锂铌比对铪铁铌酸锂晶体全息存储性能的影响

以掺杂4mol%Hf4+的LiNbO3:Fe:Hf系列晶体([Li]/[Nb]比变化)为研究对象,研究了系列晶体的可见吸收光谱,在632.8nm的写入光下晶体的衍射效率、灵敏度和抗光散射能力在不同[Li]/[Nb]下的变化规律.研究发现Hf4+的浓度达到阈值浓度后,随着[Li]/[Nb]比的增大,晶体的可见吸收边会发生红移,而且晶格中[Fe2+]/[Fe3+]也会增加,这就导致随着[Li]/[Nb]比的增加,样品的衍射效率逐渐减小,写入时间缩短,灵敏度增大.同时,在晶体中,随着[Li]/[Nb]的增大,陷阱中心Fe2Li+数量增大会使得晶体抗光散射能力减弱.     

掺镁铌酸锂晶体抗光损伤机理的研究

通过测试Mg(5mol%):LiNbO₃、Mg(4m0l%):LiNbO₃和LiNbO₃等晶体的光损伤阈值、红外透射光谱、倍频性能等,研究了Mg²⁺在Mg:LiNbO₃晶体中所处的状态以及高掺镁抗光损伤能力增强的机理。     

近化学计量比铌酸锂晶体周期极化畴反转特性研究

采用K2O作助熔剂直接拉晶法和气相输运平衡技术制备出了高质量近化学计量比铌酸锂晶体,研究了铌酸锂晶体中的[Li][Nb]比含量对其畴反转结构和极化电场的影响.实验结果表明:随着晶体中[Li][Nb]比的提高,畴极化反转电场呈明显下降趋势,使用近化学计量比铌酸锂晶体,在4.0±0.5kVmm大小极化电场条件下,成功地实现了1.0mm厚度的周期极化畴反转.并用铌酸锂晶体的Li空位缺陷模型对上述实验结果给出了合理的解释. 关键词： 近化学计量比铌酸锂晶体 周期极化 畴反转     

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.     

掺Bi离子锗铌酸盐红外发光玻璃的研究

用高温熔融法制备了Bi₂O₃掺杂的(0.9-x) GeO₂-xNb₂O₅-0.1BaO (含量x为摩尔分数, x=0, 0.04, 0.07, 0.1)系列玻璃. 测定了玻璃样品的差热分析(DTA)曲线、吸收光谱、发射光谱及X射线光电子能谱(XPS). 从DTA曲线分析得到玻璃的结晶起始温度与软化温度之差(T_x-T_g)达200℃以上. 吸收光谱中可观察到位于500, 700, 808和1000 nm处的吸收峰, 并随着Nb₂O₅含量x的增加吸收边带发生红移. 在波长为808 nm激光激发下, 观察到发光中心位于1300 nm处、荧光光谱半高宽约为200 nm的宽带发光. 荧光强度随Bi₂O₃掺杂量δ的增加先增强后减弱, 当掺杂量δ达到约0.01时, 荧光强度达到最强. 随着Nb₂O₅含量x从0.04增加到0.1时, 荧光强度逐步减弱. 样品的XPS峰分别位于159.6和164.7 eV, 它们介于Bi³⁺与Bi⁵⁺的特征结合能之间, 因此Bi³⁺与Bi⁵⁺可能同时存在于玻璃基质中. 从XPS及Bi离子的发光特性推断, 宽带的荧光发射可能起因于Bi⁵⁺. 随着Nb₂O₅含量x的增加, 荧光强度逐步减弱. 分析认为, Nb₂O₅取代GeO₂后形成了NbGe缺陷, 需要低价Bi离子进行电子补偿, 因而抑制了Bi⁵⁺形成, 致使荧光强度减弱.     

Ce:Co:LiNbO3晶体光折变性能研究

在LiNbO₃中掺进CeO₂和Co₃O₄,以Czchralski技术首次生长Ce:Co:LiNO₃, Ce:LiNbO₃, Co:LiNbO₃晶体.通过测试Ce:LiNbO₃, Co:LiNbO₃和Ce:Co:LiNbO₃晶体的指数增益系数, 位相共轭反射率和响应时间,计算晶体的有效载流子浓度和光电导.Ce离子能提高LiNbO₃晶体光折变灵敏度,Co离子能提高LiNbO₃晶体的响应速度和抗光致散射能力,从而Ce:Co:LiNbO₃晶体具有较高的指数增益系数,位相共轭反射率,响应速度.Ce:Co:LiNbO₃晶体具有优良的光折变性能.     

AN INVESTIGATION FOR THE Cd2+-VACANCIES IN RbCdF3 and CsCdF3 CRYSTALS DOPED WITH Fe3+ IMPURITIES

This paper presents high-order perturbation calculations for the zero-field splitting parameters D, F, and a of Fe³⁺-V_Cd pairs in RbCdF₃ and CsCdF₃ crystals doped with Fe³⁺ impurities. In comparison with experimental data, the present results are better than those obtained in previous work by using the phenomenological su-perposition model of spin-Hamiltonian. Moreover, the crystal fields arising from the Cd²⁺-vacancy and their induced crystal lattice distortion are analysed and calculated. It is found that the contribution from the Cd²⁺-vacancies cannot be ignored. Mena-while, we obtain that a ligand F^- along the [001]-axis moves towards the central Fe³⁺ ion by Δ= 0.0020nm in RbCdF₃ and 0.0028nm in CsCdF₃. These results are quite different from Δ = 0.0104nm and Δ = 0.0112nm, respectively, obtained in previous work by using the superposition model of spin-Hamiltonian and ignoring the effect of the vacancy.     

Gd,Co共掺杂对BiFeO3陶瓷电输运和铁磁特性的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Gd_0.05Fe_1-xCo_xO₃ (x= 0, 0.05, 0.1, 0.15, 0.2)陶瓷样品,研究Gd, Co共掺杂对BiFeO₃微观结构, 介电性能和铁磁性的影响. X射线衍射谱表明:所有样品的主衍射峰与纯相BiFeO₃相符合且 具有良好的晶体结构,随着Co³⁺掺杂量x的增大, Bi_0.95Gd_0.05Fe_1-xCo_xO₃样品的主衍射峰(104)与(110)逐渐相互重叠, 当x大于0.1时, 样品呈现正方晶系结构; J-V特性显示Gd³⁺, Co³⁺共掺杂有效地降低BiFeO₃陶瓷的漏导电流,其降低幅度为1-2个数量级; 当f=10³ Hz时, Bi_0.95Gd_0.05Fe_0.8Co_0.2O₃的介电常数是BiFeO₃的6倍, 而Bi_0.95Gd_0.05Fe_0.95Co_0.05O₃和 Bi_0.95Gd_0.05Fe_0.85Co_0.15O₃样品的介电损耗最小,均为0.01.室温下, Bi_0.95Gd_0.05Fe_1-xCo_xO₃样品磁性与BiFeO₃相比显著增强. 在磁场为30 kOe的作用下,Bi_0.95Gd_0.05Fe_1-xCo_xO₃ (x= 0, 0.05, 0.1, 0.15, 0.2)的剩余磁化强度M_r分别是BiFeO₃的34, 60, 105, 103, 180倍.样品磁性增强的主要原因是Gd, Co掺杂使BiFeO₃的晶格结构发生变化导致BiFeO₃自身储存的磁性能被释放, Gd³⁺的4f电子与Fe³⁺或Co³⁺的3d电子自旋相互作用及样品中存在局域的 Fe-O-Co磁耦合三者共同作用的结果.     

针状纳米MnxNi0.5-xZn0.5Fe2O4的共沉淀法制备及表征

通过在碱液中共沉淀Mn²⁺、Ni²⁺和Fe²⁺后制备了棒状的前躯体,前躯体于不同温度煅烧后制得了Mn_xNi_0:5-xZn_0:5Fe₂O₄棒状体. 利用X射线衍射仪和透射电镜对棒状体的物相、形貌及粒径进行了表征,并利用振动样品磁强计对磁性能进行研究. 结果表明长径比大于15的棒状,随着x值的增加,Mn_xNi_0:5-xZn_0:5Fe₂O₄样品的直径增加,长度下降,长径比变小,当x=0.5时其直径在50 nm左右而长径比减小到7～8. 随着x值的增加,样品的矫顽力先增加后减少,x值达到0.4时样品的矫顽力再次增加,当煅烧温度为600 oC,x=0.5时样品的矫顽力最大为134.3 Oe. 饱和磁化强度随着x值的增加先增加后减少,当煅烧温度为800 oC和x=0.2时达到最大为68.5 Oe.     

Fe3+离子在钠-硼玻璃中的顺磁共振

研究了Fe³⁺离子在钠-硼玻璃中的顺磁共振。在表观g=4.27处,有一条尖锐的大致对称的共振线。实验结果表明Fe³⁺离子代替接触二个钠离子的[BO₄]四面体中的硼离子位置。     

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.     

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.     

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.     

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.     

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.     

Studies of absorption spectra and the photovoltaic effect in LiNbO3:Mg:Fe crystals

The absorption spectra, photoconductivities and photovoltaic currents of LiNbO₃:Fe crystals with different Mg doping levels and Li/Nb ratios in the oxidized state have been investigated at room temperature. The Fe²⁺ ions in LiNbO₃:Mg:Fe with Mg content above a critical value are more easily oxidized than in crystals with Mg content below a critical value. The photoconductivity of LiNbO₃:Mg:Fe crystals with Mg content above a critical value is one order of magnitude higher than those with Mg content below a critical value, however, the photovoltaic current of the former is one order of magnitude lower than the latter. The differences are postulated to be due to different sites of Fe in these two classes of 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.     

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.     

Ferroelectric domain inversion in near-stoichiometric lithium niobate for high efficiency blue light generation

LiNbO₃ single crystals with a composition close to stoichiometry ([Li]/[Li+Nb]=0.496), 16 mm in diameter and 40 mm in length were grown by the Czochralski method using K₂O flux. The domain reversal characteristics of near-stoichiometric LiNbO₃ single crystals were investigated. The switching field required for 180° ferroelectric domain reversal in the near-stoichiometric crystal at room temperature was 7.5 KV/mm. This is about one third of the switching field required for conventional LiNbO₃ crystals. Domain reversal (180°) in near-stoichiometric LiNbO₃ samples of 1.0 mm thickness has been achieved. Samples have been evaluated by second harmonic generation and conversion efficiencies of up to 32% have been obtained. Received: 8 November 2000 / Accepted: 29 January 2001 / Published online: 20 June 2001