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.     

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.     

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.     

ESR study of rare-earth ions with the effective spin of 1/2 in LiNbO3 crystals

Rare-earth ions of Nd³⁺ and Er³⁺ in nearly stoichiometric and MgO-doped LiNbO₃ crystals, respectively, have been investigated by employing an X-band electron spin resonance (ESR) spectrometer. The grown crystal was heated in Li-rich powder at 1100°C in order to make it nearly stoichiometric by the vapor transport equilibrium technique. Due to the fact that the ESR linewidth is much narrower in the stoichiometric crystal than in the congruent LiNbO₃, we were able to determine the hyperfine constants of¹⁴³Nd and¹⁴⁵Nd at 4 K. By codoping MgO into LiNbO₃, a new Er³⁺ center has been observed with a differentg-tensor. We propose that the new Er³⁺ center in Mg-doped LiNbO₃ occupies the niobium site due to the local excessive Mg²⁺ ion at the lithium site, whereas Nd³⁺ and Er³⁺ in congruent crystals reside at the lithium site. The proposal is consistent with theg-value anisotropy.     

周期极化掺镁不同组分LiNbO3晶体的研究

利用气相平衡扩散法研制出掺镁不同组分的LiNbO₃晶体，并对其极化特性进行了研究.研究表明晶体的开关电场和自发极化不仅与晶体组分［Li］/［Nb］比有关而且与掺镁量有关，［Li］/［Nb］比为0.973掺入2mol% MgO的近化学比LiNbO₃晶体的开关电场仅为1.8kV/mm，是同成分晶体的1/12，且其极化结构的质量要远好于同成分LiNbO₃晶体和近化学比LiNbO₃晶体. 关键词： 气相平衡扩散 3晶体')" href="#">掺镁LiNbO₃晶体 周期极化     

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.     

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.     

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.     

Growth, optical and EPR properties of Li1.72Na0.28Ge4O9 single crystals pure and slightly doped with Cr

Single crystals of lithium-sodium-tetragermanate, a member of the solid solution series Li_2−xNa _x Ge₄O₉ with x=0.28, pure and slightly doped with Cr³⁺ ions (0.03 mol.% and 0.1 mol.%), were grown in ambient atmosphere by the Czochralski technique from stoichiometric melt. The crystals with dimensions up to 20 mm in diameter and 50 mm in length were obtained. The crystal structure has been determined by means of X-ray diffraction. Phase analysis and structural refinement of the Li_1.72Na_0.28Ge₄O₉ crystals were performed by X-ray powder diffraction using Ni-filtered Cu Kα radiation with a Siemens D5000 diffractometer. The absorption, excitation and photoluminescence spectra of the crystals were measured in the UV-VIS and IR range at low temperatures. EPR investigations were performed using a conventional X-band Bruker ELEXSYS E 500 CW-spectrometer operating at 9.5 GHz with 100 kHz magnetic field modulation. Temperature and angular dependences of the EPR spectra of the crystal samples were recorded in the 3–300 K temperature range.     

Properties of melt-grown single crystals of “YB68”

Single crystals of yttrium boride YB_n with n = 61 ± 3 were grown from the melt. Precision density and lattice parameter measurements indicate a congruent melting point at n = 61.7 and a stoichiometric composition at n = 68. Measurements of elastic constants, acoustic attenuation, electrical resistivity and optical absorption are presented. High resolution transmission electron microscopy reveals a complex crystal structure similar to that found by using X-rays. A comparison of the properties of YB_n with those of β-boron show that there are many similarities.     

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.     

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.     

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.     

Growth and comparison of physicochemical properties of pure,Ca and Sr doped NH4Sb3F10 single crystals for electro optic applications

Single crystals of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ are grown by slow evaporation technique. The effect of dopants on the growth and physicochemical properties also have been investigated and reported for the first time. The grown crystals are characterized with the aid of single crystal X-ray diffractometry to confirm the crystal structure. EDAX studies are done to confirm the presence of dopants in the crystal lattice. The vibrational frequencies of various group ligands in the crystals have been derived from the Fourier transform infrared (FT-IR) spectrum. From the optical absorption spectrum the band gap energy was calculated and it was found to be 5.76, 6.29 and 6.35 eV for pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals respectively. Thermal stability of the sample has been analysed using TG-DTA analysis. The activation energy of pure, Ca²⁺ and Sr²⁺ doped NH₄Sb₃F₁₀ crystals were calculated from the dc conductivity measurements and it is found to be 0.2728, 0.2816 and 0.3622 eV Experimental results shows improved physicochemical properties when the dopant is added to the pure material.     

Growth and characterization of pure and doped L-Lysine monohydrochloride dihydrate (L-LMHCl) nonlinear optical single crystals

Semi-organic nonlinear optical single crystals of pure, Ni²⁺ and Cd²⁺ doped L-Lysine monohydrochloride dihydrate (L-LMHCl) were grown from aqueous solution by slow evaporation technique. Single crystal X-ray diffraction analysis reveal that the pure and doped L-LMHCl crystals belong to monoclinic system with the space group P2₁. The presence of functional groups present in the pure and doped crystals was determined qualitatively by using Fourier Transform Infrared (FTIR) spectroscopy. Optical absorption studies reveal very low absorption for the doped crystal than that of the pure crystal. Dielectric studies have been carried out for the grown crystals and the results were discussed in detail.     

OH-吸收带作为铌酸锂晶体缺陷结构的探针

本文报道了一组不同Li/Nb比和另一组不同掺Mg浓度的LiNbO₃晶体室温OH^-吸收带的实验结果,观察到OH^-吸收带的三峰结构及其随Li/Nb比的变化,以及重掺Mg晶体中(6mol％MgO)OH^-吸收带转变为双峰结构,并向高能端移动54cm^-1。根据LiNbO₃的晶体结构以及Abrahams和Smyth的缺陷结构模型,对化学计量晶体、一致熔化晶体和掺Mg晶体分别进行讨论。并提出重掺Mg晶体中OH^-吸收带向高能端的移动可能是由于当掺Mg浓度超过阈值后Mg²⁺离子开始进入Nb位而引起的。 关键词：     

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.     

Enhancement of blue holographic properties in Zr4+-doped near stoichiometric Fe:LiNbO3 crystals

The near stoichiometric LiNbO₃ crystals co-doped with ZrO₂ and Fe₂O₃ have been grown from a Li-rich melt (Li/Nb=1.38, atomic ratio) by the Czochralski method in air atmosphere at the first time. The OH^? absorption and UV–vis absorption spectra were characterized to investigate the defect structure of the crystals. The appearances of the 3479 cm^?1 absorption peak and 358 nm absorption edge manifest that the composition of the grown crystal is close to the stoichiometric ratio. The blue holographic properties were also measured by the two-wave coupling experiments. As a result, in the near stoichiometric Zr:Fe:LiNbO₃ crystals, photorefractive response speed, recording sensitivity, and two-wave coupling gain coefficient are significantly enhanced. Meanwhile, the high saturation diffraction efficiency is still maintained. These findings prove that the material of near stoichiometric Zr:Fe:LiNbO₃ crystals are a promising candidate for blue photorefractive holographic recording.     

Photorefractive properties of MnO-doped near stoichiometric LiNbO3 crystals

In this paper, photorefractive properties of MnO-doped near stoichiometric LiNbO₃ (SLN) were studied. The SLN crystals doped with different concentration of Mn ions have been grown by the top-seeded-solution-growth method by adding K₂O flux to Li₂O-Nb₂O₅ melt. The crystal structures were analyzed by the UV-vis spectra and IR spectra. The photorefractive properties of SLN were experimentally studied by using two-beam coupling. The results of the two-wave coupling experiments showed that, with a He-Ne laser of 632.8 nm wavelength, the MnO-doped SLN crystals had long writing time and long erasure time constants, and the dynamic range (M/#), sensitivity (S), and diffraction efficiency were dependent on the doping concentration.     

周期极化掺镁不同组分LiNbO3晶体的研究

利用气相平衡扩散法研制出掺镁不同组分的LiNbO3晶体 ,并对其极化特性进行了研究 .研究表明晶体的开关电场和自发极化不仅与晶体组分 [Li] [Nb]比有关而且与掺镁量有关 ,[Li] [Nb]比为 0 973掺入 2mol%MgO的近化学比LiNbO3晶体的开关电场仅为 1 8kV mm ,是同成分晶体的 1 12 ,且其极化结构的质量要远好于同成分LiNbO3晶体和近化学比LiNbO3晶体 .