Switching Lead for Tin in PbHfO3 : Noncubic Structure of SnHfO3.

The removal of lead from commercialized perovskite-oxide-based piezoceramics has been a recent major topic in materials research owing to legislation in many countries. In this regard, Sn(II)-perovskite oxides have garnered keen interest due to their predicted large spontaneous electric polarizations and isoelectronic nature for substitution of Pb(II) cations. However, they have not been considered synthesizable owing to their high metastability. Herein, the perovskite lead hafnate, i.e., PbHfO3 in space group Pbam, is shown to react with SnClF at a low temperature of 300 °C, and resulting in the first complete Sn(II)-for-Pb(II) substitution, i.e. SnHfO3 . During this topotactic transformation, a high purity and crystallinity is conserved with Pbam symmetry, as confirmed by X-ray and electron diffraction, elemental analysis, and 119 Sn Mössbauer spectroscopy. In situ diffraction shows SnHfO3 also possesses reversible phase transformations and is potentially polar between ≈130-200 °C. This so-called 'de-leadification' is thus shown to represent a highly useful strategy to fully remove lead from perovskite-oxide-based piezoceramics and opening the door to new explorations of polar and antipolar Sn(II)-oxide materials.

Controlling the Orientation-Dependent Second Harmonic Generation in Hybrid Germanium Perovskites.

Manipulating the crystal orientation plays a crucial role in the conversion efficiency during second harmonic generation (SHG). Here, we provide a new strategy in controlling the surface-dependent anisotropic SHG with the precise design of (101) and (2 1 ‾ ${\bar 1}$ 0) MAGeI3 facets. Based on the SHG measurement, the (101) MAGeI3 single crystal exhibits larger SHG (1.3×(2 1 ‾ ${\bar 1}$ 0) MAGeI3). Kelvin probe force microscopy imaging shows a smaller work function for the (101) MAGeI3 compared with the (2 1 ‾ ${\bar 1}$ 0), which indirectly demonstrates the stronger intrinsic polarization on the (101) surface. X-ray photoelectron spectroscopy confirms the band bending within the (101) facet. Temperature-dependent steady-state and time-resolved photoluminescence spectroscopy show shorter lifetime and wider emission band in the (101) MAGeI3 single crystal, revealing the higher defect states. Additionally, powder X-ray diffraction patterns show the (101) MAGeI3 possesses larger in-plane polar units [GeI3]- density, which could directly enhance the spontaneous polarization in the (101) facet. Density functional theory (DFT) calculation further demonstrates the higher intrinsic polarization in the (101) facet compared with the (2 1 ‾ ${\bar 1}$ 0) facet, and the larger built-in electric field in the (101) facet facilitates surface vacancy defect accumulation. Our work provides a new angle in tuning and optimizing hybrid perovskite-based nonlinear optical materials.

Lead-Free Metal Halide Perovskite Nanocrystals: From Fundamentals to Applications.

Lead (Pb) halide perovskite nanocrystals, with the general formula APbX3 , where A=CH3 NH3+ , CH(NH2 )2+ , or Cs+ and X=Cl- , Br- , or I- , have emerged as a class of materials with promising properties due to their remarkable optical properties and solar cell performance. However, important issues still need to be addressed to enable practical applications of these materials, such as instability, mass production, and Pb toxicity. Recent studies have carried out the replacement of Pb by various less-toxic cations as Sn, Ge, Sb, and Bi. This variety of chemical compositions provide Pb-free perovskite and metal halide nanostructures with a wide spectral range, in addition to being considered less toxic, therefore having greater practical applicability. Highlighting the necessity to address and solve the toxicity problems related to Pb-containing perovskite, this review considers the prospects of the Pb-free perovskite, involving synthesis methods, and properties of them, including advantages, disadvantages, and applications.

High-Pressure and High-Temperature Dion-Jacobson Layered Perovskite Polymorphs of KWO3 F.

Two new Dion-Jacobson layered perovskite polymorphs of the known oxyfluoride compound KWO3 F are reported. A high-pressure modification was synthesized using a multianvil setup and subsequently transformed into a high-temperature phase at ∼311 °C. The crystal structures of both polymorphs were determined by use of single-crystal X-ray diffraction and are described in detail herein. Differential thermal analyses and thermogravimetric analyses were carried out to further investigate the phase transition characteristics. Bond valence (BV) and charge distribution (CHARDI) calculations confirm the occupancy of mixed O|F anion positions, and Rietveld refinements as well as MAPLE calculations support the structure models.

Elusive Double Perovskite Iodides: Structural, Optical, and Magnetic Properties.

Halide double perovskites [A2 MI MIII X6 ] are an important class of materials that have garnered substantial interest as non-toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs2 NaLnI6 (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported.

Utilisation of CO2 as "Structure Modifier" of Inorganic Solids.

Utilisation of CO2 as a chemical reagent is challenging, due to the molecule's inherent chemical stability. However, CO2 reacts promptly at high temperature (∼1000 °C) with alkaline-earth oxides to form carbonates and such reactions are used towards capture and re-utilisation. In this work, this concept is extended and CO2 is utilised as a reagent to modify the crystal structure of mixed-metal inorganic solids. Modification of the crystal structure is a "tool" used by materials scientists to tailor the physical property of solids. CO2 gas was reacted with several isostructural mixed-metal oxides Sr2 CuO3 , Sr1.8 Ba0.2 CuO3 and Ba2 PdO3 . These oxides are carefully selected to show anion vacancies in their crystal structure, to act as host sites for CO2 molecules, leading to the formation of carbonate anions, (CO3 )2- . The corresponding oxide carbonates were formed successfully and the favourable formation of SrCO3 as secondary phase was minimised via an innovative, yet simple synthetic procedure involving alternating of CO2 and air. We also derived a simple model to predict the kinetics of the reactions for the cuprates, using first-principles density functional theory and assimilating the reaction to a gas-surface process.

Solvent-Free Preparation and Moderate Congruent Melting Temperature of Layered Lead Iodide Perovskites for Thin-Film Formation.

Lead halide 2D hybrid perovskites (HP) have emerged as promising materials for photovoltaic and lighting applications. Solvent-free preparations offer greener route, but require congruent melting of halide perovskite for thin films, which has been demonstrated only for monolayered HP (n=1 of the (A)2 (MA)n-1 Pbn I3n+1 series) at the quite high temperature Tm (Tmelting ) of 171 °C. Here, we report on the solvent-free preparation (n=2, 4), thermal behaviour and melt-processed thin films of a series of HP (GABA)2 (MA)n-1 Pbn I3n+1 (n=1, 2, 4; GABA+ : 4-ammoniumbutyric acid cation). The n=1 and n=2 HP have an exceptional low congruent Tm of 126 °C and 136 °C, respectively, and, for n=1, a very good stability in the molten state. The liquid-solid reaction of molten (GABA)2 PbI4 or (GABA)2 (MA)Pb2 I7 with MAPbI3 in 1/1 (T=130 °C) or 1/2 (T=135 °C) ratio leads to pure phases of the n=2 HP and (GABA)2 (MA)3 Pb4 I11 (n=4, Tm =185 °C), respectively. Melt-processed thin films of n=1, n=2 and n=4 HP have also been prepared.

The Effect of Water on the 2-Propanol Oxidation Activity of Co-Substituted LaFe1- Cox O3 Perovskites.

Perovskites are interesting oxidation catalysts due to their chemical flexibility enabling the tuning of several properties. In this work, we synthesized LaFe1-x Cox O3 catalysts by co-precipitation and thermal decomposition, characterized them thoroughly and studied their 2-propanol oxidation activity under dry and wet conditions to bridge the knowledge gap between gas and liquid phase reactions. Transient tests showed a highly active, unstable low-temperature (LT) reaction channel in conversion profiles and a stable, less-active high-temperature (HT) channel. Cobalt incorporation had a positive effect on the activity. The effect of water was negative on the LT channel, whereas the HT channel activity was boosted for x>0.15. The boost may originate from a slower deactivation rate of the Co3+ sites under wet conditions and a higher amount of hydroxide species on the surface comparing wet to dry feeds. Water addition resulted in a slower deactivation for Co-rich catalysts and higher activity in the HT channel state.

Preparation of Bulk-Phase Nitride Perovskite LaReN3 and Topotactic Reduction to LaNiO2 -Type LaReN2.

While halide and oxide perovskites are numerous and many display outstanding properties, ABN3 perovskite nitrides are extremely rare due to synthetic challenges arising from the low chemical potential of nitrogen and a tendency to form low-coordination nitridometallate anions. We report the preparation of a perovskite nitride LaReN3 through azide-mediated oxidation at high pressure. High-resolution synchrotron diffraction shows that LaReN3 has a low-symmetry, triclinic, perovskite superstructure resulting from orbital ordering with strong spin-orbit coupling distortions. Topotactic reduction of LaReN3 above 500 °C leads to layered tetragonal LaReN2 via a probable LaReN2.5 intermediate, which is the first reported example of nitride defect perovskites. Magnetisation and conductivity measurements indicate that LaReN3 and LaReN2 are both metallic solids. The two chemical approaches presented are expected to lead to new classes of ABN3 and defect ABN3-x nitride perovskite materials.

The Key Role of the Interface in the Highly Sensitive Mechanochromic Luminescence Properties of Hybrid Perovskites.

Hybrid perovskite (HP) materials are of interest in photovoltaics and lighting applications. Here we report that hybrid perovskite composites, as crystallized powders, can behave as intelligent materials showing highly sensitive and reversible mechanochromic luminescence (MCL). Composites consisting of monolayered 2D HP and 3D HP components exhibit reversible tunable color emission upon mechanical strain. The bluish-whitish emission of the 2D HP turns into orange in the composite owing to an energy transfer process. The bright green emission, observed as soon as the composite is slightly crushed, originates from the 3D HP after efficient energy funneling from the multi-layered 2D HP produced at the 2D/3D interface by the mechanical treatment. Besides highlighting the key role of the interfaces in light emission of HP, our findings pave the way for hybrid perovskites as highly sensitive MCL smart materials for mechanosensors, security papers, or optical storage applications.

Perovskite Oxide-Halide Solid Solutions: A Platform for Electrocatalysts.

The successful integration or hybridization of perovskite oxides with their halide cousins would enable the formation of both multi-anionic and multi-cationic solid solutions with unique metal-ion sites and synergistic properties that could potentially surpass the performance of classic perovskites. However, such solid solutions had not been produced previously owing to their distinct formation energies and different synthesis conditions. Solid solutions combining perovskite oxides with fluorides were produced in this study by mechanochemical synthesis. The obtained perovskite oxide-halide solid solutions had highly mixed elements and valences, uniform element distributions, and single-phase crystalline structures. The solid solution with an optimized combination of oxides and fluorides exhibited enhanced catalytic performance in the oxygen evolution reaction.

Strong Self-Trapped Exciton Emissions in Two-Dimensional Na-In Halide Perovskites Triggered by Antimony Doping.

Soft lattice and strong exciton-phonon coupling have been demonstrated in layered double perovskites (LDPs) recently; therefore, LDPs represents a promising class of compounds as excellent self-trapped exciton (STE) emitters for applications in solid-state lighting. However, few LDPs with outstanding STE emissions have been discovered, and their optoelectronic properties are still unclear. Based on the three-dimensional (3D) Cs2 NaInCl6 , we synthesized two 2D derivatives (PEA)4 NaInCl8 :Sb (PEA=phenethylamine) and (PEA)2 CsNaInCl7 :Sb with monolayer and bilayer inorganic sheets by a combination of dimensional reduction and Sb-doping. Bright broadband emissions were obtained for the first time under ambient temperature and pressure, with photoluminescence quantum efficiency (PLQE) of 48.7 % (monolayer) and 29.3 % (bilayer), superior to current known LDPs. Spectroscopic characterizations and first-principles calculations of excited state indicate the broadband emissions originate from STEs trapped at the introduced [SbCl6 ]3- octahedron.

An Organic-Inorganic Perovskitoid with Zwitterion Cysteamine Linker and its Crystal-Crystal Transformation to Ruddlesden-Popper Phase.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.

Completely Amine-Free Open-Atmospheric Synthesis of High-Quality Cesium Lead Bromide (CsPbBr3 ) Perovskite Nanocrystals.

Cesium lead halide perovskite nanocrystals (NCs) CsPbX3 (X=Cl, Br, and I) have been prominent materials in the last few years due to their high photoluminescence quantum yield (PLQY) for light-emitting diodes and other significant applications in photovoltaics and optoelectronics. In colloidal CsPbX3 synthesis, the most commonly used ligands are oleic acid and oleylamine. The latter plays an important role in surface passivation but may also be responsible for poor colloidal stability as a result of facile proton exchange leading to the formation of labile oleylammonium halide, which pulls halide ions out of the NC surface. Herein, a facile, efficient, completely amine-free synthesis of cesium lead bromide perovskite nanocrystals using hydrobromic acid as halide source and tri-n-octylphosphane as ligand under open-atmospheric conditions is demonstrated. Hydrobromic acid serves as labile source of bromide ion, and thus this three-precursor approach (separate precursors for Cs, Pb, Br) gives more control than a conventional single-source precursor for Pb and Br (PbBr2 ). The use of HBr paved the way to eliminate oleylamine, and thus the formation of labile oleylammonium halide can be completely excluded. Various Cs:Pb:Br molar ratios were studied and optimum conditions for making very stable CsPbBr3 NCs with high PLQY were found. These completely amine-free CsPbBr3 perovskite NCs synthesized under bromine-rich conditions exhibit good stability and durability for more than three months in the form of colloidal solutions and films, respectively. Furthermore, stable tunable emission across a wide spectral range through anion exchange was demonstrated. More importantly, this work reports open-atmosphere-stable CsPbBr3 NCs films exhibiting strong PL, which can be further used for optoelectronic device applications.

Crucial Role of Water in the Mechanosynthesis of CsPbI3 and Other ABX3 Halides.

Mechanochemical synthesis of CsPbI3 , as a model system for ABX3 halides, was studied. Water was shown to strongly promote the kinetics of formation of CsPbI3 from the CsI+PbI2 mixture through increased mobility of the constituting ionic species. Since many binary and ternary halides are hygroscopic, it was concluded that the presence of small, uncontrollable and unintentional additions of water should often occur in both precursor mixtures and synthesized complex halides boosting the kinetics of formation of many, if not all, ternary organic-inorganic hybrid halides such as, for example, MAPbX3 (X=Cl, Br, I). In addition, trace amounts of water should influence the transport characteristics of complex halides. Thus, the presence of water explains, at least partially, the huge scatter in both the reported mechanochemical reaction times necessary for obtaining single-phase APbX3 perovskite halides and the activation energies of ionic diffusion in APbX3 .

Conversion/Alloying Pseudocapacitance-Dominated Perovskite KZnF3 Anode for Advanced Lithium-Based Dual-Ion Batteries.

Cost-competitive perovskite fluoride KZnF3 has been introduced for the first time as an advanced anode for high-performance lithium-based dual-ion batteries, exhibiting conversion/alloying hybrid mechanisms and dominated pseudocapacitive kinetics for Li-ion storage.

Improving Broadband White-Light Emission Performances of 2D Perovskites by Subtly Regulating Organic Cations.

Recently, 2D organic-inorganic hybrid lead halide perovskites have attracted intensive attention in solid-state luminescence fields such as single-component white-light emitters, and rational optimization of the photoluminescence (PL) performance through accurate structural-design strategies is still significant. Herein, by carefully choosing homologous aliphatic amines as templates, isotypical perovskites [DMEDA]PbCl4 (1, DMEDA=N,N-dimethylethylenediamine) and [DMPDA]PbCl4 (2, DMPDA=N,N-dimethyl-1,3-diaminopropane) having tunable and stable broadband bluish white emission properties were rationally designed. The subtle regulation of organic cations leads to a higher degree of distortion of the 2D [PbCl4 ]2- layers and enhanced photoluminescence quantum efficiencies (<1 % for 1 and 4.9 % for 2). The broadband light emissions could be ascribed to self-trapped excitons on the basis of structural characterization, time-resolved PL, temperature-dependent PL emission, and theoretical calculations. This work gives a new guidance to rationally optimize the PL properties of low-dimensional halide perovskites and affords a platform to probe the structure-property relationship.

Bright Luminous and Stable CsPbBr3 @PS Microspheres Prepared via Facile Anti-solvent Method using CTAB as Double Modifier.

The past decade has witnessed the increasing interest in cesium lead halide perovskite quantum dots (PQDs) for their excellent optical properties with higher photoluminescence efficiency and tunable emission wavelengths widely applied in white LED, photovoltaic devices, etc. Here we report the preparation of CsPbBr3 PQDs by a facile anti-solvent method using conventional quaternary ammonium bromide (CTAB) as a double modifier-both proper alkyl group protection and bromine source donator. The as-formed PQDs are well-monodispersed cubes with a size of 10-15 nm and high photoluminescence quantum yield (PLQY) of up to 43 %. To enhance the stability of PQDs, CsPbBr3 @PS microspheres were formed by electrospraying process. The microspheres not only show excellent luminous properties, but exhibit much higher stability against air and UV light irradiation due to the super hydrophobic property of polystyrene.

Recent Advances and Optoelectronic Applications of Lead-Free Halide Double Perovskites.

Organic-inorganic metal halide perovskites (most notably CH3 NH3 PbI3 ) have demonstrated remarkable physical attributes for photovoltaic and diverse optoelectronic applications, whereas concerns about toxicity owing to the use of lead in the chemical composition still motivate further exploration of new, nontoxic candidates. Lead-free halide double perovskites (HDPs), designed by the rational chemical substitution of Pb2+ with other nontoxic candidate elements, have recently attracted interest as a fascinating alternative to their Pb-based counterparts. Herein, recent advances in crystal structures, physical properties, and versatile optoelectronic applications of lead-free HDPs, such as solar cells, photodetectors, X-ray detectors, and light-emitting diodes, are reviewed. Perspectives to improve the physical and photoelectric properties of existing HDP materials are also discussed and will favor future development of new, lead-free HDP candidates.

Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2.

Non-centrosymmetric polar compounds have important technological properties. Reported perovskite oxynitrides show centrosymmetric structures, and for some of them high permittivities have been observed and ascribed to local dipoles induced by partial order of nitride and oxide. Reported here is the first hexagonal perovskite oxynitride BaWON2 , which shows a polar 6H polytype. Synchrotron X-ray and neutron powder diffraction, and annular bright-field in scanning transmission electron microscopy indicate that it crystalizes in the non-centrosymmetric space group P63 mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX3 layers. A synergetic second-order Jahn-Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W6+ cations, induce large distortions at two inequivalent face-sharing octahedra that lead to long-range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.