Colossal 3D Electrical Anisotropy of MoAlB Single Crystal.

3D anisotropic functional properties (such as magnetic, electrical, thermal, and optical properties, etc.) in a single material are not only beneficial to the multipurpose of a material, but also helpful to enrich the regulatory dimensionality of functional materials. Herein, a colossal 3D electrical anisotropy of layered MAB-phase MoAlB single crystal is introduced and dissected. Using high-temperature metal-solution method, high-quality MoAlB single crystals are obtained and a surprisingly strong out-of-plane (σa /σb  = 1.43 × 105 , at 2 K) and in-plane (σa /σc  = 12.12, at 2 K) electrical anisotropies are first observed. After a series of experimental and theoretical investigations, it is demonstrated that the 3D anisotropic crystal structure and chemical bond of MoAlB result in its 3D anisotropic phonon vibration and electronic structure, influence the corresponding electron-electron as well as electron-phonon interactions, and finally give rise to its colossal 3D anisotropy of electrical conductivity. This work experimentally and theoretically proves MoAlB single crystal possessing the 3D anisotropies of crystal structure, chemical bond, phonon vibration, electronic structure, and electrical transport, but also provides a promising platform for the future design of functionalized electronic devices as well as synthesis of new and large-sized in-plane anisotropic 2D material (MoBene).

Quenching and Electrical Current Poling Effect on Improved Ferroelectric and Piezoelectric Properties in BiFeO3-Based High-Temperature Piezoceramics.

The effects of quenching on the structural, electrical, dielectric, ferroelectric (FE), and piezoelectric properties are investigated systematically in the 0.85BiFe1-xCrxO3-0.15BaTi1-xMnxO3 (0 ≤ x ≤ 0.03) ceramics. Optimal piezoelectricity and FE Curie temperature are obtained through optimized quenching rate and temperature. Quenching effect on piezoelectricity is especially significant for the samples near morphotropic phase boundaries (MPB), which can be ascribed to quenching-induced changes in phase ratio (rhombohedral and tetragonal phase) and domain structure/defect dipole orientation. Moreover, a new poling method, that is, cooling the sample at a constant dc current across FE TC, is established to improve the piezoelectricity. This work not only reveals the possible mechanism of quenching effect on the improved piezoelectricity in the BFO-based piezoceramics (especially near the MPB) but also suggests an electric current poling strategy for improving piezoelectricity by suppressing the defect dipole effects in BFO-based and even other piezoelectrics.

Chemical Solution Route for High-Quality Multiferroic BiFeO3 Thin Films.

Bismuth ferrite (BiFeO3 ) has recently become interesting as a room-temperature multiferroic material, and a variety of prototype devices have been designed based on its thin films. A low-cost and simple processing technique for large-area and high-quality BiFeO3 thin films that is compatible with current semiconductor technologies is therefore urgently needed. Development of BiFeO3 thin films is summarized with a specific focus on the chemical solution route. By a systematic analysis of the recent progress in chemical-route-derived BiFeO3 thin films, the challenges of these films are highlighted. An all-solution chemical-solution deposition (AS-CSD) for BiFeO3 thin films with different orientation epitaxial on various oxide bottom electrodes is introduced and a comprehensive study of the growth, structure, and ferroelectric properties of these films is provided. A facile low-cost route to prepare large-area high-quality epitaxial BFO thin films with a comprehensive understanding of the film thickness, stoichiometry, crystal orientation, ferroelectric properties, and bottom electrode effects on evolutions of microstructures is provided. This work paves the way for the fabrication of devices based on BiFeO3 thin films.

Low Thermal Expansion Modulated by Off-Stoichiometric Effect in Nonstoichiometric Laves Phase Hf0.87Ta0.13Fe2+x Compounds.

Materials with a low coefficient of thermal expansion (CTE) are extremely demanded in many fields, varying from microelectronics to space technology. Here we report a novel method to achieve low CTE, which differs essentially from the conventional way that uses additives with negative thermal expansion (NTE) to compensate for the positive CTE of the matrix. The stoichiometric Hf0.87Ta0.13Fe2+x (x = 0) shows a giant NTE, which is gradually suppressed with increasing x and finally changed to near-zero thermal expansion (ZTE) at x ≈ 0.4. The excess Fe was suggested to form anti-site defects by occupying the 4f sites. As revealed by electron spin resonance (ESR) spectra, the weakened NTE is closely related to a slower ferromagnetic (FM) ordering process than observed at x = 0. In addition, the CTE can be further tuned by introducing an extra α-Fe phase to achieve a low CTE (e.g., 3.3 ppm/K for x = 1.0) with markedly enhanced mechanical properties, beneficial to applications.

Strong Electron-Phonon Coupling in the Excitonic Insulator Ta2NiSe5.

An excitonic insulating (EI) state is a fantastic correlated electron phase in condensed matter physics, driven by screened electron-hole interaction. Ta2NiSe5 is an excitonic insulator with a critical temperature (TC) of 328 K. In the current study, temperature-dependent Raman spectroscopy is used to investigate the phonon vibrations in Ta2NiSe5. The following observations were made: (1) an abnormal blue shift around TC is observed, which originates from the monoclinic to orthorhombic structural phase transition; (2) the splitting of a mode and two new Raman modes at 147 and 235 cm-1 have been observed with the formation of an EI state. With the help of first-principles calculations and temperature-dependent X-ray diffraction (XRD) experiments, it is found that the TaSe6 octahedra are "frozen" and the NiSe4 tetrahedra are greatly distorted below TC. Thus, it seems that the distortion of NiSe4 tetrahedra plays an important role in the strong electron-phonon coupling (EPC) in Ta2NiSe5, while the strong EPC, coupled with electron-hole interaction, opens the energy gap to form the EI state in Ta2NiSe5.

Observation of the Spin-Glass Behavior in Co-Based Antiperovskite Nitride GeNCo3.

Single-phase antiperovskite nitride GeNCo3 with space group Pm3̅m is successfully synthesized by a solid-gas reaction. The crystal structure, magnetism, specific heat at low temperatures, Hall effect, and electrical and thermal transport properties are widely investigated. Exhilaratingly, a canonical spin-glass (SG) behavior is observed in GeNCo3 with a freezing temperature T0 = 79.43 K, dynamical exponent zν = 6.156, and flipping time τ0 = 5.0 × 10(-12) s. The origin of the SG state in GeNCo3 is likely due to the atomic disorder introduced by the Ge vacancies. This is further proven by the measurements of Ge0.9NCo3 with more Ge deficiencies.

Defect-Free Few-Layer M4 C3 Tx (M = V, Nb, Ta) MXene Nanosheets: Synthesis, Characterization, and Physicochemical Properties.

High-quality few-layer M4 C3 Tx (M = V, Nb, Ta) MXenes are very important for applications and are necessary for clarifying their physicochemical properties. However, the difficulty in etching for themselves and the existence of MC/MC1-δ and M-Al alloy impurities in their M4 AlC3 precursors seriously hinder the achievement of defect-free few-layer M4 C3 Tx (M = V, Nb, Ta) MXenes nanosheets. Herein, three different defect-free few-layer M4 C3 Tx (M = V, Nb, Ta) nanosheets are obtained by using a universal synthesis strategy of calcination, selective etching, intercalation, and exfoliation. Comprehensive characterizations confirm their defect-free few-layer structure feature, large interlayer spacing (1.702-1.955 nm), types of functional groups (-OH, -F, -O), and abundant valance states (M5+ , M4+ , M3+ , M2+ , M0 ). M4 C3 Tx (M = V, Nb, Ta) free-standing films obtained by vacuum filtration of few-layer M4 C3 Tx inks show good hydrophilia, high thermostability, and conductivity. A roadmap on synthesis of defect-free few-layer M4 C3 Tx (M = V, Nb, Ta) nanosheets are proposed and three key points are summarized. This work provides detailed guidelines for the synthesis of other defect-free few-layer MXenes nanosheets, but also will stimulate extensive functional explorations for M4 C3 Tx (M = V, Nb, Ta) MXenes nanosheets in the future.

Origin of the Anomalous Electrical Transport Behavior in Fe-Intercalated Weyl Semimetal Td -MoTe2.

Weyl semimetal Td -MoTe2 has recently attracted much attention due to its intriguing electronic properties and potential applications in spintronics. Here, Fe-intercalated Td -Fex MoTe2 single crystals (0 < x < 0.15 ) are grown successfully. The electrical and thermoelectric transport results consistently demonstrate that the phase transition temperature TS is gradually suppressed with increasing x. Theoretical calculation suggests that the increased energy of the Td phase, enhanced transition barrier, and more occupied bands in 1T' phase is responsible for the suppression in TS . In addition, a ρα -lnT behavior induced by Kondo effect is observed with x ≥ 0.08, due to the coupling between conduction carriers and the local magnetic moments of intercalated Fe atoms. For Td -Fe0.15 MoTe2 , a spin-glass transition occurs at ≈10 K. The calculated band structure of Td -Fe0.25 MoTe2 shows that two flat bands exist near the Fermi level, which are mainly contributed by the dyz and d x 2 - y 2 ${{\rm{d}}_{{x^2} - {y^2}}}$ orbitals of the Fe atoms. Finally, the electronic phase diagram of Td -Fex MoTe2 is established for the first time. This work provides a new route to control the structural instability and explore exotic electronic states for transition-metal dichalcogenides.

Origin of the Anomalous Electrical Transports in Quasi-One-Dimensional Ta2NiSe7.

Exploration of exotic transport behavior is of great interest and importance for revealing the properties of the CDW phase of quasi-one-dimensional Ta2NiSe7. We report the anisotropic electrical transport properties of Ta2NiSe7 single crystals in the CDW phase. The anisotropic constant (γ = ρb/ρc) increased rapidly at TCDW = 60 K upon cooling. The results of the Hall resistivity show that both the concentrations and mobilities of carriers change abruptly at TCDW. The out-of-plane AMR exhibits C2 and C4 symmetry components while the in-plane AMR exhibits C2, C4, and C6 at the CDW state. The planar Hall effect is observed in Ta2NiSe7 at low temperature, which is suggested to originate from the anisotropic orbital magnetoresistance. The calculated results show that the Fermi surface of Ta2NiSe7 was slightly reconstructed due to the CDW transition. This work highlights the enhancement of Fermi surface anisotropy during CDW formation and provides a novel approach to study the CDW materials.

Colossal and reversible barocaloric effect in liquid-solid-transition materials n-alkanes.

Emerging caloric cooling technology provides a green alternative to conventional vapor-compression technology which brings about serious environmental problems. However, the reported caloric materials are much inferior to their traditional counterparts in cooling capability. Here we report the barocaloric (BC) effect associated with the liquid-solid-transition (L-S-T) in n-alkanes. A low-pressure of ~50 MPa reversibly triggers an entropy change of ~700 J kg-1 K-1, comparable to those of the commercial refrigerants in vapor-based compression systems. The Raman study and theoretical calculations reveal that applying pressure to the liquid state suppresses the twisting and random thermal motions of molecular chains, resulting in a lower configurational entropy. When the pressure is strong enough to drive the L-S-T, the configurational entropy will be fully suppressed and induce the colossal BC effect. This work could open a new avenue for exploring the colossal BC effect by evoking L-S-T materials.

Anisotropic intermediate coupling superconductivity in Cu(0.03)TaS(2).

The anisotropic superconducting state properties in Cu(0.03)TaS(2) have been investigated by magnetization, magnetoresistance and specific heat measurements. They clearly show that Cu(0.03)TaS(2) undergoes a superconducting transition at T(C) = 4.03 K. The obtained superconducting parameters demonstrate that Cu(0.03)TaS(2) is an anisotropic type-II superconductor. Combining specific heat jump ΔC/γ(n)T(C) = 1.6(4), gap ratio 2Δ/k(B)T(C) = 4.0(9) and the estimated electron-phonon coupling constant λ∼0.68, the superconductivity in Cu(0.03)TaS(2) is explained within the intermediate coupling BCS scenario. First-principles electronic structure calculations suggest that copper intercalation of 2H-TaS(2) causes a considerable increase of the Fermi surface volume and the carrier density, which suppresses the CDW fluctuation and favors the raise of T(C).

Highly Ambient-Stable 1T-MoS2 and 1T-WS2 by Hydrothermal Synthesis under High Magnetic Fields.

The phase-controlled synthesis of metallic and ambient-stable 2D MX2 (M is Mo or W; X is S) with 1T octahedral coordination will endow these materials with superior performance compared with their semiconducting 2H coordination counterparts. We report a clean and facile route to prepare 1T-MoS2 and 1T-WS2 through hydrothermal processing under high magnetic fields. We reveal that the as-synthesized 1T-MoS2 and 1T-WS2 are ambient-stable for more than 1 year. Electrochemical measurements show that 1T-MoS2 performs much better than 2H-MoS2 as the anode for sodium ion batteries. These results can provide a clean and facile method to prepare ambient-stable 1T-phase MX2.

Effects of Cr Substitution on Negative Thermal Expansion and Magnetic Properties of Antiperovskite Ga1-x Cr x N0.83Mn3 Compounds.

Negative thermal expansion (NTE) and magnetic properties were investigated for antiperovskite Ga1-x Cr x N0.83Mn3 compounds. As x increases, the temperature span (ΔT) of NTE related with Γ5g antiferromagnetic (AFM) order is expanded and shifted to lower temperatures. At x = 0.1, NTE happens between 256 and 318 K (ΔT = 62 K) with an average linear coefficient of thermal expansion, α L = -46 ppm/K. The ΔT is expanded to 81 K (151-232 K) in x = 0.2 with α L = -22.6 ppm/K. Finally, NTE is no longer visible for x ≥ 0.3. Ferromagnetic order is introduced by Cr doping and continuously strengthened with increasing x, which may impede the AFM ordering and thus account for the broadening of NTE temperature window. Moreover, our specific heat measurement suggests the electronic density of states at the Fermi level is enhanced upon Cr doping, which favors the FM order rather than the AFM one.

Reentrant spin glass behavior and magnetodielectric coupling of an Ir-based double perovskite compound, La2CoIrO6.

The structural, magnetic, electrical and dielectric properties of an Ir-based double perovskite compound, La2CoIrO6, have been investigated. The sample undergoes a paramagnetic-ferromagnetic transition at TC, followed by a reentrant spin-glass transition at lower temperatures. The reentrant spin glass state in La2CoIrO6 is associated with the competitions of the antiferromagnetic coupling between Ir4+ and Co2+ ions and the ferromagnetic clusters. La2CoIrO6 shows a semiconducting transport behavior in the temperature range 65 to 360 K and the transport behavior can be well described by the three-dimensional Mott variable range hopping conduction mechanism. Moreover, a strong frequency dependence of dielectric constant behavior for La2CoIrO6 is observed and the dielectric relaxation can be ascribed to the electron hopping between different transition metal ions. In addition, the isothermal magnetic field dependent dielectric constant measurements show that a clear magnetodielectric coupling effect exists in La2CoIrO6 at low temperatures.

Vertical La0.7Ca0.3MnO3 nanorods tailored by high magnetic field assisted pulsed laser deposition.

La0.7Ca0.3MnO3 (LCMO) thin films on (LaAlO3)0.3(Sr2AlTaO6)0.7 (001) [LSAT (001)] single crystal substrates have been prepared by high magnetic field assisted pulsed laser deposition (HMF-PLD) developed by ourselves. Uniformly sized and vertically aligned nanorod structures can be obtained under an applied high magnetic field above 5 T, and the dimension size of the nanorods can be manipulated by varying the applied magnetic field. It is found that the magnetic anisotropy is strongly correlated to the dimension size of the nanorods. A significantly enhanced low-field magnetoresistance (LFMR) of -36% under 0.5 T at 100 K can be obtained due to the enhanced carrier scattering at the vertical grain boundaries between the nanorods for the LCMO films. The growth mechanism of the nanorods has been also discussed, which can be attributed to the variation of deposition rate, adatom surface diffusion, and nucleation induced by the application of a high magnetic field in the film processing. The successful achievements of such vertical nanorod structures will provide an instructive route to investigate the physical nature of these nanostructures and achieve nanodevice manipulation.

Transparent conducting p-type thin films of c-axis self-oriented Bi2Sr2Co2O(y) with high figure of merit.

Transparent conducting p-type Bi2Sr2Co2O(y) thin films have been first grown on SrTiO3 substrates by a chemical solution deposition, showing c-axis self-orientation. The figure of merit can reach as high as 800 MΩ(-1), which is the highest value for p-type transparent conducting thin films by solution methods.

Epitaxial antiperovskite superconducting CuNNi3 thin films synthesized by chemical solution deposition.

Epitaxial antiperovskite superconducting CuNNi3 thin films have been grown by chemical solution deposition. The film is a type II superconductor and shows a Tc of 3.2 K with a transition of 0.13 K. The Hc2(0) and ξ0 are estimated to be 8.1 kOe and 201 Å, respectively.

Enhanced electronic correlation and thermoelectric response by Cu-doping in Ca3Co4O9 single crystals.

The structure, anisotropic magnetic, electrical and thermal transport properties for single crystals of Ca(3)Co(4-x)Cu(x)O(9) (x = 0, 0.2, 0.4, 0.6 and 0.8) have been investigated systematically. The Cu-doping with x = 0.2 at Co-site is sufficient to drive the low-temperature spin-glass state in the Ca(3)Co(4)O(9) system. The value of resistivity along ab-plane decreases monotonously with increasing x in the whole temperature range studied, and around room temperature, the in-plane resistivity of Ca(3)Co(3.2)Cu(0.8)O(9) is about 71% smaller than that of the undoped sample. The temperature region where the Fermi-liquid transport mechanism dominates becomes remarkably narrowed due to the Cu-doping while the electronic correlation in the system is enhanced. With further addition of Cu in the Ca(3)Co(4)O(9) system, the in-plane thermopower (S(ab)) increases slowly and the room-temperature S(ab) for Ca(3)Co(3.2)Cu(0.8)O(9) is about 17% larger than that of the undoped sample. As a result, the power factor along the ab-plane is enhanced by about 3.8 times compared to the undoped sample. The results are suggested to originate from the variations of carrier concentration and electronic correlation in this system via the different Cu-doping states: Cu(3+)/Cu(2+) (Cu(3+) major) into the CoO(2) layer for x ≤ 0.4, while Cu(2+)/Cu(3+) (Cu(2+) major) into the Ca(2)CoO(3) layers for x > 0.4.

A polar oxide with a large magnetization synthesized at ambient pressure.

The perovskite Bi2Mn4/3Ni2/3O6 is polar and combines relative permittivity behavior consistent with ferroelectricity with the magnetic response of a concentrated spin-glass. Bi2Mn4/3Ni2/3O6 is accessible by ambient pressure synthesis despite the instability of the end-members BiMnO3 and BiNiO3 under these conditions.

Growth of Sb(2)E(3) (E = S, Se) polygonal tubular crystals via a novel solvent-relief-self-seeding process.

A novel solvent-relief-self-seeding (SRSS) process was applied to grow bulk polygonal tubular single crystals of Sb(2)E(3) (E = S, Se), using SbCl(3) and chalcogen elements E (E = S, Se) as the raw materials at 180 degrees C for 7 days in ethanol solution. The products were characterized by various techniques, including X-ray powder diffraction (XRD), scanning electronic microscope (SEM), transmission electronic microscope (TEM), electronic diffraction (ED), and X-ray photoelectron spectra (XPS). The calculated electrical resistivities of the tubular single crystals in the range 20-320 K were of the order of 10(5)-10(6) Omega cm for Sb(2)S(3) and 10(3)-10(4) Omega cm for Sb(2)Se(3), respectively. The studies of the optical properties revealed that the materials formed had a band gap of 1.72 eV for Sb(2)S(3) and 1.82 eV for Sb(2)Se(3), respectively. The optimal reaction conditions for the growth of bulk tubular single crystals were that the temperature was not lower than 180 degrees C and the reaction time was not shorter than 7 days. The possible growth mechanism of tubular crystals was also discussed.