Exploring Lead‐Free Hybrid Double Perovskite Crystals of (BA)2CsAgBiBr7 with Large Mobility‐Lifetime Product toward X‐Ray Detection

Halide double perovskites have recently bloomed as the green candidates for optoelectronic applications, such as X‐ray detection. Despite great efforts, the exploration of promising organic–inorganic hybrid double perovskites toward X‐ray detection remains unsuccessful. Now, single crystals of the lead‐free hybrid double perovskite, (BA)₂CsAgBiBr₇ (BA⁺ is n‐butylammonium), featuring the unique 2D multilayered quantum‐confined motif, enable quite large μτ (mobility‐lifetime) product up to 1.21×10^?3 cm² V^?1. This figure‐of‐merit realized in 2D hybrid double perovskites is unprecedented and comparable with that of CH₃NH₃PbI₃ wafers. (BA)₂CsAgBiBr₇ crystals also exhibit other intriguing attributes for X‐ray detection, including high bulk resistivity, low density of defects and traps, and large X‐ray attenuation coefficient. Consequently, a vertical‐structure crystal device under X‐ray source yields a superior sensitivity of 4.2 μC Gy_air^?1 cm^?2.     

Room-Temperature Ferroelectric Material Composed of a Two-Dimensional Metal Halide Double Perovskite for X-ray Detection

Although two-dimensional (2D) metal–halide double perovskites display versatile physical properties due to their huge structural compatibility, room-temperature ferroelectric behavior has not yet been reported for this fascinating family. Here, we designed a room-temperature ferroelectric material composed of 2D halide double perovskites, (chloropropylammonium)₄AgBiBr₈, using an organic asymmetric dipolar ligand. It exhibits concrete ferroelectricity, including a Curie temperature of 305 K and a notable spontaneous polarization of ≈3.2 μC cm⁻², triggered by dynamic ordering of the organic cation and the tilting motion of heterometallic AgBr₆/BiBr₆ octahedra. Besides, the alternating array of inorganic perovskite sheets and organic cations endows large mobility-lifetime product (μτ=1.0×10⁻³ cm² V⁻¹) for detecting X-ray photons, which is almost tenfold higher than that of CH₃NH₃PbI₃ wafers. As far as we know, this is the first study on an X-ray-sensitive ferroelectric material composed of 2D halide double perovskites. Our findings afford a promising platform for exploring new ferroelectric materials toward further device applications.     

Alloying n‐Butylamine into CsPbBr3 To Give a Two‐Dimensional Bilayered Perovskite Ferroelectric Material

Cesium‐lead halide perovskites (e.g. CsPbBr₃) have gained attention because of their rich physical properties, but their bulk ferroelectricity remains unexplored. Herein, by alloying flexible organic cations into the cubic CsPbBr₃, we design the first cesium‐based two‐dimensional (2D) perovskite ferroelectric material with both inorganic alkali metal and organic cations, (C₄H₉NH₃)₂CsPb₂Br₇ ( 1 ). Strikingly, 1 shows a high Curie temperature (T_c=412 K) above that of BaTiO₃ (ca. 393 K) and notable spontaneous polarization (ca. 4.2 μC cm^?2), triggered by not only the ordering of organic cations but also atomic displacement of inorganic Cs⁺ ions. To our knowledge, such a 2D bilayered Cs⁺‐based metal–halide perovskite ferroelectric material with inorganic and organic cations is unprecedented. 1 also shows photoelectric semiconducting behavior with large “on/off” ratios of photoconductivity (>10³).     

An Above‐Room‐Temperature Ferroelectric Organo–Metal Halide Perovskite: (3‐Pyrrolinium)(CdCl3)

Hybrid organo–metal halide perovskite materials, such as CH₃NH₃PbI₃, have been shown to be some of the most competitive candidates for absorber materials in photovoltaic (PV) applications. However, their potential has not been completely developed, because a photovoltaic effect with an anomalously large voltage can be achieved only in a ferroelectric phase, while these materials are probably ferroelectric only at temperatures below 180 K. A new hexagonal stacking perovskite‐type complex (3‐pyrrolinium)(CdCl₃) exhibits above‐room‐temperature ferroelectricity with a Curie temperature T_c=316 K and a spontaneous polarization P_s=5.1 μC cm^?2. The material also exhibits antiparallel 180° domains which are related to the anomalous photovoltaic effect. The open‐circuit photovoltage for a 1 mm‐thick bulky crystal reaches 32 V. This finding could provide a new approach to develop solar cells based on organo–metal halide perovskites in photovoltaic research.     

High Compression‐Induced Conductivity in a Layered Cu–Br Perovskite

We show that the onset pressure for appreciable conductivity in layered copper‐halide perovskites can decrease by ca. 50 GPa upon replacement of Cl with Br. Layered Cu–Cl perovskites require pressures >50 GPa to show a conductivity of 10^?4 S cm^?1, whereas here a Cu–Br congener, (EA)₂CuBr₄ (EA=ethylammonium), exhibits conductivity as high as 2×10^?3 S cm^?1 at only 2.6 GPa, and 0.17 S cm^?1 at 59 GPa. Substitution of higher‐energy Br 4p for Cl 3p orbitals lowers the charge‐transfer band gap of the perovskite by 0.9 eV. This 1.7 eV band gap decreases to 0.3 eV at 65 GPa. High‐pressure X‐ray diffraction, optical absorption, and transport measurements, and density functional theory calculations allow us to track compression‐induced structural and electronic changes. The notable enhancement of the Br perovskite's electronic response to pressure may be attributed to more diffuse Br valence orbitals relative to Cl orbitals. This work brings the compression‐induced conductivity of Cu‐halide perovskites to more technologically accessible pressures.     

Halide Double Perovskite Ferroelectrics

Halide double perovskites have recently emerged as a promising environmentally friendly optoelectronic and photovoltaic material for their inherent thermodynamic stability, high defect tolerance, and appropriate band gaps. However, to date, no ferroelectric material based on halide double perovskites has been discovered. Herein, by hetero‐substitution of lead and cation intercalation of n‐propylamine, the first halide double perovskite ferroelectric, (n‐propylammonium)₂CsAgBiBr₇ ( 1 ), is reported and it exhibits distinct ferroelectricity with a notable saturation polarization of about 1.5 μC cm^?2. More importantly, single‐crystal photodetectors of 1 exhibit extraordinary performance with containing high on/off ratios of about 10⁴, fast response rates of 141 μs, and detectivity as high as 5.3×10¹¹ Jones. This finding opens a new way to design high‐performance perovskite ferroelectrics, and provides a viable approach in the search for stable and lead‐free optoelectronic materials as an alternative to the lead‐containing system.     

Centimeter‐Sized Single Crystal of Two‐Dimensional Halide Perovskites Incorporating Straight‐Chain Symmetric Diammonium Ion for X‐Ray Detection

Two‐dimensional (2D) AA′_n?1M_nX_3n+1 type halide perovskites incorporating straight‐chain symmetric diammonium cations define a new type of structure, but their optoelectronic properties are largely unexplored. Reported here is the synthesis of a centimeter‐sized AA′_n?1M_nX_3n+1 type perovskite, BDAPbI₄ (BDA=NH₃C₄H₈NH₃), single crystal and its charge‐transport properties under X‐ray excitation. The crystal shows a staggered configuration of the [PbI₆]^4? layers, a band gap of 2.37 eV, and a low trap density of 3.1×10⁹ cm^?3. The single‐crystal X‐ray detector exhibits an excellent sensitivity of 242 μC Gy_air^?1 cm^?2 under the 10 V bias (0.31 V μm^?1), a detection limit as low as 430 nGy_air s^?1, ultrastable response current, a stable baseline with the lowest dark current drift of 6.06×10^?9 nA cm^?1 s^?1 V^?1, and rapid response time of τ_rise=7.3 ms and τ_fall=22.5 ms. These crystals are promising candidates for the next generation of optoelectronic devices.     

Chemical Origin of the Stability Difference between Copper(I)‐ and Silver(I)‐Based Halide Double Perovskites

Recently, Cu^I‐ and Ag^I‐based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb‐based halide perovskite absorbers. However, up to date, only Ag^I‐based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu^I‐based analogues. Here we show that, owing to the much higher energy level for the Cu 3d¹⁰ orbitals than for the Ag 4d¹⁰ orbitals, Cu^I atoms energetically favor 4‐fold coordination, forming [CuX₄] tetrahedra (X=halogen), but not 6‐fold coordination as required for [CuX₆] octahedra. In contrast, Ag^I atoms can have both 6‐ and 4‐fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu^I halide double perovskites may instead lead to non‐perovskites containing [CuX₄] tetrahedra, as confirmed by our material synthesis efforts.     

Small‐Band‐Gap Halide Double Perovskites

Despite their compositional versatility, most halide double perovskites feature large band gaps. Herein, we describe a strategy for achieving small band gaps in this family of materials. The new double perovskites Cs₂AgTlX₆ (X=Cl ( 1 ) and Br ( 2 )) have direct band gaps of 2.0 and 0.95 eV, respectively, which are approximately 1 eV lower than those of analogous perovskites. To our knowledge, compound 2 displays the lowest band gap for any known halide perovskite. Unlike in A^IB^IIX₃ perovskites, the band‐gap transition in A^I₂BB′X₆ double perovskites can show substantial metal‐to‐metal charge‐transfer character. This band‐edge orbital composition is used to achieve small band gaps through the selection of energetically aligned B‐ and B′‐site metal frontier orbitals. Calculations reveal a shallow, symmetry‐forbidden region at the band edges for 1 , which results in long (μs) microwave conductivity lifetimes. We further describe a facile self‐doping reaction in 2 through Br₂ loss at ambient conditions.     

Air‐Stable,Lead‐Free Zero‐Dimensional Mixed Bismuth‐Antimony Perovskite Single Crystals with Ultra‐broadband Emission

Lead‐free zero‐dimensional (0D) organic‐inorganic metal halide perovskites have recently attracted increasing attention for their excellent photoluminescence properties and chemical stability. Here, we report the synthesis and characterization of an air‐stable 0D mixed metal halide perovskite (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O, in which individual [BiBr₆]^3? and [SbBr₆]^3? octahedral units are completely isolated and surrounded by the large organic cation C₈H₁₂N⁺. Upon photoexcitation, the bulk crystals exhibit ultra‐broadband emission ranging from 400 to 850 nm, which originates from both free excitons and self‐trapped excitons. This is the first example of 0D perovskites with broadband emission spanning the entire visible spectrum. In addition, (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O exhibits excellent humidity and light stability. These findings present a new direction towards the design of environmentally‐friendly, high‐performance 0D perovskite light emitters.     

Air‐Stable,Lead‐Free Zero‐Dimensional Mixed Bismuth‐Antimony Perovskite Single Crystals with Ultra‐broadband Emission

Lead‐free zero‐dimensional (0D) organic‐inorganic metal halide perovskites have recently attracted increasing attention for their excellent photoluminescence properties and chemical stability. Here, we report the synthesis and characterization of an air‐stable 0D mixed metal halide perovskite (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O, in which individual [BiBr₆]^3? and [SbBr₆]^3? octahedral units are completely isolated and surrounded by the large organic cation C₈H₁₂N⁺. Upon photoexcitation, the bulk crystals exhibit ultra‐broadband emission ranging from 400 to 850 nm, which originates from both free excitons and self‐trapped excitons. This is the first example of 0D perovskites with broadband emission spanning the entire visible spectrum. In addition, (C₈NH₁₂)₄Bi_0.57Sb_0.43Br₇?H₂O exhibits excellent humidity and light stability. These findings present a new direction towards the design of environmentally‐friendly, high‐performance 0D perovskite light emitters.     

Self‐Template‐Directed Synthesis of Porous Perovskite Nanowires at Room Temperature for High‐Performance Visible‐Light Photodetectors

The unique optoelectronic properties and promising photovoltaic applications of organolead halide perovskites have driven the exploration of facile strategies to synthesize organometal halide perovskites and corresponding hybrid materials and devices. Currently, the preparation of CH₃NH₃PbBr₃ perovskite nanowires, especially those with porous features, is still a great challenge. An efficient self‐template‐directed synthesis of high‐quality porous CH₃NH₃PbBr₃ perovskite nanowires in solution at room temperature using the Pb‐containing precursor nanowires as both the sacrificial template and the Pb²⁺ source in the presence of CH₃NH₃Br and HBr is now presented. The initial formation of CH₃NH₃PbBr₃ perovskite layers on the surface of the precursor nanowires and the following dissolution of the organic component of the latter led to the formation of mesopores and the preservation of the 1D morphology. Furthermore, the perovskite nanowires are potential materials for visible‐light photodetectors with high sensitivity and stability.     

Polarization‐Driven Self‐Powered Photodetection in a Single‐Phase Biaxial Hybrid Perovskite Ferroelectric

Self‐powered photodetection driven by ferroelectric polarization has shown great potential in next‐generation optoelectronic devices. Hybrid perovskite ferroelectrics that combine polarization and semiconducting properties have a promising position within this portfolio. Herein, we demonstrate the realization of self‐powered photodetection in a new developed biaxial ferroelectric, (EA)₂(MA)₂Pb₃Br₁₀ ( 1 , EA is ethylammonium and MA is methylammonium), which displays high Curie temperature (375 K), superior spontaneous polarization (3.7 μC cm^?2), and unique semiconducting nature. Strikingly, without an external energy supply, 1 exhibits an direction‐selectable photocurrent with fascinating attributes including high photocurrent density (≈4.1 μA cm^?2), high on/off switching ratio (over 10⁶), and ultrafast response time (96/123 μs); such merits are superior to those of the most active ferroelectric oxide BiFeO₃. Further studies reveal that strong inversion symmetry breaking in 1 provides a desirable driving force for carrier separation, accounting for such electrically tunable self‐powered photoactive behaviors. This work sheds light on exploring new multifunctional hybrid perovskites and advancing the design of intelligent photoelectric devices.     

Zero‐Dimensional Hybrid Cd‐Based Perovskites with Broadband Bluish White‐Light Emissions

Recently, low‐dimensional organic‐inorganic hybrid metal halide perovskites acting as single‐component white‐light emitting materials have attracted extensive attention, but most studies concentrate on hybrid lead perovskites. Herein, we present two isomorphic zero‐dimensional (0D) hybrid cadmium perovskites, (HMEDA)CdX₄ (HMEDA=hexamethylenediamine, X=Cl ( 1 ), Br ( 2 )), which contain isolated [CdX₄]^2? anions separated by [HMEDA]²⁺ cations. Under UV light excitation, both compounds display broadband bluish white‐light emission (515 nm for 1 and 445 nm for 2 ) covering the entire visible light spectrum with sufficient photophysical stabilities. Remarkably, compound 2 shows a high color rendering index (CRI) of 83 enabling it as a promising candidate for single‐component WLED applications. Based on the temperature‐dependent, powder‐dependent and time‐resolved PL measurements as well as other detailed studies, the broadband light emissions are attributed to self‐trapped excitons stemming from the strong electron‐phonon coupling.     

A Nickel(II) Nitrite Based Molecular Perovskite Ferroelectric

The X‐site ion in organic–inorganic hybrid ABX₃ perovskites (OHPs) varies from halide ion to bridging linkers like HCOO^?, N₃^?, NO₂^?, and CN^?. However, no nitrite‐based OHP ferroelectrics have been reported so far. Now, based on non‐ferroelectric [(CH₃)₄N][Ni(NO₂)₃], through the combined methodologies of quasi‐spherical shape, hydrogen bonding functionality, and H/F substitution, we have successfully synthesized an OHP ferroelectric, [FMeTP][Ni(NO₂)₃] (FMeTP=N‐fluoromethyl tropine). As an unprecedented nitrite‐based OHP ferroelectric, the well‐designed [FMeTP][Ni(NO₂)₃] undergoes the ferroelectric phase transition at 400 K with an Aizu notation of 6/mmmFm, showing multiaxial ferroelectric characteristics. This work is a great step towards not only enriching the molecular ferroelectric families but also accelerating the potential practical applications.     

(1‐Butyl‐4‐methyl‐pyridinium)[Cu(SCN)2]: A Coordination Polymer and Ionic Liquid

The compound (C₄C₁py)[Cu(SCN)₂], (C₄C₁py=1‐Butyl‐4‐methyl‐pyridinium), which can be obtained from CuSCN and the ionic liquid (C₄C₁py)(SCN), turns out to be a new organic–inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)₂]^? units, in which the thiocyanates bridge the copper ions in a μ_1,3‐fashion. The resulting one‐dimensional chains run along the a axis, separated by the C₄C₁py counterions. Powder X‐ray diffraction not only confirms the single‐crystal X‐ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature‐dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid‐state UV/Vis spectroscopy shows a broad absorption band around 18 870 cm^?1 (530 nm) and another strong one below 20 000 cm^?1 (<500 nm). The latter is attributed to the d(Cu^I)→π*(SCN)‐MLCT (metal‐to‐ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15 870 cm^?1 (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases.     

(CH3NH3)2PdCl4: A Compound with Two‐Dimensional Organic–Inorganic Layered Perovskite Structure

The synthesis of previously unknown perovskite (CH₃NH₃)₂PdCl₄ is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic–inorganic layered Pd‐based perovskites was still formed. This demonstrates that Pd‐based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance‐factor formula. The (CH₃NH₃)₂PdCl₄ phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 10⁴ cm^?1. XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic–inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic–inorganic perovskites, the synthesis of this new Pd‐based organic–inorganic perovskite may be helpful in the preparation and understanding of other organic–inorganic perovskites.     

Trapping of Oxygen Vacancies at Crystallographic Shear Planes in Acceptor‐Doped Pb‐Based Ferroelectrics

The defect chemistry of the ferroelectric material PbTiO₃ after doping with Fe^III acceptor ions is reported. Using advanced transmission electron microscopy and powder X‐ray and neutron diffraction, we demonstrate that even at concentrations as low as circa 1.7 % (material composition approximately ABO_2.95), the oxygen vacancies are trapped into extended planar defects, specifically crystallographic shear planes. We investigate the evolution of these defects upon doping and unravel their detailed atomic structure using the formalism of superspace crystallography, thus unveiling their role in nonstoichiometry in the Pb‐based perovskites.     

Temperature‐Independent Hole Mobility of a Smectic Liquid‐Crystalline Semiconductor based on Band‐Like Conduction

A liquid‐crystalline (LC) phenylterthiophene derivative, which exhibited an ordered smectic phase at room temperature, was purified by vacuum sublimation under a flow of nitrogen. During the sublimation process, thin plates with sizes of 1 mm grew on the surface of the vacuum tube. The crystals exhibited the same X‐ray diffraction patterns as the ordered smectic phase of the LC state that was formed through a conventional recrystallization process by using organic solvents. Because of the removal of chemical impurities, the hole mobility in the ordered smectic phase of the vacuum‐grown thin plates increased to 1.2×10^?1 cm² V^?1 s^?1 at room temperature, whereas that of the LC precipitates was 7×10^?2 cm² V^?1 s^?1. The hole mobility in the ordered smectic phase of the vacuum‐sublimated sample was temperature‐independent between 400 and 220 K. The electric‐field dependence of the hole mobility was also very small within this temperature range. The temperature dependence of hole mobility was well‐described by the Hoesterey–Letson model. The hole‐transport characteristics indicate that band‐like conduction affected by the localized states, rather than a charge‐carrier‐hopping mechanism, is a valid mechanism for hole transport in an ordered smectic phase.     

Benign‐by‐Design Solventless Mechanochemical Synthesis of Three‐, Two‐, and One‐Dimensional Hybrid Perovskites

Organic–inorganic hybrid perovskites have attracted significant attention owing to their extraordinary optoelectronic properties with applications in the fields of solar energy, lighting, photodetectors, and lasers. The rational design of these hybrid materials is a key factor in the optimization of their performance in perovskite‐based devices. Herein, a mechanochemical approach is proposed as a highly efficient, simple, and reproducible method for the preparation of four types of hybrid perovskites, which were obtained in large amounts as polycrystalline powders with high purity and excellent optoelectronics properties. Two archetypal three‐dimensional (3D) perovskites (MAPbI₃ and FAPbI₃) were synthesized, together with a bidimensional (2D) perovskite (Gua₂PbI₄) and a “double‐chain” one‐dimensional (1D) perovskite (GuaPbI₃), whose structure was elucidated by X‐ray diffraction.