Lighting accounts for one-fifth of global electricity consumption1. Single materials with efficient and stable white-light emission are ideal for lighting applications, but photon emission covering the entire visible spectrum is difficult to achieve using a single material. Metal halide perovskites have outstanding emission properties2,3; however, the best-performing materials of this type contain lead and have unsatisfactory stability. Here we report a lead-free double perovskite that exhibits efficient and stable white-light emission via self-trapped excitons that originate from the Jahn–Teller distortion of the AgCl6 octahedron in the excited state. By alloying sodium cations into Cs2AgInCl6, we break the dark transition (the inversion-symmetry-induced parity-forbidden transition) by manipulating the parity of the wavefunction of the self-trapped exciton and reduce the electronic dimensionality of the semiconductor4. This leads to an increase in photoluminescence efficiency by three orders of magnitude compared to pure Cs2AgInCl6. The optimally alloyed Cs2(Ag0.60Na0.40)InCl6 with 0.04 per cent bismuth doping emits warm-white light with 86 ± 5 per cent quantum efficiency and works for over 1,000 hours. We anticipate that these results will stimulate research on single-emitter-based white-light-emitting phosphors and diodes for next-generation lighting and display technologies. After alloying with metal cations, a lead-free halide double perovskite shows stable performance and remarkably efficient white-light emission, with possible applications in lighting and display technologies.

Efficient and stable emission of warm-white light from lead-free halide double perovskites

Hybrid lead halide perovskites exhibit carrier properties that resemble those of pristine nonpolar semiconductors despite static and dynamic disorder, but how carriers are protected from efficient scattering with charged defects and optical phonons is unknown. Here, we reveal the carrier protection mechanism by comparing three single-crystal lead bromide perovskites: CH3NH3PbBr3, CH(NH2)2PbBr3, and CsPbBr3. We observed hot fluorescence emission from energetic carriers with ~102-picosecond lifetimes in CH3NH3PbBr3 or CH(NH2)2PbBr3, but not in CsPbBr3. The hot fluorescence is correlated with liquid-like molecular reorientational motions, suggesting that dynamic screening protects energetic carriers via solvation or large polaron formation on time scales competitive with that of ultrafast cooling. Similar protections likely exist for band-edge carriers. The long-lived energetic carriers may enable hot-carrier solar cells with efficiencies exceeding the Shockley-Queisser limit.

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Screening in crystalline liquids protects energetic carriers in hybrid perovskites

Hybrid halide perovskites are now superstar materials leading the field of low-cost thin film photovoltaics technologies. Following the surge for more efficient and stable 3D bulk alloys, multilayered halide perovskites and colloidal perovskite nanostructures appeared in 2016 as viable alternative solutions to this challenge, largely exceeding the original proof of concept made in 2009 and 2014, respectively. This triggered renewed interest in lower-dimensional hybrid halide perovskites and at the same time increasingly more numerous and differentiated applications. The present paper is a review of the past and present literature on both colloidal nanostructures and multilayered compounds, emphasizing that availability of accurate structural information is of dramatic importance to reach a fair understanding of quantum and dielectric confinement effects. Layered halide perovskites occupy a special place in the history of halide perovskites, with a large number of seminal papers in the 1980s and 1990s. In ...

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Quantum and Dielectric Confinement Effects in Lower-Dimensional Hybrid Perovskite Semiconductors.

Developing low-cost and high-quality quantum dots (QDs) or nanocrystals (NCs) and their corresponding efficient light-emitting diodes (LEDs) is crucial for the next-generation ultra-high-definition flexible displays. Here, there is a report on a room-temperature triple-ligand surface engineering strategy to play the synergistic role of short ligands of tetraoctylammonium bromide (TOAB), didodecyldimethylammonium bromide (DDAB), and octanoic acid (OTAc) toward "ideal" perovskite QDs with a high photoluminescence quantum yield (PLQY) of >90%, unity radiative decay in its intrinsic channel, stable ink characteristics, and effective charge injection and transportation in QD films, resulting in the highly efficient QD-based LEDs (QLEDs). Furthermore, the QD films with less nonradiative recombination centers exhibit improved PL properties with a PLQY of 61% through dopant engineering in A-site. The robustness of such properties is demonstrated by the fabrication of green electroluminescent LEDs based on CsPbBr3 QDs with the peak external quantum efficiency (EQE) of 11.6%, and the corresponding peak internal quantum efficiency (IQE) and power efficiency are 52.2% and 44.65 lm W-1 , respectively, which are the most-efficient perovskite QLEDs with colloidal CsPbBr3 QDs as emitters up to now. These results demonstrate that the as-obtained QD inks have a wide range application in future high-definition QD displays and high-quality lightings.

Room-Temperature Triple-Ligand Surface Engineering Synergistically Boosts Ink Stability, Recombination Dynamics, and Charge Injection toward EQE-11.6% Perovskite QLEDs

Abstract In the past 10 years, ZnO as a semiconductor has attracted considerable attention due to its unique properties, such as high electron mobility, wide and direct band gap and large exciton binding energy. ZnO has been considered a promising material for optoelectronic device applications, and the fabrications of high quality p-type ZnO and p–n junction are the key steps to realize these applications. However, the reliable p-type doping of the material remains a major challenge because of the self-compensation from native donor defects (V O and Zn i ) and/or hydrogen incorporation. Considerable efforts have been made to obtain p-type ZnO by doping different elements with various techniques. Remarkable progresses have been achieved, both theoretically and experimentally. In this paper, we discuss p-type ZnO materials: theory, growth, properties and devices, comprehensively. We first discuss the native defects in ZnO. Among the native defects in ZnO, V Zn and O i act as acceptors. We then present the theory of p-type doping in ZnO, and summarize the growth techniques for p-type ZnO and the properties of p-type ZnO materials. Theoretically, the principles of selection of p-type dopant, codoping method and X Zn –2V Zn acceptor model are introduced. Experimentally, besides the intrinsic p-type ZnO grown at O-rich ambient, p-type ZnO (MgZnO) materials have been prepared by various techniques using Group-I, IV and V elements. We pay a special attention to the band gap of p-type ZnO by band-gap engineering and room temperature ferromagnetism observed in p-type ZnO. Finally, we summarize the devices based on p-type ZnO materials.

RaoP-Type ZnO Materials: Theory, Growth, Properties, and Devices

Very recently, all-inorganic perovskite CsPbX3 (X = Cl, Br, I) nanostructures such as nanoparticles, nanoplates, and nanorods have been extensively explored. These CsPbX3 nanostructures exhibit excellent optical properties; however, the photophysics involved is not yet clear. Herein, the emission properties and luminescence mechanism of CsPbBr3 nanosheets (NSs) were investigated using steady-state and time-resolved photoluminescence (PL) spectroscopic techniques. Moreover, two kinds of excitonic emissions (Peak 1 and Peak 2) are observed at low temperatures (<80 K) under the conditions of low excitation level. They are revealed to stem from the radiative recombination of trapped and free excitons by examining their spectral features and emission intensity dependences on excitation power. Thermally induced exchange between the two kinds of excitons is found and modeled quantitatively; this has led to the determination of an activation energy of 13 meV. Thermal redistribution of trapped excitons and thermal expansion-induced blueshift of the bandgap are jointly responsible for the abnormal temperature dependence of the position of Peak 1, whereas the latter is predominant for the monotonic blueshift of the position of Peak 2 with an increase in temperature. These results and findings shed some light on the complicated luminescence mechanism of CsPbBr3 NSs.

Luminescence and thermal behaviors of free and trapped excitons in cesium lead halide perovskite nanosheets

Engineering the Exciton Dissociation in Quantum‐Confined 2D CsPbBr3 Nanosheet Films

The role of exciton–phonon coupling in light emission in cesium lead bromide (CsPbBr3) nanosheets is investigated with combined photoluminescence spectroscopy and the multimode Brownian oscillator ...

Anomalous Temperature-Dependent Exciton–Phonon Coupling in Cesium Lead Bromide Perovskite Nanosheets

Voltage-dependent, color-tunable organic light-emitting diodes (OLEDs) are appealing tools that can be used for the visualization of electronic output signal of sensors. Nonetheless, the literature-reported color-tunable OLEDs that have a simple single-cell device structure suffer from relatively low efficiency, pronounced efficiency roll-off, color-aging, and short operation lifetime, all of which limit their practical applications. Here, a novel co-host-in-double-emissive-layer (CHIDEL) device, designed to enhance the performance of color-tunable OLEDs with the use of a single tetradentate Pt[O^ N^ C^ N] emitter, is described. When Pt-X-2 is used as a single emitter in an optimized CHIDEL device, a white OLED with tunable Commission International de I'Eclairage (CIE) coordinates from (0.47, 0.44) at 3 V to (0.36, 0.48) at 11 V, a high color rendering index of 82, and high external quantum efficiency (EQE) of up to 20.75% can be achieved. By using Pt-X-4 as a single emitter, the voltage-dependent color-tunable CHIDEL device, with CIE coordinates shifted from (0.56, 0.43) at 3 V to (0.42, 0.55) at 11 V, demonstrates a high luminance of beyond 90 000 cd m-2 and a high EQE of 23.23% at a luminance of 1300 cd m-2 . A long-lifetime time to 90% of the initial luminance (LT90 ) of almost 20 000 h is demonstrated for the color-tunable OLED with Pt-X-4 emitting dopant.

Stable, High-Efficiency Voltage-Dependent Color-Tunable Organic Light-Emitting Diodes with a Single Tetradentate Platinum(II) Emitter Having Long Operational Lifetime.

The role of exciton–phonon coupling in light emission in cesium lead bromide (CsPbBr₃) nanosheets is investigated with combined photoluminescence spectroscopy and the multimode Brownian oscillator model. A good agreement between theory and experiment in the low temperature range of 5–40 K enables us to determine several key parameters, including the dimensionless Huang–Rhys factor characterizing the exciton–longitudinal-optical phonon coupling strength and the damping constant accounting for the phonon bath (quasi-continuous acoustic phonons) dissipation. It is found that the Huang–Rhys factor of the free excitons peculiarly tends to diminish upon increasing the temperature in the interested low temperature range. However, the damping constant shows a linear increase with temperature in the interested temperature range. These new findings may deepen the understanding of the exciton–phonon coupling in CsPbBr₃ nanosheets and relevant solids.

Xiangzhou Lao

Papers

Luminescence and thermal behaviors of free and trapped excitons in cesium lead halide perovskite nanosheets

Engineering the Exciton Dissociation in Quantum‐Confined 2D CsPbBr3 Nanosheet Films

Anomalous Temperature-Dependent Exciton–Phonon Coupling in Cesium Lead Bromide Perovskite Nanosheets

Stable, High-Efficiency Voltage-Dependent Color-Tunable Organic Light-Emitting Diodes with a Single Tetradentate Platinum(II) Emitter Having Long Operational Lifetime.

Anomalous Temperature-Dependent Exciton–Phonon Coupling in Cesium Lead Bromide Perovskite Nanosheets