution of Colloidal Cesium Lead Halide-Lead Sulfide Heterostructure Nanocrystals for Optoelectronic Applications.

Heterostructures, combining perovskite nanocrystals (PNC) and chalcogenide quantum dots, could pave a path to optoelectronic device applications by enabling absorption in the near-infrared region, tailorable electronic properties, and stable crystal structures. Ideally, the heterostructure host material requires a similar lattice constant as the guest which is also constrained by the synthesis protocol and materials selectivity. Herein, we present an efficient one-pot hot-injection method to synthesize colloidal all-inorganic cesium lead halide-lead sulfide (CsPbX (X = Cl, Br, I)-PbS) heterostructure nanocrystals (HNCs) via the epitaxial growth of the perovskite onto the presynthesized PbS nanocrystals (NCs).

Vacuum-Processed Metal Halide Perovskite Light-Emitting Diodes: Prospects and Challenges.

In less than a decade, organic-inorganic metal halide perovskites (MHPs) have shown tremendous progress in the field of light-emitting applications. Perovskite light-emitting diodes (PeLEDs) have reached external quantum efficiencies (EQE) exceeding 20 % and they have been recognized as a potential contender of the commercial display technologies. However, perovskite thin films in PeLEDs are generally deposited via a spin-coating process, which is not favourable for large area device fabrication.

Room temperature synthesis of low-dimensional rubidium copper halide colloidal nanocrystals with near unity photoluminescence quantum yield.

Metal lead halide perovskite nanocrystals have emerged as promising candidates for optoelectronic applications. However, the inclusion of toxic lead is a major concern for the commercial viability of these materials. Herein, we introduce a new family of non-toxic reduced dimension RbCuX (X = Br, Cl) colloidal nanocrystals with one-dimensional crystal structure consisting [CuX] ribbons isolated by Rb cations.

Realizing Reduced Imperfections via Quantum Dots Interdiffusion in High Efficiency Perovskite Solar Cells.

Realization of reduced ionic (cationic and anionic) defects at the surface and grain boundaries (GBs) of perovskite films is vital to boost the power conversion efficiency of organic-inorganic halide perovskite (OIHP) solar cells. Although numerous strategies have been developed, effective passivation still remains a great challenge due to the complexity and diversity of these defects. Herein, a solid-state interdiffusion process using multi-cation hybrid halide perovskite quantum dots (QDs) is introduced as a strategy to heal the ionic defects at the surface and GBs.

Publisher Correction: Mixed-Dimensional Naphthylmethylammonium-Methylammonium Lead Iodide Perovskites with Improved Thermal Stability.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Hot Carriers in Halide Perovskites: How Hot Truly?

Slow hot carrier cooling in halide perovskites holds the key to the development of hot carrier (HC) perovskite solar cells. For accurate modeling and pragmatic design of HC materials and devices, it is essential that HC temperatures are reliably determined. A common approach involves fitting the high-energy tail of the main photobleaching peak in a transient absorption spectrum with a Maxwell-Boltzmann distribution.

Mixed-Dimensional Naphthylmethylammoinium-Methylammonium Lead Iodide Perovskites with Improved Thermal Stability.

Metal halide perovskite solar cells, despite achieving high power conversion efficiency (PCE), need to demonstrate high stability prior to be considered for industrialization. Prolonged exposure to heat, light, and moisture is known to deteriorate the perovskite material owing to the breakdown of the crystal structure into its non-photoactive components. In this study, we show that by combining the organic ligand 1-naphthylmethylammoinium iodide (NMAI) with methylammonium (MA) to form a mixed dimensional (NMA)(MA)PbI perovskite the optical, crystallographic and morphological properties of the newly formed mixed dimensional perovskite films under thermal ageing can be retained.

Ultrafast long-range spin-funneling in solution-processed Ruddlesden-Popper halide perovskites.

Room-temperature spin-based electronics is the vision of spintronics. Presently, there are few suitable material systems. Herein, we reveal that solution-processed mixed-phase Ruddlesden-Popper perovskite thin-films transcend the challenges of phonon momentum-scattering that limits spin-transfer in conventional semiconductors.

Perturbation-Induced Seeding and Crystallization of Hybrid Perovskites over Surface-Modified Substrates for Optoelectronic Devices.

Growing a monocrystalline layer of lead halide perovskites directly over substrates is necessary to completely harness their stellar properties in optoelectronic devices, as the single crystals of these materials are extremely brittle. We study the crystallization mechanism of perovskites by antisolvent vapor diffusion to its precursor solution and find that heterogeneous nucleation prevails in the process, with the crystallization dish walls providing the energy to overcome the nucleation barrier. By perturbing the system using sonication, we are able to introduce homogeneously nucleated seed crystals in the precursor solution.

Self-assembly of a robust hydrogen-bonded octylphosphonate network on cesium lead bromide perovskite nanocrystals for light-emitting diodes.

We report the self-assembly of an extensive inter-ligand hydrogen-bonding network of octylphosphonates on the surface of cesium lead bromide nanocrystals (CsPbBr NCs). The post-synthetic addition of octylphosphonic acid to oleic acid/oleylamine-capped CsPbBr NCs promoted the attachment of octylphosphonate to the NC surface, while the remaining oleylammonium ligands maintained the high dispersability of the NCs in non-polar solvent. Through powerful 2D solid-state P-H NMR, we demonstrated that an ethyl acetate/acetonitrile purification regime was crucial for initiating the self-assembly of extensive octylphosphonate chains.

Perovskites for Next-Generation Optical Sources.

Next-generation displays and lighting technologies require efficient optical sources that combine brightness, color purity, stability, substrate flexibility. Metal halide perovskites have potential use in a wide range of applications, for they possess excellent charge transport, bandgap tunability and, in the most promising recent optical source materials, intense and efficient luminescence. This review links metal halide perovskites' performance as efficient light emitters with their underlying materials electronic and photophysical attributes.

Ionotronic Halide Perovskite Drift-Diffusive Synapses for Low-Power Neuromorphic Computation.

Emulation of brain-like signal processing is the foundation for development of efficient learning circuitry, but few devices offer the tunable conductance range necessary for mimicking spatiotemporal plasticity in biological synapses. An ionic semiconductor which couples electronic transitions with drift-diffusive ionic kinetics would enable energy-efficient analog-like switching of metastable conductance states. Here, ionic-electronic coupling in halide perovskite semiconductors is utilized to create memristive synapses with a dynamic continuous transition of conductance states.

Enhanced Exciton and Photon Confinement in Ruddlesden-Popper Perovskite Microplatelets for Highly Stable Low-Threshold Polarized Lasing.

At the heart of electrically driven semiconductors lasers lies their gain medium that typically comprises epitaxially grown double heterostuctures or multiple quantum wells. The simultaneous spatial confinement of charge carriers and photons afforded by the smaller bandgaps and higher refractive index of the active layers as compared to the cladding layers in these structures is essential for the optical-gain enhancement favorable for device operation. Emulating these inorganic gain media, superb properties of highly stable low-threshold (as low as ≈8 µJ cm ) linearly polarized lasing from solution-processed Ruddlesden-Popper (RP) perovskite microplatelets are realized.

Spinel CoO nanomaterials for efficient and stable large area carbon-based printed perovskite solar cells.

Carbon based perovskite solar cells (PSCs) are fabricated through easily scalable screen printing techniques, using abundant and cheap carbon to replace the hole transport material (HTM) and the gold electrode further reduces costs, and carbon acts as a moisture repellent that helps in maintaining the stability of the underlying perovskite active layer. An inorganic interlayer of spinel cobaltite oxides (CoO) can greatly enhance the carbon based PSC performance by suppressing charge recombination and extracting holes efficiently. The main focus of this research work is to investigate the effectiveness of CoO spinel oxide as the hole transporting interlayer for carbon based perovskite solar cells (PSCs).

Benzyl Alcohol-Treated CHNHPbBr Nanocrystals Exhibiting High Luminescence, Stability, and Ultralow Amplified Spontaneous Emission Thresholds.

We report the high yield synthesis of about 11 nm sized CHNHPbBr nanocrystals with near-unity photoluminescence quantum yield. The nanocrystals are formed in the presence of surface-binding ligands through their direct precipitation in a benzyl alcohol/toluene phase. The benzyl alcohol plays a pivotal role in steering the surface ligands binding motifs on the NC surface, resulting in enhanced surface-trap passivation and near-unity PLQY values.

Preface to Special Issue of ChemSusChem on Perovskite Optoelectronics.

This Editorial introduces one of two companion Special Issues on "Halide Perovskites for Optoelectronics Applications" in ChemSusChem and Energy Technology following the ICMAT 2017 Conference in Singapore. More information on the other Special Issue can be found in the Editorial published in Energy Technology.

Effect of Formamidinium/Cesium Substitution and PbI on the Long-Term Stability of Triple-Cation Perovskites.

Altering cation and anion ratios in perovskites has proven an excellent means of tuning the perovskite properties and enhancing the performance. Recently, methylammonium/formamidinium/cesium triple-cation mixed-halide perovskites have demonstrated efficiencies up to 22 %. Similar to the widely explored methylammonium lead halide, excess PbI is added to these perovskite films to enhance their performances.

Modulating Excitonic Recombination Effects through One-Step Synthesis of Perovskite Nanoparticles for Light-Emitting Diodes.

The primary advantages of halide perovskites for light-emitting diodes (LEDs) are solution processability, direct band gap, good charge-carrier diffusion lengths, low trap density, and reasonable carrier mobility. The luminescence in 3 D halide perovskite thin films originates from free electron-hole bimolecular recombination. However, the slow bimolecular recombination rate is a fundamental performance limitation.

High Stability Bilayered Perovskites through Crystallization Driven Self-Assembly.

In this manuscript we reveal the formation of bilayered hybrid perovskites of a new lower dimensional perovskite family, (CHMA)(MA)PbI with n = 1-5, with high ambient stability via its crystallization driven self-assembly process. The spun-coated perovskite solution tends to crystallize and undergo phase separation during annealing, resulting in the formation of 2D/3D bilayered hybrid perovskites. Remarkably, this 2D/3D hybrid perovskites possess striking moisture resistance and displays high ambient stability up to 65 days.