Showing papers on "Orthorhombic crystal system published in 2016"

Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys

Abstract: Goldschmidt tolerance factor (t) is an empirical index for predicting stable crystal structures of perovskite materials. A t value between 0.8 and 1.0 is favorable for cubic perovskite structure, and larger (>1) or smaller (<0.8) values of tolerance factor usually result in nonperovskite structures. CH(NH2)2PbI3 (FAPbI3) can exist in the perovskite α-phase (black phase) with good photovoltaic properties. However, it has a large tolerance factor and is more stable in the hexagonal δH-phase (yellow phase), with δH-to-α phase-transition temperature higher than room temperature. On the other hand, CsPbI3 is stabilized to an orthorhombic structure (δO-phase) at room temperature due to its small tolerance factor. We find that, by alloying FAPbI3 with CsPbI3, the effective tolerance factor can be tuned, and the stability of the photoactive α-phase of the mixed solid-state perovskite alloys FA1–xCsxPbI3 is enhanced, which is in agreement with our first-principles calculations. Thin films of the FA0.85Cs0.15PbI3 p...

Ruddlesden-Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors

Abstract: The hybrid two-dimensional (2D) halide perovskites have recently drawn significant interest because they can serve as excellent photoabsorbers in perovskite solar cells. Here we present the large scale synthesis, crystal structure, and optical characterization of the 2D (CH3(CH2)3NH3)2(CH3NH3)n−1PbnI3n+1 (n = 1, 2, 3, 4, ∞) perovskites, a family of layered compounds with tunable semiconductor characteristics. These materials consist of well-defined inorganic perovskite layers intercalated with bulky butylammonium cations that act as spacers between these fragments, adopting the crystal structure of the Ruddlesden–Popper type. We find that the perovskite thickness (n) can be synthetically controlled by adjusting the ratio between the spacer cation and the small organic cation, thus allowing the isolation of compounds in pure form and large scale. The orthorhombic crystal structures of (CH3(CH2)3NH3)2(CH3NH3)Pb2I7 (n = 2, Cc2m; a = 8.9470(4), b = 39.347(2) A, c = 8.8589(6)), (CH3(CH2)3NH3)2(CH3NH3)2Pb3I10 (...

Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

Abstract: We have examined the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q ∼ (Tc−T)β, where Tc is the critical temperature and the exponent β was close to ¼, as predicted for a tricritical phase transition. However, we also observed coexistence of the cubic and tetragonal phases over a range of temperature in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI3 based solar cells.

Layered Orthorhombic Nb2O5@Nb4C3Tx and TiO2@Ti3C2Tx Hierarchical Composites for High Performance Li-ion Batteries

Abstract: Engineering electrode nanostructures is critical in developing high-capacity, fast rate-response, and safe Li-ion batteries. This study demonstrates the synthesis of orthorhombic Nb2O5@Nb4C3Tx (or @Nb2CTx) hierarchical composites via a one-step oxidation —in flowing CO2 at 850 °C —of 2D Nb4C3Tx (or Nb2CTx) MXene. The composites possess a layered architecture with orthorhombic Nb2O5 nanoparticles decorated uniformly on the surface of the MXene flakes and interconnected by disordered carbon. The composites have a capacity of 208 mAh g−1 at a rate of 50 mA g−1 (0.25 C) in 1–3 V versus Li+/Li, and retain 94% of the specific capacity with 100% Coulombic efficiency after 400 cycles. The good electrochemical performances could be attributed to three synergistic effects: (1) the high conductivity of the interior, unoxidized Nb4C3Tx layers, (2) the fast rate response and high capacity of the external Nb2O5 nanoparticles, and (3) the electron “bridge” effects of the disordered carbon. This oxidation method was successfully extended to Ti3C2Tx and Nb2CTx MXenes to prepare corresponding composites with similar hierarchical structures. Since this is an early report on producing this structure, there is much room to push the boundaries further and achieve better electrochemical performance.

Physical vapor deposition synthesis of two-dimensional orthorhombic SnS flakes with strong angle/temperature-dependent Raman responses

Abstract: Anisotropic layered semiconductors have attracted significant interest due to the huge possibility of bringing new functionalities to thermoelectric, electronic and optoelectronic devices. Currently, most reports on anisotropy have concentrated on black phosphorus and ReS2, less effort has been contributed to other layered materials. In this work, two-dimensional (2D) orthorhombic SnS flakes on a large scale have been successfully synthesized via a simple physical vapor deposition method. Angle-dependent Raman spectroscopy indicated that the orthorhombic SnS flakes possess a strong anisotropic Raman response. Under a parallel-polarization configuration, the peak intensity of Ag (190.7 cm(-1)) Raman mode reaches the maximum when incident light polarization is parallel to the armchair direction of the 2D SnS flakes, which strongly suggests that the Ag (190.7 cm(-1)) mode can be used to determine the crystallographic orientation of the 2D SnS. In addition, temperature-dependent Raman characterization confirmed that the 2D SnS flakes have a higher sensitivity to temperature than graphene, MoS2 and black phosphorus. These results are useful for the future studies of the optical and thermal properties of 2D orthorhombic SnS.

Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries.

Abstract: A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles.

Body-Centered Orthorhombic C 16 : A Novel Topological Node-Line Semimetal

Abstract: We identify by ab initio calculations a novel topological semimetal carbon phase in all-sp^{2} bonding networks with a 16-atom body-centered orthorhombic unit cell, termed bco-C_{16}. Total-energy calculations show that bco-C_{16} is comparable to solid fcc-C_{60} in energetic stability, and phonon and molecular dynamics simulations confirm its dynamical stability. This all-sp^{2} carbon allotrope can be regarded as a three-dimensional modification of graphite, and its simulated x-ray diffraction (XRD) pattern matches well a previously unexplained diffraction peak in measured XRD spectra of detonation and chimney soot, indicating its presence in the specimen. Electronic band structure calculations reveal that bco-C_{16} is a topological node-line semimetal with a single nodal ring. These findings establish a novel carbon phase with intriguing structural and electronic properties of fundamental significance and practical interest.

High-Figure-of-Merit Thermoelectric La-Doped A-Site-Deficient SrTiO3 Ceramics

Abstract: The structure and thermoelectric (TE) properties of La-doped, A-site-deficient SrTiO3 (Sr1–3x/2LaxTiO3) ceramics sintered in air and N2/5% H2 have been investigated. Air-sintered ceramics with 0.10 ≤ x 0.50 are orthorhombic with an a–a–c+ tilt system and long-range VA ordering. x = 0.15 sintered in N2/5% H2 shows the largest dimensionless TE figure-of-merit ZT = 0.41 at 973 K reported for n-type SrTiO3-based ceramics, suggesting that the accommodation of La throu...

Hydrothermally Synthesized h-MoO3 and α-MoO3 Nanocrystals: New Findings on Crystal-Structure-Dependent Charge Transport

Abstract: The charge transfer characteristics of metastable-phase hexagonal molybdenum oxide (h-MoO3) and stable-phase orthorhombic MoO3 (α-MoO3) nanocrystals have been investigated for the first time using impedance spectroscopy. The results imply that the metastable phase h-MoO3 displays a 550-fold increase (at 150 °C) in the electrical conductivity relative to the stable phase α-MoO3. The conductivity also increases as the temperature increases from 130 to 170 °C, whereby analysis shows a thermal activation energy (Ea) of ∼0.42 eV. The investigation clearly identifies that the presence of intercalated ammonium ions (NH4+) and crystal water molecules (H2O) in the internal structure of h-MoO3 plays a vital role in enhancing the charge transfer characteristics and showing an ionic conductive nature. Before the impedance investigations, the h-MoO3 and α-MoO3 nanocrystals were successfully synthesized through a wet-chemical process. Here, a controlled one-step hydrothermal route was adopted to synthesize stable-phase...

Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite

Abstract: We report the pressure-induced crystallographic transitions and optical behavior of MAPbI_3 (MA=methylammonium) using in situ synchrotron X-ray diffraction and laser-excited photoluminescence spectroscopy, supported by density functional theory (DFT) calculations using the hybrid functional B3PW91 with spin-orbit coupling. The tetragonal polymorph determined at ambient pressure transforms to a ReO_3-type cubic phase at 0.3 GPa. Upon continuous compression to 2.7 GPa this cubic polymorph converts into a putative orthorhombic structure. Beyond 4.7 GPa it separates into crystalline and amorphous fractions. During decompression, this phase-mixed material undergoes distinct restoration pathways depending on the peak pressure. In situ pressure photoluminescence investigation suggests a reduction in band gap with increasing pressure up to ≈0.3 GPa and then an increase in band gap up to a pressure of 2.7 GPa, in excellent agreement with our DFT calculation prediction.

High recoverable energy density over a wide temperature range in Sr modified (Pb,La)(Zr,Sn,Ti)O3 antiferroelectric ceramics with an orthorhombic phase

Abstract: Via incorporation of Sr2+ into (Pb,La)(Zr,Sn,Ti)O3, high recoverable energy density (Ure) is achieved in (Pb,Sr,La)(Zr,Sn,Ti)O3 (PSLZST) ceramics. All Sr2+ modified ceramics exhibit orthorhombic antiferroelectric (AFE) characteristics, and have higher ferroelectric-AFE phase switching electric field (EA, proportional to Ure) than the base composition with a tetragonal AFE phase. By properly adjusting the Sr2+ content, the Ure of PSLZST ceramics is greatly improved. This is attributed to the substitution of Pb2+ by Sr2+ with a smaller ion radius, which decreases the tolerance factor leading to enhanced AFE phase stability and thus increased EA. The best energy storage properties are achieved in the PSLZST ceramic with a Sr2+ content of 0.015. It exhibits a maximum room-temperature Ure of 5.56 J/cm3, the highest value achieved so far for dielectric ceramics prepared by a conventional sintering technique, and very small energy density variation ( 4.9 J/cm3) over ...

Is CH3NH3PbI3 Polar

Abstract: In view of the continued controversy concerning the polar/nonpolar nature of the hybrid perovskite system, CH3NH3PbI3, we report the first investigation of a time-resolved pump–probe measurement of the second harmonic generation efficiency as well as using its more traditional form as a sensitive probe of the absence/presence of the center of inversion in the system both in its excited and ground states, respectively. Our results clearly show that SHG efficiency, if nonzero, is below the limit of detection, strongly indicative of a nonpolar or centrosymmetric structure. Our results on the same samples, based on temperature dependent single crystal X-ray diffraction and P–E loop measurements, are entirely consistent with the above conclusion of a centrosymmetric structure for this compound in all three phases, namely the high temperature cubic phase, the intermediate temperature tetragonal phase and the low temperature orthorhombic phase. It is important to note that all our experimental probes are volume ...

Comparison of amorphous, pseudohexagonal and orthorhombic Nb2O5 for high-rate lithium ion insertion

Abstract: Amorphous, pseudohexagonal and orthorhombic Nb2O5 nanoparticles were synthesized using a facile and green sol–gel process followed by thermal treatment at 450 °C, 600 °C and 800 °C for 3 h in air, respectively. The resulting materials have been subjected to a detailed experimental study and comparison of their structural, electrical and electrochemical properties. The experiments have demonstrated that the pseudohexagonal Nb2O5 (TT-Nb2O5) exhibited higher storage capacity, largely due to its high specific surface area and small crystallites, and better cycling performance than both amorphous Nb2O5 (a-Nb2O5) and orthorhombic Nb2O5 (T-Nb2O5); such experimental findings were found to be associated with and thus ascribed to the lower charge transfer resistance and higher lithium ion diffusion coefficient of TT-Nb2O5 than those of a-Nb2O5 and T-Nb2O5. This research contributes to a better fundamental understanding of the relationship between the crystal structure and the crystallinity and electrochemical properties, particularly Li-ion storage properties, and leads to a possible new advancement in the research field of lithium ion batteries and pseudocapacitors.

Single-Crystal to Single-Crystal Phase Transition and Segmented Thermochromic Luminescence in a Dynamic 3D Interpenetrated AgI Coordination Network

Abstract: A new 3D AgI-based coordination network, [Ag2(pz)(bdc)·H2O]n (1; pz = pyrazine and H2bdc = benzene-1,3-dicarboxylic acid), was constructed by one-pot assembly and structurally established by single-crystal X-ray diffraction at different temperatures. Upon cooling from 298 to 93 K, 1 undergo an interesting single-crystal to single-crystal phase transition from orthorhombic Ibca (Z = 16) to Pccn (Z = 32) at around 148 K. Both phases show a rare 2-fold-interpenetrated 4-connected lvt network but incorporate different [Ag2(COO)2] dimeric secondary building units. It is worth mentioning that complex 1 shows red- and blue-shifted luminescences in the 290–170 and 140–80 K temperature ranges, respectively. The variable-temperature single-crystal X-ray crystallographic studies suggest that the argentophilic interactions and rigidity of the structure dominated the luminescence chromism trends at the respective temperature ranges. Upon being mechanically ground, 1 exhibits a slight mechanoluminescence red shift from...

Cubic and orthorhombic SnS thin‐film absorbers for tin sulfide solar cells

Abstract: The tin sulfide solar cell has acquired prominence in recent years. We present the characteristics of two polymorphs of SnS and their perspectives in thin-film solar cells. Thin-film SnS with cubic crystalline structure (SnS-CUB) was obtained via two chemical routes. This semiconductor is distinct from the more common SnS thin films of orthorhombic crystalline structure (SnS-ORT), also obtained by chemical routes. The SnS-CUB reported here with a lattice constant a of 11.587 A replaces the zinc blende structure previously reported for this material with a of 5.783 A. Thin films of SnS-CUB have an optical bandgap (Eg) of 1.66–1.72 eV and electrical conductivity (σ) of 10−6 Ω−1 cm−1. These characteristics distinguish them from SnS-ORT presented here with an Eg of 1.1 eV and σ typically higher by two orders of magnitude. We discuss the uncertainties that have prevailed in the assignment of crystalline structure for SnS-CUB and SnS-ORT. The optical and electrical properties of these two polymorphs of SnS are contrasted in the context of light-generated current density in solar cells. We conclude that the two SnS polymorphs when considered together as optical absorbers offer wider prospects for tin sulfide thin-film solar cells.

Anomalous Raman scattering and lattice dynamics in mono- and few-layer WTe2

Abstract: Tungsten ditelluride (WTe2) is a layered material that exhibits excellent magnetoresistance and thermoelectric behaviors, which are deeply related with its distorted orthorhombic phase that may critically affect the lattice dynamics of this material. Here, we report comprehensive characterization of Raman spectra of WTe2 from bulk to monolayer using experimental and computational methods. We find that mono and bi-layer WTe2 are easily identified by Raman spectroscopy since two or one Raman modes that are observed in higher-layer WTe2 are greatly suppressed below the noise level in the mono- and bi-layer WTe2, respectively. In addition, the frequency of in-plane A17 mode of WTe2 remains almost constant as the layer number decreases, while all the other Raman modes consistently blueshift, which is completely different from the vibrational behavior of hexagonal metal dichalcogenides. First-principles calculation validates experimental results and reveals that anomalous lattice vibrations in WTe2 are attributed to the formation of tungsten chains that make WTe2 structurally one-dimensional.

Synthesis and Structural Properties of Niobium Pentoxide Powders: A Comparative Study of the Growth Process

Abstract: Powders Nb2 O5 were prepared by two different synthesis method, Sol-Gel and polymeric precursors (Pechini). In the Pechini method before adding the citric acid in the process, four different solutions were used to get the samples. For Sol-gel method, two different processes were also used in obtaining powders. The precursor was completely solubilized in ethanol and then hydrolyzed with ammonia and water. The calcination of the samples was between 500 and 750°C. The resulting powders were characterized by Scanning Electron Microscopy (SEM), Brunauer, Emmett and Teller (BET) surface area measurements, UV-visible and Raman spectroscopy. The formation of T−Nb2 O5 orthorhombic took place upon calcination at 7500C. Crystallite sizes were determined using the Scherrer method which resulted in an uniformed size of about 25 − 65nm. Ultraviolet-Visible diffuse reflectance spectroscopy indicated a variation in the optical band gap values (3.32-3.40 eV) in crystal growth process. The Raman vibrational modes indicate the presence of the orthorhombic phase of the material.

Thermoelectric properties of orthorhombic group IV-VI monolayers from the first-principles calculations

Abstract: Two-dimensional (2D) materials may have potential applications in thermoelectric devices. In this work, we systematically investigate the thermoelectric properties of orthorhombic group IV-VI monolayers $\mathrm{AB}$ (A=Ge and Sn; B=S and Se) by the first-principles calculations and semiclassical Boltzmann transport theory. The spin-orbit coupling (SOC) is included to investigate their electronic transport, which produces observable effects on power factor, especially for n-type doping. According to calculated $ZT$, the four monolayers exhibit diverse anisotropic thermoelectric properties, although they have similar hinge-like crystal structure. The GeS along zigzag and armchair directions shows the strongest anisotropy, while SnS and SnSe show mostly isotropic efficiency of thermoelectric conversion, which can be understood by the strength of anisotropy of their respective power factor, electronic and lattice thermal conductivities. Calculated results show that $ZT$ for different carriers of n- and p-type has little difference for GeS, SnS and SnSe. It is found that GeSe, SnS and SnSe show better thermoelectric performance compared to GeS in n-type doping, and SnS and SnSe exhibit higher efficiency of thermoelectric conversion in p-type doping. Compared to a lot of 2D materials, orthorhombic group IV-VI monolayers $\mathrm{AB}$ (A=Ge and Sn; B=S and Se) may possess better thermoelectric performance due to higher power factor and lower thermal conductivity. Our work would be beneficial to further experimental study.

Composition dependent optical, structural and photoluminescence characteristics of cesium tin halide perovskites

Abstract: In this article we report the structural and optical properties of varying compositions of lead free inorganic perovskite (CsSnX3 (X = Br, Cl, I)) and its tunable photoluminescence covering the entire visible to near-IR region. Optical band gap studies for prepared inorganic cesium tin halide compositions show a significant (53.5%) blue shift in the absorption spectra as the halide composition varies from I to Br and Cl. As the halide composition was varied from Cl to I, an intense and tunable PL emission was observed at room temperature covering a wide range from Vis-near IR region (420–950 nm). X-ray diffraction studies revealed that undoped compositions were orthorhombic (CsSnI3), cubic (CsSnBr3) and monoclinic (CsSnCl3) in structure at room temperature. For mixed halides, the lattice constant was found to increase gradually as the size of halide cation increases from Cl− to Br− and I−.

Microstructural characterization and strengthening mechanisms of a 12Cr-ODS steel

Abstract: The microstructure of the 12Cr-ODS steel was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron backscatter diffraction (EBSD) techniques. The results showed that the microstructure consisted of fine and elongated grains, high density of dislocations, and large concentration of nm-scale oxide particles, which were identified as five types of crystal structures by high resolution TEM (HRTEM) imaging, such as monoclinic and cubic Y 2 O 3 , hexagonal and orthorhombic Y 2 TiO 5 , and cubic Y 2 Ti 2 O 7 . The dominant {001} component and weaker parallel to normal direction texture were observed. Besides, the yield stress was experimentally measured and quantitatively estimated. The findings indicated that theoretical calculation was in accordance with the experimental measurements, and strengthening contributions from solid-solution atoms and grain boundaries were linearly additive, whereas those from dislocations and oxide dispersoids were averaged by root mean square summation.

Free Carriers versus Excitons in CH3NH3PbI3 Perovskite Thin Films at Low Temperatures: Charge Transfer from the Orthorhombic Phase to the Tetragonal Phase

Abstract: We have investigated the dynamic optical properties of CH3NH3PbI3 (MAPbI3) perovskite thin films at low temperatures using time-resolved photoluminescence, optical transient absorption (TA), and THz TA spectroscopy. Optical spectroscopic results indicate that the high-temperature tetragonal phase still remains in the MAPbI3 thin films at low temperatures in addition to the major orthorhombic phase. The fast charge transfer from the orthorhombic phase to the tetragonal phase is likely to suppress the formation of excitons in the orthorhombic phase. Consequently, the near-band-edge optical responses of the photocarriers in both the tetragonal and orthorhombic phases of the MAPbI3 thin films are more accurately described by a free-carrier model, rather than an excitonic model even at low temperatures.

Crystallographic Investigations into Properties of Acentric Hybrid Perovskite Single Crystals NH(CH3)3SnX3 (X = Cl, Br)

Abstract: The hybrid perovskites with special optoelectronic properties have attracted more attention to the scientific and industrial applications. However, because of the toxicity and instability of lead complexes, there is interest in finding a nontoxic substitute for the lead in the halides perovskites and solving the ambiguous crystal structures and phase transition of NH(CH3)3SnX3 (X = Cl, Br). Here, we report the bulk crystal growths and different crystal morphologies of orthorhombic hybrid perovskites NH(CH3)3SnX3 (X = Cl, Br) in an ambient atmosphere by bottom-seeded solution growth (BSSG) method. More importantly, detailed structural determination and refinements, phase transition, band gap, band structure calculations, nonlinear optical (NLO) properties, XPS, thermal properties, and stability of NH(CH3)3SnX3 (X = Cl, Br) single crystals are demonstrated. NH(CH3)3SnCl3 single crystal undergoes reversible structural transformation from orthorhombic space group Cmc21 (no. 36) to monoclinic space group Cc (n...

Structural, Vibrational, and Electronic Study of Sb2S3 at High Pressure

Abstract: Antimony trisulfide (Sb2S3), found in nature as the mineral stibnite, has been studied under compression at room temperature from a joint experimental and theoretical perspective. X-ray diffraction and Raman scattering measurements are complemented with ab initio total-energy, lattice-dynamics, and electronic structure calculations. The continuous changes observed in the volume, lattice parameters, axial ratios, bond lengths, and Raman mode frequencies as a function of pressure can be attributed to the different compressibility along the three orthorhombic axes in different pressure ranges, which in turn are related to the different compressibility of several interatomic bond distances in different pressure ranges. The structural and vibrational properties of Sb2S3 under compression are compared and discussed in relation to isostructural Bi2S3 and Sb2Se3. No first-order phase transition has been observed in Sb2S3 up to 25 GPa, in agreement with the stability of the Pnma structure in Bi2S3 and Sb2Se3 previ...

High-pressure behavior of methylammonium lead iodide (MAPbI3) hybrid perovskite

Abstract: In this paper we provide an accurate high-pressure structural and optical study of the MAPbI3 hybrid perovskite. Structural data show the presence of a phase transition toward an orthorhombic structure around 0.3 GPa followed by full amorphization of the system above 3 GPa. After releasing the pressure, the system keeps the high-pressure orthorhombic phase. The occurrence of these structural transitions is further confirmed by pressure induced variations of the photoluminescence signal at high pressure. These variations clearly indicate that the bandgap value and the electronic structure of MAPI change across the phase transition.

BaCdSnS4 and Ba3CdSn2S8: syntheses, structures, and non-linear optical and photoluminescence properties

Abstract: Two non-centrosymmetric metal chalcogenides, BaCdSnS4 and Ba3CdSn2S8, were synthesized using a high temperature solid-state reaction in an evacuated silica tube. Although the two compounds have the same building units in their structures, namely CdS4, SnS4 and BaS8 units, both of them have different structures. BaCdSnS4 crystallizes in the orthorhombic space group Fdd2 and its structure can be characterized by the two-dimensional ∞[Cd–Sn–S] layers composed of corner- and edge-sharing CdS4 and SnS4 tetrahedra with Ba atoms located between the two adjacent ∞[Cd–Sn–S] layers. Ba3CdSn2S8 crystallizes in the space group I3d of the orthorhombic system and the CdS4 and SnS4 groups are connected with each other via corner-sharing to form a three-dimensional framework, which is different from the 2D ∞[Cd–Sn–S] layer structure in BaCdSnS4. The UV-vis-NIR diffuse-reflectance spectra show that the experimental band gaps are about 2.30 eV for BaCdSnS4 and 2.75 eV for Ba3CdSn2S8, respectively. IR and Raman measurement results indicate that their transparent ranges are up to 25 μm. Second-order NLO measurements show that BaCdSnS4 exhibits strong powder second-harmonic generation (SHG) intensities at 2.09 μm laser pumping that are ∼5 and 0.7 times that of AgGaS2 in the particle size 38–55 and 150–200 μm, respectively, whereas Ba3CdSn2S8 only exhibits SHG intensities of about 0.8 and 0.1 times that of AgGaS2 at the same particle sizes. The origin of the NLO response in BaCdSnS4 may originate from the macroscopic arrangement of the SnS4 and CdS4 tetrahedra. Furthermore, the photoluminescence properties of the two compounds have also been investigated and show obvious blue and green light emission.

Ferroelectric polarization switching with a remarkably high activation-energy in orthorhombic GaFeO3 thin films

Abstract: Orthorhombic GaFeO3 (o-GFO) with the polar Pna21 space group is a prominent ferrite owing to its piezoelectricity and ferrimagnetism, coupled with magnetoelectric effects. Herein, we demonstrate large ferroelectric remanent polarization in undoped o-GFO thin films by adopting either a hexagonal strontium titanate (STO) or a cubic yttrium-stabilized zirconia (YSZ) substrate. The polarization-electric-field hysteresis curves of the polar c-axis-grown o-GFO film on a SrRuO3/STO substrate show the net switching polarization of ~35 μC cm−2 with an unusually high coercive field (Ec) of ±1400 kV cm−1 at room temperature. The positive-up and negative-down measurement also demonstrates the switching polarization of ~26 μC cm−2. The activation energy for the polarization switching, as obtained by density-functional theory calculations, is remarkably high, 1.05 eV per formula unit. We have theoretically shown that this high value accounts for the extraordinary high Ec and the stability of the polar Pna21 phase over a wide range of temperatures up to 1368 K. Researchers have clarified why the measured remanent polarization of orthorhombic GaFeO3 is about 50 times smaller than its predicted value. Multiferroics are rare materials that simultaneously show ferroelectricity and ferromagnetism, making them potentially useful for sensors and electrically controllable magnetic memories. Now, by growing thin films of the multiferroic material orthorhombic GaFeO3 on cubic and hexagonal substrates, Hyun Myung Jang of Pohang University of Science and Technology in Korea and co-workers have observed ferroelectric polarization switching that has an extraordinarily high coercive field at room temperature. Numerical calculations revealed that this switching has a remarkably high activation energy. This finding both explains the unusually high coercive field and clarifies the puzzling discrepancy between observed values for the remanent polarization of orthorhombic GaFeO3 and those calculated in previous studies. The polarization-electric-field hysteresis curves of the polar c-axis-grown orthorhombic GaFeO3 (o-GFO) film on a SrRuO3/STO substrate show the net switching polarization of ~35 μC cm−2 with an unusually high coercive field (Ec) of ±1400 kV cm−1 at room temperature. The positive-up and negative-down measurement also demonstrates the switching polarization of ~26 μC cm−2. The activation energy for the polarization switching, as obtained by density-functional theory calculations, is remarkably high, 1.05 eV per formula unit. We have theoretically shown that this high value accounts for the extraordinary high Ec and the stability of the polar Pna21 phase over a wide range of temperature up to 1368 K.

Orthorhombic two-dimensional crystal form of purple membrane (bacteriorhodopsin/membrane protein structure/halobacteria/crystallization)

Abstract: A new two-dimensional crystal form of purple membrane has been obtained in vitro. It is produced by the joint use of a cationic detergent, dodecyltrimethylammonium chlo- ride, and the nonionic detergent, Triton X-100. It primarily forms large, rolled-up sheets that look like needles in the light microscope. Liposomes and tubes are also observed. The ab- sorption maximum of the new form of purple membrane is blue-shifted by 6 nm and its density is slightly lower than the natural form of purple membrane. The new form of purple membrane is orthorhombic with space group p2212i and cell dimensions 57.6 X 73.5 A. Four molecules of bacteriorhodopsin occupy the unit cell with an area per molecule close to that found in the native p3 structure. The projected structure to 6.5-A resolution was determined by electron microscopy and dif- fraction. It shows an identical molecular structure to that of the p3 form and determines the position of the polypeptide boundary.