High-harmonic generation in Weyl semimetal ß-WP2 crystals.

As a quantum material, Weyl semimetal has a series of electronic-band-structure features, including Weyl points with left and right chirality and corresponding Berry curvature, which have been observed in experiments. These band-structure features also lead to some unique nonlinear properties, especially high-order harmonic generation (HHG) due to the dynamic process of electrons under strong laser excitation, which has remained unexplored previously. Herein, we obtain effective HHG in type-II Weyl semimetal ß-WP2 crystals, where both odd and even orders are observed, with spectra extending into the vacuum ultraviolet region (190 nm, 10th order), even under fairly low femtosecond laser intensity. In-depth studies have interpreted that odd-order harmonics come from the Bloch electron oscillation, while even orders are attributed to Bloch oscillations under the "spike-like" Berry curvature at Weyl points. With crystallographic orientation-dependent HHG spectra, we further quantitatively retrieved the electronic band structure and Berry curvature of ß-WP2. These findings may open the door for exploiting metallic/semimetallic states as solid platforms for deep ultraviolet radiation and offer an all-optical and pragmatic solution to characterize the complicated multiband electronic structure and Berry curvature of quantum topological materials.

Non-hydrostatic pressure-dependent structural and transport properties of BiCuSeO and BiCuSO single crystals.

High-pressure experiments usually expect a hydrostatic condition, in which the physical properties of materials can be easily understood by theoretical simulations. Unfortunately, non-hydrostatic effect is inevitable in experiments due to the solidification of the pressure transmitting media under high pressure. Resultantly, non-hydrostaticity affects the accuracy of the experimental data and sometimes even leads to false phenomena. Since the non-hydrostatic effect is extrinsic, it is quite hard to analyze quantitatively. Here, we have conducted high pressure experiments on the layered BiCuXO (X = S and Se) single crystals and quantitatively analyzed their pronounced non-hydrostatic effect by high throughput first-principles calculations and experimental Raman spectra. Our experiments find that the BiCuXO single crystals sustain the tetragonal structure up to 55 GPa (maximum pressure in our experiment). However, their pressure-dependent Raman shift and electric resistance show anomalous behaviors. Through optimization of thousands of crystal structures in the high throughput first-principles calculations, we have obtained the evolution of the lattice constants under external pressures, which clearly substantiates the non-hydrostatical pressure exerted in BiCuXO crystals. Our work indicates that the high throughput first-principles calculations could be a handy method to investigate the non-hydrostatic effect on the structural and electronic properties of materials in high pressure experiments.

Electrical scattering mechanism evolution in un-doped and halogen-doped Bi2O2Se single crystals.

Recently the layered oxide semiconductor Bi2O2Se was hotly explored for its ultrahigh mobility and ultrafast photo-response whose physical origins need to be further explored or elucidated. Here, we have grown halogen (Cl, Br, I) doped and un-doped Bi2O2Se single crystals by a melt-solidification method. Comparative electrical transport characterizations and detailed data-analysis substantiate that the electron-electron scattering is the major source of resistivity in un-doped Bi2O2Se crystals; however, in halogen-doped Bi2O2Se crystals, electron-electron scattering is only effective at low temperature (<60 K) and subsequently electron-phonon-interaction scattering is dominated to resistivity. Hall measurement and analysis show that electron concentration of halogen-doped Bi2O2Se (∼1020 cm-3) is one-order higher than un-doped one (∼1019 cm-3), but the carrier mobility of halogen-doped Bi2O2Se at 2 K (∼102 cm2 V-1 s-1) is reduced by more than two orders than un-doped ones (∼104 cm2 V-1 s-1). Three kinds of relaxation time (due to the impurity scattering, electron-electron scattering and electron-phonon scattering), calculated by linear-response theory and electron-/phonon-dispersion, are in agreement with experimental results quantitatively. The scattering mechanism evolution from sole electron-electron scattering (un-doped Bi2O2Se) to electron-phonon scattering (doped Bi2O2Se) at high temperature (>60 K) is attributed to the net effect of decreased screened Coulomb-interaction and increased Fermi energy in halogen-doped Bi2O2Se. This work may provide clues of physical origins of superior electrical/photoelectrical properties of Bi2O2Se.

Anomalous transport and magnetic properties induced by slight Cu valence alternation in layered oxytelluride BiCuTeO.

In this paper, we report on the transport and magnetic properties of layered oxytelluride BiCuTeO polycrystals with slight mixed valence of Cu. The temperature-dependent electrical resistivity reveals degenerate semiconductor behavior (similar to metals). Under the action of an external magnetic field, the BiCuTeO polycrystal sample exhibits unsaturated magnetic resistance (MR) of about 8% at 2 K and 9 Tesla. The Hall resistivities show nonlinear behavior, suggesting the coexistence of both electrons and holes in the sample. When the temperature is decreased to around 110 K, the dominant carriers are changed from electrons to holes from the viewpoint of electrical transport, which is supported by the calculated temperature-dependent Fermi energy. Meanwhile, at low temperatures (<100 K), the impurity magnetic moment formed by a small amount of positive divalent copper exhibits short-range magnetism (a spin-glass-like feature), which gives rise to a narrow magnetic hysteresis loop. Our work may benefit in-depth understanding of physical properties of BiCuTeO-based materials.

Infrared and Raman spectra of Bi2O2X and Bi2OX2 (X = S, Se, and Te) studied from first principles calculations.

The bismuth oxychalcogenide compounds contain many different kinds of materials, such as Bi2O2X and Bi2OX2 (X = S, Se, and Te). These materials have different but similar layered crystal structures and exhibit various interesting physical properties. Here, we have theoretically investigated their Raman and infrared spectra by first principles calculations based on density functional theory. It is found that in Bi2O2Se the calculated frequency of the A1g Raman active mode is in good agreement with the experimental measurements while the other three modes are ambiguous or not observed yet. The Raman and infrared spectra of other materials are also presented and need further confirmation. Our work provides the structural fingerprints of these materials, which could be helpful in identifying the crystal structures in future experiments.

One-step synthesis of zerovalent-iron-biochar composites to activate persulfate for phenol degradation.

A novel zerovalen-iron-biochar composite (nZVI/SBC) was synthesized by using FeCl3-laden sorghum straw biomass as the raw material via a facile one-step pyrolysis method without additional chemical reactions (e.g., by NaBH4 reduction or thermochemical reduction). The nZVI/SBC was successfully employed as an activator in phenol degradation by activated persulfate. XRD, SEM, N2 adsorption-desorption and atomic absorption spectrophotometry analysis showed that the nanosized Fe0 was the main component of the 4ZVI/SBC activator, which was a mesopore material with an optimal FeCl3·6H2O/biomass impregnation mass ratio of 2.7 g/g. The 4ZVI/SBC activator showed an efficient degradation of phenol (95.65% for 30 min at 25 °C) with a large specific surface area of 78.669 m2·g-1. The recovery of 4ZVI/SBC activator after the degradation reaction of phenol can be realized with the small amount of dissolved iron in the water. The 4ZVI/SBC activator facilitated the activation of persulfate to degrade phenol into non-toxic CO2 and H2O. The trend of Cl-, SO4 2- and NO3 - affected the removal efficiency of phenol by using the 4ZVI/SBC activator in the following order: NO3 - > SO4 2- > Cl-. The one-step synthesis of the nanosized zerovalent-iron-biochar composite was feasible and may be applied as an effective strategy for controlling organic waste (e.g. phenol) by waste biomass.

Preparation, Structure Evolution, and Metal-Insulator Transition of Na xRhO2 Crystals (0.25 ≤ x ≤ 1).

The triangular lattice Na xRhO2 contains a 4d Rh element with large spin-orbit coupling, and the electron-electron correlation effect is expected to have some novel physical properties. Here we report NaRhO2 crystal growth by Na2CO3 vapor growth and a series of Na xRhO2 (0.25 ≤ x ≤ 1) crystals prepared using the chemical desodiation method. Na xRhO2 reveals a layer structure with the space group R3̅ m, and the lattice parameter a evolves from 3.09 to 3.03 Å and c from 15.54 to 15.62 Å when x decreases from 1.0 to 0.2. Decreasing potassium concentration leads to a contraction of the RhO6 octahedral layers, which may be attributed to a higher covalency of Rh-O bonds. More important, the metal-insulator transition in Na xRhO2 was observed in resistivity along the ab plane. The conducting mechanism of Na xRhO2 is strongly dependent on x. Two-dimensional variable range hopping (VRH) mechanisms (0.67 ≤ x ≤ 1) and metallic behaviors (0.42 and 0.47) are observed in temperature-dependent resistivity. The origin of this metal-insulator transition was discussed on the basis of the Ioffe-Regel criterion. Our work demonstrates the strong correlation between sodium concentration and physical properties of Na xRhO2.

Giant positive magnetoresistance in half-metallic double-perovskite Sr2CrWO6 thin films.

Magnetoresistance (MR) is the magnetic field-induced change of electrical resistance. The MR effect not only has wide applications in hard drivers and sensors but also is a long-standing scientific issue for complex interactions. Ferromagnetic/ferrimagnetic oxides generally show negative MR due to the magnetic field-induced spin order. We report the unusually giant positive MR up to 17,200% (at 2 K and 7 T) in 12-nm Sr2CrWO6 thin films, which show metallic behavior with high carrier density of up to 2.26 × 1028 m-3 and high mobility of 5.66 × 104 cm2 V-1 s-1. The possible mechanism is that the external magnetic field suppresses the long-range antiferromagnetic order to form short-range antiferromagnetic fluctuations, which enhance electronic scattering and lead to the giant positive MR. The high mobility may also have contributions to the positive MR. These results not only experimentally confirm that the giant positive MR can be realized in oxides but also open up new opportunities for developing and understanding the giant positive MR in oxides.

The Microstructural Characterization of Multiferroic LaFeO3-YMnO3 Multilayers Grown on (001)- and (111)-SrTiO3 Substrates by Transmission Electron Microscopy.

The microstructure of multiferroic LaFeO3-YMnO3 (LFO-YMO) multilayers grown on (001)- and (111)-SrTiO3 substrates is characterized by the transmission electron microscopy (TEM). Detailed TEM characterization reveals that LFO-YMO multilayers grown on both substrates have clear layer-by-layer morphology and distinct chemical-composition layered structure. The most notable feature is that LFO-YMO multilayers grown on (001)-SrTiO3 substrate have three types of domains, while those on (111)-SrTiO3 have only one. The multi-/twin- domain structure can be qualitatively explained by the lattice mismatch in this system. The details of the domain structure of LFO-YMO multilayers are crucial to understanding their magnetic properties.

Transition between strong and weak topological insulator in ZrTe5 and HfTe5.

ZrTe5 and HfTe5 have attracted increasingly attention recently since the theoretical prediction of being topological insulators (TIs). However, subsequent works show many contradictions about their topolog-ical nature. Three possible phases, i.e. strong TI, weak TI, and Dirac semi-metal, have been observed in different experiments until now. Essentially whether ZrTe5 or HfTe5 has a band gap or not is still a question. Here, we present detailed first-principles calculations on the electronic and topological prop-erties of ZrTe5 and HfTe5 on variant volumes and clearly demonstrate the topological phase transition from a strong TI, going through an intermediate Dirac semi-metal state, then to a weak TI when the crystal expands. Our work might give a unified explain about the divergent experimental results and propose the crucial clue to further experiments to elucidate the topological nature of these materials.

Composition and temperature-dependent phase transition in miscible Mo1-xWxTe2 single crystals.

Transition metal dichalcogenides (TMDs) WTe2 and MoTe2 with orthorhombic Td phase, being potential candidates as type-II Weyl semimetals, are attracted much attention recently. Here we synthesized a series of miscible Mo1-xWxTe2 single crystals by bromine vapor transport method. Composition-dependent X-ray diffraction and Raman spectroscopy, as well as composition and temperature-dependent resistivity prove that the tunable crystal structure (from hexagonal (2H), monoclinic (ß) to orthorhombic (Td) phase) can be realized by increasing W content in Mo1-xWxTe2. Simultaneously the electrical property gradually evolves from semiconductor to semimetal behavior. Temperature-dependent Raman spectroscopy proves that temperature also can induce the structural phase transition from ß to Td phase in Mo1-xWxTe2 crystals. Based on aforementioned characterizations, we map out the temperature and composition dependent phase diagram of Mo1-xWxTe2 system. In addition, a series of electrical parameters, such as carrier type, carrier concentration and mobility, have also been presented. This work offers a scheme to accurately control structural phase in Mo1-xWxTe2 system, which can be used to explore type-II Weyl semimetal, as well as temperature/composition controlled topological phase transition therein.

Experimental Observation of Anisotropic Adler-Bell-Jackiw Anomaly in Type-II Weyl Semimetal WTe_{1.98} Crystals at the Quasiclassical Regime.

The asymmetric electron dispersion in type-II Weyl semimetal theoretically hosts anisotropic transport properties. Here, we observe the significant anisotropic Adler-Bell-Jackiw (ABJ) anomaly in the Fermi-level delicately adjusted WTe_{1.98} crystals. Quantitatively, C_{W}, a coefficient representing the intensity of the ABJ anomaly along the a and b axis of WTe_{1.98} are 0.030 and 0.051 T^{-2} at 2 K, respectively. We found that the temperature-sensitive ABJ anomaly is attributed to a topological phase transition from a type-II Weyl semimetal to a trivial semimetal, which is verified by a first-principles calculation using experimentally determined lattice parameters at different temperatures. Theoretical electrical transport study reveals that the observation of an anisotropic ABJ along both the a and b axes in WTe_{1.98} is attributed to electrical transport in the quasiclassical regime. Our work may suggest that electron-doped WTe_{2} is an ideal playground to explore the novel properties in type-II Weyl semimetals.

Predicted Quantum Topological Hall Effect and Noncoplanar Antiferromagnetism in K_{0.5}RhO_{2}.

The quantum anomalous Hall (QAH) phase is a two-dimensional bulk ferromagnetic insulator with a nonzero Chern number in the presence of spin-orbit coupling (SOC) but in the absence of applied magnetic fields. Associated metallic chiral edge states host dissipationless current transport in electronic devices. This intriguing QAH phase has recently been observed in magnetic impurity-doped topological insulators, albeit, at extremely low temperatures. Based on first-principles density functional calculations, here we predict that layered rhodium oxide K_{0.5}RhO_{2} in the noncoplanar chiral antiferromagnetic state is an unconventional three-dimensional QAH insulator with a large band gap and a Néel temperature of a few tens of Kelvins. Furthermore, this unconventional QAH phase is revealed to be the exotic quantum topological Hall effect caused by nonzero scalar spin chirality due to the topological spin structure in the system and without the need of net magnetization and SOC.

Experimental Observation of Topological Edge States at the Surface Step Edge of the Topological Insulator ZrTe_{5}.

We report an atomic-scale characterization of ZrTe_{5} by using scanning tunneling microscopy. We observe a bulk band gap of ∼80 meV with topological edge states at the step edge and, thus, demonstrate that ZrTe_{5} is a two-dimensional topological insulator. We also find that an applied magnetic field induces an energetic splitting of the topological edge states, which can be attributed to a strong link between the topological edge states and bulk topology. The relatively large band gap makes ZrTe_{5} a potential candidate for future fundamental studies and device applications.

Dramatically decreased magnetoresistance in non-stoichiometric WTe2 crystals.

Recently, the layered semimetal WTe2 has attracted renewed interest owing to the observation of a non-saturating and giant positive magnetoresistance (~10(5)%), which can be useful for magnetic memory and spintronic devices. However, the underlying mechanisms of the giant magnetoresistance are still under hot debate. Herein, we grew the stoichiometric and non-stoichiometric WTe2 crystals to test the robustness of giant magnetoresistance. The stoichiometric WTe2 crystals have magnetoresistance as large as 3100% at 2 K and 9-Tesla magnetic field. However, only 71% and 13% magnetoresistance in the most non-stoichiometry (WTe1.80) and the highest Mo isovalent substitution samples (W0.7Mo0.3Te2) are observed, respectively. Analysis of the magnetic-field dependent magnetoresistance of non-stoichiometric WTe2 crystals substantiates that both the large electron-hole concentration asymmetry and decreased carrier mobility, induced by non-stoichiometry, synergistically lead to the decreased magnetoresistance. This work sheds more light on the origin of giant magnetoresistance observed in WTe2.

Metal-insulator transition in SrIrO3 with strong spin-orbit interaction.

The thickness-dependent metal-insulator transition is observed in meta-stable orthorhombic SrIrO3 thin films synthesized by pulsed laser deposition. SrIrO3 films with thicknesses less than 3 nm demonstrate insulating behaviour, whereas those thicker than 4 nm exhibit metallic conductivity at high temperature, and insulating-like behaviour at low temperature. Weak/Anderson localization is mainly responsible for the observed thickness-dependent metal-insulator transition in SrIrO3 films. Temperature-dependent resistance fitting shows that electrical-conductivity carriers are mainly scattered by the electron-boson interaction rather than the electron-electron interaction. Analysis of the magneto-conductance proves that the spin-orbit interaction plays a crucial role in the magneto-conductance property of SrIrO3.

Photocatalytic oxidation and removal of arsenite by titanium dioxide supported on granular activated carbon.

Arsenic contamination in drinking water is a worldwide concern. Photocatalysis can rapidly oxidize arsenite, i.e. As(III), to less labile arsenate, i.e. As(V), which then can be removed by adsorption on to various adsorbents. This study investigated the photocatalytic oxidation of arsenite in aqueous solution by granular activated carbon supporting a titanium dioxide photocatalyst (GAC-TiO2). The effects of photocatalyst dosage, solution pH values, initial concentration of As(III) and co-anions (SO4(2-), PO4(3-), SiO3(2-) and Cl-) on the oxidation of As(III) were studied. The photocatalytic oxidation of As(III) took place in minutes and followed first-order kinetics. The presence of phosphate and silicate significantly decreased As(III) oxidation, while the effect of sulphate, chloride was insignificant. The oxidation efficiency of As(III) was observed to increase with increasing pH. The results suggest that the supported photocatalyst developed in this study is an ideal candidate for pre-oxidation treatment of arsenic-contaminated water.