Regulating The Electronic Configuration of Low-Dimensional Hybrid Perovskites via Organic Cations for Self-Powered Ultraviolet Photodetectors.

Ultraviolet photodetectors (UPDs) based on low-dimensional halide perovskites have undergone rapid development. Here, regulation of the electronic configuration of low-dimensional hybrid perovskites are reported via organic cations for self-powered UPDs. For the first time, it is determine that the rational design of organic cation phenyl alkylammonium can effectively prevent phonon scattering thus increasing charge carrier extraction in low dimensional lead chlorine perovskite thin-films. As a result, the exciton-binding energy can be reduced to 62.91 meV in (PMA)2 PbCl4 perovskite films with a charge-carrier mobility of 0.335 cm2  V-1  s-1 . The fabricated (PMA)2 PbCl4 -based self-powered UPDs has achieved a high detectivity of 6.32 × 1013 jones with a low noise current of 0.35 pA Hz-1/2 under zero bias. A further demonstration of images with high UV to visible light rejection ratio under weak-light illumination of 70 nW cm-2 highlights the feasible potential application of low-dimensional perovskite.

High-Efficiency and Emission-Tunable Inorganic Blue Perovskite Light-Emitting Diodes Based on Vacuum Deposition.

The fabrication of perovskite light-emitting diodes (PeLEDs) with vacuum deposition shows great potential and commercial value in realizing large-area display panel manufacturing. However, the electroluminescence (EL) performance of vacuum-deposited PeLEDs still lags behind the counterparts fabricated by solution process, especially in the field of blue PeLEDs. Here, the fabrication of high-quality CsPbBr3- x Clx film through tri-source co-evaporation is reported to achieve high photoluminescence quantum yield (PLQY). Compared with the conventional traditional dual-source co-evaporation, the tri-source co-evaporation method allows for freely adjustable elemental ratios, enabling the introduction of the lattice-matched Cs4 Pb(Br/Cl)6 phase with the quantum-limited effect into the inorganic CsPb(Br/Cl)3 emitter. By adjusting the phase distribution, the surface defects of the emitter can be effectively reduced, leading to better blue emission and film quality. Further, the effects of Cs/Pb ratio and Br/Cl ratio on the PLQY and carrier recombination dynamics of perovskite films are investigated. By optimizing the deposition rate of each precursor source, spectrally stable blue PeLEDs are achieved with tunable emission ranging from 468 to 488 nm. Particularly, the PeLEDs with an EL peak at 488 nm show an external quantum efficiency (EQE) of 4.56%, which is the highest EQE value for mixed-halide PeLEDs fabricated by vacuum deposition.

Cation-Deficient Perovskites Greatly Enhance the Electrocatalytic Activity for Oxygen Reduction Reaction.

Many perovskite oxides (ABO3 ) are considered the most promising alternatives to noble metal catalysts for oxygen reduction reaction (ORR) due to their high intrinsic activities. However, their electrocatalytic performance is often limited by poor electrical conductivity and low specific surface area. Here an electrochemically induced calcium-leaching process is reported to greatly increase the electrochemical surface area (ECSA) of La0.6 Ca0.4 MnO3 (LCMO64). The ECSA of the activated, Ca-deficient LCMO64 is ≈33.84% higher than that of the unactivated materials, demonstrating superior electrocatalytic ORR performance to the benchmark commercial Pt/C catalyst in an alkaline solution. Theoretical analysis coupled with electrochemical surface state probing and pH-dependent microkinetic modeling suggests that this catalyst with the identified most favorable state under ORR operating conditions reaches the Sabatier optimum of alkaline ORR. This reconstructed LCMO64 is among the best-performing ORR catalysts ever reported, providing new insights into the design of advanced perovskite materials with optimal surface chemistry.

Strong Second- and Third-Harmonic Generation in 1D Chiral Hybrid Bismuth Halides.

Breaking the symmetry of a crystal structure can enable even-order nonlinear activities, including second-harmonic generation (SHG). The emerging chiral hybrid organic-inorganic metal halides feature unique optical and electronic properties and flexible crystal structures, making them a class of promising nonlinear optical materials. However, their nonlinear response performances are currently inferior to traditional nonlinear crystals, because of the lack of research on resonant enhancement and third-harmonic generation (THG). Herein, we designed chiral hybrid bismuth halides with naturally nonsymmetrical structure to enable SHG. Simultaneously, these chiral compounds preserve 1D crystal structures to create strong free exciton, broad self-trapped exciton (STE), and discrete band energy levels, which facilitate the resonant enhancement of SHG and THG susceptibilities. These new chiral films showcase superior effective SHG susceptibility (χ(2) ∼ 130.5 pm V-1 at an interesting wavelength of 1550 nm), exceeding that of the reference, a commercial LiNbO3 (χ(2) ∼ 83.4 pm V-1) single-crystal film. Furthermore, their THG intensities are even higher than their SHG intensities, with effective THG susceptibility (χ(3)) being ∼9.0 × 106 pm2 V-2 at 1550 nm (37 times that of the reference monolayer WS2). Their high SHG and THG performances indicate the promising future of these 1D chiral hybrid bismuth halides toward nonlinear optical applications.

Efficient and large-area all vacuum-deposited perovskite light-emitting diodes via spatial confinement.

With rapid advances of perovskite light-emitting diodes (PeLEDs), the large-scale fabrication of patterned PeLEDs towards display panels is of increasing importance. However, most state-of-the-art PeLEDs are fabricated by solution-processed techniques, which are difficult to simultaneously achieve high-resolution pixels and large-scale production. To this end, we construct efficient CsPbBr3 PeLEDs employing a vacuum deposition technique, which has been demonstrated as the most successful route for commercial organic LED displays. By carefully controlling the strength of the spatial confinement in CsPbBr3 film, its radiative recombination is greatly enhanced while the nonradiative recombination is suppressed. As a result, the external quantum efficiency (EQE) of thermally evaporated PeLED reaches 8.0%, a record for vacuum processed PeLEDs. Benefitting from the excellent uniformity and scalability of the thermal evaporation, we demonstrate PeLED with a functional area up to 40.2 cm2 and a peak EQE of 7.1%, representing one of the most efficient large-area PeLEDs. We further achieve high-resolution patterned perovskite film with 100 µm pixels using fine metal masks, laying the foundation for potential display applications. We believe the strategy of confinement strength regulation in thermally evaporated perovskites provides an effective way to process high-efficiency and large-area PeLEDs towards commercial display panels.

Highly Luminescent Zero-Dimensional Organic Copper Halides for X-ray Scintillation.

The present work reports highly efficient flexible and reabsorption-free scintillators based on two zero-dimensional (0D) organic copper halides (TBA)CuX2 (TBA = tetrabutylammonium cation; X = Cl, Br). The (TBA)CuX2 exhibit highly luminescent green and sky-blue emissions peaked at 510 and 498 nm, with large Stokes shifts of 224 and 209 nm and high photoluminescence quantum yields (PLQYs) of 92.8% and 80.5% at room temperature for (TBA)CuCl2 and (TBA)CuBr2 single crystals (SCs), respectively. Interestingly, above room temperature, their PLQYs increase with temperature and reach near unity at 320 and 345 K for (TBA)CuCl2 and (TBA)CuBr2, respectively. The excellent properties originate from self-trapped excitons (STEs) in individual [CuX2]- quantum rods, which is demonstrated by the temperature-dependent PL, ultrafast transient absorption (TA) combined with density functional theory (DFT) calculations. The (TBA)CuX2 scintillators show bright radioluminescence (RL), impressive linear response to dose rate in a broad range, and high light yields. Their potential application in X-ray imaging is demonstrated by using (TBA)CuX2 composite scintillation screens. Importantly, flexible scintillators are demonstrated to be superior than flat ones for imaging nonplanar objects by conformally coating, which produce accurate images with negligible distortion.

Efficient Dual-Band White-Light Emission with High Color Rendering from Zero-Dimensional Organic Copper Iodide.

Broad-band white-light emissions from organic-inorganic lead halide hybrids have attracted considerable attention in energy-saving solid-state lighting (SSL) applications. However, the toxicity of lead in these hybrids hinders their commercial prospects, and the low photoluminescence quantum yields (PLQYs) cannot meet the requirements for efficient lighting. Here, we report a highly efficient dual-band white-light emission from organic copper iodide, (C16H36N)CuI2, which exhibits a high PLQY of 54.3% and excellent air stability. The single-crystalline (C16H36N)CuI2 possesses a unique zero-dimensional (0D) structure, in which the isolated [Cu2I4]2- dimers are periodically embedded in the wide band gap organic framework of C16H36N+. This perfect 0D structure can cause significant quantum confinement and strong electron-phonon coupling, which contributes to efficient emissions from self-trapped excitons (STEs). Photophysical studies revealed the presence of two self-trapped emitting states in [Cu2I4]2- dimers, whose populations are highly sensitive to the temperature that governs the molecular environment for [Cu2I4]2- dimers and the thermal activation energy of STEs. An ultraviolet (UV) excited white light-emitting diode fabricated using this single-phase white-light emitter exhibits a high color rendering index (CRI) of 78. The new material provides a promising emitter, having a high PLQY and a high CRI simultaneously, for SSL and display applications.

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

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.

Nanoscale diffractive probing of strain dynamics in ultrafast transmission electron microscopy.

The control of optically driven high-frequency strain waves in nanostructured systems is an essential ingredient for the further development of nanophononics. However, broadly applicable experimental means to quantitatively map such structural distortion on their intrinsic ultrafast time and nanometer length scales are still lacking. Here, we introduce ultrafast convergent beam electron diffraction with a nanoscale probe beam for the quantitative retrieval of the time-dependent local deformation gradient tensor. We demonstrate its capabilities by investigating the ultrafast acoustic deformations close to the edge of a single-crystalline graphite membrane. Tracking the structural distortion with a 28-nm/700-fs spatio-temporal resolution, we observe an acoustic membrane breathing mode with spatially modulated amplitude, governed by the optical near field structure at the membrane edge. Furthermore, an in-plane polarized acoustic shock wave is launched at the membrane edge, which triggers secondary acoustic shear waves with a pronounced spatio-temporal dependency. The experimental findings are compared to numerical acoustic wave simulations in the continuous medium limit, highlighting the importance of microscopic dissipation mechanisms and ballistic transport channels.

Ultrafast atomic-scale visualization of acoustic phonons generated by optically excited quantum dots.

Understanding the dynamics of atomic vibrations confined in quasi-zero dimensional systems is crucial from both a fundamental point-of-view and a technological perspective. Using ultrafast electron diffraction, we monitored the lattice dynamics of GaAs quantum dots-grown by Droplet Epitaxy on AlGaAs-with sub-picosecond and sub-picometer resolutions. An ultrafast laser pulse nearly resonantly excites a confined exciton, which efficiently couples to high-energy acoustic phonons through the deformation potential mechanism. The transient behavior of the measured diffraction pattern reveals the nonequilibrium phonon dynamics both within the dots and in the region surrounding them. The experimental results are interpreted within the theoretical framework of a non-Markovian decoherence, according to which the optical excitation creates a localized polaron within the dot and a travelling phonon wavepacket that leaves the dot at the speed of sound. These findings indicate that integration of a phononic emitter in opto-electronic devices based on quantum dots for controlled communication processes can be fundamentally feasible.

Diffraction of quantum dots reveals nanoscale ultrafast energy localization.

Unlike in bulk materials, energy transport in low-dimensional and nanoscale systems may be governed by a coherent "ballistic" behavior of lattice vibrations, the phonons. If dominant, such behavior would determine the mechanism for transport and relaxation in various energy-conversion applications. In order to study this coherent limit, both the spatial and temporal resolutions must be sufficient for the length-time scales involved. Here, we report observation of the lattice dynamics in nanoscale quantum dots of gallium arsenide using ultrafast electron diffraction. By varying the dot size from h = 11 to 46 nm, the length scale effect was examined, together with the temporal change. When the dot size is smaller than the inelastic phonon mean-free path, the energy remains localized in high-energy acoustic modes that travel coherently within the dot. As the dot size increases, an energy dissipation toward low-energy phonons takes place, and the transport becomes diffusive. Because ultrafast diffraction provides the atomic-scale resolution and a sufficiently high time resolution, other nanostructured materials can be studied similarly to elucidate the nature of dynamical energy localization.

Observing (non)linear lattice dynamics in graphite by ultrafast Kikuchi diffraction.

In materials, the nature of the strain-stress relationship, which is fundamental to their properties, is determined by both the linear and nonlinear elastic responses. Whereas the linear response can be measured by various techniques, the nonlinear behavior is nontrivial to probe and to reveal its nature. Here, we report the methodology of time-resolved Kikuchi diffraction for mapping the (non)linear elastic response of nanoscale graphite following an ultrafast, impulsive strain excitation. It is found that the longitudinal wave propagating along the c-axis exhibits echoes with a frequency of 9.1 GHz, which indicates the reflections of strain between the two surfaces of the material with a speed of ∼4 km/s. Because Kikuchi diffraction enables the probing of strain in the transverse direction, we also observed a higher-frequency mode at 75.5 GHz, which has a relatively long lifetime, on the order of milliseconds. The fluence dependence and the polarization properties of this nonlinear mode are entirely different from those of the linear, longitudinal mode, and here we suggest a localized breather motion in the a-b plane as the origin of the nonlinear shear dynamics. The approach presented in this contribution has the potential for a wide range of applications because most crystalline materials exhibit Kikuchi diffraction.

Structural dynamics of surfaces by ultrafast electron crystallography: experimental and multiple scattering theory.

Recent studies in ultrafast electron crystallography (UEC) using a reflection diffraction geometry have enabled the investigation of a wide range of phenomena on the femtosecond and picosecond time scales. In all these studies, the analysis of the diffraction patterns and their temporal change after excitation was performed within the kinematical scattering theory. In this contribution, we address the question, to what extent dynamical scattering effects have to be included in order to obtain quantitative information about structural dynamics. We discuss different scattering regimes and provide diffraction maps that describe all essential features of scatterings and observables. The effects are quantified by dynamical scattering simulations and examined by direct comparison to the results of ultrafast electron diffraction experiments on an in situ prepared Ni(100) surface, for which structural dynamics can be well described by a two-temperature model. We also report calculations for graphite surfaces. The theoretical framework provided here allows for further UEC studies of surfaces especially at larger penetration depths and for those of heavy-atom materials.

Triggering and guiding HV discharge in air by filamentation of single and dual fs pulses.

The triggering and guiding of the stationary high voltage (HV) discharges at 5-40 kV are demonstrated by using plasma filaments generated by single and dual femtosecond(fs) laser pulses in air. A significant reduction of the breakdown voltage threshold due to the pre-ionization of the air gap by laser pulse filamentaion was observed. The amount of free electrons of filaments generated by different pulse configurations was compared by sonography method. The lifetime of filaments is measured by using time-resolved fluorescence spectrum, and the lifetime of filaments generated by dual fs laser pulses was doubled due to the re-ionization by the succeeding pulse. The triggering ability of dual fs laser pulses was demonstrated to be enhanced due to the longer lifetime of filaments.

Efficient characterization of regional mesenteric blood flow by use of laser speckle imaging.

We present a noninvasive full-field method--laser speckle imaging (LSI)--for measuring the regional mesenteric blood flow without scanning. A system of LSI was designed and validated in a model experiment. Dynamics of regional blood flow in the rat mesentery under the influence of noradrenaline were monitored by this method. Spatial and temporal characteristics of the mesenteric blood-flow response were achieved with high resolution. These suggested that LSI might provide a new approach to microcirculation studies.