Showing papers on "Tetragonal crystal system published in 2015"

Bulk crystal growth of hybrid perovskite material CH3NH3PbI3

Abstract: Organic–inorganic hybrid perovskite materials have been receiving considerable attention due to their promising applications in many optoelectronic fields. However, some of the fundamental properties of perovskite materials are still disputed, because most of them are derived from a thin-film state. To comprehend the intrinsic characteristics in a single crystal, herein we report, for the first time, the bulk crystal growth of CH3NH3PbI3. Single crystals of tetragonal CH3NH3PbI3 with dimensions of 10 mm × 10 mm × 8 mm were grown by a temperature-lowering method in HI solution. Studies in to the refinement and orientations of the CH3NH3PbI3 single crystal structure were conducted based on a high quality crystal. The absorption edge of a CH3NH3PbI3 single crystal was located at about 836 nm, indicating that the band gap of CH3NH3PbI3 is approximately 1.48 eV, which is close to the theoretical results and smaller than those derived from polycrystalline and thin-films. CH3NH3PbI3 crystal exhibits a relatively wide absorption (from 250 nm to 800 nm) and a relatively good thermal stability.

Influence of crystal structure of nanosized ZrO2 on photocatalytic degradation of methyl orange.

Abstract: Nanosized ZrO2 powders with near pure monoclinic, tetragonal, and cubic structures synthesized by various methods were used as catalysts for photocatalytic degradation of methyl orange. The structural and textural properties of the samples were analyzed by X-ray diffraction, Raman spectroscopy, TEM, UV-vis, X-ray photoelectron spectroscopy (XPS), and N2 adsorption measurements. The performance of synthesized ZrO2 nanoparticles in the photocatalytic degradation of methyl orange under UV light irradiation was evaluated. The photocatalytic activity of the pure monoclinic ZrO2 sample is higher than that of the tetragonal and cubic ZrO2 samples under optimum identical conditions. The characterization results revealed that monoclinic ZrO2 nanoparticles possessed high crystallinity and mesopores with diameter of 100 A. The higher activity of the monoclinic ZrO2 sample for the photocatalytic degradation of methyl orange can be attributed to the combining effects of factors including the presence of small amount of oxygen-deficient zirconium oxide phase, high crystallinity, large pores, and high density of surface hydroxyl groups.

BaTiO3–BiYbO3 perovskite materials for energy storage applications

Abstract: Novel perovskite-type (1 − x)BaTiO3–xBiYbO3 solid solutions with x = 0.00–0.20 were synthesized using conventional solid-state reaction methods. A systematic structural change from ferroelectric tetragonal to pseudo-cubic phase was observed at about x = 0.050–0.051 at room temperature. Dielectric measurements revealed a gradual change from normal ferroelectric behavior to highly diffusive and dispersive relaxor-like characteristics, wherein the phase transition temperature shifted to a higher temperature with increasing frequency. With an increase in the BiYbO3 content, the nonlinearity of the (1 − x)BaTiO3–xBiYbO3 ceramic was weakened obviously. The bulk ceramics were characterized by high polarization maxima and low remnant polarization, which exhibit slim P–E hysteresis loops. The results demonstrate that the (1 − x)BaTiO3–xBiYbO3 ceramics are promising lead-free relaxor materials for energy storage applications.

Enhanced energy storage properties of NaNbO3 modified Bi0.5Na0.5TiO3 based ceramics

Abstract: (1 − x)BNTBT-xNN ceramics were prepared by conventional solid state reaction method. X-ray fluorescence analysis shows that the volatilization of Na element occurs during sintering process, the resulted concentration variation of V ′ Na − V O − V ′ Na defect dipoles facilitate the grain growth. XRD analysis and dielectric properties analysis indicate that rhombohedral polar phase and tetragonal weakly polar phase coexist in BNTBT ceramics at room temperature. By increasing the NN amount, the rhombohedral polar phase content sharply decreases, leading to a smaller remnant polarization. The dielectric anomaly corresponding to the depolarization temperature disappears from the temperature range investigated. According to the XRD results, the amount of tetragonal weakly polar phase decreases with increasing NN content and the structure evolves toward a pseudocubic symmetry. The phase structure change results in more slim P–E loops. The optimum energy storage properties was obtained for the composition of x = 0.10, with energy storage density of 0.71 J/cm3 at 7 kV/mm and a good temperature stability around 25–150 °C.

Intrinsic femtosecond charge generation dynamics in single crystal CH3NH3PbI3

Abstract: Hybrid metal–organic perovskite solar cells have astounded the solar cell community with their rapid rise in efficiency while maintaining low-cost fabrication. The intrinsic material photophysics related to the generation of free charges, their dynamics and efficiency, however, remains to be understood. As fabrication techniques improve, larger crystal grain sizes have been shown to be a critical factor for improving both the optical and transport properties of the hybrid metal halide perovskites. In this work, we use pulses of multi-THz frequency light in the ultra-broadband 1–30 THz (4–125 meV) range to observe the ac conductivity in large single crystal CH3NH3PbI3. Our spectra reveal the ultrafast dynamics and efficiencies of free charge creation and extremely high charge carrier mobility as high as 500–800 cm2 V−1 s−1. While quasi-equilibrium analysis of efficiencies through the Saha equation suggests a binding energy on the order of 49 meV, an observed reflectance feature appearing at high pump fluence occurs at 12 meV and is consistent with an orbital transition of the exciton, indicating a much lower Rydberg energy of 17 meV at room temperature. The signature of the exciton is found to vanish on a 1 ps time scale commensurate with the appearance of mobile carriers, consistent with thermal dissociation of the exciton to the continuum in the room temperature tetragonal phase.

Impact of crystalline defects and size on X-ray line broadening: A phenomenological approach for tetragonal SnO2 nanocrystals

Abstract: Nanocrystalline tin oxide (SnO2) powders with different grain size were prepared by chemical precipitation method. The reaction was carried out by varying the period of hydrolysis and the as-prepared samples were annealed at different temperatures. The samples were characterized using X-ray powder diffractometer and transmission electron microscopy. The microstrain and crystallite size were calculated for all the samples by using Williamson-Hall (W-H) models namely, isotropic strain model (ISM), anisotropic strain model (ASM) and uniform deformation energy density model (UDEDM). The morphology and particle size were determined using TEM micrographs. The directional dependant young’s modulus was modified as an equation relating elastic compliances (sij) and Miller indices of the lattice plane (hkl) for tetragonal crystal system and also the equation for elastic compliance in terms of stiffness constants was derived. The changes in crystallite size and microstrain due to lattice defects were observed while ...

Characterization of an abnormal photoluminescence behavior upon crystal-phase transition of perovskite CH3NH3PbI3

Abstract: Solution-processed hybrid perovskite of CH3NH3PbI3 (MAPbI3) exhibits an abnormal luminescence behavior at around the tetragonal–orthorhombic phase transition temperature. The combination of time resolved photoluminescence (PL), variable excitation power PL, and variable-temperature X-ray diffraction (XRD) allows us to clearly interpret the abnormal luminescence features in the phase transition region of MAPbI3. Both PL and XRD results unambiguously prove the coexistence of the tetragonal and orthorhombic phases of MAPbI3 in the temperature range of 150 to 130 K. The two luminescence features observed in the orthorhombic phase at T < 130 K originate from free excitons and donor–acceptor-pair (DAP) transitions, respectively. The comprehensive understanding of optical properties upon phase transition in MAPbI3 will benefit the development of new optoelectronic devices.

New insights into organic–inorganic hybrid perovskite CH3NH3PbI3 nanoparticles. An experimental and theoretical study of doping in Pb2+ sites with Sn2+, Sr2+, Cd2+ and Ca2+

Abstract: This paper presents the synthesis of the organic–inorganic hybrid perovskite, CH3NH3PbI3, doped in the Pb2+ position with Sn2+, Sr2+, Cd2+ and Ca2+. The incorporation of the dopants into the crystalline structure was analysed, observing how the characteristics of the dopant affected properties such as the crystalline phase, emission and optical properties. XRD showed how doping with Sn2+, Sr2+ and Cd2+ did not modify the normal tetragonal phase. When doping with Ca2+, the cubic phase was obtained. Moreover, DR-UV-Vis spectroscopy showed how the band gap decreased with the dopants, the values following the trend Sr2+ Cd2+ > Sr2+ for the tetragonal structure and Pb2+ > Ca2+ for the cubic phase. The electron localization function (ELF) analysis showed similar electron localizations for undoped and Sn2+-doped tetragonal structures, which were different from those doped with Sr2+ and Cd2+. Furthermore, when Cd2+ was incorporated, the Cd–I interaction was strengthened. For Ca2+ doping, the Ca–I interaction had a greater ionic nature than Cd–I. Finally, an analysis based on the non-covalent interaction (NCI) index is presented to determine the weak-type interactions of the CH3NH3 groups with the dopant and I atoms. To our knowledge, this kind of analysis with these hybrid systems has not been performed previously.

Determination of Thermal Expansion Coefficients and Locating the Temperature-Induced Phase Transition in Methylammonium Lead Perovskites Using X-ray Diffraction

Abstract: Lead halogen perovskites, and particularly methylammonium lead iodine, CH3NH3PbI3, have recently attracted considerable interest as alternative solar cell materials, and record solar cell efficiencies have now surpassed 20%. Concerns have, however, been raised about the thermal stability of methylammonium lead iodine, and a phase transformation from a tetragonal to a cubic phase has been reported at elevated temperature. Here, this phase transition has been investigated in detail using temperature-dependent X-ray diffraction measurements. The phase transformation is pinpointed to 54 °C, which is well within the normal operating range of a typical solar cell. The cell parameters were extracted as a function of the temperature, from which the thermal expansion coefficient was calculated. The latter was found to be rather high (αv = 1.57 × 10–4 K–1) for both the tetragonal and cubic phases. This is 6 times higher than the thermal expansion coefficient for soda lime glass and CIGS and 11 times larger than tha...

Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites

Abstract: The nature of the photoconductivity in solution-processed films of methylammonium lead iodide perovskite is investigated by determining the variation of the photoconductive response with temperature. Ultrabroadband terahertz (THz) photoconductivity spectra in the 0.3–10 THz range can be reproduced well by a simple Drude-like response at room temperature, where free charge carrier motion is characterized by an average scattering time. The scattering time determined from Drude fits in the 0.3–2THz region increases from ∼4 fs at 300 K (tetragonal phase; mobility of ∼27 cm2 V–1 s–1) to almost ∼25 fs at 77 K (orthorhombic phase, mobility of ∼150 cm2 V–1 s–1). For the tetragonal phase (temperature range 150 < T < 300 K) the scattering time shows a ∼T–3/2 dependence, approaching the theoretical limit for pure acoustic phonon (deformation potential) scattering. Hence, electron–phonon, rather than impurity scattering, sets the upper limit on free charge transport for this perovskite.

Mechanical properties of organic–inorganic halide perovskites, CH3NH3PbX3 (X = I, Br and Cl), by nanoindentation

Abstract: We report an experimental study of the mechanical properties of the organic–inorganic halide perovskites, CH3NH3PbX3 (X = I, Br and Cl). Nanoidentation on single crystals was used to obtain Young's moduli (E) and hardnesses (H) of this class of hybrid materials, which have attracted considerable attention for photovoltaic applications. The measured Young's moduli of this family lie in the range 10–20 GPa and a trend of ECl > EBr > EI is observed. The physical properties are consistent with the underlying crystal structure. In particular, the results are in reasonable agreement with recent calculations using density functional theory and align with expectations based upon bond energy, packing, and hydrogen-bonding considerations. The anisotropy in these systems is quite small, with E100 > E110 for the cubic bromide and chloride cases and E112 ≈ E100 for the tetragonal iodide perovskites. Interestingly, CH3NH3PbI3 is harder than the Br- and Cl-based perovskites.

Observation of Superconductivity in Tetragonal FeS

Abstract: The possibility of superconductivity in tetragonal FeS has attracted considerable interest because of its similarities to the FeSe superconductor. However, all efforts made to pursue superconductivity in tetragonal FeS have failed so far, and it remains controversial whether tetragonal FeS is metallic or semiconducting. Here we report the observation of superconductivity at 5 K in tetragonal FeS that is synthesized by the hydrothermal reaction of iron powder with sulfide solution. The obtained samples are highly crystalline and less air-sensitive, in contrast to those reported in the literature, which are meta-stable and air-sensitive. Magnetic and electrical properties measurements show that the samples behave as a paramagnetic metal in the normal state and exhibit superconductivity below 5 K. The high crystallinity and the stoichiometry of the samples play important roles in the observation of superconductivity. The present results demonstrate that tetragonal FeS is a promising new platform to realize h...

Asynchronous Crystal Cell Expansion during Lithiation of K+-Stabilized α-MnO2

Abstract: α-MnO2 is a promising material for Li-ion batteries and has unique tunneled structure that facilitates the diffusion of Li(+). The overall electrochemical performance of α-MnO2 is determined by the tunneled structure stability during its interaction with Li(+), the mechanism of which is, however, poorly understood. In this paper, a novel tetragonal-orthorhombic-tetragonal symmetric transition during lithiation of K(+)-stabilized α-MnO2 is observed using in situ transmission electron microscopy. Atomic resolution imaging indicated that 1 × 1 and 2 × 2 tunnels exist along c ([001]) direction of the nanowire. The morphology of a partially lithiated nanowire observed in the ⟨100⟩ projection is largely dependent on crystallographic orientation ([100] or [010]), indicating the existence of asynchronous expansion of α-MnO2's tetragonal unit cell along a and b lattice directions, which results in a tetragonal-orthorhombic-tetragonal (TOT) symmetric transition upon lithiation. Such a TOT transition is confirmed by diffraction analysis and Mn valence quantification. Density functional theory (DFT) confirms that Wyckoff 8h sites inside 2 × 2 tunnels are the preferred sites for Li(+) occupancy. The sequential Li(+) filling at 8h sites leads to asynchronous expansion and symmetry degradation of the host lattice as well as tunnel instability upon lithiation. These findings provide fundamental understanding for appearance of stepwise potential variation during the discharge of Li/α-MnO2 batteries as well as the origin for low practical capacity and fast capacity fading of α-MnO2 as an intercalated electrode.

New Insights Into BiVO4 Properties as Visible Light Photocatalyst

Abstract: Bismuth vanadate has attractive photocatalytic properties under visible light. The influence of structure and morphology of BiVO4 nanomaterials on its photocatalytic properties in the UV and the visible domain was investigated. The selection of different sets of synthetic parameters in aqueous solution—pH or the use of organic additives—allowed the formation of tetragonal zircon, tetragonal scheelite, and monoclinic scheelite structure and different morphologies of that last phase. First, the tetragonal zircon was found to be the only inactive structure. Then, the best material for photocatalytic degradation of rhodamine B in solution and stearic acid deposited directly on the photocatalyst is the core–shell tetragonal zircon–monoclinic scheelite system prepared in the presence of sodium dodecyl sulfate. The enhanced properties are explained by the presence of strong surface acidic sites corresponding to the presence of surface sulfate residues rather than to the specific morphology of the material. Addit...

Superconductivity-induced re-entrance of the orthorhombic distortion in Ba1-xKxFe2As2.

Abstract: Detailed knowledge of the phase diagram and the nature of the competing magnetic and superconducting phases is imperative for a deeper understanding of the physics of iron-based superconductivity. Magnetism in the iron-based superconductors is usually a stripe-type spin-density-wave, which breaks the tetragonal symmetry of the lattice, and is known to compete strongly with superconductivity. Recently, it was found that in some systems an additional spin-density-wave transition occurs, which restores this tetragonal symmetry, however, its interaction with superconductivity remains unclear. Here, using thermodynamic measurements on Ba1-xKxFe2As2 single crystals, we show that the spin-density-wave phase of tetragonal symmetry competes much stronger with superconductivity than the stripe-type spin-density-wave phase, which results in a novel re-entrance of the latter at or slightly below the superconducting transition.

A Crystal-Chemical Framework for Relaxor versus Normal Ferroelectric Behavior in Tetragonal Tungsten Bronzes

Abstract: Tetragonal tungsten bronzes (TTBs), an important class of oxides known to exhibit ferroelectricity, undergo complex distortions, including rotations of oxygen octahedra, which give rise to either incommensurately or commensurately modulated superstructures. Many TTBs display broad, frequency-dependent relaxor dielectric behavior rather than sharper frequency-independent normal ferroelectric anomalies, but the exact reasons that favor a particular type of dielectric response for a given composition remain unclear. In this contribution the influence of incommensurate/commensurate displacive modulations on the onset of relaxor/ferroelectric behavior in TTBs is assessed in the context of basic crystal-chemical factors, such as positional disorder, ionic radii and polarizabilities, and point defects. We present a predictive crystal-chemical model that rationalizes composition–structure–properties relations for a broad range of TTB systems.

Phase stability and transformations in the halide perovskite CsSnI3

Abstract: We employ the quasiharmonic approximation to study the temperature-dependent lattice dynamics of the four different phases of cesium tin iodide $({\mathrm{CsSnI}}_{3})$. Within this framework, we obtain the temperature dependence of a number of structural properties, including the cell volume, bulk modulus, and Gr\"uneisen parameter. The Gibbs free energy of each phase is compared against the temperature-dependent Helmholtz energy obtained from the equilibrium structure within the harmonic approximation. We find that the black tetragonal perovskite phase is not dynamically stable up to at least 500 K, with the phonon dispersion displaying negative optic modes, which pass through all of the high-symmetry wave vectors in the Brillouin zone. The main contributions to the negative modes are found to be motions of the Cs atom inside the perovskite cage. The black cubic perovskite structure shows a zone-boundary instability, indicated by soft modes at the special $\mathbf{q}$ points $M$ and $R$. These modes are present in calculations at the equilibrium (0 K) lattice constant, while at finite temperature additional negative modes develop at the zone center, indicating a ferroelectric instability. The yellow crystal, composed of one-dimensional $({\mathrm{SnI}}_{6}){}_{n}$ double chains, has the same heat of formation as the orthorhombic perovskite phase at 0 K, but becomes less energetically favorable at higher temperatures, due to its higher free energy.

Probing the Degradation Mechanism of Li2MnO3 Cathode for Li-Ion Batteries

Abstract: Capacity and voltage fading of Li2MnO3 is a major challenge for the application of this category of material, which is believed to be associated with the structural and chemical evolution of the materials. This paper reports the detailed structural and chemical evolutions of Li2MnO3 cathode captured by using aberration corrected scanning/transmission electron microscopy (S/TEM) after certain numbers of charge–discharge cycling of the batteries. It is found that structural degradation occurs from the very first cycle and is spatially initiated from the surface of the particle and propagates toward the inner bulk as the cyclic number increases, featuring the formation of the surface phase transformation layer and gradual thickening of this layer. The structure degradation is found to follow a sequential phase transformation: monoclinic C2/m → tetragonal I41 → cubic spinel, which is consistently supported by the decreasing lattice formation energy based on DFT calculations. For the first time, high spatial r...

Experimental evidence of new tetragonal polymorphs of silicon formed through ultrafast laser-induced confined microexplosion

Abstract: Ordinary materials can transform into novel phases at extraordinary high pressure and temperature. The recently developed method of ultrashort laser-induced confined microexplosions initiates a non-equilibrium disordered plasma state. Ultra-high quenching rates overcome kinetic barriers to the formation of new metastable phases, which are preserved in the surrounding pristine crystal for subsequent exploitation. Here we demonstrate that confined microexplosions in silicon produce several metastable end phases. Comparison with an ab initio random structure search reveals six energetically competitive potential phases, four tetragonal and two monoclinic structures. We show the presence of bt8 and st12, which have been predicted theoretically previously, but have not been observed in nature or in laboratory experiments. In addition, the presence of the as yet unidentified silicon phase, Si-VIII and two of our other predicted tetragonal phases are highly likely within laser-affected zones. These findings may pave the way for new materials with novel and exotic properties.

Growth of epitaxial orthorhombic YO1.5-substituted HfO2 thin film

Abstract: YO1.5-substituted HfO2 thin films with various substitution amounts were grown on (100) YSZ substrates by the pulsed laser deposition method directly from the vapor phase. The epitaxial growth of film with different YO1.5 amounts was confirmed by the X-ray diffraction method. Wide-area reciprocal lattice mapping measurements were performed to clarify the crystal symmetry of films. The formed phases changed from low-symmetry monoclinic baddeleyite to high-symmetry tetragonal/cubic fluorite phases through an orthorhombic phase as the YO1.5 amount increased from 0 to 0.15. The additional annular bright-field scanning transmission electron microscopy indicates that the orthorhombic phase has polar structure. This means that the direct growth by vapor is of polar orthorhombic HfO2-based film. Moreover, high-temperature X-ray diffraction measurements showed that the film with a YO1.5 amount of 0.07 with orthorhombic structure at room temperature only exhibited a structural phase transition to tetragonal phase a...

Thermal Decomposition of Bismuth Oxysulfide from Photoelectric Bi2O2S to Superconducting Bi4O4S3

Abstract: With the addition of oxygen into the chain-like bismuth sulfide of Bi2S3, there are two interesting functional compounds of Bi2O2S (photoelectric) and Bi4O4S3 (superconducting) containing the PbO-like [Bi2O2] layers. Nanoscale Bi2O2S crystals with an indirect band gap of 1.12 eV are synthesized via a facile hydrothermal method. This semiconductor shows excellent photoelectric response under the irradiation of visible light lamp at room temperature. Theoretical calculations and packing factor model both indicate that the loosely packed Bi2O2S is an excellent photoelectric material. When the Bi2O2S phase was annealed at 500 °C in an evacuated quartz tube, nanocrystals of Bi4O4S3 were obtained. The powder X-ray diffraction and electron microscope analyses (SEM, TEM, EDX) confirmed the thermal decomposition from orthorhombic Bi2O2S to tetragonal Bi4O4S3. The superconducting transition temperature of Bi4O4S3 was observed to be 4.6 K from the temperature-dependence measurements of electrical resistivity and mag...

Narrow-Band Green Emitting Nitridolithoalumosilicate Ba[Li2(Al2Si2)N6]:Eu2+ with Framework Topology whj for LED/LCD-Backlighting Applications

Abstract: Eu2+- as well as Ce3+-doped Ba[Li2(Al2Si2)N6] and its related Mg-substituted compounds Ba[(Mg2–xLix) (Al4–xSix)N6]:Eu2+ (x = 0–2) with x = 1.6, 1.8 have been synthesized by metathesis reactions in tantalum ampules. Crystal structures were solved and refined from single-crystal X-ray diffraction data. All three compounds crystallize in tetragonal space group P4/ncc (no. 130) (Z = 4, Ba[Li2(Al2Si2)N6]:Eu2+: a = 7.8282(4), c = 9.9557(5) A, R1 = 0.0144, wR2 = 0.0366). Their crystal structures, exhibiting the novel framework topology whj, consist of a highly condensed anionic tetrahedra network of disordered (Li/Mg)N4 and (Al/Si)N4 units connected to each other by common edges and corners. The degree of condensation (i.e., atomic ratio (Al,Li,Mg,Si):N) is κ = 1. The Ba2+-position is coordinated eight-fold by N3– in form of a truncated square pyramid. Upon doping with Eu2+, narrow-band emission in the green to yellow spectral range is observed (λem = 532–562 nm, fwhm ≈ 1962 cm–1). Ce3+-doped crystals of Ba[Li2(...

Relaxor ferroelectricity and electric-field-driven structural transformation in the giant lead-free piezoelectric (Ba,Ca)(Ti, Zr)O-3

Abstract: There is great interest in lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O-3 (15/10BCTZ) because of its exceptionally large piezoelectric response Liu and Ren, Phys. Rev. Lett. 103, 257602 (2009)]. In this paper, we have analyzed the nature of: (i) crystallographic phase coexistence at room temperature, (ii) temperature-and field-induced phase transformation to throw light on the atomistic mechanisms associated with the large piezoelectric response of this system. A detailed temperature-dependent dielectric and lattice thermal expansion study proved that the system exhibits a weak dielectric relaxation, characteristic of a relaxor ferroelectric material on the verge of exhibiting a normal ferroelectric-paraelectric transformation. Careful structural analysis revealed that a ferroelectric state at room temperature is composed of three phase coexistences, tetragonal (P4mm)+ orthorhombic (Amm2) + rhombohedral (R3m). We also demonstrate that the giant piezoresponse is associated with a significant fraction of the tetragonal phase transforming to rhombohedral. It is argued that the polar nanoregions associated with relaxor ferroelectricity amplify the piezoresponse by providing an additional degree of intrinsic structural inhomogeneity to the system.

Bismuthates: BaBiO3 and related superconducting phases

Abstract: BaBiO3 has the perovskite structure, but tilting of the BiO6 octahedra destroy the ideal cubic symmetry except at temperatures above 820 K. BaBiO3 is a diamagnetic semiconductor due to a charge density wave (CDW), which is equivalent to a Ba2Bi3+Bi5+O6 representation. Recent calculations and experimental results confirm that there is no significant deviation from the oxidation states of 3+ and 5+. Superconductivity with a Tc as high as 13 K occurs for BaPb1−xBixO3 phases where the 6s band is about 25% filled, and superconductivity with a Tc as high as 34 K occurs for Ba1−xKxBiO3 phases where the 6s band is about 35% filled. Structures in these two solid solutions can have cubic, tetragonal, orthorhombic, or monoclinic symmetry. However, superconductivity has only been observed when the symmetry is tetragonal.

Transition from the Tetragonal to Cubic Phase of Organohalide Perovskite: The Role of Chlorine in Crystal Formation of CH3NH3PbI3 on TiO2 Substrates

Abstract: The role of chlorine in the superior electronic property and photovoltaic performance of CH3NH3PbI(3–x)Clx perovskite has attracted recent research attention. Here, we study the impact of chlorine in the perspective of the crystal structure of the perovskite layer, which can provide important understanding of its excellent charge mobility and extended lifetimes. In particular, we find that in the presence of chlorine (PbCl2 or CH3NH3Cl), when CH3NH3PbI3 films are deposited on a TiO2 mesoporous layer instead of a planar TiO2 substrate, a stable cubic phase rather than the commonly observed tetragonal phase is formed in CH3NH3PbI3 perovskite at room temperature. The relative peak intensity of two major facets of cubic CH3NH3PbI3 crystals, (100)C and (200)C facets, can also be easily tuned, depending on the film thickness. Furthermore, compared with pristine CH3NH3PbI3 perovskite films, in the presence of chlorine, CH3NH3PbI3 crystals grown on planar substrates exhibit strong preferred orientations on (110)T...