Raman scattering study of reduced Er:LiNbO3 crystals

Raman spectra of as-grown and reduced (or annealed) Er:LiNbO₃ crystals, which have different cut orientations, varied Li/Nb ratio, and different Er-doping levels of 0.2, 0.4, 0.6, 1.0, and 2.0 mol%, were recorded at room temperature over a wavenumber range of 50–1000 cm^-1 by use of backward scattering geometries. The spectra are assigned on the basis of their Raman scattering features and previous relevant work. A weak but well-resolved peak around 633 cm^-1 appears in the E(TO) spectra that were recorded under the configuration of X(ZY)X̄(for an X-cut sample) or Y(ZX)Ȳ(for a Y-cut sample) for all crystals studied. The appearance of this peak in the E(TO) spectrum provides further evidence for a previous attribution of this peak to E(TO₉) mode. Some additional peaks distributed in the low wavenumber region ranging from 101–137 cm^-1 are attributed to Er³⁺ fluorescence with a wavelength range of 490.41–491.3 nm. The reduction effects include a significant drop of the Raman scattering intensity and a slight narrowing instead of a broadening in the linewidth. The reduction procedure hardly affects the spectral shape and the wavenumber of most of the phonons. The anneal effect is similar to the reduction effect and both effects are not as obvious as the vapor transport equilibration (VTE) effect. In addition, the present Raman scattering result provides evidence for our earlier reported individual result on light-induced diffraction from strongly reduced Er:LiNbO₃ crystals. PACS 42.70.Hj; 81.05.-t; 63.20.-e; 78.30.-j.     

Electro-optic properties in undoped and Cr-doped LiNbO3 crystals

3 along the ferroelectric c axis in pure and chromium-doped crystals. We have studied four series of samples with various crystal compositions and doping concentrations to separate the influence of the intrinsic defects related to the non-stoichiometry and the effect of the introduction of chromium. In pure and slightly doped crystals, the electro-optic coefficient r_c shows a non-monotonous dependence on the controlled crystal composition, which reflects a similar behaviour of the corresponding dielectric permittivity. In the highly Cr-doped crystals r_c displays a large decrease with increasing Cr concentration whatever the crystal composition. The results have been discussed by means of the LiNbO₃ structure and the substitution site dynamics. Received: 14 November 1997/Accepted: 2 January 1998     

Fast photorefractive response in strongly reduced near-stoichiometric LiNbO(3) crystals

The photorefractive response time of LiNbO(3) crystal is of the order of minutes, and such a long response time limits the crystal's practical applications. We report the photorefractive properties of nominally pure near-stoichiometric LiNbO(3) crystal that is strongly reduced in vacuum. A short photorefractive response time of the order of 100 ms is measured at a wavelength of 514.5 nm, with incident light intensity of 1.6 W/cm (2) , and possible corresponding mechanisms are discussed. To our knowledge this is the first experimental evidence of a subsecond photorefractive response in pure LiNbO(3) crystals. The diffraction efficiency of a holographic grating written in this reduced crystal is low but can be enhanced by an externally applied electric field.     

Light-induced absorption in reduced congruent and near-stoichiometric Er:LiNbO3 crystals

Light-induced absorption (LIA) in thermally reduced congruent and near-stoichiometric Er:LiNbO₃ crystals, which have different cuts of crystal (X- and Y-cut) and different doping levels of Er³⁺ (0.2, 0.4, 0.6 and 1.0 mol %), has been studied within continuous-wave light intensity by using polarized 632.8 nm beam as probe light and polarized 488 nm beam as pump light. Effects of thermal reduction condition, pump intensity, Li/Nb ratio and Er-doping level on the LIA are summarized and discussed. Studies on spectral characteristics of both linear absorption and light-induced absorption show that photo-ionization of bipolarons into small polarons plays a predominant role in the LIA process. The role of the Er³⁺ ion in the LIA is investigated by studying the doping level and the thermal reduction effects on the absorption and emission properties of Er³⁺. The results show the possibility that the Er³⁺ ion directly participates in the light-induced charge transport is small. It affects the LIA only via the bypassing part of pump intensity to excite near-infrared emissions of Er³⁺. The thermaleffect on the LIA is demonstrated. A two-center model with inclusion of the thermal contribution can qualitatively explain two major LIA characteristics that include the appearance of a slow stage in the LIA procedure and the unsaturation behavior of the LIA coefficient in high pump intensity regime. In addition, the pump depletion effect on the LIA characteristics is discussed. The possibility of pump beam fanning arising from light-induced scattering is ruled out experimentally. PACS 42.70.Hj; 42.70.Ln; 42.70.Mp; 42.65.Hw; 81.05.-t     

Hydrogen-related donor in silicon crystals grown in a hydrogen atmosphere

Neutron transmutation doped (NTD) silicon crystals grown in a hydrogen atmosphere have been investigated by infrared absorption spectroscopy at a low temperature (10 K). An effective-mass-like donor state HD^0/+ has been found at 110.8 meV below the conduction band bottom after rapid thermal annealing (RTA). The HD^0/+ formation mechanism after NTD and RTA is briefly discussed, and tentatively attributed to H atoms present in the vicinity of some residual irradiation defects, like a complex of a H atom and a H-saturated vacancy.     

Optical properties of LiNbO3:Cr crystals co-doped with germanium oxide

Lithium niobate (LiNbO₃) crystals doped with chromium ions show a clear green colouring reflecting the absorption profile of the dominating [Cr]_Li defect centres. A significant change in its colouration takes place when it is co-doped with other valency impurities such as Mg²⁺, Sc³⁺ and W⁶⁺, above a certain threshold concentration. This concentration singularity has been attributed to the formation of [Cr]_Nb centres coexisting with the [Cr]_Li centres.In this work, we extended the investigation on the effect of co-dopant ions in Cr:LiNbO₃ to tetravalent cation such as GeO₂. A singularity in the relative intensity of the ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ absorption band was observed for a concentration of ～1.5 mol%, compared with 4.5 mol% for Mg²⁺. The photoluminescence emission spectra also reveal a new emission band, at a lower energy than the [Cr]_Li centre, corresponding to this threshold concentration. A charge compensation model is proposed to explain the role of cation impurities and results are compared with those of other valence impurities.     

Anisotropy of electrooptical interaction in LiNbO3 crystals

Results of studying the conditions for optimum electrooptical (EO) interaction in lithium niobate crystals are presented. Analytical formulas are obtained for calculating refractive indices of natural waves and their polarizations for basis X-, Y-, and Z-cuts of crystals for arbitrary orientations of the wave vector of an optical wave. Conditions are found for the appearance of intermode EO interaction causing the orientation of polarization plane of natural waves to become a function of the external electric field.     

LiNbO3:Fe晶体中光写入平面光波导的导光特性研究

从光折变效应的单中心模型和载流子的光伏迁移机理出发给出了高斯片光在LiNbO3:Fe晶 体中导致的折射率变化分布的解析表达式.利用片光以“三明治”辐照方式在LiNbO3:Fe晶 体中写入了平面光波导结构.用切片干涉法测量了波导区的折射率分布，并对波导进行了简 单的导光测试.根据射线方程以及波导的折射率分布对光写入波导的导光特性进行了模拟计 算分析.研究结果表明，在LiNbO3:Fe晶体中光写入光波导是可行的. 关键词： LiNbO3:Fe晶体 光辐照法 平面光波导 导光特性 高斯片光     

Investigation of optical photorefractive properties of Zr:Fe:LiNbO3 crystals

A series of Zr:Fe:LiNbO₃ crystals with various levels of ZrO₂ doping were grown by Czochraski technique. The optical damage resistance and photorefractive properties were deeply explored. The results showed that the ability optical damage resistance increased remarkably when the concentration of ZrO₂ is over threshold concentration, but which is lower than that of traditional damage resistant additive MgO. While, the holographic storage properties can be greatly enhanced by proper level of ZrO₂ doping in Fe:LiNbO₃. In terms of ions' site occupation model, the photo-damage resistant ability enhancement and the change of the photorefractive properties were discussed.     

New long-lived memory effects in LiNbO3 crystals

This paper describes a new way of recording information by changing the potential contour at the surface of z-cut crystals of LiNbO₃. The effect of various kinds of external perturbations on the rate of decay of optical images written using this method is investigated, along with the possibility of writing information on crystals with transition-metal impurities. Fiz. Tverd. Tela (St. Petersburg) 40, 337–339 (February 1998)     

Photorefractive properties of LiNbO3:Zn crystals related to the defect structure

LiNbO₃:Zn single crystals and powders were studied by precise X-ray diffraction methods. Structural refinement yielded new models of the intrinsic defect structure valid for different Zn concentration ranges. For concentrations up to 7 at. % in the crystal, Zn ions incorporate onto Li sites; at higher concentrations Zn ions are found on both Li and Nb sites. Photorefractive properties of LiNbO₃:Zn are discussed in the context of the deduced defect models. A smooth increase in the photoconductivity up to 7 at. % Zn is accounted for by a decrease of Nb antisites. Steeper growth of the photoconductivity at higher Zn concentrations is related to vanishing Li vacancies. Received: 17 November 2000 / Revised version: 23 January 2001 / Published online: 20 April 2001     

Photorefractive and optical scattering properties of Zr:Fe:LiNbO3 crystals

The LiNbO₃ crystal co-doped with ZrO₄ and Fe₂O₃ has been grown with [Li]/[Nb]=0.85 and 1.20, respectively, by the Czochralski method in air atmosphere. The incident exposure energy flux threshold for the light-induced scattering was characterized to investigate the scattering properties of the crystals. Applying the results of the incident exposure energy flux threshold effect, the photorefractive properties at different laser wavelengths (473 nm and 532 nm) were also measured by using the typical two-wave coupling experiments. The results show that Zr:Fe:LiNbO₃ crystal has a larger refractive index change, higher recording sensitivity and larger two-wave coupling gain coefficient at 473 nm wavelength than those obtained at 532 nm wavelength under the same experimental conditions. Moreover, the photorefractive properties decrease with the increasing [Li]/[Nb] ratios. The material of Zr:Fe:LiNbO₃ crystal is a promising candidate for blue photorefractive holographic recording.     

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.     

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.     

New hydrogen associated paramagnetic centre in LiNbO3

A new hydrogen associated paramagnetic centre (g=2.0028±0.0005, A=3±0.5 mT at 77K) was observed in LiNbO₃. This centre is identified as an OH^2? ion, produced as a result of an electron capture by a diamagnetic OH^? ion, substituting the O^2? ion in LiNbO₃. An experimental procedure for detecting the EPR spectrum of the new centre is established. It is based on the observation of the more rapid destruction of O^? and Nb⁴⁺ ions under UV-irradiation at 77 K as compared to the OH^2? ions obtained after γ-irradiation of LiNbO₃ crystals at 77 K.     

Two-center holographic recording in highly doped LiNbO3 crystals

In this paper, we report the observation of electron tunneling during two-center recording in LiNbO₃:Fe:Mn doped with high Fe concentration. Unlike tunneling in the singly doped lithium niobate that erases the hologram, the effect in two-center recording can improve the diffraction efficiency of the hologram after the recording while it is kept in the dark. A detailed study of this effect in LiNbO₃:Fe:Mn is presented both theoretically and experimentally. We show that the hologram strength may increase or decrease due to tunneling, depending on the experimental condition of recording. PACS 42.40.-i; 42.70.Ln; 42.40.Lx     

化学计量比LiNbO3晶体的激光显微拉曼光谱研究

对用助熔剂提拉法生长的近化学计量比LiNbO3晶体进行了激光显微拉曼光谱测试分析,与同成分LiNbO3晶体相比较,A1(TO)与E(TO)模的谱线数目、频率基本不变,验证了LiNbO3晶体属置换式固溶体的结论.738cm-1处拉曼振动峰（A1(LO)模）的相对强度随晶体中Li2O含量的增加发生了明显的变化,在两种掺杂晶体中,此振动峰已经消失.根据Li空位模型,从占位和结构上进行了分析讨论.在152和872cm-1处拉曼振动峰半高宽随晶体中Li/Nb的增大而变窄,对二者关系进行了线性拟合,利用拟合公式可根据拉曼振动峰半高宽计算晶体中的Li/Nb值. 关键词： 化学计量比 拉曼光谱 线性拟合 半高宽     

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.