La2SrSc2O7: A-Site Cation Disorder Induces Ferroelectricity in Ruddlesden-Popper Layered Perovskite Oxide.

Rational design of ferroelectrics in layered perovskites, like n = 2 Ruddlesden-Popper (RP) phase A3B2O7, has been achieved by the hybrid-improper ferroelectric (HIF) mechanism, in which an electric polarization is induced via a trilinear coupling to nonpolar BO6 octahedral rotation and tilt distortions around crystallographic axes. In the present work, hybrid improper ferroelectricity in n = 2 RP-type La2SrSc2O7 induced by the disordering of Sr2+/La3+ cations on the A-sites in rocksalt ([Sr/La]Rs = 25/75) and perovskite ([Sr/La]Pv = 50/50) layers is demonstrated through experimental and theoretical investigations. The ferroelectric A21am structure (a-a-c+ in Glazer notation) at room temperature and the second-order phase transition to paraelectric Amam structure (a-a-c0) at TC ∼ 600 K are determined by a combination of X-ray and neutron diffraction and optical second harmonic generation. The ferroelectric hysteresis loop measurements prove the switchable electric polarization indicative of ferroelectricity. These results represent an unprecedented example of ferroelectricity in the n = 2 RP family of Ln2AB2O7 with inequivalent Ln3+ and A2+ cations. Combining the abovementioned experimental results with the first-principles calculations, we verify the role of Sr/La distributions in regulating the interlayer rumpling, which, in addition to the structural tolerance factor, is key to controlling the structural distortions of RP phases. The stabilization of the ferroelectric, a-a-c+ distorted structure is a consequence of the disordered Sr/La distribution on the A-sites, which suppresses the rumpling-induced octahedral deformations in competition with the octahedral rotations and thus enables the concurrence of a0a0c+ rotations and a-a-c0 tilts required for the HIF mechanism. This work demonstrates the possibility of altering the crystal symmetry of RP phases through the A-site cation disorder and provides a complementary approach to the rational design of new HIF materials.

Decoding Upconversion-Emitting Phase in Complex Composites Through Single-Particle-Level Upconversion Imaging and Density Functional Theory Calculations.

The crystal structure and phase stability of a host lattice plays an important role in efficient upconversion phenomena. In stable hosts, lanthanides doping should not generally change the crystal structure of the host itself. But when phase of a system drastically changes after lanthanide doping resulting in multiple phases, accurate identification of upconverting phase remains a challenge. Herein, an attempt to synthesize lanthanide-doped NiMoO4 by microwave hydrothermal method produced MoO3/Yb2Mo4O15/NiMoO4 micro-nano composite upconversion phosphor. A combined approach of density functional theory (DFT) calculations and single-particle-level upconversion imaging has been employed to elucidate the phase stability of different phases and upconversion properties within the composite. Through single-particle-level imaging under 980 nm excitation, an unprecedented resolution in visualizing individual emitting and non-emitting regions within the composite has been achieved, thereby allowing to accurately assign the Yb2Mo4O15 as a sole upconversion emitting phase in the composite. Result of the DFT calculation further shows that the Yb2Mo4O15 phase is the most thermodynamically preferred over other lanthanide-doped phases in the composite. This comprehensive understanding not only advances the knowledge of upconversion emission from composite materials but also holds promise for tailoring optical properties of materials for various applications, including bioimaging, sensing, and photonics, where controlled light emission is crucial.

A-Site and B-Site Charge Orderings in an s-d Level Controlled Perovskite Oxide PbCoO3.

Perovskite PbCoO3 synthesized at 12 GPa was found to have an unusual charge distribution of Pb2+Pb4+3Co2+2Co3+2O12 with charge orderings in both the A and B sites of perovskite ABO3. Comprehensive studies using density functional theory (DFT) calculation, electron diffraction (ED), synchrotron X-ray diffraction (SXRD), neutron powder diffraction (NPD), hard X-ray photoemission spectroscopy (HAXPES), soft X-ray absorption spectroscopy (XAS), and measurements of specific heat as well as magnetic and electrical properties provide evidence of lead ion and cobalt ion charge ordering leading to Pb2+Pb4+3Co2+2Co3+2O12 quadruple perovskite structure. It is shown that the average valence distribution of Pb3.5+Co2.5+O3 between Pb3+Cr3+O3 and Pb4+Ni2+O3 can be stabilized by tuning the energy levels of Pb 6s and transition metal 3d orbitals.

Structural origin of the anisotropic and isotropic thermal expansion of K2NiF4-Type LaSrAlO4 and Sr2TiO4.

K2NiF4-type LaSrAlO4 and Sr2TiO4 exhibit anisotropic and isotropic thermal expansion, respectively; however, their structural origin is unknown. To address this unresolved issue, the crystal structure and thermal expansion of LaSrAlO4 and Sr2TiO4 have been investigated through high-temperature neutron and synchrotron X-ray powder diffraction experiments and ab initio electronic calculations. The thermal expansion coefficient (TEC) along the c-axis (αc) being higher than that along the a-axis (αa) of LaSrAlO4 [αc = 1.882(4)αa] is mainly ascribed to the TEC of the interatomic distance between Al and apical oxygen O2 α(Al-O2) being higher than that between Al and equatorial oxygen O1 α(Al-O1) [α(Al-O2) = 2.41(18)α(Al-O1)]. The higher α(Al-O2) is attributed to the Al-O2 bond being longer and weaker than the Al-O1 bond. Thus, the minimum electron density and bond valence of the Al-O2 bond are lower than those of the Al-O1 bond. For Sr2TiO4, the Ti-O2 interatomic distance, d(Ti-O2), is equal to that of Ti-O1, d(Ti-O1) [d(Ti-O2) = 1.0194(15)d(Ti-O1)], relative to LaSrAlO4 [d(Al-O2) = 1.0932(9)d(Al-O1)]. Therefore, the bond valence and minimum electron density of the Ti-O2 bond are nearly equal to those of the Ti-O1 bond, leading to isotropic thermal expansion of Sr2TiO4 than LaSrAlO4. These results indicate that the anisotropic thermal expansion of K2NiF4-type oxides, A2BO4, is strongly influenced by the anisotropy of B-O chemical bonds. The present study suggests that due to the higher ratio of interatomic distance d(B-O2)/d(B-O1) of A2(2.5+)B(3+)O4 compared with A2(2+)B(4+)O4, A2(2.5+)B(3+)O4 compounds have higher α(B-O2), and A2(2+)B(4+)O4 materials exhibit smaller α(B-O2), leading to the anisotropic thermal expansion of A2(2.5+)B(3+)O4 and isotropic thermal expansion of A2(2+)B(4+)O4. The "true" thermal expansion without the chemical expansion of A2BO4 is higher than that of ABO3 with a similar composition.

High oxide-ion conductivity through the interstitial oxygen site in Ba7Nb4MoO20-based hexagonal perovskite related oxides.

Oxide-ion conductors are important in various applications such as solid-oxide fuel cells. Although zirconia-based materials are widely utilized, there remains a strong motivation to discover electrolyte materials with higher conductivity that lowers the working temperature of fuel cells, reducing cost. Oxide-ion conductors with hexagonal perovskite related structures are rare. Herein, we report oxide-ion conductors based on a hexagonal perovskite-related oxide Ba7Nb4MoO20. Ba7Nb3.9Mo1.1O20.05 shows a wide stability range and predominantly oxide-ion conduction in an oxygen partial pressure range from 2 × 10-26 to 1 atm at 600 °C. Surprisingly, bulk conductivity of Ba7Nb3.9Mo1.1O20.05, 5.8 × 10-4 S cm-1, is remarkably high at 310 °C, and higher than Bi2O3- and zirconia-based materials. The high conductivity of Ba7Nb3.9Mo1.1O20.05 is attributable to the interstitial-O5 oxygen site, providing two-dimensional oxide-ion O1-O5 interstitialcy diffusion through lattice-O1 and interstitial-O5 sites in the oxygen-deficient layer, and low activation energy for oxide-ion conductivity. Present findings demonstrate the ability of hexagonal perovskite related oxides as superior oxide-ion conductors.

Water-oriented magnetic anisotropy transition.

Water reorientation is essential in a wide range of chemical and biological processes. However, the effects of such reorientation through rotation around the metal-oxygen bond on the chemical and physical properties of the resulting complex are usually ignored. Most studies focus on the donor property of water as a recognized σ donor-type ligand rather than a participant in the π interaction. Although a theoretical approach to study water-rotation effects on the functionality of a complex has recently been conducted, it has not been experimentally demonstrated. In this study, we determine that the magnetic anisotropy of a Co(II) complex can be effectively controlled by the slight rotation of coordinating water ligands, which is achieved by a two-step structural phase transition. When the water molecule is rotated by 21.2 ± 0.2° around the Co-O bond, the directional magnetic susceptibility of the single crystal changes by approximately 30% along the a-axis due to the rotation of the magnetic anisotropy axis through the modification of the π interaction between cobalt(II) and the water ligand. The theoretical calculations further support the hypothesis that the reorientation of water molecules is a key factor contributing to the magnetic anisotropy transition of this complex.

High-Brightness Red-Emitting Phosphor La3(Si,Al)6(O,N)11:Ce3+ for Next-Generation Solid-State Light Sources.

A novel high-brightness red-emitting phosphor, La3(Si,Al)6(O,N)11:Ce3+ (LSA), which can potentially be used as a laser-excited light source, is demonstrated. Laser-excited phosphor system has great potential for use as a white-light source, as it is orders of magnitude brighter than white LEDs. Although conventional yellow-green phosphors show excellent luminescent properties even under high-power laser excitation, red-emitting phosphors, which are essential to achieve a high color-rendering index and low color-temperature, show quantum efficiency quenching. This limits the output power in multiphosphor excitation systems. Ce3+ should successfully tolerate high-power excitation due to the shortest emission lifetime seen in rare-earth ions, caused by the 5d1-4f1 spin-allowed transition; however, a red-emitting Ce3+-doped phosphor of practical use has not been realized. LSA is described by the crystal-field modification of a yellow-emitting phosphor, La3Si6N11:Ce3+, with substitution of Al in Si sites. LSA shows 640 nm red emission together with tolerance for high-power excitation and thermal quenching, suggesting its significant potential for industrial applications that require ultrahigh brightness.

Electronic structure, thermodynamic stability and high-temperature sensing properties of Er-α-SiAlON ceramics.

α-SiAlON ceramics have been in use as engineering ceramics in the most arduous industrial environments such as molten metal handling, cutting tools, gas turbine engines, extrusion molds, thermocouple sheaths, protective cover for high-temperature sensors, etc., owing to their outstanding mechanical, thermal and chemical stability. Taking advantage of the intrinsic properties of α-SiAlONs, we investigate, in this paper, the possibility of using the Er-doped α-SiAlON (Er-α-SiAlON) ceramic as a high-temperature sensing material via its unique near-infrared to visible upconversion property. We first use neutron diffraction and density functional theory calculations to study the electronic structure and thermodynamic stability of Er-α-SiAlON. It is found that the interstitial doping of Er stabilizes the α-SiAlON structure via chemical bonds with O-atoms with N:O ratio of 5:2 in the seven-fold coordination sites of the Er3+ ion. Temperature-dependent upconversion emissions are then studied under 980 and 793 nm excitations over a temperature range of 298-1373 K and the fluorescence intensity ratio (FIR) technique has been employed to investigate the temperature sensing behavior. Temperature-dependent Raman behavior is also investigated. We demonstrate that using Er-α-SiAlON as a sensing material, the limit of temperature measurement via the FIR technique can be pushed well beyond 1200 K.

Room Temperature Zero Thermal Expansion in a Cubic Cobaltite.

Zero thermal expansion (ZTE) materials are highly desired in modern industries where high-precision processing is necessary. However, ZTE materials in pure form are extremely rare. The most widely used are Invar alloys, where the ZTE is intimately associated with spontaneous magnetic ordering, known as the magnetovolume effect (MVE). Despite tremendous studies, there is still no consensus on the microscopic origin of MVE in Invar alloys. Here, we report the discovery of room-temperature isotropic ZTE in a pure-form cobaltite perovskite, A-site disordered La0.5Ba0.5CoO3-x. The temperature window of the anomalous thermal expansion shows large tunability by simply altering the oxygen content, making this material a promising candidate for practical applications. Furthermore, we unveil with compelling experimental evidence that the ZTE originates from an isostructural transition between antiferromagnetic large-volume phase and ferromagnetic small-volume phase, which might shed light on the MVE in Invar alloys.

Ammonothermal Synthesis, X-Ray and Time-of-Flight Neutron Crystal-Structure Determination, and Vibrational Properties of Barium Guanidinate, Ba(CN3H4)2.

We report the crystal structure of Ba(CN3H4)2 as synthesized from liquid ammonia. Structure solution based on X-ray diffraction data suffers from a severe pseudo-tetragonal problem due to extreme scattering contrast, so the true monoclinic symmetry is detectable only from neutron powder diffraction patterns, and structure solution and refinement was greatly aided by density-functional theory. The symmetry lowering is due to slight deviations of the guanidinate anion from the mirror plane in space group P 4 ‾ b2, a necessity of hydrogen bonding. At 300 K, barium guanidinate crystallizes in P21/c with a=6.26439(2) Å, b=16.58527(5) Å, c=6.25960(2) Å, and a monoclinic angle of ß=90.000(1)°. To improve the data-to-parameter ratio, anisotropic displacement parameters from first-principles theory were incorporated in the neutron refinement. Given the correct structural model, the positional parameters of the heavy atoms were also refinable from X-ray diffraction of a twinned crystal. The two independent guanidinate anions adopt the all-trans- and the anti-shape. The Ba cation is coordinated by eight imino nitrogens in a square antiprism with Ba-N contacts between 2.81 and 3.04 Å. The IR and Raman spectra of barium guanidinate were compared with DFT-calculated phonon spectra to identify the vibrational modes.

Crystal and Magnetic Structures of La2CoPtO6 Double Perovskite.

We investigated the crystal structure and magnetic structure in cobaltite-platinate double perovskite of La2CoPtO6, employing various techniques of X-ray diffraction, neutron diffraction, and the extended X-ray absorption fine structure analysis. It is shown that the crystal symmetry is maintained as P21/n in the temperature range of <500 °C, whereas the lattice constants and the Co-Co distances undergo a continuous structural evolution toward the high-symmetry phases with increasing temperature. The Co-O bonds were overall longer and had a larger degree of structural and thermal disorders than the Pt-O bonds. As for the magnetism, an antiferromagnetic order is stabilized in the Co2+ sublattice at temperatures below 28 K. It is demonstrated that owing to the substantial distortions (quantified by a distortion parameter Σ > 0.03 Å) of the Co-Co networks, the system is not subject to spin frustration effect. Details in the magnetic structure are determined; at 12 K, the Co magnetic moment was (0.8, 0, 2.7) Bohr magneton, the magnetic propagation vector was (-0.5, 0, 0.5), and the magnetic symmetry was preferably Γ1(Ag).

Crystal structures, magnetic properties, and DFT calculation of B-site defected 12L-perovskites Ba2La2MW2O12 (M = Mn, Co, Ni, Zn).

The synthesis, crystal structures and magnetic properties of Ba2La2MW2O12 (M = Mn, Co, Ni, Zn) were investigated. They crystallize in the 12-layer polytype of the perovskite structure with a regular cation defect in the B-site. The results of neutron diffraction measurements reveal that they adopt a rhombohedral structure with a space group R - 3 and have a cation ordering between Ba and La ions in the A-site. In these compounds, the magnetic M ions form the 2D triangular lattice. From the results of magnetic measurements, the ferromagnetic ordering of M2+ ions for M = Co (T C = 1.3 K) and Ni (6.2 K) and the paramagnetic behavior (T > 1.8 K) with an antiferromagnetic interaction for M = Mn are observed. From the DFT calculation, their band structures and magnetic interactions are discussed.

Large Magnetovolume Effect Induced by Embedding Ferromagnetic Clusters into Antiferromagnetic Matrix of Cobaltite Perovskite.

Materials that show negative thermal expansion (NTE) have significant industrial merit because they can be used to fabricate composites whose dimensions remain invariant upon heating. In some materials, NTE is concomitant with the spontaneous magnetization due to the magnetovolume effect (MVE). Here the authors report a new class of MVE material; namely, a layered perovskite PrBaCo2 O5.5+x (0 ≤ x ≤ 0.41), in which strong NTE [ß ≈ -3.6 × 10-5 K-1 (90-110 K) at x = 0.24] is triggered by embedding ferromagnetic (F) clusters into the antiferromagnetic (AF) matrix. The strongest MVE is found near the boundary between F and AF phases in the phase diagram, indicating the essential role of competition between the F-clusters and the AF-matrix. Furthermore, the MVE is not limited to the PrBaCo2 O5.5+x but is also observed in the NdBaCo2 O5.5+x . The present study provides a new approach to obtaining MVE and offers a path to the design of NTE materials.

Real-time observations of lithium battery reactions-operando neutron diffraction analysis during practical operation.

Among the energy storage devices for applications in electric vehicles and stationary uses, lithium batteries typically deliver high performance. However, there is still a missing link between the engineering developments for large-scale batteries and the fundamental science of each battery component. Elucidating reaction mechanisms under practical operation is crucial for future battery technology. Here, we report an operando diffraction technique that uses high-intensity neutrons to detect reactions in non-equilibrium states driven by high-current operation in commercial 18650 cells. The experimental system comprising a time-of-flight diffractometer with automated Rietveld analysis was developed to collect and analyse diffraction data produced by sequential charge and discharge processes. Furthermore, observations under high current drain revealed inhomogeneous reactions, a structural relaxation after discharge, and a shift in the lithium concentration ranges with cycling in the electrode matrix. The technique provides valuable information required for the development of advanced batteries.

Soft ferromagnetism in mixed valence Sr(1-x)La(x)Ti(0.5)Mn(0.5)O3 perovskites.

The structural, magnetic and electrical properties of the mixed Ti-Mn oxides Sr(1-x)La(x)Ti(0.5)Mn(0.5)O3 (0 ≤ x ≤ 0.5) are reported. At room temperature the oxides have a cubic structure in space group Pm3m for x ≤ 0.25 and rhombohedral in R3c for 0.3 ≤ x ≤ 0.50. X-ray absorption spectroscopic measurements demonstrate the addition of La(3+) is compensated by the partial reduction of Mn(4+) to Mn(3+). Variable temperature neutron diffraction measurements show that cooling Sr(0.6)La(0.4)Ti(0.5)Mn(0.5)O3 results in a first order transition from rhombohedra to an orthorhombic structure in Imma. Complex magnetic behaviour is observed. The magnetic behaviour of the mixed valent (Mn(3+/4+)) examples is dominated by ferromagnetic interactions, although cation disorder frustrates long range magnetic ordering.