Complex study of the structural and optical homogeneity of lithium niobate crystals

Methods of Raman spectroscopy, laser conoscopy, optical microscopy, and electron spin resonance have been used to study the photorefractive properties and structural and optical homogeneity of the following lithium niobate (LiNbO₃) crystals: nominally pure crystals of congruent composition (LiNbO_3con); LiNbO₃:Cu[0.015 wt %] crystals grown from a melt of congruent composition and nominally pure crystals of stoichiometric composition grown from a melt with 58.6 mol % Li₂O (LiNbO_3st). A small deformation of optical indicatrix and regular microdomain structures of fractal type are revealed for the LiNbO₃:Cu[0.015 wt %]; the microdomain structures may be due to the nonuniform impurity incorporation into the structure. It is shown that oxygen octahedra in the LiNbO₃:Cu[0.015 wt %] crystal are deformed in comparison with the octahedra in LiNbO_3st and LiNbO_3con crystals and that the main and impurity cations are clusterized along the polar axis. It is established that the LiNbO₃:Cu[0.015 wt %] crystal exhibits photorefractive properties not only due to the presence of intrinsic defects with localized electrons, as in the case of LiNbO_3st, but also due to the charge exchange in copper cations (Cu²⁺ → Cu⁺) under illumination.     

Calculation of local electric fields in displacive-type ferroelectrics: LiNbO3

The method is suggested for calculating the intensity and potential of a local electric field in displacive-type ferroelectrics which is based on the introduction of a transitional zone between the region of the discrete localization of ions and the homogeneously polarized medium. The method is exemplified on the calculation of the contribution of Li⁺ ions to the local electric field in the lithium niobate structure. It is shown that the method provides fast convergence of the results in the calculation of the field intensity and high relative accuracy of the calculated electric-field potential inside the crystal. The contribution of the induced dipoles to the local electric field is calculated, and it is shown that the stability of the LiNbO₃ structure is provided by considerable anisotropy in the polarizability of Nb-O bonds. The method is applicable to any ionic crystal.     

Growth and optical damage resistance of Sc,Er Co‐doped LiNbO3 crystals

A series of Sc:Er:LiNbO₃ crystals have been grown by Czochralski method. Their ultraviolet‐visible (UV‐Vis) absorption spectra was measured and discussed to investigate their defect structure. The optical damage resistance of Sc:Er:LiNbO₃ crystals was characterized by the transmitted beam pattern distortion method. It increases remarkably when the concentration of Sc₂O₃ exceeds a threshold concentration. The optical damage resistance of Sc (3.0mol %):Er:LiNbO₃ is much higher than that of the Er:LiNbO₃. The intrinsic and extrinsic defects were discussed to explain the enhance of the optical damage resistance in the Sc:Er:LiNbO₃ crystals. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In doping effect on optical properties in Zn:In:Fe:LiNbO3 crystals

A series of Zn:In:Fe:LiNbO₃ crystals were prepared by Czochralski method. The crystal composition and defect structure were analyzed by ICP‐OE/MS, UV–vis and IR spectroscopy. The results show that with increasing In³⁺ doping concentration in melt, the segregation coefficients of both Zn and In ions decrease. The optical damage resistance of Zn:In:Fe:LiNbO₃ crystals was studied by the transmitted beam pattern distortion method. It is found that the optical damage resistance of Zn:In(3mol%):Fe LiNbO₃ crystals is two orders of magnitude higher than that of Zn:Fe:LiNbO₃. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photorefractive Properties of Stoichiometric Lithium Niobate Single Crystals

The specific features of photorefractive light scattering in nominally pure stoichiometric (Li/Nb = 1) sin- gle crystals grown from a melt with 58.6 mol % Li₂O (LiNbO₃st) and in the stoichiometric single crystals grown from a melt of congruent composition in the presence of K₂O flux (LiNbO₃stK₂O) have been investi- gated. At an excitation power of 30 mW, LiNbO₃stK₂O single crystals are found to exhibit a stronger photo- refractive effect than LiNbO₃st single crystals.     

Increased optical damage resistance of Zr:LiNbO3 crystals

Zr: LiNbO₃ crystals has been grown. The crystal composition and phase are analyzed by X‐ray diffration. The optical damage resistance ability of Zr: LiNbO₃ crystals is studied by the Sénarmont compensation method and the transmitted beam pattern distortion method. The saturated value of the birefringence change of 6 mol% Zr: LiNbO₃ crystal is 1.01×10^‐4, which is seven times smaller than that of congruent pure LiNbO₃ crystal. The results of UV‐Visible and IR absorption spectra of Zr: LiNbO₃ crystals powerfully confirm that the optical damage resistance threshold concentration of the Zr⁴⁺ ions doped in LiNbO₃ crystals is about 6 mol% in the melt. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Double‐frequency properties of In:LiNbO3 crystals

1 mol%, 2 mol%, 3 mol%, 4 mol% and 5 mol% In³⁺ doped LiNbO₃ crystals were grown by the Czochralski method, respectively. Oxidized treatment of some crystals was carried out. The infrared transmission spectra and photo‐damage resistance of the samples were measured. The results showed that the OH^‐ absorption peaks of In(3mol%):LiNbO₃, In(4mol%):LiNbO₃ and In(5mol%):LiNbO₃ crystals were located at about 3508 cm^‐1, while those of In(1mol%):LiNbO₃ and In(2mol%):LiNbO₃ crystals were located at about 3484cm^‐1. When the doped In³⁺ concentration reached its threshold in LiNbO₃ crystal, photo‐damage resistance of In:LiNbO₃ crystals was two orders of magnitude higher than that of pure LiNbO₃ crystal. The experimental results of the second harmonic generation (SHG) showed that the phase matching temperatures of In:LiNbO₃ crystals were lower than those of Zn:LiNbO₃ and Mg:LiNbO₃ crystals and the SHG efficiency reached 38%. Oxidization treatment was also found to make the dark trace resistance of crystals increase. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructure and optical properties of Zn:Mn:Fe:LiNbO3 crystals

Zn:Mn:Fe:LiNbO₃ crystals were prepared by Czochralski technique. Its microstructure was measured and analyzed by UV‐Vis absorption spectra. The optical damage resistance of Zn:Mn:Fe:LiNbO₃ crystals was characterized by the transmitted beam pattern distortion method. It increases remarkably when the concentration of ZnO is over a threshold concentration. Its value in Zn(7.0 mol%):Mn:Fe:LiNbO₃ crystal is about three orders of magnitude higher that in the Mn:Fe:LiNbO₃ crystal. The dependence of the defects on the optical damage resistance was discussed. The non‐volatile holographic storage was realized in all crystals, and the sensitivity of the Zn(7.0 mol%):Mn:Fe:LiNbO₃ crystal is much higher than that of others. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of Mg/Er co‐doping on the principal laser parameters of LiNbO3 crystals

Mg: Er: LiNbO₃ crystals were grown by the Czochralski technique with various concentrations of MgO = 2 mol%, 4 mol%, 6 mol% and the fixed concentration of Er₂O₃= 1 mol% in the melt, and the 8 mol%Mg: 1 mol%Er: LiNbO₃ crystal was fabricated by the Czochralski technique with special technology process. The crystals were treated by polarization, reduction and oxidation. The segregation coefficients of Mg²⁺ and Er³⁺ in Mg: Er: LiNbO₃ crystals were measured by X‐ray fluorescence spectrograph, as well as the crystal's defect structure and optical properties were analyzed by the UV‐Vis, IR and fluorescent spectroscopy. The pump wavelength and the surge wavelength were determined. Using m‐line method tested optical damage resistance of those crystals, the results show that photodamage threshold of Mg: Er: LiNbO₃ crystals are higher than that of Er: LiNbO₃ crystal, and the oxidation treat could enhance the photodamage resistant ability of crystals while the reduction treat could depress the ability. The optical damage resistance of 8 mol%Mg: 1 mol%Er: LiNbO₃ crystal was the strongest among the samples, which was two orders magnitude higher than that of 1 mol%Er: LiNbO₃ crystal. The dependence of the optical properties on defect structure of Mg: Er: LiNbO₃ crystals was discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of LiNbO<Subscript>3</Subscript>:Er Crystals and concentration dependences of their properties

A series of lithium niobate (LiNbO₃) crystals of congruent and stoichiometric compositions, doped with erbium, have been grown under non-steady-state thermal conditions. A series of LiNbO₃:Zn crystals, nominally pure LiNbO₃ crystals of congruent and stoichiometric compositions, and a LiNbO₃:B crystal have also been grown. Both growth conditions and concentration dependences of physicochemical, ferroelectric, and structural characteristics of LiNbO₃:Er crystals are investigated. The growth regular domain microstructures and periodic nanostructures in LiNbO₃:Er crystals are analyzed by optical microscopy and atomic force microscopy (AFM). A comparative study of the optical homogeneity and photorefractive properties of LiNbO₃:Er crystals of congruent and stoichiometric compositions and the Raman spectra of LiNbO₃ crystals of different compositions is performed.     

Specific features of growth of single crystals of complex oxides with an oxygen deficit

Some methods for estimating the concentration of vacancies in crystals and procedures for decreasing their number are considered by the example of LiNbO₃, SrTiO₃, YAlO₃, and PbWO₄ crystals. In LiNbO₃ crystals, nonstoichiometry was determined by comparing the density determined via X-ray diffraction with the experimental value. In SrTiO₃ and YAlO₃ crystals, the vacancy concentration was estimated with methods based on additivity of refractions. The vacancy concentration in the LiNbO₃ and PbWO₄ crystals was decreased by doping them with elements of lower valence and annealing in air and vacuum. Some specific features of the growth of PbWO₄ crystals affecting their quality are discussed. Peculiarities of the formation of lithium niobate, strontium titanate, yttrium orthoaluminate, and lead tungstate crystals are considered.     

Torsion method for measuring piezooptic coefficients

We develop and describe analytically a torsion method for measuring piezooptic coefficients associated with shear stresses. It is shown that the method enables to increase significantly the accuracy of determination of piezooptic coefficients. The method and the appropriate apparatus are verified experimentally on the example of LiNbO₃ crystals. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and Photo‐Damage Resistance of Li‐Rich LiNbO3 Crystals Co‐Doped with Zn2+/Er3+

The pure congruent LiNbO₃, Er:LiNbO₃ and Zn,Er co‐doped Li‐rich LiNbO₃ crystals were grown by Czochralski method. The X‐ray diffraction method and ultraviolet‐visible absorption spectra of the crystals were used to analyze the structure of the crystals. The photo‐damage ability resistance of the crystals was measured. The Zn,Er co‐doped Li‐rich LiNbO₃ crystals show a decrease in lattice constant values, a shift in absorption edge of ultraviolet‐visible absorption spectra towards shorter wavelength, and three orders of magnitude increase in photo‐damage resistance compared to congruent LiNbO₃ crystal. The intrinsic and extrinsic defects are discussed to explain the enhance of the photo‐damage ability resistance     

Investigation on photorefractive properties of doped lithium niobate

Cu:LiNbO₃ crystal and Fe:Cu:LiNbO₃ crystals were grown by the Czochralski method from congruent melt. The OH^‐ absorption spectrum of doped lithium niobate crystals was measured. The photorefractive properties of doped crystals were studied by the two‐wave coupling method. The results of the two‐wave coupling experiments showed that as the concentration of doping ions increased, the diffraction efficiency and the dynamic range enhanced, the holographic response time shortened. The recording time of Fe(0.10wt%): Cu(0.10wt%): LiNbO₃ crystal is only a tenth of that of Cu(0.05wt%): LiNbO₃ crystal. Among all samples, the dynamic range of the Fe(0.10wt%): Cu(0.10wt%): LiNbO₃ crystal was the most largest (up to 40.78). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and optical damage resistance of Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Hf:Fe:LiNbO₃ crystals were grown in air by the Czochralski technique with various ratios of [Li]/[Nb]=0.94, 1.05, 1.20 in melt. The defect structure and location of doped ions were analyzed by the UV‐visible and infrared spectroscopy. The optical damage resistance ability of Hf:Fe:LiNbO₃ crystals was measured by the photo‐induced birefringence change and the transmitted light spot distortion method. The results show that the optical damage resistance ability of Hf:Fe:LiNbO₃ crystals is enhanced with the increase of the [Li]/[Nb] ratio. The dependence of the optical damage resistance of Hf:Fe:LiNbO₃ crystals on the defect structure is discussed in detail. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical damage resistance of Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Hf:Fe:LiNbO₃ crystals were grown in air by the Czochralski technique with various [Li]/[Nb] ratios ([Li]/[Nb]=0.94, 1.05, 1.20) in melt. The defect structure and location of doped ions were analyzed by the UV‐visible absorption spectra. The optical damage resistance of Hf:Fe:LiNbO₃ crystals was investigated by the photoinduced birefringence change and the transmitted light spot distortion method. The results show that the optical damage resistance ability of Hf:Fe:LiNbO₃ crystals decreases with the increase of the [Li]/[Nb] ratio. The dependence of the optical damage resistance of Hf:Fe:LiNbO₃ crystals on the defect structure is discussed in detail. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of the Electrophysical Properties of Lithium Metaniobate Single Crystals with Deliberately Introduced Dopants

The effect of the dopants Ti, V, Cr. Mn, Ni, Ho, Er, Tm deliberately introduced into the melt of Czochralski grown lithium niobate (LiNbO₃) crystals on their electrophysical properties — electric conductivity, dielectric permittivity and loss tangent — has been studied. The characteristics were measured at temperatures up to 1200°C. The mechanism of dopant introduction into the crystalline lattice and the nature of electric conductivity of LiNbO₃ at varius temperatures are discussed.     

Effect of post treatment on the photorefractive properties of Ru‐doped lithium niobate

The effect of post treatment on the photorefractive properties of Ru‐doped lithium niobate was studied. The absorption spectra examination of Ru‐doped LiNbO₃ crystals with different post treatments showed that the absorption coefficient at 530 nm increased after the reduced treatment was employed and the absorption edge of the reduced crystal shifted towards the infrared band. On the contrary, the trend reversed after the oxidized treatment was employed. In addition, the photorefractive properties were investigated with the two‐beam coupling method conducted via a 532 nm solid state laser. It was found that the oxidized Ru:LiNbO₃ had smaller exponential gain coefficient and diffraction efficiency because the charges in the shallow level were exchanged to the deep level. On the other hand, the reduced Ru:LiNbO₃ crystals had larger exponential gain coefficient and diffraction efficiency due to the increase of the Ru³⁺ which existed in the shallow level. The response times of both oxidized and reduced Ru:LiNbO₃ were longer than those of the as‐grown ones. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and optical damage resistance of In:Fe:Cu:LiNbO3 crystals with various [Li]/[Nb] ratios

In:Fe:Cu:LiNbO₃ crystals were grown in air by the Czochralski technique with various [Li]/[Nb] ratios of 0.946, 1.050, 1.200, and 1.380 in melt. Based on the ICP‐AES (inductively coupled plasma atomic emission spectrometry) analyzed results, the chemical formula of the triple‐doped In:Fe:Cu:LiNbO₃ crystals were obtained. It can be seen that the near‐stoichiometric ratio value is between 1.050 and 1.200 for our samples. The optical damage resistance of In:Fe:Cu:LiNbO₃ crystals was characterized by changes in light‐induced birefringence and it increases with the increasing of [Li]/[Nb] ratios. The dependence of the optical damage resistance on the defect structure of In:Fe:Cu:LiNbO₃ crystals is discussed in detail based on the obtained chemical formulas. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and optical damage properties of In:Zn:LiNbO3 waveguide substrate

In:Zn:LiNbO₃ crystals doped with different indium concentrations were grown by Czochralski technique. The optical damage threshold value and ultraviolet‐visible absorption spectra of the In:Zn:LiNbO₃ crystals were measured. The In:Zn:LiNbO₃ crystals were made into optical waveguide substrates using hexanedioic acid as proton exchange agent. The optical damage resistant ability of those optical waveguide substrates was investigated by the m‐line method. The optical damage threshold values of In(2mol.%):Zn(3mol.%):LiNbO₃ crystal and optical waveguide substrate are two orders of magnitude higher than those of pure LiNbO₃. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)