Comparative studies of microwave absorption in the singlet paramagnets HoVO<Subscript>4</Subscript> and HoBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in strong pulsed magnetic fields

Microwave absorption in the tetragonal singlet paramagnets HoVO₄ (zircon structure) and HoBa₂Cu₃O _x (x ≈ 6, layered perovskite structure) is studied and compared in pulsed magnetic fields up to 40 T at low temperatures. These paramagnets are characterized by a singlet-doublet scheme of the low-lying levels of the Ho³⁺ ion in a crystal field. In a magnetic field directed along the tetragonal axis, HoVO₄ exhibits resonance absorption lines at wavelengths of 871, 406, and 305 μm, which correspond to electron transitions between the low-lying levels of the Ho³⁺ ion in the crystal field. The positions and intensities of these absorption lines in HoVO₄ are well described in terms of the crystal-field formalism with the well-known interaction parameters. The absorption spectra of HoBa₂Cu₃O _x at a wavelength of 871 μm exhibit broad resonance absorption lines against the background of strong nonresonance absorption. The effects of low-symmetry (orthorhombic, monoclinic) crystal-field components, the deviation of a magnetic field from a symmetry axis, and various pair interactions on the absorption spectra of the HoVO₄ and HoBa₂Cu₃O _x crystals are discussed. Original Russian Text ? Z.A. Kazeĭ, V.V. Snegirev, M. Goaran, L.P. Kozeeva, M.Yu. Kameneva, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 133, No. 3, pp. 632–645.     

Phase transformations in perovskites TbBaCo2−x FexO5 + γ

The transport, magnetic, and elastic properties of TbBaCo_2?x Fe_xO_{5 + γ} are investigated. It is shown that these compounds exhibit first-order metal-insulator and antiferromagnet-weak ferromagnet transitions in the orthorhombic phase (x < 0.12), while these transitions are not observed in the tetragonal phase (x > 0.12). In the concentration range corresponding to the orthorhombic phase, doping with iron stabilizes the weakly ferromagnetic phase. However, the tetragonal phase is antiferromagnetic. Oxygen vacancies are assumed to be ordered in the orthorhombic case and disordered in the tetragonal phase. An analysis of Young’s modulus, magnetostriction, and effects of pressure and substitution of the O¹⁸ oxygen isotopes for O¹⁶ indicates a weak correlation between magnetic transformations and the crystal lattice.     

Temperature dependence of oxygen content and phase transition in Y1Ba2Cu3O9−x compounds

Systematic TGA (Thermogravimetric analysis), magnetic susceptibility measurements and X-ray diffraction investigations have been made on the temperature dependence of oxygen content and phase transition in Y₁Ba₂Cu₃O_9–x compounds. The experimental results show that reversible oxygen relief and absorption appeared during heating and cooling in the temperature range of 400–950°C. A low cooling rate leads to higher oxygen content and quenching can suppress oxygen absorption. The deoxidation process is accompanied by a change of the cell constants,a andb increase whilec decreases with reduced oxygen content while the phase transition from the ortorhombic to the tetragonal system appeares. Nevertheless, this transition is a gradually changing process, no critical point of transition exists. Quenching stress and defects have a pronounced influence on the absorption and relief of oxygen. Maximum rates of oxygen relief and absorption were obtained at about 650°C. Oxygen absorption and desorption can be obtained only in an athermal process. Magnetic susceptibility measurements show that diamagnetic and paramagnetic suceptibilities increase obviously with increasing oxygen content. Deoxidation and oxygen absorption can be restrained by adding Fe to the Y₁Ba₂Cu₃O_9–x phase, which suggests that deoxidation and oxygen absorption are very sensitive to crystal structure and lattice distortions.     

Fe-induced magnetic transition in YBa2(Cu1−x 57Fe x )3O6 by NQR and Mössbauer spectroscopy

Nuclear quadrupole resonance spectroscopy (around 30 MHz) on the chain site Cu(1) nuclei in oxygen deficient YBa₂(Cu_1?x Fe _x )₃O₆ doped with different amounts of⁵⁷Fe (x≤0.01) reveal an onset of magnetic order at low temperatures represented by a symmetrical doublet contribution to the nuclear quadrupole resonance (NQR) spectrum. The onset temperatureT _N2 depends on the concentration of Fe reaching 130 K forx=0.01. The splitting forx=0.01 at 100 K corresponds to a net internal field of 0.09 T with a distribution of ≈0.08 T representing about 70 percent of the Cu(1) nuclei.⁵⁷Fe and⁵⁷Co Mössbauer spectroscopy at 4.2 K with and without an external magnetic field of 5 T revealed that belowx=0.00015 Fe spins are decoupled from the Cu(2) moments in the antiferromagnetic state. Results are interpreted in terms of the magnetic model structure suggested by Kadowaki et al. [1].     

Specific features of the electron paramagnetic resonance spectrum in the vicinity of the convergence of the transitions of gadolinium centers in Pb5(Ge1 − x Si x )3O11

An anomalous electron paramagnetic resonance spectrum of the transitions ?1/2 ? +1/2 of four Gd³⁺-Si dimer clusters in the Pb₅(Ge_{1 ? x} Si _x )₃O₁₁ crystals doped with gadolinium has been found in the vicinity of the orientation of the magnetic field along the optic axis of the crystal. It has been assumed that this spectrum is caused by rapid transitions between the spin packets of the initial resonances due to the crossrelaxation. A computer simulation of the spectrum has been carried out. The results obtained adequately describe the experiment.     

EPR study of the diluted magnetic semiconductor CuGa1−xMnxTe2

Electron paramagnetic resonance (EPR) experiments were made in the diluted magnetic semiconductor CuGa_1−xMn_xTe₂, in the temperature range 70<T<300 K. The samples were synthesized by direct fusion of stoichiometric mixtures of the elements, with Mn composition from x=0.0 to 0.25. The EPR spectra were measured as function of temperature, Mn composition, and field orientation. The temperature variation of the resonance field shows a critical point at about 235 K, and is associated with a transition from the ferromagnetic to the superparamagnetic state. The resonance field was also measured as a function of the field angle, and displays a well-defined uniaxial symmetry. This uniaxial field depends on the Mn concentration and is due to tetragonal distortions induced by Mn²⁺ at Ga sites, and the demagnetizing effects due to formation of ferromagnetism (FM) Mn-clusters.     

Specific heat of Tb x Y1−x Sb mixed crystals

The specific heat of Tb _x Y_1?x Sb mixed crystals (x=0, 0.103, 0.383, 0.428, 0.467, 0.635, 0.928 and 1.0) has been measured between 1.6 and 20°K using an adiabatic calorimeter. The crystal field potential is described well taking into account only 4th order terms, and the overall splitting of the ground multiplet⁷F₆ of the Tb³⁺ ion has been found to be 115°K independent of the concentrationx. Forx>0.46 the specific heat curves exhibit a behaviour typical for a second order phase transition. For lower concentrations a normal Schottky anomaly is found and no evidence for magnetic order was detected. The experimental results which are in agreement with magnetic measurements are compared with molecular field calculations including crystal field and exchange interaction.     

Ferromagnetism in the high-pressure phases of (GaSb)1−x Mnx

The electrophysical and magnetic properties of recently discovered high-pressure phases in the GaSb-Mn system with simple cubic and tetragonal structures have been examined. It has been shown that samples with the primitive cubic structure for low temperatures are in the ferromagnetic state and the Curic temperature depends on the initial manganese content and reaches T _c = 280 K for x = 0.6. It has been shown that these samples for a manganese content x ≤ 0.5 are in the semiconducting state with large impurity conduction and pass to the metallic state as x increases. The GaSbMn phase with the tetragonal structure has ferromagnetic properties up to temperatures of T ～450 K (at which the phase begins to decay) and exhibits metallic properties. The magnetization at T = 77.3 K is equal to M = 0.58 μ_B and 0.28 μ_B per manganese ion for the simple cubic and tetragonal phases, respectively.     

Effect of Li2O content on physical and structural properties of vanadyl doped alkali zinc borate glasses

The effect of Li₂O content in vanadyl doped 20ZnO+xLi₂O+(30−x)Na₂O+50B₂O₃ (5≤x≥25) glasses has been studied with respect to their physical and structural properties. The absence of sharp peaks in XRD spectra of these glass samples confirms the amorphous nature. The physical parameters like density, refractive index, ionic concentration and electronic polarizability vary non-linearly with x mol% depending on the diffusivities of alkali ions. EPR and optical absorption spectra reveal that the resonance signals are characteristics of VO²⁺ ions in tetragonally compressed octahedral site. Spin-Hamiltonian, crystal field, tetragonal field and bonding parameters are found to be in good agreement with the other reported glass systems. The tetragonal distortion (g_⊥-g_∥) and Dt reveals that their values vary non-linearly with Li₂O content and reaches a minimum at x=10 mol%. An anomaly of character has been observed in all the properties of vanadyl doped glass systems, which gives a clear indication of mixed alkali effect.     

57Fe Mössbauer spectroscopy studies of Sr2Fe1−x Cr x Mo1−x W x O6 double perovskite compounds

Polycrystalline double perovskites Sr₂Fe_1?x Cr _x Mo_1?x W _x O₆ with x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30 have been prepared by sold state reactions. A continuous decrease of the tetragonal unit cell parameters α and c with increasing x values is observed. The highest Curie temperature T _C = 426 K is recorded for the x = 0.10 compound. ⁵⁷Fe Mössbauer spectroscopy measurements indicate a non-integral electronic configuration of ～3d^5.3 for the Fe ions at the ordered double perovskite structure for x ≤ 0.20, which reaches ～3d^5.4 for x = 0.30. Fe–Mo/W anti-site and anti-phase boundary defects are observed in all samples in equal concentrations of around 3% of the total number of Fe ions in their structure.     

Transition from antiferromagnetic to ferromagnetic state of systems LaMnO3+λ and La1−x Srx(Mn1−x/2Nb x/2)O3

The crystal structure and magnetic and elastic properties of the system LaMnO_3+λ are investigated for various concentrations of oxygen. Upon an increase in the oxygen concentration, the orbital-ordered phase is transformed into an orbital-disordered phase via a two-phase crystal-structure state in the interval 0.04<λ<0.06. The transition is accompanied by a jumplike increase in the Curie temperature and spontaneous magnetization. An analysis of the magnetic properties in weak fields and of the temperature dependence of the Young modulus reveals the properties typical of the orbital-ordered antiferromagnetic phase up to λ=0.08. It is proposed that the two-phase state is associated with the martensite type of the orbital order-disorder phase transformation. The system La_1?x Sr_x(Mn_{1 ?x/2}Nb _x/2)O₃ in which all manganese ions are in the trivalent state exhibits a sequence of antiferromagnetic-ferromagnetic (x>0.2) and ferromagnetic-spin glass (x>0.4) transitions. In both systems, the orbital-disordered phases are ferromagnetic, indicating the crucial role of orbital ordering in the formation of magnetic properties.     

Magnetic properties and specific heat of Tm1−xLuxCu2Si2

The tetragonal TmCu₂Si₂ compound is the only magnetically ordered material of the RECu₂Si₂ group for which crystal field parameters were determined. Quadrupole splitting measured by means of Mössbauer spectroscopy showed that two lowest lying states are nonmagnetic singlets. Therefore, this material is likely to have an induced magnetic moment, mainly due to mixing of the two lowest states. We performed specific heat and magnetic susceptibility measurements of Tm_1−xLu_xCu₂Si₂ (x = 0, 0.025, 0.050, 0.10, 0.25, 0.50 and 1) alloys to determine the crystal field level scheme and compare it with the Mössbauer data. The saturation magnetization of the antiferromagnetic phase was calculated to be 3.2 μ_B and the moment is directed along the tetragonal c axis. No direct experimental evidence is known to support this prediction.     

Re-entrant magnetic behaviour in amorphous Fe-rich Fe100−x Zr x alloys

We report results of⁵⁷Fe Mössbauer measurements on the magnetically concentrated re-entrant amorphous Fe₁₀₀?xZr _x alloys (8≤x≤12) which give convincing evidence for a microscopic origin of the low-temperature magnetization anomaly atT _f<T _c. This is shown by an anomalous increase in the magnetic hyperfine field and in the relative intensities of the (?m=0)-Mössbauer lines belowT _f upon cooling. No evidence was found for an antiferromagnetic phase. The shape of the hyperfine-field distribution atT=4.2 K in zero external field and in a field of 3 T is unchanged, indicating homogeneous behaviour of all Fe moments near saturation. Ferromagnetic order is not long-ranged, but determined by exchange-coupled magnetic clusters. The cluster moment nearT _c is found to decrease strongly with increasing Fe content and extrapolates to zero atx≈96.     

Inhomogeneous lattice distortions in a Zn1 − x CrxSe crystal

The structure of a Zn_1?x Cr_xSe semiconductor crystal with x = 0.0029 was studied using thermal neutron diffraction. It was detected that the diffraction patterns of the crystal contain regions of diffuse scattering concentrated in the vicinity of the strong Bragg reflections. It was shown that the diffuse scattering was caused by transverse displacements of lattice atoms induced by chromium impurities, which undergo static tetragonal Jahn-Teller distortions in ZnSe.     

Preparation and properties of the system CoPxS2−x

Lattice parameters were determined for members of the system CoP_xS_2?x (0 ≤ x ≥ 1). A cubic region was observed for 0 ≤ x ≤ 0·5 and a tetragonal region for 0·5 < x ≤ 1. Magnetization and susceptibility measurements were made on the sample CoP_xS_2?x (0 ≤ x ≤ 0·5) from 4·2 to 500°K and to 9·5 kOe. The ferromagnetic Curie temperature decreased almost linearly with composition from a value of 122(1)°K for x = 0 to 23(1)°K at x = 0·3. The saturation magnetization passed through a maximum at 41·5(2) e.m.u./g at x = 0·05, increasing from 40·0(2) e.m.u./g for x = 0, and then decreased to below 15 e.m.u./g for x = 0·3. The paramagnetic data gave a P²_eff/CO²⁺ that increased linearly with phosphorus substitution from 4·4(2)μ_B at x = 0 to 5·5(2)μ_B² at x = 0·5. The Weiss constant decreased almost linearly from 150(3)°K for x = 0 to 85(2)°K for x = 0·3. The magnetic properties of this system are compared with those of the system CoAs_xS_2?x and CoSe_xS_2?x. Changes, with composition, in the Curie and Weiss temperatures are almost identical in the three systems for x ≤ 0·25. As with CoAs_xS_2?x the ferromagnetic moment reaches a maximum at x = 0·05 and then decreases with increasing x, although the magnetic interactions remain ferromagnetic for all x ≤ 0·5.     

The nature of anomalies in the magnetoresistance of antiferromagnetic YBa2Cu3O6+x

The characteristic d-type angular dependence of the in-plane magnetoresistance on the orientation of the external magnetic field in the (ab) plane for the antiferromagnetic tetragonal crystal YBa₂Cu₃O_6+x (x ～ 0.3) is considered theoretically. This dependence is interpreted in terms of the efficient hole transfer through the low-lying purely oxygen O 2pe _u doublet, which is not hybridized with the $b_{1g} (d_{{}_x2_ - {}_y2} )$ ground state. The external magnetic field determines the orientation of the strong exchange field acting on the b _1g e _u : ³ E _u triplet state of the hole-type CuO₄ center. The spin-orbit interaction results in orbital polarization of the E _u doublet, which is responsible for the d-type spatial anisotropy of the hole transport. The available experimental data make it possible to evaluate the parameter of the effective spin Hamiltonian. The influence of spin-vibronic effects on the hole transfer is analyzed.     

Magnetic microstructure of strontium-substituted thulium ferromanganites Tm0.65Sr0.35Mn1 ? x Fe x O3 (x = 0.3?0.4)

The structural and magnetic properties of the Tm_0.65Sr_0.35Mn_{1 ? x} Fe _x O₃ (x = 0.3?0.4) have been studied by methods of magnetic resonance and differential thermomagnetic analysis. A magnetic phase separation has been revealed in structurally single-phase samples.     

35Cl NQR and XRD Studies on Cs2[Ag(I) x Au(I)1 − x Cl2][Au(III)Cl4]

³⁵Cl NQR and XRD have been investigated on the solid solution Cs₂[Ag(I) _x Au(I)_1???x Cl₂][Au(III)Cl₄] which yielded NQR lines by annealing. The crystal forms a tetragonal cell in the whole range of x. However, a change of the modification occurs at x?≈?0.85. The increase of c and decrease of a were observed in the range of 0.0?≤?x?≤?0.7.     

Anomalous magnetocaloric effect in van vleck paramagnet HoVO<Subscript>4</Subscript> near energy level crossing

The anomalous magnetocaloric effect in singlet rare-earth paramagnets near energy level crossing has been experimentally observed for the first time. The magnetization and differential magnetic susceptibility of Ho_{1 ? x} Y _x VO₄ crystals (x = 0, 0.5) measured along the tetragonal axis in a pulsed magnetic field with various change rates near the crossover field, dH/dt, from 3 × 10³ to 2.5 × 10² T/s are compared to the data in static magnetic fields down to 0.1 K. These data indicate the large negative magnetocaloric effect in the pulsed magnetic field, so that the crystal with the initial temperature T ₀ = 4.2 K is cooled much lower than 1 K. The experimental data are qualitatively described in the crystal field model with various interactions including hyperfine interactions and with the known interaction parameters.