Core/Shell Perovskite Nanocrystals: Synthesis of Highly Efficient and Environmentally Stable FAPbBr3/CsPbBr3 for LED Applications

Lead halide perovskite nanocrystals (PeNCs) are promising materials for applications in optoelectronics. However, their environmental instability remains to be addressed to enable their advancement into industry. Here the development of a novel synthesis method is reported for monodispersed PeNCs coated with all inorganic shell of cesium lead bromide (CsPbBr₃) grown epitaxially on the surface of formamidinium lead bromide (FAPbBr₃) NCs. The formed FAPbBr₃/CsPbBr₃ NCs have photoluminescence in the visible range 460–560 nm with narrow emission linewidth (20 nm) and high optical quantum yield, photoluminescence quantum yield (PLQY) up to 93%. The core/shell perovskites have enhanced optical stability under ambient conditions (70 d) and under ultraviolet radiation (50 h). The enhanced properties are attributed to overgrowth of FAPbBr₃ with all‐inorganic CsPbBr₃ shell, which acts as a protective layer and enables effective passivation of the surface defects. The use of these green‐emitting core/shell FAPbBr₃/CsPbBr₃ NCs is demonstrated in light‐emitting diodes (LEDs) and significant enhancement of their performance is achieved compared to core only FAPbBr₃‐LEDs. The maximum current efficiency observed in core/shell NC LED is 19.75 cd A^‐1 and the external quantum efficiency of 8.1%, which are approximately four times and approximately eight times higher, respectively, compared to core‐only devices.     

Metal Halide Perovskite Arrays: From Construction to Optoelectronic Applications

Inorganic semiconductor arrays revolutionize many areas of electronics, optoelectronics with the properties of multifunctionality and large-scale integration. Metal halide perovskites are emerging as candidates for next-generation optoelectronic devices due to their excellent optoelectronic properties, ease of processing, and compatibility with flexible substrates. To date, a series of patterning technologies have been applied to perovskites to realize array configurations and nano/microstructured surfaces to further improve device performances. Herein, various construction methods for perovskite crystal or thin film arrays are summarized. The optoelectronic applications of the perovskite arrays are also discussed, in particular, for photodetectors, light-emitting diodes, lasers, and nanogratings.     

Halide Perovskite Materials for Energy Storage Applications

Halide perovskites, traditionally a solar‐cell material that exhibits superior energy conversion properties, have recently been deployed in energy storage systems such as lithium‐ion batteries and photorechargeable batteries. Here, recent progress in halide perovskite‐based energy storage systems is presented, focusing on halide perovskite lithium‐ion batteries and halide perovskite photorechargeable batteries. Halide‐perovskite‐based supercapacitors and photosupercapacitors are also discussed. The photorechargeable batteries and photorechargeable supercapacitors employ solar energy to photocharge the battery; this saves energy and improves device portability. These lightweight, integrated halide perovskite‐based systems, which are pertinent to electric vehicles and portable electronic devices, are reviewed in detail. Suggestions on future research into the design of halide‐perovskite‐based energy storage materials are also given. This review provides a foundation for the development of integrated lightweight energy conversion and storage materials.     

Recent Developments of Optoelectronic Synaptic Devices Based on Metal Halide Perovskites

Massive data processing with high computing efficiency and low operating power is required owing to the rapid development of artificial intelligence and information technology. However, the von Neumann structure computing system with the separated memory and processor can cause large energy consumption and a low running speed during massive data processing. Therefore, the brain-inspired neuromorphic computing system is developed, that can provide hardware support for emulating biological synaptic functions and realizing highly intensive data processing with low power consumption. As a neuromorphic device, the optoelectronic synaptic device (OSD) is regarded as an ideal device to replace the von Neumann-based computer because of its ultrafast signal transmission, large bandwidth, low energy consumption, and wireless communication. Owing to their unique optoelectronic property, metal halide perovskites (MHPs) have received growing attention as effective photosensitive materials in OSDs. Therefore, the review introduces the recent progress on OSDs based on MHPs (MHPs-OSDs) including the structures and properties of MHPs, and the architectures and performance characteristics of MHPs-OSDs. Furthermore, applications of MHPs-OSDs are presented. Finally, the outlook and opportunity of MHPs-OSDs are discussed.     

Ferroic Halide Perovskite Optoelectronics

Metal halide perovskites (MHPs) as one of the most active materials gained tremendous attention in the past decade because of their outstanding performance in optoelectronics. Owing to their perovskite structure, ferroelectricity is anticipated in this class of materials. However, whether MHPs are ferroelectric or not remains elusive. Recently, discussion regarding ferroelasticity in MHPs has been also raised. In addition, ionic motion and structural dynamics are well known in MHPs. The interplay of these phenomena including electric polarization, strain, ionic motion, and structural dynamics can have a significant impact on optoelectronics. Therefore, understanding the mechanism behind these phenomena and their interactions is critical in addressing the controversy about ferroicity of MHPs and developing functional devices. Here, the current findings about MHP's ferroicity are summarized and evaluated and a perspective for the future is provided. It is suggested that ionic motion and associated phenomena, coupled with ferroic behavior, are the main drivers behind MHPs functionality. The challenges are also discussed in probing MHPs’ ferroicity and what new measurement modalities are needed to fully understand and characterize MHP behavior. Finally, it is discussed how ferroic and strain can affect the optoelectronic performance of MHPs and how they can be used for engineering of higher performance devices.     

Metal Halide Perovskites for Laser Applications

Metal halide perovskites have drawn tremendous attention in optoelectronic applications owing to the rapid development in photovoltaic and light-emitting diode devices. More recently, these materials are demonstrated as excellent gain media for laser applications due to their large absorption coefficient, low defect density, high charge carrier mobility, long carrier diffusion length, high photoluminescence quantum yield, and low Auger recombination rate. Despite the great progress in laser applications, the development of perovskite lasers is still in its infancy and the realization of electrically pumped lasers has not yet been demonstrated. To accelerate the development of perovskite-based lasers, it is important to understand the fundamental photophysical characteristics of perovskite gain materials. Here, the structure and gain behavior in various perovskite materials are discussed. Then, the effects of charge carrier dynamics and electron–phonon interaction on population inversion in different types of perovskite materials are analyzed. Further, recent advances in perovskite-based lasers are also highlighted. Finally, a perspective on perovskite material design is presented and the remaining challenges of perovskite lasers are discussed.     

Optoelectronic Synapses and Photodetectors Based on Organic Semiconductor/Halide Perovskite Heterojunctions: Materials,Devices, and Applications

Both photodetectors (PDs) and optoelectronic synaptic devices (OSDs) are optoelectronic devices converting light signals into electrical responses. Optoelectronic devices based on organic semiconductors and halide perovskites have aroused tremendous research interest owing to their exceptional optical/electrical characteristics and low-cost processability. The heterojunction formed between organic semiconductors and halide perovskites can modify the exciton dissociation/recombination efficiency and modulate the charge-trapping effect. Consequently, organic semiconductor/halide perovskite heterojunctions can endow PDs and OSDs with high photo responsivity and the ability to simulate synaptic functions respectively, making them appropriate for the development of energy-efficient artificial visual systems with sensory and recognition functions. This article summarizes the recent advances in this research field. The physical/chemical properties and preparation methods of organic semiconductor/halide perovskite heterojunctions are briefly introduced. Then the development of PDs and OSDs based on organic semiconductor/halide perovskite heterojunctions, as well as their innovative applications, are systematically presented. Finally, some prospective challenges and probable strategies for the future development of optoelectronic devices based on organic semiconductor/halide perovskite heterojunctions are discussed.     

Metal Halide Perovskite Light‐Emitting Devices: Promising Technology for Next‐Generation Displays

As the requirements and expectation for displays in society are growing, higher standards of the display technology are proposed, including wider color gamut, higher color purity, and higher resolution. The recent emergence of light‐emitting halide perovskites has come with numerous advantages, such as high charge‐carrier mobility, tunable emission wavelength, narrow emission linewidth, and intrinsically high photoluminescence quantum yield. Recent advancement of perovskite‐based light‐emitting diodes (PeLEDs) as a promising technology for next‐generation displays is reviewed. Here, how the attractive optical and electrical properties of perovskite materials can be translated into high PeLED performance are discussed, and working mechanisms and optimization approaches of both perovskite materials and the respective devices are analyzed. On the material side this includes the control of size and composition of perovskites grains and nanocrystals, surface and interface passivation, doping and alloying, while on the device side this includes the interfacial engineering and energy level adjustments, and photon emission enhancement. Several challenges such as performance of blue PeLEDs, the environmental and operational stability of PeLEDs, and the toxicity issues of lead halide perovskites are discussed, and perspectives on future developments of perovskite materials and PeLEDs for the display technology are offered.     

Role of Metal Contacts on Halide Perovskite Memristors

Halide perovskites are promising candidates for resistive memories (memristors) due to their mixed electronic/ionic conductivity and the real activation mechanism is currently under debate. In order to unveil the role of the metal contact and its connection with the activation process, four model systems are screened on halide perovskite memristors: Nearly inert metals (Au and Pt), low reactivity contacts (Cu), highly reactive contact (Ag and Al), and pre-oxidized metal in the form of AgI. It is revealed that the threshold voltage for activation of the memory effect is highly connected with the electrochemical activity of the metals. Redox/capacitive peaks are observed for reactive metals at positive potentials and charged ions are formed that can follow the electrical field. Activation proceeds by formation of conductive filaments, either by the direct migration of the charged metals or by an increase in the concentration of halide vacancies generated by this electrochemical reaction. Importantly, the use of pre-oxidized Ag⁺ ions leads to very low threshold voltages of ≈0.2 V indicating that an additional electrochemical reaction is not needed in this system to activate the memristor. Overall, the effect of the metal contact is clarified, and it is revealed that AgI is a very promising interfacial layer for low-energy applications.     

Strategic Doping in Metal Halide Perovskites for Thermoelectrics

Metal halide perovskites (MHPs) have not only shown unique merits of ultralow thermal conductivity compared to traditional inorganic thermoelectric (TE) materials, but also featured superior Seebeck effect to organic semiconductors, thereby affording great prospect in TE field. However, their severely poor electrical conductivity significantly hinders TE applications, which results from the restrained doping efficiency due to the limited accommodation capability of heterogeneous dopants and the heavy compensation from interior defects in MHPs. Realizing high-effectiveness electrical doping in MHPs becomes imperative yet remains extremely challenging. This Minireview is therefore intended to sort out the diversified doping strategies and highlight their underlying impacts on both thermal and electrical transportation in MHPs. These strategies are systematically classified into bulk and surface/interface doping as dictated by where the dopants are implemented while unravelling how they critically impact TE properties in distinctive means. A rational guideline is hence derived to strengthen electrical doping towards desirable perovskite TEs.     

Recent Progress on Synthesis,Characterization, and Applications of Metal Halide Perovskites@Metal Oxide

Metal halide perovskites (MHPs) have become a promising candidate in a myriad of applications, such as light-emitting diodes, solar cells, lasing, photodetectors, photocatalysis, transistors, etc. This is related to the synergy of their excellent features, including high photoluminescence quantum yields, narrow and tunable emission, long charge carrier lifetimes, broad absorption spectrum along with high extinction absorptions coefficients, among others. However, the main bottleneck is the poor stability of the MHPs under ambient conditions. This is imposing severe restrictions with respect to their industrialized applications and commercialization. In this context, metal oxide (MO_x) coatings have recently emerged as an efficient strategy toward overcoming the stabilities issues as well as retaining the excellent properties of the MHPs, and therefore facilitate the development of the related devices’ stabilities and performances. This review provides a summary of the recent progress on synthetic methods, enhanced features, the techniques to assess the MHPs@MO_x composites, and applications of the MHPs@MO_x. Specially, novel approaches to fabricate the composites and new applications of the composites are also reported in this review for the first time. This is rounded by a critical outlook about the current MHPs’ stability issues and the further direction to ensure a bright future of MHPs@MO_x.     

Hierarchical Chiral Self-Assembly of Lead Halide Perovskite Nanocrystals by Oriented Phase Transition

Self-assembly of lead halide perovskite nanocrystals (NCs) into close-packed, long-range-ordered nanostructures can effectively modulate their photoelectronic properties, yet significantly challenging. Herein, an efficient approach is reported to induce the hierarchical self-assembly of perovskite CsPbBr₃ NCs by phase transition using chiral cysteine ligands, yielding asymmetric Cs₄PbBr₆ nanorods (NRs) with the circularly polarized luminescent response. An interfacial phase transition process is found during the conversion of CsPbBr₃ nanocubes to Cs₄PbBr₆ NCs initiated by cysteine molecules. Then the Cs₄PbBr₆ NCs aggregate sequentially to form nanoclusters, which further self-assemble into the chiral Cs₄PbBr₆ NRs. Molecular dynamics simulations reveal that the Cs₄PbBr₆ nanochains gradually approach each other to achieve an asymmetric structure, and the simulated circular dichroism spectrum further supports the formation of a chiral structure. This work offers a facile method for the hierarchical chiral self-assembly of lead halide perovskite nanostructures, which brings new insights to explore chiral nanostructures by modulating the surface chemistry and post self-assembly.     

Photoelectrochemically Active and Environmentally Stable CsPbBr3/TiO2 Core/Shell Nanocrystals

Inherent poor stability of perovskite nanocrystals (NCs) is the main impediment preventing broad applications of the materials. Here, TiO₂ shell coated CsPbBr₃ core/shell NCs are synthesized through the encapsulation of colloidal CsPbBr₃ NCs with titanium precursor, followed by calcination at 300 °C. The nearly monodispersed CsPbBr₃/TiO₂ core/shell NCs show excellent water stability for at least three months with the size, structure, morphology, and optical properties remaining identical, which represent the most water‐stable inorganic shell passivated perovskite NCs reported to date. In addition, TiO₂ shell coating can effectively suppress anion exchange and photodegradation, therefore dramatically improving the chemical stability and photostability of the core CsPbBr₃ NCs. More importantly, photoluminescence and (photo)electrochemical characterizations exhibit increased charge separation efficiency due to the electrical conductivity of the TiO₂ shell, hence leading to an improved photoelectric activity in water. This study opens new possibilities for optoelectronic and photocatalytic applications of perovskites‐based NCs in aqueous phase.     

Rational Design of Colloidal Core/Shell Quantum Dots for Optoelectronic Applications

Colloidal core/shell quantum dots (QDs) are promising for solar technologies because of their excellent optoelectronic properties including tunable light absorption/emission spectra, high photoluminescence quantum yield (PLQY), suppressed Auger recombination, efficient charge separation/transfer, and outstanding photo-/thermal-/chemical stability. In this review, engineered core/shell QDs with various types of band structures and corresponding device performance in luminescent solar concentrators (LSCs), light-emitting diodes (LEDs), solar-driven photoelectrochemical (PEC) devices, and QDs-sensitized solar cells (QDSCs) are summarized. In particular, the applications of interfacial layer engineering and eco-friendly, heavy metal-free core/shell QDs in optoelectronic devices are highlighted. Finally, strategies towards the developments and practical perspectives of core/shell QDs are briefly mentioned to offer guidelines for achieving prospective high-efficiency and long-term stable QD devices.     

p‐Si/SnO2/Fe2O3 Core/Shell/Shell Nanowire Photocathodes for Neutral pH Water Splitting

Silicon is one of the promising materials for solar water splitting and hydrogen production; however, it suffers from two key factors, including the large external potential required to drive water splitting reactions at its surface and its instability in the electrolyte. In this study, a successful fabrication of novel p‐Si/n‐SnO₂/n‐Fe₂O₃ core/shell/shell nanowire (css‐NW) arrays, consisting of vertical Si NW cores coated with a thin SnO₂ layer and a dense Fe₂O₃ nanocrystals (NCs) shell, and their application for significantly enhanced solar water reduction in a neutral medium is reported. The p‐Si/n‐SnO₂/n‐Fe₂O₃ css‐NW structure is characterized in detail using scanning, transmission, and scanning transmission electron microscopes. The p‐Si/n‐SnO₂/n‐Fe₂O₃ css‐NWs show considerably improved photocathodic performances, including higher photocurrent and lower photocathodic turn‐on potential, compared to the bare p‐Si NWs or p‐Si/n‐SnO₂ core/shell NWs (cs‐NWs), due to increased optical absorption, enhanced charge separation, and improved gas evolution. As a result, photoactivity at 0 V versus reversible hydrogen electrode and a low onset potential in the neutral solution are achieved. Moreover, p‐Si/n‐SnO₂/n‐Fe₂O₃ css‐NWs exhibit long‐term photoelectrochemical stability due to the Fe₂O₃ NCs shell well protection. These results reveal promising css‐NW photoelectrodes from cost‐effective materials by facile fabrication with simultaneously improved photocathodic performance and stability.     

Ternary Oxide Nanocrystals: Universal Laser‐Hydrothermal Synthesis,Optoelectronic and Electrochemical Applications

Ternary oxide nanocrystals (TONs) have received growing attention for their great potential applications in optoelectronics and electrochemistry despite the current scarcity of universal, facile, and green synthesis methods. Here, we introduce a universal laser‐hydrothermal approach for various TONs and demonstrate their potential for high‐performance photodetectors (PDs) and pseudocapacitors. The obtained clean surface is derived by laser ablation in liquid (LAL) and subsequent hydrothermal growth. The LAL‐generated precursors contain many kinds of highly reactive species, including H⁺, OH^?, metal ions, and clusters, which facilitate the fast and facile formation of various TONs in the subsequent hydrothermal process. The universality of the method is systematically proven by the synthesis of a series of TONs, including Zn₂GeO₄, NiCo₂O₄, Zn₂SnO₄, ZnFe₂O₄, ZnMnO₃, and Fe₂GeO₄. Significantly, the absence of chemical additives, such as surfactants, guarantees highly clean surfaces, which further benefits the electron transport through the nanocrystals, and thus in the resultant devices. This is also exemplified by a Zn₂GeO₄‐nanorod‐based, deep‐ultraviolet PD and NiCo₂O₄ nanocrystal supercapacitors.     

Solvothermal Synthesis of High‐Quality All‐Inorganic Cesium Lead Halide Perovskite Nanocrystals: From Nanocube to Ultrathin Nanowire

Recently, all‐inorganic cesium lead halide (CsPbX₃, X = Cl, Br, I) perovskite nanocrystals have drawn much attention because of their outstanding photophysical properties and potential applications. In this work, a simple and efficient solvothermal approach to prepare CsPbX₃ nanocrystals with tunable and bright photoluminescent (PL) properties, controllable composition, and morphology is presented. CsPbX₃ nanocubes are successfully prepared with bright emission high PL quantum yield up to 80% covering the full visible range and narrow emission line widths (from 12 to 36 nm). More importantly, ultrathin CsPbX₃ (X = Cl/Br, Br, and Br/I) nanowires (with diameter as small as ≈2.6 nm) can be prepared in a very high morphological yield (almost 100%). A strong quantum confinement effect is observed in the ultrathin nanowires, in which both the absorption and emission peaks shift to shorter wavelength range compared to their bulk bandgap. The reaction parameters, such as temperature and precursors, are varied to investigate the growth process. A white light‐emitting device prototype device with wide color gamut covering up to 120% of the National Television System Committee standard has been demonstrated by using CsPbBr₃ nanocrystals as the green light source. The method in this study provides a simple and efficient way to prepare high‐quality CsPbX₃ nanocrystals.     

核/壳结构CdSe/CdS纳米晶的制备及其光稳定性

在水溶液中制备了CdSe纳米晶和核/壳结构CdSe/CdS纳米晶,用X射线粉末衍射和X射线光电子能谱对其进行了表征.比较了新制样品与放置30天后样品的吸收光谱和发射光谱,结果表明核/壳结构CdSe/CdS纳米晶具有更好的光学稳定性,可望在光致发光器件和生物荧光标记上得到应用.     

Shining Light on the Photoluminescence Properties of Metal Halide Perovskites

Lead halide perovskites are a remarkable class of materials that have emerged over the past decade as being suitable for application in a broad range of devices, such as solar cells, light‐emitting diodes, lasers, transistors, and memory devices. While they are often solution‐processed semiconductors deposited at low temperatures, perovskites exhibit properties one would only expect from highly pure inorganic crystals that are grown at high temperatures. This unique phenomenon has resulted in fast‐paced progress toward record device performance. Unfortunately, the basic science behind the remarkable nature of these materials is still not well understood. This review assesses the current understanding of the photoluminescence properties of metal halide perovskite materials and highlights key areas that require further research. Furthermore, the need to standardize the methods for characterization of PL in order to improve comparability, reliability, and reproducibility of results is emphasized.     

Mixed Halide Formation in Lead-Free Antimony-Based Halide Perovskite for Boosted CO2 Photoreduction: Beyond Band Gap Tuning

Photocatalytic conversion of carbon dioxide (CO₂) into value-added fuels is a vastly promising anthropogenic chemical carbon cycle to combat the greenhouse effect while meeting the ever-increasing energy demand. Recently, lead-based halide perovskites have demonstrated great potential in various applications including photochemical reduction of CO₂. However, in view of lead toxicity, the exploration of a lead-free alternative is crucial for long term application. Herein, a series of lead-free mixed halide perovskites Cs₃Sb₂Cl_xBr_9−x (0 ≤ x ≤ 9) is prepared via a facile antisolvent recrystallization technique, where the incorporation of a secondary halide enhances the charge transfer and separation while allowing precise tuning of bandgap between 2.59 and 2.90 eV. Theoretical calculations further reveal that the formation of mixed Cl/Br halides engenders favorable charge redistribution due to lower octahedral distortion, which in turn strengthens CO₂ adsorption and activation. Under visible light illumination, the optimal dual halide perovskite, Cs₃Sb₂Cl₄Br₅ manifests substantial twofold and fourfold enhancements of CH₄ yield over the single halide perovskite, Cs₃Sb₂Br₉ and Cs₃Sb₂Cl₉, respectively. In brief, this study provides a compelling demonstration of lead-free mixed halide perovskites for photocatalytic CO₂ reduction, and it is anticipated to drive further application of perovskite-based photocatalysts toward a diverse range of artificial photoredox reactions.