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In this work, we presented investigations on the microstructural, magnetic, dielectric and conductive properties of (1-x)Na0.5Bi0.5TiO3-xCoFe2O4 (NBT-CFO) composite ceramics (x = 0.1, 0.2, 0.3 and 0.5). The composites were synthesized using the in-situ sol-gel method, and the resulting CFO/NBT embedded structure was observed in the 0.9NBT–0.1CFO sample. Rietveld refinement confirmed that the embedded structure had remarkable effects on the c/a ratios of NBT-CFO composites. Increasing normalization saturation magnetizations were observed with increasing of CFO contents, thus revealing the influence of phase interfaces on magnetism. Dielectric relaxation anomalies were observed on both temperature dependent permittivity and loss spectra. Two sets of anomalies in these spectra were caused by space charges on the phase interfaces of embedded CFO grains and the NBT matrix. The conduction behavior of ceramics with and without the embedded structure obeyed the double power law and Jonscher's fraction power law, respectively, which inferred a transformation from the AC to the DC conduction mechanism with the disappearance of the embedded structure.

Water evaporation and steam production have been recognized to be considerably crucial due to the vast applications, ranging from waste water treatment, water purification, to alternative green energy solutions by water splitting, catalysis, and in-door heating. Albeit the big variety of photothermal conversion materials (PCMs) developed for this purpose, certain drawbacks, e.g. high cost, complicated synthesis, weak/narrow absorbance, bulkiness, and low evaporation rate, have hindered the application potential. Herein, we report the dual-phase molybdenum nitride nanorambutans, synthesized by a facile method, for solar steam generation. Not only the inherent properties, including strong full-spectrum absorbance, high-efficiency photothermal conversion, and super-hydrophilicity, benefit their water evaporation performance, the interconnected open mesopores of the nanorambutans further boost their capability of light harvesting and water/vapor transportation. Solar energy conversion efficiency of ∼97% under one sun together with excellent cycling stability has been demonstrated. In the desalination systems, integrating with the high salt rejection rate, the nanorambutans film can produce a water evaporation rate as high as ∼1.70 kg m −2 h −1 with an efficiency of ∼98%. Besides its compact size, the record-breaking water evaporation performance of these nanorambutans has exceeded the previous best inorganic PCM. This work introduces molybdenum nitride as a new PCM for efficient solar steam generation and all applications that can benefit from highly localized heating from nano to macro scale.

Morphotropic phase boundaries (MPB) consisting of rhombohedral and orthorhombic phases formed within the range of 0.1 ≤ x ≤ 0.15 in Bi1-xErxFe0.97Ti0.03O3 ceramics. Orthorhombic phase transition was verified by the appearance of a new mode at 310 cm−1 in Raman spectra. Bridging phases as intermedia phases of MPB were rare in Bi1-xErxFe0.97Ti0.03O3. Polarization and permittivity improved at MPB. Moreover, impedance spectroscopy revealed additional arcs with a distinct small polaron conduction mechanism. Er3+ ions enhanced magnetic properties and induced a permittivity change at Neel temperature. The magnetodielectric effect resulted in a permittivity change rate of ~1% at 10000 Oe.

We present extensive investigations of the crystallographic phase diagram and electronic properties of the Fe-based superconductor FeSe under extreme conditions (high pressure (HP) and low temperature (LT)) by synchrotron X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). An isostructural phase transition (Tetragonal (T) →high-pressure Tetragonal (Tʹ)) is discovered in FeSe at ∼2.8 GPa based on the axial ratio c/a with finer pressure step as observed in Fe-As-based superconductor such as EuFe2As2. We also find a pressure-induced Tʹ → MnP-type phase transition at 7.6 GPa in FeSe, which is consistent with the documented pressure-induced high-spin → low-spin transition (∼6–7 GPa). These results reveal the pressure-induced structural phase transition sequence in FeSe at room temperature to be T → Tʹ → Tʹ+MnP-type at pressures of 0–10.6 GPa, enriching the crystallographic phase diagram. The HPLT XRD data also indicate that a sluggish structural phase transition (Cmma → Pnma) begins at 7.5 GPa, and these two phases coexist up to 26.5 GPa. The HP X-ray absorption near-edge spectroscopy (XANES) measurement shows that Eo of Se experiences a pressure-induced shift to high energy, evidencing strongly charge transfer between Fe and Se under high pressure. Our results shed lights on the correlation between crystallographic/electronic structure and superconductivity in this material.

Manganese (Mn)-based antiperovskite structures (Mn3AX, where A and X represent the 3d transition-metal elements and N or C atoms, respectively) have attracted growing attention because of their novel electronic and magnetic properties. However, the lack of an effective approach to regulate the magnetic coupling in Mn3AX crystal structure, particularly in antiferromagnetic ground states, hinders their further design and applications. Herein, robust high-temperature ferrimagnetic order with a Curie temperature (TC) in the range of ∼390–420 K was successfully achieved in Mn3GaxNx (x = 0.5, 0.6, and 0.7) via composition-deficient engineering. A systematic investigation, including synchrotron X-ray diffraction, neutron powder diffraction, pair distribution function, X-ray absorption near-edge structure, magnetic characterization, and first-principles calculations, convincingly indicated that the redistribution of partial atoms in the antiferromagnetic ground state was responsible for the observed long-range magnetic order. These results not only provide a new perspective into the design and construction of high-temperature ferrimagnets based on the Mn3AX structure, but also open up a promising avenue for the further design of Mn3AX-based spintronic or other multifunctional devices.

In this study, a series of Bi2Te2-xS1+x compounds were prepared by traditional melting-quenching-annealing process. In the range of 0.03 ≤ x ≤ 0.25, Bi2Te2-xS1+x compounds possess the Bi2Te3 structure. S atoms preferentially fully occupy the Te(2) sites, while any extra S atoms randomly occupy the Te(1) sites. Experimental results and phonon dispersion calculations demonstrate that the strong coupling of the phonon density of state contributed by Bi and Te(1) atoms results in the low avoided-crossing frequencies, sound velocities, Debye temperature and therefore the low lattice thermal conductivities. Moreover, substitutions of extra S atoms on the Te(1) site intensifies alloy phonon scattering that further suppresses the lattice thermal conductivity. An ultra-low lattice thermal conductivity of 0.49 W m−1 K−1 is achieved at 523 K. Doping with Cl increases the room temperature carrier concentration, resulting in a significantly enhanced power factor from 1.5 mW m−1 K−2 for the Bi2Te1.93S1.07 sample to 1.7 mW m−1 K−2 for the Cl-doped sample at 323 K. Furthermore, doping with Cl enhances phonon point defect scattering that leads to a suppression of the thermal conductivity to 0.41 W m−1 K−1 at 573 K. As a result of the optimization of the electronic transport properties and the reduction in the lattice thermal conductivity, Bi2Te1.93S1.065Cl0.005 sample achieved the highest ZT of 0.67 at 623 K which is superior to intrinsic Bi2Te3 in the whole temperature range.

In this paper, a novel composite La0.9Ca0.1Fe0.9Nb0.1O3-δ/Sc0.2Zr0.8O2−δ (LCFNb/ScSZ) is developed and investigated as a fuel electrode candidate for direct electrolyzing carbon dioxide (CO2) in solid oxide electrolysis cells (SOECs). XRD patterns of LCFNb powder sintered in CO2 at 850 °C for 10 h indicate that no secondary phases are found during the heat treatment and linear thermal expansion results prove that the LCFNb is compatible with ScSZ electrolyte used in this work. The electrolyser with porous LCFNb membrane cathode fabricated by infiltration method shows impressive electrochemical performance. The current density of 1.97 A/cm2 at 2.0 V at 800 °C is obtained. The polarization resistance Rp of the SOEC decreases with the increase of the applied voltage between the electrodes. The obtained lowest Rp is as low as 0.113 Ω cm2 at 2.0 V and this value is much lower than its many other perovskite and nickle-based counterparts. Besides, the LCFNb/ScSZ cathode shows excellent stability in pure CO2 at different applied voltage, especially at 2.0 V. Furthermore, the LCFNb/ScSZ electrode exhibits the current efficiencies close to theoretical ones for CO2 electrolysis, indicating that the LCFNb/ScSZ composite ceramic is an excellent cathode for zirconia-based high temperature electrolyser.

(Gadolinium) Gd-doped antiperovskite compounds Mn 3 Cu 1−x Gd x N were synthesized by the conventional solid-state reaction. With increasing Gd concentration, two magnetic transitions appeared at a high Curie temperature (T C1 ) corresponding to paramagnetic (PM)-ferromagnetic (FM) transition and a low temperature (T C2 ) ascribed to the FM-antiferromagnetic (AFM) transition. The magnetic relaxation results show the formation of a magnetic metastable state after the FM-AFM transition at low temperature (lower than T C2 ), forming a novel magnetic-step feature in the process from AFM to FM under a certain magnetic field.

We systematically investigate the influence of high pressure on the electronic transport properties of layered ferromagnetic materials; in particular, those of ${\mathrm{Fe}}_{3}{\mathrm{GeTe}}_{2}$. Its crystal sustains a hexagonal phase under high pressures up to 25.9 GPa, while the Curie temperature decreases monotonously with the increasing pressure. By applying appropriate pressures, the experimentally measured anomalous Hall conductivity, ${\ensuremath{\sigma}}_{xy}^{A}$, can be efficiently controlled. Our theoretical study reveals that this finding can be attributed to the shift of the spin--orbit-coupling-induced splitting bands of Fe atoms. With loading compression, ${\ensuremath{\sigma}}_{xy}^{A}$ reaches its maximal value when the Fermi level lies inside the splitting bands and then attenuates when the splitting bands float above the Fermi level. Further compression leads to a prominent suppression of the magnetic moment, which is another physical cause of the decrease in ${\ensuremath{\sigma}}_{xy}^{A}$ at high pressure. These results indicate that the application of pressure is an effective approach in controlling the anomalous Hall conductivity of layered magnetic materials, which elucidates the physical mechanism of the large intrinsic anomalous Hall effect.

The high-pressure effect on valence fluctuation of the ThCr2Si2-type intermetallic compound EuNi2P2 has been investigated using in situ synchrotron Mossbauer spectroscopy (SMS). The isomer shift of 151Eu in EuNi2P2 increases monotonically with increasing pressure up to 50 GPa, suggesting a valence transition of the Eu from mixed toward trivalent. The synchrotron angle-dispersive X-ray diffraction (AD-XRD) experiment shows that EuNi2P2 remains in the tetragonal structure up to 32.5 GPa at room temperature. We propose that the evolutions of bonding distance with pressure have an obvious effect on the valence fluctuation.

The extremely large magnetoresistance (XMR) in nonmagnetic semimetals has inspired growing interest owing to both intriguing physics and potential applications. We report results of synchrotron X-ray diffraction (SXRD) and electrical transport measurements on TaAs2 under pressure up to ~ 37 GPa, which revealed an anisotropic compression of the unit cell, formation of unusual As-As bonds above 9.5 GPa, and enhancement of metallicity. Interestingly, the MR of TaAs2 under pressure changed gently, which at 1.7 GPa is 96.6% and at 36.6 GPa is still 36.7%. The almost robust MR under pressure could be related to the nearly stable electronic structure unveiled by the ab initio calculations. The discovery would expand the potential use of XMR even under high pressure., Comment: 15 pages, 7 figures including those in supporting information

The layered Cr2Ge2Te6 (CrGT) has captured vast attentions because it is capable of retaining the long-range ferromagnetic order even in its monolayer form, thus offering potential applications in spintronic devices. We report herein the Raman spectra of CrGT under pressure up to 35.1 GPa at room temperature. We observed a structural phase transition at ∼14 GPa as was revealed by a change in pressure derivate frequencies of the E g 3 and A g 1 modes. Both of the two peaks became broad and the A g 1 mode eventually disappeared with further increasing the pressure. Raman modes above 26.4 GPa could not be experimentally observed, suggesting that the CrGT was pressed into the amorphous phase. Interestingly, a pressure-induced soft phonon mode is identified in CrGT at ∼23 GPa by dynamical property calculation. The phonon instability at the Brillouin zone boundary T point is suggested as the driving force for the experimentally observed crystalline-to-crystalline phase transition at ∼ 18 GPa. The appearance of soft phonon might indicate the possibility of superconductivity induced by much higher pressure.

As one of important semiconductor photocatalysts, bismuth oxide chloride (BiOCl) crystallizes into a tetragonal matlockite structure with the space group of P4/nmm. In this work, the in situ high-pressure angle-dispersive X-ray diffraction experiments and the first-principle calculations were performed on BiOCl, in order to explore the crystal and electronic structure evolution processes upon compression. At 15.1 GPa, BiOCl undergoes a tetragonal to tetragonal isostructural phase transition and then completely transforms into a high-pressure tetragonal phase at 22.1 GPa, which adopts the same crystal structure as that of the low-pressure tetragonal phase. According to the ab initio calculation results, the redistribution of Bader charge between the Bi, O, Cl ions under high pressure induces the isostructural phase transition in BiOCl and causes the different electronic structures between the high-pressure and low-pressure phases. The pressure-induced crystal and electronic structure changes in BiOCl could...

CrAs was observed to possess the bulk superconductivity under high-pressure conditions. To understand the superconducting mechanism and explore the correlation between the structure and superconductivity, the high-pressure structural evolution of CrAs was investigated using the angle-dispersive X-ray diffraction (XRD) method. The structure of CrAs remains stable up to 1.8 GPa, whereas the lattice parameters exhibit anomalous compression behaviors. With increasing pressure, the lattice parameters a and c both demonstrate a nonmonotonic change, and the lattice parameter b undergoes a rapid contraction at similar to 0.18-0.35 GPa, which suggests that a pressure-induced isostructural phase transition occurs in CrAs. Above the phase transition pressure, the axial compressibilities of CrAs present remarkable anisotropy. A schematic band model was used to address the anomalous compression behavior of CrAs. The present results shed light on the structural and related electronic responses to high pressure, which play a key role toward understanding the superconductivity of CrAs.

As a follow-up of our previous work on pressure-induced metallization of the 2H_{c}-MoS_{2} [Chi et al., Phys. Rev. Lett. 113, 036802 (2014)PRLTAO0031-900710.1103/PhysRevLett.113.036802], here we extend pressure beyond the megabar range to seek after superconductivity via electrical transport measurements. We found that superconductivity emerges in the 2H_{a}-MoS_{2} with an onset critical temperature T_{c} of ca. 3 K at ca. 90 GPa. Upon further increasing the pressure, T_{c} is rapidly enhanced beyond 10 K and stabilized at ca. 12 K over a wide pressure range up to 220 GPa. Synchrotron x-ray diffraction measurements evidenced no further structural phase transition, decomposition, and amorphization up to 155 GPa, implying an intrinsic superconductivity in the 2H_{a}-MoS_{2}. DFT calculations suggest that the emergence of pressure-induced superconductivity is intimately linked to the emergence of a new flat Fermi pocket in the electronic structure. Our finding represents an alternative strategy for achieving superconductivity in 2H-MoS_{2} in addition to chemical intercalation and electrostatic gating.

The influence of external pressure on the structural properties of manganese monophosphides (MnP) at room temperature has been studied using in situ angle dispersive synchrotron x-ray powder diffraction (AD-XRD) with a diamond anvil cell. The crystal structure of MnP is stable between 0 to 15 GPa. However, the compressibility of b-axis is much larger than those of a- and c-axes. From this result we suggested that the occurrence of superconductivity in MnP was induced by suppression of the long-range antiferromagnetically ordered state rather than a structural phase transition. Furthermore, the present experimental results show that the Pnma phase of MnP undergoes a pressure-induced structural phase transition at ~15.0 GPa. This finding lighted up-to-date understanding of the common prototype B31 structure (Strukturbericht Designation: B31) in transition metal monophosphides. No additional structural phase transition was observed up to 35.1 GPa (Run 1) and 40.2 GPa (Run 2) from the present AD-XRD results. With an extensive crystal structure searching and ab initio calculations, we predict that MnP underwent two pressure-induced structural phase transitions of Pnma → P213 and P213 → Pm-3m (CsCl-type) at 55.0 and 92.0 GPa, respectively. The structural stability and the electronic structures of manganese monophosphides under high pressure are also briefly discussed.

Indium selenide (In2Se3) could be used as the phase-change random access memory device and thermoelectric material. The high-pressure investigations are important to the applications on In2Se3 and other A2B3-type materials. In this study, we performed the in situ angle-dispersive X-ray diffraction and Raman spectra experiments and the first-principle calculations on In2Se3 under high pressure, and observed a series of structure phase transitions from experiments and metallized phenomena from calculations. In2Se3 transforms from the original rhombohedral structure (phase I) to a distorted monoclinic structure (phase II) and further to a Bi2Te3-type structure (phase III) at about 0.81 and 5.02 GPa, respectively. And then, phase III′ of In2Se3 adopts a similar structure with phase III from about 20.6 GPa. At pressures above about 32.1 GPa, In2Se3 starts to crystallize into a defective Th3P4-type structure (phase IV). According to the first-principle calculations, the structural transitions in the compression...

Activated carbon was treated at 5 GPa up to 1600 °C, and the structural evolution in the graphitization process was investigated. The graphitization temperature is equal to 1200 °C at 5 GPa, reflected by X-ray diffraction (XRD) patterns. Honeycomb-like structures in micron scale come into being in the high-pressure sintering temperature range of 1000−1100 °C and slice-like structures appear after graphitization. The existence of D and D’ lines in the Raman spectra for the graphitized-activated carbon indicates that there are still some disordered structures. The continuous occurrence of variable-range hopping, the approximately linear ρ–T relationship, and semimetal conduction mechanism accords with the graphitization process.

Raman spectroscopy and angle dispersive X-ray diffraction (XRD) experiments of bismuth selenide (Bi2Se3) have been carried out to pressures of 35.6 and 81.2 GPa, respectively, to explore its pressure-induced phase transformation. The experiments indicate that a progressive structural evolution occurs from an ambient rhombohedra phase (Space group (SG): R-3m) to monoclinic phase (SG: C2/m) and eventually to a high pressure body-centered tetragonal phase (SG: I4/mmm). Evidenced by our XRD data up to 81.2 GPa, the Bi2Se3 crystallizes into body-centered tetragonal structures rather than the recently reported disordered body-centered cubic (BCC) phase. Furthermore, first principles theoretical calculations favor the viewpoint that the I4/mmm phase Bi2Se3 can be stabilized under high pressure (>30 GPa). Remarkably, the Raman spectra of Bi2Se3 from this work (two independent runs) are still Raman active up to ~35 GPa. It is worthy to note that the disordered BCC phase at 27.8 GPa is not observed here. The remarkable difference in atomic radii of Bi and Se in Bi2Se3 may explain why Bi2Se3 shows different structural behavior than isocompounds Bi2Te3 and Sb2Te3.

Silver nanocluster doped ZnO thin films were fabricated on fused quartz substrates at different temperatures by pulsed laser deposition (PLD) using a silver-ZnO mosaic target. X-ray diffraction (XRD) measurements showed that ZnO and doped silver nanoclusters crystallized with preferred c-axis orientation. Scanning electron microscopic (SEM) images of the sample fabricated at 450 degrees C and the X-ray photoelectron spectroscopy (XPS) showed the radius of the silver clusters to be about 3-16 nm. Under 266 nm laser excitation, the photoluminescence (PL) spectra exhibited a peak at 414-420 nm for silver nanocluster doped ZnO thin films deposited at different temperatures. Through the investigation of the energy level of the defects in ZnO thin films, the energy levels of the zinc vacancy (VznEVzn = 3.031eV) and the interstitial zinc atom (Zn-i, E-Zn, = 2.95 eV) were found to be consistent with the peak wavelengths of 414 and 420 run. We suggest that this violet emission originates from an electronic transition between the interstitial-zinc level and the valence band, or between the bottom of the conduction band and the V(Zn)level. (c) 2005 Elsevier B.V. All rights reserved.

Phase transition of solid-state materials is a fundamental research topic in condensed matter physics, materials science and geophysics. It has been well accepted and widely proven that isostructural compounds containing different cations undergo same pressure-induced phase transitions but at progressively lower pressures as the cation radii increases. However, we discovered that this conventional law reverses in the structural transitions in 122-type iron-based superconductors. In this report, a combined low temperature and high pressure X-ray diffraction (XRD) measurement has identified the phase transition curves among the tetragonal (T), orthorhombic (O) and the collapsed-tetragonal (cT) phases in the structural phase diagram of the iron-based superconductor AFe2As2 (A = Ca, Sr, Eu, and Ba). The cation radii dependence of the phase transition pressure (T → cT) shows an opposite trend in which the compounds with larger ambient radii cations have a higher transition pressure.

Here, we report comprehensive studies on the high-pressure structural and electrical transport properties of the layered transition metal chalcogenide (Cr2S3) up to 36.3 GPa. A structural phase transition was observed in the rhombohedral Cr2S3 near 16.5 GPa by the synchrotron angle dispersive X-ray diffraction measurement using a diamond anvil cell. Through in situ resistance measurement, the electric resistance value was detected to decrease by an order of three over the pressure range of 7–15 GPa coincided with the structural phase transition. Measurements on the temperature dependence of resistivity indicate that it is a semiconductor-to-metal transition in nature. The results were also confirmed by the electronic energy band calculations. Above results may shed a light on optimizing the performance of Cr2S3 based applications under extreme conditions.

Cu{sub 3}N band structures and phonon dispersion curves under pressure are calculated using first-principles density functional theory and density functional perturbation theory with the local density approximation by the plane-wave pseudopotential method. The band structures are similar to other full-potential calculations. The indirect band gap is about 0.13 eV and decreases with increasing pressure. Simultaneous softening of the M{sub 3} and R{sub 25} zone boundary phonon modes was found and the possible associated successive structural phase transitions were discussed. The mode Grueneisen parameters for optic modes were obtained and the frequency versus pressure relationship was well fitted to second-order polynomials. The quadric relationship between the soft-mode frequency and pressure was also well reproduced for the M{sub 3} and R{sub 25} soft modes. The large difference of the soft-mode-driven transition pressures for the first high-pressure phases of ReO{sub 3} and Cu{sub 3}N were also discussed.

The phase transition, amorphization, and crystallization behaviors of the topological insulator bismuth selenide (Bi2Se3) were discovered by performing in situ high-pressure angle-dispersive x-ray diffraction experiments during an increasing, decreasing, and recycling pressure process. In the compression process, Bi2Se3 transforms from the original rhombohedral structure (phase I(A)) to a monoclinic structure (phase II) at about 10.4 GPa, and further to a body-centered tetragonal structure (phase III) at about 24.5 GPa. When releasing pressure to ambient conditions after the complete transformation from phase II to III, Bi2Se3 becomes an amorphous solid (AM). In the relaxation process from this amorphous state, Bi2Se3 starts crystallizing into an orthorhombic structure (phase I(B)) about five hours after releasing the pressure to ambient. A review of the pressure-induced phase transition behaviors of A2B3-type materials composed from the V and VI group elements is presented.