Chiral Perovskites: Promising Materials toward Next‐Generation Optoelectronics

Halide perovskites have emerged as a type of extremely promising material for their diverse chemical and electronic structures along with their brilliant optoelectronic properties. The introduction of chirality into perovskite scaffolds, generating a novel concept of chiral perovskite materials, offers an immense step forward toward the development of smart optoelectronic and spintronic materials and devices. The present Review summarizes recent advances in such an emerging field regarding the design and construction of chiral perovskite materials, along with their optoelectronic performances. In addition, an outlook of future challenges as well as the potential significance of the chiral perovskite family on the optical communication is proposed.     

Lead‐Free Organic–Inorganic Hybrid Perovskites for Photovoltaic Applications: Recent Advances and Perspectives

Organic–inorganic hybrid halide perovskites (e.g., MAPbI₃) have recently emerged as novel active materials for photovoltaic applications with power conversion efficiency over 22%. Conventional perovskite solar cells (PSCs); however, suffer the issue that lead is toxic to the environment and organisms for a long time and is hard to excrete from the body. Therefore, it is imperative to find environmentally‐friendly metal ions to replace lead for the further development of PSCs. Previous work has demonstrated that Sn, Ge, Cu, Bi, and Sb ions could be used as alternative ions in perovskite configurations to form a new environmentally‐friendly lead‐free perovskite structure. Here, we review recent progress on lead‐free PSCs in terms of the theoretical insight and experimental explorations of the crystal structure of lead‐free perovskite, thin film deposition, and device performance. We also discuss the importance of obtaining further understanding of the fundamental properties of lead‐free hybrid perovskites, especially those related to photophysics.     

Hybrid Organic–Inorganic Perovskite Photodetectors

Hybrid organic–inorganic perovskite materials garner enormous attention for a wide range of optoelectronic devices. Due to their attractive optical and electrical properties including high optical absorption coefficient, high carrier mobility, and long carrier diffusion length, perovskites have opened up a great opportunity for high performance photodetectors. This review aims to give a comprehensive summary of the significant results on perovskite‐based photodetectors, focusing on the relationship among the perovskite structures, device configurations, and photodetecting performances. An introduction of recent progress in various perovskite structure‐based photodetectors is provided. The emphasis is placed on the correlation between the perovskite structure and the device performance. Next, recent developments of bandgap‐tunable perovskite and hybrid photodetectors built from perovskite heterostructures are highlighted. Then, effective approaches to enhance the stability of perovskite photodetector are presented, followed by the introduction of flexible and self‐powered perovskite photodetectors. Finally, a summary of the previous results is given, and the major challenges that need to be addressed in the future are outlined. A comprehensive summary of the research status on perovskite photodetectors is hoped to push forward the development of this field.     

Uncovering the Mechanism Behind the Improved Stability of 2D Organic–Inorganic Hybrid Perovskites

2D organic–inorganic hybrid perovskites (OIHPs) may resolve the stability problem of bulk OIHPs. First‐principles calculations are employed to investigate the mechanism behind their favorable material properties. Two processes are identified to play a critical role: First, the 2D structure supports additional distortions that enhance the intrinsic structural stability. Second, the surface terminations of 2D OIHPs suppress degradation effects due to humidity. Having uncovered the stabilization mechanism, 2D OIHPs are designed with optimal stability and favorable electronic properties.     

Efficient Room‐Temperature Phosphorescence from Organic–Inorganic Hybrid Perovskites by Molecular Engineering

Solution‐processed organic–inorganic hybrid perovskites are promising emitters for next‐generation optoelectronic devices. Multiple‐colored, bright light emission is achieved by tuning their composition and structures. However, there is very little research on exploring optically active organic cations for hybrid perovskites. Here, unique room‐temperature phosphorescence from hybrid perovskites is reported by employing novel organic cations. Efficient room‐temperature phosphorescence is activated by designing a mixed‐cation perovskite system to suppress nonradiative recombination. Multiple‐colored phosphorescence is achieved by molecular design. Moreover, the emission lifetime can be tuned by varying the perovskite composition to achieve persistent luminescence. Efficient room‐temperature phosphorescence is demonstrated in hybrid perovskites that originates from the triplet states of the organic cations, opening a new dimension to the further development of perovskite emitters with novel functional organic cations for versatile display applications.     

2D Ruddlesden–Popper Perovskites for Optoelectronics

Conventional 3D organic–inorganic halide perovskites have recently undergone unprecedented rapid development. Yet, their inherent instabilities over moisture, light, and heat remain a crucial challenge prior to the realization of commercialization. By contrast, the emerging 2D Ruddlesden?Popper‐type perovskites have recently attracted increasing attention owing to their great environmental stability. However, the research of 2D perovskites is just in their infancy. In comparison to 3D analogues, they are natural quantum wells with a much larger exciton binding energy. Moreover, their inner structural, dielectric, optical, and excitonic properties remain to be largely explored, limiting further applications. This review begins with an introduction to 2D perovskites, along with a detailed comparison to 3D counterparts. Then, a discussion of the organic spacer cation engineering of 2D perovskites is presented. Next, quasi‐2D perovskites that fall between 3D and 2D perovskites are reviewed and compared. The unique excitonic properties, electron–phonon coupling, and polarons of 2D perovskites are then be revealed. A range of their (opto)electronic applications is highlighted in each section. Finally, a summary is given, and the strategies toward structural design, growth control, and photophysics studies of 2D perovskites for high‐performance electronic devices are rationalized.     

Tunable Spin Characteristic Properties in Spin Valve Devices Based on Hybrid Organic–Inorganic Perovskites

The hybrid organic–inorganic perovskites (HOIPs) form a new class of semiconductors which show promising optoelectronic device applications. Remarkably, the optoelectronic properties of HOIP are tunable by changing the chemical components of their building blocks. Recently, the HOIP spintronic properties and their applications in spintronic devices have attracted substantial interest. Here the impact of the chemical component diversity in HOIPs on their spintronic properties is studied. Spin valve devices based on HOIPs with different organic cations and halogen atoms are fabricated. The spin diffusion length is obtained in the various HOIPs by measuring the giant magnetoresistance (GMR) response in spin valve devices with different perovskite interlayer thicknesses. In addition spin lifetime is also measured from the Hanle response. It is found that the spintronic properties of HOIPs are mainly determined by the halogen atoms, rather than the organic cations. The study provides a clear avenue for engineering spintronic devices based on HOIPs.     

Photonics and Optoelectronics of 2D Metal‐Halide Perovskites

In the growing list of 2D semiconductors as potential successors to silicon in future devices, metal‐halide perovskites have recently joined the family. Unlike other conversional 2D covalent semiconductors such as graphene, transition metal dichalcogenides, black phosphorus, etc., 2D perovskites are ionic materials, affording many distinct properties of their own, including high photoluminescence quantum efficiency, balanced large exciton binding energy and oscillator strength, and long carrier diffusion length. These unique properties make 2D perovskites potential candidates for optoelectronic and photonic devices such as solar cells, light‐emitting diodes, photodetectors, nanolasers, waveguides, modulators, and so on, which represent a relatively new but exciting and rapidly expanding area of research. In this Review, the recent advances in emerging 2D metal‐halide perovskites and their applications in the fields of optoelectronics and photonics are summarized and insights into the future direction of these fields are offered.     

Ligand-Assisted Self-Assembly of 3D Perovskite Nanocrystals into Chiral Inorganic Quasi-2D Perovskites (n = 3) with Ligand-Ratio-Dependent Chirality Inversion

Chiral inorganic quasi-2D perovskites are prepared by self-assembling 3D perovskites in solution for the first time. The quasi-2D perovskite synthesized is a pure-phase perovskite with <n> = 3 and is periodically arranged, which is a big breakthrough in quasi-2D inorganic perovskites.  With the individual chiral CsPbBr₃ nanocrystals (NCs) assemble into quasi-2D perovskite, the g-factor significantly improved (≈5 × 10⁻³). In addition, the chiroptical activity of quasi-2D perovskites is explored to be improved with the lateral size increasing. In the first stage of assembly, chiral optical activity is increased due to the lateral size-dependent optical activity, while the changes in the later stages are attributable to the chiral morphology. Interestingly, chirality inversion is found to be correlated to the number of ligands. It is believed that different conformers of chiral ligands caused by steric hindrance of the original ligand oleylamine result in opposite circular dichroism (CD) polarities. The chirality inversion phenomenon is universal, regardless of the choice of ligands. This work opens up a new path for the synthesis of quasi-2D perovskites and provides more opportunities for the modulation of chiral optical activity.     

Halogenated‐Methylammonium Based 3D Halide Perovskites

3D perovskites with typical structure of ABX₃ are emerging as key materials to achieve high‐performance optoelectronic devices. The variation of A‐site cation is promising to achieve enhanced properties; however, is limited to a few available choices of methylamine, formamidine, and cesium. In this work, halogenated‐methylammoniums are developed as A cation to broaden the family of hybrid perovskites. Single crystals and colloidal nanocrystals of halogenated‐methylammoniums based perovskites are successfully synthesized, showing bright future as alternatives for device exploration. In particular, the improved thermal stability and low exciton binding energy from single crystals measurements are demonstrated and bright tunable emission from blue to green for colloidal nanocrystals is achieved.     

Excitonic Properties of Chemically Synthesized 2D Organic–Inorganic Hybrid Perovskite Nanosheets

2D organic–inorganic hybrid perovskites (OIHPs) represent a unique class of materials with a natural quantum‐well structure and quasi‐2D electronic properties. Here, a versatile direct solution‐based synthesis of mono‐ and few‐layer OIHP nanosheets and a systematic study of their electronic structure as a function of the number of monolayers by photoluminescence and absorption spectroscopy are reported. The monolayers of various OIHPs are found to exhibit high electronic quality as evidenced by high quantum yield and negligible Stokes shift. It is shown that the ground exciton peak blueshifts by ≈40 meV when the layer thickness reduces from bulk to monolayer. It is also shown that the exciton binding energy remains effectively unchanged for (C₆H₅(CH₂)₂NH₃)₂PbI₄ with the number of layers. Similar trends are observed for (C₄H₉NH₃)₂PbI₄ in contrast to the previous report. Further, the photoluminescence lifetime is found to decrease with the number of monolayers, indicating the dominant role of surface trap states in nonradiative recombination of the electron–hole pairs.     

3D Nanoprinting of Perovskites

As competing with the established silicon technology, organic–inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low‐cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in‐plane, low‐aspect‐ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic–inorganic metal halide perovskites. The method is based on guiding evaporation‐induced perovskite crystallization in mid‐air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on‐demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular‐solid transition. With varying the pulling direction, a layer‐by‐layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.     

A 2D Conductive Organic–Inorganic Hybrid with Extraordinary Volumetric Capacitance at Minimal Swelling

Rational design and synthesis of 2D organic–inorganic hybrid materials is important for transformative technological advances for energy storage. Here, a 2D conductive hybrid lamella and its intercalation properties for thin‐film supercapacitors are reported. The 2D organic–inorganic hybrid lamella comprises periodically stacked 2D nanosheets with 11.81 Å basal spacing, and is electronically conductive (605 S m^?1). In contrast to the pre‐existing organic‐based 2D materials, this material has extremely low gas‐permeable porosity (16.5 m² g^?1) in contrast to the high ionic accessibility. All these structural features collectively contribute to the high capacitances up to 732 F cm^?3, combined with small structural swelling at as low as 4.8% and good stability. At a discharge time of 6 s, the thin‐film intercalation electrode delivers an energy density of 24 mWh cm^?3, which universally outperforms the surface‐dominant capacitive processes in porous carbons.     

Hybrid Perovskite Light‐Emitting Diodes Based on Perovskite Nanocrystals with Organic–Inorganic Mixed Cations

Organic–inorganic hybrid perovskite materials with mixed cations have demonstrated tremendous advances in photovoltaics recently, by showing a significant enhancement of power conversion efficiency and improved perovskite stability. Inspired by this development, this study presents the facile synthesis of mixed‐cation perovskite nanocrystals based on FA_{(1?x )}Cs_x PbBr₃ (FA = CH(NH₂)₂). By detailed characterization of their morphological, optical, and physicochemical properties, it is found that the emission property of the perovskite, FA_{(1?x )}Cs_x PbBr₃, is significantly dependent on the substitution content of the Cs cations in the perovskite composition. These mixed‐cation perovskites are employed as light emitters in light‐emitting diodes (LEDs). With an optimized composition of FA_0.8Cs_0.2PbBr₃, the LEDs exhibit encouraging performance with a highest reported luminance of 55 005 cd m^?2 and a current efficiency of 10.09 cd A^?1. This work provides important instructions on the future compositional optimization of mixed‐cation perovskite for obtaining high‐performance LEDs. The authors believe this work is a new milestone in the development of bright and efficient perovskite LEDs.     

2D Ruddlesden–Popper Perovskites Microring Laser Array

3D organic–inorganic hybrid perovskites have featured high gain coefficients through the electron–hole plasma stimulated emission mechanism, while their 2D counterparts of Ruddlesden–Popper perovskites (RPPs) exhibit strongly bound electron–hole pairs (excitons) at room temperature. High‐performance solar cells and light‐emitting diodes (LEDs) are reported based on 2D RPPs, whereas light‐amplification devices remain largely unexplored. Here, it is demonstrated that ultrafast energy transfer along cascade quantum well (QW) structures in 2D RPPs concentrates photogenerated carriers on the lowest‐bandgap QW state, at which population inversion can be readily established enabling room‐temperature amplified spontaneous emission and lasing. Gain coefficients measured for 2D RPP thin‐films (≈100 nm in thickness) are found about at least four times larger than those for their 3D counterparts. High‐density large‐area microring arrays of 2D RPPs are fabricated as whispering‐gallery‐mode lasers, which exhibit high quality factor (Q ≈ 2600), identical optical modes, and similarly low lasing thresholds, allowing them to be ignited simultaneously as a laser array. The findings reveal that 2D RPPs are excellent solution‐processed gain materials potentially for achieving electrically driven lasers and ideally for on‐chip integration of nanophotonics.     

Elucidation of Photoluminescence Blinking Mechanism and Multiexciton Dynamics in Hybrid Organic–Inorganic Perovskite Quantum Dots

Halide perovskites (ABX₃) have emerged as promising materials in the past decade owing to their superior photophysical properties, rendering them potential candidates as solar cells, light‐emitting diode displays, and lasing materials. To optimize their utilization into optoelectronic devices, fundamental understanding of the optical behaviors is necessary. To reveal the comprehensive structure–property relationship, CH₃NH₃PbBr₃ (MAPbBr₃) perovskite quantum dots (PQDs) of three different sizes are prepared by controlling the precipitation temperature. Photoluminescence (PL) blinking, a key process that governs the emission efficiency of the PQD materials, is investigated in detail by the time‐resolved spectroscopic measurements of individual dots. The nature of the generated species in the course of blinking events is identified, and the mechanism governing the PL blinking is studied as a function of PQD sizes. Further, the practical applicability of MAPbBr₃ PQDs is assessed by studying the multiexciton dynamics under high photoexcitation intensity under which most of the display devices work. Ultrafast transient absorption spectroscopy helped in uncovering the volume‐dependent Auger recombination rates, which are further explored by comparing the early‐time transitions related to surface trap states and higher band states.