Structural properties and Raman spectroscopy of orthorhombic (Eu1−xPrx)0.6Sr0.4MnO3 (0≤x≤1.0)

The effect of Pr doping on structural properties and room temperature Raman spectroscopy measurements is investigated in manganites (Eu_1−xPr_x)_0.6Sr_0.4MnO₃ (0≤x≤1.0) with fixed carrier concentration. The result of the Rietveld refinement of x-ray powder diffraction shows that these compounds crystallize in an orthorhombic distorted structure with a space group Pnma. It is evident that, with increasing Pr substitution, three types of orthorhombic structures can be distinguished. The phonon frequencies of the three main peaks, in room temperature Raman-scattering measurements, have been discussed together with their structural characteristics, such as bond-length, bond-angles, and the change of orthorhombic structure type. With the increase of Pr content, the mode at 491  cm⁻¹ also shows a corresponding change. A step effect becomes evident, which seems to indicate the close dependence between the frequency shift of this mode and the change in crystal symmetry. This further supports the notion that the mode at 491  cm⁻¹ is closely correlated with the Jahn–Teller distortion. Moreover, we have found that the lowest frequency peak (assigned as an A_1g phonon mode) depends linearly on the tolerance factor t.     

Reinvestigation of the magnetic structure of Ca3Mn2Ge3O12

Precise neutron diffraction experiments performed on powdered antiferromagnetic garnet Ca₃Mn₂Ge₃O₁₂ lead to a complex non collinear magnetic structure. In the absence of magnetic field, it is three dimensional with eight spin directions and belongs to ¹I_41/a. At a critical magnetic field spin-flop mechanism occurs with a lowering of the magnetic symmetry which becomes triclinic. In addition to tetragonal anisotropy, both single ion orthorhombic anisotropy and its antisymmetrical counterpart for definite pairs of ions are required to explain both the observed structure and its behaviour in a magnetic field.     

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn²⁺ and Cu²⁺ ions doped calcium cadmium acetate hexahydrate (CaCd(CH₃COO)₄·6H₂O) have been reported. The investigation has been carried out in the temperature range between room temperature (～ 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH₃ groups which become frozen at ～ 128 K. The incorporation of Cu²⁺ and Mn²⁺ probes at Ca²⁺ and Cd²⁺ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca²⁺ and Cd²⁺ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.     

Ce emission in hexagonal and orthorhombic phases of CaSO4

CaSO₄ exists in several phases. The most common phase of CaSO₄ is orthorhombic and reported Ce³⁺ emission corresponds to this phase. However, significant change in the emission of Ce³⁺ is observed when CaSO₄ crystallizes in hexagonal phases. The emission is observed at 354 nm as compared to the spilt band at 305 and 326 nm for the orthorhombic phase. The preparation procedure and photoluminescence spectra for orthorhombic and hexagonal phases are described in this paper.     

Conductivity and specific heat anomalies at the low temperature transition in the stoichiometric YFe2O4

Anomalies were found in electrical conductivity and specific heat at the two-step transition in the stoichiometric YFe₂O₄. It is concluded that the transition is a new type of Verwey transition: i.e., ordering of ionic charge, Fe²⁺ and Fe³⁺, accompanied by lattice distortion and antiferromagnetic spin ordering.     

Magnetische struktur von columbiten MnTa2O6 und CoNb2O6

By means of neutron diffraction we found for MnTa₂O₆S₁S₂ S₃S₄ with a magnetic unit which is the same as the chemical. Whereas the chemical unit of CoNb₂O₆ is doubled in c-direction; all spins in the chemical unit are parallel. Therefore the orthorhombic symmetry of the crystal structure cannot be maintained. In both compositions are the spins parallel to the a-axis.     

A comment on the structure of K2CuF4

The structure of K₂CuF₄ has been investigated by X-ray diffraction. Some samples displayed a multi-domain structure which arises from the possibility of the co-existence of the x and y axes in the [110]_p direction of a pseudo K₂NiF₄-type structure. The structure was determined using a single-domain crystal to be of orthorhombic symmetry, D¹⁸_2h-Bbcm, with four molecules per unit cell. The displacement of F^- ions can be explained by the orbital ordering model assumed by Khomskii and Kugel.     

Temperature and composition dependence of vibrational modes in Sm1−xLaxAlO3

At room temperature and for x₀ ～ 0.43, the system Sm_1?xLa_xAlO₃ undergoes a first order phase transition in which an orthorhombic structure transforms into a rhomboedral structure as x increases. This phase transition was investigated by Raman scattering experiments on polycrystalline compounds in the range 0 ? x ? 1. The dependence of low frequency modes on x is reported and compared with their well known temperature dependence. Soft modes have been observed in the orthorhombic (D_2h¹⁶) and rhomboedral (D_3d⁶) phases. It was found that the first order phase transition is probably driven by a double degenerate mode whose two components in the low symmetry phase display a linear composition dependence of their squared frequencies. The source of anomalous behaviour of Raman bands near the phase transition is discussed.     

EPR spectra of Fe centers in layered TlGaSe2 single crystal

A single-crystal TlGaSe₂ doped by paramagnetic Fe ions has been studied at room temperature by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra were interpreted to correspond to the transitions among spin multiplet (S=5/2, L=0) of Fe³⁺ ion, which are splitted by the local ligand crystal field (CF) of orthorhombic symmetry. Four equivalent Fe³⁺ centers have been observed in the EPR spectra and the local symmetry of crystal field at the Fe³⁺ site and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of GaSe₄ tetrahedrons, and the rhombic distortion of the CF is caused by the Tl ions located in the trigonal cavities between the tetrahedral complexes.     

Structural phase transition in superconducting BaPb0.75Bi0.25O3

The room temperature crystallographic properties of distorted perovskite-type system BaPb_1-xBi_xO₃ were examined by using X-ray diffraction analysis. In addition, structural temperature changes were investigated for superconducting BaPb_0.75Bi_0.25O₃ crystals with T_c=11.4K. It was found that the room temperature structure of BaPb_1-xBi_xO₃ has an orthorhombic symmetry in the range of O≤×?0.9 and a monoclinic one in 0.9?×≤1, and that superconducting BaPb_0.75Bi_0.25O₃ shows a structural transition from an orthorhombic to a monoclinic phase at about 160K.     

Twinned EPR spectra of Fe centers in ternary layered TlGaS2 crystal

TlGaS₂ single crystal doped by paramagnetic Fe³⁺ ions has been studied by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra reveal a nearly orthorhombic symmetry of the crystal field (CF) on the Fe³⁺ ions. Two groups each consisting of four equivalent Fe³⁺ centers were observed in the EPR spectra. The local symmetry of the crystal field on the Fe³⁺ centers and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of the GaS₄ tetrahedrons. The rhombic distortion of the sulfur ligand CF is attributed to the effect of Tl ions located in the trigonal cavities between the tetrahedral complexes. The observed twinning of the resonance lines indicates a presence of two non-equivalent positions of Tl ions that confirms their zigzag alignment in the TlGaS₂ crystal structure.     

Nd5Fe18B18 (Nd1.11Fe4B4), a new nowotny-like phase. structural and magnetic properties

The crystal structure of a ternary compound, whose chemical composition is Nd₅Fe₁₈B₁₈, has been determined. Nd atoms on the one hand, Fe and B atoms on the other hand, form 2 different substructures, both of tetragonal symmetry. In a previous investigation¹ only incommensurate or very long period ordering along the $\overrightarrow{c}$ directions between the 2 substructures was proposed, with non-definite composition. The whole structure is now described in the Pccn orthorhombic space group (a=b=7.117Å ; c = 35.07Å). This compound appears then as a new Nowotny-like phase. Fe atoms are essentially non magnetic. Ferromagnetic order between Nd atoms occurs only below 14 K. 2^nd order Crystalline Electric Fiel (CEF) terms are deduced from the anisotropy of the paramagnetic susceptibility. Higher order CEF terms must also be considered.     

Preparation and luminescence properties of Y2(WO4)3: Eu3+

A red-emitting Y₂(WO₄)₃: Eu³⁺ phosphor (orthorhombic high temperature phase, anhydride) is prepared by two different methods: the firing of mixtures of constituent oxides and that of precipitates from aqueous solutions. After optimizing preparation conditions, the cathodoluminescence brightness reaches 56% that of Y₂O₂S: Eu³⁺, a commercial red phosphor for color TV. Formation of a high temperature phase below the reported transition temperature is noted in the fired precipitates. This phase occurrence is shown to depend on the treatment of the precipitates to be fired. Reflection difference measurement of Eu-doped and undoped samples assigns an excitation band of about 245 nm to the Eu-O charge transfer band. Different by-products in the two preparation methods are identified by measuring emission spectra under selective excitation. Reversible hydration-dehydration of the phosphor is demonstrated by successively measuring photoluminescence first in vacuum and then in air at various temperatures. No deterioration of luminescence efficiency is observed after repeating this reversible structural change.     

掺入Ni2+和V3+对α-Al2O3晶体光谱精细结构、晶体局域结构和零场分裂参量的影响

应用晶体场理论和不可约张量算符方法构造了3d2/3d8态离子在C3v对称晶场中包含自旋-轨道相互作用、自旋-自旋相互作用、自旋-其它轨道相互作用和其它轨道-其它轨道相互作用四种微观磁效应的45阶可完全对角化的能量哈密顿矩阵.利用该矩阵,计算了V³⁺∶α-Al₂O₃和Ni²⁺∶α-Al₂O₃晶体的光谱精细结构、晶体局域结构和零场分裂参量,研究了掺入两种互补态离子Ni²⁺和V³⁺对同种晶体的光谱精细结构、晶体局域结构和零场分裂参量的影响,理论计算值和实验值相符.研究发现：掺杂没有改变晶体的光谱精细结构和能级分裂条数,但改变了能级间距|掺杂也没有改变晶体的对称性,但使晶体局域结构发生了一定程度的畸变| Ni²⁺∶α-Al₂O₃晶体局域结构的伸长畸变量大于V³⁺∶α-Al₂O₃晶体,键角的变化量小于V³⁺∶α-Al₂O₃晶体.     

Lattice vibrations in the orthorhombic commensurate charge density wave phase of 2H-TaSe2

Lattice vibrations in 2H-TaSe₂ have been reinvestigated by Raman scattering in view of the recent orthorhombic structure of the commensurate charge density wave (CCDW) phase. The renormalization of six charge density waves on two layers gives four A_g modes and two B_1g modes in the orthorhombic CCDW phase, in place of two A_1g modes and two E_2g modes in the hexagonal CCDW phase which had been believed. The splitting of the E_2g modes to the A_g and B_1g modes in the orthorhombic symmetry depends on the interlayer interaction. The observed small splitting less than 3 cm^-1 shows the weak interlayer interaction. The energies of the four A_g modes and the two B_1g modes are presented as a function of temperature.     

Phase transition in (1−x)Ba(Y1/2Nb1/2) O3-xPbTiO3 solid solution with two morphotropic phase boundaries studied by Raman spectroscopy

New (1−x)Ba(Y_1/2Nb_1/2)O₃-xPbTiO₃ ceramics have been synthesized by conventional mixed-oxide process. Two morphotropic phase boundaries (MPBs) corresponding to the rhombohedral-orthorhombic and orthorhombic-tetragonal phases are observed with increasing PT. The appearance of E(2TO₁), E(2TO₂), silent, R_l and E(4LO) modes indicates the presence of an orthorhombic symmetry. Remarkable variation with two MPBs appears in the whole frequency region, where the rhombohedral modes change into the tetragonal ones in the system.     

Synthesis,structure and magnetic properties of layered manganate Sr4Mn3−xCrxO10 (x=0, 0.2)

The manganates Sr₄Mn_3−xCr_xO₁₀ (x=0 and 0.2) have been synthesized by solid state reaction. Powder X-ray diffraction analysis shows orthorhombic symmetry with space group Cmca for both compounds. The magnetic susceptibility measurements show an antiferromagnetic transition at 192 and 176 K for x=0 and 0.2, respectively. The magnetic susceptibility data were estimated using a model based on spin exchange antiferromagnetic interactions in isolated (Mn⁴⁺) trimer; a paramagnetic contribution due to the chromium ions was added in the case of Cr-doped materials.     

Effect of Eu contents on the structure and properties of BaLa2ZnO5:Eu phosphors

A series of Eu³⁺ doped BaLa₂ZnO₅ was prepared by a Pechini-type sol-gel method. The effect of Eu³⁺ concentration on the structure and the luminescent properties of the samples BaLa_2−xEu_xZnO₅ were investigated by powder X-ray diffraction (XRD) and photoluminescence (PL) spectra. The sample adopts the tetragonal or orthorhombic structure as the Eu³⁺ concentration reaches below 1.2 or over 1.6, respectively. The sample is a mixture of tetragonal and orthorhombic phases as the contents of dopants lie between 1.2 and 1.6. The phosphor offers the strongest red light as content of Eu³⁺ is 0.4. In addition, the crystallization processes of the complex precursors were examined by simultaneous thermogravimetry and differential thermal analysis (TG-DTA), and also the optimal heating temperature was investigated.     

Ionic to electronic dominant conductivity in Al2(WO4)3 at high pressure and high temperature

Electrical conduction and crystal structure of Al₂(WO₄)₃ at 400 °C have been studied as a function of pressure up to 5.5 GPa using impedance methods and synchrotron radiation X-ray diffraction, respectively. AC impedance spectroscopy and DC polarization measurements reveal an ionic to electronic dominant transition in electrical conductivity at a pressure as low as 0.9 GPa. Conductivity increases with pressure and reaches a maximum at 4.0 GPa, where the conductivity value is 5 orders of magnitude greater than the 1 atm value. Upon decompression, the conductivity retains the maximum value until the sample is cooled at 0.5 GPa. The high pressure-temperature X-ray diffraction results show that the lattice parameters decrease as pressure increases and the crystal structure undergoes an orthorhombic to tetragonal-like transformation at a pressure ∼3.0 GPa. The change of conduction mechanism from ionic to electronic may be explained by means of pressure-induced valence change of W⁶⁺→W⁵⁺, which results in electron transfer between W⁵⁺-W⁶⁺ sites at high pressure.