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.     

Co,Zn共掺铌酸锂电子结构和吸收光谱的第一性原理研究

利用基于密度泛函的第一性原理的计算方法,研究了Co单掺及Co和Zn共掺LiNbO_3晶体的电子结构和吸收光谱.研究显示,各掺杂体系铌酸锂晶体的带隙均较纯铌酸锂晶体变窄. Co:LiNbO_3晶体禁带宽度为3.32 eV; Co:Zn:LiNbO_3晶体, Zn的浓度低于阈值或达到阈值时,禁带宽度分别为2.87或2.75 eV. Co:LiNbO_3晶体在可见-近红外光波段2.40, 1.58, 1.10 eV处形成吸收峰,这些峰归结于Co 3d分裂轨道的跃迁;加入抗光折变离子Zn~(2+),在1.58, 1.10 eV处的吸收峰增强,可以认为Zn~(2+)与Co~(2+)之间存在电荷转移,使e_g轨道电子减少,但并不影响t_(2g)轨道电子.结果表明,晶体中的Co离子在不同共掺离子下可充当深能级中心(2.40 eV),或可充当浅能级中心(1.58 eV),两种情况下,掺入近阈值的Zn离子均有助于实现优化存储.     

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.     

Cu,Fe掺杂LiNbO_3晶体电子结构和光学性质的第一性原理研究

利用基于密度泛函理论的第一性原理对Cu,Fe单掺及共掺LiNbO_3晶体的电子结构和光学性质进行了计算.结果显示:Cu,Fe单掺杂LiNbO_3晶体禁带内均产生了杂质能级,主要由Cu3d,Fe3d轨道及O 2p轨道贡献;共掺LiNbO_3晶体禁带内出现了双能级结构,深能级由Cu3d和O2p轨道贡献,浅能级由Fe3d和O2p轨道贡献.Cu,Fe单掺和共掺LiNbO_3晶体带隙依次缩小,在可见光区的光吸收明显增强.共掺LiNbO_3在445和630nm左右分别表现出一个宽吸收峰,比单掺LiNbO_3晶体表现出更好的光吸收性质.研究表明,Fe占Nb位比Fe占Li位的双掺样品在双光存储应用中更有优势;同时,浓度比[Fe2+]/[Fe3+]值的适当降低有助于这种优势的形成.     

Nonvolatile hologram storage properties of tri-doped Zn:Ce:Cu:LiNbO3 crystals

Congruent Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was grown by the Czochralski method in air. The occupation mechanism of the Zn²⁺ was discussed by an infrared transmittance spectrum. The nonvolatile holographic recording in Zn(7 mol%):Ce:Cu:LiNbO₃ single crystal was measured by two-photon fixed method. Zn(7 mol%):Ce:Cu:LiNbO₃ single crystals present the faster recording time and higher light-induced scattering resistance ability comparing with Ce:Cu:LiNbO₃ single crystals.     

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.     

Structure and optical damage resistance of near-stoichiometric Zn:Fe:LiNbO3 crystals

A series of near-stoichiometric Zn:Fe:LiNbO₃ crystals were grown by the high-temperature top-seed solution growth (HTTSSG) method from stoichiometric melts doped with 6 mol% K₂O. Infrared (IR) transmission spectra were measured and discussed in terms of the defect structure of the near-stoichiometric Zn:Fe:LiNbO₃ crystals. The results of the transmitted beam pattern distortion method show that the optical damage resistance of the near-stoichiometric Zn:Fe:LiNbO₃ crystals increases rapidly when the ZnO concentration exceeds a threshold value. The threshold value concentration of ZnO of the near-stoichiometric Zn:Fe:LiNbO₃ crystals is much lower than that of the congruent LiNbO₃ crystals. The dependence of the optical damage resistance on the defect structure of the near-stoichiometric Zn:Fe:LiNbO₃ crystals are discussed, and the holographic recording properties of the near-stoichiometric Zn:Fe:LiNbO₃ crystals are investigated.     

Fe:Mg:LiNbO3晶体电子结构和吸收光谱的第一性原理研究

基于密度泛函理论的第一性原理, 研究了LiNbO₃晶体以及不同Mg浓度的Fe:Mg:LiNbO₃晶体的电子结构和吸收光谱. 研究结果显示: 掺铁铌酸锂晶体的杂质能级由Fe 的3d轨道和O的2p轨道贡献, 禁带宽度为2.845 eV; 对于Mg, Fe共掺样品, Mg的浓度小于或等于阈值时, 禁带宽度分别为2.901 和2.805 eV; 掺铁铌酸锂晶体的吸收谱在2.3和2.6 eV处分别存在一个吸收峰, 其强度因Mg的浓度不同而发生变化. 研究结果还表明, 不同浓度的Mg对晶体内Fe²⁺和Fe³⁺的浓度以及占位产生了不同的影响. 还提出了光电子的形成不应单独考虑铁的轨道电子态, 而应同时考虑与铁成键的氧的轨道电子态的观点.     

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.     

（Ce，Cu）：LiNbO3晶体非挥发全息记录理论研究与优化

根据双中心带输运模型，对（Ce，Cu）：LiNbO3晶体双中心非挥发全息记录进行了理论研究与优化。推导了（Ce，Cu）：LiNbO3晶体的微观参量，采用数值方法通过严格求解模拟双中心带输运方程来模拟全息记录过程。分析了记录过程中，记录与敏化光强、Ce和Cu掺杂浓度以及晶体微观参量对（Ce，Cu）：LiNbO3晶体双中心全息记录的影响。发现（Ce，Cu）：LiNbO3晶体非挥发全息记录中实现高衍射效率与固定效率的主导因素是深中心Cu，在记录过程中，深中心Cu建立起了很强的空间电荷场。数值模拟的结果经过实验验证，最高饱和与固定衍射效率别为60．5％和53．8％。     

Grating spacing dependence of nonvolatile holographic recording with arbitrary charge transport lengths

Grating spacing dependence of nonvolatile holographic recording in doubly doped lithium niobate crystals is theoretically investigated allowing arbitrary charge transport lengths. It is shown that the nonvolatile refractive index modulation initially increases with increasing grating spacing, then a saturation behavior arises because of the dominant bulk photovoltaic effect. Although different charge transport length results in different nonvolatile refractive index modulation, the grating spacing dependence of nonvolatile holographic recording obeys almost the same rules for arbitrary charge transport lengths. The experimental results obtained by recording nonvolatile holograms in LiNbO₃:Cu:Ce crystals with different grating spacing are consistent with the theoretical analyses.     

On-line induced absorption measurement on PbWO4, YAlO3:Ce and CsI scintillating crystals

On-line measured radiation-induced absorption spectra and their kinetics are presented for the doped PbWO₄, YAlO₃:Ce and CsI crystals. In the doubly doped PbWO₄:Mo,Y crystals the saturation level of the induced absorption increased with Mo concentration up to 2750 ppm. With a higher concentration it again gradually decreased. Yttrium co-doping around 100 ppm improved considerably the radiation hardness of Mo-doped PbWO₄. Characteristic recovery time of these crystals was about 30 min. Positive influence of Zr⁺⁴ co-doping on characteristics of a set of YAlO₃:Ce samples resulted in decrease in the induced absorption intensity. The presence of very slow recovery processes was in good agreement with thermoluminescence characteristics above room temperature reported earlier. An absorption band round 420 nm appeared in as-grown CsI crystals doped with Tl, and was related to the oxygen contamination.     

低能离子轰击后铌酸锂晶体表面层的性质

从实验中观察到,低能离子轰击后的铌酸锂晶体表面层在3500—6500?之间出现至少两个光吸收峰,表面的相对暗电导率增加两个数量级。这表明离子轰击后的铌酸锂中产生了附加的光吸收和电导激活中心。在离子轰击过程中,由于某些原子基团和原子的优先溅射,在表面层中造成相当大的化学计量比偏离,它直接影响晶体的光学和电学性质。XPS(X射线电子能谱)测试结果证实,这一表面层的构成符合铌酸锂缺陷结构的空位模型。讨论了附加激活中心的成因,并据此解释了Ar⁺/O⁺混合离子轰击铌酸锂晶体所得到的结果。 关键词：     

LiNbO3∶Cr∶Cu晶体吸收特性及非挥发全息存储研究

研究了LiNbO3∶Cr∶Cu晶体的吸收特性,发现LiNbO3∶Cr∶Cu（含0.14 wt.% Cr2O3 和 0.011 wt.% CuO）晶体存在两个明显的吸收峰,中心波长分别位于480 nm和660 nm; 随着Cr的含量逐渐减小,Cu的含量逐渐增大,短波段不存在明显吸收峰,掺Cr的含量越大,中心波长在660 nm处的吸收越大；633 nm红光虽然位于中心波长为660 nm的吸收峰内,但它无助于光折变过程.分别采用390 nm紫外光和488 nm蓝光作为敏化光,514 nm绿光作为记录光的记录方案,实现了非挥发全息记录,掺入适量的Cr( 比如NCr=2.795×1025 m－3,NCr/ NCu=1)有助于全息记录性能的提高.     

Material optimization for low scattering noise during nonvolatile holographic recording in doubly doped LiNbO3 crystals

Scattering noises in four kinds of lithium niobate crystals with the same double doping system, which are LiNbO3:Fe:Mn, LiNbOs:Ce:Mn, LiNbOs:Ce:Cu, and LiNbOs:Fe:Cu, are observed and compared experimentally. The results show that nonvolatile holographic recording can effectively suppress scattering noise, which mainly depends on recombination coefficients of both the shallower centers and the deeper centers. The small recombination coefficients of the shallower centers and the large recombination coefficients of the deeper centers benefit the amplification of the signal gratings and the suppression of the noise gratings.In addition, the initial seed scattering also impacts the recorded scattering noise, and the little seed scattering results in low scattering noise. The theoretical simulations are performed for confirmation. Among the four kinds of doubly doped crystals, in LiNbOs:Ce:Cu the performances of nonvolatile recording are the best with low scattering noise and high diffraction efficiency.     

Effect of WO3 on the spectroscopic properties in Er/Yb co-doped bismuth–borate glasses

The spectroscopic properties of Er³⁺/Yb³⁺ co-doped Bi₂O₃–B₂O₃–WO₃ (BBW) glasses were analyzed and discussed. The effect of WO₃ content on the absorption spectra, the Judd–Ofelt parameters Ω_t (t=2, 4, 6), emission spectra and the lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition were also investigated. With the substitution of WO₃ for B₂O₃, the measured lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition increase from 0.98 to 1.31 ms and from 38.2% to 49.2%, respectively. The effective width of emission band and the emission cross-section both decrease slightly. And the emission spectra is analyzed via the different curve (σ_e−σ_a) of BBW glasses, the influence of OH⁻is also discussed.     

High temperature transport processes in lithium niobate

The electrical conductivity of single crystal lithium niobate (LiNbO₃) was determined as a function of temperature for various oxygen partial pressures. The electrical conductivity is proportional to P_o2^−1/4 which can be explained by a defect equilibrium involving singly ionized oxygen vacancies and electrons.

Measurements of electrical transport numbers at 1000°K show the electrical conductivity of LiNbO₃ to be ionic at one atmosphere of oxygen and electronic at low oxygen partial pressures.

Thermoelectric measurements indicate that LiNbO₃ at low oxygen partial pressures is n-type and that the concentration of electrons at 1000°K and in an atmosphere of 50% C0/50% CO₂a is 4 × 10¹⁷cm³ with a mobility of 1.7 cm²V sec.

The diffusion of oxygen in LiNbO₃ was determined as a function of temperature at an oxygen partial pressure of 70 Torr. by measuring O¹⁸/O¹⁶ isotope exchange with the gas phase as a function of time. The diffusion data may be represented by D = 3.03 × 10⁻⁶ exp (−29.4 kcal mole⁻¹/RT)cm²sec. Consideration of the Nernst-Einstein relation for oxygen and the variation in conductivity with Li₂O activity indicate that the ionic conduction is caused by transport of lithium ions.     

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.     

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.