Two-dimensional (2D) halide perovskites have emerged as outstanding semiconducting materials thanks to their superior stability and structural diversity. However, the ever-growing field of optoelectronic device research using 2D perovskites requires systematic understanding of the effects of the spacer on the structure, properties, and device performance. So far, many studies are based on trial-and-error tests of random spacers with limited ability to predict the resulting structure of these synthetic experiments, hindering the discovery of novel 2D materials to be incorporated into high-performance devices. In this review, we provide guidelines on successfully choosing spacers and incorporating them into crystalline materials and optoelectronic devices. We first provide a summary of various synthetic methods to act as a tutorial for groups interested in pursuing synthesis of novel 2D perovskites. Second, we provide our insights on what kind of spacer cations can stabilize 2D perovskites followed by an extensive review of the spacer cations, which have been shown to stabilize 2D perovskites with an emphasis on the effects of the spacer on the structure and optical properties. Next, we provide a similar explanation for the methods used to fabricate films and their desired properties. Like the synthesis section, we will then focus on various spacers that have been used in devices and how they influence the film structure and device performance. With a comprehensive understanding of these effects, a rational selection of novel spacers can be made, accelerating this already exciting field.

The 2D Halide Perovskite Rulebook: How the Spacer Influences Everything from the Structure to Optoelectronic Device Efficiency.

Over the last two decades, halide perovskites (HPs) have been identified as one of the most promising materials in photovoltaic and light-emitting devices. This has led to major breakthroughs in materials science but has also brought about a general misunderstanding and misuse of the term “perovskite”. In this Viewpoint, we will address the definition of a perovskite, with a main focus on the subgroup of perovskites that consist of heavier halides (Cl, Br, and I), both fully inorganic and hybrid organic−inorganic ones, as well as the many variants that can be found within this subgroup. In doing so, we will clarify what defines, in our opinion, a halide perovskite and discuss the commonly misnamed nonperovskite crystal structures. A perovskite crystal lattice is defined as a network of cornersharing BX6 octahedra that crystallize with a general ABX3 (or equivalent) stoichiometry, as is shown in Figures 1 and 2a.

What Defines a Halide Perovskite

The research in circularly polarized luminescence has attracted wide interest in recent years. Efforts on one side are directed toward the development of chiral materials with both high luminescence efficiency and dissymmetry factors, and on the other side, are focused on the exploitations of these materials in optoelectronic applications. This review summarizes the recent frontiers (mostly within five years) in the research in circularly polarized luminescence, including the development of chiral emissive materials based on organic small molecules, compounds with aggregation-induced emissions, supramolecular assemblies, liquid crystals and liquids, polymers, metal-ligand coordination complexes and assemblies, metal clusters, inorganic nanomaterials, and photon upconversion systems. In addition, recent applications of related materials in organic light-emitting devices, circularly polarized light detectors, and organic lasers and displays are also discussed.

Frontiers in circularly polarized luminescence: molecular design, self-assembly, nanomaterials, and applications

Circularly polarized light exhibits promising applications in future displays and photonic technologies. Circularly polarized luminescence (CPL) from chiral luminophores is an ideal approach to directly generating circularly polarized light, in which the energy loss induced by the circularly polarized filters can be reduced. Among various chiral luminophores, organic micro-/nano-structures have attracted increasing attention owing to the high quantum efficiency and luminescence dissymmetry factor. Herein, the recent progress of CPL from organic micro-/nano-structures is summarized. Firstly, the design principles of CPL-active organic micro-/nano-structures are expounded from the construction of micro-/nano-structure and the introduction of chirality. Based on these design principles, several typical organic micro-/nano-structures with CPL activity are introduced in detail, including self-assembly of small molecules, self-assembly of π-conjugated polymers, and self-assembly on micro-/nanoscale architectures. Subsequently, we discuss the external stimuli that can regulate CPL performance, including solvents, pH value, metal ions, mechanical force, and temperature. We also summarize the applications of CPL-active materials in organic light-emitting diodes, optical information processing, and chemical and biological sensing. Finally, the current challenges and prospects in this emerging field are presented. It is expected that this review will provide a guide for the design of excellent CPL-active materials.

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Circularly polarized luminescence from organic micro-/nano-structures.

The host-guest chemistry of metal-organic frameworks (MOFs) has enabled the derivation of numerous new functionalities. However, intrinsically chiral MOFs (CMOFs) with helical channels have not been used to realize crystalline circularly polarized luminescence (CPL) materials. Herein, enantiomeric pairs of MOF crystals are reported, where achiral fluorophores adhere to the inner surface of helical channels via biology-like H-bonds and hence inherit the helicity of the host MOFs, eventually amplifying the luminescence dissymmetry factor (glum ) of the host l/d-CMOF (±1.50 × 10-3 ) to a maximum of ±0.0115 for the composite l/d-CMOF⊃fluorophores. l/d-CMOF⊃fluorophores in pairs generate bright color-tunable CPL and almost ideal white CPL (0.33, 0.32) with a record-high photoluminescence quantum yield of ≈30%, which are further assembled into a white circularly polarized light-emitting diode. The present strategy opens a new avenue for propagating the chirality of MOFs to realize universal chiroptical materials.

Enantiomeric MOF Crystals Using Helical Channels as Palettes with Bright White Circularly Polarized Luminescence.

Circularly polarized luminescent (CPL) materials are promising in applications such as 3D displays and quantum communication. Hybrid organic-inorganic copper(I) iodides have been rapidly developed due to their intense photoluminescence and structural diversity; nevertheless, the reported Cu-I clusters rarely show CPL activities. In this study, we introduced chiral organic molecules R/S-methylbenzylammonium (R/S-MBA) into Cu-I inorganic skeletons to achieve chiral tetranuclear (R/S-MBA)4Cu4I4 clusters with intense orange luminescence and CPL activity at room temperature. These enantiomeric (R/S-MBA)4Cu4I4 clusters show oppositely signed circular dichroism (CD) signals, which agree well with their simulated electronic CD spectra. The crystallization-induced helical arrangement of (R/S-MBA)4Cu4I4 clusters and their largely distorted polynuclear configuration demonstrate a new platform for the study of chiral-related properties.

Circularly Polarized Luminescence from Chiral Tetranuclear Copper(I) Iodide Clusters.

The discovery of new halide perovskite-type structures could favor the exploration of optoelectronic materials, as in the case of double perovskites applied in solar cells, light-emitting diodes, and X-ray detectors. In this work, we propose a strategy for designing quadruple perovskites by heterovalent cation transmutation from double perovskites. Two stable quadruple perovskite halides, i.e., Cs4CdSb2Cl12 and Cs4CdBi2Cl12, with a vacancy-ordered three-dimensional (3D) crystal structure were predicted through symmetry analysis and density functional theory (DFT) calculations. The title perovskite halides are also electronically 3D with direct forbidden bandgaps. Following the indication provided by the DFT results, Cs4CdSb2Cl12 and Cs4CdBi2Cl12 as unique quadruple perovskites were successfully synthesized by a solvothermal method. The steady-state photoluminescence (PL) shows wide emission, while the transient PL exhibits carrier recombination lifetime on the order of microseconds at low temperature. The quadruple perovskite halides provide an alternative platform for promising optoelectronic material design in addition to simple and double perovskites.

Material Design and Optoelectronic Properties of Three-Dimensional Quadruple Perovskite Halides

Bournonite CuPbSbS3: An electronically-3D, defect-tolerant, and solution-processable semiconductor for efficient solar cells

https://onlinelibrary.wiley.com/doi/pdf/10.1002/eem2.12082

Bing Xia

Papers

Circularly Polarized Luminescence from Chiral Tetranuclear Copper(I) Iodide Clusters.

Material Design and Optoelectronic Properties of Three-Dimensional Quadruple Perovskite Halides

Bournonite CuPbSbS3: An electronically-3D, defect-tolerant, and solution-processable semiconductor for efficient solar cells

Reversible Release and Fixation of Bromine in Vacancy-Ordered Bromide Perovskites

p‐Type Transparent Quadruple Perovskite Halide Conductors: Fact or Fiction?