Elastic behavior of some manganite-based orthorhombic RMnO3 (R=Sm,Eu, Gd,Dy) multiferroics

A series of multiferroic materials with the compositional formula, RMnO₃ (where R=Sm, Eu, Gd, Dy) were prepared by the well-known citrate sol–gel technique. After characterizing the samples structurally, a systematic investigation of elastic behavior has been undertaken and it has been found that the elastic moduli are increasing continuously with decreasing ionic radii of the dopant ion. Variation of longitudinal velocity with temperature for all the samples, over a temperature range 80–300 K has also been studied and the observed experimental behavior is explained using four theoretical models. It has been concluded that Lakkad's model explains the variation of Young's modulus with temperature in a better way than the other ones.     

NMR study of hyperfine interactions in R1−xLuxFe2 (R = Gd, Tb)

Spin-echo NMR measurements on ¹⁵⁵Gd, ¹⁵⁹Tb and ¹⁷⁵Lu have been done for the cubic Laves phase compounds Gd_1−xLu_xFe₂ and Tb_1−xLu_xFe_x. The observed hyperfine fields of Gd and Lu in those compounds increase with increasing Lu concentration. The concentration dependence of the Lu hyperfine field is qualitatively discussed.     

Magnetic ordering in RCoSi2 (R = Tb, Dy, Ho) compounds

The crystal and magnetic structures of TbCoSi₂, DyCoSi₂ and HoCoSi₂ were studied by neutron diffraction using polycrystalline samples. At 4.2 K all three exhibit antiferromagnetic ordering: DyCoSi₂ and HoCoSi₂ of collinear. TbCoSi₂ of complex spiral types.     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

Magnetic properties and hyperfine interactions in RCo2B2 (R = Nd,Gd, Tb)

The magnetic properties of RCo₂B₂ compounds which crystallize in the ThCr₂Si₂ structure with R = Nd, Gd, Tb have been investigated. The magnetic structure is ferromagnetic for NdCo₂B₂ and GdCo₂B₂, T_c equals 32 and 26 K respectively and antiferromagnetic for TbCo₂B₂ (T_N = 19 K). Curie-Weiss behaviour is exhibited by all the compounds and the effective moments derived indicate that Co is diamagnetic. The difference in magnetic properties between RCo₂B₂ and other isomorphous RCo₂X₂ (X = Si, Ge) is discussed. Mössbauer studies of ¹⁵⁵Gd in GdCo₂B₂ yielded the hyperfine interaction parameters and determined the direction of the magnetization to be in the basal plane. The electric quadropole interaction at 4.1 K is 580 MHz sec^?1, this is the largest ever found in an intermetallic Gd containing compound.     

Luminescent properties of R2(MoO4)3:Eu (R=La, Y, Gd) phosphors prepared by sol-gel process

A series of red phosphors R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) have been synthesized by sol-gel method. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA), and the properties of these resulting phosphors have also been characterized by photoluminescence (PL) spectra and reflectance spectra. Field emission scanning electron microscopy (FE-SEM) was also used to characterize the shape and the size of the samples. The results of TG-DTA and XRD indicated that all of the R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) phosphors crystallized completely at 650 °C. Y_0.8Eu_1.2(MoO₄)₃ and Gd_0.8Eu_1.2(MoO₄)₃ have two structures, monoclinic and orthorhombic, while La_0.8Eu_1.2(MoO₄)₃ only adopts monoclinic structure. The luminescent properties of phosphors R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) are dependent on their structures to some extent. The orthorhombic Y_0.8Eu_1.2(MoO₄)₃ and Gd_0.8Eu_1.2(MoO₄)₃ phosphors show very similar luminescent properties, which differ from those of phosphors with monoclinic structure. For all of R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) phosphors, intense red emission is obtained by exciting at ∼394 and ∼465 nm which are owing to the sharp ⁷F₀→⁵L₆ and ⁷F₀→⁵D₂ lines of Eu³⁺. Two strongest lines at 394 and 465 nm in excitation spectra of these phosphors match well with the two popular emissions from near-UV and blue GaN-based LEDs, so they could be used as red components for white light-emitting diodes.     

Structural and magnetic properties of hydrides R3Fe29−xVxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and intrinsic magnetic properties of the hydrides R₃Fe_29−xV_xH_y (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed in this work. The lattice constants , and c and the unit cell volume of R₃Fe_29−xV_xH_y decrease with increasing rare-earth atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in regular anisotropic expansions along the a-, b-, and c-axes in this series of hydrides. Abnormal crystallographic and magnetic properties of Ce₃Fe_27.5V_1.5H_6.5, like Ce₃Fe_27.5V_1.5, suggest that the Ce ion is non-triply ionized. Hydrogenation leads to the increase in both Curie temperature for all the compounds and in the saturation magnetization at 4.2 K and RT for R₃Fe_29−xV_x with R=Y, Ce, Nd, Sm, Gd, and Dy, except for Tb. Hydrogenation also leads to a decrease in the anisotropy field at 4.2 K and RT for R₃Fe_29−xV_x with R=Y, Ce, Nd, Gd, Tb, and Dy, except for Sm. The Ce₃Fe_27.5V_1.5 and Gd₃Fe_28.4V_0.6 show the larger storage of hydrogen with y=6.5 and 6.9 in these hydrides.     

Heat capacities of Laves phase compounds RMn2 (R = Y, Gd and Er)

Measurements of heat capacity indicate that the Mn moment in YMn₂ has an itinerant character and an additional C_M is observable even above T_N. In GdMn₂, the Gd moments are in disorder at T_N simultaneously with the Mn moments. The CEF contributions in ErMn₂ are observed and are calculated using a single-ion Hamiltonian.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Structural and electrical studies of Ba5RTi3V7O30 (R=Ho,Gd, La) compounds

The ferroelectric ceramics Ba₅RTi₃V₇O₃₀ (R=Ho, Gd, La) have been synthesized by solid-state reaction technique. Preliminary X-ray structural analysis confirmed a single-phase formation of the compound in orthorhombic structure. Surface morphology of the compounds was studied by scanning electron microscopy (SEM). Detailed studies of electrical properties (i.e., dielectric constant, loss tangent, ac conductivity) as a function of temperature (RT-773 K) and at four different frequencies (1 kHz, 10 kHz, 100 kHz and 1 MHz) show ferroelectric–paraelectric phase transition of the compounds of diffuse-type. The activation energy has been evaluated from ac conductivity following Arrhenius equation. The conductivity pattern shows that it is strongly frequency dependent and obeys Jonscher's power relation.     

Relaxation and conductivity behaviour in the compounds: FeRGe2O7 (R=Pr,Tb)

AC measurements were performed on the thortveitite-like layered compounds, FeRGe₂O (R=Pr,Tb) in order to study their dielectric features, e.g. as a function of temperature. The main electrical response lies on impedance plots composed of two successive arcs with depressed centers. Bulk conductivity behavior is mostly Arrhenius for the measured temperatures. The associated bulk activation energies are close to 1 eV. Raw data were used to follow the temperature dependence of the dynamic parameters, ε′(ω) and σ′(ω). From logarithmic σ′(ω) vs. ω curves the dc component was obtained. ε′(ω) vs. log ω curves exhibit a dispersive behavior at low frequencies, reflecting blocking effects. E_dc and E_ac activation energies were also calculated, the last one obtained from σ′(ω) vs. 1000/T plots. Conductivity results suggest the occurrence of an extrinsic conducting mechanism. A structural instability was detected via the temperature dependence of permittivity, which has been ascribed to the presence of Ga-O-Ga bonds having associated angles different of 180°. Analyses of the results show that the interchange of Tb and Pr in the general formula FeRGe₂O₇ (R=Pr, Tb) involves only small differences in their global ac and dc behavior.     

Magnetic properties of the compounds R2Sc3Si4 (R=Gd, Tb, Dy, Ho, Er)

The magnetization of R₂Sc₃Si₄ compounds is measured in static magnetic fields up to 14 kOe in the temperature range 77–300 K. It is established that all compounds in the given series are paramagnetic at these temperatures. The paramagnetic Curie points are determined, and the effective magnetic moments are calculated. The measurements are performed on polycrystalline samples. Fiz. Tverd. Tela (St. Petersburg) 41, 1804–1805 (October 1999)     

Electronic and magnetic properties of the rare earth intermetallic compounds RRu4Sn6 (R=Nd, Sm, Gd, Tb, Dy and Ho)

A number of compounds of structural formula RRu₄Sn₆ (R=rare-earth element) have previously been reported to form in the tetragonal crystal structure with space group I4¯2m. In this structure the R atoms are well isolated from each other. We embarked on this study to investigate the physical properties and to compare with earlier results obtained on the strongly correlated, low charge-carrier density compound CeRu₄Sn₆. Here we report our results of crystallographic, electrical resistivity, and magnetic studies on this family of compounds. In contrast to the behaviour in CeRu₄Sn₆, magnetic ordering is evident at low temperatures in the compounds with R=Sm, Gd, and Dy, as is evidenced by well-resolved anomalies in the temperature dependence of the electrical resistivity and static magnetic susceptibility.     

Magnetic properties of R2WO6 (where R=Nd, Sm, Eu, Gd, Dy and Ho)

The magnetic and electrical measurements carried out on the R₂WO₆ tungstates showed a paramagnetic behaviour for samples with R=Nd, Gd, Dy and Ho and more complex one for samples with R=Sm and Eu in the temperature range 4.2-280 K and an insulating state at room temperature. With increasing atomic number of the R element the Curie-Weiss temperature increases from −43.5 K for Nd₂WO₆ to −2.7 K for Ho₂WO₆, excluding Sm₂WO₆ and Eu₂WO₆ compounds for that the Curie-Weiss region is not observed and the imaginary part of susceptibility is close to zero. The effective magnetic moment is close to the theoretical one for the free R ion and the magnetic moment measured in magnetic field of 14 T and at temperature of 4.2 K, generally, does not reach the saturation state. The temperature independent residual susceptibility is negative for Nd₂WO₆ and positive for the remaining compounds suggesting different proportions of the Landau, Pauli and van Vleck contributions to the total susceptibility. An increase of the orbital magnetic contribution to the total magnetic moment is suggested from the fitting of the Landé factor in the compounds under study.     

Temperature induced structural transformation in RRh3B2 (R  Sm,Gd) compounds

Quadrupole interaction measurements as a function of temperature in ¹¹¹In doped SmRh₃B₂ compounds show a structural transformation in the vicinity of ¹¹¹Cd probe nuclei. The results are consistent with a local structural change from hexagonal CaCu₅ type to the base centred monoclinic which prevails for heavy rare-earth compounds.     

Heat capacity of EuMnO3 and Eu0.7A0.3MnO3 (A=Ca,Sr) compounds

We carried out the heat capacity calculation of the magnetoresistance compounds EuMnO₃ and Eu_0.7A_0.3MnO₃ (where A=Ca and Sr) as a function of temperature from 5 to 100 K, using the Rigid Ion Model (RIM). The results on heat capacity for EuMnO₃ and Eu_0.7A_0.3MnO₃ (A=Ca and Sr) obtained by us are in good agreement with the measured values. Although strong electron–phonon interactions are present in these compounds but the lattice part of the specific heat also deserves proper attention. The parent compound EuMnO₃ exhibits two magnetic transitions at 35 and 47 K due to weak ferromagnetic (FM) component and antiferromagnetic (AF) ordering. In addition, we have reported cohesive energy (φ), molecular force constant (f), compressibility (β), Restrahalen frequency (υ₀), Debye temperature (θ_D) and Gruneisen parameter (γ) in the temperature range 5 K?T?100 K.     

Magnetic,dielectric and magnetoelectric properties of new family of orthorhombic multiferroic Eu1−xYxMNO3 manganites

Multiferroic ground states with a spatially modulated antiferromagnetic structure and electric polarization have been revealed in Eu_1−xY_xMnO₃ (0.2?x?0.5$0.2?x?0.5$) single crystals. While the slightly substituted (x?0.1$x?0.1$) compounds exhibited a transition from the incommensurate (IC) to the canted antiferromagnetic (CAF) state at _TCA<_TN$T_{\mathrm{CA}}<T_{\mathrm{N}}$, the transitions from IC to commensurate ferroelectric (C/FE) phase were observed at _Tlock<_TN$T_{\mathrm{lock}}<T_{\mathrm{N}}$ for x>0.2$x>0.2$. Various phase transitions were observed in the magnetic fields up to 250 kOe along a, b, c axes by magnetization, magnetostriction and electric polarization measurements which show an existence of a spontaneous electric polarization below T_lock.     

Magnetic susceptibility measurements for some of the intermetallic compounds R2Pt (R = Gd,Tb, Dy,Ho, Er)

The magnetic properties of some of the intermetallic compounds R₂Pt have been studied by means of susceptibility measurements. The compounds are probably ferrimagnetic or they possess some noncollinear structure. With the exception of Gd₂Pt two magnetic transitions with temperature are observed. At 4.2 K the magnetization of Tb₂Pt shows appreciable hysteresis. In the paramagnetic region the compounds confirm the free ion picture of the R³⁺ except for Gd₂Pt which is still in a nonparamagnetic state even at 300 K.     

Magnetic properties of off-stoichiometric R2Co3Zn14 (R=Y,Gd) single crystals

Single crystal X-ray diffraction data indicate that the R₂Co₃Zn₁₄ (R=Gd, Y) phase crystallizes non-stoichiometrically with a mixed occupancy of Co/Zn atoms on the 12-coordinated transition metal site and one of the three zinc sites. The crystals are rhombohedral with R-3m space group. Magnetization measurements provide no evidence of localized 3d electron moment in Y₂Co_2.3Zn_14.7 which is non-magnetic down to 1.8 K. Thermodynamic and transport measurements on two Gd₂Co_3+xZn_14−x crystals reveal that the extra cobalt influences temperature below which the samples enter into an antiferromagnetic state: T_N=31.5(3) K for Gd₂Co₃Zn₁₄ and 28(1) K for Gd₂Co_4.2Zn_12.8. A lower magnetic ordering temperature of T_mag=6.0(2) K is common in both Gd samples.