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.     

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.     

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     

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.     

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.     

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%.     

OH-absorption properties of the optical damage region in codoped In/Mg:LiNbO3 crystals with various Li/Nb ratios

OH-absorption properties of the optical damage region in a series of codoped In/Mg:LiNbO₃ crystals with various Li/Nb ratios have been investigated. The OH⁻-associated vibrational peak at 3507 cm⁻¹ is confirmed to occur in crystals with Li/Nb ratio of 0.94. For codoped In/Mg:LiNbO₃ crystals with Li/Nb ratio of 1.05 and 1.20, the OH⁻-associated vibrational peaks are detected at 3536 and 3507 cm⁻¹ as well. A new peak at 3518 cm⁻¹ attributed to a (In_Nb)²⁻-OH⁻-(Mg_Nb)³⁻ defect center is revealed in crystals with Li/Nb ratio 1.38. When the “In-Mg threshold” concentration is reached, the optical damage resistance ability of codoped In/Mg:LiNbO₃ crystals is greatly improved.     

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.     

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.     

Dopant occupancy and optical properties of Er3+ in Er/Zn-codoped lithium niobate crystal

The effect of Zn²⁺ ion on the dopant occupancy and optical characteristic of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal is reported. The intense 1.54 μm and relatively weak green upconversion emissions are observed for Er (1 mol%)/Zn (6 mol%):LiNbO₃ crystal. The OH^? absorption and the time-resolved spectra show that the Zn²⁺ codoping decreases the threshold concentration of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal. The experimental results here imply that the potential application of Er³⁺-doped LiNbO₃ crystal can be designed and optimized on the basis of the theoretical investigations.     

Optical spectroscopy and laser parameters of Zn2+/Er3+/Yb3+-tridoped LiNbO3 crystal

The Zn/Er/Yb:LiNbO₃ and Er/Yb:LiNbO₃ crystals were grown by the Czochralski technique. The laser characteristics of 1.54 μm emission were predicted based on the Judd–Ofelt theory, and the intensity parameters Ω_t (Ω₂=7.23×10^?20 cm², Ω₄=3.15×10^?20 cm² and Ω₆=1.43×10^?20 cm²) were obtained. The stimulated emission cross sections (σ_em) at 1.54 μm emission in Zn/Er/Yb:LiNbO₃ were calculated based on the McCumber theory and the Füchtbauer–Ladenburg theory. The gain cross section spectrum of Zn/Er/Yb:LiNbO₃ crystal was also investigated. Under 980 nm excitation, a lenghthening lifetime of 1.54 μm emission and an enhancement of green upconversion emission were observed for Zn/Er/Yb:LiNbO₃ crystal. The studies on the power pump dependence and the upconversion mechanism suggested that both green and red upconversion emissions were populated via the three-photon process, and Zn²⁺ ion tridoping increases the probability of cross relaxation process between the two neighboring Er³⁺ ions.     

Growth and optical properties of In:Nd:LiNbO3 crystals

In, Nd double-doped LiNbO₃ (LN) crystals have been grown for the first time. Their infrared (IR) transmission spectra were measured and discussed to investigate their structure and defects. The optical damage resistance of Nd:In:LiNbO₃ crystals were characterized by straightly observing transmission facula distortion method. The optical damage resistance of In (4.0 mol%):Nd:LiNbO₃ was much higher than that of Nd:LiNbO₃. The defects were discussed in this paper to explain the optical damage resistance in the In:Nd:LiNbO₃ crystals.     

X-ray excited luminescence of Ce:Li2CaSiO4, Ce:CaBPO5 and Ce:LiCaPO4

Three materials Ce:Li₂CaSiO₄, Ce:CaBPO₅ and Ce:LiCaPO₄ were synthesized as polycrystalline samples for scintillation application in neutron detection. Ce³⁺ optical spectroscopy was investigated. Then, under X-rays excitation, Ce:Li₂CaSiO₄ and Ce:LiCaPO₄ present light yields about 7800 ph/MeV and 5900 ph/MeV, respectively. A self trapped exciton loss mechanism has been evidenced and competes with the cerium emission.     

Luminescence and Scintillation Characterization of Cs2NaGdBr6: Ce3+ Single Crystal

Luminescence and scintillation properties of newly discovered bromo-elpasolites Cs₂NaGdBr₆: Ce³⁺ (CNGB: Ce³⁺) are presented. Single crystals of CNGB: Ce³⁺ with dimensions up to Ø7×10 mm³ are successfully grown by the Bridgman technique. X-ray excited luminescence measurements of the grown samples showed a broad emission band in the wavelength range from 365 to 470 nm. It offered an energy resolution of 5.1% (FWHM) at 662 keV for 10% Ce sample. The light output of the investigated samples increases along with cerium concentration. A maximum light yield of ～36,800 ph/MeV is measured for the 10% Ce sample crystal. Under γ-ray excitation, CNGB: Ce³⁺ crystals showed three exponential decay time components. The scintillation mechanism in the sample crystal is presented.     

The influence of Zn2+ ion on the 1.5 μm laser properties of LiNbO3 crystal heavily doped with Er3+ ion

The spectral characteristics of 1.54 μm emission in a series of Zn/Er:LiNbO₃ crystals with heavy Er content and variable Zn content were reported. The inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the concentration of Er³⁺ ion in the crystal. The absorption and emission spectra of Zn/Er:LiNbO₃ crystals were measured. Based on Judd–Ofelt theory, the spectral parameters such as intensity parameters Ω_t (t=2, 4 and 6), transition strengths, radiative transition probabilities, radiative lifetime and fluorescence branching ratio have been obtained in Zn/Er:LiNbO₃ system. The emission cross section corresponding to ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ion was obtained according to Füchtbauer–Ladenburg theory. The gain cross section of Er:LiNbO₃ crystal codoped with 6 mol% Zn²⁺ ions were also discussed in this work.     

Peculiarities of luminescent properties of cerium doped YAG transparent nanoceramics

Optical and luminescence properties of transparent nanosized cerium doped Y₃Al₅O₁₂ (YAG:Ce) ceramics have been studied. YAG:Ce nanoceramics were obtained by means of low temperature and high pressure (LTHP) sintering method. Nanoceramic samples were sintered in the 2–8 GPa pressure range, whereas Ce³⁺ concentration was varied in the 0.5–5 at. % range. It is shown that, in contrast to the single crystal, a strong rise of absorption coefficient was detected already at wavelength shorter than 400 nm in all nanoceramic samples studied. Furthermore, in nanoceramic samples unusual UV emission band near 3.1 eV was observed, which is not observed in the YAG:Ce single crystal. High pressure applied during nanoceramics sintering leads to significant changes in their optical and luminescence properties.     

Polarization-independent rapidly tunable optical add-drop multiplexer utilizing non-polarizing beam splitters in Ti:LiNbO3

A polarization-independent four-port wavelength-tunable optical add drop multiplexer (OADM) that utilizes non-polarizing relaxed beam splitters has been analyzed and demonstrated in Ti:LiNbO₃ at the 1530 nm wavelength regime. The design utilizes an asymmetric interferometer configuration with strain induced index grating for polarization coupling along its arms that are shifted in position relative to each other. Experimental results of the filter response agree with theoretical predictions. Electrooptic tuning over a range of 15.7 nm at a rate of 0.08 nm/V has been measured. A temporal response < 46 ns to a 20 V step change in tuning voltage has been demonstrated. Fiber-to-fiber insertion loss is ~ 6.5 dB.     

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.     

Growth and characterization of pure and doped bis thiourea zinc acetate: Semiorganic nonlinear optical single crystals

Metal–organic coordination complex single crystals bis thiourea zinc acetate (BTZA) and Cd²⁺ doped BTZA have been synthesized and grown successfully by slow-cooling technique from their aqueous solutions. Single crystals of pure and Cd²⁺ doped BTZA with dimensions of 35 × 4 × 2 mm³ and 10 × 5 × 6 mm³, respectively were obtained with well defined morphology. The as grown single crystals are characterized by single crystal XRD studies and melting point measurements which reveal the incorporation of metallic dopants has not changed the structure of the parent crystal. The powder X-ray diffractogram of the grown crystals has been recorded and the various planes of reflection identified shows shift in the peak positions. The metal coordination with thiourea through sulphur in pure and Cd²⁺ doped BTZA were ascertained by FTIR studies and optical absorption study to identify the UV cut-off range. The presence of metals in pure and Cd²⁺ doped BTZA crystal lattice were confirmed by atomic absorption spectroscopy (AAS). The thermal decomposition of pure and Cd²⁺ doped BTZA crystals were investigated by thermo gravimetric analyses (TGA) and differential thermal analysis (DTA) indicate that doped crystals are more stable than pure crystals. The dielectric response of the crystals were studied in the frequency range 100 Hz–5 MHz at different temperatures and the results are discussed. Second harmonic generation (SHG) measurement confirms that the pure and Cd²⁺ doped BTZA have nonlinear optical (NLO) property. Laser damage threshold value of 12.44 MW/cm² has been determined using Q-switched Nd:YAG laser operating at 1064 nm and with 8 ns pulses in single shot mode for pure BTZA single crystal is reported for the first time.