Perovskite Single Crystals: Synthesis,Optoelectronic Properties,and Application

Recently, lead halide perovskite (PVSK) polycrystalline films have drawn much attention as photoactive material and scored tremendous achievements in solar cells, photodetectors, light-emitting diodes, and lasers owing to their engrossing optoelectronic properties and facile solution-processed fabrication. However, large amounts of grain boundaries unfavorably induce ion migration, surface defect, and poor stability, impeding PVSK polycrystalline film-based optoelectronic devices from practical application. In comparison with the polycrystalline counterparts, PVSK single crystals (SCs) with lower trap density serve as a better platform for not only fundamental research but also device applications. In light of this, the idea of using PVSK single crystals (SCs) to construct the optoelectronic devices is then proposed. Since then, a series of synthesis methods of PVSK SCs have emerged. In this review, recent progress of synthesis method of PVSK SCs is tried to be summarized and their advantages and limitations are analyzed. And then, the optoelectronic properties including carrier dynamic, defects, ion migration, and instability issues in these 3D and 2D PVSK SCs are overviewed and accordingly the proper device configurations of corresponding solar cells, photodetectors, X-ray, γ-ray detectors, etc., are proposed. It is believed that this review can provide the guidance for the further development of PVSK SCs and their applications.     

Conjugated Polymer–Assisted Grain Boundary Passivation for Efficient Inverted Planar Perovskite Solar Cells

Grain boundaries in lead halide perovskite films lead to increased recombination losses and decreased device stability under illumination due to defect‐mediated ion migration. The effect of a conjugated polymer additive, poly(bithiophene imide) (PBTI), is investigated in the antisolvent treatment step in the perovskite film deposition by comprehensive characterization of perovskite film properties and the performance of inverted planar perovskite solar cells (PSCs). PBTI is found to be incorporated within grain boundaries, which results in an improvement in perovskite film crystallinity and reduced defects. The successful defect passivation by PBTI yields reduces recombination losses and consequently increases power conversion efficiency (PCE). In addition, it gives rise to improved photoluminescence stability and improved PSC stability under illumination which can be attributed to reduced ion migration. The optimal devices exhibit a PCE of 20.67% compared to 18.89% of control devices without PBTI, while they retain over 70% of the initial efficiency after 600 h under 1 sun illumination compared to 56% for the control devices.     

Grain Boundary Perfection Enabled by Pyridinic Nitrogen Doped Graphdiyne in Hybrid Perovskite

The solution processing in hybrid perovskite films inevitably results in the formation of detrimental defects at grain boundaries (GBs) that deteriorate the optoelectronic properties and bring about severe hysteresis as well as operational instability. Here, an effective scenario to alleviate the imperfection issue at perovskite GBs via incorporating pyridinic nitrogen-doped graphdiyne (N-GDY) is proposed. Taking full advantage of periodic acetylenic linkages and introduced pyridinic N atoms, the deep-level trap states like Pb–I antisite defects and under-coordinated Pb atoms are considerably passivated, thus diminishing the undesired non-radiative recombination. Additionally, the spatial confinement coupling with electrostatic repulsion effect originated from the intrinsic 2D structure of N-GDY, has been identified to deal with the halide ion migration behavior. Such contributions are further theoretically evidenced with the charge density delocalization as well as the ion migration energy barrier elevation. The authors unprecedentedly verified the superiorities based on the flexible chemical-tailorability of atomic crystal GDY materials toward polycrystalline perovskite related energy conversion devices.     

Enhancing Resistive Switching Performance and Ambient Stability of Hybrid Perovskite Single Crystals via Embedding Colloidal Quantum Dots

Hybrid organic‐inorganic halide perovskites are actively pursued for optoelectronic technologies, but the poor stability is the Achilles’ heel of these materials that hinders their applications. Very recently, it has been shown that lead sulfide (PbS) quantum dots (QDs) can form epitaxial interfaces with the perovskite matrix and enhance the overall stability. In this work, it is demonstrated that embedding QDs can significantly modify the transport property of pristine perovskite single crystals, endowing them with new functionalities besides being structurally robust and free from grain boundaries. Resistive switching memory devices are constructed using solution‐processed CH₃NH₃PbBr₃ (MAPbBr₃) perovskite single crystals and the QD‐embedded counterparts. It is found that QDs could significantly enhance the charge transport and reduce the current–voltage hysteresis. The pristine singe crystal device exhibits negative differential resistance, while the QD‐embedded crystals are featured with filament‐type switching behavior and much improved device stability. This study underscores the potential of QD‐embedded hybrid perovskites as a new media for advanced electronic devices.     

Revealing Nanomechanical Domains and Their Transient Behavior in Mixed-Halide Perovskite Films

Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behavior is still to be understood. Here, a combination of atomic-force, optical, and compositional X-ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. Mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus (YM) than the bulk parent material, are revealed. These mechanical boundaries are associated with the presence of bromide-rich clusters as visualized by nano-X-ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties toward the bulk YM. This behavior is attributed to light-induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. This work highlights critical links between mechanical, chemical, and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity.     

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse-Bias Stability

Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI₃) thin single crystals are selected as a prototype to improve single-crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI₃ thin single crystals are achieved by one bifunctional molecule 3-mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb²⁺ of MAPbI₃ single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single-crystal MAPbI₃ solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse-bias stability. Finally, the cross-link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single-crystal perovskite solar cells, photodetectors, X-ray detectors, etc.     

Carbon Nanoparticles as Versatile Auxiliary Components of Perovskite-Based Optoelectronic Devices

Metal halide perovskite-based optoelectronics has experienced an unprecedented development in the last decade, while further improvements of efficiency, stability, and economic gains of such devices require novel engineering concepts. The use of carbon nanoparticles as versatile auxiliary components of perovskite-based optoelectronic devices is one strategy that offers several advantages in this respect. In this review, first, a brief introduction is offered on metal halide perovskites and on the major performance characteristics of related optoelectronic devices. Then, the versatility and merits of different kinds of carbon nanoparticles, such as graphene quantum dots and carbon dots, are discussed. The tunability of their electronic properties is focused upon, their interactions with perovskite components are analyzed, and different strategies of their implementation in optoelectronic devices are introduced, which include solar cells, light-emitting diodes, luminescent solar concentrators, and photodetectors. It is shown how carbon nanoparticles influence charge carriers extraction and transport, promote perovskite crystallization, allow for efficient passivation, block ion migration, suppress hysteresis, enhance their environmental stability, and thus improve the performance of perovskite-based optoelectronic 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.     

Humidity‐Induced Degradation via Grain Boundaries of HC(NH2)2PbI3 Planar Perovskite Solar Cells

The sensitivity of organic–inorganic perovskites to environmental factors remains a major barrier for these materials to become commercially viable for photovoltaic applications. In this work, the degradation of formamidinium lead iodide (FAPbI₃) perovskite in a moist environment is systematically investigated. It is shown that the level of relative humidity (RH) is important for the onset of degradation processes. Below 30% RH, the black phase of the FAPbI₃ perovskite shows excellent phase stability over 90 d. Once the RH reaches 50%, degradation of the FAPbI₃ perovskite occurs rapidly. Results from a Kelvin probe force microscopy study reveal that the formation of nonperovskite phases initiates at the grain boundaries and the phase transition proceeds toward the grain interiors. Also, ion migration along the grain boundaries is greatly enhanced upon degradation. A post‐thermal treatment (PTT) that removes chemical residues at the grain boundaries which effectively slows the degradation process is developed. Finally, it is demonstrated that the PTT process improves the performance and stability of the final device.     

Crystallization of 2D Hybrid Organic–Inorganic Perovskites Templated by Conductive Substrates

2D hybrid organic–inorganic perovskites are valued in optoelectronic applications for their tunable bandgap and excellent moisture and irradiation stability. These properties stem from both the chemical composition and crystallinity of the layer formed. Defects in the lattice, impurities, and crystal grain boundaries generally introduce trap states and surface energy pinning, limiting the ultimate performance of the perovskite; hence, an in-depth understanding of the crystallization process is indispensable. Here, a kinetic and thermodynamic study of 2D perovskite layer crystallization on transparent conductive substrates are provided—fluorine-doped tin oxide and graphene. Due to markedly different surface structure and chemistry, the two substrates interact differently with the perovskite layer. A time-resolved grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to monitor the crystallization on the two substrates. Molecular dynamics simulations are employed to explain the experimental data and to rationalize the perovskite layer formation. The findings assist substrate selection based on the required film morphology, revealing the structural dynamics during the crystallization process, thus helping to tackle the technological challenges of structure formation of 2D perovskites for optoelectronic devices.     

A New Descriptor for Complicated Effects of Electronic Density of States on Ion Migration

Halide perovskites have attracted much attention because of their excellent optoelectronic properties, such as high light absorption, long carrier diffusion length, and high defect tolerance. Ion migration induced device performance degradation, which is not yet fully understood, has become the key obstacle for commercialization of halide perovskites. Here, a general mechanism is proposed, which can build up the connection between the ion migration barrier and the electronic density of states, to clarify the origin of low barrier for ion migration. Density functional theory (DFT) simulation results show that the low barrier is caused by a significant energy difference in band centers between Pb²⁺ and the isolating halogen anion or by the small number of density of states. Following the explored mechanism, two strategies are proposed to boost barriers via DFT combination CI-NEB simulations: 1) halide double perovskites and 2) B-site doping. Furthermore, the finding not only deepens the understanding of ion migration in halide perovskites but also paves a new path for the commercialization of halide perovskite optoelectronic devices.     

Switched-On: Progress,Challenges, and Opportunities in Metal Halide Perovskite Transistors

Field-effect transistors (FETs) are key elements in modern electronics and hence are attracting immense scientific and commercial attention. The recent emergence of metal halide perovskite materials and their tremendous success in the field of photovoltaics have triggered the exploration of their application in other (opto)electronic devices, including FETs and phototransistors. In this review, the current status of the field is discussed, the challenges are highlighted, and an outlook for the future perspectives of perovskite FETs is provided. First, attention is drawn to the device physics and the fundamental processes that influence these devices, including the role of ion migration and defects, effects of temperature, light, and measurement conditions. Next, the performance of perovskite transistors and phototransistors reported to date are surveyed and critically assessed. Finally, the key challenges that impede perovskite transistor progress are outlined and discussed. The insights gained from the study of other perovskite optoelectronic devices may be adopted to address these challenges and advance this exciting field of research closer to the industrial application are examined.     

Understanding the Role of Grain Boundaries on Charge-Carrier and Ion Transport in Cs2AgBiBr6 Thin Films

Halide double perovskites have gained significant attention, owing to their composition of low-toxicity elements, stability in air, and recent demonstrations of long charge-carrier lifetimes that can exceed 1 µs. In particular, Cs₂AgBiBr₆ is the subject of many investigations in photovoltaic devices. However, the efficiencies of solar cells based on this double perovskite are still far from the theoretical efficiency limit of the material. Here, the role of grain size on the optoelectronic properties of Cs₂AgBiBr₆ thin films is investigated. It is shown through cathodoluminescence measurements that grain boundaries are the dominant nonradiative recombination sites. It also demonstrates through field-effect transistor and temperature-dependent transient current measurements that grain boundaries act as the main channels for ion transport. Interestingly, a positive correlation between carrier mobility and temperature is found, which resembles the hopping mechanism often seen in organic semiconductors. These findings explain the discrepancy between the long diffusion lengths >1 µm found in Cs₂AgBiBr₆ single crystals versus the limited performance achieved in their thin film counterparts. This work shows that mitigating the impact of grain boundaries will be critical for these double perovskite thin films to reach the performance achievable based on their intrinsic single-crystal properties.     

Surface Reconstruction Engineering with Synergistic Effect of Mixed-Salt Passivation Treatment toward Efficient and Stable Perovskite Solar Cells

Surface passivation treatment is a widely used strategy to resolve trap-mediated nonradiative recombination toward high-efficiency metal-halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in-depth understanding of its passivation mechanism. Here, a systematic study on a mixed-salt passivation strategy of formamidinium bromide (FABr) coupled with different F-substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F-substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed-salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high-quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed-salt treatment. In addition, the introduction of the moisture resisted F-substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long-term stability under a high humid atmosphere as well as operational conditions.     

Donor–π–Acceptor Type Porphyrin Derivatives Assisted Defect Passivation for Efficient Hybrid Perovskite Solar Cells

In recent years, hybrid perovskite solar cells (PSCs) have attracted much attention owing to their low cost, easy fabrication, and high photoelectric conversion efficiency. Nevertheless, solution-processed perovskite films usually show substantial structural disorders, resulting in ion defects on the surface of lattice and grain boundaries. Herein, a series of D–π–A porphyrins coded as CS0 , CS1 , and CS2 that can effectively passivate the perovskite surface, increase V_OC and FF, reduce the hysteresis effect, enhance power conversion efficiency to be higher than 22%, and improve the device stability is developed. The results in this study demonstrated that the donor–π–acceptor type porphyrin derivatives are promising passivators that can improve the cell performance of PSCs.     

Single Crystal Perovskite Solar Cells: Development and Perspectives

The efficiency of perovskite solar cells has increased to a certified value of 25.2% in the past 10 years, benefiting from the superior properties of metal halide perovskite materials. Compared with the widely investigated polycrystalline thin films, single crystal perovskites without grain boundaries have better optoelectronic properties, showing great potential for photovoltaics with higher efficiency and stability. Additionally, single crystal perovskite solar cells are a fantastic model system for further investigating the working principles related to the surface and grain boundaries of perovskite materials. Unfortunately, only a handful of groups have participated in the development of single crystal perovskite solar cells; thus, the development of this area lags far behind that of its polycrystalline counterpart. Therefore, a review paper that discusses the recent developments and challenges of single crystal perovskite solar cells is urgently required to provide guidelines for this emerging field. In this progress report, the optical and electrical properties of single crystal and polycrystalline perovskite thin films are compared, followed by the recent developments in the growth of single crystal perovskite thin films and the photovoltaic applications of this material. Finally, the challenges and perspectives of single crystal perovskite solar cells are discussed in detail.     

Composition Engineering of Perovskite Single Crystals for High-Performance Optoelectronics

Composition engineering, with its advantages to effectively tune semiconductor properties by regulating chemical stoichiometry, is a proven strategy to boost the efficiency and stability of ABX₃ perovskite photoelectronic devices. Compared with its counterpart polycrystalline perovskite film, single crystalline is the ideal model for exploring its fundamental scientific issues. In this review, a critical overview of recent advances of the growth strategies, properties, and functional applications of multicomponent perovskite single crystals (SCs) is presented. First, the underlying advantages of composition engineering of perovskite SCs are discussed and then the different composition tuning strategies, including A-site, B-site, X-site, and simultaneous A- and X-site engineering, are systematically summarized. Subsequently, the benefits of composition engineering are highlighted for optimizing photovoltaic and photoelectronic devices. Lastly, controversies and remaining challenges for the development of composition engineering of perovskite SCs are discussed and a brief perspective regarding further investigation in this field is provided.     

Enhancing Ion Migration in Grain Boundaries of Hybrid Organic–Inorganic Perovskites by Chlorine

Ionicity plays an important role in determining material properties, as well as optoelectronic performance of organometallic trihalide perovskites (OTPs). Ion migration in OTP films has recently been under intensive investigation by various scanning probe microscopy (SPM) techniques. However, controversial findings regarding the role of grain boundaries (GBs) associated with ion migration are often encountered, likely as a result of feedback errors and topographic effects common in to SPM. In this work, electron microscopy and spectroscopy (scanning transmission electron microscopy/electron energy loss spectroscopy) are combined with a novel, open‐loop, band‐excitation, (contact) Kelvin probe force microscopy (BE‐KPFM and BE‐cKPFM), in conjunction with ab initio molecular dynamics simulations to examine the ion behavior in the GBs of CH₃NH₃PbI₃ perovskite films. This combination of diverse techniques provides a deeper understanding of the differences between ion migration within GBs and interior grains in OTP films. This work demonstrates that ion migration can be significantly enhanced by introducing additional mobile Cl^? ions into GBs. The enhancement of ion migration may serve as the first step toward the development of high‐performance electrically and optically tunable memristors and synaptic devices.     

Influence of Bulky Organo‐Ammonium Halide Additive Choice on the Flexibility and Efficiency of Perovskite Light‐Emitting Devices

Perovskite light‐emitting diodes (LEDs) require small grain sizes to spatially confine charge carriers for efficient radiative recombination. As grain size decreases, passivation of surface defects becomes increasingly important. Additionally, polycrystalline perovskite films are highly brittle and mechanically fragile, limiting their practical applications in flexible electronics. In this work, the introduction of properly chosen bulky organo‐ammonium halide additives is shown to be able to improve both optoelectronic and mechanical properties of perovskites, yielding highly efficient, robust, and flexible perovskite LEDs with external quantum efficiency of up to 13% and no degradation after bending for 10 000 cycles at a radius of 2 mm. Furthermore, insight of the improvements regarding molecular structure, size, and polarity at the atomic level is obtained with first‐principles calculations, and design principles are provided to overcome trade‐offs between optoelectronic and mechanical properties, thus increasing the scope for future highly efficient, robust, and flexible perovskite electronic device development.     

Lead-Free Double Perovskite Cs2AgBiBr6: Fundamentals,Applications, and Perspectives

Cs₂AgBiBr₆, as a benchmark lead-free double perovskite, has emerged as a promising alternative to lead-based perovskites because of its high stability, non-toxicity, exceptional optoelectronic properties, and multifunctionality. To encourage further research on Cs₂AgBiBr₆ and its broad applications, in this review, its fundamental properties including the structure-property relation, synthesis, stability, origin of absorption and photoluminescence, electron-phonon coupling, role of defects, charge carrier dynamics, and bandgap modulation are comprehensively emphasized. The recent progress on the wide applications including solar cells, light/X-ray detectors, and ferroelectric/magnetic devices are highlighted. Moreover, the challenges of Cs₂AgBiBr₆ materials and related applications are discussed and perspectives are provided for guiding the future development of this research area.