Defect structure and optical damage resistance of Hf:Fe:LiNbO3 crystals

A series of Hf:Fe:LiNbO₃ crystals were grown by the Czochralski technique with various doping concentrations of HfO₂. Their defect structures were analyzed by the UV-visible absorption spectra and infrared absorption spectra. The optical damage resistance 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 enhances remarkably with the HfO₂ concentration increasing when the HfO₂ concentration is lower than its threshold concentration (4 mol%). However, when the HfO₂ concentration exceeds its threshold concentration, the optical damage resistance ability of the crystals returns to decrease. This unusual behavior is explained by using the photovoltaic field produced in the 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.     

The effect of In doping on optical properties of Fe:LiNBO3 crystals

Fe:LiNbO₃ and In:Fe:LiNbO₃ crystals were grown by Czochralski method. The absorption spectra were measured to investigate their defect structure. The photo damage resistance and photorefractive properties were measured. The photo damage resistance of the In:Fe:LiNbO₃ crystal in which the In concentration is above the threshold value is one order of magnitude higher than that of the Fe:LiNbO₃ crystal. The mechanisms of the violet shift of the absorption edge and the enhancement of the photorefractive effect of In:Fe:LiNbO₃ crystals were investigated.     

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.     

Defect structure and optical damage resistance of Zn:Fe:LiNbO<Subscript>3</Subscript> crystals

A series of Zn:Fe:LiNbO₃ crystals were prepared by the Czochralski technique with 0.015 wt. % Fe₂O₃ content and various concentrations of ZnO. The ultraviolet-visible absorption spectra and the infrared absorption spectra of the Zn:Fe:LiNbO₃ crystals were detected in order to investigate their defect structure. Their optical damage resistance was characterized by the photoinduced birefringence change and transmission facula distortion method. The optical damage resistance of the Zn:Fe:LiNbO₃ crystals increases remarkably when the concentration of ZnO is over its threshold concentration (more than 6.0 mol. %). The effects of defects on the optical damage resistance of the Zn:Fe:LiNbO₃ crystals are discussed in detail. Received: 25 October 2002 / Revised version: 6 January 2003 / Published online: 22 May 2003 RID="*" ID="*"Corresponding author. Fax: +86-451/2300-926, E-mail: zzxxhhdoctor@sina.com     

Structure and optical damage resistance of Zn:Mn:Fe:LiNbO3 crystals

The new non-volatile holographic storage materials, Zn:Mn:Fe:LiNbO₃ crystals, were prepared by Czochralski technique. Their microstructure was measured and analyzed by infrared (IR) transmission 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 Mn:Fe:LiNbO₃ crystal. The photoinduced birefringence change was measured by the Sénarmont's method. It decreased with ZnO concentration increasing. The dependence of the defects on the optical damage resistance was discussed.     

Defect structure and nonvolatile hologram storage properties in Hf:Fe:Mn:LiNbO3 crystals

A series of Hf:Fe:Mn:LiNbO₃ crystals with various levels of HfO₂ doping were grown by Czochralski technique. The infrared spectra and ultraviolet spectra were measured and discussed to investigate their structure and defects. The optical damage resistance was characterized by the transmitted beam pattern distortion method. The nonvolatile two-color holographic recording experimental results showed that the recording speed was faster with the increase of HfO₂ doping concentration and at the same time little loss of nonvolatile diffraction efficiencies could be achieved.     

Photorefractive centers in LiNbO3, studied by optical-, Mössbauer- and EPR-methods

The photorefractive properties of LiNbO₃∶Fe and LiNbO₃∶Cu have been studied in combination with optical absorption-, Mössbauer- and EPR-measurements. The charge states of Fe in successively reduced LiNbO₃∶Fe have been investigated with respect to the influence on the photorefractive sensitivity and saturation value of the refractive index change. The results of this experiment demonstrate clearly the close correlation between the concentration of Fe²⁺ impurities and the optical absorption band around 2.6 eV in LiNbO₃∶Fe, which is known to give rise to an anisotropic charge transport upon optical excitation. The resulting photocurrents determine the photorefractive sensitivity mainly in the initial state of halographic exposure. With increasing conversion from Fe³⁺ to Fe²⁺ the photorefractive sensitivity saturates and the saturation value of the refractive index change decreases remarkably. In the case of LiNbO₃∶Cu a similar behaviour of the photorefractive storage parameters after successive reduction treatments has been observed qualitatively. However, in contradiction to LiNbO₃∶Fe the Cu²⁺ centers cannot be related to the photorefractive sensitivity of LiNbO₃∶Cu. These results are discussed with respect to the predictions of two models concerning the microscopic nature of the photorefractive process in doped LiNbO₃.     

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.     

Influence of post-growth treatment on the optical properties of In:Ce:Cu:LiNbO3 crystals

Congruent In (3 mol%):Ce:Cu:LiNbO₃ crystals have been grown by the Czochralski method in air. Some crystal samples were reduced in Li₂CO₃ power, and others were oxidized in Nb₂O₅ power. The structure of crystals was studied by an infrared transmittance spectrum. The resistance ability to optical damage and the photorefractive properties were measured by light-induced scattering experiments and two-beam coupling, respectively. It has been found that the reduction treatment increased the photoconductivity , which resulted in decreased erasure time and diffraction efficiency, but higher light-induced scattering resistance ability. The oxidation treatment caused the inverse affect. Finally, the nonvolatile holographic recording in In:Ce:Cu:LiNbO3 crystals is realized.     

Optical damage resistance of Ce:Fe:LiNbO3 crystals with various Li/Nb ratios

Ce:Fe:LiNbO₃ crystals were grown by the Czochralski technique with various ratios of Li/Nb = 0.94, 1.05, 1.20 and 1.38 in the melt. Their UV–Vis absorption spectra were measured in order to investigate their defect structures and their optical damage resistance was characterized by the photoinduced birefringence change and transmission facual distortion method. The optical damage resistance of Ce:Fe:LiNbO₃ crystals improves with the Li/Nb ratio increases. The dependence of the optical damage resistance on the defect structure of Ce:Fe:LiNbO₃ crystals is discussed in detail.     

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.     

Enhancement of nonvolatile blue photorefractive properties in LiNbO<Subscript>3</Subscript>:In:Fe:Cu crystals

The nonvolatile photorefractive characteristics of LiNbO₃:Fe:Cu and In-doped LiNbO₃:Fe:Cu crystals are investigated. The stronger nonvolatile blue photorefraction observed can be ascribed to its remarkable characteristic of being in phase between the two gratings recorded in shallow and deep trap centers, which is one or two orders of magnitude higher than those obtained in conventional two-color recordings under the same recording conditions. Furthermore, it is interesting that, compared with LiNbO₃:Fe:Cu, the recording properties, such as the saturation refractive index change, nonvolatile sensitivity and response time at 488 nm wavelength are enhanced in LiNbO₃:In:Fe:Cu crystals under the same recording conditions. The so-called damage-resistant dopants such as In³⁺ ions in red photorefraction are not damage resistant at 488 nm wavelength but they enhance the blue photorefraction. PACS  42.40.Ht; 42.40.Lx; 42.70.Ln     

Growth and optical properties of Mg, Fe Co-doped LiTaO3 crystal

Mg, Fe double-doped LiTaO₃ and LiNbO₃ crystals have been grown by Czochralski method. The optical properties were measured by two-beam coupling experiments and transmitted facula distortion method. The results showed that the photorefractive response speed of Mg:Fe:LiTaO₃ was about three times faster than that of Fe:LiTaO₃, whereas the photo-damage resistance was two orders of magnitude higher than that of Fe:LiTaO₃. In this paper, site occupation mechanism of impurities was also discussed to explain the high photo-damage resistance and fast response speed in Mg:Fe:LiTaO₃ crystal.     

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.     

Properties of thermally fixed holograms in photorefractive LiNbO<Subscript>3</Subscript>:Zn:Fe crystals

We have investigated the properties of thermally fixed holograms in LiNbO₃ crystals doped with the optical damage inhibitor Zn as well as the photorefractive Fe dopants. Time decays of fixed holograms at different temperatures showed a single thermally activated process with an activation energy of ∼1.08 eV. We have also studied the effect of an external electric field on the diffraction efficiency of these holograms. Results analysis has provided a new method to determine the photovoltaic field of the samples as well as the effective concentration of photorefractive traps.     

Influence of post-growth treatment on the holographic storage properties of In:Fe:LiNbO3

The congruent In (3 mol%):Fe (0.03 wt%): LiNbO₃ crystal has been grown by Czochralski method in air. Some crystal samples were reduced in Li₂CO₃ powder, and others were oxidized in Nb₂O₅ powder. The defects and ions location in crystal were investigated by infrared (IR) transmission spectrum. The photorefractive properties were measured by two-wave coupling and light-induced scattering resistance experiments. In the oxidized sample, the photovoltaic effect was the dominant process during recording. However, for the as-grown sample as well as the reduced, the photorefractive effect was governed by the diffuse field and the photovoltaic field, together. In addition, the reduction treatment made the photoconductivity increase, which resulted in shorter erasure time and lower diffraction efficiency, but higher light-induced scattering resistance ability. The oxidation treatment caused the inverse effect.     

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.     

Ce:Co:LiNbO3晶体光折变性能研究

在LiNbO₃中掺进CeO₂和Co₃O₄,以Czchralski技术首次生长Ce:Co:LiNO₃, Ce:LiNbO₃, Co:LiNbO₃晶体.通过测试Ce:LiNbO₃, Co:LiNbO₃和Ce:Co:LiNbO₃晶体的指数增益系数, 位相共轭反射率和响应时间,计算晶体的有效载流子浓度和光电导.Ce离子能提高LiNbO₃晶体光折变灵敏度,Co离子能提高LiNbO₃晶体的响应速度和抗光致散射能力,从而Ce:Co:LiNbO₃晶体具有较高的指数增益系数,位相共轭反射率,响应速度.Ce:Co:LiNbO₃晶体具有优良的光折变性能.     

Photorefractive properties for holographic application of Ce:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Ce:Fe:LiNbO₃ crystals with various [Li]/[Nb] ratios were grown by the Czochralski method from melts having compositions varying between 48.6 and 58 mol% Li₂O. The Ce, Li and Nb concentrations in the grown Ce:Fe:LiNbO₃ crystals were analyzed by the inductively coupled plasma atomic emission spectrometer (ICP-AES). It was found that as the [Li]/[Nb] ratio increases in the melt, the [Li]/[Nb] ratio in the crystal and the distribution coefficients of Ce ions increase also. The photorefractive properties of the Ce:Fe:LiNbO₃ crystals were experimentally studied by the two-wave coupling method. The results show that as the [Li]/[Nb] ratio increases, the dynamic range decreases, but the photorefractive sensitivity and the signal-to-noise ratio improve. In a coherent volume 0.192 cm³ of a Ce:Fe:LiNbO₃ crystal with [Li]/[Nb] ratio of 1.2, 3800 holograms with 800×600 pixels have been successfully multiplexed in a compact volume holographic data storage system.