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 strong dependence of the resistivity as a function of the crystal structure. Optical absorption measurements indicate that 1-4 behave as direct-gap semiconductors with energy band gaps distributed in the range of 1.25-1.75 eV. The compounds exhibit an intense near-IR photoluminescence (PL) emission in the 700-1000 nm range (1.1-1.7 eV) at room temperature. We show that solid solutions between the Sn and Pb compounds are readily accessible throughout the composition range. The optical properties such as energy band gap, emission intensity, and wavelength can be readily controlled as we show for the isostructural series of solid solutions CH3NH3Sn(1-x)Pb(x)I3 (5). The charge transport type in these materials was characterized by Seebeck coefficient and Hall-effect measurements. The compounds behave as p- or n-type semiconductors depending on the preparation method. The samples with the lowest carrier concentration are prepared from solution and are n-type; p-type samples can be obtained through solid state reactions exposed in air in a controllable manner. In the case of Sn compounds, there is a facile tendency toward oxidation which causes the materials to be doped with Sn(4+) and thus behave as p-type semiconductors displaying metal-like conductivity. The compounds appear to possess very high estimated electron and hole mobilities that exceed 2000 cm(2)/(V s) and 300 cm(2)/(V s), respectively, as shown in the case of CH3NH3SnI3 (1). We also compare the properties of the title hybrid materials with those of the "all-inorganic" CsSnI3 and CsPbI3 prepared using identical synthetic methods.

The synthesis, crystal growth, and structural and optoelectronic characterization has been carried out for the perovskite compound CsPbBr 3 . 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.

CsSnI(3) is an unusual perovskite that undergoes complex displacive and reconstructive phase transitions and exhibits near-infrared emission at room temperature. Experimental and theoretical studies of CsSnI(3) have been limited by the lack of detailed crystal structure characterization and chemical instability. Here we describe the synthesis of pure polymorphic crystals, the preparation of large crack-/bubble-free ingots, the refined single-crystal structures, and temperature-dependent charge transport and optical properties of CsSnI(3), coupled with ab initio first-principles density functional theory (DFT) calculations. In situ temperature-dependent single-crystal and synchrotron powder X-ray diffraction studies reveal the origin of polymorphous phase transitions of CsSnI(3). The black orthorhombic form of CsSnI(3) demonstrates one of the largest volumetric thermal expansion coefficients for inorganic solids. Electrical conductivity, Hall effect, and thermopower measurements on it show p-type metallic behavior with low carrier density, despite the optical band gap of 1.3 eV. Hall effect measurements of the black orthorhombic perovskite phase of CsSnI(3) indicate that it is a p-type direct band gap semiconductor with carrier concentration at room temperature of ∼ 10(17) cm(-3) and a hole mobility of ∼585 cm(2) V(-1) s(-1). The hole mobility is one of the highest observed among p-type semiconductors with comparable band gaps. Its powders exhibit a strong room-temperature near-IR emission spectrum at 950 nm. Remarkably, the values of the electrical conductivity and photoluminescence intensity increase with heat treatment. The DFT calculations show that the screened-exchange local density approximation-derived band gap agrees well with the experimentally measured band gap. Calculations of the formation energy of defects strongly suggest that the electrical and light emission properties possibly result from Sn defects in the crystal structure, which arise intrinsically. Thus, although stoichiometric CsSnI(3) is a semiconductor, the material is prone to intrinsic defects associated with Sn vacancies. This creates highly mobile holes which cause the materials to appear metallic.

Metal-organic frameworks--a class of porous hybrid materials built from metal ions and organic bridges--have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m(2) g(-1)). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g(-1)) and carbon dioxide (2,315 mg g(-1))--gases of high importance in the contexts of clean energy and climate alteration, respectively--in excellent agreement with predictions from modelling.

The recent observations of superconductivity at temperatures up to 55K in compounds containing layers of iron arsenide [1,2,3,4] have revealed a new class of high temperature superconductors that show striking similarities to the more familiar cuprates. In both series of compounds, the onset of superconductivity is associated with the suppression of magnetic order by doping holes and/or electrons into the band [5] leading to theories in which magnetic fluctuations are either responsible for or strongly coupled to the superconducting order parameter [6]. In the cuprates, theories of magnetic pairing have been invoked to explain the observation of a resonant magnetic excitation that scales in energy with the superconducting energy gap and is suppressed above the superconducting transition temperature, Tc. Such resonant excitations have been shown by inelastic neutron scattering to be a universal feature of the cuprate superconductors [7], and have even been observed in heavy fermion superconductors with much lower transition temperatures [8,9,10]. In this paper, we show neutron scattering evidence of a resonant excitation in Ba0.6K0.4Fe2As2, which is a superconductor below 38 K [4], at the momentum transfer associated with magnetic order in the undoped compound, BaFe2As2, and at an energy transfer that is consistent with scaling in other strongly correlated electron superconductors. As in the cuprates, the peak disappears at Tc providing the first experimental confirmation of a strong coupling of the magnetic fluctuation spectrum to the superconducting order parameter in the new iron arsenide superconductors.Unconventional superconductivity has been the subject of considerable theoretical and experimental interest since the discovery of superconductivity in CeCu 2 Si 2 and other heavy fermion compounds [11], an interest that was only intensified by the discovery of cuprate superconductors with transition temperatures in excess of 100 K [6]. Although significant progress has been made, the origin of unconventional superconductivity is still not understood. The observation of a magnetic resonance in the spin excitation spectrum which appears concurrently with the onset of superconductivity in both the high T c cuprates [12,13,14,15,16] and the heavy fermion superconductors [8,9,10] offers the tantalizing possibility of a unifying theme for unconventional superconductivity that spans a diverse range of superconducting materials. Recently, a new family of superconductors containing layers of Fe 2 As 2 has been discovered with T c s in excess of 50 K stimulating considerable experimental and theoretical activity [1,2,3]. Although there is mounting evidence that the superconductivity in this new family is also unconventional [17], there is as yet no consensus concerning the mechanism giving rise to superconductivity or even the superconducting pairing symmetry. In this letter, we describe neutron scattering data that confirm for the first time the existence of a resonant spin excitation below T c in the iron arsenide ma...

We introduce a new class of molecular iodosalt compounds for application in next-generation solar cells. Unlike tin-based perovskite compounds CsSnI3 and CH3NH3SnI3, which have Sn in the 2+ oxidation state and must be handled in an inert atmosphere when fabricating solar cells, the Sn in the molecular iodosalt compounds is in the 4+ oxidation state, making them stable in air and moisture. As an example, we demonstrate that, using Cs2SnI6 as a hole transporter, we can successfully fabricate in air a solid-state dye-sensitized solar cell (DSSC) with a mesoporous TiO2 film. Doping Cs2SnI6 with additives helps to reduce the internal device resistance, improving cell efficiency. In this way, a Z907 DSSC delivers 4.7% of energy conversion efficiency. By using a more efficient mixture of porphyrin dyes, an efficiency near 8% with photon confinement has been achieved. This represents a significant step toward the realization of low-cost, stable, lead-free, and environmentally benign next-generation solid-state solar cells.

Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co(2+) and Mo(4+) centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.

We report the observation of local structural dipoles that emerge from an undistorted ground state on warming, in contrast to conventional structural phase transitions in which distortions emerge on cooling. Using experimental and theoretical probes of the local structure, we demonstrate this behavior in binary lead chalcogenides, which were believed to adopt the ideal, undistorted rock-salt structure at all temperatures. The behavior is consistent with a simple thermodynamic model in which the emerging dipoles are stabilized in the disordered state at high temperature due to the extra configurational entropy despite the fact that the undistorted structure has lower internal energy. Our findings shed light on the anomalous electronic and thermoelectric properties of the lead chalcogenides. Similar searches may show that the phenomenon is more widespread.