Optical properties of the ternary compound Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se:Co

We present the results of experimental studies of the optical properties of cobalt-doped Cd _x H_1−x Se (x = 0.18) single crystals with cobalt ion concentrations of NCo = 5·10¹⁸, 5·10¹⁹, and 1·10²⁰ cm⁻³ at T = 90 K and 300 K. The composition (x = 0.18) of the Cd _x Hg_1−x Se solid solution was selected so that the hypothetical resonance level is found on the bottom of the conduction band. We show that the cobalt ions in the mercury selenide can form a resonance donor level only for cobalt concentrations N_Co < 5·10¹⁸ cm⁻³. For N_Co ∼ 5·10¹⁸ cm⁻³, the cobalt ions substitute for mercury atoms, forming a solid solution and leading to an increase in the bandgap width and a change in the physical properties. The solubility of cobalt in the HgSe lattice can be greater than 5%–10%. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 73–77, January–February, 2007.     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

Dielectric and polar order behaviors of BaTiO<Subscript>3</Subscript>-Bi(Mg<Subscript>1/2</Subscript>Ti<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramics

New perovskite solid solution ceramics of (1−x)BaTiO₃-xBi(Mg_1/2Ti_1/2)O₃ ((1−x)BT-xBMT, x≤0.09) were synthesized by the solid-state reaction technique. X-ray diffraction studies have revealed a stable single perovskite structure for all samples. Dielectric measurements were carried out at different frequencies and temperatures. The polarization evolutions with temperatures were measured to investigate the ferroelectric properties. All the compositions show features of ferroelectrics with diffuse phase transition, though the temperature T _m of their dielectric constant maximum ε _m is frequency dependent. The dielectric constant peak ε(T) of (1−x)BT-xBMT ceramics become broad with increasing BMT content. During the temperature range of ε(T) peak summit, (1−x)BT-xBMT ceramics present quasi-linear dielectric phenomenon under high electric field with very high dielectric constant.     

Lattice dynamics of Eu<Subscript>1-x</Subscript>Y<Subscript>x</Subscript>MnO<Subscript>3</Subscript> (0 ≤ x ≤ 0.5)

A systematic and detailed study of Raman and infrared active lattice excitations in the orthorhombic multiferroic manganite Eu_1−xY_xMnO₃ (0 ≤ x ≤ 0.5) was carried out at room temperature. For the infrared active phonon modes the eigenfrequencies, damping constants and oscillator strengths were analyzed by Fourier-Transform Infrared Spectroscopy in the far infrared frequency range. For the Raman active phonons the same analysis for eigenfrequencies and damping constants was carried out using Raman spectroscopy in the range from 200 cm⁻¹ to 700 cm⁻¹. Y doping leads to mode-dependent phonon frequency shifts up to 8%. These are interpreted in terms of the interplay between the decrease of the reduced ion masses and the axis-dependent change of bond lengths. The latter leads to a bond softening along the a-axis and a strengthening along the c-axis, for which the highest phonon frequency increase is observed. The application of both Raman and Infrared Spectroscopy gives us sensitivity not only to symmetry properties via the selection rules but also to the involvement of different ion types within the unit cell. It is clearly shown that the disorder induced effects are of minor impact on the lattice properties and solely detected on the rare earth sites. The MnO₆ octahedra remain unaffected and show the same behavior as in the stochiometric RMnO₃ making Eu_1−xY_xMnO₃ an excellent model system for a quasi-continuous fine-tuning of the lattice parameters relevant for the appearance of multiferroicity.     

EPR and optical absorption studies of Cu<Superscript>2+</Superscript> ions in [ZnPd(CN)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O<Subscript>2</Subscript>)] single crystals

A Cu²⁺-doped single crystal of catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-m-cyanopaladate(II) [ZnPd(CN)₄(C₄H₁₂N₂O₂)] complex has been investigated by electron paramagnetic resonance (EPR) technique at room temperature. EPR spectra indicate that Cu²⁺ ions substitute for magnetically equivalent Zn²⁺ ions and form octahedral complexes in [ZnPd(CN)₄(C₄H₁₂N₂O₂)] hosts. The crystal field affecting the Cu²⁺ ion is nearly axial. The optical absorption studies show two bands at 322 nm (30864 cm⁻¹) and 634 nm (15337 cm⁻¹) which confirm the axial symmetry. The spin Hamiltonian parameters and the relevant wave function are determined.     

Raman scattering and electrical properties of Tl<Subscript>x</Subscript>Cu<Subscript>1−x</Subscript>GaSe<Subscript>2</Subscript> solid solutions

The results of the study of Raman scattering and photo-emf in Tl _x Cu_1−x GaSe₂ single crystals are presented. The objective of this work was to reveal some features of optical and phonon spectra, to study regularities of their variation with composition and, on this basis, to create prerequisites to extend the possibilities of their practical applications.     

Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).     

Nature of low-energy excitations in La<Subscript>1.87</Subscript>Sr<Subscript>0.13</Subscript>CuO<Subscript>4</Subscript> superconducting cuprate

The spectra of the conductivity and dielectric constant of La_1.87Sr_0.13CuO₄ cuprate have been directly measured in the frequency range of 0.3 to 1.2 THz (10–40 cm⁻¹) and the temperature range of 5 to 300 K in the E | c polarization (the electric field vector of radiation is perpendicular to the copper-oxygen planes). Excitation has been observed in the superconducting phase, and its nature has been attributed to the transverse optical excitation of the condensate of Cooper pairs, which appears because Josephson junctions between CuO planes are modulated due to in-plane magnetic and charge stripes. Additional quasiparticle absorption of unknown origin has been detected at frequencies below ≈15 cm⁻¹ at liquid helium temperatures.     

Exciton absorption spectra of Cs<Subscript>2</Subscript>CdI<Subscript>4</Subscript> and Rb<Subscript>2</Subscript>CdI<Subscript>4</Subscript> ferroelastic solid solutions

The exciton absorption spectra of thin films of (Cs_{1 − x} Rb _x )₂CdI₄ solid solutions have been investigated and the refractive index n(λ) in their transparency window in the concentration range of 0 ≤ x ≤ 1 has been measured. The exciton-band parameters and optical permittivity ɛ_∞(x) have been found to linearly depend on the concentration. It is established that excitons are incorporated into the CdI₂ sublattice of the solid solutions and belong to intermediate-coupling ones. The characteristics of excitons in ferroelastics are compared with the corresponding parameters for CdI₂, RbI, and CsI, which are used as components to synthesize ternary compounds.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Specific features of the EPR spectra of KTaO<Subscript>3</Subscript>: Mn nanopowders

The electron paramagnetic resonance spectra of KTaO₃: Mn nanocrystalline powders in the temperature range from 77 to 620 K have been measured and studied for the first time. The change observed in the spectra has been investigated as a function of the doping level. The doping regions in which Mn²⁺ ions are individual paramagnetic impurities have been established, as well as the regions where the dipole-dipole and exchange interactions of these ions begin to occur. The spin-Hamiltonian constants for the spectrum of non-interacting individual Mn²⁺ ions have been determined as follows: g = 2.0022, D = 0.0170 cm⁻¹, and A = 85 × 10⁻⁴ cm⁻¹. A significant decrease in the axial constant D in the KTaO₃: Mn nanopowder, as compared to the single crystal, has been explained by the remoteness of the charge compensator from the paramagnetic ion and by the influence of the surface of the nanoparticle. It has been assumed that the Mn²⁺ ions are located near the surface and do not penetrate deep into the crystallites.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

Polarization modes in the Ba<Subscript>2</Subscript>Mg<Subscript>2</Subscript>Fe1<Subscript>2</Subscript>O<Subscript>22</Subscript> multiferroic

The spectra of complex permittivity of a Ba₂Mg₂Fe₁₂O₂₂ single crystal belonging to the family of Y-type hexaferrites have been measured over a wide temperature range (10–300 K) with the aim of determining the dynamic parameters of the phonon and magnetic subsystems in the terahertz and infrared frequency ranges (3–4500 cm⁻¹). A factor-group analysis of the vibrational modes has been performed, and the results obtained have been compared with the experimentally observed resonances. The oscillator parameters of all nineteen phonon modes of E _u symmetry, which are allowed by the symmetry of the Ba₂Mg₂Fe₁₂O₂₂ crystal lattice, have been calculated. It has been found that, at temperatures below 195 and 50 K, the spectral response exhibits new absorption lines due to magnetic excitations.     

Band structure and dominating electron-scattering mechanisms in Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis>−<Emphasis Type="Italic">y</Emphasis></Subscript>Mn<Subscript>x</Subscript>Fe<Subscript>y</Subscript>Se

Magnetic and kinetic properties as well as transmission and absorption spectra of Hg _1−x−y Mn _x Fe _ySe (0.09 ≤ x ≤ 0.099 and 0.001 ≤ y ≤ 0.01) crystals are investigated at H ≈ 0.5–6 kOe in the temperature range T = 77–300 K. The band parameters are determined on the basis of experimental data. It is found that in the crystals under study at T ≈ 300 K, electron scattering by polar optical phonons dominates, direct optical band-to-band transitions occur, and replacement of a part of Mn atoms by Fe for x + y = 0.1 results in an increase in E_g ^op with Fe content. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 35–39, March, 2007.     

Specific features of structural states in the BiFeO<Subscript>3</Subscript>-YMnO<Subscript>3</Subscript> solid solutions

The (1 − x)BiFeO_3−x YMnO₃ solid solutions have been found to undergo the following sequence of phase transformations with increasing x: R3c → Pbnm → C2 → Pnma → P6₃ cm. It has been established that the Pbnm and Pnma phases have different orientations of atomic displacements and can exhibit antiferroelectric properties.     

Antiferromagnetic interactions in Er-doped SnO<Subscript>2</Subscript> DMS nanoparticles

Diluted magnetic semiconductor (DMS) nanoparticles of Sn_1−x Er _x O₂ (x = 0.0, 0.02, 0.04, and 0.1) were prepared by sol–gel method. The X-ray diffraction patterns showed SnO₂ rutile structure for all samples with no impurity peaks. The decrease in crystallite size with Er concentration was confirmed from TEM measurements (from 12 to 4 nm). The UV–Visible absorption spectra of Er-doped SnO₂ nanoparticles showed blue shift in band gap compared to undoped SnO₂. The electron spin resonance analysis of Er-doped SnO₂ nanoparticles indicate Er³⁺ in a rutile lattice and also decrease in intensity with Er concentration above x = 0.02. Temperature-dependent magnetization studies and the inverse susceptibility curves indicated increased antiferromagnetic interaction with Er concentration.     

Phase transitions and the dielectric and piezoelectric properties of ceramic solid solutions based on BiScO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript>

The ferroelectric and piezoelectric properties of ceramic solid solutions having a composition of (1−x)(Bi_0.9Nd_0.1)(Sc_0.9 B _0.1)O_{3 − x} PbTiO₃ (x = 0.60–0.66; B = Lu, Yb, Er, Y) and obtained by solid state reaction were studied. An increase in the Curie temperature was found upon an increase in the concentration of lead titanate, while a drop occured upon the doping of the A and B sublattices. It was shown that at high temperatures, MnO₂ and Bi₂O₃ additives lead to a reduction in the total conductivity and a dielectric loss of less than one order of magnitude. In modified ceramics, an increase in the d ₃₃ and k _t piezoelectric coefficients was observed as well. The effects of dielectric relaxation that are determined by the composition of the ceramics were revealed.     

Temperature Dependence of the Transmission Spectra of Silicate Glasses Containing CdS<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Semiconducting Nanocrystals

The transmission spectra of silicate glasses containing CdS_{1 − x} Se _x semiconducting nanocrystals of various sizes are investigated in the temperature range 20–300°C. It is shown that for explaining optical properties of these materials, not only the nanocrystal sizes, but also the structural changes occurring in nanocrystals during their formation must be taken into account.     

Universal behavior of CePd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Rh<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> ferromagnet at the quantum critical point

The heavy-fermion metal CePd_1−x Rh _x can be tuned from ferromagnetism at x = 0 to the nonmagnetic state at some critical concentration x _c . The non-Fermi liquid behavior (NFL) at x ≃ x _c is recognized by the power-law dependence of the specific heat C(T) given by the electronic contribution susceptibility X(T) and volume expansion coefficient α(T) at low temperatures: C/T ∝ X(T) ∝ α(T)/T∝ 1/ √T. We also demonstrate that the behavior of the normalized effective mass M _N ^* observed in CePd_1−x Rh _x at x ≃ 0.8 agrees with that of M _N ^* observed in paramagnetic CeRu₂Si₂ and conclude that these alloys exhibit the universal NFL thermodynamic behavior at their quantum critical points. We show that the NFL behavior of CePd_1−x Rh _x can be accounted for within the frameworks of the quasiparticle picture and fermion condensation quantum phase transition, while this alloy exhibits a universal thermodynamic NFL behavior that is independent of the characteristic features of the given alloy such as its lattice structure, magnetic ground state, dimension, etc. The text was submitted by the authors in English.     

Optical spectra and excited state relaxation dynamics of Sm<Superscript>3+</Superscript> in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript> single crystal

Single crystals of gadolinium orthosilicate Gd₂SiO₅ containing 0.5 at% and 5 at% of Sm³⁺ were grown by the Czochralski method. Optical absorption spectra, luminescence spectra and luminescence decay curves were recorded for these systems at 10 K and at room temperature. Comparison of optical spectra recorded in polarized light revealed that the anisotropy of this optically biaxial host affects the intensity distribution within absorption and emission bands related to transitions between multiplets rather than the overall band intensity. It has been found that among four bands of luminescence related to the ⁴G_5/2→⁶H_J (J=5/2–11/2) transitions of Sm³⁺ in the visible and near infrared region the ⁴G_5/2 →⁶H_7/2 one has the highest intensity with a peak emission cross section of 3.54×10⁻²¹ cm² at 601 nm for light polarized parallel to the crystallographic axis c of the crystal. The luminescence decay curve recorded for Gd₂SiO₅:0.5 at% Sm³⁺ follows a single exponential time dependence with a lifetime 1.74 ms, in good agreement with the ⁴G_5/2 radiative lifetime τ _rad=1.78 ms calculated in the framework of Judd-Ofelt theory. Considerably faster and non-exponential luminescence decay recorded for Gd₂SiO₅:5 at% Sm³⁺ sample was fitted to that predicted by the Inokuti-Hirayama theory yielding the microparameter of Sm³⁺–Sm³⁺ energy transfer C _da=1.264×10⁻⁵² cm⁶×s⁻¹.