High-resolution Synchrotron X-ray Powder Diffraction Research Articles

Temperature-dependent synchrotron XRD study and electrical properties of the (1-x)BZT-(x)BCT lead-free piezoceramics

In recent years, researchers have shown the feasibility of the BZT-xBCT lead-free piezoelectric ceramics for using in various applications such as actuator, energy harvester, high-frequency ultrasonic transducer, etc. However, little evidence of temperature-dependent electrical properties of the BZT-xBCT ceramic was found. Moreover, some researchers have utilized Raman spectroscopy to observe the phase transition of the BZT-xBCT ceramic, but the Raman spectra of ferroelectric polymorphic phases are almost identical and hard to distinguish. In contrast, synchrotron radiation exhibits a high degree of monochromatization and collimation with smaller wavelength than x-ray tubes, resulting in the improvement of resolution for identifying the overlapping peaks. Therefore, this work aims to determine phase coexistence of the BZT-xBCT ceramic near phase boundary region by using high-resolution synchrotron x-ray powder diffraction in comparison with the temperature-dependent electrical properties. This work found that the occurrence of thermally-induced polymorphic phase transformations for the BZT-xBCT ceramics plays a significant role in the observed temperature-dependent electrical properties. Moreover, this work observed a trace of surface damaged layer (the presence of low-angle shoulder in the synchrotron XRD profiles) from mechanical grinding during sample preparation for XRD measurement, which has not previously been found in the BZT-xBCT ceramics. These finding will help to better understand the temperature-dependent functional properties of the BZT-xBCT ceramic for transferring into practical applications.

Mechanistically Guided Materials Chemistry: Synthesis of Ternary Nitrides, CaZrN2 and CaHfN2.

Recent computational studies have predicted many new ternary nitrides, revealing synthetic opportunities in this underexplored phase space. However, synthesizing new ternary nitrides is difficult, in part because intermediate and product phases often have high cohesive energies that inhibit diffusion. Here, we report the synthesis of two new phases, calcium zirconium nitride (CaZrN2) and calcium hafnium nitride (CaHfN2), by solid state metathesis reactions between Ca3N2 and MCl4 (M = Zr, Hf). Although the reaction nominally proceeds to the target phases in a 1:1 ratio of the precursors via Ca3N2 + MCl4 → CaMN2 + 2 CaCl2, reactions prepared this way result in Ca-poor materials (CaxM2-xN2, x < 1). A small excess of Ca3N2 (ca. 20 mol %) is needed to yield stoichiometric CaMN2, as confirmed by high-resolution synchrotron powder X-ray diffraction. In situ synchrotron X-ray diffraction studies reveal that nominally stoichiometric reactions produce Zr3+ intermediates early in the reaction pathway, and the excess Ca3N2 is needed to reoxidize Zr3+ intermediates back to the Zr4+ oxidation state of CaZrN2. Analysis of computationally derived chemical potential diagrams rationalizes this synthetic approach and its contrast from the synthesis of MgZrN2. These findings additionally highlight the utility of in situ diffraction studies and computational thermochemistry to provide mechanistic guidance for synthesis.

Using synchrotron high-resolution powder X-ray diffraction for the structure determination of a new cocrystal formed by two active principle ingredients.

The crystal structure of a new 1:1 cocrystal of carbamazepine and S-naproxen (C15H12N2O·C14H14O3) was solved from powder X-ray diffraction (PXRD). The PXRD pattern was measured at the high-resolution beamline CRISTAL at synchrotron SOLEIL (France). The structure was solved using Monte Carlo simulated annealing, then refined with Rietveld refinement. The positions of the H atoms were obtained from density functional theory (DFT) ground-state calculations. The symmetry is orthorhombic with the space group P212121 (No. 19) and the following lattice parameters: a = 33.5486 (9), b = 26.4223 (6), c = 5.3651 (10) Å and V = 4755.83 (19) Å3.

Phases study for AgNb(Ta,W)O3 lead-free antiferroelectric ceramics

Uncovering lead-free materials with an exceptionally high recoverable energy density is vital for the creation of future pulse power capacitors. This study determined that introducing Tungsten (W) and Tantalum (Ta) into the Nb-site of AgNbO3 lead-free antiferroelectric ceramics, while offsetting this with vacancies at the Ag-site, can effectively maintain the electrical homogeneity. Additionally, employing this co-doping approach can secure the antiferroelectric phases by lowering the necessary temperatures for M1-M2 and M2-M3 phase transitions. This may prove advantageous in the creation of novel AgNbO3-based energy storage ceramics. The use of in-situ high-resolution synchrotron powder x-ray diffraction (SPXD) at varying temperatures revealed for the first time that in 10 at% W doped AgNbO3, the M1 and M2 phases in the temperature range of −193 to ∼150 °C are more appropriately fitted as the non-polar Pbcm space group, whereas the M3 phase aligns with the mixed of non-polar Pbcm and polar Pmc21 space groups.

Polymorphism of Carbamazepine Pharmaceutical Cocrystal: Structural Analysis and Solubility Performance.

Polymorphism is a common phenomenon among single- and multicomponent molecular crystals that has a significant impact on the contemporary drug development process. A new polymorphic form of the drug carbamazepine (CBZ) cocrystal with methylparaben (MePRB) in a 1:1 molar ratio as well as the drug's channel-like cocrystal containing highly disordered coformer molecules have been obtained and characterized in this work using various analytical methods, including thermal analysis, Raman spectroscopy, and single-crystal and high-resolution synchrotron powder X-ray diffraction. Structural analysis of the solid forms revealed a close resemblance between novel form II and previously reported form I of the [CBZ + MePRB] (1:1) cocrystal in terms of hydrogen bond networks and overall packing arrangements. The channel-like cocrystal was found to belong to a distinct family of isostructural CBZ cocrystals with coformers of similar size and shape. Form I and form II of the 1:1 cocrystal appeared to be related by a monotropic relationship, with form II being proven to be the thermodynamically more stable phase. The dissolution performance of both polymorphs in aqueous media was significantly enhanced when compared with parent CBZ. However, considering the superior thermodynamic stability and consistent dissolution profile, the discovered form II of the [CBZ + MePRB] (1:1) cocrystal seems a more promising and reliable solid form for further pharmaceutical development.

Structural Reconstruction of Hydrothermally Grown BaTiO3 Nanoparticles Based on High-Resolution Synchrotron Powder X-ray Diffraction

Barium titanate (BaTiO3) is a versatile material for industrial and research purposes owing to its various and excellent properties, including its ferroelectricity. The demand for ultrafine BaTiO3 nanoparticles via a robust synthesis route capable of mass production, such as hydrothermal reactions, has increased owing to the rapid advancement of highly integrated electronic components. In this study, BaTiO3 nanopowders smaller than 150 nm are synthesized using a facile hydrothermal method to obtain ultrafine and highly uniform nanoparticles. The synthesized nanopowders are analyzed via high-resolution synchrotron powder X-ray diffraction experiments. Based on Rietveld refinement studies, a three-phase composite model is shown to be reasonable for investigating the nanopowders. The analytical results are summarized in detail for a set of BaTiO3 nanopowders. Nanoparticles are reconstructed based on the thicknesses obtained from the calculated phase weight fractions for each case.

Structural effects of Mn-substitution in β-FeSe

In the present work the structural and microstructural properties of Mn substituted β-FeSe are inspected by using high-resolution synchrotron X-ray powder diffraction data collected between 10 K and 150 K. It is demonstrated that the thermal increase of the structural strain in the tetragonal phase progressively breaks the 4-fold symmetry at the local scale, qualitatively tracing the development of anisotropy measured in some physical properties, generally ascribed to nematicity. This result points to a close relationship and interplay between structural strain and physical properties; with this notion, the structural strain can be considered as the origin of the unexpected anisotropy observed in some physical properties. Remarkably, incommensurate satellite peaks are observed in the diffraction pattern collected in the low-temperature orthorhombic phase field, likely related to the occurrence of a charge-density-wave instability.

Nature of magnetic transitions and evidence for magnetoelastic coupling in the biskyrmion-host hexagonal compound MnNiGa

The hexagonal compound MnNiGa with Ni2In-type structure has emerged as an important biskyrmion-host system in which these textures are super-stable over a wide temperature range extending from 16 K to the Curie temperature TC ∼350 K under moderate fields. Both the intensity of the external magnetic field and the presence of magnetoelastic coupling are known to play key role in the stability of the skyrmionic textures. Here we present the results of the first comprehensive investigation of the order of the phase transitions and its field dependence along with magnetoelastic (i.e., spin-lattice) coupling using a combined magnetization and high-resolution synchrotron x-ray powder diffraction (SXRPD) study of MnNiGa. The temperature dependence of the magnetization M(T) exhibits a paramagnetic to collinear ferromagnetic (FM) transition at TC (∼347 ± 0.5 K) with thermal hysteresis and negative slope in the Arrott plots across the TC suggesting its first order character. The M(T) plot in the collinear FM phase exhibits an anomalously decreasing behaviour after reaching its peak value at 300 K followed by a step-like change below 210 K due to an additional spin reorientation transition (SRT) to a non-collinear FM phase with TSRT∼200 ± 1 K. The SRT also shows thermal hysteresis characteristic of a first order phase transition. Our field dependent studies reveal stabilization of the collinear FM phase to higher temperatures and destabilization of the SRT transition setting an upper limit on the magnetic field for the observation of biskyrmions in this system. The Rietveld analysis of the SXRPD data reveals anomalies in the unit cell parameters at TC and TSRT without any change in the crystal symmetry. The modelling of the temperature dependence of the unit cell volume in terms of the Debye-Grüneisen equation reveals significant deviation from phonon contributions and the presence of the quadratic spin-lattice coupling below the FM TC, in the precursor SRT regime as well as below TSRT. The present results on the magnetoelastic coupling in the hexagonal MnNiGa may provide the necessary insight towards understanding the extreme sensitivity of the magnetic skyrmionic textures to external stresses.

Electron doping of a double-perovskite flat-band system

Electronic structure calculations indicate that the Sr2FeSbO6 double perovskite has a flat-band set just above the Fermi level that includes contributions from ordinary subbands with weak kinetic electron hopping plus a flat subband that can be attributed to the lattice geometry and orbital interference. To place the Fermi energy in that flat band, electron-doped samples with formulas Sr2-xLaxFeSbO6 (0 ≤ x ≤ 0.3) were synthesized, and their magnetism and ambient temperature crystal structures were determined by high-resolution synchrotron X-ray powder diffraction. All materials appear to display an antiferromagnetic-like maximum in the magnetic susceptibility, but the dominant spin coupling evolves from antiferromagnetic to ferromagnetic on electron doping. Which of the three subbands or combinations is responsible for the behavior has not been determined.

High pO2 Flux Growth and Characterization of NdNiO3 Crystals

Single crystals of the perovskite nickelate NdNiO3 with dimensions of up to 50 μm on edge have been successfully grown using the flux method at a temperature of 400 °C and oxygen pressure of 200 bar. The crystals were investigated by a combination of techniques, including high-resolution synchrotron X-ray single-crystal and powder diffraction and physical property measurements such as magnetic susceptibility and resistivity. Resistivity measurements revealed a metal-insulator transition (MIT) at TMIT~180 K with apparent thermal hysteresis; however, no superlattice peaks or peak splitting below TMIT, which corresponds to a structural transition from Pbnm to P21/n, was observed. The successful growth of NdNiO3 crystals at relatively low temperatures and oxygen pressure provides an alternative approach for preparing single crystals of interesting perovskites such as RNiO3 (R = Sm-Lu) and parent phases of superconducting square planar nickelates.

Comment on "Structural transition and superconductivity in hydrothermally synthesized FeX (X = S, Se)" by U. Pachmayr, N. Fehn and D. Johrendt, Chem. Commun., 2016, 52, 194.

The occurrence of triclinic structural modification of β-FeSe was reported in the literature; in particular this polymorph was claimed to be observed at low temperature in samples prepared by hydrothermal synthesis. The establishment of triclinic symmetry was argued based on peculiar features characterizing some selected X-ray powder diffraction lines. Using high-resolution synchrotron X-ray powder diffraction, the same features were observed for an aged β-FeSe sample prepared by a solid state synthesis technique. Moreover, by refining the anisotropic microstrain parameters it was demonstrated that the diffraction pattern can be fairly fitted by applying the well-recognized orthorhombic structural model adopted for the low temperature phase of β-FeSe. This result indicates that the occurrence of the triclinic polymorph for β-FeSe can be ruled out.

Halogen- and hydrogen-bonded self-assembled fibrillar networks of substituted 1,3:2,4-dibenzylidene-D-sorbitols (DBS).

Substituting the sole primary hydroxyl group of the low molecular weight organogelator (LMOG), 1,3:2,4-dibenzylidene-D-sorbitol (DBS), with a halogen atom (Cl, Br, or I; i.e., 6-Cl-DBS, 6-Br-DBS, or 6-I-DBS) drastically alters the supramolecular self-assembled fibrillar network (SAFiN) that forms when the molecules aggregate. The SAFiN varies depending on the solvent properties, impacting the role of non-covalent hydrogen- and halogen-bonding interactions along and between fibers. The halogenated DBS derivatives have more coherent crystalline fibers than DBS, with larger length-to-width aspect ratios. High-resolution synchrotron powder X-ray diffraction of each wet-state gel in toluene and DFT optimization obtained complete structures for the three halogenated DBS derivatives in their SAFiNs. The presence of a halogen atom reduces the reliance on hydrogen bonding by enabling new halogen bonding interactions that impact the self-assembly behavior, especially in solvents of higher polarity. For 6-I-DBS and 6-Br-DBS, the primary forces driving molecular self-assembly are C-H⋯π and intermolecular halogen-to-halogen interactions, and there is one unique molecule in each unit cell. However, the Cl atoms of 6-Cl-DBS are not close, and its SAFiN structures rely more on hydrogen bonding. As a result, the enhanced hydrogen bonding, electronic differences among the halogens, and spatial factors allow its unit cell to include two independent molecules of 6-Cl-DBS.

Self-Activating Strontium Orthoborate Blue Phosphors Induced by Cation and Anion Deficiencies and Their Rare-Earth-Free White Ultraviolet Light-Emitting Diodes.

Self-activating blue-light-emitting strontium orthoborate phosphors, viz., Sr3B2+xO6+3x/2 and Sr3B2+xO6+3x/2-δ (x ranges from -0.3 to 0.1), were obtained by varying the number of BO3/2 and anion deficiencies. The integrated intensity observed from the oxygen 1s profile obtained via X-ray photoelectron spectroscopy indicated the relative concentrations of the oxygen vacancies in the Sr3B2+xO6+3x/2 (x = 0, -0.1, and -0.3) and Sr3B2O6-δ phosphors. The structures of Sr3B2O6, Sr3B2.1O6.15, Sr3B1.9O5.85, and Sr3B2O6-δ with crystal orientations were analyzed based on high-resolution synchrotron powder X-ray diffraction data. A mixture of rare-earth-free blue Sr3B2O6-δ and yellow Sr2.45Ba0.5Na0.05Al0.95Sn0.05O4-αF1-δ phosphors, incorporated on a 315 nm UV-LED chip, can generate a white-light UV-LED.

Deformation of the triangular spin- 12 lattice in Na2SrCo(PO4)2

Crystal structure and thermodynamic properties of Na$_2$SrCo(PO$_4$)$_2$, the chemical sibling of the triangular quantum spin-liquid candidate Na$_2$BaCo(PO$_4$)$_2$, are reported. From single crystal x-ray diffraction and high-resolution synchrotron x-ray powder diffraction, the compound was found to crystallize in the monoclinic space group $P2_1/a$ at room temperature, in contrast to the trigonal Na$_2$BaCo(PO$_4$)$_2$. Above 650 K, the symmetry of Na$_2$SrCo(PO$_4$)$_2$ changes to $C2/m$, while around 1025 K a further transformation toward trigonal symmetry is observed. The monoclinic symmetry leads to a small deformation of the CoO$_6$ octahedra beyond the trigonal distortion ubiquitous in this structure type, and results in the stronger $g$-tensor anisotropy ($g_{\text{z}}/g_{\text{xy}} = 1.6 $) as well as the increased XXZ anisotropy ($J_{\text{z}}/J_{\text{xy}} = 2.1$) compared to the Ba compound ($g_{\text{z}}/g_{\text{xy}} = 1.1 $, $J_{\text{z}}/J_{\text{xy}} = 1.5$), while the average coupling strength, $J_{\text{av}}/k_{\text{B}}=(2J_{\text{xy}}+J_{\text{z}})/3k_\text{B}\simeq 1.3\,\text{K}$, remains unchanged. The N\'{e}el temperature increases from 140 mK (Ba) to 600 mK (Sr), and an uncompensated in-plane moment of $0.066(4)\mu_{\text{B}}/\text{f.u.}$ appears. We show that the ordering temperature of a triangular antiferromagnet is capably controlled by its structural distortions.

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi12B8.

Achieving kinetic control to synthesize metastable compounds is a challenging task, especially in solid-state reactions where the diffusion is slow. Another challenge is the unambiguous crystal structure determination for metastable compounds when high-quality single crystals suitable for single-crystal X-ray diffraction are inaccessible. In this work, we report an unconventional means of synthesis and an effective strategy to solve the crystal structure of an unprecedented metastable compound LiNi12B8. This compound can only be produced upon heating a metastable layered boride, HT-Li0.4NiB (HT: high temperature), in a sealed niobium container. A conventional heating and annealing of elements do not yield the title compound, which is consistent with the metastable nature of LiNi12B8. The process to crystallize this compound is sensitive to the annealing temperature and dwelling time, a testament to the complex kinetics involved in the formation of the product. The unavailability of crystals suitable for single-crystal X-ray diffraction experiments prompted solving the crystal structure from high-resolution synchrotron powder X-ray diffraction data. This compound crystallizes in a new structure type with space group I4/mmm (a = 10.55673(9) Å, c = 10.00982(8) Å, V = 1115.54(3) Å3, Z = 6). The resulting complex crystal structure of LiNi12B8 is confirmed by scanning transmission electron microscopy and solid-state 11B and 7Li NMR spectroscopy analyses. The extended Ni framework with Li/Ni disorder in its crystal structure resulted in the spin-glass or cluster glass type magnetic ordering below 24 K. This report illustrates a “contemporary twist” to traditional methodologies toward synthesizing a metastable compound and provides a recipe for solving structures by combining the complementary characterization techniques in the cases where the traditionally used single-crystal X-ray diffraction method is nonapplicable.

Apatite, Ca10(PO4)6(OH,F,Cl)2: Structural Variations, Natural Solid Solutions, Intergrowths, and Zoning

Thirty-three samples from natural apatite (Ap) solid solutions, ideal structural formula [9]Ca12[7]Ca23([4]PO4)3[3](F,OH,Cl), (Z = 2) were examined with electron-probe microanalysis, synchrotron high-resolution powder X-ray diffraction (HRPXRD), and Rietveld refinements. Apatite has space group P63/m for the general chemical formula above. In Ap, the two different Ca sites are generally occupied by Ca, Mn, Sr, Na, or REE3+ cations; the P site is occupied by P, Si, or S, and the X is occupied by F, OH, Cl, O2−, or (CO3)2− anions. However, it may be possible for CO32− + F− anions to partially replace PO43− groups. In this study, the unit-cell parameters a, c, and c/a ratio, vary smoothly and non-linearly with the unit-cell volume, V. The data falls on two distinct trend lines. The average &lt;P-O&gt;[4] distance is nearly constant across the Ap series, whereas the average &lt;O-P-O&gt;[6] angle decreases linearly. The coordination numbers for the atoms are given in square brackets in the general chemical formula above. The average &lt;Ca1-O&gt;[9], &lt;Ca2-O&gt;[6], &lt;Ca2-O,X&gt;[7], and Ca2-X distances change non-linearly with increasing V. Although Cl− anion is larger than OH− and F− anions, the c unit-cell parameter in F-Ap is larger than that in Cl-Ap. In Cl-Ap, the Ca2 polyhedra are larger than in F-Ap, so the O and Cl anions are under-bonded, which cause the Ca1 polyhedra to contract and charge balance the anions. Alternatively, the Ca1 polyhedra are smaller in Cl-Ap than in F-Ap, so the Ca1 polyhedra in Cl-Ap cause the c axis to contract compared to that in F-Ap.

Thermal evolution of the EuBaCo2O5.5 crystal structure

Crystal structure of the EuBaCo2O5.502(1) perovskite obtained by equilibration and slow cooling in closed ampoule is studied between 100 and 400 ​K by high-resolution synchrotron powder X-ray diffraction, and its thermally induced phase transitions by differential scanning calorimetry (DSC). The low-temperature Pmma perovskite supercell 2ap 2bp 2cp has Eu and Ba alternating along c, Co3+ coordination square pyramids and octahedra alternating along b and orbital-order alternating along a. The last order is lost upon warming through a transition topping at 365 ​K (ΔS ​≈ ​2.25R per mole EuBaCo2O5.5 by DSC) that forms an ap 2bp 2cp supercell as refined at 380 and 400 ​K. The DSC detects also the twin magnetic phase transition at 248 ​K and 269 ​K as weak endothermic effects upon heating (ΔS ​≈ ​0.41 ​J/molK and 0.19 ​J/molK, resp.). Intermittent negative thermal expansion of some cobalt coordination polyhedra is discussed in the context of possible Co3+ spin states and of the DSC entropy change at the structure transition.

Temperature-dependent crystal structure investigation of 4f hybridized thermoelectric clathrate Ba8-xCexAuySi46-y.

Thermoelectric materials allow for conversion of waste heat into electrical energy, and they represent a green solution for improving our energy efficiency. Inclusion of 4f electrons near the Fermi level may boost the Seebeck coefficient, which is essential for high thermoelectric performance. In this study, Ce was successfully substituted for Ba on the guest atom sites in the type-I clathrate Ba8-xCexAuySi46-y and the material was characterized using high-resolution synchrotron powder X-ray diffraction data measured from 100 K to 1000 K to investigate potential structural implications of the inclusion of a 4f element. The thermal expansion and bonding of the host structure are not affected by the presence of Ce, as seen from the linear coefficient of unit-cell thermal expansion of 7.30 (8) × 10-6 K-1 and the average host Debye temperature of 404 (7) K determined from the multi-temperature atomic displacement parameters, both of which are similar to values obtained for pure Ba8AuySi46-y. The anisotropic atomic displacement parameters on the guest atom site in the large clathrate cage populated by Ba surprisingly reveals isotropic behavior, which is different from all other clathrates reported in literature, and thus represents a unique host-guest bonding situation.

Structural Variations across Wolframite Solid Solutions, (Fe,Mn)WO4

The crystal structure of four samples from natural wolframite solid solutions, (Fe,Mn)WO4, was obtained with synchrotron high-resolution powder X-ray diffraction (HRPXRD) data, Rietveld refinements, space group P2/c, and Z = 2. Wolframite solid solutions extend from ferberite (FeWO4) to hübnerite (MnWO4). The W and (Mn,Fe) cations are in six-fold coordination. This study shows that the unit-cell parameters, a, b, c, and β angle, vary linearly with the unit-cell volume, V, across the wolframite series. The average &lt;Mn,Fe–O&gt; distance increases linearly because of larger Mn2+ (0.83 Å) replacing smaller Fe2+ (0.78 Å) cations, whereas the average &lt;W–O&gt; distance increases slightly because of the higher effective charge of the smaller Fe2+ cation. The distortions of the two types of polyhedra across the series are discussed.

Disorder-Induced Structural Complexity in the Barlowite Family of S = 1/2 Kagomé Magnets

We present a comprehensive structural and magnetic characterization of the barlowite family of S = 1/2 kagomé magnets, Cu4(OH)6FX, where X = Cl, Br, or I. Through high-resolution synchrotron X-ray and neutron powder diffraction measurements, we reveal two sources of structural complexity within this family of materials, namely, compositional disorder of the halide species that occupy sites in between the kagomé layers and the positional disorder of the interlayer Cu2+ ions that persists well into the Pnma structural ground state. We demonstrate that understanding these inherent structural disorders is key as they correlate with the degree of partial order in the magnetic ground states of these quantum frustrated magnets.