Suppressed Ion Migration by Heterojunction Layer for Stable Wide-Bandgap Perovskite and Tandem Photovoltaics.

Wide-bandgap (WBG) perovskite has demonstrated great potential in perovskite-based tandem solar cells. The power conversion efficiency (PCE) of such devices has surpassed 34%, signifying a new era for renewable energy development. However, the ion migration reduces the stability and hinders the commercialization, which is yet to be resolved despite many attempts. A big step forward has now been achieved by the simulation method. The detailed thermodynamics and kinetics of the migration process have been revealed for the first time. The stability has been enhanced by more than 100% via the heterojunction layer on top of the WBG perovskite film, which provided extra bonding for kinetic protection. Hopefully, these discoveries will open a new gate for WBG perovskite research and accelerate the application of perovskite-based tandem solar cells.

Defect Engineering: Can it Mitigate Strong Coulomb Effect of Mg2+ in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries (RMBs) have been considered a promising "post lithium-ion battery" system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market. However, the sluggish diffusion kinetics of bivalent Mg2+ in the host material, related to the strong Coulomb effect between Mg2+ and host anion lattices, hinders their further development toward practical applications. Defect engineering, regarded as an effective strategy to break through the slow migration puzzle, has been validated in various cathode materials for RMBs. In this review, we first thoroughly understand the intrinsic mechanism of Mg2+ diffusion in cathode materials, from which the key factors affecting ion diffusion are further presented. Then, the positive effects of purposely introduced defects, including vacancy and doping, and the corresponding strategies for introducing various defects are discussed. The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized. Finally, the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

All-Inorganic CsPbBr3 Perovskite Planar-Type Memristors as Optoelectronic Synapses.

Mimicking fundamental synaptic working principles with memristors contributes an essential step toward constructing brain-inspired, high-efficiency neuromorphic systems that surpass von Neumann system computers. Here, an electroforming-free planar-type memristor based on a CsPbBr3 single crystal is proposed and exhibits excellent resistive switching (RS) behaviors including stable endurance, ultralow power consumption, and fast switching speed. Furthermore, an optically tunable RS performance is demonstrated by manipulating irradiation intensity and wavelength. Optical analysis techniques such as steady-state photoluminescence and time-resolved photoluminescence are employed to investigate the distribution of Br ions and vacancies before and after quantitative polarization, describing migration dynamic processes to elucidate the RS mechanism. Importantly, a CsPbBr3 single crystal, as the optoelectronic synapse, shows unique potential to emulate photoenhanced synaptic functions such as excitatory postsynaptic current, paired-pulse facilitation, long-term potentiation/depression, spike-timing-dependent plasticity, spike-voltage-dependent plasticity, and learning-forgetting-relearning process with ultralow per synapse event energy consumption. A classical Pavlov's dog experiment is simulated with a combination of optical and electrical stimulation. Finally, pattern recognition with simulated artificial neural networks based on our synapse reached an accuracy of 93.11%. The special strategy and superior RS characteristics of optoelectronic synapses provide a pathway toward high-performance, energy-efficient neuromorphic electronics.

PEAI Surface Treatment for Low Ion Migration and High-Performance FAPbBr3 Single-Crystal X-ray Detectors.

Organometal halide perovskite single crystals (SCs) are the most promising candidates for the next generation of radiation detection materials. However, surface defects severely affect their detection performance and limit further applications. Here, we identified the surface defect types of FAPbBr3 SCs and employed phenethylammonium iodide (PEAI) solution to treat the crystal surface and to investigate their effects on ion migration, photoelectric performance, and X-ray detection performance. Our experimental results demonstrated that the surface defects, such as the metallic Pb and Br vacancies, can be effectively passivated by both the PEAI and the two-dimensional (2D) PEA2PbI4 layers. The PEAI layer can elongate the carrier lifetime, lower the trap density, and suppress ion migration in FAPbBr3 SCs. The 2D PEA2PbI4 layer can form a dense and full surface coverage, suppress ion migration, and lower the dark current of the SCs. The X-ray sensitivity of the PEAI-passivated FAPbBr3 SC detectors is 227.93 µCGyair-1 cm-2, which is an order of magnitude higher than that of the pristine FAPbBr3 SC detectors. This work demonstrates that surface treatment plays a critical role in the crystal quality and the X-ray detection performance of SCs.

Inhibiting Ion Migration and Stabilizing Crystal-Phase in Halide Perovskite via Directly Incorporated Fluoride Anion.

Fluoride anion (F-) with extremely high electronegativity has been under intensive investigation in perovskite solar cells due to its remarkable defect suppression and greatly improvement of device performance. Nevertheless, these researches only focus on surface, grain boundaries or interface modification, the directly insertion of F- into crystal lattice of regular lead halide perovskite films is still unrevealed. Herein, F- was successfully incorporated into perovskite lattice by overcoming the insolubility of PbF2 via the introduced pyridinium halide as a novel volatile solubilizing ligand. The strong electronegativity of F- can strongly increase the binding energy of all the ions in CsPbI2Br and inhibit their defect formations. A trace amount of F- incorporation not only enhanced the optoelectronic properties but also effectively mitigated the ion migration and phase separation simultaneously. The photovoltaic performance and operational stability of perovskite solar cells were significantly improved with a champion efficiency of 17.78% (38.01%) under AM 1.5G (1000 lux indoor light). Moreover, F- can also be directly inserted into hybrid perovskite lattice and greatly stabilized crystal-phase, enabling efficient fully MA-free FAPbI3 devices with 25.10% efficiency. Our strategy sheds light on F-containing perovskites and provides a promising way to tackle ion migration and stabilize crystal-phase in halide perovskites.

Bidirectional Inhibiting Interfacial Ion Migration in the Inorganic Hole Transport Layer for Perovskite Light-Emitting Diodes.

Cu2ZnSnS4 (CZTS) is strong candidate for hole transport in perovskite light emitting diodes (PeLEDs) due to their cost-effectiveness, deep highest occupied molecular orbital (HOMO), and high hole mobility. However, its inherent polymetallic ions usually deteriorate the quality of the perovskite emission layer (EML) affecting device performance. In this study, a bidirectional anchoring strategy is proposed by adding 15-crown-5 ether (15C5) into CZTS hole transport layer (HTL) to suppress the reaction between HTL and EML. The 15C5 molecule interacts with Cu+, Zn2+ and Sn2+ cations forming host-guest complexes to impede their migration, which is elucidated by density functional theory calculations. Additionally, 15C5 can neutralize lead (Pb) defects by the abundant oxygen (O) and high electronegative cavities to reduce the nonradiative recombination of FAPbBr3 film. This bidirectional anchoring strategy effectively improves hole charge transport efficiency and suppresses nonradiative recombination at the HTL/EML interface. As a result, the optimized PeLEDs present a 3.5 times peak external quantum efficiency (EQE) from 3.12% to 11.08% and the maximum luminance (Lmax) increased from 24495 to 50584 cd m-2. These findings offer innovative insights into addressing the metal ion migration issue commonly observed in inorganic HTLs.

Revealing and Inhibiting the Facet-related Ion Migration for Efficient and Stable Perovskite Solar Cells.

Ion migration is a major issue hindering the long-term stability of perovskite solar cells (PSCs). As an intrinsic characteristic of metal halide perovskite materials, ion migration is closely related to the atomic arrangement and coordination, which are the basic characteristic differences among various facets. Herein, we report the facet-related ion migration, and then achieve the inhibition of ion migration in perovskite through finely modulating the facet orientation. We show that the (100) facet is substantially more vulnerable to cationic migration than the (111) facet. The main reason for this difference in migration is that the cationic migration route in the (111) facet deviates from that in the (100) facet, which increases the active migration energy and weakens the contribution from the electric field during operation. We prepare a (111)-dominated perovskite film by incorporating a facile and green addition of water (H2O) into the antisolvent, further achieving a power conversion efficiency (PCE) of 26.0% (25.4% certification) on regular planar PSCs and 25.8% on inverted PSCs. Moreover, the unencapsulated PSCs can maintain 95% of their initial PCE after 3500-hours operation under simulated AM1.5 illumination at the maximum power point.

Rapid Recovery of Degraded Perovskite Single-Crystal Radiation Detectors via Infrared Healing.

Radiation detectors based on metal halide perovskite (MHP) single crystals (SCs) have exhibited exceptional sensitivity, low detection limit, and remarkable energy resolution. However, the operational stability issue still dramatically impedes their commercialization due to degradation induced by high-energy irradiation and large bias. Here, we propose an innovative infrared healing strategy to restore the devices that have undergone severe damage from both long-term biasing and X-ray irradiation. Compared to the slow and inefficient intrinsic self-healing process of MHPs, the infrared healing method demonstrates the capacity to achieve rapid recovery of the detection performance of the degraded devices within just 1 h. We reveal that the healing mechanism is mainly related to the reduction of the ion-migration activation energy in MHP SCs under infrared illumination, which promotes the back diffusion of the displaced ions to their original lattice positions and remedies defects. Finally, the healing effect is further confirmed through the gamma-ray spectroscopy acquisition with degraded MHP SCs, whose energy resolution at 59.5 keV of 241Am source is improved from 36% to 12% following infrared illumination. These results present infrared healing as a simple and economic method to extend the service life of MHP SC-based detectors.

Crown Ethers with Different Cavity Diameters Inhibit Ion Migration and Passivate Defects toward Efficient and Stable Lead Halide Perovskite Solar Cells.

Organic-inorganic hybrid metal halide perovskite solar cells have been considered as one of the most promising next-generation photovoltaic technologies. Nevertheless, perovskite defects and Li+ ionic migration will seriously affect the power conversion efficiency and stability of the formal device. Herein, we designed two crown ether derivatives (PC12 and PC15) with different cavity diameters, which selectively bind to different metal cations. It is found that PC15 in perovskite precursor solution can actively regulate the nucleation and crystallization processes and passivate the uncoordinated Pb2+ ions, while PC12 at the interface between the perovskite layer and hole-transporting layer can effectively inhibit the migration of Li+ ions and reduce nonradiative recombination losses. Therefore, PC12 and PC15 can act as "lubricant" and defect passivators, as well as inhibitors of ion migration, when they are synergistically applied at the surface and bulk of perovskite layer. Consequently, the optimized device achieved a champion efficiency of 24.8% with significantly improved humidity, thermal, and light stability.

LiNbO3 and LiTaO3 Coating Effects on the Interface of the LiCoO2 Cathode: A DFT Study of Li-Ion Transport.

In solid-state batteries, the interface between cathodes and solid electrolytes is crucial and coating layers play a vital role. LiNbO3 has been known as a promising coating material, whereas recent studies showed its degradation via releasing oxygen and lithium during cycling. This computational study addresses the elucidation of essential characteristics of the coating materials by examining LiNbO3 and its counterpart LiTaO3 interfaces to a representative layered cathode, LiCoO2. Employing the interface CALYPSO method, we constructed explicit models of both coatings on LiCoO2. Our findings indicate that LiTaO3 offers easier Li+ migration at the interface due to the smaller difference in Li adiabatic potential at the interface, whereas LiNbO3 more effectively suppresses oxygen activity at high delithiation states via lowering the O 2p states. This comparative analysis provides essential insights into optimizing coating materials for improved battery performance.

In-Situ Growth of One-Dimensional Blocking Layer to Mitigate Deficient Surface of Single-Crystal Perovskites.

Organic-inorganic halide perovskite (OIHP) single crystals are promising for optoelectronic application, but their high surface trap density and associated ion migration hinders device performance and stability. Herein, a one-dimensional (1D) perovskites are designed and proposed as blocking layer at the crystal/electrode interface to mitigate the surface issues. As a model system, the interface ion migration in Cs0.05FA0.95PbI3 (FA=formamidinium) single-crystal perovskite solar cells (PSCs) is obviously suppressed, leading to increase of T90 lifetime from 260 to 1000 hours, five times better than previously reported results. Besides, the reduction of surface iodide ion vacancies inhibits nonradiative recombination, thus increasing the efficiency from 22.1% to 23.8%, which is one of the highest values for single-crystal PSCs. Since the deficient crystal surface is a universal and open issue, our strategy is instructive for optimizing diverse single-crystal perovskite devices.

Lattice Manipulation with Di-Tertiary Ammonium Spacer in Bismuth Bromide Perovskite Directs Efficient Charge Transport and Suppressed Ion Migration for Photodetector Applications.

Bismuth halide hybrid perovskites have emerged as promising alternatives to their lead halide homologs because of high chemical stability, low toxicity, and structural diversity. However, their advancements in optoelectronic field are plagued with poor charge transport, due to considerable microstrain triggered by bulky spacer. Herein, the di-tertiary ammonium spacer (N,N,N',N'-tetramethyl-1,4-butanediammonium, TMBD) is explored to direct stable 1D bismuth bromide lattice structure with relaxed microstrain. Compared to the primary pentamethylenediamine (PD)2+, the (TMBD)2+ adopting alternating alignment enables a unique H-bonds mode to distort the configuration of inorganic layers to form corner-sharing [BiBr5] near-regular chains with narrower bandgap, lower exciton binding energy, and reduced carrier-lattice interactions, thereby facilitating charge-carrier transport. Moreover, the (TMBD)2+ spacers largely suppress ion migration in perovskite lattice, as substantiated by the experimental and theoretical investigations. Consequently, (TMBD)BiBr5 single crystal photodetector delivers a 185-fold increase in current on/off ratio with respect to (PD)BiBr5 under white light irradiation, considerable responsivity (≈82.97 mA W-1), detectivity (≈8.06 ×1011 Jones) under weak light (0.02 mW cm-2) irradiation, in the top rank of the reported hybrid bismuth halide perovskites. This finding offers novel design criterion for high-performance lead-free perovskites.

Assembling the 2D-3D-2D Heterostructure of Quasi-2D Perovskites for High-Performance Solar Cells.

Quasi-two-dimensional (quasi-2D) layered perovskites with mixed dimensions offer a promising avenue for stable and efficient solar cells. However, randomly distributed three-dimensional (3D) perovskites near the film surface limit the device performance of quasi-2D perovskites due to increased nonradiative recombination and ion migration. Herein, we construct a 2D (n = 4 top)-3D-2D (n = 2 bottom) heterostructure of quasi-2D perovskites by using 3-chlorobenzylamine iodine, which can effectively reduce defect density and restrain ion migration. A champion efficiency of 22.22% for quasi-2D perovskite solar cells is achieved due to remarkably reduced nonradiative voltage loss and increased electron extraction. Additionally, the 2D-3D-2D perovskite solar cells also exhibit excellent thermal and humidity stabilities, retaining over 90 and 85% of the initial efficiencies after 2000 h under a heat stress of 65 °C and at air ambient of ∼50% humidity, respectively. Our results provide a general approach to tune perovskite films for suppressing ion migration and achieving high-performance perovskite solar cells.

Sliding Memristor in Parallel-Stacked Hexagonal Boron Nitride.

Sliding ferroelectricity in 2D materials, arising from interlayer sliding-induced interlayer hybridization and charge redistribution at the van der Waals interface, offers a means to manipulate spontaneous polarization at the atomic scale through various methods such as stacking order, interfacial contact, and electric field. However, the practical application of extending 2D sliding ferroelectricity remains challenging due to the contentious mechanisms and the complex device structures required for ferroelectric switching. Here, a sliding memristor based on a graphene/parallel-stacked hexagonal boron nitride/graphene tunneling device, featuring a stable memristive hysteresis induced by interfacial polarizations and barrier height modulations, is presented. As the tunneling current density increases, the memristive window broadens, achieving an on/off ratio of ≈103 and 2 order decrease of the trigger current density, attributed to the interlayer migration of positively charged boron ions and the formation of conductive filaments, as supported by the theoretical calculations. The findings open a path for exploring the sliding memristor via a tunneling device and bridge the gap between sliding ferroelectricity and memory applications.

Unveiling Energy Conversion Mechanisms and Regulation Strategies in Perovskite Solar Cells.

Despite recent revolutionary advancements in photovoltaic (PV) technology, further improving cell efficiencies toward their Shockley-Queisser (SQ) limits remains challenging due to inherent optical, electrical, and thermal losses. Currently, most research focuses on improving optical and electrical performance through maximizing spectral utilization and suppressing carrier recombination losses, while there is a serious lack of effective opto-electro-thermal coupled management, which, however, is crucial for further improving PV performance and the practical application of PV devices. In this article, the energy conversion and loss processes of a PV device (with a specific focus on perovskite solar cells) are detailed under both steady-state and transient processes through rigorous opto-electro-thermal coupling simulation. By innovatively coupling multi-physical behaviors of photon management, carrier/ion transport, and thermodynamics, it meticulously quantifies and analyzes energy losses across optical, electrical, and thermal domains, identifies heat components amenable to regulation, and proposes specific regulatory means, evaluates their impact on device efficiency and operating temperature, offering valuable insights to advance PV technology for practical applications.

Microscale Lateral Perovskite Light Emitting Diode Realized by Self-Doping Phenomenon.

High-definition near-eye display technology has extremely close sight distance, placing a higher demand on the size, performance, and array of light-emitting pixel devices. Based on the excellent photoelectric performance of metal halide perovskite materials, perovskite light-emitting diodes (PeLEDs) have high photoelectric conversion efficiency, adjustable emission spectra, and excellent charge transfer characteristics, demonstrating great prospects as next-generation light sources. Despite their potential, the solubility of perovskite in photoresist presents a hurdle for conventional micro/nano processing techniques, resulting in device sizes typically exceeding 50 µm. This limitation impedes the further downsizing of perovskite-based components. Herein, we propose a plane-structured PeLED device that can achieve microscale light-emitting diodes with a single pixel device size < 2 µm and a luminescence lifetime of approximately 3 s. This is accomplished by fabricating a patterned substrate and regulating ion distribution in the perovskite through self-doping effects to form a PN junction. This breakthrough overcomes the technical challenge of perovskite-photoresist incompatibility, which has hindered the development of perovskite materials in micro/nano optoelectronic devices. The strides made in this study open up promising avenues for the advancement of PeLEDs within the realm of micro/nano optoelectronic devices.

Characterization of flavor volatiles in raw and cooked pigmented onion (Allium cepa L) bulbs: A comparative HS-GC-IMS fingerprinting study.

Variations in volatile flavor components in pigmented onion bulbs (purple, white, and yellow) before and after cooking were characterized by headspace gas chromatography-ion migration spectrometry (HS-GC-IMS) to investigate their odor traits. Results showed that 39 and 45 volatile flavor compounds were identified from pigmented onion bulbs before and after cooking via the HS-GC-IMS fingerprinting, respectively. Sulfurs (accounting for 50.65%-63.42%), aldehydes (13.36%-22.11%), and alcohols (11.32%-17.94%) ranked the top three prevailing compound categories in all pigmented onions (both raw and cooked). Compared to the raw colored onion bulbs, the relative proportion of sulfurs in cooked onions decreased, whereas the relative proportion of alcohols, esters, pyrazines, and furans increased. Two reliable prediction models were established through orthogonal partial least squares-discriminant analysis (OPLS-DA), and 8 and 22 distinctive odor compounds were sieved out by variable importance in projection (VIP>1.0) as volatile labels, respectively. Both principal component analysis (PCA) and clustering heatmap exhibited favorable distinguishing effects for various pigmented onion bulbs before and after cooking. These results might offer insights into understanding the odor characteristics of different pigmented onions.

Scalable and Selective Electrochemical Hydrogenation of Polycyclic Arenes.

The reduction of aromatic compounds constitutes a fundamental and ongoing area of investigation. The selective reduction of polycyclic aromatic compounds to give either fully or partially reduced products remains a challenge, especially in applications to complex molecules at scale. Herein, we present a selective electrochemical hydrogenation of polycyclic arenes conducted under mild conditions. A noteworthy achievement of this approach is the ability to finely control both the complete and partial reduction of specific aromatic rings within polycyclic arenes by judiciously varying the reaction solvents. Mechanistic investigations elucidate the pivotal role played by in situ proton generation and interface regulation in governing reaction selectivity. The reductive electrochemical conditions show a very high level of functional-group tolerance. Furthermore, this methodology represents an easily scalable reduction (demonstrated by the reduction of 1 kg scale starting material) using electrochemical flow chemistry to give key intermediates for the synthesis of specific drugs.

Effect of Metal-Organic Frameworks with Different Ligand Structures (ZIF-11 & ZIF-23) on the Optoelectronic Performance of Perovskite Photodetectors.

Crystal engineering using passivation to reduce perovskite defects is crucial to improving the quality of perovskite crystals and optoelectronic properties. Because of their unique properties, metal-organic framework materials have been used as an emerging and effective passivator for perovskite materials and optoelectronic devices. This paper focuses on the differences in the optoelectronic properties of zeolite imidazolium ester framework materials (ZIF-11 & ZIF-23) doped with different conjugated ring ligands for perovskite photodetectors. This paper proposes a simple and effective method to dope zeolite imidazolium ester framework nanoparticles (ZIF-11 & ZIF-23) into organic-inorganic perovskite MAPbI3 films. The crystalline quality of the perovskite films was improved after doping with ZIF-11 and ZIF-23. Meanwhile, the performance of the planar photoconductive devices was significantly improved. The photoresponsivity of the photodetector doped with ZIF-23 was 0.185A/W, and the detectivity was 4.22 × 1012 Jones. The photoresponsivity of the photodetector doped with ZIF-23 was 0.164 A/W, and the detectivity was 3.27 × 1012 Jones. The devices maintained long-time operational stability, operating without significant degradation for 480 s under the 1.2 V bias voltage operating condition. In addition, we observed a significant suppression of the ion migration process in ZIF-23 for a voltage-controlled ion migration process. The potential application of perovskite and MOF heterojunction materials for image information acquisition and storage is demonstrated.

Enhancing Performance and Stability of p-i-n Perovskite Solar Cells with Ag-Cu Codeposited Alloy Electrodes.

In the development of back electrodes for perovskite solar cells (PSCs), the major challenges are stability and cost. To address this, we present an innovative approach: Simultaneous evaporation of two independently controlled sources of metal materials was performed to achieve a uniform distribution of the alloy electrodes. In this study, Ag-Cu alloys (the molar ratio of Ag/Cu is 7/3) with a high-index crystal face (111) and a work function matching perovskite were prepared using a codeposition technique. These properties mitigate nonradiative carrier recombination at the interface and reduce the energy barrier for carrier migration. Consequently, compared to Ag based PSCs (22.77%), the implementation of Ag-Cu alloy (Ag/Cu is 7/3)-based PSCs resulted in a power conversion efficiency of 23.72%. In a 1500 h tracking test in ambient air, the Ag-Cu alloy (Ag/Cu is 7/3)-based PSCs maintained their initial efficiency of 86%. This can be attributed to almost no migration of elements from the Ag-Cu alloy electrode to the perovskite layer. Our work presents a vital strategy for improving the stability of PSCs and reducing the costs associated with the back electrode in PSCs.