Jianshi Zhou

Combined Charge Carrier Transport and Photoelectrochemical Characterization of BiVO4 Single Crystals: Intrinsic Behavior of a Complex Metal Oxide

Bismuth vanadate (BiVO4) is a promising photoelectrode material for the oxidation of water, but fundamental studies of this material are lacking. To address this, we report electrical and photoelectrochemical (PEC) properties of BiVO4 single crystals (undoped, 0.6% Mo, and 0.3% W:BiVO4) grown using the floating zone technique. We demonstrate that a small polaron hopping conduction mechanism dominates from 250 to 400 K, undergoing a transition to a variable-range hopping mechanism at lower temperatures. An anisotropy ratio of ~3 was observed along the c axis, attributed to the layered structure of BiVO4. Measurements of the ac field Hall effect yielded an electron mobility of ~0.2 cm(2) V(-1) s(-1) for Mo and W:BiVO4 at 300 K. By application of the Gärtner model, a hole diffusion length of ~100 nm was estimated. As a result of low carrier mobility, attempts to measure the dc Hall effect were unsuccessful. Analyses of the Raman spectra showed that Mo and W substituted for V and acted as donor impurities. Mott-Schottky analysis of electrodes with the (001) face exposed yielded a flat band potential of 0.03-0.08 V versus the reversible H2 electrode, while incident photon conversion efficiency tests showed that the dark coloration of the doped single crystals did not result in additional photocurrent. Comparison of these intrinsic properties to those of other metal oxides for PEC applications gives valuable insight into this material as a photoanode.

Reduction of the bulk modulus at high pressure in CrN

Nitride coatings are increasingly demanded in the cutting- and machining-tool industry owing to their hardness, thermal stability and resistance to corrosion. These properties derive from strongly covalent bonds; understanding the bonding is a requirement for the design of superhard materials with improved capabilities. Here, we report a pressure-induced cubic-to-orthorhombic transition at approximately 1 GPa in CrN. High-pressure X-ray diffraction and ab initio calculations show an unexpected reduction of the bulk modulus, K0, of about 25% in the high-pressure (lower volume) phase. Our combined theoretical and experimental approach shows that this effect is the result of a large exchange striction due to the approach of the localized Cr:t3 electrons to becoming molecular-orbital electrons in Cr-Cr bonds. The softening of CrN under pressure is a manifestation of a strong competition between different types of chemical bond that are found at a crossover from a localized to a molecular-orbital electronic transition.

Intra- versus intergranular low-field magnetoresistance of Sr2FeMoO6 thin films

Thin films of (001)-oriented Sr2FeMoO6 have been epitaxially deposited on LaAlO3 and SrTiO3 (001) substrates. Comparison of their transport and magnetic properties with those of polycrystalline ceramic samples shows a metallic versus semiconductor temperature dependence and a saturation magnetization Ms at 10 K of 3.2 μB/f.u. in the film as against 3.0 for a tetragonal polycrystalline sample. However, the Curie temperature TC≈389 K is reduced from 415 K found for the tetragonal ceramic, which lowers Ms at 300 K in the thin films to 2.0 μB/f.u. compared to 2.2 μB/f.u. in the ceramics. A Wheatstone bridge arrangement straddling a bicrystal boundary has been used to verify that spin-dependent electron transfer through a grain boundary is responsible for the low-field magnetoresistance found in polycrystalline samples below TC.

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

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.

Effect of tolerance factor and local distortion on magnetic properties of the perovskite manganites

The substitutions of rare earths for La on the magnetic properties of the perovskites La0.7−xRxA0.3MnO3 (0<x<0.7), R=Pr or Gd and A=Ca, Sr, or Ba have shown that small substitution of Pr slightly increases the coercive field Hc and magnetization M, and strongly improves the magnetoresistance (MR) while lowering Tc. On the other hand, the substitution of Gd lowers Hc, M and Tc, however, increases MR of the system La0.7−xGdxSr0.3MnO3 at temperature <Tc. Large differences in the A-site ionic radii rA of the AMnO3 perovskites proved detrimental. The optimal composition has been discussed for the half-metallic ferromagnet of a spin-switch device based on the manganese oxides.

Grain-boundary room-temperature low-field magnetoresistance in Sr2FeMoO6 films

Thin films of (001)-oriented Sr2FeMoO6 have been epitaxially deposited or LaAlO3 and SrTiO3 (001) substrates by pulsed laser deposition. The deposition conditions were optimized. Single-phase Sr2FeMoO6 was obtained in 100 mTorr 99.999% Ar gas at 825 °C. Transport and magnetic data showed a metallic temperature dependence and a saturation magnetization Ms at 10 K of 3.2μB/f.u. However, the Curie temperature TC≈380 K was reduced from 415 K found for tetragonal polycrystalline best ceramics, which lowers Ms at 300 K in the thin films to 1.5μB/f.u. compared to 2.2μB/f.u. in the ceramics. A low remanence was attributed to the presence of antiphase boundaries. A Wheatstone bridge arrangement straddling a bicrystal boundary was used to verify that spin-dependent electron transfer through a grain boundary and not an antiphase boundary is responsible for the low-field magnetoresistance found in polycrystalline samples below TC.

Twisting phonons in complex crystals with quasi-one-dimensional substructures

A variety of crystals contain quasi-one-dimensional substructures, which yield distinctive electronic, spintronic, optical and thermoelectric properties. There is a lack of understanding of the lattice dynamics that influences the properties of such complex crystals. Here we employ inelastic neutron scatting measurements and density functional theory calculations to show that numerous low-energy optical vibrational modes exist in higher manganese silicides, an example of such crystals. These optical modes, including unusually low-frequency twisting motions of the Si ladders inside the Mn chimneys, provide a large phase space for scattering acoustic phonons. A hybrid phonon and diffuson model is proposed to explain the low and anisotropic thermal conductivity of higher manganese silicides and to evaluate nanostructuring as an approach to further suppress the thermal conductivity and enhance the thermoelectric energy conversion efficiency. This discovery offers new insights into the structure-property relationships of a broad class of materials with quasi-one-dimensional substructures for various applications.

Enhancement of room temperature magnetoresistance in double perovskite ferrimagnets

The double perovskite Sr2FeMoO6 is a half-metallic ferrimagnet exhibiting significant magnetoresistance (MR) at 300 K in a magnetic field H<2 kOe. A preliminary study of the influence of isovalent and aliovalent substitutions for Sr2+ on the magnitude of the room-temperature MR is reported. Of the polycrystalline samples, Sr1.9A0.1FeMoO6 (A=Ca, Ba, La or Pr), the best result was obtained with the Ba(0.1) sample, which showed a factor of 2 enhancement of the MR over that previously reported for Sr2FeMoO6.

Effects of (Al,Ge) double doping on the thermoelectric properties of higher manganese silicides

Experiments and analysis have been carried out to investigate the effects of Al and (Al,Ge) doping on the microstructure and thermoelectric properties of polycrystalline higher manganese silicide (HMS) samples, which were prepared by solid-state reaction, ball milling, and followed by spark plasma sintering. It has been found that Al doping effectively increases the hole concentration, which leads to an increase in the electrical conductivity and power factor. By introducing the second dopant Ge into Al-doped HMS, the electrical conductivity is increased, and the Seebeck coefficient is decreased as a result of further increased hole concentration. The peak power factor is found to occur at a hole concentration between 1.8 × 1021 and 2.2 × 1021 cm−3 measured at room temperature. The (Al,Ge)-doped HMS samples show lower power factors owing to their higher hole concentrations. The mobility of Mn(Al0.0035GeySi0.9965-y)1.8 with y = 0.035 varies approximately as T−3/2 above 200 K, suggesting acoustic phonon sca...

A New Pnictide Superconductor without Iron

LiCu(2)P(2) and LiFeP have been synthesized by conventional solid-state reaction. LiCu(2)P(2) has a crystal structure similar to that of BaFe(2)As(2); LiFeP has the same crystal structure as that of LiFeAs. Resistivity and magnetization measurements reveal that they become superconductive at 3.5 K for LiCu(2)P(2) and 4.1 K for LiFeP.