Luminescence of Mn2+ in SrGa12O19, LaMgGa11O19, and BaGa12O19

Lattice parameters are given of SrGa₁₂O₁₉, BaGa₁₂O₁₉, and LaMgGa₁₁O₁₉, three new gallates with the magnetoplumbite structure. The luminescence of the compounds without and with activation by Mn²⁺ is reported. The quantum efficiencies of the Mn²⁺ phosphors are between 15% (BaGa₁₂O₁₉:Mn) and 70% ({Sr_1?xLa_x}Ga_12?xMg_xO₁₉:Mn). The emission strongly resembles that of Mn²⁺ in MgGa₂O₄. The fine structure of the Mn²⁺ emission band at 77°K is due to phonon coupling.     

A Suberato-Pillared Mn(II) Coordination Polymer: Hydrothermal Synthesis, Crystal Structure, and Magnetic Properties of Mn2(H2O)[O2C(CH2)6CO2]2

A suberato-pillared Mn(II) coordination polymer Mn₂(H₂O)(C₈H₁₂O₄)₂ was hydrothermally synthesized at 170°C for 3 days and characterized by single-crystal X-ray diffraction. Crystal data: monoclinic, C2/c, Z=4, a=26.544(5), b=7.617(2), c=9.187(2) Å, β=105.38(2)°, V=1791.0(7) ų, R₁=0.064 and wR₂=0.162. The compound shows a layered structure consisting of inorganic Mn oxygen polyhedral layers and organic regions. The inorganic Mn oxygen layers are generated from Mn₂O₁₀ bioctahedral units, which share corners with neighbors to form zigzag chains along the [001] direction and are, along the [010] direction, further connected by carboxylate groups of the suberato ligands and hydrogen bonds. The magnetic studies indicated that the compound becomes antiferromagnetic at low temperatures with T_Néel=12 K and follows Curie-Weiss law χ_m(T+22.429)= 4.48 cm³ mol⁻¹ K between 25 and 300 K. Upon heating in Ar stream, Mn₂(H₂O)(C₈H₁₂O₄)₂ decomposes in three steps.     

Hydrothermal Synthesis and Spectroscopic and Magnetic Behavior of the Mn7(HOXO3)4(XO4)2(X=As, P) Compounds. Crystal Structure of Mn7(HOAsO3)4(AsO4)2

The Mn₇(HOXO₃)₄(XO₄)₂ (X=As, P) compounds have been synthesized by using hydrothermal conditions. The arsenate phase was obtained under autogeneous pressure at 170°C. However, more drastic conditions at both pressure and temperature were necessary in the attainment of the phosphate compound. The crystal structure of Mn₇(HOAsO₃)₄(AsO₄)₂ was solved using single-crystal data. The unit-cell parameters are a=6.810(3) Å, b=8.239(2) Å, c=10.011(4) Å, α=104.31(2)°, β=108.94(3)°, γ=101.25(2)°. Triclinic, P-1 with Z=1. The isostructural Mn₇(HOPO₃)₄(PO₄)₂ phase was characterized from X-ray powder diffraction techniques. The crystal structure of both compounds consists of zig-zag chains constructed by dimeric edge-sharing Mn₂O₁₀ octahedra linked through the MnO₅ trigonal bipyramids. The three-dimensional framework is completed by the connection between isolated MnO₆ entities to the dimers octahedra and trigonal bipyramids. The existence of hydrogenarsenate and hydrogenphosphate anions has been confirmed by IR and Raman spectroscopies. Magnetic measurements indicate the existence of antiferromagnetic interactions in both compounds, which are slightly stronger in the arsenate phase.     

Epitaxial stabilization of (110)-layered perovskites of the RE2Ti2O7 (RE=La, Nd, Sm, Gd) family

Thin films of RE₂Ti₂O₇ (RE=La, Nd, Sm, Gd) were deposited on single crystal SrTiO₃ (110) substrates at 900 °C using pulsed laser deposition. X-ray diffraction (XRD) results showed sharp (00k) peaks (in θ-2θ scans) with narrow rocking curves (ω-scan peak widths of 0.4-0.9°), indicating that all compositions adopted the (110)-layered perovskite structure. While this is the stable structure for RE=La and Nd, it is metastable for RE=Sm and Gd. The metastable compounds are formed directly through epitaxial stabilization at these high temperatures and are shown to be isostructural to monoclinic La₂Ti₂O₇. The a, b, and c lattice parameters decreased monotonically with decreasing size of the RE cation, while the monoclinic angle remained fairly constant. The epitaxial relationship between the (110)-layered RE₂Ti₂O₇ films and the SrTiO₃(110) substrate was found by XRD and transmission electron microscopy to be . The single-phase, metastable, epitaxial, 100 nm thick films maintained the layered perovskite structure even after annealing at 900 °C for two hours in 200 Torr of oxygen.     

A neutron diffraction study of the d and d lithium garnets Li3Nd3W2O12 and Li5La3Sb2O12

The garnets Li₃Nd₃W₂O₁₂ and Li₅La₃Sb₂O₁₂ have been prepared by heating the component oxides and hydroxides in air at temperatures up to 950 °C. Neutron powder diffraction has been used to examine the lithium distribution in these phases. Both compounds crystallise in the space group with lattice parameters a=12.46869(9) Å (Li₃Nd₃W₂O₁₂) and a=12.8518(3) Å (Li₅La₃Sb₂O₁₂). Li₃Nd₃W₂O₁₂ contains lithium on a filled, tetrahedrally coordinated 24d site that is occupied in the conventional garnet structure. Li₅La₃Sb₂O₁₂ contains partial occupation of lithium over two crystallographic sites. The conventional tetrahedrally coordinated 24d site is 79.3(8)% occupied. The remaining lithium is found in oxide octahedra which are linked via a shared face to the tetrahedron. This lithium shows positional disorder and is split over two positions within the octahedron and occupies 43.6(4)% of the octahedra. Comparison of these compounds with related d⁰ and d¹⁰ phases shows that replacement of a d⁰ cation with d¹⁰ cation of the same charge leads to an increase in the lattice parameter due to polarisation effects.     

Temperature-dependent structural study of microporous CsAlSi5O12

CsAlSi₅O₁₂ crystals were synthesized at high temperature by slow cooling of a vanadium oxide flux. Single-crystal X-ray diffraction structure analysis and electron microprobe analyses yielded the microporous CAS zeolite framework structure of Cs_0.85Al_0.85Si_5.15O₁₂ composition. High-temperature single-crystal and powder X-ray diffraction studies were utilized to analyze anisotropic thermal expansion. Rietveld refined cell constants from powder diffraction data, measured in steps of 25 °C up to 700 °C, show a significant decrease in expansion above 500 °C. At 500 °C, a displacive, static disorder-dynamic disorder-type phase transition from the acentric low-temperature space group Ama2 to centrosymmetric Amam (Cmcm in standard setting) was found. Thermal expansion below the phase transition is governed by rigid-body TO₄ rotations accompanied by stretching of T-O-T angles. Above the phase transition at 500 °C all atoms, except one oxygen (O6), are fixed on mirror planes. Temperature-dependent polarized Raman single-crystal spectra between −270 and 300 °C and unpolarized spectra between room temperature and 1000 °C become increasingly less resolved with rising temperature confirming the disordered static-disordered dynamic type of the phase transition.     

High-temperature neutron diffraction study of the cation ordered perovskites TbBaMn2O5+x and TbBaMn2O5.5−y

The miscibility of TbBaMn₂O_5+x and TbBaMn₂O_5.5−y has been investigated at 100-600 °C using in situ powder neutron diffraction. No miscibility is observed, and the two phases remain oxygen stoichiometric (x,y=0) at 600 °C. Structure refinement results show that neither material undergoes a phase transition in this temperature range. TbBaMn₂O₅ is Mn²⁺/Mn³⁺ charge ordered and any charge melting transition is >600 °C. This symmetry-broken charge ordering is remarkably robust in comparison to that in other oxides.     

Ternary rare-earth titanium antimonides: Phase equilibria in the RE-Ti-Sb (RE=La, Er) systems and crystal structures of RE2Ti7Sb12 (RE=La, Ce, Pr, Nd) and RETi3(SnxSb1-x)4 (RE=Nd, Sm)

Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 °C. In the La-Ti-Sb system, the previously known compound La₃TiSb₅ was confirmed and the new compound La₂Ti₇Sb₁₂ (own type, Cmmm, Z=2, a=10.5446(10) Å, b=20.768(2) Å, and c=4.4344(4) Å) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La₂Ti₇Sb₁₂ consists of a complex arrangement of TiSb₆ octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi₃(Sn_xSb_1−x)₄ for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) Å, b=10.0846(7) Å, and c=24.2260(16) Å for NdTi₃(Sn_0.1Sb_0.9)₄; a=5.7590(4) Å, b=10.0686(6) Å, and c=24.1167(14) Å for SmTi₃(Sn_0.1Sb_0.9)₄). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets.     

Hydrothermal synthesis, thermal, structural, spectroscopic and magnetic studies of the Mn5−xCox(HPO4)2(PO4)2(H2O)4 (x=1.25, 2, 2.5 and 3) finite solid solution

The Mn_5−xCo_x(HPO₄)₂(PO₄)₂(H₂O)₄ (x=1.25, 2, 2.5, 3) finite solid solution has been synthesized by mild hydrothermal conditions under autogeneous pressure. The phases crystallize in the C2/c space group with Z=4, belonging to the monoclinic system. The unit-cell parameters obtained from single crystal X-ray diffraction are: a=17.525(1), b=9.0535(6), c=9.4517(7) Å, β=96.633(5) ° being R1=0.0436, wR2=0.0454 for Mn75Co25; a=17.444(2), b=9.0093(9), c=9.400(1) Å, β=96.76(1) ° being R1=0.0381, wR2=0.0490 for Mn60Co40; a=17.433(2), b=8.9989(9), c=9.405(1) Å, β=96.662(9) ° being R1=0.0438, wR2=0.0515 for Mn50Co50 and a=17.4257(9), b=8.9869(5), c=9.3935(5) Å, β=96.685(4) ° being R1=0.0296, wR2=0.0460 for Mn40Co60. The structure consists of a three dimensional network formed by octahedral pentameric entities (Mn,Co)₅O₁₆(H₂O)₆ sharing vertices with the (PO₄)³⁻ and (HPO₄)²⁻ tetrahedra. The limit of thermal stability of these compounds is, approximately, 165 °C, near to this mean temperature the phases loose their water content in two successive steps. IR spectra show the characteristic bands of the water molecules and the phosphate and hydrogen-phosphate oxoanions. The diffuse reflectance spectra are consistent with the presence of MO₆ octahedra environments in slightly distorted octahedral geometry, except for the M(3)O₆ octahedron which presents a remarkable distortion and so a higher Dq parameter. The mean value for the Dq and B-Racah parameter for the M(1),(2)O₆ octahedra is 685 and 850 cm⁻¹, respectively. These parameters for the most distorted M(3)O₆ polyhedron are 825 and 880 cm⁻¹, respectively. The four phases exhibit antiferromagnetic couplings as the major magnetic interactions. However, a small spin canting phenomenon is observed at low temperatures for the two phases with major content in the anisotropic-Co(II) cation.     

Crystal structure and physical properties of the quaternary manganese-bearing pavonite homologue Mn1.34Sn6.66Bi8Se20

The quaternary manganese tin bismuth selenide, Mn_1.34Sn_6.66Bi₈Se₂₀ was synthesized by combining constituent elements at 723 K. Single crystal structure determination revealed that Mn_1.34Sn_6.66Bi₈Se₂₀ is isostructural to the mineral pavonite, AgBi₃S₅, crystallizing in the monoclinic space group C2/m (#12) with a=13.648(3) Å; b=4.175(1) Å; c=17.463(4) Å; β=93.42(3)°. In the structure, two kinds of layered modules, denoted A and B, alternate along [0 0 1]. Module A consists of paired chains of face-sharing monocapped trigonal prisms (around Bi/Sn) separated by a single chain of edge-sharing octahedra (around Mn/Sn). Module B represents a NaCl-type fragment of edge-sharing [(Bi/Sn)Se₆] octahedra. Mn_1.34Sn_6.66Bi₈Se₂₀ is an n-type narrow gap semiconductor with E_g∼0.29 eV. At 300 K, thermopower, electrical conductivity and lattice thermal conductivity values are −123 μV/K, 47 S/cm and 0.6 W/m K, respectively. Mn_1.34Sn_6.66Bi₈Se₂₀ is paramagnetic at high temperatures and undergoes antiferromagnetic transition at T_N=10 K.     

Synthesis, crystal structure and magnetic properties of the Sr2Al0.78Mn1.22O5.2 anion-deficient layered perovskite

A new layered perovskite Sr₂Al_0.78Mn_1.22O_5.2 has been synthesized by solid state reaction in a sealed evacuated silica tube. The crystal structure has been determined using electron diffraction, high-resolution electron microscopy, and high-angle annular dark field imaging and refined from X-ray powder diffraction data (space group P4/mmm, a=3.89023(5) Å, c=7.8034(1) Å, R_I=0.023, R_P=0.015). The structure is characterized by an alternation of MnO₂ and (Al_0.78Mn_0.22)O_1.2 layers. Oxygen atoms and vacancies, as well as the Al and Mn atoms in the (Al_0.78Mn_0.22)O_1.2 layers are disordered. The local atomic arrangement in these layers is suggested to consist of short fragments of brownmillerite-type tetrahedral chains of corner-sharing AlO₄ tetrahedra interrupted by MnO₆ octahedra, at which the chain fragments rotate over 90°. This results in an averaged tetragonal symmetry. This is confirmed by the valence state of Mn measured by EELS. The relationship between the Sr₂Al_0.78Mn_1.22O_5.2 tetragonal perovskite and the parent Sr₂Al_1.07Mn_0.93O₅ brownmillerite is discussed. Magnetic susceptibility measurements indicate spin glass behavior of Sr₂Al_0.78Mn_1.22O_5.2. The lack of long-range magnetic ordering contrasts with Mn-containing brownmillerites and is likely caused by the frustration of interlayer interactions due to presence of the Mn atoms in the (Al_0.78Mn_0.22)O_1.2 layers.     

Multianvil high-pressure/high-temperature preparation, crystal structure, and properties of the new oxoborates Dy4B6O14(OH)2 and Ho4B6O14(OH)2

This paper reports about two new hydrogen-containing rare-earth oxoborates RE₄B₆O₁₄(OH)₂ (RE=Dy, Ho) synthesized under high-pressure/high-temperature conditions from the corresponding rare-earth oxides, boron oxide, and water using a Walker-type multianvil equipment at 8 GPa and 880 °C. The single crystal structure determination of Dy₄B₆O₁₄(OH)₂ showed: Pbcn, a=1292.7(2), b=437.1(2), , Z=2, R1=0.0190, and wR2=0.0349 (all data). The isotypic holmium species revealed: Pbcn, a=1292.8(2), b=436.2(2), , Z=2, R1=0.0206, and wR2=0.0406 (all data). The compounds exhibit a new type of structure, which is built up from layers of condensed BO₄-tetrahedra. Between the layers, the rare-earth cations are coordinated by 7+2 oxygen atoms. Furthermore, we report about temperature-resolved in situ powder diffraction measurements, DTA/TG, and IR-spectroscopic investigations into RE₄B₆O₁₄(OH)₂ (RE=Dy, Ho).     

Synthesis and crystal structure of (ThCu3)(Mn3+2Mn4+2)O12, a new ferrimagnetic perovskite-like compound

Single crystals of [ThCu₃](Mn³⁺₂Mn⁴⁺₂]O₁₂, a ferrimagnetic perovskite-like compound, have been synthesized by hydrothermal conditions at 600°C and 2 kbar. They have been found to be cubic, of space group Im3, with a = 7.359 Å, and isostructural with [NaMn₃](Mn³⁺₂Mn⁴⁺₂)O₁₂. The crystal structure has been refined by single-crystal X-ray diffraction data. The Th⁴⁺ cations are surrounded by slightly distorted icosahedra; the ThO distance is 2.556 Å. The Cu²⁺ cations are also surrounded by 12 oxygens, which are arranged as three mutually perpendicular rectangles of different size, the smallest and the largest of which are almost squares. The three sets of CuO distances are 1.973, 2.800, and 3.238 Å. The octahedral MnO distance is 1.950 Å. A test based on neutron diffraction powder data indicated that the square sites are occupied by only the Cu²⁺ cations.     

Crystal Structure Refinement and Magnetic Properties of Fe4(P2O7)3 Studied by Neutron Diffraction and Mössbauer Techniques

Fe₄(P₂O₇)₃ was prepared from Fe(PO₃)₃ and FePO₄ at 940°C under oxygen. The unit cell is monoclinic, space group P2₁/n, with a=7.389(2) Å, b=21.337(1) Å, c=9.517(2) Å, β=90(1)°, and Z=4. The crystallographic structure has been determined from a single crystal through direct methods and difference Fourier synthesis and refined to R=0.10 (R_w=0.09). The three-dimensional framework is built up from Fe₂O₉ clusters of two face-sharing octahedra, linked by bent diphosphates P₂O₇ (P-O-P∼156°). Fe₄(P₂O₇)₃ is antiferromagnetic below T_N=50 K. The magnetic structure has been determinated by means of powder neutron diffraction. There are four antiferromagnetic iron sublattices corresponding to the four crystallographically distinct iron atoms. The magnetic moments are antiferromagnetically coupled inside the Fe₂O₉ dimers, in agreement with the Goodenough rules. They are parallel to the c axis and have 4.55(5) μ_B value at 1.7 K. The magnetic interactions are discussed. Mössbauer spectra are fitted with four doublets and sextuplets in the paramagnetic and antiferromagnetic states, respectively. Their rather high isomer shifts are explained by the inductive effect.     

Crystal and Magnetic Structures of Ba4Mn3O10

A polycrystalline sample of Ba₄Mn₃O₁₀ has been prepared and characterized by X-ray diffraction (290 K), neutron diffraction (290, 80, 5 K) and magnetometry (5≤T(K)≤1000). At 290 K the compound is paramagnetic and isostructural with Ba₄Ti₂PtO₁₀. Mn₃O₁₂ trimers, built up from MnO₆ octahedra, are linked through common vertices to form corrugated sheets perpendicular to the y-axis of the orthorhombic unit cell (Space group Cmca, a=5.6850(1), b=13.1284(1), c=12.7327(1) Å); Ba atoms occupy the space between the layers. On cooling, the magnetic susceptibility shows a broad maximum at ∼130 K, and a sharp transition at 40 K. Neutron diffraction has shown that long-range antiferromagnetic order is present at 5 K but not at 80 K, although magnetometry at 5 K has revealed a remanent magnetization (0.002 μ_B per Mn) which is below the detection limit of the neutron experiment.     

Synthesis and crystal structure of Ln2MGe4O12, Ln=rare-earth element or Y; M=Ca, Mn, Zn

The crystal structure of the promising optical materials Ln₂M²⁺Ge₄O₁₂, where Ln=rare-earth element or Y; M=Ca, Mn, Zn and their solid solutions has been studied in detail. The tendency of rare-earth elements to occupy six- or eight-coordinated sites upon iso- and heterovalent substitution has been studied for the Y_2−xEr_xCaGe₄O₁₂ (x=0-2), Y_2−2xCe_xCa_1+xGe₄O₁₂ (x=0-1), Y₂Ca_1−xMn_xGe₄O₁₂ (x=0-1) and Y_2−xPr_xMnGe₄O₁₂ (x=0-0.5) solid solutions. A complex heterovalent state of Eu and Mn in Eu₂MnGe₄O₁₂ has been found.     

Crystal structure of the monoclinic and cubic polymorphs of BiMn7O12

The complex perovskite BiMn₇O₁₂ occurs with two polymorphic structures, cubic and monoclinic. Currently their crystal structures are investigated with high-resolution synchrotron powder X-ray diffraction at room temperature. Rietveld analysis reveals unusual behavior for, respectively, the oxygen and bismuth atoms in the monoclinic and cubic phases. Bond valence calculations indicate that all the Mn atoms in both the phases are in trivalent state. Possible roles of the 6s² lone-pair electrons of Bi³⁺ in BiMn₇O₁₂ are discussed in comparison with the LaMn₇O₁₂ phase that is isomorphic to monoclinic BiMn₇O₁₂. Multiple roles of the lone-pair electrons are revealed, causing (i) A-site cation deficiency, (ii) octahedral tilting, (iii) A-site cation displacement, and (iv) Mn³⁺ Jahn-Teller (JT) distortion. Relationships between the monoclinic and cubic phases are discussed with emphasis on the MnO₂ and MnO₆ local structural aspects. All Mn atoms in the monoclinic polymorph have distorted coordination consistent with JT-active Mn(III) high spin, whereas for the cubic polymorph, the B-site Mn atoms show regular octahedral coordination.     

Preparation of Mn3O4 nanocrystallites by low-temperature solvothermal treatment of γ-MnOOH nanowires

The preparation of trimanganese tetroxide (Mn₃O₄) nanocrystallites from γ-MnOOH nanowires under mild conditions has been achieved by two steps: first, γ-MnOOH nanowires with a mean diameter of about 12 nm and lengths of up to several micrometers were directly prepared via hydrothermal reaction between KMnO₄ and toluene in water at 180°C for 24 h; then, pure Mn₃O₄ nanocrystallites could be obtained by solvothermal treatment of the γ-MnOOH nanowires in ethylenediamine (EDA) and ethylene glycol (EG) at 150°C for 24 h. It was found that the Mn₃O₄ product obtained in EDA comprised well-defined nanocrystallites with the size in the range of 15-35 nm, while the one obtained in EG consisted of aggregated nanoparticles with the size of less than 18 nm.The possible formation mechanism of nanocrystalline Mn₃O₄ in EDA and EG and reasons for the different effects of various solvents on the products were also proposed.     

Subsolidus phase equilibria and properties in the system Bi2O3:Mn2O3±x:Nb2O5

Subsolidus phase relations have been determined for the Bi-Mn-Nb-O system in air (750-900 °C). Phases containing Mn²⁺, Mn³⁺, and Mn⁴⁺ were all observed. Ternary compound formation was limited to pyrochlore (A₂B₂O₆O′), which formed a substantial solid solution region at Bi-deficient stoichiometries (relative to Bi₂(Mn,Nb)₂O₇) suggesting that ≈14-30% of the A-sites are occupied by Mn (likely Mn²⁺). X-ray powder diffraction data confirmed that all Bi-Mn-Nb-O pyrochlores form with structural displacements, as found for the analogous pyrochlores with Mn replaced by Zn, Fe, or Co. A structural refinement of the pyrochlore 0.4000:0.3000:0.3000 Bi₂O₃:Mn₂O_3±x:Nb₂O₅ using neutron powder diffraction data is reported with the A and O′ atoms displaced (0.36 and 0.33 Å, respectively) from ideal positions to 96g sites, and with Mn²⁺ on A-sites and Mn³⁺ on B-sites (Bi_1.6Mn²⁺_0.4(Mn³⁺_0.8Nb_1.2)O₇, (?227), a=10.478(1) Å); evidence of A or O′ vacancies was not found. The displacive disorder is crystallographically analogous to that reported for Bi_1.5Zn_0.92Nb_1.5O_6.92, which has a similar concentration of small B-type ions on the A-sites. EELS spectra for this pyrochlore were consistent with an Mn oxidation between 2+ and 3+. Bi-Mn-Nb-O pyrochlores exhibited overall paramagnetic behavior with negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. At 300 K and 1 MHz the relative dielectric permittivity of Bi_1.600Mn_1.200Nb_1.200O₇ was ≈128 with tan δ=0.05; however, at lower frequencies the sample was conductive which is consistent with the presence of mixed-valent Mn. Low-temperature dielectric relaxation such as that observed for Bi_1.5Zn_0.92Nb_1.5O_6.92 and other bismuth-based pyrochlores was not observed. Bi-Mn-Nb-O pyrochlores were readily obtained as single crystals and also as textured thin films using pulsed laser deposition.