Controlling inversion disorder in a stoichiometric spinel magnet.

In the study of frustrated quantum magnets, it is essential to be able to control the nature and degree of site disorder during the growth process, as many measurement techniques are incapable of distinguishing between site disorder and frustration-induced spin disorder. Pyrochlore-structured spinel oxides can serve as model systems of geometrically frustrated three-dimensional quantum magnets; however, the nature of the magnetism in one well-studied spinel, ZnFe2O4, remains unclear. Here, we demonstrate simultaneous control of both stoichiometry and inversion disorder in the growth of ZnFe2O4 single crystals, directly yielding a revised understanding of both the collective spin behavior and lattice symmetry. Crystals grown in the stoichiometric limit with minimal site inversion disorder contravene all the previously suggested exotic spin phases in ZnFe2O4. Furthermore, the structure is confirmed on the [Formula: see text] space group with broken inversion symmetry that induces antiferroelectricity. The effective tuning of magnetic behavior by site disorder in the presence of robust antiferroelectricity makes ZnFe2O4 of special interest to multiferroic devices.

Assessing the Novel Mixed Tutton Salts K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 for Thermochemical Heat Storage Applications: An Experimental-Theoretical Study.

In this paper, novel mixed Tutton salts with the chemical formulas K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 were synthesized and studied as compounds for thermochemical heat storage potential. The crystallographic structures of single crystals were determined by X-ray diffraction. Additionally, a comprehensive computational study, based on density functional theory (DFT) calculations and Hirshfeld surface analysis, was performed to calculate structural, electronic, and thermodynamic properties of the coordination complexes [MII(H2O)6]2+ (MII = Mn, Ni, and Cu), as well as to investigate intermolecular interactions and voids in the framework. The axial compressions relative to octahedral coordination geometry observed in the crystal structures were correlated and elucidated using DFT investigations regarding Jahn-Teller effects arising from complexes with different spin multiplicities. The spatial distributions of the frontier molecular orbital and spin densities, as well as energy gaps, provided further insights into the stability of these complexes. Thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques were also applied to identify the thermal stability and physicochemical properties of the mixed crystals. Values of dehydration enthalpy and storage energy density per volume were also estimated. The two mixed sulfate hydrates reported here have low dehydration temperatures and high energy densities. Both have promising thermal properties for residential heat storage systems, superior to the Tutton salts previously reported.

Single-Crystal Nanostructure Arrays Forming Epitaxially through Thermomechanical Nanomolding.

For nanostructures in advanced electronic and plasmonic systems, a single-crystal structure with controlled orientation is essential. However, the fabrication of such devices has remained challenging, as current nanofabrication methods often suffer from either polycrystalline growth or the difficulty of integrating single crystals with substrates in desired orientations and locations to create functional devices. Here we report a thermomechanical method for the controlled growth of single-crystal nanowire arrays, which enables the simultaneous synthesis, alignment, and patterning of nanowires. Within such diffusion-based thermomechanical nanomolding (TMNM), the substrate material diffuses into nanosized cavities under an applied pressure gradient at a molding temperature of ∼0.4 times the material's melting temperature. Vertically grown face-centered cubic (fcc) nanowires with the [110] direction in an epitaxial relationship with the (110) substrate are demonstrated. The ability to control the crystal structure through the substrate takes TMNM a major step further, potentially allowing all fcc and body-centered cubic (bcc) materials to be integrated as single crystals into devices.

Crystal Structures of AlCr2 and MoSi2 : Same Structure Type vs. Different Bonding Pattern.

In a joint effort utilizing modified sample preparation, microscopy, X-ray diffraction and micro-fabrication, it became possible to prepare single crystals of the "hidden" phase AlCr2 . High-resolution X-ray diffraction analysis is described in detail for two crystals with the similar overall composition, but different degree of disorder, which seems to be the main cause for the differing unit cell parameters. Chemical bonding analysis of AlCr2 in comparison to prototypical MoSi2 shows pronounced differences reflecting the interchange of main group element vs. transition metal as majority component.

Investigation of structural, optical and mechanical behaviour of pure and Cr doped L-asparagine monohydrate single crystals.

Pure and chromium (Cr) doped L-asparagine monohydrate (LAM) single crystals were grown by using evaporation controlled solution growth technique. XRD analysis confirmed the orthorhombic crystal system with space group P212121 of grown crystals. Cr-incorporation decreased the cell parameters and unit cell volume of the crystals. Intermolecular interactions were analysed through Hirshfeld and fingerprint studies. SEM analysis showed the appearance of pits on the smooth surface of pure crystal due to Cr-addition. UV-Vis analysis showed high transparency, low cut-off and direct band gap of 5.42 eV and 5.51 eV for pure and Cr doped crystals, respectively. Fundamental functional groups were identified by FTIR and Raman spectroscopy. The thermal stability and melting point of the crystals were investigated using TGA/DSC analysis. The dielectric constant for doped LAM was increased to 44 as compare to dielectric constant of pure crystal which was 32. Both crystals showed low dielectric loss, having values 0.04 and 0.006 for pure LAM and doped crystals, respectively. In Vickers microhardness test, Cr doping was found to change the nature of pure LAM crystal from 'soft' to 'hard' as Meyer's index changed from 2.48 to 1.24.

Electric-Field Manipulation of Magnetic Chirality in a Homo-Ferro-Rotational Helimagnet.

Ferro-rotational (FR) materials, renowned for their distinctive material functionalities, present challenges in the growth of homo-FR crystals (i.e., single FR domain). This study explores a cost-effective approach to growing homo-FR helimagnetic RbFe(SO4)2 (RFSO) crystals by lowering the crystal growth temperature below the TFR threshold using the high-pressure hydrothermal method. Through polarized neutron diffraction experiments, it is observed that nearly 86% of RFSO crystals consist of a homo-FR domain. Notably, RFSO displays remarkable stability in the FR phase, with an exceptionally high TFR of ≈573 K. Furthermore, RFSO exhibits a chiral helical magnetic structure with switchable ferroelectric polarization below 4 K. Importantly, external electric fields can induce a single magnetic domain state and manipulate its magnetic chirality. The findings suggest that the search for new FR magnets with outstanding material properties should consider magnetic sulfates as promising candidates.

Diamond for High-Power, High-Frequency, and Terahertz Plasma Wave Electronics.

High thermal conductivity and a high breakdown field make diamond a promising candidate for high-power and high-temperature semiconductor devices. Diamond also has a higher radiation hardness than silicon. Recent studies show that diamond has exceptionally large electron and hole momentum relaxation times, facilitating compact THz and sub-THz plasmonic sources and detectors working at room temperature and elevated temperatures. The plasmonic resonance quality factor in diamond TeraFETs could be larger than unity for the 240-600 GHz atmospheric window, which could make them viable for 6G communications applications. This paper reviews the potential and challenges of diamond technology, showing that diamond might augment silicon for high-power and high-frequency compact devices with special advantages for extreme environments and high-frequency applications.

Structural trends and itinerant magnetism of the new cage-structured compound HfMn2Zn20.

A new cage-structured compound-HfMn2Zn20-belonging to theAB2C20(A, B= transition or rare earth metals, andC= Al, Zn, or Cd) family of structures has been synthesized via the self-flux method. The new compound crystallizes in the space groupFd3¯mwith lattice parametera≈ 14.0543(2) Å (Z= 8) and exhibits non-stoichiometry due to Mn/Zn mixing on the Mn-site and an underoccupied Hf-site. The structure refines to Hf0.93Mn1.63Zn20.37and follows lattice size trends when compared to other HfM2Zn20(M= Fe, Co, and Ni) structures. The magnetic measurements show that this compound displays a modified Curie-Weiss behavior with a transition temperature around 22 K. The magnetization shows no saturation, a small magnetic moment, and near negligible hysteresis, all signs of itinerant magnetism. The Rhodes-Wohlfarth ratio and the spin fluctuation parameters ratio both confirm the itinerant nature of the magnetism in HfMn2Zn20.

Growth and characterizations of Ba2Ti2Fe2As4O single crystals.

Single crystals of a new iron-based superconductor Ba2Ti2Fe2As4O have been grown successfully via a Ba2As3-flux method in a sealed evacuated quartz tube. Bulk superconductivity with Tc ∼ 21.5 K was demonstrated in resistivity and magnetic susceptibility measurements after the as-grown crystals were annealed at 500 °C in vacuum for a week. X-ray diffraction patterns confirm that the annealed and the as-grown crystals possess the identical crystallographic structure of Ba2Ti2Fe2As4O. Energy-dispersive x-ray spectra indicate that partial Ti/Fe substitution exists in the [Fe2As2] layers and the annealing process redistributes the Ti within the Fe-plane. The ordered Fe-plane stabilized by annealing exhibits superconductivity with magnetic vortex pinned by Ti.

Single-Crystal Growth of P2-Type Layered Oxides with Increased Exposure of {010} Planes for High-Performance Sodium-Ion Batteries.

An increase in the size of single-crystal particles can effectively reduce the interfacial side reactions of layered oxides for sodium-ion batteries at high voltages but may result in sluggish Na+ transport. Herein, single-crystal Na0.66Ni0.26Zn0.07Mn0.67O2 with increased proportions of {010} planes is synthesized by adding low-cost NaCl as the molten salt. With the assistance of a NaCl molten salt, the median diameter (D50) of single-crystal Na0.66Ni0.26Zn0.07Mn0.67O2 increases to 10.46 µm relative to that of the comparison sample without NaCl (6.57 µm). Electrolyte decomposition on the surface of single-crystal Na0.66Ni0.26Zn0.07Mn0.67O2 is considerably suppressed, owing to a decrease in the specific surface area. Moreover, the increased exposure of {010} planes is favorable for improving the Na+ transport kinetics of single-crystal particles. Therefore, at 100 mA g-1, single-crystal Na0.66Ni0.26Zn0.07Mn0.67O2 exhibits a high-capacity retention of 96.6% after 100 cycles, which is considerably greater than that of the comparison sample (86.8%). Moreover, the rate performance of single-crystal Na0.66Ni0.26Zn0.07Mn0.67O2 (average discharge capacity of 81.2 mAh g-1) is superior to that of the comparison sample (average discharge capacity of 61.2 mAh g-1) at 2000 mA g-1. This work provides a new approach for promoting the single-crystal growth of layered oxides for highly stable interfaces at high voltages without compromising Na+ transport kinetics.

Upper Critical Field and Tunneling Spectroscopy of Underdoped Na(Fe,Co)As Single Crystals.

A comprehensive study of superconducting properties of underdoped NaFe0.979Co0.021As single crystals by a combination of upper critical field measurements and incoherent multiple Andreev reflection effect (IMARE) spectroscopy is presented. The Hc2(T) temperature dependences are measured at magnetic fields up to 16 T with in-plane and out-of-plane field directions and considered within single-band and two-band models in order to estimate the Hc2(0) value. In IMARE spectroscopy probes, the magnitude, characteristic ratio, and temperature dependence of the superconducting order parameters (ΔL,S(T)) are determined locally and directly. A possible k-space anisotropy of the large superconducting gap is demonstrated. We show that usage of a quadruple of λij0 coupling constants obtained in the IMARE experiment can significantly reduce the number of free parameters required to fit the Hc2(T) dependence within a two-band approach (from six to two).

Strong magnetic anisotropy in PrRu2Ga8and PrCo2Al8single crystals.

Single crystals ofLnRu2Ga8andLnCo2Al8(Ln= La and Pr) were grown using a Ga/Al self-flux method. An orthorhombic CaCo2Al8-type structure with space groupPbam(No.55) of them was identified by x-ray diffraction. LaRu2Ga8and LaCo2Al8are Pauli paramagnetic down to 2 K, while PrRu2Ga8and PrCo2Al8show antiferromagnetic (AFM) order at 2.5 and 5 K, respectively. Strong magnetic anisotropy in PrRu2Ga8and PrCo2Al8single crystals was found by an anisotropic magnetic measurement. The field-induced FM state was observed in both PrRu2Ga8and PrCo2Al8forH||c. However, in the case of H⊥c, the AFM state is robust. The strong magnetic anisotropy in PrRu2Ga8FM and PrCo2Al8is due to their anisotropic magnetic interactions that FM interactions are dominant in the case ofH||cwhile AFM interactions forH⊥c.

Growth, Structure and Optical Characterization of Rb3Ti3P5O20 Single Crystal.

Phosphate crystals attract much attention on account of their rich crystal structures and excellent physical and chemical properties. Herein, Rb3Ti3P5O20 single crystals were grown by the high temperature solution method using Rb2CO3 and NH4H2PO4 as the fluxes. This crystal, with non-centrosymmetric Pca21 space group, presents a three-dimensional framework structure composed of [TiO6] octahedron, [PO4] tetrahedra, and [P2O7] dimers. The electronic structure was measured via X-ray photoelectron spectroscopy. The measurements found that Rb3Ti3P5O20 has stronger Ti-O ionic bonding properties and weaker P-O covalent bonding properties compared to RbTiOPO4. Optical measurements indicated that Rb3Ti3P5O20 has a 3.54 eV band gap and a wide transmission range (0.33-4.5 µm). Theoretical calculations showed that Rb3Ti3P5O20 crystals have a moderate birefringence of 0.079 at 1064 nm. In addition, the relationship of the structure-property was studied using first-principles method. The results demonstrated that TiO6 octahedron played a significant role for the optical properties.

Investigation of Superconductivity in Ce-Doped (La,Pr)OBiS2 Single Crystals.

Single crystals of Ce-doped (La,Pr)OBiS2 superconductors, the multinary rare-earth elements substituted ROBiS2, were successfully grown. The grown crystals typically had a size of 1-2 mm and a plate-like shape with a well-developed c-plane. The c-axis lattice constants of the obtained (La,Ce,Pr)OBiS2 single crystals were approximately 13.6-13.7 Å, and the superconducting transition temperature was 1.23-2.18 K. Valence fluctuations of Ce and Pr were detected through X-ray absorption spectroscopy analysis. In contrast to (Ce,Pr)OBiS2 and (La,Ce)OBiS2, the superconducting transition temperature of (La,Ce,Pr)OBiS2 increased with the increasing concentrations of the tetravalent state at the R-site.

Effect of uranium deficiency on normal and superconducting properties in unconventional superconductor UTe2.

Single crystals of the unconventional superconductor UTe2have been grown in various conditions which result in different superconducting transition temperature as well as normal state properties. Stoichiometry of the samples has been characterized by the single-crystal x-ray crystallography and electron microprobe analyses. Superconducting samples are nearly stoichiometric within an experimental error of about 1%, while non-superconducting sample significantly deviates from the ideal composition. The superconducting UTe2showed that the large density of states was partially gapped in the normal state, while the non-superconducting sample is characterized by the relatively large electronic specific heat as reported previously.

Achieving Giant Piezoelectricity and High Property Uniformity Simultaneously in a Relaxor Ferroelectric Crystal through Rare-Earth Element Doping.

The low uniformity in properties of relaxor ferroelectric crystals is a long-standing issue in the ferroelectric community, which limits the available volume of the entire crystal boule. The aim of this study is to develop a relaxor ferroelectric crystal with improved property uniformity and excellent piezoelectricity. To this end, Pb(In1/2 Nb1/2 )O3 -Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 is doped with Nd2 O3 (Nd-PIN-PMN-PT) to improve the crystal performance. Along the crystal boule, the piezoelectric coefficient d33 varies from 2800 to 3500 pC N-1 , and the dielectric constant ranges from 8400 to 9800, with variations of 25% and 16%, respectively. Such high property uniformity results in over 75% available volume of the crystal boule, compared to 30-50% for undoped crystals grown by Bridgman method. At the electric field of 1 kV cm-1 , the converse piezoelectric response is up to 4780 pm V-1 . In addition, its Curie temperature (TC ) and coercive field (EC ) are above 150 °C and 3 kV cm-1 , respectively. Compared with Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 crystal (d33 : 1500 pC N-1 , TC : 135 °C, EC : 2.3 kV cm-1 ), the larger piezoelectricity, the higher TC and EC , and improved uniformity make Nd-PIN-PMN-PT crystals promising candidates for advanced piezoelectric applications.

Electronic properties of TaAs2topological semimetal investigated by transport and ARPES.

We have performed electron transport and angle-resolved photo-emission spectroscopy (ARPES) measurements on single crystals of transition metal dipnictide TaAs2cleaved along the (2¯01) surface which has the lowest cleavage energy. A Fourier transform of the Shubnikov-de Haas oscillations shows four different peaks whose angular dependence was studied with respect to the angle between magnetic field and the [2¯01] direction. The results indicate elliptical shape of the Fermi surface cross-sections. Additionally, a mobility spectrum analysis was carried out, which also reveals at least four types of carriers contributing to the conductance (two kinds of electrons and two kinds of holes). ARPES spectra were taken on freshly cleaved (2¯01) surface and it was found that bulk states pockets at constant energy surface are elliptical, which confirms the magnetotransport angle dependent studies. First-principles calculations support the interpretation of the experimental results. The theoretical calculations better reproduce the ARPES data if the theoretical Fermi level (FL) is increased, which is due to a small n-doping of the samples. This shifts the FL closer to the Dirac point, allowing investigating the physics of the Dirac and Weyl points, making this compound a platform for the investigation of the Dirac and Weyl points in three-dimensional materials.

Growth and Optical Properties of the Whole System of Li(Mn1-x,Nix)PO4 (0 ≤ x ≤ 0.5) Single Crystals.

A series of single crystals of Li(Mn1-x,Nix)PO4 (x = 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.08, 0.10, 0.15, 0.20, and 0.50) have been grown to large sizes up to 5 mm in diameter and 120 mm in length using the floating zone method for the first time. The comprehensive characterizations of the as-grown crystals were performed before further physical property measurements. The composition of the grown crystals was determined by energy-dispersive X-ray spectroscopy. The crystal structures were characterized by the X-ray powder diffraction method with a GSAS fitting for structural refinement, which reveals a high phase purity of the as-obtained crystals. The polarized microscopic images and Laue patterns prove the excellent quality of the single crystals. Oriented cuboids with sizes of 2.7 × 3.8 × 2.1 mm3 along the a, b, and c crystalline directions were cut and polished for further anisotropic magnetic and transparent measurements. We also first proposed a new potential application in the non-linear optical (NLO) and laser generation application for LiMPO4 (M = transition metal) materials. The optical and laser properties, such as the absorption spectra and the second harmonic generation (SHG), have been investigated and have furthermore confirmed the good quality of the as-grown single crystals.

Neutron diffraction experiment with the Y116S variant of transthyretin using iBIX at J-PARC: application of a new integration method.

Transthyretin (TTR) is one of more than 30 amyloidogenic proteins, and the amyloid fibrils found in patients afflicted with ATTR amyloidosis are composed of this protein. Wild-type TTR amyloids accumulate in the heart in senile systemic amyloidosis (SSA). ATTR amyloidosis occurs at a much younger age than SSA, and the affected individuals carry a TTR mutant. The naturally occurring amyloidogenic Y116S TTR variant forms more amyloid fibrils than wild-type TTR. Thus, the Y116S mutation reduces the stability of the TTR structure. A neutron diffraction experiment on Y116S TTR was performed to elucidate the mechanism of the changes in structural stability between Y116S variant and wild-type TTR through structural comparison. Large crystals of the Y116S variant were grown under optimal crystallization conditions, and a single 2.4 mm3 crystal was ultimately obtained. This crystal was subjected to time-of-flight (TOF) neutron diffraction using the IBARAKI biological crystal diffractometer (iBIX) at the Japan Proton Accelerator Research Complex, Tokai, Japan (J-PARC). A full data set for neutron structure analysis was obtained in 14 days at an operational accelerator power of 500 kW. A new integration method was developed and showed improved data statistics; the new method was applied to the reduction of the TOF diffraction data from the Y116S variant. Data reduction was completed and the integrated intensities of the Bragg reflections were obtained at 1.9 Šresolution for structure refinement. Moreover, X-ray diffraction data at 1.4 Šresolution were obtained for joint neutron-X-ray refinement.

Redetermination of the crystal structure of R 5Si4 (R = Pr, Nd) from single-crystal X-ray diffraction data.

The crystal structures of praseodymium silicide (5/4), Pr5Si4, and neodymium silicide (5/4), Nd5Si4, were redetermined using high-quality single-crystal X-ray diffraction data. The previous structure reports of Pr5Si4 were only based on powder X-ray diffraction data [Smith et al. (1967 ▸). Acta Cryst. 22 940-943; Yang et al. (2002b ▸). J. Alloys Compd. 339, 189-194; Yang et al., (2003 ▸). J. Alloys Compd. 263, 146-153]. On the other hand, the structure of Nd5Si4 has been determined from powder data [neutron; Cadogan et al., (2002 ▸). J. Phys. Condens. Matter, 14, 7191-7200] and X-ray [Smith et al. (1967 ▸). Acta Cryst. 22 940-943; Yang et al. (2002b ▸). J. Alloys Compd. 339, 189-194; Yang et al., (2003 ▸). J. Alloys Compd. 263, 146-153] and single-crystal data with isotropic atomic displacement parameters [Roger et al., (2006 ▸). J. Alloys Compd. 415, 73-84]. In addition, the anisotropic atomic displacement parameters for all atomic sites have been determined for the first time. These compounds are confirmed to have the tetra-gonal Zr5Si4-type structure (space group: P41212), as reported previously (Smith et al., 1967 ▸). The structure is built up by distorted body-centered cubes consisting of Pr(Nd) atoms, which are linked to each other by edge-sharing to form a three-dimensional framework. This framework delimits zigzag channels in which the silicon dimers are situated.