Optical properties of LiNbO3:Mg(5.21 mol %) and LiNbO3:Fe(0.009 mol %):Mg(5.04 mol %) crystals

Using methods of electronic spectroscopy, laser conoscopy, photoinduced (photoreactive) light scattering, and Raman light-scattering spectroscopy, we have studied the optical homogeneity, optical transmission, and photorefractive properties of single crystals LiNbO₃:Mg(5.21 mol %) and LiNbO₃:Fe(0.009 mol %):Mg(5.04 mol %) that were grown from congruent melts. We have ascertained that doping with “nonphotorefractive” Mg²⁺ cations causes suppression of the photorefractive effect in a lithium-niobate crystal. Upon double doping (Fe:Mg), if the concentration of Mg²⁺ cations exceeds the threshold concentration, the photorefractive effect is almost not observed and the presence of “photorefractive” Fe cations does not affect the photorefractive effect as strongly as in congruent crystals doped with Fe.     

Structural homogeneity of photorefractive LiNbO<Subscript>3</Subscript> crystals doped with 0.03–4.5 mol % of ZnO

Using the electronic spectroscopy method, the laser-conoscopy method, and the Raman light-scattering method, we have studied the structural homogeneity of LiNbO₃ crystals doped with 0.03–4.5 mol % of ZnO. We have found that, as the laser radiation power is increased to 90 mW, the conoscopic patterns of crystals show additional distortions, which are attributed to the manifestation of the photorefractive effect. For the LiNbO₃ crystal doped with 4.5 mol % of ZnO, in which the photorefractive effect is low, we have revealed a considerable shift (compared to the remaining crystals) of the optical absorption edge toward the shortwavelength range, which indicates a high structural homogeneity of this crystal. We have shown that, in the LiNbO₃ crystal doped by 0.05 mol % ZnO, due to the displacement of Nb_Li and Li□ structural defects by Zn²⁺ cations, the crystal structure is ordered and, simultaneously, the number of defects with localized electrons decreases.     

Photorefractive light scattering in LiNbO3: Cu crystals

The time dependence of the photorefractive light scattering in lithium niobate single crystals of the congruent composition (LiNbO₃) doped by “photorefractive” Cu cations (0.015 wt %) is studied for a radiation power of 160 mW. The data for the photorefractive scattering are confirmed by changes in Raman scattering spectra.     

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.     

Enhanced nonvolatile holographic properties in Zn,Ru and Fe co-doped LiNbO3 crystals

A series of LiNbO₃ crystals doped with various concentrations of ZnO and fixed concentrations of RuO₂ and Fe₂O₃ have been grown by the Czochralski method from the congruent melts. The type of charge carriers was determined by Kr⁺ laser (476 nm) and He–Ne laser (633 nm). The results revealed that the holes were the dominant charge carriers at blue light irradiation. Dual-wavelength and two-color techniques were employed to investigate the nonvolatile holographic storage properties of Ru:Fe:LiNbO₃ and Zn doped Ru:Fe:LiNbO₃ crystals. The essential parameters of blue nonvolatile holographic storage in Zn:Ru:Fe:LiNbO₃ crystals were enhanced greatly with the increase of Zn concentration. This indicates that the damage resistant dopants Zn²⁺ ions enhance the photorefractive properties at 476 nm wavelength instead of suppressing the photorefraction. The different mechanisms of blue photorefractive and nonvolatile holographic storage properties by dual wavelength recording in Zn:Ru:Fe:LiNbO₃ crystals were discussed.     

Light scattering in single crystals of nonlinear-optical photorefractive LiNbO<Subscript>3</Subscript>:Cu and LiNbO<Subscript>3</Subscript>:Zn

Comparative studies are made of the photorefractive scattering of light in nonlinear single crystals of lithium niobate with congruent compositions (LiNbO₃) doped with "photorefractive" Cu [0.015 mass %] and "nonphotorefractive" Zn [0.5 mass %] cations. For the first time it is found that single crystals doped with "photorefractive" and "nonphotorefractive" cations have different indicatrices for photorefractive light scattering. The aperture angle for photorefractive scattering reaches its steady state value more rapidly with high laser powers than with low. However, at high powers laser induced heating of the crystal is greater, and this leads to a narrowing of the scattering indicatrix. It is also found that photorefractive scattering in these single crystals depends on the region of the boule from which a sample has been cut. This indicates that there is a nonuniform distribution over the boule of the imperfections with localized electrons which determine the magnitude of the photorefractive effect.     

Specific features of growth and structure of LiNbO<Subscript>3</Subscript> : Zn crystals near the ZnO concentration threshold of 6.76 mol %

The crystallization conditions and Raman spectra of LiNbO₃ : Zn crystals (0.02–8.91 mol % ZnO in the melt) have been investigated. It has been established that the most favorable conditions for growing optically and compositionally homogeneous heavily doped LiNbO₃ : Zn crystals, which are characterized by a low photorefractive effect, are implemented in the ZnO concentration range of ~4.0–6.76 mol % in the melt. Since the distribution coefficient K _eff decreases significantly with an increase in the ZnO concentration in the melt, one can obtain LiNbO₃ : Zn crystals with significantly different defect structures but identical zinc concentrations. A change in the zinc concentration in crystals has been shown to induce a stepwise change in the sequence order of the main (Li and Nb) and doping (Zn) cations and vacancies and stepwise anisotropic expansion of the oxygen octahedra along the polar axis. The number of kinks in the concentration behavior of the spectral-line widths (five kinks for the lines with frequencies of 630 (A ₁(TO)) and 876 cm^–1 (A ₁(LO))) significantly exceeds the number of thresholds (two) known from the literature.     

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 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 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.     

Site spectroscopy of Hf doping in Hf-doped LiNbO3 crystals

By means of Raman scattering spectroscopy we determine the site location occupied by Hf ions in photorefractive damage resistant Hf-doped LiNbO₃. At room temperature the two lowest frequency phonons are related to sites B (Nb) and A (Li), and are used to directly probe the dopant ion. For the low concentration range, the Hf ions go into the sites A whereas, for high concentration, Hf ions occupy both sites A and B. Results are compared with data obtained for pure congruent and stoichiometric crystals, and the proposed mechanism of incorporation of Hf ions in the LiNbO₃ lattice explains the threshold in the behaviour of photorefractive properties.     

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.     

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.     

Photorefractive and Raman light scattering in lithium niobate ferroelectric crystal

Using the methods of photorefractive and Raman light scattering, we study subtle features of the structure of LiNbO₃ single crystals with different Li/Nb ratios (pure and doped with nonphotorefractive cations) grown by different methods. We reveal that, upon the irradiation of a single crystal with visible laser light, locally fluctuating micro- and nanostructures are initially formed in it, with their physical parameters being different from the corresponding parameters of the single crystal in the absence of the photorefractive effect. Upon an increase in the irradiation intensity and in the course of time, more and more such micro-structures are formed, and they are transformed into static micro- and nanoformations, which are subsequently converted into a continuous laser track. The speckle structure of photorefractive scattering is studied in detail. We show that the photorefractive effect in single crystals of the stoichiometric composition is fairly strong for their use as materials for recording and storing information.     

The effect of stoichiometry and Mg doping on the Raman spectra of LiNbO3:Mg crystals

LiNbO₃:Mg crystals doped with 0–8 mol. % Mg with stoichiometric, intermediate and congruent compositions were systematically investigated by Raman spectroscopy in backscattering y(zx)y, y(zz)y and z(xx)z geometries. The damping was found to be a very sensitive parameter for the characterization of the crystal composition. The half-widths of E(TO₃)–E(TO₉) and A ₁(TO₁)–A ₁(TO₄) bands having significant composition dependence for the undoped LiNbO₃ crystals show only a weak Mg concentration dependence below the photorefractive threshold, which is a consequence of the counteracting effect of the decreasing Nb_Li and increasing Mg_Li contents. The half-widths of the bands, however, increase linearly with growing Mg content for samples above the threshold, irrespective of the Li/Nb ratio. The change in the Mg concentration dependence at a given Li/Nb ratio determines the same threshold value as that concluded from IR and UV spectroscopic measurements. The half-width of the main A ₁(LO₄) band at 873 cm^-1 increases linearly with growing Mg concentration, but no threshold effect is observed. However, the ratio of the area of the main band and the high-frequency sideband shows a threshold effect that can be interpreted by the existing defect incorporation models. The small Raman band at about 740 cm^-1 attributed earlier to Nb_Li vibration is also detected in above-threshold LiNbO₃:Mg crystals, which can be explained by the vibration of Nb ions in Mg₄Nb₂O₉ defect clusters appearing at high Mg concentrations. PACS 77.84.Dy; 63.20.Mt; 42.70.Mp; 78.30.-j     

Growth and photorefractive properties of near-stoichiometric In:Fe:Cu:LiNbO3 crystals

The near-stoichiometric LiNbO₃ crystal co-doped with In₂O₃, Fe₂O₃, and CuO has been grown from a Li-rich melt (Li/Nb = 1.38, atomic ratio) by the Czochralski method in air atmosphere for the first time. The OH⁻ absorption spectra were characterized to investigate the structure defects of the crystals. The appearance of the 3506 cm⁻¹ absorption peak manifests that the composition of the grown crystal is close to the stoichiometric ratio. The photorefractive properties were also measured by the two-wave coupling experiments. The results show that the near-stoichiometric In:Fe:Cu:LiNbO₃ crystal has a larger refractive index change, higher recording sensitivity and larger two-wave coupling gain coefficient than those obtained in the congruent In:Fe:Cu:LiNbO₃ crystal under the same experimental conditions. The material of near-stoichiometric In:Fe:Cu:LiNbO₃ crystal is a promising candidate for blue photorefractive holographic recording.     

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.     

LiNbO3 with the damage-resistant impurity indium

We report on a detailed investigation (EPR, SHG, optical absorption, luminescence and Raman scattering) on the new damage-resistant impurity indium in LiNbO₃, where the increased photoconductivity strongly reduces the photorefractive effect. EPR and optical absorption measurements point to a complete disappearance of the Nb antisite in LiNbO₃: In for all In concentrations. We believe that the very effective driving out of Nb antisites by In is due to the trivalent charge state of In and the possibility of charge self-compensation. Similarities in the properties of Mg-, Zn- or Indoped samples are discussed. Simultaneous doping with In and Zn leads to an addition of both contributions, in particular for optical frequency doubling and luminescence. Raman studies prove that In does not improve the stoichiometry of the crystals. Indium doping provides the possibility to control simultaneously phase-matching conditions and to reduce drastically photorefraction. Therefore, In co-doped LiNbO₃ compositions are promising materials for applications after solving contemporary growth problems.     

Raman spectra of lithium niobate crystals heavily doped with zinc and magnesium

We have examined the Raman spectra of heavily doped lithium niobate single crystals (at close-to-threshold concentrations of doping cations): LiNbO₃:Zn (4.5 mol % ZnO), LiNbO₃:Mg (5.01 mol %):Fe (0.005 mol %), LiNbO₃:Mg (5.1 mol %), and LiNbO₃:Mg (5.3 mol % MgO). Low-intensity lines with frequencies at 209, 230, 298, 694, and 880 cm^–1 have been revealed for the first time. Analysis of the data from the literature on lattice dynamics calculations from first principles (ab initio) does not make it possible to unambiguously state that these lines correspond to fundamental vibrations of the А ₂ symmetry species, which are forbidden for the С _3V ⁶ (R3c) space group. At the same time, ab initio calculations unambiguously indicate that the experimentally observed low-intensity “superfluous” lines with the frequencies at 104 and 119 cm^–1 cannot correspond to vibrations of the А ₂ symmetry species. It is most likely that they correspond to two-particle states of acoustic phonons with a total wave vector equal to zero.