Er3+/Yb3+共掺Gd3Sc2Ga3O12晶体的上转换发光

研究了提拉法生长的Er³⁺/Yb³⁺:Gd₃Sc₂Ga₃O₁₂和Er³⁺:Gd₃Sc₂Ga₃O₁₂晶体在室温下320—1700nm范围的吸收光谱和500—750nm范围内的上转换荧光谱,同时对其上转换荧光的可能发生机制、途径以及上转换过程可能对Er^{3+相似文献}   

第一性原理研究LuAlO3中掺杂Ce3+的4f-5d跃迁性质

通过对基态4f电子采用杂化密度泛函理论方法、对5d激发态采用限制性布居方法,研究了LuAlO₃:Ce³⁺体系4f-5d跃迁的相关性质．结果表明,伴随着4f到5d的跃迁,Ce³⁺与8个最近邻配位O原子的平均键长缩短了0.05 ?,而且Stokes位移计算值与实验值相当吻合．在优化计算得到的LuAlO₃:Ce³⁺体系4f基态局域构型基础上,采用角重叠模型计算了5d能级的晶场分裂,与实验结果吻合较好.     

Er3+/Ce3+共掺TeO2-Bi2O3-TiO2玻璃的热稳定性和光谱特性研究

用高温熔融法制备了Er³⁺/Ce³⁺共掺新型碲酸盐玻璃(TeO₂-Bi₂O₃-TiO₂).采用差热分析方法研究了玻璃的热稳定性,测试并分析了不同Ce³⁺离子掺杂浓度下Er³⁺离子的吸收光谱、上转换光谱和荧光光谱特性.研究结果表明,制备的碲酸盐玻璃具有很好的热稳定性,玻璃析晶温度Tx与玻璃转变温度Tg之差(ΔT=Tx-Tg)达到了185 ℃,高于其它文献的报道|同时,Ce3+离子共掺引入的能量转移(Ce³⁺∶2F5/2+Er³⁺∶4I11/2→Ce³⁺∶2F7/2+Er³⁺∶4I13/2)有效地抑制了Er³⁺离子上转换发光并显著增强了1.53 μm波段荧光强度,而发射截面随着Ce³⁺离子掺杂浓度相应增大.优异的热稳定性以及光谱性能揭示Er³⁺/Ce³⁺共掺碲酸盐玻璃是一种潜在的制备宽带掺铒光纤放大器的理想增益介质.     

Er3+/Ce3+共掺碲铋酸盐玻璃的制备及光谱特性提高研究

采用高温熔融退火法制备了系列 80TeO₂-10Bi₂O₃-10TiO₂-0.5Er₂O₃-xCe₂O₃ (x=0,0.25, 0.5,0.75,1.0 mol%)和(80-y) TeO₂-10Bi₂O₃-10TiO₂-yWO₃-0.5Er₂O₃-0.75Ce₂O₃ (y=3,6,9,12 mol%)的碲铋酸盐玻璃.测试了玻璃样品400-1700 nm范围内的吸收光谱, 975 nm抽运下的上转换发光谱和1.53 μm波段荧光谱, 以及808 nm激励下的Er³⁺离子荧光寿命和无掺杂玻璃样品的Raman光谱, 并结合Judd-Ofelt理论和McCumber理论计算了Er³⁺离子光谱参数.结果表明, 在掺Er³⁺碲铋酸盐玻璃中引入Ce³⁺离子进行Er³⁺/Ce³⁺共掺, 通过Er³⁺离子⁴I_11/2能级与Ce³⁺离子²F_5/2 能级间基于声子辅助的能量传递过程,可以有效抑制Er³⁺离子上转换发光并明显增强其 1.53 μm波段荧光;同时,在现有Er³⁺/Ce³⁺共掺玻璃组分基础上引入WO₃, 可进一步提高1.53 μm波段荧光并展宽其荧光发射谱. 研究结果对于获取优异光谱特性的宽带掺Er³⁺光纤放大器玻璃基质具有实际意义.     

NaF晶体中电荷补偿掺杂Ce3+离子光谱性质的从头算

用从头算研究NaF晶体中Ce³⁺占据Na⁺格位时的光谱性质,电荷补偿由占据格位第一配位壳层的两个氟原子被氧取代 (O_F^') 或第二配位壳层的两个Na空位(_Na^') 来提供. 首先采用基于DFT的超单胞模型方法优化了Ce³⁺的局域结构,并构造以Ce为中心的镶嵌团簇,对其进行基于波函数理论的CASSCF/CASPT2/RASSI-SO计算,获得Ce³⁺的4f¹和5d¹组态分裂能级能量. 通过将4f→5d跃迁能量计算值与低温实验激发光谱比较,发现实验观测到的最低4f→5d跃迁谱带(390 nm)来自于两个最近邻O_F^'补偿的Ce³⁺离子,并不是文献中的两个次近邻V_Na^' 补偿的Ce³⁺. 最后从5d¹组态能级重心位移和晶场分裂两方面分析了由两个最近邻O_F^'取代造成最低4f→5d 跃迁红移约8000 cm^-1的原因.     

Er3+：GdVO4中Er3+离子的光谱参数计算和晶场中能级分裂的讨论

对Er³⁺：GdVO₄样品的光谱参数以及Er³⁺在晶场中能级的分裂情况进行了研究. 首先对样品进行了吸收光谱的测量，接着用Judd-Ofelt理论拟合出了Er³⁺在GdVO₄晶体中的强度参量Ω_t，并由此计算了跃迁的振子强度、自发辐射跃迁速率、荧光分支比和积分发射截面. 通过计算结果可以发现有较多能级之间的跃迁都有大于10^-6的振子强度和大于10^-18cm的积分发射截面，并且具有较高的荧光分支比，特别是²H_11/2→⁴I_15/2，⁴S_3/2→⁴I_15/2，⁴F_9/2→⁴I_15/2和⁴I_13/2→⁴I_15/2等几个强发光能级除了具有较大的振子强度和积分发射截面外还有很好的应用前景，因此也更加值得关注. 最后还利用群论讨论了Er³⁺离子在GdVO₄晶场中各能级的分裂情况并对各Stark子能级的J_z混杂情况进行了分析.     

Ce3+ 掺杂高密度氧化物玻璃的闪烁性能研究

用高温熔融法制备了以SiO₂-B₂O₃-Al₂O₃-Gd₂O₃为基质系统Ce³⁺掺杂的玻璃样品, 测试样品的密度、紫外——可见透射光谱、紫外激发光谱和主要的闪烁性能, 并且把一部分闪烁性能和PbWO晶体及BGO晶体做比较. 着重研究了不同Ce³⁺掺杂浓度与Gd³⁺ 离子的含量对玻璃样品闪烁性能的影响规律. 结果表明: 玻璃样品具有较大的密度; 样品的X射线激发发射光谱发射峰位置都在390 nm左右, 当Ce³⁺ 离子的掺杂浓度为1.0 mol%(摩尔分数)、Gd₂O₃含量为15 mol%时, 玻璃样品的发光峰强度达到BGO晶体发光强度的90%; 同样验证了Ce³⁺ 离子具有浓度猝灭效应; Gd³⁺可以敏化Ce³⁺离子发光, 但是Gd³⁺离子到达一定浓度时, 反而会产生猝灭效应, 降低了Ce³⁺ 离子的发光. Ce³⁺ 离子掺杂SiO₂-B₂O₃-Al₂O₃-Gd₂O₃系统的闪烁玻璃有望替代闪烁晶体广泛应用于高能物理中.     

Tm3+/Yb3+ ∶LaF3纳米体系中掺杂Yb3+ 离子对Tm3+ 离子荧光发射的影响

为研究Yb³⁺离子浓度变化对Tm³⁺离子在蓝色波段荧光强度的影响,以NaF和La(NO₃)₃为原料,采用水热法制备了Tm³⁺和Yb³⁺共掺的Tm³⁺/ Yb³⁺∶LaF₃纳米颗粒.用X射线衍射对LaF₃纳米颗粒进行表征的结果显示,纳米晶体结构呈六方相.透射电镜的观测结果显示,纳米颗粒样品大小均匀、分散性良好.在波长为800 nm的激光激发下,观测到了上转换蓝光发射,其中包括波长为474 nm和479 nm的较强的荧光辐射(相应的跃迁为1G4→3H6)和波长位于450 nm的强度较弱的荧光发射(相应的跃迁为1D2→3F4).通过观测不同Yb³⁺离子浓度条件下共掺Tm³⁺/Yb³⁺∶LaF₃样品的荧光光谱,研究了Yb³⁺离子掺杂浓度对于Tm³⁺离子的荧光发射的影响,并探讨了产生这种现象的原因.研究结果显示,对于1G4→3H6跃迁产生的荧光发射(474 nm),当Yb³⁺离子浓度增大时,反向能量传递速率的增加导致了荧光强度的增大.然而,当Yb³⁺离子浓度增大到一定程度时,Yb³⁺离子激发态能级寿命的减少将引发荧光强度的下降.相比较而言,Yb³⁺离子的浓度的变化对于1D2→3F4跃迁产生的位于450 nm处荧光强度的影响较弱.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(t=2, 4, 6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

Gd2O3:Eu3+纳米晶的燃烧合成及光致发光性质

采用柠檬酸作燃烧剂用燃烧合成法制备了Gd₂O₃:Eu³⁺纳米晶.用X射线衍射仪(XRD)、高分辨透射电子显微镜(HRTEM)和荧光分光光度计等对Gd₂O₃:Eu³⁺纳米晶的结构、形貌和发光性能进行了分析.结果表明：不同柠檬酸与稀土离子配比(C/M)制备的样品经800℃ 退火1 h后，均得到了纯立方相的Gd₂O₃:Eu³⁺纳米晶，晶粒尺寸约为30 nm，尺寸分布较窄，其中以C/M=1.0时制备的纳米晶结晶性最好，发光强度最大.Gd₂O₃:Eu³⁺纳米晶主发射峰位置均在612 nm处 (⁵D₀→⁷F₂跃迁)，激发光谱中电荷迁移态发生红移，观察到Gd³⁺向Eu³⁺的有效能量传递.对柠檬酸与稀土离子配比(C/M)对结晶度、发光性质等的影响也进行了分析和讨论.     

Physical properties of BaMg1/3Nb2/3O3-BaCo1/3Nb2/3O3 solid solutions

Structural, electric and magnetic properties of Ba₃Mg_1−xCo_xNb₂O₉ based dielectric ceramic compounds have been studied. The samples, prepared by a solid state reaction method, were characterised by X-ray powder diffraction (XRPD), electron microscopy (SEM), dielectric (ε(T)) and magnetic measurements (χ⁻¹(T)). The XRPD analyses showed that the crystal structure of these compounds does change by the increase of substitution degree, passing from a superstructure hexagonal-type, (no. 164), space group (SG) to a simple structure cubic-type, (no. 221), SG. However, the evolution of the elementary unit cell lattice parameter can be followed and it exhibit a linear increasing tendency with increase in the substitution, indicating the existence of a solid solution through out the investigated range of substitution (0-1). The microstructure analysis shows a variation in the grain size and also the porosity of the samples with the degree of substitution. The results are in good agreement with that of dielectric measurements, which also showed that the dielectric constant (ε) increases with the increase of cobalt content. The magnetic characterization of cobalt substituted samples showed an antiferromagnetic type super-exchange interaction between these magnetic ions. At the same time, the values of effective magnetic momentum (μ_eff) are close to the value that corresponds to Co²⁺ free ions. The study highlights the possibility of modelling these materials by substitutions, in order to improve properties of negative-positive-zero (NPO) type dielectric applications.     

La0.67Ca0.33MnO3薄膜皮秒光电效应

在1064 nm波长脉冲激光（脉宽25 ps）的照射下，钙钛矿氧化物薄膜La0.67Ca0.33MnO3/SrTiO3具有超快光电效应，对激光脉冲显示ps量级的响应时间，上升沿响应时间300 ps，半高宽700 ps，同时，对激光能量的响应灵敏度为500 mV/mJ。     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Giant dielectric relaxation in SrTiO3-SrMg1/3Nb2/3O3 and SrTiO3-SrSc1/2Ta1/2O3 solid solutions

Ceramic samples of (1−x)SrTiO₃-xSrMg_1/3Nb_2/3O₃ and (1−x)SrTiO₃-xSrSc_1/2Ta_1/2O₃ were prepared, and their dielectric properties were studied at x=0.005–0.15 and 0.01–0.1, respectively, at frequencies 10 Hz–1 MHz and at temperatures 4.2–350 K. A giant dielectric relaxation was observed in the temperature range 150–300 K, and not so strong but well-developed relaxation was found in the temperature range 20–90 K. The activation energy U and the relaxation time τ₀ were determined to be 0.21–0.3 eV and from 10⁻¹¹ to 10⁻¹² s for the high-temperature relaxation and 0.01–0.02 eV and 10⁻⁸–10⁻¹⁰ s for the low-temperature relaxation, respectively. The additional local charge compensation of the heterovalent impurities Mg²⁺ and Nb⁵⁺ (or Sc³⁺ and Ta⁵⁺) by free charge carriers or the host ion vacancies is suggested to be the underlying physical mechanism of the relaxation phenomena. On the basis of this mechanism, the Maxwell-Wagner model and the model of reorienting dipole centers Mg²⁺ (or Sc³⁺) associated with the oxygen vacancy are proposed to explain the high-temperature relaxation with some arguments in favor of the latter model. The polaron-like model with the Nb⁵⁺-Ti³⁺ center is suggested as the origin of the low-temperature relaxation. The reasons for the absence of ferroelectric phase transitions in the solid solutions under study are also discussed. From Fizika Tverdogo Tela, Vol. 44, No. 11, 2002, pp. 1948–1957. Original English Text Copyright ? 2002 by Lemanov, Sotnikov, Smirnova, Weihnacht. This article was submitted by the authors in English.     

La2/3Ca1/3MnO3/Eu2CuO4/La2/3Ca1/3MnO3磁性隧道结的制备与表征

采用磁控溅射，紫外线光刻和离子束刻蚀制备了La_2/3Ca_1/3MnO₃/Eu₂CuO₄/La_2/3Ca_1/3MnO₃磁性隧道结.通过对获得的磁性隧道结的I-V特性测量，发现非线性的I-V特性，显示结样品的隧穿特性.有趣的是发现在电极材料La_2/3Ca_1/3MnO₃的金属-绝缘体转变温度(Tp)以下，I-V曲线出现一个跳变.随着温度降低，开始出现跳变的临界电流增大，但是跳变都发生在同样的电压下～209mV.当电流增大或减小在跳变点附近出现回滞.这一跳变只发生在铁磁金属态，表明这是一个磁性相关联的效应，可能对应一种新的磁性开关过程.虽然，目前对这一现象背后的物理机理还不清楚，但是，这一现象有可能在未来自旋电子学器件方面具有潜在的应用价值. 关键词： 庞磁电阻 磁性隧道结 开关效应     

Phase formation and characterization of Sr3Y2Ge3O12, Sr3In2Ge3O12, and Ca3Ga2Ge3O12 doped by trivalent europium

This work reports on the phase formation during a solid-state reaction of Eu³⁺-doped garnets with the general formula A₃B₂Ge₃O₁₂ (A=Ca, Sr and B=Ga, In, Y) and their luminescent properties. It is shown by XRD and DTA/TG experiments that the garnet-phase formation is completed at 1100-1200 °C. Moreover, it turned out that the position of the oxygen to europium charge-transfer band and the intensity of the forbidden 4f-4f transitions of Eu³⁺ is dependent on the covalent interaction between the Eu³⁺ activator and the surrounding oxygen anions. The investigated red-emitting luminescent materials show high lumen equivalents and deep red emission at the same time, which makes them attractive for the application in LEDs (light emitting diodes), in particular for near UV-emitting LEDs.     

The ν3 and 2ν3 bands of SO3, SO3, SO3, and SO3

This sixth of a series of publications on the high-resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the ν₃ and 2ν₃ infrared bands of the four symmetric top isotopomers ³²S¹⁶O₃, ³²S¹⁸O₃, ³⁴S¹⁶O₃, and ³⁴S¹⁸O₃. An internal coupling between the l=0(A₁^′) and l=2(E^′) levels of the 2ν₃ states was observed. This small perturbation results in a level crossing between |k−l|=9 and 12, in consequence of which the band origins of the A₁^′,l=0 “ghost” states could be determined to a high degree of accuracy. Ground and upper state rotational constants as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species ³²S¹⁶O₃ and ³⁴S¹⁶O₃ vary only slightly, as do the constants for the ³²S¹⁸O₃, ³⁴S¹⁸O₃ pair. The S-O bond lengths for the vibrational ground states of the species ³²S¹⁶O₃, ³⁴S¹⁶O₃, ³²S¹⁸O₃, and ³⁴S¹⁸O₃ are, respectively, 141.981 99(1), 141.979 38(6), 141.972 78(8), and 141.969 93(8) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.     

Temperature-dependent photoluminescence in La2/3Ca1/3MnO3

Visible photoluminescence and its temperature dependence of La_2/3Ca_1/3MnO₃ in the temperature range 138-293 K were measured. It was observed that the main broad band centered at ∼1.77 eV with the shoulders at ∼1.57 and ∼1.90 eV existed in the entire temperature range. It can be well fitted by three Gaussian curves B₁, B₂ and B₃ centered at ∼1.52, ∼1.75 and ∼1.92 eV, respectively. The intensities of the peak B₁ and B₂ vary as temperature increases. In the entire temperature range, the intensity of B₁ increases with increasing temperature, whereas that of B₂ decreases. The photoluminescence mechanisms for La_2/3Ca_1/3MnO₃ are presented based on the electronic structures formed by the interactions among spin, charge and lattice, in which B₁ was identified with the charge transfer excitation of an electron from the lower Jahn-Teller split e_g level of a Mn³⁺ ion to the e_g level of an adjacent Mn⁴⁺ ion, B₂ is assigned to the transition between the spin up and spin down e_g bands separated by Hund's coupling energy E_J and B₃ is attributed to the transition, determined by the crystal field energy E_C, between a t_2g core electron of Mn³⁺ to the spin up e_g bands of Mn⁴⁺ by a dipole allowed charge transfer process.     

Fluoride glasses in the InF3-GaF3-YF3-PbF2-CaF2-ZnF2 system

New glasses have been synthesized in a multicomponent system based on indium fluoride. Samples of a few mm in thickness were obtained. They are transparent and homogeneous. Main physical properties such as density, characteristic temperatures, density, thermal expansion and refractive index have been measured. The evolution versus composition is reported for samples with the formula: (35−x) InF₃-xGaF₃-10YF₃-25PbF₂-15CaF₂-15ZnF₂. T_g lies between 260 and 296 °C while melting starts around 480 °C. Glass samples are stable at room temperature. By comparison with other standard fluoride glasses, they exhibit higher refractive index and density.     

RbIO3-HIO3和CsIO3-HIO3两个赝二元系的研究

用X射线衍射及差热分析法研究了两系统的相平衡。确定了RbH₂(IO₃)₃的结构(三斜晶系,点阵常数:a=8.338?,b=8.244?,c=8.254?,α=60.66°,β=85.58°,γ=66.01°,z=2)。密度D_m=4.61g/cm³。CsIO₃-HIO₃系中有两个化合物:CsH(IO₃)₂(为质子导体)和3CsIO₃·17HIO₂。 关键词：