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CuAl2-type transition-metal (Tr) zirconides are superconductor family, and the Tr-site element substitution largely modifies its transition temperature (Tc). Here, we synthesized polycrystalline samples of Fe1-xNixZr2 by arc melting. From magnetic susceptibility measurements, bulk superconductivity was observed for 0.4 < x < 0.8, and the highest Tc of 2.8 K was observed for x = 0.6. Specific heat measurements were also performed, bulk superconductivity was observed for 0.4 < x < 0.8, and the highest Tc of 2.6 K was observed for x = 0.6. The obtained superconductivity phase diagram exhibits dome-shaped trend, which is similar to unconventional superconductors, where magnetic fluctuations are essential for superconductivity. In addition, from the c/a lattice constant ratio analysis, we show the possible relationship between the suppression of bulk superconductivity in the Ni-rich compositions and a collapsed tetragonal transition., Comment: 16 pages, 8 figures, SI

As thermoelectric generators can convert waste heat into electricity, they play an important role in energy harvesting. The metal chalcogenide AgBiSe2 is one of the high-performance thermoelectric materials with low lattice thermal conductivity (klat), but it exhibits temperature-dependent crystal structural transitions from hexagonal to rhombohedral, and finally a cubic phase as the temperature rises. The high figure-of-merit ZT is obtained only for the high-temperature cubic phase. In this study, we utilized the high-entropy-alloy (HEA) concept for AgBiSe2 to stabilize the cubic phase throughout the entire temperature range with enhanced thermoelectric performance. We synthesized high-entropy-type AgBiSe2-2xSxTex bulk polycrystals and realized the stabilization of the cubic phase from room temperature to 800 K for x > 0.6. The ultra-low klat at of 0.30 Wm^-1K^-1 and the high peak ZT 0.9 at around 750 K were realized for cubic AgBiSe2-2xSxTex without carrier tuning. In addition, the average ZT value of x = 0.6 and 0.7 for the temperature range of 360-750 K increased to 0.38 and 0.40, respectively, which are comparable to the highest previously reported values., Comment: 44 pages, 8 figures

We report the first observation of bulk superconductivity of a ${\eta}$-carbide-type oxide Zr$_{4}$Pd$_{2}$O. The crystal structure and the superconducting properties were studied through synchrotron X-ray diffraction, magnetization, electrical resistivity, and specific heat measurement. The superconducting transition was observed at $T_{\mathrm{c}}$ = 2.73 K. Our measurement revealed that the ${\eta}$-carbide-type oxide superconductor Zr$_{4}$Pd$_{2}$O shows an enhanced upper critical field ${\mu_{\mathrm{0}}H_{\mathrm{c2}}\mathrm{(0)}}$ = 6.72 T, which violates the Pauli-Clogston limit ${\mu_{\mathrm{0}}H_{\mathrm{P}}}$ = 5.29 T. On the other hand, we found that the enhanced upper critical field is absent in a Rh analogue Zr$_{4}$Rh$_{2}$O. The large ${\mu_{\mathrm{0}}H_{\mathrm{c2}}\mathrm{(0)}}$ of Zr$_{4}$Pd$_{2}$O would be raised from strong spin-orbit coupling with Pd-4$d$ electrons. The discovery of new superconducting properties for Zr$_{4}$Pd$_{2}$O would shed light on the further development of ${\eta}$-carbide-type oxide superconductors., Comment: 12 pages, 4 figures, 3 tables

We investigated the temperature evolution of crystal structure of orthorhombic CoZr3, which is a superconductor with a transition temperature of 4.3 K, by synchrotron and laboratory (CuK{\alpha}) X-ray diffraction. Uniaxial negative thermal expansion along the c-axis, which is similar to that observed in tetragonal CoZr2, has been observed at a wide temperature range of T = 90-800 K in CoZr3, while a-and b-axis exhibit positive thermal expansion., Comment: 9 pages, 3 figures, supplemental materials

The motivation of this work is our recent observation of the robustness of superconductivity in a High-entropy (HE) superconductor Ag0.2In0.2Sn0.2Pb0.2Bi0.2Te (CsCl-type) to external pressure. The superconducting transition temperature (Tc) of Ag0.2In0.2Sn0.2Pb0.2Bi0.2Te is almost constant with pressure, described as robustness of superconductivity to pressure, whereas the PbTe with zero configurational entropy of mixing exhibits a clear decrease in Tc with pressure. Here, we investigated the atomic displacement parameters (Uiso), the atomic-vibration characteristics, and the electronic states of metal tellurides (MTe) with various configurational entropy of mixing (DSmix) at the M site. The Uiso for the M site is clearly increased by M-site alloying with DSmix > 1.1R, which is the evidence of local disorder introduced by the increase in DSmix via the solution of three or more M elements. The revealed vibrational density of states (DOS) shows a remarkable broadening with DSmix > 1.1R, which indicates glassy characteristics of atomic vibration in HE MTe with a NaCl-type structure (low-pressure phase). On the electronic states of the CsCl-type (high-pressure) phases, where the robustness of Tc is observed, blurry electronic band structure appears with increasing DSmix, which indicates the evolution of blurry (glassy) electronic states in HE MTe with the CsCl-type structure. The estimated electronic DOS at Fermi energy cannot explain the changes in Tc for HE MTe when assuming conventional electron-phonon superconductivity, but the conventional explanation seems to work for PbTe. Therefore, the pairing mechanisms in MTe with DSmix > 1.1R are affected by glassy phonon and/or blurry electronic states in MTe, and the robustness of superconductivity would be originating from unique electron-phonon coupling., Comment: 25 pages, 5 figures, Supplemental Information

The superconducting properties and structural parameters, including the Gr\"uneisen parameter ({\gamma}G), of the BiCh2-based (Ch: S, Se) layered superconductor LaO0.5F0.5BiS2-xSex were investigated. The superconducting transition temperature (Tc) increased with increasing Se concentration (x), and bulk superconductivity was induced by Se substitution. {\gamma}G exhibited a larger value when x greater than 0.4, where the superconducting properties were improved. These results suggest that the increase of lattice anharmonicity is preferable for superconductivity in LaO0.5F0.5BiS2-xSex. The discussion includes data for related superconductors REO0.5F0.5BiS2 (RE = Pr, Nd), where a positive correlation between {\gamma}G and Tc is revealed for Se-poor samples. In addition, specific heat analyses suggest the presence of a low-energy optical phonon mode for LaO0.5F0.5BiS2-xSex., Comment: 23 pages, 7 figures, supplemental data

We studied Gr\"uneisen parameter ({\gamma}G) to investigate lattice anharmonicity in a layered BiS2-based superconductor system REO1-xFxBiS2 (RE = La, Ce, Pr, Nd), where in-plane chemical pressure was tuned by substituting the RE elements. With increasing in-plane chemical pressure, bulk modulus remarkably increases, and a high {\gamma}G is observed for RE = Nd. The dependence of {\gamma}G on in-plane chemical pressure exhibits a good correlation with Tc, and a higher Tc is achieved when {\gamma}G is large for RE = Nd. In addition, {\gamma}G shows a slight decrease by a decrease of F concentration (x) in REO1-xFxBiS2. Our results show that the anharmonic vibration of Bi along the c-axis is present in REO1-xFxBiS2, and the enhancement of the anharmonicity is positively linked to superconducting Tc and pairing mechanisms., Comment: 15 pages, 5 figures

Compositionally complex alloys (CCAs) are a new category of high-entropy materials containing more than two high-entropy phases in an alloy sample. We applied the concept of CCA to a A15-type compound superconductor V3X where X site is occupied by Al, Si, Ga, Ge, and Sn. The V3X sample shows bulk superconductivity with a transition temperature (Tc) of 6.4 K, which is close to the Tc of V3Ge. The upper critical field (Bc2(0)) of V3X estimated from magnetic susceptibility is 8.8 T, which is ~50% higher than that of V3Ge (Bc2(0) = 5.8 T). The presence of at least five different A15 phases with high configurational entropy of mixing were revealed. We consider that the examined V3X sample is an example system of CCA-type superconducting intermetallic compound., Comment: 20 pages, 5 figures + 1 supplemental figure

Solid-state synthesis from powder precursors is the primary processing route to advanced multicomponent ceramic materials. Designing ceramic synthesis routes is usually a laborious, trial-and-error process, as heterogeneous mixtures of powder precursors often evolve through a complicated series of reaction intermediates. Here, we show that phase evolution from multiple precursors can be modeled as a sequence of pairwise interfacial reactions, with thermodynamic driving forces that can be efficiently calculated using ab initio methods. Using the synthesis of the classic high-temperature superconductor YBa$_2$Cu$_3$O$_{6+x}$ (YBCO) as a representative system, we rationalize how replacing the common BaCO$_3$ precursor with BaO$_2$ redirects phase evolution through a kinetically-facile pathway. Our model is validated from in situ X-ray diffraction and in situ microscopy observations, which show rapid YBCO formation from BaO$_2$ in only 30 minutes. By combining thermodynamic modeling with in situ characterization, we introduce a new computable framework to interpret and ultimately design synthesis pathways to complex ceramic materials.

Crystallography and dielectric properties in Dion-Jacobson layered perovskites, CsNdNb$_2$O$_7$ and RbNdNb$_2$O$_7$, have been examined in dense polycrystalline samples, and polarization hysteresis loops that substantiate ferroelectricity have been observed at room temperature. The theoretical mechanism for the spontaneous polarization, "hybrid improper ferroelectric mechanism,'' induced by a combination of two types of non-polar octahedral rotations, is confirmed in these two phases. Our samples show remanent polarizations of 2-3 $\mu$C/cm$^2$, which are much larger than those obtained in polycrystalline samples with the hybrid improper ferroelectricity reported so far. A dielectric constant in CsNdNb$_2$O$_7$ exhibits an anomaly at 625 K, corresponding to the ferroelectric transition, as previously revealed by x-ray and neutron diffractometry. No dielectric anomaly is observed for RbNdNb$_2$O$_7$ throughout the temperature range studied here ($\leq$ 773 K), which is consistent with the previous diffractometry showing the persistence of polar $I2cm$ symmetry up to 790 K., Comment: 7 pages, 3 figures, accepted for publication by JJAP

Polycrystalline samples of Sr1-xRExFBiS2 (RE: La, Ce, Pr, Nd, and Sm) were synthesized via the solid-state reaction and characterized using synchrotron X-ray diffraction. Although all the Sr0.5RE0.5FBiS2 samples exhibited superconductivity at transition temperatures (Tc) within the range of 2.1-2.7 K under ambient pressure, the estimated superconducting volume fraction was small. This indicated the non-bulk nature of superconductivity in these samples under ambient pressure. A dramatic evolution of the bulk superconducting phases was achieved on applying an external hydrostatic pressure. Near pressures below 1 GPa, bulk superconductivity was induced with a Tc of 2.5-2.8 K, which is termed as the low-P phase. Moreover, the high-P phase (Tc = 10.0-10.8 K) featuring bulk characteristics was observed at higher pressures. Pressure-Tc phase diagrams indicated that the critical pressure for the emergence of the high-P phase tends to increase with decreasing ionic radius of the doped RE ions. According to the high-pressure X-ray diffraction measurements of Sr0.5La0.5FBiS2, a structural phase transition from tetragonal to monoclinic also occurred at approximately 1.1 GPa. Thus, this phase transition indicates a pressure-induced superconducting-superconducting transition similar to the transition in LaO0.5F0.5BiS2. Bulk superconducting phases in Sr0.5RE0.5FBiS2 induced by the external hydrostatic pressure effect are expected to be useful for evaluating the mechanisms of superconductivity in BiCh2-based superconductors., Comment: 14 pages, 7 figures

We have investigated low-temperature crystal structure of BiCh2-based compounds LaO1-xFxBiSSe (x = 0, 0.01, 0.02, 0.03, and 0.5), in which anomalous two-fold-symmetric in-plane anisotropy of superconducting states has been observed for x = 0.5. From synchrotron X-ray diffraction experiments, a structural transition from tetragonal to monoclinic was observed for x = 0 and 0.01 at 340 and 240 K, respectively. For x = 0.03, a structural transition and broadening of the diffraction peak were not observed down to 100 K. These facts suggest that the structural transition could be suppressed by 3% F substitution in LaO1-xFxBiSSe. Furthermore, the crystal structure for x = 0.5 at 4 K was examined by low-temperature (laboratory) X-ray diffraction, which confirmed that the tetragonal structure is maintained at 4 K for x = 0.5. Our results suggest that the two-fold-symmetric in-plane anisotropy of superconducting states observed for LaO0.5F0.5BiSSe was not originated from structural symmetry lowering., Comment: 15 pages, 5 figures + 3 supplemental figures

We report the synthesis and thermoelectric transport properties of As-doped layered pnictogen oxyselenides NdO0.8F0.2Sb1-xAsxSe2 (x < 0.7), which are predicted to show high-performance thermoelectric properties based on first-principles calculation. The crystal structure of these compounds belongs to the tetragonal P4/nmm space group (No. 129) at room temperature. The lattice parameter c decreases with increasing x, while a remains almost unchanged among the samples. Despite isovalent substitution of As for Sb, electrical resistivity significantly rises with increasing x. Very low thermal conductivity of less than 0.8 W/mK is observed at temperatures between 300 and 673 K for all the examined samples. For As-doped samples, the thermal conductivity further decreases above 600 K. Temperature-dependent synchrotron X-ray diffraction indicates that an anomaly also occurs in the c-axis length at around 600 K, which may relate to the thermal transport properties., Comment: 21 pages, 9 figures

We report the Se substitution effects on the crystal structure, superconducting properties, and valence states of self-doped BiCh2-based compound CeOBiS2-xSex. Polycrystalline CeOBiS2-xSex samples with x = 0-1.0 were synthesized. For x = 0.4 and 0.6, bulk superconducting transitions with a large shielding volume fraction were observed in magnetic susceptibility measurements; the highest transition temperature (Tc) was 3.0 K for x = 0.6. A superconductivity phase diagram of CeOBiS2-xSex was established based on Tc estimated from the electrical resistivity and magnetization measurements. The emergence of superconductivity in CeOBiS2-xSex was explained with two essential parameters of in-plane chemical pressure and carrier concentration, which systematically changed with increasing Se concentration., Comment: 15 pages, 8 figures

Superconducting transition temperature (Tc) reported in SnAs-based layered compound NaSn$_2$As$_2$ varies from 1.2 to 1.6 K, implying that its superconductivity is critically sensitive to non-stoichiometry. Here, we demonstrate that Na-doping on the Sn site (Na$_{1+x}$Sn$_{2-x}$As$_2$) is effective in enhancing superconductivity, leading to Tc = 2.1 K for x = 0.4. First-principles calculation indicates that such a doping, or Na$_{\rm Sn}$ antisite defects, is energetically favored over other cation vacancies. Our results pave the way for increasing Tc of layered tin pnictide superconductors., Comment: 21 pages, 9 figures, 1 Table

Polycrystalline samples of layered pnictogen diselenide NdO0.8F0.2Sb1-xBixSe2 (x = 0 to 0.8) were successfully synthesized by solid-state reactions. Electrical resistivity in the synthesized samples was systematically decreased with an increase in Bi content x. Crystal structure analysis using synchrotron X-ray diffraction suggests that insulator to metal transition upon Bi doping correlates with anomalous change in c-axis length and/or corrugation in conducting layer. The emergence of superconductivity under high pressure is demonstrated using diamond anvil cell (DAC) with boron-doped diamond electrodes, for x = 0.3 and 0.7 as the representative samples. For Sb-rich one (x = 0.3), we observed a superconducting transition with Tconset = 5.3 K at 50 GPa, which is the first-ever report of the superconductivity in layered SbCh2-based (Ch: chalcogen) compounds. The Tconset of x = 0.3 increased with increasing pressure and reached 7.9 K at 70.8 GPa, followed by the gradual decrease in Tc up to 90 GPa. For Bi-rich one (x = 0.7), a superconducting transition with Tconset = 5.9 K was observed at 43.5 GPa, which is the almost comparable to that of x = 0.3; besides, upper critical field (Hc2) is evaluated to be ~10 T for x = 0.7, which is higher than that of x = 0.3 (Hc2 = 6.7 T at 50 GPa).

Although SbSe2-based layered compounds have been predicted to be high-performance thermoelectric materials and topological materials, most of these compounds obtained experimentally have been insulators so far. Here, we present the effect of Bi substitution on the thermoelectric properties of SbSe2-based layered compounds NdO0.8F0.2Sb1-xBixSe2 (x = 0-0.4). The room temperature electrical resistivity is decreased to 8.0 * 10^-5 ohmm for x = 0.4. The electrical power factor is calculated to be 1.4 * 10^-4 W/mK^2 at 660 K, which is in reasonable agreement with combined Jonker and Ioffe analysis. The room-temperature lattice thermal conductivity of less than 1 W/mK is almost independent of x, in contrast to the point-defect scattering model for conventional alloys. The present work provides an avenue for exploring SbSe2-based insulating and BiSe2-based conducting systems., Comment: 19 pages, 8 figures, 1 table. arXiv admin note: text overlap with arXiv:1805.07850

To investigate the interlayer interaction in the recently synthesized high-entropy-alloy-type (HEA-type) REO0.5F0.5BiS2 superconductors (RE: rare earth), we have systematically synthesized samples with close lattice parameters and different mixing entropy (DSmix) for the RE site. The crystal structure was investigated using synchrotron X-ray diffraction and Rietveld refinement. For the examined samples with different DSmix, the increase in DSmix does not largely affect the bond lengths and the bond angle of the BiS2 conducting layer but clearly suppresses the in-plane disorder at the in-plane S1 site, which is the parameter essential for the emergence of bulk superconductivity in the REO0.5F0.5BiS2 system. Bulk nature of superconductivity is enhanced by the increase in DSmix for the present samples. The results of this work clearly show that the increase in mixing entropy at the blocking layer can positively affect the emergence of bulk superconductivity in the conducting layer, which is the evidence of the interaction between the high entropy states of the blocking layers and the physical properties of the conducting layers., Comment: 13 pages, 6 figures, 1 table revised version for SSC

Inspired by the recent first-principles calculations showing the high thermoelectric performance of layered pnictogen chalcogenides, we experimentally characterise the crystal structure and high-temperature transport properties of the layered antimony selenides REOSbSe2 (RE = La, Ce). The crystal structure of REOSbSe2 was the tetragonal P4/nmm space group, consisting of alternate stacks of SbSe2 and REO layers. These two compounds were n-type semiconductors. The optical band gaps of LaOSbSe2 and CeOSbSe2 were evaluated to be 1.0 and 0.6 eV, respectively. The room-temperature thermal conductivity was 1.5 Wm-1K-1 for RE = La and 0.8 Wm-1K-1 for RE = Ce. These relatively low thermal conductivities were comparable to those of isostructural layered bismuth chalcogenides. We substituted O2- with F- ions to introduce electrons as charged carriers to optimize the thermoelectric performance, but increasing the electrical conductivity was still challenging., Comment: to be published in J. Phys. Soc. Jpn

Superconductors with a van der Waals (vdW) structure have attracted a considerable interest because of the possibility for truly two-dimensional (2D) superconducting systems. We recently reported NaSn2As2 as a novel vdW-type superconductor with transition temperature (Tc) of 1.3 K. Herein, we present the crystal structure and superconductivity of new material Na1-xSn2P2 with Tc = 2.0 K. Its crystal structure consists of two layers of a buckled honeycomb network of SnP, bound by the vdW forces and separated by Na ions, as similar to that of NaSn2As2. Amount of Na deficiency (x) was estimated to be 0.074(18) using synchrotron X-ray diffraction. Bulk nature of superconductivity was confirmed by the measurements of electrical resistivity, magnetic susceptibility, and specific heat. First-principles calculation using density functional theory shows that Na1-xSn2P2 and NaSn2As2 have comparable electronic structure, suggesting higher Tc of Na1-xSn2P2 is resulted from increased density of states at the Fermi level due to Na deficiency. Because there are various structural analogues with tin-pnictide (SnPn) conducting layers, our results indicate that SnPn-based layered compounds can be categorized into a novel family of vdW-type superconductors, providing a new platform for studies on physics and chemistry of low-dimensional superconductors., Comment: 15 pages, 5 figures, to be published in Scientific Reports

In order to understand the mechanisms behind the emergence of superconductivity by the chemical pressure effect in REO0.5F0.5BiS2 (RE = La, Ce, Pr, and Nd), where bulk superconductivity is induced by the substitutions with a smaller-radius RE, we performed synchrotron powder X-ray diffraction, and analyzed the crystal structure and anisotropic displacement parameters. With the decrease of the RE3+ ionic radius, the in-plane disorder of the S1 sites significantly decreased, very similar to the trend observed in the Se-substituted systems: LaO0.5F0.5BiS2-xSex and Eu0.5La0.5FBiS2-xSex. Therefore, the emergence of bulk superconductivity upon the suppression of the in-plane disorder at the chalcogen sites is a universal scenario for the BiCh2-based superconductors. In addition, we indicated that the amplitude of vibration along the c-axis of the in-plane chalcogen sites may be related to the Tc in the BiCh2-based superconductors.

We have synthesized a new layered oxychalcogenide La2O2Bi3AgS6. From synchrotron X-ray diffraction and Rietveld refinement, the crystal structure of La2O2Bi3AgS6 was refined using a model of the P4/nmm space group with a = 4.0644(1) {\AA} and c = 19.412(1) {\AA}, which is similar to the related compound LaOBiPbS3, while the interlayer bonds (M2-S1 bonds) are apparently shorter in La2O2Bi3AgS6. The tunneling electron microscopy (TEM) image confirmed the lattice constant derived from Rietveld refinement (c ~ 20 {\AA}). The electrical resistivity and Seebeck coefficient suggested that the electronic states of La2O2Bi3AgS6 are more metallic than those of LaOBiS2 and LaOBiPbS3. The insertion of a rock-salt-type chalcogenide into the van der Waals gap of BiS2-based layered compounds, such as LaOBiS2, will be a useful strategy for designing new layered functional materials in the layered chalcogenide family., Comment: 11 pages, 1 table, 5 figures

In this work, we address the issue of peaking of piezoelectric response at a particular composition in the morphotropic phase boundary (MPB) region of (Pb0.940Sr0.06)(ZrxTi1-x)O3 (PSZT) piezoelectric ceramics. We present results of synchrotron x-ray powder diffraction, dielectric, piezoelectric and sound velocity studies to critically examine the applicability of various models for the peaking of physical properties. It is shown that the models based on the concepts of phase coexistence, polarization rotation due to monoclinic structure, tricritical point and temperature dependent softening of elastic modulus may enhance the piezoelectric response in the MPB region in general but cannot explain its peaking at a specific composition. Our results reveal that the high value of piezoelectric response for the MPB compositions in PSZT at x=0.530 is due to the softening of the elastic modulus as a function of composition. The softening of elastic modulus facilitates the generation of large piezoelectric strain and polarization on approaching the MPB composition of x=0.530. This new finding based on the softening of elastic modulus may pave the way forward for discovering/designing new lead-free environmentally friendly piezoelectric materials and revolutionize the field of piezoelectric ceramics., Comment: 37 Pages

We have investigated the crystal structure and physical properties of LaO1-xFxBiSSe to reveal the intrinsic superconductivity phase diagram of the BiCh2-based layered compound family. From synchrotron X-ray diffraction and Rietveld refinements with anisotropic displacement parameters, we clearly found that the in-plane disorder in the BiSSe layer was fully suppressed for all x. In LaO1-xFxBiSSe, metallic conductivity and superconductivity are suddenly induced by electron doping even at x = 0.05 and 0.1 with a monoclinic structure. In addition, x (F concentration) dependence of the transition temperature (Tc) for x = 0.2-0.5 with a tetragonal structure shows an anomalously flat phase diagram. With these experimental facts, we have proposed the intrinsic phase diagram of the ideal BiCh2-based superconductors with less in-plane disorder., Comment: 21 pages, 6 figures, 3 supplemental materials

We have synthesized AgSn1-xBixSe2 polycrystalline samples to investigate the effect of partial substitution of mixed-valence Sn by Bi3+ to the superconductivity of the valence-skip superconductor AgSnSe2. The Bi-substituted AgSn1-xBixSe2 were obtained up to x = 0.2, but an insulating phase Ag2SnBi2Se5 with a NaCl-type structure showed up above x = 0.3. The superconducting transition temperature increased from 4.5 K (x = 0) to 5.0 K (x = 0.1) by Bi substitution. The enhancement of superconductivity by the suppression of the valence-skip states of Sn suggests that the valence-skip states of Sn are not positively linked to the pairing mechanisms of superconductivity in the AgSnSe2 system., Comment: 18 pages, 9 figures and 2 tables including Supplemental Materials

Ferroelectricity in stuffed aluminate sodalites is demonstrated in the present study. The present results indicate that stuffed aluminate sodalites exhibit excellent performance as a pyroelectric energy harvester, suggesting that they exhibit great promise as a class of materials for highly efficient energy harvesting devices. (See manuscript for the full abstract)

The band gaps of isostructural Bi2OS2 and LaOBiS2 were examined using optical absorption and discussed with the band structures calculated based on the crystal structures determined using synchrotron X-ray diffraction. The Bi 6p and S 3p orbitals in the Bi-S plane were computationally predicted to constitute the bands near the Fermi level. The optical reflectance spectra of Bi2OS2 and LaOBiS2 showed optical band gaps of ca. 1.0 eV, which were close to the computationally calculated direct band gaps of ca. 0.8 eV. Our results show that Bi2OS2 and LaOBiS2 are semiconductors containing direct band gaps of 0.8-1.0 eV, and they are suggested to be candidates for optoelectronic materials in the near-infrared region without highly toxic elements., Comment: in Solid State Communications (2015)

BiCh2-based superconductors (Ch: S, Se) are a new series of layered superconductor. However, mechanisms for the emergence of superconductivity in BiCh2-based superconductors have not been clarified. In this study, we have investigated crystal structure of two series of optimally-doped BiCh2-based superconductors, Ce1-xNdxO0.5F0.5BiS2 and LaO0.5F0.5Bi(S1-ySey)2, using powder synchrotron x-ray diffraction in order to reveal the relationship between crystal structure and superconducting properties of the BiCh2-based family. We have found that an enhancement of in-plane chemical pressure would commonly induce bulk superconductivity in both systems. Furthermore, we have revealed that superconducting transition temperature for REO0.5F0.5BiCh2 superconductors could universally be determined by degree of in-plane chemical pressure., Comment: 18 pages, 4 figures, two supplementary information (Figure S1 and Table S1)

The antiferrodistortive (AFD) phase transition for a pseudotetragonal composition of Pb(Zr0.530Ti0.470)O3 (PZT) doped with 6% Sr has been investigated using sound velocity (4 to 320K), high resolution synchrotron X-ray powder diffraction (100 to 800K) and high resolution as well as high flux neutron powder diffraction measurements (4K) to settle the existing controversies about the true ground state of PZT in the morphotropic phase boundary (MPB) region. The multiplet character of the neutron diffraction profiles of (3/2 1/2 1/2)pc (pseudocubic or pc indices) and (3/2 3/2 1/2)pc superlattice peaks, appearing below the AFD transition temperature, rules out the rhombohedral R3c space group. The true ground state is confirmed to be monoclinic in the Cc space group in agreement with the predictions of the first principles calculations and earlier findings for pure PZT in the MPB region. 6% Sr2+ substitution and the use of high wavelength ({\lambda}=2.44{\AA}) neutrons have played key role in settling the existing controversies about the true ground state of PZT in the MPB region., Comment: This paper was published in Phys. Rev. B on 24 October 2011

The controversies about the structure of the true ground state of pseudorhombohedral compositions of Pb(ZrxTi1-x)O3 (PZT) are addressed using a 6% Sr2+ substituted sample with x=0.550. Sound velocity measurements reveal a phase transition at Tc~279K. The temperature dependence of FWHM of (h00)pc peaks and the unit cell volume also show anomalies around 279K even though there is no indication of any change of space group in the synchrotron X-ray powder diffraction (SXRD) patterns. The neutron powder diffraction patterns reveal appearance of superlattice peaks below Tc~279K confirming the existence of an antiferrodistortive phase transition. The Rietveld analysis of the room temperature and low temperature SXRD data below Tc shows that the structure corresponds to single monoclinic phase in the Cm space group while the analysis of neutron powder diffraction data reveals that the structure of the ground state phase below Tc corresponds to the Cc space group. Our analysis shows that the structural models for the ground state phase based on R3c space group with or without the coexistence of the room temperature monoclinic phase in the Cm space group can be rejected., Comment: This paper was published in Phys. Rev. B on 30 November 2012

We present here results of high resolution synchrotron x-ray diffraction (SXRD) and dielectric studies in conjunction with Landau theory considerations on (Pb0.94Sr0.06)(ZrxTi1-x)O3 compositions in the vicinity of the morphotropic phase boundary (MPB) to find evidence for the flattening of the free energy surface at the MPB proposed in recent ab-initio studies on strongly piezoelectric ceramics. SXRD results reveal that the tetragonal and pseudorhombohedral monoclinic compositions with x=0.515 and 0.550 transform directly into the cubic paraelectric phase, whereas for 0.520

We investigate the magnetic field effect on the spin gap state in CeRu2Al10 by measuring the magnetization and electrical resistivity. We found that the magnetization curve for the magnetic field H//c shows a metamagnetic-like anomaly at H*~4 T below T_0=27 K, but no anomaly for H//a and H//b. A shoulder of the electrical resistivity at Ts~5 K for I//c is suppressed by applying a longitudinal magnetic field above 5 T. Many anomalies are also found in the magnetoresistance for Hkc below ~5 K. The obtained magnetic phase diagram consists of at least two or three phases below T_0. These results strongly indicate the existence of a fine structure at a low energy side in a spin gap state with the excitation energy of 8 meV recently observed in the inelastic neutron scattering experiments., Comment: 4 pages, 6 figures, to be submitted to JPSJ

We studied the transport properties of CeRu_2Al_10 single crystals. All the transport properties show largely anisotropic behaviors below T_0. Those along the a- and c-axes show similar behaviors, but are different from those along the b-axis. This suggests that the system could be viewed as a two-dimensional system. The results of the thermal conductivity and thermoelectric power could be explained by assuming the singlet ground state below T_0. However, the ground state is not simple but has some kind of structure within a spin gap., Comment: 4 pages, 5 figures

We investigate the thermal and transport properties of CexLa1-xRu2Al10 to clarify the origin of the recently discovered mysterious phase below T0=27 K in CeRu2Al10 where a large magnetic entropy is released, however, the existence of an internal magnetic field is ruled out by 27Al-NQR measurement. We find that T0 decreases with decreasing x and disappears at x~0.45. T0 of CeRu2Al10 is suppressed down to 26 K under H=14.5 T along the a-axis. These results clearly indicate that the transition has a magnetic origin and is ascribed to the interaction between Ce ions. Considering the results of specific heat, magnetic susceptibility, thermal expansion, and electrical resistivity and also 27Al NQR, we propose that the transition originates from the singlet pair formation between Ce ions. Although its properties in a Ce dilute region is basically understood by the impurity Kondo effect, CeRu2Al10 shows a Kondo-semiconductor-like behavior. The phase transition at T0 may be characterized as a new type of phase transition that appears during the crossover from the dilute Kondo to the Kondo semiconductor., Comment: 10 pages, 5 figures