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     

The correlation of doping ions to holographic storage properties of Mg:Mn:Fe:LiNbO3 crystals

The congruent Mn(0.1 wt%):Fe(0.03 wt%):LiNbO₃ crystals doped with different concentration of MgO(0,1,3,6 mol%) have been grown by Czochralski method in air atmosphere. Some crystal samples were reduced in Li₂CO₃ powder. The defects and doping ions location in crystals were investigated by UV-Vis. absorption spectrum as well as infrared transmittance spectrum analysis. In two wave coupling experiments we determined the writing time, maximum diffraction efficiency and the erasure time of four crystal samples with He-Ne laser at 633 nm. The results indicated that Mg(3 mol%):Fe:Mn:LiNbO₃ was the most proper holographic recording media material among four crystals in the paper.     

Deposition of ZnO multilayer on LiNbO3 single crystals by DC-magnetron sputtering

Zinc oxide (ZnO) thin films were deposited on LiNbO₃ (LN) single crystals with 200 nm thicknesses by three different ways, where coating of zinc (Zn) film was followed by thermal oxidation for four, two, and one steps with 50, 100, and 200 nm thicknesses repeatedly. Sample, which was produced at 4-step of deposition and oxidation of Zn layer, showed high transmittance and low structural defect due to a lower photoluminescence intensity and Urbach energy. Average grain size in X-ray diffraction (XRD), scanning electron microscopy (SEM) micrograph, and atomic force microscopy (AFM) images for multilayer of ZnO was lower than monolayer of ZnO thin films. Applying multilayer coating technique leads to decrease of surface roughness and scattering on light on surface and fabrication of LiNbO₃ waveguides with lower optical loss.     

The influences of ZnO doping concentration on structure and photorefractive properties of Zn:Fe:LiNbO3 crystals grown by TSSG method

In this paper, LiNbO₃ crystals doped with same concentration of Fe₂O₃ and with different concentration of ZnO have been grown by the top-seeded-solution-growth (TSSG) method. Their IR transmittance spectra, UV-vis absorption spectra, lattice constants, and Curie temperature were measured. In two-wave coupling experiments, writing and erasure time constants, and maximum diffraction efficiency of the crystals were measured and compared with those of congruent LiNbO₃ (CLN) crystals doped with same ions. The crystals grown by TSSG method show shorter writing time, erasure time, and lower diffraction efficiency than the CLN crystals. The influences of ZnO doping concentration on photorefractive properties are studied.     

Nonvolatile photorefractive holographic recording in Sc:Ce:Cu:LiNbO3

In this paper experimental studies of nonvolatile photorefractive holographic recording in Ce:Cu:LiNbO₃ crystals doped with Sc(0,1,2,3 mol%) were carried out. The Sc:Ce:Cu:LiNbO₃ crystals were grown by the Czochralski method and oxidized in Nb₂O₅ powders. The nonvolatile holographic recording in Sc:Ce:Cu:LiNbO₃ crystals was realized by the two-photon fixed method. We found that the recording time of Sc:Ce:Cu:LiNbO₃ crystal became shorter with the increase of Sc doping concentration, especially doping with Sc(3 mol%), which exceeds the so-called threshold, and there was little loss of nonvolatile diffraction efficiencies between Sc(3 mol%):Ce:Cu:LiNbO₃ and Ce:Cu:LiNbO₃ crystals.     

ZnO-doped LiNbO<Subscript>3</Subscript> single crystals studied by X-ray and density measurements

Energy Dispersive X-ray Fluorescence Spectroscopy, X-ray diffraction and density measurements were conducted on undoped and ZnO-doped congruent LiNbO₃ single crystals grown by the Czochralski method. Based on the experimental results, an intrinsic defect evolution model was proposed. When ZnO was doped into the congruent LN crystals, the Zn ions replaced first the Li ions and increased the density. Then, the Zn ions simultaneously replaced the Li ions and the antisite Nb_Lis until all Nb_Li ions were replaced, which increased the density further. After that, the Zn ions substituted Nb ions in the Nb-sublattice sites with the reduction of the Li vacancies as self-compensation and thus reduced the density. When the Li vacancies disappeared completely, the Zn ions substituted simultaneously both Li ions in the Li-sublattice sites and Nb ions in the Nb-sublattice sites. The simultaneous substitution might finally lead to the generation of oxygen vacancies and decreased the density further. PACS 61.72.-y; 06.30.Dr; 61.10.-i     

Effects of forming gas annealing on LiNbO3 single crystals

Z-cut congruent LiNbO₃ single crystals were annealed in 95%N₂+5%H₂ at high temperatures. X-ray diffraction showed that 2θ of (0 0 0 6) peak is obviously reduced by 0.6° and 1.0° for the samples annealed at 600 and 900 °C, respectively. A new peak appears at the high-energy side of O 1s spectrum in X-ray photoelelectron spectroscopy (XPS) analyses, and the leakage current is greatly increased. It is proposed that hydrogen is incorporated in LiNbO₃ single crystals through forming gas annealing at temperatures up to 900 °C and exists in LiNbO₃ as a proton bound to an oxygen ion through O-H bond with its electron donated.     

The effect of MgO doping on optical properties of LiNbO3 single crystals

Undoped and MgO doped Lithium niobate single crystals were grown by the Czochralski technique. Comparative study of the optical properties of undoped and 7 mol% MgO doped LiNbO₃ crystal was undertaken. The effect of doping on refractive indices as well as second harmonic generation has been experimentally analyzed. The results of the polarization characteristics of second harmonic generation (SHG) support the major contribution of Li-O bonds to optical nonlinearity. MgO doping reduces the number of localized excitons and the grown LiNbO₃ crystal approaches the stoichiometric composition. This causes blue shift in the absorption edge of the crystals.     

Principles of X-ray diffractometry of surface acoustic waves

Theoretical fundamentals of modern methods of X-ray diffractometry of surface acoustic waves (SAW) are considered briefly. X-ray diffraction on SAW-modulated crystals under total external reflection conditions and the Bragg conditions for the YZ-cut of the LiNbO₃ crystal is considered. Agreement of theoretical and experimental results makes it possible to use them for SAW diagnostics. Possibilities and limitations of listed methods for determining the SAW field parameters are discussed.     

Application of interference microscopy to the study of hologram build-up in LiNbO3 crystals

Interference microscopy was applied to direct microscopic observation of temporal evolution of phase holograms in LiNbO₃:Fe photorefractive crystals. First a hologram was recorded in the sample, and diffraction efficiency was monitored during hologram build-up using inactinic laser light. Thus kinetics of hologram build-up could be determined. The initial hologram was erased using white light. Then a series of write-erase cycles were performed with increasing exposure times. Holograms were observed by interference microscope after each exposure. The time elapsed between the exposure and the microscopic observation was negligible compared to the relaxation time of the hologram. The obtained temporal evolution of the grating profile gives a deeper insight into the physical mechanism of hologram formation in photorefractive materials than simple diffraction efficiency measurements. A congruently grown sample of LiNbO₃ doped with 10⁻³ mol/mol Fe in melting was studied by this method. Sample thickness was set to 300 μm to allow correct microscopic observation. Plane-wave holograms were recorded in the samples using an Ar-ion laser at λ = 488.0 nm of grating constants of 3, 6.5 and 8.8 μm.     

Investigation of nonvolatile holographic storage in LiNbO3:Mn:Ce:Fe crystal

We investigate the persistent holographic recording in triply doped LiNbO₃:Mn:Ce:Fe crystals at different oxidation/reduction states. The experimental results show that there is an optimum oxidation/reduction state, which results in the best dynamic range M/#. Compared with doubly doped LiNbO₃:Ce:Fe, we found that the nonvolatile diffraction efficiency and the best dynamic range M/# obtained in triply doped samples are larger than that obtained in doubly doped samples. The reason for the increase of the crystal about the nonvolatile diffraction efficiency and the dynamic range M/# was also explained.     

Structural, optical and electrochromic properties of Nb-doped MoO3 thin films

Niobium (Nb) doped molybdenum trioxide (MoO₃) thin films have been synthesized using spray pyrolysis deposition technique. The structural changes were observed with the help of X-ray diffraction technique. With increasing Nb concentration, the structure of MoO₃ undergoes a phase transformation from α-orthorhombic to amorphous with nano-sized grains. The thread like reticulated morphology is converted into spongy like structure at higher Nb concentration (9 at% Nb). It is seen that Nb doping can lead to significant surface morphology changes in MoO₃ films. It was found that the coloration efficiency increases with doping concentration. With increasing Nb concentration charge capacity, reversibility and electrochemical stability increases. The improvement is attributed to the amorphous structure of the doped samples that favors easy intercalation and deintercalation processes. Hence, we have successfully demonstrated formation of an adequate host for electrochromic devices with Nb (9 at%) doped MoO₃ samples.     

Second and third order nonlinear optical properties of nanostructured ZnO thin films deposited on α-BBO and LiNbO3

The nanocrystalline ZnO films were deposited on α-BaB₂O₄ (0 0 1 2) and LiNbO₃ (0 0 0 1) single crystals by RF-magnetron sputtering technique. Their structure was studied using X-ray diffractometry, scanning electron microscopy and atomic force microscopy. Besides, the optical absorption spectra were investigated. The second and third harmonic generation measurements were performed by means of the rotational Maker fringe technique using Nd:YAG laser at 1064 nm in picoseconds regime. Finally, the second and third order nonlinear susceptibilities were determined and their values have been found and compared.     

Preparation and characterization of GaN films by radio frequency magnetron sputtering and carbonized-reaction technique

Radio frequency magnetron sputtering/post-carbonized-reaction technique was adopted to prepare good-quality GaN films on Al₂O₃(0 0 0 1) substrates. The sputtered Ga₂O₃ film doped with carbon was used as the precursor for GaN growth. X-ray diffraction (XRD) pattern reveals that the film consists of hexagonal wurtzite GaN. X-ray photoelectron spectroscopy (XPS) shows that no oxygen can be detected. Electrical and room-temperature photoluminescence measurements show that good-quality polycrystalline GaN films were successfully grown on Al₂O₃(0 0 0 1) substrates.     

X-ray induced luminescence of LiNbO3

X-ray induced luminescence has been observed in pure as well as Ni, Cu and Eu-doped LiNbO₃. The emission spectrum for both, pure congruently grown and doped samples, consists of a well-defined band peaked at ≈425 nm. The shape and height of this band is also independent of the amount of radiation-induced coloring in the crystal. It has been concluded that the emission corresponds to an intrinsic and bulk recombination process.     

Influence of heat treatment on structure and some physical properties of lithium boro-niobate glass

The glass composition (90?mol% Li₂B₄O₇–10?mol% Nb₂O₅) was prepared by the melt quenching technique. The quenched sample was heat treated at 480°C, 545°C and 630°C for 5?h and heat treated at 780°C with different time. The times were 5, 10, 15, 20, 28, and 36?h. The glass and glass ceramics were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and dc conductivity as a function of temperature. Lithium niobate (LiNbO₃) and lithium diborate (Li₂B₄O₇) were the main phases in glass ceramic addition to traces from LiNb₃O₈. Crystallite size of the main phases determined from the X-ray diffraction peaks are in the range <100?nm. The fraction of crystalline (LiNbO₃) phase increases with increase the heat treatment temperature and time. The relation between physical properties and structure were studied.     

The role of the dopant in the magnetism of Fe-doped SnO2 films

Transparent pure and Fe-doped SnO₂ thin films were grown by pulsed laser deposition technique on LaAlO₃ substrates. X-ray diffraction shows that the films are polycrystalline and have the rutile structure. Surprisingly, the pure film presents magnetic-like behavior at room temperature with a saturated magnetization of almost one-third of the doped film (∼3.6 and 11.3 emu/g, respectively) and its magnetization could not be attributed to any impurity phase. Taking into account the magnetic moment measured in the pure film, the effective contribution of the impurity in the doped one can be inferred to be ∼2 μ_B per Fe atom. A large magnetic moment was also predicted by an ab initio calculation in the doped system, which increases if an oxygen vacancy is present near the Fe impurity.     

Study of near-infrared nonvolatile two-center holographic recording in LiNbO3:Fe:Rh crystal

The near-infrared nonvolatile holographic recording has been realized in a doubly doped LiNbO₃:Fe:Rh crystal by the traditional two-center holographic recording scheme, for the first time. The recording performance of this crystal has been investigated by recording with 633 nm red light, 752 nm red light and 799 nm near-infrared light and sensitizing with 405 nm purple light. The experimental results show that, co-doped with Fe and Rh, the near-infrared absorption and the photovoltaic coefficient of shallow trap Fe are enhanced in this LiNbO₃:Fe:Rh crystal, compared with other doubly doped LiNbO₃ crystals such as LiNbO₃:Fe:Mn. It is also found that the sensitizing light intensity affects the near-infrared recording sensitivity in a different way than two-center holographic recording with shorter wavelength, and the origin of experimental results is analyzed.     

Impedance spectroscopy and piezoresponse force microscopy analysis of lead-free (1 − x) K0.5Na0.5NbO3 − xLiNbO3 ceramics

(1 ? x) K_0.5Na_0.5NbO₃ ? xLiNbO₃ (where x = 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) (KNLN) perovskite structured ferroelectric ceramics were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that single phase was formed for pure KNN while a small amount of second phase (K₆Li₄Nb₁₀O₃₀, ～3%) was present in LN doped KNN ceramics. Phase analysis indicated the change in the crystal structure from orthorhombic to tetragonal with increase in LN content. The electrical behavior of the ceramics was studied by impedance spectroscopy technique in the high temperature range. Impedance analysis was performed using an equivalent circuit model. The impedance response in pure KNN and KNLN ceramics could be deconvoluted into two contributions, associated with the bulk (grains) and the grain boundaries. Activation energies for conductivity were found to be strongly frequency dependent. The activation energy obtained from dielectric relaxation data was attributed to oxygen vacancies. From PFM we found that the composition with 6.5 wt.% LN displays stronger piezocontrast as compared to pure KNN implying an evidence of a pronounced piezoelectric coefficient.     

X-ray photoelectron spectroscopy of Sm-doped CaO-MgO-Al2O3-SiO2 glasses and glass ceramics

Sm³⁺ doped CaO-MgO-Al₂O₃-SiO₂ glass and glass ceramics have been prepared. The diopside crystal (CaMgSi₂O₆) was identified in the glass ceramics by X-ray diffraction analysis. X-ray photoelectron spectra of the glass and glass ceramics were measured by a monochromatised Al-Kα XPS instrument. Sm 3d core level spectra for the Sm doped samples showed that Sm ions are predominantly in the Sm (III) state in glass and glass ceramics. The O 1s core spectra could be fitted by summing the contributions from bridging oxygen (BO) and non bridging oxygen (NBO) for samarium undoped glass, BO, NBO and Si-O-Sm for the doped glass. The O 1s XPS spectrum of undoped glass ceramics was curve fitted with BO and NBO in glass phase, as well as SiOSi, SiOMg and SiOCa in diopside. In addition to the five components above mentioned, SiOSm in diopside also appeared in O 1s XPS spectra of samarium doped glass ceramics. According to the fitting results, we demonstrate that the Sm₂O₃ exist in glass network as a glass modifier. After heat treatment, nearly all the Sm³⁺ existed in diopside phase as the substitution for Ca²⁺.