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.     

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.     

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.     

Influence of Li/Nb ratios on defect structure and photorefractive properties of Zn: In: Fe: LiNbO3 crystals

A series of Zn: In: Fe: LiNbO₃ crystals are grown by the Czochralski technique with various ratios of Li/Nb = 0.94, 1.05, 1.20 and 1.38 in the melt. The Zn, In, Fe, Nb and Li concentrations in the crystals are analyzed by inductively coupled plasma (ICP) spectrometry. The results indicate that with increasing the [Li]/[Nb] ratio in melt, [Li]/[Nb] ratio increases and goes up continuously in the crystal, the segregation coefficients of both Zn and In ions decrease. The absorption spectra measurement and two-wave coupling experiment are employed to study the effect of [Li]/[Nb] ratio on photorefractive properties of Zn: In: Fe: LiNbO₃ crystals. It is found that the [Li]/[Nb] ratio increases, the write time is shortened and the photorefractive sensitivity is improved.     

Intensity dependence of two-center nonvolatile holographic recording in LiNbO3:Cu:Ce crystals

Nonvolatile photorefractive gratings have been recorded in LiNbO₃:Cu:Ce crystals by using a He–Ne laser (633 nm) for recording and an argon ion laser (458 nm) for sensitizing. The sensitizing light increases the recording sensitivity by a−bexp(−I_s/c) and saturation behavior will appear with high enough intensity of sensitizing light. The recording light increases the slope of η^1/2 as a function of time during the initial stages of hologram formation by sublinear I^x_r (x<1) and thus the recording light decreases the recording sensitivity. The dependence of saturation diffraction efficiency on the intensities of the recording and sensitizing light shows that there is a maximum dynamic range of the recording process.     

Investigation of nonvolatile holographic storage in LiNbO3:Mn:Ce:Fe crystal

We investigate the persistent holographic recording in triply doped LiNbO₃:Mn:Ce:Fe crystals at different oxidation/reduction states. The experimental results show that there is an optimum oxidation/reduction state, which results in the best dynamic range M/#. Compared with doubly doped LiNbO₃:Ce:Fe, we found that the nonvolatile diffraction efficiency and the best dynamic range M/# obtained in triply doped samples are larger than that obtained in doubly doped samples. The reason for the increase of the crystal about the nonvolatile diffraction efficiency and the dynamic range M/# was also explained.     

Effect of [Li]/[Nb] ratios on the photorefraction and scattering properties in In: Fe: Cu: LiNbO3 crystals at 488 nm wavelength

The high sensitivity, fast response and the high quality reconstructions are observed in various [Li]/[Nb] ratios In:Fe:Cu:LiNbO₃ crystals at 488 nm wavelength based on the two-beam coupling experiment. The strong blue photorefraction is contributed by the two-center effect and the remarkable characteristic of being in phase between the two gratings recorded in shallow and deep trap centers. The blue photorefraction is enhanced significantly with the increasing of [Li]/[Nb] ratios under the same experimental conditions. The sensitivity S" is reduced to 0.46 J/cm, simultaneously the response time is as fast as 4.4 s and the erase phenomenon is not obvious in In:Fe:Cu:LiNbO₃ crystals which [Li]/[Nb] ratio is 0.986 in crystal. Increasing [Li]/[Nb] ratios improve the damage-resistant ability of the crystals, but lead to a more serious beam fanning. Experimental results definitely show that the near-stoichiometric In: Fe: Cu: LiNbO₃ crystal becomes a promising candidate for blue photorefractive holographic recording.     

Effects of forming gas annealing on LiNbO3 single crystals

Z-cut congruent LiNbO₃ single crystals were annealed in 95%N₂+5%H₂ at high temperatures. X-ray diffraction showed that 2θ of (0 0 0 6) peak is obviously reduced by 0.6° and 1.0° for the samples annealed at 600 and 900 °C, respectively. A new peak appears at the high-energy side of O 1s spectrum in X-ray photoelelectron spectroscopy (XPS) analyses, and the leakage current is greatly increased. It is proposed that hydrogen is incorporated in LiNbO₃ single crystals through forming gas annealing at temperatures up to 900 °C and exists in LiNbO₃ as a proton bound to an oxygen ion through O-H bond with its electron donated.     

Growth and optical properties of Hf,Ce co-doped lithium niobate crystals

In this paper, a series of Hf,Ce co-doped lithium niobate crystals with various HfO₂ concentrations were grown by Czochralski method. The ultraviolet-visible absorption spectra and the infrared transmittance spectra were measured to study defect structure of the crystals. The optical damage resistance was measured by the transmitted facula distortion method. The results showed that the optical damage resistance of Hf:Ce:LiNbO₃ was greatly improved when the Hf-doping concentration was above 4 mol%.     

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.     

Preparation and holographic storage properties of tri-doped Mg:Mn:Fe:LiNbO3 crystals

Doping MgO, MnO and Fe₂O₃ in LiNbO₃ crystals, tri-doped Mg:Mn:Fe:LiNbO₃ single crystals were prepared by the conventional Czochralski method. The UV-vis absorption spectra were measured and the shift mechanism of absorption edge was also investigated in this paper. In Mg:Mn:Fe:LiNbO₃ crystal, Mn and Fe locate at the deep level and the shallow level, respectively. The two-photon holographic storage is realized in Mg:Mn:Fe:LiNbO₃ crystals by using He-Ne laser as the light source and ultraviolet as the gating light. The results indicated that the recording time can be significantly reduced for introducing Mg²⁺ in the Mg:Mn:Fe:LiNbO₃ crystal.     

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.     

Improvement of photorefractive properties in Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Photorefractive properties of Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios have been investigated at 488 nm wavelength based on the two-wave coupling experiment. High diffraction efficiency and large recording sensitivity are observed and explained. The decrease in Li vacancies is suggested to be the main contributor to the increase in the photoconductivity and subsequently to the induction of the improvement of recording sensitivity. The saturation diffraction efficiency is measured up to 80.2%, and simultaneously the recording sensitivity of 0.91 cm/J is achieved to in the Hf:Fe:LiNbO3 crystal grown from the melt with the [Li]/[Nb] ratio of 1.20, which is significantly enhanced as compared with those of the Hf:Fe:LiNbO3 crystal with the [Li]/[Nb] ratio of 0.94 in melt under the same experimental conditions. Experimental results definitely show that increasing the [Li]/[Nb] ratio in crystal is an effective method for Hf:Fe:LiNbO3 crystal to improve its photorefractive properties.     

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.     

Theoretical explanation of g factors for Ti ions in LiNbO3 and LiTaO3 crystals

The EPR g factors g_// and g_⊥ for Ti³⁺ ions at the trigonal octahedral Li⁺ sites of LiNbO₃ and LiTaO₃ crystals are calculated from the third-order perturbation formulas of g factors for 3d¹ ion in trigonal symmetry. In the calculations, the crystal-field parameters are obtained from the structural data by using the superposition model. The calculated values are in reasonable agreement with the observed values. The results are discussed.     

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.     

Deposition of ZnO multilayer on LiNbO3 single crystals by DC-magnetron sputtering

Zinc oxide (ZnO) thin films were deposited on LiNbO₃ (LN) single crystals with 200 nm thicknesses by three different ways, where coating of zinc (Zn) film was followed by thermal oxidation for four, two, and one steps with 50, 100, and 200 nm thicknesses repeatedly. Sample, which was produced at 4-step of deposition and oxidation of Zn layer, showed high transmittance and low structural defect due to a lower photoluminescence intensity and Urbach energy. Average grain size in X-ray diffraction (XRD), scanning electron microscopy (SEM) micrograph, and atomic force microscopy (AFM) images for multilayer of ZnO was lower than monolayer of ZnO thin films. Applying multilayer coating technique leads to decrease of surface roughness and scattering on light on surface and fabrication of LiNbO₃ waveguides with lower optical loss.     

Effect of the parameters on diffraction efficiency after thermal fixing for reflection geometry hologram storage in LiNbO3:Fe

For reflection geometry hologram storage in LiNbO₃:Fe, we have shown that the diffraction efficiency increases with doping level and thickness of storage material monotonically. When the acute angle between reference and z-axis is large enough for getting a relative small Bragg angle that is needed for angle multiplexing, smaller angle does good to diffraction efficiency after thermal fixing. And for absorption coefficient, there is an appropriate value responding to optimal diffraction efficiency after thermal fixing and we develop a theoretical model that predicts achievable diffraction efficiency after thermal fixing as a function of crystal thickness, doping level, acute angle between reference and z-axis and absorption coefficient. We compare this model with experiment results and get a good agreement.     

掺镁铌酸锂亚微米结构畴反转的研究

研究了掺镁铌酸锂(MgO：LiNbO₃)的极化特性及其畴壁运动的性质,通过调节多个脉冲外加电场来控制畴壁的运动,在背向反转效应作用下,反转畴发生劈裂,制备出均匀的掺镁铌酸锂亚微米周期畴结构,并分析探讨了掺镁铌酸锂亚微米结构的成因及其反转机理. 关键词： 亚微米畴结构 掺镁铌酸锂 背向反转     

Theoretical expression for change of extraordinary refractive index in annealed proton exchanged LiNbO3 optical waveguides

A general expression for the change in extraordinary refractive index of the annealed proton exchanged LiNbO₃ waveguide has been deduced. The expression deduced explains the experimental results of decrease in change of extraordinary refractive index with annealing. The effect of annealing time has also been incorporated following Cao's model (Cao, Ramaswamy, Srivastava, J. Lightwave Technol. 10 (1992) 1302–1313). The concentration profile of protons in the annealed waveguide has been deduced theoretically, which is consistent with the previous results. The spontaneous polarization has been considered as the central mechanism for change in extraordinary refractive index due to proton exchange with annealing.