Optical and EPR spectroscopy of manganese ions in Sr3Ga2Ge4O14 crystals

Results of investigations of the spectroscopic properties of manganese-activated single crystals of Sr₃Ga₂Ge₄O₁₄ by the methods of optical and EPR spectroscopy are reported. It is shown that magnagese activator ions form substitutional centers Mn³⁺ and Mn²⁺ in 1a-octahedral positions of the Sr₃Ga₂Ge₄O₁₄ lattice. Changes in the opticla properties of Sr₃Ga₂Ge₄O₁₄: Mn after vacuum thermal annealing are attributed to charge transfer of some of the manganese ions (Mn³⁺→Mn²⁺). The relationship between the spectroscopical properties of Mn²⁺ ions and the crystallochemical structure of the system are discussed. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 779–783, November–December, 1997.     

Crystal growth and optical properties of Tm:La3Ga5SiO14 single crystals

High optical quality Tm:La₃Ga₅SiO₁₄ single crystals with dopant concentration of 1 at. % Tm³⁺ ions were grown by the Czochralski method. The structure was studied by the X-ray powder diffraction method. The absorption spectrum and fluorescence spectrum of Tm³⁺:La₃Ga₅SiO₁₄ crystals were measured at room temperature. PACS 42.70.-a; 42.70.Hj; 61.10.Nz; 61.66.Fn; 78.20.-e; 78.90.+t; 81.10.-h     

Dispersion of light and EDGE absorption of thin Y2O3 films

We measured the dispersion of light in thin Y₂O₃ films in the visible and near UV regions of the spectrum. The spectrum of edge absorption is investigated. We found the parameters of a single-oscillator approximation and determined the dispersion energy and the ionicity of bonding. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 651–654, September–October, 1997.     

Luminescence centers in yttrium silicate and germanate

Luminescence spectra for isostructural Y₂SiO₅ and Y₂GeO₅ are investigated. The spectra are resolved into elementary components by the Alentsev—Fock method. Bands with maxima in regions of 2.6, 2.3, and 2.05 eV in the spectra of Y₂SiO₅ luminescence and in regions of 2.55, 2.25, and 2.0 eV in the spectra of Y₂GeO₅ luminescence are considered as radiative recombination of excited associative donor-acceptor Y³⁺−O²⁻ pairs. The indicated bands are related to certain distances between yttrium (the donor) and oxygen (the acceptor). A band with a maximum of 2.95 eV in Y₂SiO₅ and 3.0 eV in Y₂GeO₅ occurs in recombination of electrons with holes trapped by an anionic sublattice. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 528–531, July–August, 1998.     

Spectroscopic properties of Er/Ce-codoped La3Ga5SiO14

The Er-single-doped and Er/Ce-codoped La₃Ga₅SiO₁₄ polycrystalline powders are synthesized by the solid-phase synthesis method. The room-temperature luminescence spectra of the samples are investigated. The Near-infrared-region spectroscopic properties of Er³⁺ ions in the La₃Ga₅SiO₁₄ systems are analysed with Judd-Ofelt theory and rate equations. The effective deactivating effect of Ce³⁺ ions on Er³⁺ ions is confirmed.     

Vibrational spectra of thin films of lead and bismuth tungstates

The IR reflection spectra are investigated for the systems “thin film of PbWO₄ or Bi₂WO₆-molten quartz v-SiO₂ substrate” within the region of 400–1600 cm⁻¹ at T=295 K. Interference in the thin films is considered. Interpretation of the bands belonging to the PbWO₄ and Bi₂WO₆ films is carried out. I. Franko L’vov State University, 50, Dragomanova St., 290005, L’vov, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 459–461, May–June, 1998.     

The absorption spectrum of radiation-colored SrCl2-Ce crystals

We investigate the spectra of the x-ray radiation-induced absorption of SrCl₂−Ce crystals over the spectral range 345–830 nm and their temperature transformations in the interval from 77 to 450 K. We found that radiative color centers are characterized by a complex spectrum of induced absorption that contains wide bands of photochromic PC (750, 519, 378 nm) and PC⁺ (620, 446, 340 nm) centers and quasi-linear bands of Ce²⁺ centers. The most significant thermal transformations of radiative color centers occur in the vicinity of the thermostimulated luminescence peak of 394 K, at which the holes of the PC⁺ centers recombine with the electrons of the Ce²⁺ centers. Ivan Franko L’vov State University, 8, Kirilla i Mefodiya St., L’vov 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 545–547, July–August, 1997.     

Observation of ferrobielastic switching in langasite crystals under a uniaxial static pressure

Ferrobielastic switching is observed by measuring the change in the frequency of a compound acoustic cavity made from a langasite (La₃Ga₅SiO₁₄) single crystal, under uniaxial pressure. The effect is detected from the jump in the cavity frequency at the point of switching. In quartz the measured value of the pressure at the point of switching is found to be much higher, 740 MPa. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 5, 338–340 (10 September 1997)     

Luminescence centers in Sc2O3

Sc₂O₃ luminescence spectra are studied. The spectra are separated into elementary bands by the Alentsev–Fock method. It is established that the luminescence spectra consist of a number of overlapping bands with maxima at 3.5; 3.05; 2.65; 2.35, and 2.05 eV. The band at 3.5 eV is interpreted as emission of self-localized excitons, and the other bands, as defect-center recombination. L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 776–778, November–December, 1997.     

Structural changes of piezoelectric La3Ga5SiO14 induced by paramagnetic ions revealed by Ga multiple quantum magic angle spinning

Experimental evidence that nuclear magnetic resonance (NMR) can detect structural changes of piezoelectric La₃Ga₅SiO₁₄ induced by dilute paramagnetic ions is presented. Gd³⁺ and Eu³⁺ cations have been incorporated into La₃Ga₅SiO₁₄ monocrystals. As expected, the line-width of the tetrahedral ²⁹Si magic angle spinning (MAS) NMR spectra as well as the inverse of the T₂ relaxation time of ⁷¹Ga increases with the concentration of the paramagnetic ions. A surprising result is shown by ⁷¹Ga multiple quantum (MQ) MAS NMR spectrum, which changes with the concentration of paramagnetic ions. The changes in the ⁷¹Ga MQMAS spectra can be explained by a more ordonated distribution of Ga ions inside the oxygen tetrahedra. The ⁷¹Ga MQMAS NMR spectra allow identification of the one octahedral and two tetrahedral Ga sites.     

Magnetooptical method of measuring the characteristics of the reservoir of spin-spin interactions in paramagnets

Based on the phenomenon of coherent spin Raman scattering a magnetooptical method of measuring the characteristics of the reservoir of electronic spin-spin interactions in paramagnets was implemented. A formula relating the intensity of the inelastically scattered light to the temperature of the spin-spin reservoirs under conditions of saturation of the EPR of paramagnetic ions has been derived. For the Ce³⁺ ions in the (Ce_xLa_1−x)₂Mg₃(NO₃)₁₂·24H₂O crystal values of the time of spin-lattice relaxation of the spin-spin reservoir and the local magnetic field have been measured, and a relation between the spin-spin reservoir temperature and the external magnetic field strength under conditions of stationary saturation of the EPR of the Ce³⁺ ions has been obtained. V. I. Ul’yanov-Lenin Kazan State University,18, Lenin St., Kazan, 420008, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 76–81, January–February, 1997.     

Performance of Nd:YLF laser by using crystal electrooptic Q-switch

The polarization rotating coefficient and the laser-damage threshold of La₃Ga₅SiO₁₄ crystal at 1064 nm are measured, which are 1.1 deg/mm and , respectively. The working principle and the design method of electrooptic Q-switch based on La₃Ga₅SiO₁₄ crystal, which has the optical activity, are reported. The performance of Nd:YLF laser with the electrooptic Q-switch of La₃Ga₅SiO₁₄ crystal was studied. The output pulses with an energy of 379 mJ, a duration of 8.7 ns and repetition of 10 Hz are achieved.     

Polarization effect in langasite crystals

The variation of the resonance frequency of piezoelectric resonators subjected to a constant electric field is demonstrated with longitudinal vibrations in La₃Ga₅SiO₁₄ (langasite) crystal rods at temperatures between −60 and +80°C. For the rods whose longtudinal axis makes angle α with the crystal axis in the plane of the axes and [0001], the change in the frequency is proportional to the field strength and depends on α. For a field of ±1.5 × 10⁶ V/m and α = 15°, the relative change in the frequency is ±120 × 10⁻⁶. It is shown that La₃Ga₅SiO₁₄ crystals offer a set of physical parameters that makes them promising for electrically controlled acoustoelectronic devices and for devices based on nonlinear interaction between acoustic waves.     

Optical properties of the proton conductor (NH2(CH3)2)2CoCl4

Based on the data from optical-spectral studies of (NH₂(CH₃)₂)₂CoCl₄ crystals, the existence of high-temperature phase transitions at 419, 380, 352, and 313 K is confirmed. It was shown that with the exception of the first transition, they are related to a considerable extent to rearrangement of the network of hydrogen bonds and are not accompanied by, considerable deformation of the lattice. In this connection the character of the electron-phonon interaction remains unchanged in the entire temperature range of the measurements. The (NH₂(CH₃)₂)₂CoCl₄ structure at room temperature is close to that of the ordered low-temperature phases of such isomorphous crystals as β-K₂SO₄. I. Franko State University, L’vov, Ukraine, 8, Kirill and Mefodii St., UA-290005, L’vov. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 412–418, May–June, 1998.     

Rearrangement of the Ultrasmooth Surface of La3Ga5SiO14 Crystals at Heating

The morphology and phase composition of the surface of La₃Ga₅SiO₁₄ (langasite) crystals at annealing in a temperature range 1000–1200°C have been studied using electron and atomic force microscopy. It has been shown that trigonal lanthanum oxide (La₂O₃) crystals with sizes to 3–4 μm, as well as a microstructure with sizes to 50 μm with gallium excess, with the approximate composition of 15 mol % La₂O₃, 65 mol % Ga₂O₃, and 20 mol % SiO₂ are formed on the surface of langasite crystals annealed in air at temperatures above 1100°C. Possible reasons for thermal destruction of the compound can be a significant rearrangement of the disordered crystal structure of langasite caused by the interaction with air oxygen and under the intense surface diffusion of atoms of the crystal, as well as the incongruent character of melting of the La₃Ga₅SiO₁₄ compound. The revealed thermal destruction of the surface of langasite crystals should be taken into account when using this material to fabricate piezoelectric elements for operation at high temperatures.

     

X-ray photoelectron spectroscopy study of the electronic structure of La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3+δ</Subscript> solid solutions

The electronic structure of La_1–x Ga _x MnO_3+δ. solid solutions is studied by X-ray photoelectron spectroscopy (XPS). The valence state of the manganese is estimated by various methods: by analyzing the difference in the binding energies of the Mn2p_3/2 and O1s electronic levels, analyzing exchange splitting in the spectrum of Mn3s, and from the dependence of the binding energy of the XPS spectrum of Mn2p_3/2 on the calcium concentration. The state of oxidation of the manganese in the compositions containing calcium lies between Mn³⁺ and Mn⁴⁺. The efficacies of these methods are compared. A correlation is found between the type of crystalline structure of La_1–x Ga _x MnO_3+δ. (0 ≤ x < 1) and the binding energy of the Mn2p_3/2 peak. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 419–427, May–June, 2009.     

Spectroscopy of Sm3+ activator centers in Ca3Ga2Ge4O14 single crystals

Results of investigations of spectroscopic properties of Ca₃Ga₂Ge₄O₁₄ single crystals activated with Sm³⁺ ions are reported. It is shown that Sm³⁺ ions in Ca₃Ga₂Ge₄O₁₄ form a type of activator quasicenter whose nature is associated with disordering of the matrix. I. Franko Lvov State University, 50, Dragomanov St., Lvov, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 296–298, March–April, 1998.     

Jahn-Teller effect on Sm3+ ions in fluctuating-valence compounds

The dynamic and static Jahn-Teller effects are observed in ESR on rare-earth ions, specifically, on Sm³⁺ ions in the fluctuating-valence material SmB₆. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 10, 645–648 (25 November 1997)     

Sputtering of AlxGa1−x As semiconductor targets by Ar+ ions with energies of 2–14 keV

Investigations of the sputtering of Al_xGa_1−x As semiconductor solid solutions by Ar⁺ ions with energies of 2–14 keV are performed. The dependence of the sputtering yield on the energy and angle of incidence of the ions are determined and the character of the surface relief formed during the sputtering is investigated. A comparison with theory shows that the best agreement between theory and experiment is achieved when the Haff-Switkowski formula is used together with Yudin’s stopping cross section. It is shown that the surface binding energies obtained differ from the atomization energies by an amount approximately equal to the amorphization energy. Zh. Tekh. Fiz. 67, 113–117 (June 1997)     

IS α-Al2O3/ La0.8Sr0.2Ga0.8Mg0.2O3–δ really a new ionic conductor composite?really a new ionic conductor composite?

The recent interest in the (Sr, Mg) doped LaGaO₃ family compounds as electrolyte for Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFCs) has suggested the study of the system α-Al₂O₃/La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ as a possible new ionic conductor composite. The studies concerning the electrical and microstructural characterization of the system α-Al₂O₃/La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ, in a wide compositions range, are reported and discussed. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.