Vibrational spectra and elastic,piezoelectric, and magnetoelectric properties of HoFe3(BO3)4 and HoAl3(BO3)4 crystals

Raman spectra of light are obtained for HoFe₃(BO₃)₄ and HoAl₃(BO₃)₄ crystals at various temperatures and are used for determining the frequencies of crystal lattice vibrations at the center of the Brillouin zone. It is also found that the HoFe₃(BO₃)₄ crystal exhibits a phase transition at T _c ≈ 366 K. The magnetoelectric effect in the paramagnetic phase of these compounds is studied experimentally. The lattice vibration frequencies, elastic and piezoelectric moduli, Born dynamic charges, and the high-frequency permittivity are calculated using the density functional method. A peculiar behavior of the transverse acoustic vibration branch is observed in the Γ → Z direction of the Brillouin zone of the HoFe₃(BO₃)₄ crystal. The electric polarization induced by an external field is estimated using the calculated values of piezoelectric moduli and experimental values of magnetostriction.     

Features of magnetic and magnetoelectric properties of rare-earth multiferroic PrFe3(BO3)4 with the singlet ground state

The features of magnetization of rare-earth multiferroic PrFe₃(BO₃)₄ with the singlet ground state have been investigated theoretically. The magnetic anisotropy of the crystal has been studied. The temperature dependences of anisotropy constants have been calculated. The phase H-T diagram has been constructed. The dependences of the behavior of magnetization vectors of magnetic sublattices on the external magnetic field have been obtained. The magnetoelectric effect has been investigated, and the dependences of polarization on the temperature and field have been found for its various orientations. The theoretical data have been compared with the experimental data and their good agreement has been established.     

Magnetostriction and thermal expansion of HoAl3(BO3)4

The magnetostriction and thermal expansion of rare-earth aluminoborate HoAl₃(BO₃)₄ have been studied theoretically. The calculated field and temperature dependences of the multipole moments of the Ho³⁺ ion in HoAl₃(BO₃)₄ made it possible to describe the known experimental data and to predict possible anomalies of thermal expansion. It has been shown that, for the direction of the field B ‖ c, the nonmonotonic character of magnetostriction along the axis a is determined by the multipole moments, the main of which is β _J 〈O ₄ ⁰ 〉. For B ‖ a and B ‖ b, the maximum moments are β _J 〈O ₄ ² 〉and α _J 〈O ₂ ² 〉; their variation with the field and temperature explain well the form of magnetostriction. It has been established that the greater value of magnetostriction Δa/a for B ‖ b than for B ‖ a and the greater value of magnetostriction for the field in the basal plane than for B ‖ c are caused by greater variations in the field of actual multipole moments.     

Giant natural circular dichroism of vibronic transitions in HoAl3(BO3)4

The giant natural optical activity of vibronic replicas of the f–f ⁵ I ₈ → ⁵ F ₂ transition in HoAl₃(BO₃)₄ is observed. It exceeds the optical activity related to purely electronic transitions by two orders of magnitude and corresponds to the almost complete circular polarization of the transitions. This effect is explained by the local distortions of the crystal in the excited electronic state, which lead to the mixing of electron and vibrational wavefunctions and, as a consequence, to the delocalization of the vibronic wavefunction and the enhancement of spatial dispersion, which is responsible for the optical activity.     

Magnetization,magnetoelectric polarization,and specific heat of HoGa3(BO3)4

A comprehensive experimental and theoretical study of magnetic, magnetoelectric, thermal, and spectroscopic characteristics of HoGa₃(BO₃)₄ gallium borate single crystals has been performed. A large magnetoelectric effect exceeding its values found in all iron and aluminum borates except HoAl₃(BO₃)₄ has been observed. The magnetoelectric polarization of HoGa₃(BO₃)₄ equals ΔP _ba (B _a ) ≈ ?1020 μC/m² at T = 5 K in a magnetic field of 9 T. The theoretical treatment based on the crystal field model for rare-earth ions provides a unified approach for the consistent interpretation of all measured characteristics. The crystal-field parameters are determined. The temperature (in the 3–300 K range) and magnetic field (up to 9 T) dependences of the magnetization, the Schottky anomaly in the temperature dependence of the specific heat, and its shift in the field B ‖ c are described. To compare the thermal properties of HoGa₃(BO₃)₄ with those of HoAl₃(BO₃)₄ exhibiting record values of the polarization, the specific heat of HoAl₃(BO₃)₄ at various B values and the temperature dependence of the polarization ΔP _b (T) in the applied magnetic field of 9 T have been measured.     

Magnetic properties of HoFe3(BO3)4

The magnetic properties of an antiferromagnet with trigonal symmetry, namely, HoFe₃(BO₃)₄, have been investigated theoretically. The calculations have been performed in the molecular field approximation and in the framework of the crystal field model for the rare-earth subsystem. Extensive experimental data on the magnetic properties of HoFe₃(BO₃)₄ have been interpreted and good agreement between theory and experiment has been achieved using the obtained theoretical dependences. The spontaneous spin-reorientation transition and the spin-reorientation transition induced by a magnetic field B ‖ a from the easy-axis to easy-plane state, as well as the spin-flop transition in a magnetic field B ‖ c, have been described. It has been shown that the spontaneous spin-reorientation transition is a magnetic analog of the Jahn-Teller effect. The temperature dependences of the initial magnetic susceptibility at temperatures ranging from 2 to 300 K, the nonlinear curves of magnetization for B ‖ c and B ⊥ c in a magnetic field up to 1.2 T (which indicate the occurrence of first-order phase transitions), and their evolution with variations in the temperature have been described, as well as the temperature and field dependences of the magnetization in a magnetic field up to 9 T. The parameters of the trigonal crystal field for the rare-earth ion Ho³⁺ and the parameters of the Fe-Fe and Ho-Fe exchange interactions have been determined in the course of interpretation of the experimental data.     

Antiferromagnetic resonance and magnetic anisotropy in single crystals of the YFe3(BO3)4-GdFe3(BO3)4 system

The antiferromagnetic resonance in single crystals of the YFe₃(BO₃)₄-GdFe₃(BO₃)₄ system is studied in the frequency range 25–140 GHz and the temperature range 4.2–50.0 K. It is established that the YFe₃(BO₃)₄ crystal containing only the magnetic subsystem of Fe³⁺ ions is an antiferromagnet with an easy anisotropy plane. The temperature dependences of the gaps in the antiferromagnetic resonance spectra of GdFe₃(BO₃)₄ and Y _x Gd_{1 ? x} Fe₃(BO₃)₄ are used to calculate the contributions of the Fe³⁺ and Gd³⁺ subsystems to the magnetic anisotropy of these crystals. The contributions are found to be close in magnitude and have opposite signs. This leads to a relatively weak uniaxial anisotropy field in the crystals under investigation. Since the exchange interaction between the Gd³⁺ and Fe³⁺ ions magnetizes the magnetic subsystem of gadolinium, both subsystems start to contribute simultaneously at the Néel temperature of the iron subsystem.     

Magnetic properties of the rare-earth ferroborate SmFe3(BO3)4

The magnetic properties of trigonal antiferromagnet SmFe₃(BO₃)₄ are studied experimentally and theoretically. The measured characteristics are considered in terms of a theoretical approach based on the molecular field approximation and a crystal field model for a rare-earth ion. The temperature dependences of the initial magnetic susceptibility and the field and temperature dependences of magnetization in fields up to 5 T are described, and the anomaly in the magnetization curve for B ⊥ c near 1 T, which points to a first-order phase transition, is analyzed.     

Linear electro-optic properties of YCa4O(BO3)3

We have characterized the effective linear electro-optic coefficients of YCa4O(BO3)3 (YCOB) relative to KH2PO4 and KD2PO4 at 632.8 nm. We measured a maximum r(eff) value of 10.8 +/- 1.4 pm/V for YCOB in a transverse electric field configuration for propagation along the X or the alpha dielectric axis, with the electric field applied along the Z or the gamma dielectric axis. We also found effective coefficients of 10.7 +/- 1.0 and 3.4 +/- 0.4 pm/V for YCOB in longitudinal configurations. The remaining values of r(eff) for various transverse applied voltages were found to be less than 3 pm/V. The excellent thermomechanical properties of this crystal, coupled with moderate electro-optic coefficients, make YCOB and its isomorphs potential candidates for use as high-average-power electro-optic switches.     

Specific heat of YFe3(BO3)4, Y0.5Gd0.5Fe3(BO3)4, and GdFe3(BO3)4

The specific heat was measured in the range 0.4–300 K in YFe₃(BO₃)₄, Y_0.5Gd_0.5Fe₃(BO₃)₄, and GdFe₃(BO₃)₄ single crystals. Sharp anomalies were found at temperatures of first-order structural, second-order antiferromagnetic, and first-order spin-reorientational transitions. A Néel temperature of about 37 K was found to be virtually independent of presence of rare-earth ions, indicating rather weak coupling of Gd and Fe subsystems. The contribution of the magnetic system to specific heat was separated through the scaling procedure allowing determination of the magnetic entropy of Fe and Gd subsystems. At the lowest temperatures, the specific heat in GdFe₃(BO₃)₄ exhibits a Schottky-type anomaly, which is due to Gd³⁺ eightfold degenerate ground-level splitting by the internal magnetic field of the Fe subsystem of about 7 T. The text was submitted by the authors in English.     

Spectroscopic properties and structure of the ErFe3(BO3)4 single crystal

Single crystals of the ErFe₃(BO₃)₄ borate were synthesized and their structure was studied. Absorption spectra of the Er³⁺ ion in σ- and π-polarizations of f-f transitions ⁴ I _15/2 → ⁴ I _13/2, ⁴ I _11/2, ⁴ I _9/2, ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, and ⁴ F _7/2 were measured. The refractive index and birefringence were measured as a function of the wavelength. The transition intensities were analyzed within the Judd-Ofelt theory, and the following parameters of the theory were obtained: Ω₂ = 7.056 × 10^?20 cm², Ω₄ = 1.886 × 10^?20 cm², and Ω₆ = 2.238 × 10^?20 cm². Using these parameters, the radiative transition probabilities, luminescence branching ratios, and radiative lifetimes of multiplets were calculated.     

Nonlinear optical properties of LaCa(4)O(BO(3))(3)

We have grown LaCa(4)O (BO(3))(3) (LaCOB), an isostructural member of GdCa(4)O(BO(3))(3) (GdCOB) family and characterized its nonlinear optical properties. At 1064nm, d(eff) of 0.52+/-0.05 pm /V and an angular sensitivity of 1224+/-184(cm rad)(-1) for type I frequency doubling in LaCOB were determined relative to those of KTiOPO(4) , beta-BaB(2)O(4) , KD(2)PO(4) , LiB(3)O(5) , YCa(4)O(BO(3))(3) (YCOB), and GdCOB. The d(alphabetabeta) and d(gammabetabeta) coefficients of the nonlinear optical tensor for LaCOB, GdCOB, and YCOB were determined to be equivalent within the experimental uncertainty and have values of ?0.26+/-0.04?pm/V and ?1.69+/-0.17?pm /V , respectively. From phase-matching angle measurements at 1064 and 1047nm, we predict that LaCOB is noncritically phase matched at 1042+/-1.5 nm .     

Luminescent properties of Yb-doped LaSc3(BO3)4 under VUV excitation

Ytterbium doped borate crystals are promising laser media, e.g. in ${\mathrm{LaSc}}_3({\mathrm{BO}}_3{)}_4$ (LSB) matrices large distance between ytterbium ions results in reduced concentration quenching of the ytterbium f–f luminescence [Petermann, K., Fagundes-Peters, D., Johansen, O., Mond, M., Peters, V., Romero, J.J., Kutovoi, S., Speiser, J., Giesen, A., 2005. Highly Yb-doped oxides for thin-disc lasers. J. Crystal Growth 275, 135-140]. ${\mathrm{Yb}}^{3+}$ ions in complex oxides in addition to the 4f $\to$ 4f transitions often manifest fast charge transfer luminescence (CTL) in the UV-visible range. In some borates it was not observed at all, like in orthoborates of Sc, Y and La [Van Pieterson, L., Heeroma, M., de Heer, E., Meijerink, A., 2000. Charge transfer luminescence of ${\mathrm{Yb}}^{3+}$. J. Lumin. 91, 177–193]; in haloborates ${\mathrm{Sr}}_2{\mathrm{B}}_5{\mathrm{O}}_9\mathrm{X}$, where X = Cl, Br, the UV/visible luminescence was attributed to ytterbium CTL though it looked substantially different from other matrices [Dotsenko, V.P., Berezovskaya, I.V., Pyrogenko, P.V., Efryushina, N.P., Rodniy, P.A., Eijk van, C.W.E., Sidorenko, A.V., 2002. Valence states and luminescence properties of ytterbium ions in strontium haloborates. J. Solid State Chem. 166, 271–276]; while in oxyborate ${\mathrm{Li}}_2{\mathrm{Lu}}_5{\mathrm{O}}_4({\mathrm{BO}}_3{)}_3$ “classical” CTL was observed [Jubera, V., Garcia, A., Chaminade, J.P., Guillen, F., Sablayrolles, Jean, Fouassier, C., 2007. ${\mathrm{Yb}}^{3+}$ and ${\mathrm{Yb}}^{3+}\text{-}{\mathrm{Eu}}^{3+}$ luminescent properties of the ${\mathrm{Li}}_2{\mathrm{Lu}}_5{\mathrm{O}}_4({\mathrm{BO}}_3{)}_3$ phase. J. Lumin. 124(1), 10–14]. In this work the luminescence properties of another borate, namely LSB doped by Yb are presented.     

Determination of the magnetic structure of SmFe(3)(BO(3))(4) by neutron diffraction: comparison with other RFe(3)(BO(3))(4) iron borates

Temperature dependent neutron diffraction studies were performed on SmFe(3)(BO(3))(4). The crystallographic structure was determined to stay as R32 over the whole studied temperature range of 2?K?相似文献   

Optical properties and laser potential of dysprosium doped YAl 3 (BO 3 ) 4 (YAB) crystal

The absorption and emission spectra were measured at 5 and 300 v K. The positions of the selected Dy 3+ levels and their Stark components, determined from optical spectra at 5K, are presented. In this work an attempt is made to assess the potential of dysprosium doped YAl 3 (BO 3 ) 4 crystal as a laser active material operating near 570 v nm. The emission cross-section of a potential laser line at 570 v nm connected with 4 F 9/2 M 6 H 13/2 transition was estimated.     

Modulation of magnetic properties and enhanced magnetoelectric effects in MnW_(1-x)Mo_xO_4 compounds

In this letter, we investigate the magnetic and ferroelectric properties of polycrystalline MnW1-xMoxO4 （x = 0, 0.05, 0.10, 0.20） compounds. The substitution of nonmagnetic Mo6＋ ions for W6＋ ions modifies the magnetic transition tem- peratures of MnW1-xMoxO4 by changing the Mn-O-Mn bond. As a result, distinct ferroelectric properties and enhanced magnetoelectric effects are observed in Mo6＋-doped MnWO4 compounds. The effects of substitution of Mo6＋ ions on magnetic properties and magnetoelectric coupling are discussed.     

Electronic and magnetic properties of the iron borate Fe2BO4

Polycrystalline Fe₂BO₄ was prepared by solid state reactions and its electronic and magnetic properties were investigated by Mössbauer spectroscopy and magnetization measurements. The Mössbauer spectra of Fe₂BO₄ below 270 K indicate the presence of Fe²⁺ and Fe³⁺ sites in the structure, in a ratio 1 : 1. Above this temperature electron delocalization sets in between the divalent and trivalent iron ions and Fe^2.5+ states are observed. The temperature dependence of the Mössbauer spectra and magnetization measurements clearly show the onset of magnetic order below 155 K.     

Comparison of the Absorption Spectra of Nd3+ Ions in the NdFe3(BO3)4, Nd0.5Gd0.5Fe3(BO3)4, and Ho0.75Nd0.25Fe3(BO3)4 Crystals

Physics of the Solid State - The polarized optical absorption spectra in the region of a series of the f–f  transitions of Nd3+ ions in the Ho0.75Nd0.25Fe3(BO3)4,...     

The growth,thermal and nonlinear optical properties of single-crystal GdAl3(BO3)4

The nonlinear optical single-crystals GdAl₃(BO₃)₄ (GAB), space group R32, were grown by the top-seed solution growth (TSSG) method. The thermal properties and the nonlinear optical characteristics have been investigated. The two principal coefficients of thermal expansion along (100) and (001) were measured to be 5.30 × 10⁻⁶, 1.88 × 10⁻⁵ K⁻¹. The transmission spectrum was measured and the second-harmonic generation (SHG) was presented. By way of our designed cross superimposed laser crystal multiplier, the frequency doubling laser at wavelength 457.5 nm was measured to be 18.2 mW and the facular properties indicated the multiplier contributed to the improvement of the frequency doubling conversion efficiency.