A broad organic–inorganic series of hybrid metal iodide perovskites with the general formulation AMI3, where A is the methylammonium (CH3NH3+) or formamidinium (HC(NH2)2+) cation and M is Sn (1 and 2) or Pb (3 and 4) are reported. The compounds have been prepared through a variety of synthetic approaches, and the nature of the resulting materials is discussed in terms of their thermal stability and optical and electronic properties. We find that the chemical and physical properties of these materials strongly depend on the preparation method. Single crystal X-ray diffraction analysis of 1–4 classifies the compounds in the perovskite structural family. Structural phase transitions were observed and investigated by temperature-dependent single crystal X-ray diffraction in the 100–400 K range. The charge transport properties of the materials are discussed in conjunction with diffuse reflectance studies in the mid-IR region that display characteristic absorption features. Temperature-dependent studies show a ...

Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties.

The hybrid organic–inorganic perovskite (CH3NH3)PbI3 may find application in next generation solid-state sensitised solar cells. Although this material and related perovskites were discovered many decades ago, questions remain concerning their diverse structural chemistry and unusual properties. The article presents a review of previous work and provides a detailed description of the preparation, structural characterisation and physical characteristics of (CH3NH3)PbI3. The phase changes exhibited by (CH3NH3)PbI3 have been probed using variable temperature powder and single crystal X-ray diffraction, combined with differential scanning calorimetry, thermogravimetric analysis and phase contrast transmission electron microscopy. The optical band gap for (CH3NH3)PbI3 determined by UV-Visible spectroscopy was compared to values obtained from density-of-state simulation of the electronic band structure.

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Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3) PbI3 for solid-state sensitised solar cell applications

The synthesis, crystal growth, and structural and optoelectronic characterization has been carried out for the perovskite compound CsPbBr3. This compound is a direct band gap semiconductor which meets most of the requirements for successful detection of X- and γ-ray radiation, such as high attenuation, high resistivity, and significant photoconductivity response, with detector resolution comparable to that of commercial, state-of-the-art materials. A structural phase transition which occurs during crystal growth at higher temperature does not seem to affect its crystal quality. Its μτ product for both hole and electron carriers is approximately equal. The μτ product for electrons is comparable to cadmium zinc telluride (CZT) and that for holes is 10 times higher than CZT.

Crystal Growth of the Perovskite Semiconductor CsPbBr3: A New Material for High-Energy Radiation Detection

A new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic–inorganic (A = organic) MHPs are reviewed with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH3NH3PbI3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2-dimensional compounds, where rele...

Intriguing Optoelectronic Properties of Metal Halide Perovskites

This Perspective outlines basic structural and optical properties of lead halide perovskite colloidal nanocrystals, highlighting differences and similarities between them and conventional II–VI and III–V semiconductor quantum dots. A detailed insight into two important issues inherent to lead halide perovskite nanocrystals then follows, namely, the advantages of defect tolerance and the necessity to improve their stability in environmental conditions. The defect tolerance of lead halide perovskites offers an impetus to search for similar attributes in other related heavy metal-free compounds. We discuss the origins of the significantly blue-shifted emission from CsPbBr3 nanocrystals and the synthetic strategies toward fabrication of stable perovskite nanocrystal materials with emission in the red and infrared parts of the optical spectrum, which are related to fabrication of mixed cation compounds guided by Goldschmidt tolerance factor considerations. We conclude with the view on perspectives of use of th...

Lead Halide Perovskite Nanocrystals in the Research Spotlight: Stability and Defect Tolerance

The hydrolysis of SnF2 in concentrated aqueous solution resulted in the formation of the tin(II) fluoride oxide, Sn4OF6. This is the first evidence for the formation of a basic tin(II) fluoride from an aqueous system. The crystal structure of Sn4OF6 has been determined using single-crystal X-ray diffraction and refined by full-matrix least-squares analysis to R= 0.0199. The compound crystallises in the orthorhombic space group P212121 with a= 16.088(3), b= 10.681 (2), c= 4.940(1)A and Z= 4. The structure consists of a three-dimensional polymeric network of bridging fluorine and oxygen atoms. Tin is present in four distinct sites one showing tetragonal-based pyramidal geometry while the others all show trigonal-pyramidal geometry with a fourth bridging fluorine atom at 2.4–2.5 A. The non-bonding electrons are stereochemically active and appear to point into irregular channels which run parallel to the c axis.

Hydrolysis of tin(II) fluoride and crystal structure of Sn4OF6

Variable-temperature Mossbauer studies have been carried out on 119Sn-enriched samples of CsSnBr3, Cs4SnBr6, CsSnCl3 and Cs4SnCl6. Significant changes found in the chemical isomer shift and quadrupole splitting or linewidth parameters with temperature are compared with changes in electrical conductivity. In each case the shift decreases with increasing temperature over a range of temperatures to a value which coincides with a minimum in the linewidth and with maximum conductivity. The changes observed are consistent with the direct population of solid-state bands by the non-bonding electrons on the tin(II) and with the changes expected from orbital-matching arguments.

High-temperature Mössbauer studies on 119Sn-enriched caesium tin(II) chlorides and bromides

Crystal structure of hexaaquacobalt(II) hexafluorostannate(IV), (Co(H2O)6)(SnF6)

Solid‐state properties of materials of the type cs4mx6 (where m = tin or lead and x = chloride or bromide)

Hydrolysis of Tin(II) Fluoride and Crystal Structure of Sn4OF6.

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