X-ray spectra and electronic structure of Li x NbO2 superconductor and other niobium oxide compounds

X-ray emission Nb and OK spectra and O1s total photoelectron yield spectra for superconductor Li_0.71NbO₂ and other niobium oxide compounds NbO, BaNb₄O₆, Ba₂Nb₅O₉, BaNb₅O₈. LiNbO₂, NbO₂, LiNbO₃ were investigated. It was found that in stoichiometric LiNbO₂, niobium oxidation degree is 3+. Under the lithium deintercalation down to Li_0.71NbO₂ composition, the niobium ions oxidation degree increases up to 3.3+. As more electrons are supplied by Nb to fill the O2p band, the degree of O2p-Nb4d hybridization is increased. Using the full-potential linear muffin-tin orbital method, the self-consistent band structure calculations of Li _x NbO₂ (x=1.0; 0.7; 0.5) compounds were carried out. Agreement between partial Nb4d and O2p densities of states and corresponding X-ray spectra was observed. For thex=0.7; 0.5 the Fermi level is placed on the slope of sharp density of states peak formed mostly by the Nb4d states. With the decrease ofx thep-d hybridization becomes stronger, although remains well below the values typical for the high-temperature superconductors.     

Dominant Cr3+ centers in LiNbO3 under hydrostatic pressure

Low-temperature luminescence spectra of stoichiometric Cr: LiNbO₃ and of congruent Cr, Mg: LiNbO₃ were studied. Cr³⁺ impurity ions preferentially occupy Li⁺ sites (Cr_Li) in the LiNbO₃ crystal lattice, while Cr³⁺ ions substituting for Nb⁵⁺ ions (Cr_Nb) occur in addition to Cr_Li centers in codoped Cr, Mg: LiNbO₃ crystals. Application of a high hydrostatic pressure leads to a transformation of (dominant in concentration) Cr³⁺ centers from low-to high-crystal-field centers. Due to a strong pressure-induced blue shift of the ⁴ T ₂ state resulting in crossing with the ² E state, the replacement of the broad band ⁴ T ₂ → ⁴ A ₂ emission by a narrow R-line emission ² E → ⁴ A ₂ occurs in the luminescence spectra of the samples. This effect of level crossing was observed for the dominant Cr _Li ³⁺ and Cr _Nb ³⁺ centers at pressures which correlated well with estimations based on the ⁴ T ₂-² E energy gap (230 and 1160 cm^?1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^?1/kbar, respectively).     

Optical characterization of Cr3+ centers in LiNbO3

Low-temperature luminescence spectra of stoichiometric Cr:LiNbO₃, congruent Cr:LiNbO₃ and congruent Cr,Mg:LiNbO₃ were studied. Dominant low-field and minor high-crystal-field optical centers are the Cr³⁺ impurity ions that preferentially occupy Li⁺ sites (Cr_Li) in the Cr:LiNbO₃ crystals. Low-field centers related to Cr³⁺ substitution of Nb⁵⁺ (Cr_Nb) occur in addition to Cr_Li in co-doped Cr,Mg:LiNbO₃ samples. Application of high hydrostatic pressure leads to the transformation of dominant Cr³⁺ centers from low- to high-field type due to strong pressure-induced blue shift of the ⁴ T ₂ state, resulting in its crossing with the ² E state of Cr³⁺. This level-crossing effect was observed for the dominant Cr³⁺ _Li and Cr³⁺ _Nb centers at pressures that correlate well with estimations based on the ⁴ T ₂-² Eenergy gap (230 cm^-1 and 1160 cm^-1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^-1/kbar, respectively). We also studied inhomogeneous broadeningof the ² E?⁴ A ₂transitions at ambient pressure for the minor high-field “defect” Cr³⁺ _Li centers in congruent LiNbO₃. A fine structure in the spectral response of these centers was observed. The obtained results are discussed on the basis of a microscopic hierarchic model for perturbed Cr³⁺ ions in the LiNbO₃ lattice. Received: 25 June 2001 / Published online: 2 November 2001     

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.     

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.     

Photoelectric fields in lithium niobate crystals

Photovoltaic and diffusion fields in nominally pure single crystals of stoichiometric composition (R = Li/Nb = 1) grown in the presence of 6 wt% K₂O flux (LiNbO₃ stoich. K₂O) in nominally pure single crystals of complementary composition (LiNbO₃), complementary single crystals doped with Zn²⁺, Er³⁺ at wavelength of 476, 514.5, 530 nm are defined according to parameters of photo induced light scattering indicatrix. Photo induced changes of crystals’ refractive index are defined.     

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.     

Structural disorder and optical properties of congruent lithium niobate crystals doped with zink and boron

From the concentration dependence of the widths and intensities of Raman lines and from the patterns of photoinduced light scattering, it is found that the mechanism of incorporation of Zn²⁺ cations into the LiNbO₃ crystal structure changes with increasing concentration of zinc in the melt, which leads to an abrupt anisotropic expansion of oxygen octahedra along the polar axis. In this case, the number of kinks in the concentration dependence of linewidths (5) considerably exceeds the number of concentration threshold (2) known from the literature. It is shown that B³⁺ ions almost do not enter the cationic sublattice of the LiNbO₃ crystal but changes the melt structure, so that the LiNbO₃:B crystal is characterized by a high structural and optical homogeneity and a low photorefractive effect.     

Photorefractive properties for holographic application of Ce:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Ce:Fe:LiNbO₃ crystals with various [Li]/[Nb] ratios were grown by the Czochralski method from melts having compositions varying between 48.6 and 58 mol% Li₂O. The Ce, Li and Nb concentrations in the grown Ce:Fe:LiNbO₃ crystals were analyzed by the inductively coupled plasma atomic emission spectrometer (ICP-AES). It was found that as the [Li]/[Nb] ratio increases in the melt, the [Li]/[Nb] ratio in the crystal and the distribution coefficients of Ce ions increase also. The photorefractive properties of the Ce:Fe:LiNbO₃ crystals were experimentally studied by the two-wave coupling method. The results show that as the [Li]/[Nb] ratio increases, the dynamic range decreases, but the photorefractive sensitivity and the signal-to-noise ratio improve. In a coherent volume 0.192 cm³ of a Ce:Fe:LiNbO₃ crystal with [Li]/[Nb] ratio of 1.2, 3800 holograms with 800×600 pixels have been successfully multiplexed in a compact volume holographic data storage system.     

Optical homogeneity,defects, and photorefractive properties of stoichiometric,congruent, and zinc-doped lithium niobate crystals

Using the laser-conoscopy method, the photorefractive light-scattering method, and the Raman light-scattering method, we have studied the structural and optical homogeneities and photorefractive properties of (i) stoichiometric lithium niobate crystals (LiNbO₃(stoich)), which were grown from a melt with 58.6 mol % of Li₂O; (ii) congruent crystals (LiNbO₃(congr)); and (iii) congruent crystals that were doped with Zn²⁺ cations (LiNbO₃:Zn; [Zn] = 0.03–1.59 mol %). We have shown that the speckle-structure of the photorefractive light scattering in all the crystals is three-layer. The shapes of the second and third layers repeat in general the shape of the first layer. We have shown that the differences that are observed between the Raman spectra, the photorefractive light scattering, and the conoscopic patterns of the examined crystals are caused by the fact that defects are distributed inhomogeneously over the volume of these crystals and that Zn²⁺ cations are incorporated inhomogeneously into the lattice. This leads to the appearance of local changes in the elastic characteristics of the crystal and to the appearance of mechanical stresses, which locally change the optical indicatrix and, correspondingly, the conoscopic pattern and the Raman spectrum.     

Study on the formation during the production of lead-free piezoceramics at the morphotropic phase boundary

Because of the environmental concerns, the manufacture of ceramics based on lead titanate zirconate [Pb(Zr_1−xTi_x)O₃−PZT] has been condemned because of the lead toxicity. In this context, the electromechanical properties of sodium, potassium and lithium niobate [(Na_0.5−x/2K_0.5−x/2Li_x)NbO₃−NKLN] at the morphotropic phase boundary granted these materials the position of most suitable candidate to replace PZT. However, the production of these ceramics is rather critical mainly because of a natural tendency of forming secondary phases. To help with the studies of the synthesis of this lead-free piezoceramic, this work presents an evaluation of the crystallization of the (Na_0.47K_0.47Li_0.06)NbO₃ phase by solid-state reactions. TG-DTA, XRD, dilatometric and ferroelectric hysteresis analyses indicated that a secondary phase (K₃Li₂Nb₅O₁₅) crystallizes at temperatures above 850 C and also during the sintering of the powders compacts at 1080 C. To prevent the formation of this phase, the addition of Na₂Nb₂O₆.nH₂O microfibers obtained through a microwave hydrothermal synthesis was performed in the sintering process. After to this addition, the suppression of the K₃Li₂Nb₅O₁₅ phase occurred and an increase of the NKLN electrical properties was then obtained.     

Dopant occupancy and optical properties of Er3+ in Er/Zn-codoped lithium niobate crystal

The effect of Zn²⁺ ion on the dopant occupancy and optical characteristic of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal is reported. The intense 1.54 μm and relatively weak green upconversion emissions are observed for Er (1 mol%)/Zn (6 mol%):LiNbO₃ crystal. The OH^? absorption and the time-resolved spectra show that the Zn²⁺ codoping decreases the threshold concentration of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal. The experimental results here imply that the potential application of Er³⁺-doped LiNbO₃ crystal can be designed and optimized on the basis of the theoretical investigations.     

Evidence of different β-phases in highly protonated z-cut H:LiNbO3 waveguides by raman scattering

3 waveguides is demonstrated by the Raman scattering technique. Multimode waveguides have been produced by using pyrophosphoric, benzoic, and diluted benzoic acids as a proton source. The proton-exchanged (PE) layers are subjected to annealing (APE samples) with different rates of cooling: slow (s) and quick (q). The effect of Li-H replacing is considered in the frequency range below 800 cm^-1 and about 3500 cm^-1 (OH modes). The analysis of the spectral data leads to some important conclusions about the changes in the H:LiNbO₃ lattice. We demonstrate that applying (s) ? (q) procedures on H_xLi_1-xNbO₃ waveguides with x>0.56 leads to phase transitions between different states. The high-temperature phase modifications (metastable at room temperature) are characterized by strongly broadened q-Raman bands which imply a high degree of disorder. Although the Raman measurements support the presence of different phases in H:LiNbO₃ waveguides, some conclusions, different from those reported elsewhere, have been made. Received: 16 November 1998 / Accepted: 14 December 1998 / Published online: 24 February 1999     

Regular domain structures fabricated by an electron beam in stoichiometric LiNbO3 crystals

Electron beam writing of regular domain structures in Z-cuts 0.75 mm thick of stoichiometric and close to stoichiometric LiNbO₃ crystals has been carried out. Crystals have been grown by the Czochralski method from a melt with excess Li₂O (58.6 mol %) and from a congruent-composition melt in the presence of 6 wt % K₂O alkali solvent (flux). In both crystals, threshold charge doses required to form individual domains have been determined, and the optimal conditions of periodic structure patterning by sequential local irradiations have been found. Domain gratings of similar type (with periods of 6.5, 7, and 10 ??m) are formed in both types of stoichiometric crystals.     

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     

Lithium intercalation in MoO3: A comparison between crystalline and disordered phases

We report properties of lithium-intercalated MoO₃ crystalline and thin-film which are potential cathode materials for high energy density batteries. Discharge and charge reactions of MoO₃ electrodes in a non-aqueous Li⁺-electrolyte have been studied. The kinetically accessible discharge range amounts to 0x1.5 for Li insertion in Li _x MoO₃. Transport parameters such as the Li⁺ chemical diffusion coefficient, thermodynamic factor and ionic conductivity are investigated during the Li⁺ insertion process and discussed with respect to the crystallinity of the cathode material.     

A Mössbauer and ESR study of LiNbO3-Fe2O3 for low Fe2O3 concentrations

Samples of the system LiNbO₃-Fe₂O₃ prepared by water quenching and by the double-roller quenching method in the range up to 24 mol% Fe₂O₃ were investigated by Mössbauer and ESR spectroscopy. In the water quenched samples up to 11 mol% Fe₂O₃ only the Fe³⁺ and the Fe²⁺ valence states could be detected. The Fe²⁺ concentration decreased with increasing Fe₂O₃ content. Above 11 mol% Fe₂O₃ magnetically split Mössbauer spectra indicated the presence of Fe₂O₃ clusters. The isomer shift values of Fe³⁺ as a function of Fe₂O₃ concentration showed jumps at 6 and 11 mol% Fe₂O₃, whereas no significant changes could be detected in the quadrupole splitting values. The ESR data already exhibited the existence of isolated Fe³⁺ ions and of clusters with Fe-Fe distances less than 8 Å for the lowest Fe₂O₃ concentration. The cluster signal intensity increased with increasing Fe₂O₃ content. The roller quenched samples showed increased Fe²⁺ concentration as compared to the water quenched samples, which suggests that slow quenching results in iron oxidation and cluster formation. For low Fe₂O₃ concentrations a valence state change Fe³⁺Fe²⁺ can easily be obtained by heat treatments in various atmospheres, whereas for higher Fe₂O₃ contents (9.8 mol%) precipitations of-Fe (in reducing atmosphere) and Fe₂O₃ (in air) could be observed in addition to the valence state changes of a remaining part of dissolved Fe ions. On the basis of the obtained results a model was suggested for the unusual behaviour of the lattice parameters observed in LiNbO₃-Fe₂O₃.     

X-ray diffraction study on precipitate of Er:LiNbO3 induced by vapor transport equilibration

An X-ray powder diffraction study was performed on vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals with different doping levels (0.2, 0.4 and 2.0% Er per cation site), different cut orientations (X- and Z-cuts) and different VTE durations (120, 150 and 180 h). Their diffraction characteristics were compared with those of pure congruent LiNbO₃ and as-grown Er:LiNbO₃. The most significant characteristic is the appearance of additional weak and broad peaks around the 2θ angles 30° and 59° in the diffraction patterns of both X- and Z-cut 2.0 mol% doped VTE crystals, confirming that they precipitated. A further comparison of their diffraction data with the powder diffraction files indicated that the new phase in these precipitated crystals is ErNbO₄, which has an approximate concentration of 1.0%, 1.065%, 1.485% for 120, 150 and 180 h crystals, respectively. The crystalline grain sizes of the new phase are 132.2∼184.1?. The unit cell parameters of the as-grown and VTE crystals were also determined from diffraction data; the variation from pure LiNbO₃ to as-grown Er:LiNbO₃ was qualitatively explained according to the crystal structure of LiNbO₃ and using the concept of ionic radius. VTE brings the crystal closer to a stoichiometric composition, thus causing the contraction of the lattice constants. Finally, a tentatively qualitative explanation for precipitate formation is given on the basis of crystal structure. Received: 2 August 2000 / Accepted: 29 March 2001 / Published online: 20 June 2001     

Electro-optic coefficients of a non-congruent lithium niobate fabricated by vapour transport equilibration: Composition effect

Composition effect on electro-optic (EO) properties of a LiNbO₃ (LN) single-crystal has been investigated in a Li₂O-content range of 47.0–49.95 mol%. Some non-congruent LN crystals with different Li₂O-contents were prepared by performing Li-deficient or Li-rich vapour transport equilibration treatments on as-grown congruent LN crystals. Unclamped EO coefficients γ₁₃ and γ₃₃ of these samples were measured by a Mach–Zehnder interferometric method. The measurements show that in the Li-deficient regime both γ₁₃ and γ₃₃ increase by ～8% as Li₂O-content decreases from the congruent 48.6 mol% to the 47.0 mol% in the Li-deficient regime. The feature is desired for the EO application of the Li-deficient crystal. In the near-stoichiometric regime, both γ₁₃ and γ₃₃ reveal a non-monotonic dependence. As the Li₂O-content increases from the 48.6 mol%, the EO coefficient decreases. Around Li₂O-content 49.5 mol%, a minimum is reached. After that, the EO coefficient recovers slowly. At the stoichiometric composition, it recovers to a value close to that at the congruent point. Comparison shows that different crystal growth methods give rise to different defect structure features and hence different composition effects.     

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.