Magnetoresistance is the change in a material's electrical resistance in response to an applied magnetic field. Materials with large magnetoresistance have found use as magnetic sensors, in magnetic memory, and in hard drives at room temperature, and their rarity has motivated many fundamental studies in materials physics at low temperatures. Here we report the observation of an extremely large positive magnetoresistance at low temperatures in the non-magnetic layered transition-metal dichalcogenide WTe2: 452,700 per cent at 4.5 kelvins in a magnetic field of 14.7 teslas, and 13 million per cent at 0.53 kelvins in a magnetic field of 60 teslas. In contrast with other materials, there is no saturation of the magnetoresistance value even at very high applied fields. Determination of the origin and consequences of this effect, and the fabrication of thin films, nanostructures and devices based on the extremely large positive magnetoresistance of WTe2, will represent a significant new direction in the study of magnetoresistivity.

PACS 72.15.Gd -Magnetoresistance of metals and alloys PACS 71.55.Ak -Impurity and defect levels in semimetals PACS 61.72.Cc -Annealing crystal defectsAbstract -High quality single crystals of WTe2 were grown using a Te flux followed by a cleaning step involving self-vapor transport. The method is reproducible and yields consistently higher quality single crystals than are typically obtained via halide assisted vapor transport methods. Magnetoresistance (MR)values at 9 Tesla and 2 Kelvin as high as 1.75 million %, nearly an order of magnitude higher than previously reported for this material, were obtained on crystals with residual resistivity ratio (RRR) of approximately 1250. The MR follows a near B 2 law (B = 1.95(1)) and, assuming a semiclassical model, the average carrier mobility for the highest quality crystal was found to be 167,000 cm 2 /Vs at 2 K. A correlation of RRR, MR ratio and average carrier mobility (µavg) is found with the cooling rate during the flux growth.

Elevated levels of fluoride (F(-)) in groundwaters of granitic and basaltic terrains pose a major environmental problem and are affecting millions of people all over the world. Hydroxyapatite (HA) has been shown to be a strong sorbent for F(-); however, low permeability of synthetic HA results in poor sorption efficiency. Here we provide a novel method of synthesizing nano- to micrometer sized HA on the surfaces of granular limestone to improve the sorption efficiency of the HA-based filter. Our experiments with granular limestone (38-63, 125-500 μm) and dissolved PO4(3-) (0.5-5.3 mM) as a function of pH (6-8) and temperature (25-80 °C) indicated rapid formation of nano- to micrometer sized HA crystals on granular limestone with the maximum surface coverage at lower pH and in the presence of multiple additions of aqueous PO4(3-). The HA crystal morphology varied with the above variables. The sorption kinetics and magnitude of F(-) sorption by HA-coated-fine limestone are comparable to those of pure HA, and the F(-) levels dropped to below the World Health Organization's drinking water limit of 79 μM for F(-) concentrations commonly encountered in contaminated potable waters, suggesting that these materials could be used as effective filters. Fluorine XANES spectra of synthetic HA reacted with F(-) suggest that the mode of sorption is through the formation of fluoridated-HA or fluorapatite at low F(-) levels and fluorite at high F(-) loadings.

Single crystals of LiIn 2 SbO 6 (LIAO) have been synthesized using a Li 2 MoO 4 flux and characterized with X-ray diffraction. The compound crystallizes in a new structure type with a rutile-related framework. Like others in the rutile-related family, LIAO is formed of chains of edge-sharing octahedra. The chain structure, with a width that alternates between single and double octahedra, has not previously been reported in a rutile-related material. The framework is formed via corner sharing by the chains in a checkerboard arrangement, with Li + residing in tetrahedral sites in the resulting, identically-alternating channels. Solid-state 6/7Li NMR spectroscopy and ab initio spectral calculations verify the presence of tetrahedrally coordinated lithium. The solution determined here contradicts previous reports of this material as a cation-ordered variant of LiSbO 3 . The relationship between this new structure and LiSbO 3 and others in the rutile-related family is discussed. Variable temperature powder X-ray diffraction and diffuse reflectance show that LIAO has high thermal stability and a large direct band gap of 3.9 eV. AC impedance spectroscopy reveals that LIAO is a relatively poor Li conductor, displaying a conductivity of 1.3 × 10 −7 S/cm at 623 K, along with an activation energy for charge transport of 1.1 eV. This material presents an opportunity to explore a new subfamily of rutile-related materials in which alternating-width chains may provide an independent avenue for tuning desired properties.

Effective stability constants for cysteine and lysine with five different iron sources were evaluated along with their behavior in solution. The values obtained for ferric chloride-cysteine, ferrous sulfate-cysteine, ferric chloride-lysine, ferrous sulfate-lysine, hydrogen-reduced lysine, and electrolytic-reduced lysine were 6.81 × 102 to 2.78 × 103, 1.33 × 105 to 1.36 × 105, 6.00 × 10−4 to 7.64 × 10−3, 6.37 ×10−4 to 4.82× 10−3, 9.34 × 10−2 to 1.38 × 10−1, and 4.18 × 10−4 to 7.27 × 10−4, respectively. No measurable complexation occurred with hydrogen- and electrolytic-reduced iron with cysteine nor with ferric orthophosphate and cysteine or lysine. The stability of soluble ferric cysteine over the pH range 2.0 to 7.4 indicates that this complex has the potential to be used as an iron additive in food. Approximately half of the hydrogen and electrolytic reduced iron and only 0.11% of ferric orthophosphate were soluble in acid, whereas ferric chloride and ferrous sulfate were completely soluble. Qualitative evaluation of the iron-amino acid systems over a range of pH from 2.0 to 12.0 indicated that there was a mixed valence state of free iron in most cases with low pH favoring reduction and high pH oxidation, until precipitation of iron hydroxides occurred.

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The anion-deficient fluorite-related family of materials exhibits a number of commercially useful properties arising from the specific arrangement of anion vacancies in each structure. One recently reported member, Zn 0.456 In 1.084 Ge 0.46 O 3 , is the only known example with its particular complex structure in which cation coordinations span one 4-coordinate (4b), two 6-coordinate (8e and 16f), and one 8-coordinate (4a) site. A new, complete, solid solution (Cu x Zn 1−x ) 0.456 In 1.084 Ge 0.46 O 3 , (0 ≤ x ≤ 1) has been discovered via the isovalent substitution of Cu 2+ for Zn 2+ , significantly expanding the known phase space of this structure. Synchrotron X-ray data confirm the ZIGO structure over the entire composition range. Inclusion of Cu in the structure is found to occur exclusively at the 16f site, increasing the number of cations mixed on that site from three to four, while all others remain singly occupied, including the other 6-coordinate (8e) position. Furthermore, transmission electron microscopy investigations show no evidence of long-range cation ordering. Thus, disorder on the 16f site appears remarkably favorable in this otherwise highly ordered structure. Nonideal trends in the lattice parameters and diffuse reflectance spectra as a function of Cu content are examined. Further implications of the mixed order and disorder in the solid solution for materials discovery and possible properties of interest are briefly discussed.

Fluoridation of HfO2 was carried out with three commonly used solid-state fluoridation agents: PVDF, PTFE, and NH4HF2. Clear and reproducible differences are observed in the reaction products of the fluoropolymer reagents and NH4HF2 with the latter more readily reacting in air. Strong evidence of distinct, previously unreported hafnium oxyfluoride phases is produced by both reactions, and efforts to isolate them were successful for the air-NH4HF2 reaction. Synchrotron XRD, 19F NMR, and elemental analysis were employed to characterize the phase-pure material which appears to be analogous to known Zr–O–F phases with anion-deficient α-UO3 structures such as Zr7O9F10. Comparison with the hydrolysis of β-HfF4 under identical conditions depicts that the NH4HF2 route produces the oxyfluoride with greater selectivity and at lower temperatures. Thermodynamic calculations were employed to explain this result. Potential reaction pathways for the NH4HF2 fluoridation of HfO2 are discussed.