Influence of doping on OH absorption in LiNbO3 crystals

Undoped, Cr doped and Mg, Cr codoped LiNbO₃ crystals were grown by conventional Czochralski technique. Comparative study was carried out using Fourier transform infrared (FTIR) and UV‐Visible spectroscopy. Infrared optical absorption for OH^– ion has been used to study the effect of dopants on the crystals. The peak position of OH^– shift to 3535 cm^‐1 for Mg, Cr codoped crystals compared to 3484 cm^‐1 for undoped and Cr doped crystals. Prominent absorption bands are found in the visible region centered at 480 nm (20833 cm^‐1) and 653 nm (15313 cm^‐1) in Cr doped crystals. Whereas in Mg, Cr codoped crystals these broad absorption bands are red shifted to 517 nm (19342 cm^‐1) and 678 nm (14749 cm^‐1). UV cutoff in Cr doped crystals shift towards higher wavelength compared to undoped LiNbO₃ crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and optical damage resistance of Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Hf:Fe:LiNbO₃ crystals were grown in air by the Czochralski technique with various ratios of [Li]/[Nb]=0.94, 1.05, 1.20 in melt. The defect structure and location of doped ions were analyzed by the UV‐visible and infrared spectroscopy. The optical damage resistance ability 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 is enhanced with the increase of the [Li]/[Nb] ratio. The dependence of the optical damage resistance of Hf:Fe:LiNbO₃ crystals on the defect structure is discussed in detail. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructure and optical properties of Zn:Mn:Fe:LiNbO3 crystals

Zn:Mn:Fe:LiNbO₃ crystals were prepared by Czochralski technique. Its microstructure was measured and analyzed by UV‐Vis absorption 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 the Mn:Fe:LiNbO₃ crystal. The dependence of the defects on the optical damage resistance was discussed. The non‐volatile holographic storage was realized in all crystals, and the sensitivity of the Zn(7.0 mol%):Mn:Fe:LiNbO₃ crystal is much higher than that of others. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical absorption spectra of LiNbO3, Fe:LiNbO3, and Zn:Fe:LiNbO3 single crystals grown by Bridgman method

The optical absorption spectra of LiNbO₃ (LN), Fe:LiNbO₃ (Fe:LN), and Zn:Fe:LiNbO₃ (Zn:Fe:LN) single crystals grown by Bridgman method were measured and compared. The absorption characteristics of the samples and the effects of growth process conditions on the absorption spectra were investigated. The Fe, Zn and Li concentrations in the crystals were analyzed by inductively coupled plasma (ICP) spectrometry. The results indicated that the overall Fe ion and Fe²⁺ concentration in Fe:LN and Zn:Fe:LN crystals increased along the growing direction. The incorporation of ZnO in Fe:LN crystal induced increase of Fe²⁺ in the crystal. Among Fe‐doped and Zn:Fe‐codoped LN single crystals, 3 mol% ZnO doped Fe:LN had a biggest change of Fe²⁺ ion concentration from bottom to top part of crystal. The effects of technical conditions (atmosphere and thermal history) on Fe²⁺ ion concentration were discussed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and light‐induced scattering of Zr‐doped near‐stoichiometric Mn:Fe:LiNbO3 crystals grown by TSSG method

Near‐stoichiometric Mn:Fe:LiNbO₃ crystals doped with various concentration of ZrO₂ were grown by top seed solution growth (TSSG) method in the air atmosphere. The Zr concentration in the crystal was determined by inductively coupled plasma optical emission spectrometer. The defect structures were analyzed by means of ultraviolet‐visible and infrared transmittance spectra. The appearance of vibration peak at 3466 cm^‐1 in infrared spectra manifested that Li/Nb ratio in crystals approached to stoichiometric proportion. The fundamental absorption edge represented continuous red‐shift which was discrepancy with congruent doped LiNbO₃ crystals showed that doping ions possessed different location mechanism. The light‐induced scattering of the doped stoichiometric LiNbO₃crystals were quantitatively scaled via incident exposure energy. The results demonstrated that Zr(2 mol%):Mn:Fe:LiNbO₃ crystal had the weakest light‐induced scattering and the mechanism related to their defect structures was discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and optical fixing holographic storage of Mg:Mn:Fe:LiNbO3 crystals

Mg:Mn:Fe:LiNbO₃ crystals were grown by the Czochralski method. The defect structure was analyzed by UV‐vis spectra and IR spectra. The holographic storage of Mg:Mn:Fe:LiNbO₃ crystals was measured by the two color fixed method. The results show that with the increase of MgO doping concentration, the writing time becomes shorter, the dynamic range decreases, photorefractive sensitivity increases and fixing diffraction efficiency decreases. When the MgO doping concentration exceeds 4.5 mol%, the fixing diffraction efficiency approaches zero. The effect of doping Mg ions on the holographic storage properties of Mn:Fe:LiNbO₃ crystals is discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical damage resistance of Hf:Fe:LiNbO3 crystals with various [Li]/[Nb] ratios

Hf:Fe:LiNbO₃ crystals were grown in air by the Czochralski technique with various [Li]/[Nb] ratios ([Li]/[Nb]=0.94, 1.05, 1.20) in melt. The defect structure and location of doped ions were analyzed by the UV‐visible absorption spectra. The optical damage resistance of Hf:Fe:LiNbO₃ crystals was investigated by the photoinduced birefringence change and the transmitted light spot distortion method. The results show that the optical damage resistance ability of Hf:Fe:LiNbO₃ crystals decreases with the increase of the [Li]/[Nb] ratio. The dependence of the optical damage resistance of Hf:Fe:LiNbO₃ crystals on the defect structure is discussed in detail. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improved blue photorefractive properties of near‐stoichiometric LiNbO3:Mn:Fe:Zr crystal

Near‐stoichiometric LiNbO₃ single crystal tri‐doped with ZrO₂, MnO and Fe₂O₃ was grown from Li‐riched melt by Czochralski method. The defect structures and composition of these crystals were analyzed by means of ultraviolet‐visible and infrared transmittance spectra. The appearance of 3466 cm^‐1 peak in infrared spectra showed that the crystal grown from Li‐riched melt was near stoichiometric. The photorefractive properties at the wavelength of 488 nm and 633 nm were investigated with two‐beam coupling experiment, respectively. The experimental results showed that the response speed and sensitivity were enhanced significantly and the high diffraction efficiency was obtained at 488 nm wavelength. This manifested that near‐stoichiometric LiNbO₃:Mn:Fe:Zr crystal was an excellent candidate for holographic storage. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation on the blue photorefractive properties varied with MgO codoping in Ru:Fe:LiNbO3 crystals

Mg:Ru:Fe:LiNbO₃ crystals with various doping concentration of MgO have been grown by Czochralski method. The type of charge carriers and photorefractive properties in Mg:Ru:Fe:LiNbO₃ crystals were measured by two‐wave coupling method using Kr⁺ laser (476 nm) and He‐Ne laser (633 nm) as light sources. We found that holes were the dominant charge carriers under blue light irradiation while electrons were the dominant charge carriers under red light irradiation. Mg²⁺ ions behaved no longer as damage resistant, but promoter to the photorefractive properties at 476 nm wavelength. The photorefractive properties under blue light improved with the increase concentration of Mg²⁺ ions. The enhancement mechanisms of the blue photorefractive were suggested. Experimental results definitely showed that Mg‐doped two‐centre Ru:Fe:LiNbO₃ was a promising blue photorefraction material for holographic volume storage.     

In doping effect on optical properties in Zn:In:Fe:LiNbO3 crystals

A series of Zn:In:Fe:LiNbO₃ crystals were prepared by Czochralski method. The crystal composition and defect structure were analyzed by ICP‐OE/MS, UV–vis and IR spectroscopy. The results show that with increasing In³⁺ doping concentration in melt, the segregation coefficients of both Zn and In ions decrease. The optical damage resistance of Zn:In:Fe:LiNbO₃ crystals was studied by the transmitted beam pattern distortion method. It is found that the optical damage resistance of Zn:In(3mol%):Fe LiNbO₃ crystals is two orders of magnitude higher than that of Zn:Fe:LiNbO₃. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of reduction/oxidation treatment on blue photorefraction in In:Fe:Cu:LiNbO3 crystals

In:Fe:Cu:LiNbO₃ crystals with reduced/oxidized treatments were prepared by the Czochralski method. The defect structure was analyzed by the UV‐Visible absorption spectra. The blue photorefractive properties, such as the refractive index change, response time, recording sensitivity, dynamic range as well as two‐wave coupling gain coefficient, were also investigated at 488 nm wavelength using the two‐wave coupling experiment. Comparing the as‐grown and oxidized In:Fe:Cu:LiNbO₃ crystals, the reduced sample has the highest recording sensitivity and largest dynamic range. Meanwhile, the high diffraction efficiency is still maintained. Experimental results definitely show that reduction treatment is an effective method to improve the blue photorefractive performance of In:Fe:Cu:LiNbO₃ crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High photorefractive sensitivity and fast response time of near‐stoichiometric and MgO doped LiNbO3:Fe crystals

Congruent LiNbO₃:Fe and LiNbO₃:Mg,Fe crystals were grown by Czochralski method, and vapor transport equilibration technique was employed to improve the [Li]/[Nb] ratios of these crystals. The influence of stoichiometry and MgO dopant on the photorefractive sensitivity and response time of LiNbO₃:Fe crystals was investigated. Both stoichiometry and MgO dopant can effectively reduce the amount of intrinsic defects, but MgO can also decrease the concentration of Fe²⁺ ions in Li‐sites. Near‐stoichiometric and MgO doped LiNbO₃:Fe crystal has high photorefractive sensitivity and fast response time. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and optical damage resistance of In:Fe:Cu:LiNbO3 crystals with various [Li]/[Nb] ratios

In:Fe:Cu:LiNbO₃ crystals were grown in air by the Czochralski technique with various [Li]/[Nb] ratios of 0.946, 1.050, 1.200, and 1.380 in melt. Based on the ICP‐AES (inductively coupled plasma atomic emission spectrometry) analyzed results, the chemical formula of the triple‐doped In:Fe:Cu:LiNbO₃ crystals were obtained. It can be seen that the near‐stoichiometric ratio value is between 1.050 and 1.200 for our samples. The optical damage resistance of In:Fe:Cu:LiNbO₃ crystals was characterized by changes in light‐induced birefringence and it increases with the increasing of [Li]/[Nb] ratios. The dependence of the optical damage resistance on the defect structure of In:Fe:Cu:LiNbO₃ crystals is discussed in detail based on the obtained chemical formulas. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and Photo‐Damage Resistance of Li‐Rich LiNbO3 Crystals Co‐Doped with Zn2+/Er3+

The pure congruent LiNbO₃, Er:LiNbO₃ and Zn,Er co‐doped Li‐rich LiNbO₃ crystals were grown by Czochralski method. The X‐ray diffraction method and ultraviolet‐visible absorption spectra of the crystals were used to analyze the structure of the crystals. The photo‐damage ability resistance of the crystals was measured. The Zn,Er co‐doped Li‐rich LiNbO₃ crystals show a decrease in lattice constant values, a shift in absorption edge of ultraviolet‐visible absorption spectra towards shorter wavelength, and three orders of magnitude increase in photo‐damage resistance compared to congruent LiNbO₃ crystal. The intrinsic and extrinsic defects are discussed to explain the enhance of the photo‐damage ability resistance     

Dependence of refractive indexes dispersion for LiNbO3 on impurity

The effect of the impurities of the transition metals Co, Mn, Cr, Fe, Ni, Cu on the dispersion of the refractive indexes of LiNbO₃ is studied. The dispersion curves for LiNbO₃ are compared to those for the pure crystals. The relation between the difference of the refractive indexes of the pure and doped LiNbO₃ and the ionic radius of the impurity is established.     

Double‐frequency properties of In:LiNbO3 crystals

1 mol%, 2 mol%, 3 mol%, 4 mol% and 5 mol% In³⁺ doped LiNbO₃ crystals were grown by the Czochralski method, respectively. Oxidized treatment of some crystals was carried out. The infrared transmission spectra and photo‐damage resistance of the samples were measured. The results showed that the OH^‐ absorption peaks of In(3mol%):LiNbO₃, In(4mol%):LiNbO₃ and In(5mol%):LiNbO₃ crystals were located at about 3508 cm^‐1, while those of In(1mol%):LiNbO₃ and In(2mol%):LiNbO₃ crystals were located at about 3484cm^‐1. When the doped In³⁺ concentration reached its threshold in LiNbO₃ crystal, photo‐damage resistance of In:LiNbO₃ crystals was two orders of magnitude higher than that of pure LiNbO₃ crystal. The experimental results of the second harmonic generation (SHG) showed that the phase matching temperatures of In:LiNbO₃ crystals were lower than those of Zn:LiNbO₃ and Mg:LiNbO₃ crystals and the SHG efficiency reached 38%. Oxidization treatment was also found to make the dark trace resistance of crystals increase. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation on photorefractive properties of doped lithium niobate

Cu:LiNbO₃ crystal and Fe:Cu:LiNbO₃ crystals were grown by the Czochralski method from congruent melt. The OH^‐ absorption spectrum of doped lithium niobate crystals was measured. The photorefractive properties of doped crystals were studied by the two‐wave coupling method. The results of the two‐wave coupling experiments showed that as the concentration of doping ions increased, the diffraction efficiency and the dynamic range enhanced, the holographic response time shortened. The recording time of Fe(0.10wt%): Cu(0.10wt%): LiNbO₃ crystal is only a tenth of that of Cu(0.05wt%): LiNbO₃ crystal. Among all samples, the dynamic range of the Fe(0.10wt%): Cu(0.10wt%): LiNbO₃ crystal was the most largest (up to 40.78). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Defect structure and spectroscopic characteristics of codoped Hf: Er: LiNbO3 crystals

Codoped Hf: Er: LiNbO₃ crystals have been grown by the Czochralski technique. Defect structures of the crystals were analyzed by IR absorption spectra, and the compositions of the crystals were measured by X‐ray fluorescent spectrograph. A new OH^–‐associated vibrational peak at 3492 cm^–1 was revealed in 6 mol % Hf: 1 mol % Er: LiNbO₃ crystal. It was attributed to (Hf_Nb)^–‐OH^–‐(Er_Nb)^2– defect centers. The Er³⁺ concentrations in crystals gradually decreased with the increase of the codoped Hf⁴⁺ concentrations in the melts. The emission characteristics of the crystals were investigated by the fluorescence spectrum. It was found that the luminescent intensity in codoped 6 mol % Hf: 1 mol % Er: LiNbO₃ crystal was 3.5 times stronger than that in single doped 1 mol % Er: LiNbO₃ crystal. The luminescent enhancement effect was successfully explained on the basis of defect structure of the crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Micro‐Pulling Down Growth of Co‐doped Lithium Niobate Single Crystal Fibers According Er and Mg Contents and Photolumenescence Properties

The Er³⁺doped Mg:LiNbO₃single crystal fibers employed in our experiment were grown in air by a micro‐pulling down (μ‐PD) method from host materials of a congruent Li/Nb (0.945) ratio which were melt‐doped with a nominal molar concentration of 1, 3, 5% MgO and 0.6% Er₂O₃. The X‐ray diffraction analysis results indicated that the co‐doped crystals main tained the same structural characteristics as the undoped LiNbO₃, however the lattice parameters with Mg differed; c (Å) value decreased, and a (Å) increased than of pure LiNbO₃. The influence of dopants on the photoluminescence (PL) properties of the Er:Mg:LiNbO₃ single crystal fibers excited by laser lines of 514 nm was reported. Also, the PL properties according to temperature and the excitation power of Er:Mg:LiNbO₃ crystal fibers were analyzed.     

Optical damage resistance of Mg:Ce:Fe:LiNbO3 crystals

Mg:Ce:Fe:LiNbO₃ crystals were prepared with fixed concentrations of Fe₂O₃ and CeO₂, and differing concentrations of MgO by the Czochralski technique. Their infrared transmission spectra were measured in order to investigate their defect structures and their optical damage resistance was characterized by the photoinduced birefringence change and transmission facula distortion method. The optical damage resistance of Mg:Ce:Fe:LiNbO₃ crystals increases remarkably when the concentration of MgO exceeds a threshold concentration. The dependence of the optical damage resistance on the defect structure of Mg:Ce:Fe:LiNbO₃ crystals is discussed in detail. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)