The use of photoinduced light scattering for the evaluation of photoelectric fields in Lithium Niobate Crystals

The photovoltaic and diffusion fields in nominally pure single crystals of stoichiometric composition (R = Li/Nb = 1) grown from the melt with 58.6 mol % of Li₂O (LiNbO₃ stoich), in the nominally pure single crystals of congruent composition (LiNbO₃), and in congruent single crystals doped with Cu²⁺, Zn²⁺, and Gd³⁺ are found from the parameters of the photoinduced light scattering indicatrix obtained with the use of a 60-mW He-Ne laser.     

Investigation of optical homogeneity and photorefractive properties of lithium-niobate single crystals by the Raman-spectroscopy and laser-conoscopy methods

Photorefractive properties and structural and optical homogeneity of (1) LiNbO₃:Cu crystals ([Cu] = 0.015 mas %) grown from a congruent melt, (2) nominally pure stoichiometric crystals grown from a melt with 58.6 mol % of Li₂O (LiNbO_3stoich), and (3) nominally pure congruent crystals (LiNbO_3congr) have been studied using the Raman-spectroscopy method with excitation in the UV, visible, and near-IR ranges; the laser-conoscopy method; and the electron paramagnetic resonance-spectroscopy method. In optically uniaxial LiNbO₃ crystals, a weak optical biaxiality has been revealed, which is attributed to an insignificant deformation of the optical indicatrix. This deformation can be caused both by the initial structural inhomogeneity of crystals and by the photorefractive effect. It has been shown that, under the action of light, charge exchange of copper cations Cu²⁺ → Cu⁺ takes place in the crystal LiNbO₃:Cu ([Cu] = 0.015 mas %). The LiNbO₃:Cu crystal exhibits photorefractive properties not only because of the occurrence of intrinsic defects with electrons localized at them, as is the case with the LiNbO_3stoich and LiNbO_3congr crystals, but also due to the charge exchange of copper cations under the action of the laser radiation.     

Ferroelectric domain inversion in near-stoichiometric lithium niobate for high efficiency blue light generation

LiNbO₃ single crystals with a composition close to stoichiometry ([Li]/[Li+Nb]=0.496), 16 mm in diameter and 40 mm in length were grown by the Czochralski method using K₂O flux. The domain reversal characteristics of near-stoichiometric LiNbO₃ single crystals were investigated. The switching field required for 180° ferroelectric domain reversal in the near-stoichiometric crystal at room temperature was 7.5 KV/mm. This is about one third of the switching field required for conventional LiNbO₃ crystals. Domain reversal (180°) in near-stoichiometric LiNbO₃ samples of 1.0 mm thickness has been achieved. Samples have been evaluated by second harmonic generation and conversion efficiencies of up to 32% have been obtained. Received: 8 November 2000 / Accepted: 29 January 2001 / Published online: 20 June 2001     

Conversion of broadband thermal radiation in lithium niobate crystals of various compositions

The conversion of the broadband thermal radiation in stoichiometric (R = 1) lithium niobate single crystals that are grown from melt with 58.6 mol % of LiO₂, congruent (R = Li/Nb = 0.946) melt with the K₂O flux admixture (4.5 and 6.0 wt %), and congruent melt and in congruent single crystals doped with the Zn²⁺, Gd³⁺, and Er³⁺ cations is studied. It is demonstrated that the conversion efficiency of the stoichiometric crystal that is grown from the melt with 58.6 mol % of LiO₂ is less than the conversion efficiency of congruent crystal. In addition, the stoichiometric and almost stoichiometric crystals and the doped congruent crystals exhibit the blue shift of the peak conversion intensity in comparison with a nominally pure congruent crystal. For the congruent crystals, the conversion intensities peak at 520 and 495 nm, respectively.     

Characterization of stoichiometric LiNbO3 grown from melts containing K2O

The growth of LiNbO₃ single crystals from a melt with the Li/Nb ratio of 0.946, to which 6 wt.% K₂O has been added, leads to stoichiometric specimens, essentially free of potassium, with (50±0.15) mol% Li₂O in the crystal. This is established by studying the composition dependence of the following properties: linewidths of the electron paramagnetic resonance (EPR) of Fe³⁺, energy of the fundamental absorption edge, Raman linewidths of phonon modes, and dispersion of the optical birefringence. Comparison of the results with relevant calibration scales leads to the above composition. In all cases the Li₂O content was found to be closer to 50% than that of a LiNbO₃ crystal vapor-phase equilibrated to 49.9mol% Li₂O. The photorefractive effect at light intensities I10⁷ W/m² is suppressed in this stoichiometric material. The features of the ternary system K₂O-Li₂O-Nb₂O₅, which are possibly responsible for the unexpected growth of stoichiometric LiNbO₃ from the indicated melts, are discussed.     

Origin of the generally defined absorption edge of non-stoichiometric lithium niobate crystals

The ultraviolet absorption edges of LiNbO₃ crystals with different Li₂O contents and MgO doping concentrations were investigated. The generally defined absorption edges at absorption coefficient α=15 or 20 cm⁻¹ of all these crystals fit the Urbach rule perfectly. The origin of this absorption edges in non-stoichiometric LiNbO₃ crystals is attributed to the presence of Li vacancies.     

Damage profiles in LiNbO3 by low-energy H+ implantation

Low-energy 120 and 150 keV H⁺ was implanted in z-cut LiNbO₃ at room temperature. The fluence of H⁺ is 5?×?10¹⁶ ions/cm². The damage profiles in LiNbO₃ induced by implantation were investigated using Rutherford backscattering/channelling. The damage profiles were extracted using the channelling results. The experimental damage profiles in LiNbO₃ were analyzed and compared to the simulated results from TRIM. The results show a good consistency between experimental and simulated results. The present results are useful for the fabrication of H-implanted waveguides of oxide crystals, especially LiNbO₃.     

Spectroscopic properties of Er<Superscript>3+</Superscript> in Sc:LiNbO<Subscript>3</Subscript> crystal

The results of Er³⁺ ion spectroscopic analysis in Sc:LiNbO₃ crystals were reported. The line strengths from the ground state to the excited state were evaluated from the measured unpolarized absorption spectrum and analyzed by using standard Judd–Ofelt theory. For Sc(3 mol. %):Er (1 mol. %):LiNbO₃ crystal, the obtained intensity parameters are: Ω₂=3.72×10^-20 cm², Ω₄=1.07×10^-20 cm², and Ω₆=0.98×10^-20 cm². The fluorescence spectra and microsecond time-resolved spectra were investigated in the visible region. The excited state absorption transition strengths at 800 nm excitation were evaluated based on Judd–Ofelt theory. The results obtained here were compared to results from other research on Er:LiNbO₃ crystals. PACS 71.20.Eh; 77.84.Dy; 42.70.Hj; 42.62.Fi; 42.65.Ky     

Praseodymium-doped Ti:LiNbO3 waveguides

3 by diffusion doping is investigated by means of secondary neutral mass spectrometry and secondary ion mass spectrometry. The diffusion of praseodymium in LiNbO₃ can be described by Fick’s laws of diffusion with a concentration-independent diffusion coefficient and a limited solubility of praseodymium in LiNbO₃ increasing exponentially with rising temperature. The diffusion depends on the Li₂O content of the LiNbO₃ crystal. For LiNbO₃ crystals with a nominal slight difference in the congruent composition, the diffusion constants and activation energies for Z-cut LiNbO₃ are 3.28×10^-5 cm²/s and 2.27 eV, and 1.39×10^-5 cm²/s and 2.24 eV, respectively. Titanium-doped waveguides are formed in Pr:LiNbO₃ and characterised in relation to waveguide loss and absorption in the visible and near infrared. Received: 17 September 1998 / Accepted: 11 November 1998     

Photorefractive light scattering in lithium niobate crystals doped with Mg2+, B3+, Y3+, and Ta5+

We have investigated the photorefractive (photoinduced) light scattering in lithium niobate single crystals: LiNbO₃, LiNbO₃:B, LiNbO₃:Y(0.46 mas %), LiNbO₃:Y(0.24):Mg(0.63 mas %), and LiNbO₃:Ta(1.13):Mg(0.0109 mas %) that were grown from congruent melts. We have found that the shape of the speckle structure of this scattering and the kinetics of the development of its indicatrix depend substantially on the type of the impurity dopant in the lithium niobate crystal. We have observed that, upon laser irradiation of crystals doped with Y³⁺, Ta⁵⁺:Mg²⁺, and Y³⁺:Mg²⁺, the shape of their scattering indicatrix changes with time. At the same time, the LiNbO₃:B crystal is characterized by a complete absence of time changes in its speckle structure, which indicates that the photorefractive effect in this crystal is substantially lowered.     

Thermoluminescence and opitical absorption of BaF2 crystals

Abstract

Nominally pure and Dy-doped BaF₂ crystals were investigated concerning their optical absorption (OA) and thermoluminescence (TL) properties. Peaks at 120—150 and 200°C were observed for a heating rate of 1.7°C/s. The TL response for γ-rays and the TL emission spectra were obtained for these peaks. Except for the purest crystal, all BaF₂ crystals produced OA bands before irradiation typical of Ce³⁺ ions. After irradiation, Dy doped crystals showed bands due to Dy²⁺ ions. A nominally pure sample gave bands related to Ce²⁺ ions and photochromic centers of Ce³⁺ ions. and photochromic centres of Ce³⁺ ions. The correlation between some OA bands and TL peaks is discussed.     

Effects of the ordering of structural units of the cationic sublattice of LiNbO3:Zn crystals and their manifestation in Raman spectra

We have studied the Raman spectra of congruent crystals of lithium niobate (LiNbO₃) that were doped with Zn²⁺ ions in the range of concentration of 0–1.59 mol %. We have revealed a region of a more ordered structure such that the order of sequence of basic ions, impurity ions, and vacancies along the polar axis of the cationic sublattice is more regular, while the oxygen octahedra are close to ideal. In this case, crystals have a higher optical quality and are more stable with respect to optical damage. An increased ordering of the structure is realized because small amounts of Zn²⁺ cations displace Nb_Li defects and order the alternation of cations and vacancies along the polar axis and make the crystal less defect with respect to Li⁺ vacancies. Our results are important for industrial production of optically perfect lithium-niobate crystals by doping a congruent crystal with small concentrations of Zn²⁺ ions, since, in this case, technological regimes of crystal growth almost do not differ from regimes of growing of nominally pure congruent crystals.     

The Mössbauer spectrum of synthetic hureaulite: Fe5 2+(H2O)4(PO4H)2(PO4)2

The crystal structure of synthetic ferrous hureaulite, Fe₅ ²⁺ (H₂O)₄(PO₄H)₂(PO₄)₂, was refined from single-crystal X-ray data. It is monoclinic, space group C2/c, with a=17.487(4), b=9.017(2), c=9.338(2) Å, β=96.27(3)°, V=1463.6(6) Å³, Z=4 and D _calc=3.327 g/cm³. This end member of the hureaulite series was crystallized under distinctly acidic conditions, by a method that gives perfect crystals, large enough for X-ray single crystal studies. The main feature of the hureaulite structure is that it has an equal number of normal (PO₄)³⁺ and acid (PO₄H)²⁺ tetradentate groups. These are centered on Fe²⁺ atoms and share corners with edge-linked octahedra, forming pentamer units. The five Fe²⁺ atoms are distributed on three distinct sites in these units. This can be directly observed in the Mössbauer spectrum at 295 K, which contains three doublets whose relative intensities correspond to the 1:2:2 distributions of crystallographic sites.     

Nonvolatile hologram storage properties of tri-doped Zn:Ce:Cu:LiNbO3 crystals

Congruent Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was grown by the Czochralski method in air. The occupation mechanism of the Zn²⁺ was discussed by an infrared transmittance spectrum. The nonvolatile holographic recording in Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was measured by two-photon fixed method. Zn(7 mol%):Ce:Cu:LiNbO₃ single crystals present the faster recording time and higher light-induced scattering resistance ability comparing with Ce:Cu:LiNbO₃ single crystals.     

Manifestation of the specific structural features of lithium niobate single crystals of different composition in their Raman spectra

The Raman spectra of nominally pure lithium niobate single crystals of congruent, close to stoichiometric, and stoichiometric compositions and congruent lithium niobate single crystals doped with Gd³⁺, Y³⁺, and Mg²⁺ ions have been investigated. Weak lines whose widths anomalously decrease with an increase in cation sublattice disordering at a change in the single crystal composition were found for the first time. These lines may be indicative of fine ordering processes involving structural units of the cation sublattice, as a result of which this sublattice is disordered as a whole.     

Concentration dependences of IR absorption spectra in the range of stretching vibrations of OH groups of congruent lithium-niobate crystals doped with zinc and magnesium

The concentration behavior of the parameters of spectral lines that correspond to stretching vibrations of OH groups in the IR absorption spectra of LiNbO₃:Zn (0.04–4.46 mol % ZnO) and LiNbO₃:Mg (0.19–5.91 mol % MgO) crystals has been studied. It has been found that, in the range of threshold concentrations of Zn²⁺ and Mg²⁺ doping cations, the line parameters experience a jump. In this case, the widths of some lines decrease, which indicates the ordering of OH groups in the crystal. It has been shown that nonstoichiometric crystals are characterized by the occurrence of different positions of OH groups and different values of the quasi-elastic constants of O–H bonds in the crystal structure. In the stoichiometric LiNbO₃ crystal, all the positions of OH groups are the same, and the quasi-elastic constants of O–H bonds are identical.     

Preparation and holographic storage properties of tri-doped Mg:Mn:Fe:LiNbO3 crystals

Doping MgO, MnO and Fe₂O₃ in LiNbO₃ crystals, tri-doped Mg:Mn:Fe:LiNbO₃ single crystals were prepared by the conventional Czochralski method. The UV-vis absorption spectra were measured and the shift mechanism of absorption edge was also investigated in this paper. In Mg:Mn:Fe:LiNbO₃ crystal, Mn and Fe locate at the deep level and the shallow level, respectively. The two-photon holographic storage is realized in Mg:Mn:Fe:LiNbO₃ crystals by using He-Ne laser as the light source and ultraviolet as the gating light. The results indicated that the recording time can be significantly reduced for introducing Mg²⁺ in the Mg:Mn:Fe:LiNbO₃ crystal.     

Specific features of the dark conductivity in lithium niobate crystals of congruent composition

The temperature dependence of the dark conductivity in a series of doped and nominally undoped LiNbO₃ crystals of congruent composition is studied. The activation energies for the ionic and electronic contributions to the dark conductivity are determined, and the H⁺, ion diffusion coefficient is estimated. The correlation between the ionic and electronic contributions to the dark conductivity is established.     

High-field EPR Study of the Effect of Chloride on Mn2+ Ions in Frozen Aqueous Solutions

The effect of chloride concentration on Mn²⁺ (S = 5/2, I = 5/2) ions in frozen aqueous solutions is studied by high-field high-frequency electron paramagnetic resonance (HFEPR). The usually six sharp lines characteristic of Mn²⁺ ions, arising from the m _s  = ?1/2 → 1/2 transition, is modified by the addition of Cl^? anions and the six resonances become much broader and more complex. This new feature likely arises from the ligation of one Cl^? anion to a hydrated Mn²⁺ ion forming a [Mn(H₂O)₅Cl]^? complex. This complex increases linearly with Cl^? concentration with an association constant of K _{a, apparent} = 61 M^?1. The structure of the putative chloride complex was studied using density functional theory calculations and the expected zero-field interaction of such a manganese center was calculated using the superposition model. The predicted values were similar to those determined from the simulation of the spectrum of the m _s  = ?5/3 → ?3/2 transition of the chloride complex. This effect of Cl^? anions occurs at biologically relevant concentration and can be used to probe the Mn²⁺ ions in cellular and protein environments.     

Thermoluminescence of pure and doped ThO2

Thermoluminescence (TL) measurements in the temperature range 295–675 K indicate the existence of at least five trapping centres for single crystals of nominally pure “reduced” ThO₂ and three trapping centres for “oxidized” ThO₂. Deliberate doping with Ca²⁺, Y³⁺ and Ta⁵⁺ impurities decreases TL emission. For reduced ThO₂, accidentally incorporated rare-earth impurities, Pr³⁺, Tb³⁺, Er³⁺ act as the electron-hole recombination sites. In oxidized crystals the impurity Fe³⁺ is thought to be involved in the recombination process. In the temperature range 80–295 K an additional eight trapping centres exist for both oxidized and reduced ThO₂. For the reduced crystals the emission is probably associated with Fe in the +2 state, and in the +3 state for oxidized crystals. The differences in the TL glow curve intensities are partially explained by differences in the temperature dependence of the luminescence efficiency of the different recombination centres.