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.     

Mg2+对Fe:LiNbO3晶体光折变响应时间的影响

在Fe:LiNbO₃中掺进3mol%和6mol%MgO,生长了Mg:Fe:LiNbO₃晶体.测试了Mg:Fe:LiNbO₃晶体抗光致散射能力、衍射效率、响应时间和光电导.推导响应时间与光电导之间的关系.在Fe:LiNbO₃晶体中掺进6mol%的Mg²⁺,它的抗光致散射能力比Fe:LiNbO₃晶体提高一个数量级,响应速度比Fe:LiNbO₃晶体提高四倍.     

Space charge field limitations in photorefractive LiNbO3:Fe crystals

We use holographic techniques for the investigation of strongly oxidized LiNbO₃:Fe crystals with small Fe²⁺ concentrations and compare the results with theoretical predictions. Experimental evidence is presented for enhanced phase shifts between light intensity pattern and refractive index grating and for limitations of optically induced space charge fields in photovoltaic crystals due to the low concentration of filled traps. Our findings do not support the model of a nonlocal photovoltaic effect in LiNbO₃.     

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.     

Mg:Fe:LiNbO3晶体的生长及光学性能研究

在Fe:LiNbO₃中掺进MgO和Fe₂O₃以提拉技术生长Mg:Fe:LiNbO₃晶体.对晶体进行极化和还原处理.测试晶体的吸收光谱,Mg:Fe:LiNbO₃晶体吸收边相对Fe:LiNbO₃晶体发生紫移.测试晶体的红外光谱,Mg:(5 mol%)Fe:LiNbO₃晶体OH^-吸收峰由Fe:LiNbO₃晶体的3482 cm^-1移到3534 cm^-1.采用锂空位模型阐述Mg:Fe:LiNbO₃晶体,吸收边和OH-吸收峰移动的机理.测试晶体的抗光致散射能力.Mg:(5 mol%)Fe:LiNbO₃晶体抗光致散射能力比Fe:LiNbO₃晶体提高一个数量级以上.测试晶体的衍射效率和响应时间.Mg:Fe:LiNbO₃晶体响应速度比Fe:LiNbO₃晶体提高四倍.     

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.     

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.     

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.     

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.     

Charge transport properties of undoped congruent lithium niobate crystals

Time-resolved light-induced birefringence measurements based on a phase compensation technique are used to determine the charge transport properties of congruent, nominally-undoped lithium niobate crystals (LiNbO₃). Some of the crystals are conventionally oxidized. The steady-state space-charge field E _pv, the bulk photovoltaic coefficient β, and the photoconductivity σ _ph are determined in the intensity range (30–30 000) W/cm². The photovoltaic coefficient β increases by one order of magnitude over this intensity range, the space-charge field E _pv even by two orders of magnitude. We discuss the results in the context of the known one- and two-center charge transport models for LiNbO₃. The experimental findings presented here are of relevance for the long-standing problem of optical damage in such crystals, which inhibits their use in high-intensity applications like nonlinear optics.     

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     

Reduction-induced polarons and optical response of Mg-doped LiNbO<Subscript>3</Subscript> crystals

We studied the visible and IR dispersion of absorption coefficient and refractive index for congruent LiNbO₃ and Mg:LiNbO₃ crystals before and after chemical reduction at different annealing temperatures. The concentration of Mg in Mg:LiNbO₃ samples was just below or above the photorefractive threshold. The reduction-induced changes in the absorption coefficient reveal the formation of polarons typical for doped LiNbO₃ crystals. It was shown that the polaron concentration is maximal when the Mg concentration is just below the photorefractive threshold and the annealing temperature is near 500 °C. This temperature is optimal for the most efficient polaron formation at all considered concentrations of Mg. The fitting of the experimental absorption dispersion curves indicates that intermediate polarons are formed in LiNbO₃:Mg crystals preferably. The spectral dependence of transmission for samples of lithium niobate of various thicknesses was studied. The results indicate that there are spatial regions with much greater absorption than that of bulk crystals. We assume that, in general, polarons are localized in thin near-surface regions. The spectral dependence of the refractive index in the vicinity of the phonon absorption edge indicates some essential changes of the phonon subsystem taking place after reduction. The infrared contribution into the dispersion of the dielectric function real part increases considerably after reduction. PACS 71.38.Ht; 71.38.-k; 78.20.Ci     

The effect of stoichiometry and Mg doping on the Raman spectra of LiNbO3:Mg crystals

LiNbO₃:Mg crystals doped with 0–8 mol. % Mg with stoichiometric, intermediate and congruent compositions were systematically investigated by Raman spectroscopy in backscattering y(zx)y, y(zz)y and z(xx)z geometries. The damping was found to be a very sensitive parameter for the characterization of the crystal composition. The half-widths of E(TO₃)–E(TO₉) and A ₁(TO₁)–A ₁(TO₄) bands having significant composition dependence for the undoped LiNbO₃ crystals show only a weak Mg concentration dependence below the photorefractive threshold, which is a consequence of the counteracting effect of the decreasing Nb_Li and increasing Mg_Li contents. The half-widths of the bands, however, increase linearly with growing Mg content for samples above the threshold, irrespective of the Li/Nb ratio. The change in the Mg concentration dependence at a given Li/Nb ratio determines the same threshold value as that concluded from IR and UV spectroscopic measurements. The half-width of the main A ₁(LO₄) band at 873 cm^-1 increases linearly with growing Mg concentration, but no threshold effect is observed. However, the ratio of the area of the main band and the high-frequency sideband shows a threshold effect that can be interpreted by the existing defect incorporation models. The small Raman band at about 740 cm^-1 attributed earlier to Nb_Li vibration is also detected in above-threshold LiNbO₃:Mg crystals, which can be explained by the vibration of Nb ions in Mg₄Nb₂O₉ defect clusters appearing at high Mg concentrations. PACS 77.84.Dy; 63.20.Mt; 42.70.Mp; 78.30.-j     

Study of near-infrared nonvolatile two-center holographic recording in LiNbO3:Fe:Rh crystal

The near-infrared nonvolatile holographic recording has been realized in a doubly doped LiNbO₃:Fe:Rh crystal by the traditional two-center holographic recording scheme, for the first time. The recording performance of this crystal has been investigated by recording with 633 nm red light, 752 nm red light and 799 nm near-infrared light and sensitizing with 405 nm purple light. The experimental results show that, co-doped with Fe and Rh, the near-infrared absorption and the photovoltaic coefficient of shallow trap Fe are enhanced in this LiNbO₃:Fe:Rh crystal, compared with other doubly doped LiNbO₃ crystals such as LiNbO₃:Fe:Mn. It is also found that the sensitizing light intensity affects the near-infrared recording sensitivity in a different way than two-center holographic recording with shorter wavelength, and the origin of experimental results is analyzed.     

Structure and nonvolatile holographic recording of Mg:Ce:Cu:LiNbO3 crystals

A series of Mg:Ce:Cu:LiNbO₃ crystals has been grown by Czochralski method. Their infrared transmittance spectra and ultraviolet-visible absorption spectra were measured and discussed to investigate their defect structure. The nonvolatile holographic recording of Mg:Ce:Cu:LiNbO₃ crystals was characterized by the two-photon fixed method. We found that the recording time of Mg:Ce:Cu:LiNbO₃ crystals became shorter and nonvolatile diffraction efficiency decreases with the increase of Mg doping concentration, especially doping with Mg approaches and exceeds the so-called threshold. And the nonvolatility vanishes when the concentration of MgO exceeds 4 mol%. The intrinsic and extrinsic defects were discussed to explain the nonvolatile holographic properties in the Mg:Ce:Cu:LiNbO₃ crystals.     

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.     

The correlation of doping ions to holographic storage properties of Mg:Mn:Fe:LiNbO3 crystals

The congruent Mn(0.1 wt%):Fe(0.03 wt%):LiNbO₃ crystals doped with different concentration of MgO(0,1,3,6 mol%) have been grown by Czochralski method in air atmosphere. Some crystal samples were reduced in Li₂CO₃ powder. The defects and doping ions location in crystals were investigated by UV-Vis. absorption spectrum as well as infrared transmittance spectrum analysis. In two wave coupling experiments we determined the writing time, maximum diffraction efficiency and the erasure time of four crystal samples with He-Ne laser at 633 nm. The results indicated that Mg(3 mol%):Fe:Mn:LiNbO₃ was the most proper holographic recording media material among four crystals in the paper.     

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.     

Intrinsic photorefractive centers in LiNbO3:Fe

In LiNbO₃:Fe,Me crystals (Me = K, Mg, Zn) elementary holograms are recorded and erased with frequency-doubled, ordinarily polarized pulses of a Q-switched Nd:YAG laser. At high light intensities (I > 10⁹ Wm^–2) holographic sensitivities and saturation values of refractive index changes grow with increasing intensity and a contribution to photo-conductivity appears increasing quadratically withI. The intensity-dependent parts of the holographic quantities are diminished by increasing the lithium content of the samples or by doping the crystals with magnesium or zinc. Experimental results can be described by a two-center charge transport model, which is the Fe^2+/3+ model supplemented by shallow traps, namely niobium ions occupying lithium sites.