杯[8]芳烃-硝酸稀土配合物的红外光谱及荧光性能

合成了以对叔丁基杯[8]芳烃(LH₈)、硝酸根及DMF为配体,单一稀土RE³⁺(Sm³⁺、Eu³⁺、Tb³⁺、Dy³⁺)及混合稀土Tb³⁺:Ln³⁺(Ln=La³⁺,Gd³⁺,Y³⁺)为中心的7种稀土配合物,对其进行了元素分析、摩尔电导、热谱、红外光谱及荧光性能研究.荧光光谱的测试表明所有Tb³⁺及其共掺杂配合物具有较强的特征荧光发射,荧光惰性离子La³⁺、Gd³⁺、Y³⁺对Tb³⁺的荧光有增强作用,其中Y³⁺的荧光增强作用最大,Gd³⁺次之,La³⁺最小.     

Y3+和Gd3+对LaBO3:Eu3+发光粉结构和发光性能的影响

采用溶胶凝胶-燃烧法合成了系列不同掺杂浓度Y³⁺和Gd³⁺的LaBO₃∶Eu³⁺发光粉,对其结构、形貌和发光性能进行了表征。XRD研究结果表明：发光粉的结构与基质掺杂离子的种类和掺杂浓度有关系。荧光光谱结果表明：适量比例Y³⁺和Gd³⁺离子掺杂将提高LaBO₃∶Eu³⁺发光粉的发光强度。Y³⁺和Gd³⁺离子最佳掺杂摩尔分数分别为1.5%和12.5%。⁵D₀→⁷F₂与⁵D₀→⁷F₁跃迁发射的相对强度比值说明：掺杂改变LaBO₃∶Eu³⁺中Eu³⁺局域环境的对称性。发光性能改变主要受晶体结构、掺杂离子电负性影响。Gd³⁺离子掺杂更有利于发光粉结构稳定性和发光性能的改善。     

NaZnLa(PO4)2中Ce3+和Tb3+的发光

采用高温固相反应合成了NaZnLa(PO₄)₂中掺杂Ce³⁺、Tb³⁺的荧光体,对其晶体结构、发光行为进行了研究,并尝试对NaZnLa(PO₄)₂:Ce,Tb荧光体进行调制。NaZnLa(PO₄)₂是LaPO₄的同构物,为单斜晶系独居石结构,从XRD谱数据得到NaZnLa(PO₄)₂基质的晶胞参数为a=0.6823nm,b=0.7045nm,c=0.6497nm,β=1039°,v=0.303nm³,其晶胞参数与单斜LaPO₄的晶胞参数相似。在NaZnLa(PO₄)₂:Ce,Tb荧光体中,Ce³⁺对Tb³⁺有良好的敏化作用,掺杂适量的BO₃^3-、Al³⁺、Dy³⁺,可以增强发光亮度。     

Dy3+掺杂Ge-Ga-S-CsI玻璃中红外发光特性研究

用熔融淬冷法制备了系列掺杂浓度的Dy³⁺:Ge-Ga-S-CsI硫卤玻璃样品,测试了样品拉曼光谱、折射率、吸收光谱、近红外及中红外荧光谱.应用Judd-Ofelt理论计算了Dy³⁺离子的强度参数 (Ω_i, i=2,4,6)、自发辐射跃迁概率(A)、荧光分支比(β)、以及辐射寿命(τ_rad)等光谱参数.研究了810 nm激光抽运下样品中红 关键词： 硫系玻璃 中红外发光 3+掺杂')" href="#">Dy³⁺掺杂 多声子弛豫     

钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.     

两种宽谱带蓝光发射材料的制备、表征及光学特性

合成了两种以钙为中心金属离子的有机电致发光材料2-(2-羟基苯基)苯并噻唑钙Ca(BTZ)₂和2-(2-羟基苯基苯并噻唑)-(1,10-邻菲罗啉)合钙Ca(BTZ)₂phen。通过红外光谱、紫外-可见光吸收光谱、循环伏安曲线、原子力显微镜以及光致发光光谱表征了材料的结构、光学带隙、能带结构、成膜性以及光学性能。实验结果表明,在DMSO溶液中,Ca(BTZ)₂的紫外吸收峰主要为290,330,422nm;Ca(BTZ)₂phen的紫外吸收峰主要为292,330,428nm。Ca(BTZ)₂的荧光发射峰为458nm和500nm,色坐标为x=0.2176,y=0.3223;Ca(BTZ)₂phen的荧光发射峰主要为465nm和514nm,色坐标为x=0.2418,y=0.3817。利用真空热蒸镀法可以得到均匀致密的Ca(BTZ)₂phen的薄膜,其粗糙度为1.56。Ca(BTZ)₂薄膜也有望通过旋涂制备。实验发现Ca(BTZ)₂与Ca(BTZ)₂phen的荧光光谱几乎覆盖整个可见光区域,为宽谱带发光材料,有望设计成合理的器件结构实现白光发射。     

NaLn4-x(SiO4)3F：xRE3+(Ln=La,Gd;RE=Tb,Dy, Sm,Tm)荧光材料的发光性能

利用简单的高温固相法合成稀土离子掺杂的NaLn_4-x(SiO₄)₃F:xRE³⁺(Ln=La, Gd; RE=Tb, Dy, Sm, Tm)系列荧光粉,利用X射线粉末衍射仪和荧光分光光度计分别测试其物相结构和荧光性能。结果表明,所合成样品均为纯的六方晶系结构,在紫外光激发下所合成样品均表现出所掺杂稀土离子的f-f特征能级跃迁,Tb³⁺、Dy³⁺、Sm³⁺和Tm³⁺等激活离子分别发出蓝绿色、白色、橙色以及蓝色等荧光发射。     

Gd3+/Y3+共掺对Nd:CaF2晶体光谱性能的影响

通过坩埚下降法生长了系列共掺Nd,Gd:CaF₂和Nd,Y:CaF₂晶体, 研究了Gd³⁺/Y³⁺共掺对Nd³⁺光谱性能以及Nd:CaF₂晶体晶胞参数的影响规律. 对于0.5 at.%Nd, x at.%Gd(x=2,5,8,10):CaF₂系列晶体, 当调控Gd³⁺掺杂浓度为2 at.%时, 具有最大的荧光寿命499 μs; 当Gd³⁺掺杂浓度为5 at.%时, 具有最大的吸收截面1.47×10^-20 cm², 最大的发射截面1.9×10^-20 cm²; 当Gd³⁺掺杂浓度为8 at.%时, 具有最佳的发射带宽29.03 nm. 对于0.6 at.%Nd, xat.%Y(x=2, 5, 8, 10):CaF₂系列晶体, Y³⁺掺杂浓度为5 at.%时, 有最大的吸收截面2.41×10^-20 cm², 最大的发射截面3.17×10^-20 cm²; 当Y³⁺掺杂浓度为10 at.%时, 具有最长的荧光寿命359.4 μs,并且具有最大发射带宽26 nm.     

Dy,Co共掺杂对BiFeO3陶瓷磁特性和磁相变温度Tc的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0, 0.05, 0.1, 0.15)陶瓷样品. 实验结果表明: 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⁺掺杂量的增大, Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品的主 衍射峰由双峰(104)与(110)逐渐重叠为单峰(110), 当掺杂量x>0.05时, 样品呈现正方晶系结构; SEM形貌分析可知: Dy³⁺, Co³⁺共掺杂使BiFeO₃晶粒尺度由原来的3—5 μ减小到约1 μ. 室温下, BiFeO₃样品表现出较弱的铁磁性, 随着Dy³⁺和Co³⁺掺杂, BiFeO₃样品的铁磁性显著提高. 在外加磁场为30 kOe的作用下, Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0.05, 0.1, 0.15)的M_r分别为0.43, 0.489, 0.973 emu/g; M_S分别为0.77, 1.65, 3.08 emu/g. BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品磁矩M随着温度T的升高而逐渐减小, Dy掺杂使BiFeO₃样品的T_N由644 K升高到648 K, 而T_C基本没有变化. Dy和Co共掺杂导致BiFeO₃样品磁相变温度T_C由870 K降低到780 K, 其T_C变化主要取决于Fe-O-Fe反铁磁超交换作用的强弱和磁结构的相对稳定性. 关键词： 铁磁电材料 磁滞回线 磁相变温度     

在NaGdF4：Tm3+, Dy3+中Gd3+间的能量迁移及Gd3+-Dy3+能量传递量子效率

基于量子剪裁基本原理,通过光谱技术研究NaGdF₄:Tm³⁺,Dy³⁺在一个真空紫外光子激发下获得两个蓝色光子的可能性。在这种化合物中,量子剪裁通过下转换,即通过应用不同镧系离子间的能量传递进行。通过对Tm 4f¹²-4f¹¹5d激发,部分能量从Tm³⁺离子5d态直接传递给Gd³⁺,然后在Gd³⁺-Tm³⁺之间发生交叉弛豫,剩余能量从Gd³⁺传递给Dy³⁺,产生两个可见光子发射,一个来自Tm³⁺的¹G₄-³H₆跃迁,另一个来自Dy³⁺的⁴F_9/2-⁶H_15/2跃迁。主要研究获得以NaGdF₄:Tm³⁺,Dy³⁺为基础的新型具有更高效率,更高稳定性和更强真空紫外(VUV)吸收量子剪裁发光粉的可能性。各种光谱技术,如光致发光、激发和衰减等被用来表征不同Dy³⁺浓度掺杂NaGdF₄中Gd³⁺晶格间能量迁移引起的施主Gd³⁺和受主Dy³⁺之间的能量传递。结果表明Gd³⁺离子之间存在能量迁移,随之交换相互作用引起施主与受主(Gd³⁺-Dy³⁺)之间的能量传递。通过Bursh-tein等人关于激发态的弛豫理论,施主-受主能量传递参数k_DS可以从Gd³⁺的⁶P_7/2发射的衰减计算出。Gd³⁺-Dy³⁺能量传递量子效率也可以得到。NaGdF₄:Tm³⁺和NaGdF₄:Tm³⁺,Dy³⁺是由水热法制备的,NaGdF₄:Dy³⁺是由文献[4]方法制备的。发射光谱和激发光谱通过自制的VUV光谱仪和F-4500测量。衰减曲线由OPO激光器激发获得Gd³⁺-Dy³⁺之间能量传递量子效率在受主浓度大约在N_A=0.6%时达到最佳值,并且明显地观测到浓度猝灭效应。     

惰性稀土离子和抗衡离子对2-噻吩乙醛酸-铕配合物荧光性能的影响

研究了惰性稀土离子和抗衡离子对一系列2-噻吩乙醛酸-铕配合物荧光性能的影响。分别在2-噻吩乙醛酸-邻菲罗啉-铕和2-噻吩乙醛酸-三苯基氧化膦-铕两个体系中按不同比例掺入钇和钆,研究了它们的荧光光谱。结果表明,钇的加入对2-噻吩乙醛酸-邻菲罗啉-铕体系的荧光强度有很强的敏化作用,并且随加入量的增加,这种敏化作用逐渐增强。钇的加入对2-噻吩乙醛酸-三苯基氧化膦-铕体系则呈现出弱的敏化作用,且在一定程度上具有猝灭作用,但这两种作用都是很微小的。钆在少量加入时对2-噻吩乙醛酸-三苯基氧化膦-铕体系具有猝灭作用,当大量加入时则呈现出很强的敏化作用。不同的抗衡离子对配合物的影响是明显的。在二元配合物中,氯化物体系的固体荧光强度最大;在三元配合物中,硝酸盐体系的固体荧光强度最大。     

均苯三甲酸铕及铕镧配合物的合成及荧光性质

以均苯三甲酸为配体,水热条件下合成了均苯三甲酸铕及铕镧系列发光配合物La_xEu_1-x(BTC)·nH₂O(x=0,0.1,0.3,0.5,0.7,0.9),通过元素分析及化学滴定法测定了配合物的组成。用红外光谱对其进行了表征,确定了该系列配合物的组成为La_xEu_1-x(BTC)·nH₂O。研究了系列配合物的荧光性质,荧光光谱表明:该类配合物均能发出强的铕离子的特征荧光,并且镧元素的掺入能增强铕配合物的发光强度,但发射峰的位置基本上没有变化;其中⁵D₀→⁷F₁和⁵D₀→⁷F₂的跃迁发射较强,且均劈裂为两个峰(587,593nm)和(611,618nm),这是由于铕离子所处的配位环境引起的。     

Aging behavior and ionic conductivity of ceria-based ceramics: a comparative study

An understanding of high-temperature aging effects on the electrical properties of electrolytes is very important in selecting optimum compositions for practical applications. The aging behavior and mechanisms of doped zirconia ceramics have been extensively studied. However, little information is available regarding the aging behavior of ceria-based electrolytes. The present study has demonstrated that a high-temperature aging at 1000 °C has a significant effect on the ionic conductivity of the Y- or Gd-doped ceria (Ce_1−xY_xO_2−δ and Ce_1−xGd_xO_2−δ), especially in the case of the Gd doping. The aging behavior is characterized by a critical dopant concentration, above which the aging has a detrimental effect on the conductivity of the doped ceria ceramics. The aging behavior in the doped ceria cannot be explained using the aging mechanisms applied to the doped zirconia. Instead, the formation of the microdomains in the doped ceria has been acknowledged to be the main contribution to the aging behavior of the Y- or Gd-doped ceria ceramics. The formation ability of microdomains has been estimated to be in the order of La³⁺>Gd³⁺>Y³⁺, based on the degree of size mismatch between the dopant ion and Ce⁴⁺ ion. The critical dopant concentrations at which the microdomains start to form for La³⁺, Gd³⁺ and Y³⁺ in the doped ceria ceramics are x=0.15, 0.2 and 0.25, respectively. This critical dopant concentration is also an important indication: below which the conductivity is governed by only the association enthalpy, and above which the conductivity is dominated mainly by the microdomains rather than the association enthalpy.     

稀土离子对人血清白蛋白动态结构性质影响的23Na NMR研究

利用²³Na作为探针磁核,通过弛豫分析发现:稀土离子与HSA络合后使蛋白质分子体积膨胀,链段活动性增加,表现为相关时间(τ_c)减小;HSA可能至少有了3个高亲和位点可络合稀土离子;稀土离子诱导的HSA动态结构变化在某种程度上具有可逆性,即当高亲和位上的稀土离子被螯合剂在取后,膨胀伸展的结构趋于恢复原有状态。     

Simultaneous doping with La and Y for Ba- and Ce-sites in BaCeO3 and the ionic conduction

Powder X-ray diffraction (XRD) analysis showed that the single phase perovskite-type structure of Ba_1−xLa_xCe_0.90−xY_0.10+xO₃₋ (0 x 0.40, =0.05) could be maintained in a wide region of doping level by simultaneous partial substitution of La³⁺ for Ba²⁺-site and Y³⁺ for Ce⁴⁺-site in BaCeO₃. The conduction properties of these oxides were investigated using various electrochemical methods in the same concentration of oxygen vacancy (=0.05). At high oxygen partial pressure, these oxides exhibited a mixed oxide ionic and p-type electronic conduction while at low oxygen partial pressure their conduction was almost protonic. Among these oxides, BaCe_0.90Y_0.10O₃₋ exhibited the highest conductivities with a value of 1.24×10⁻¹ S/cm in dry oxygen, and 5.65×10⁻² S/cm in wet hydrogen at 1000°C. Both of the proton and oxide ion conductivities under oxygen and under hydrogen atmospheres decreased monotonically with the increasing substitution for Ba²⁺- and Ce⁴⁺-sites. The decreases in ion conductivities appear to relate to the decreased free volume (V_f) of crystal lattice as well as the increased distortion of lattice from ideal cubic perovskite structure.     

近紫外光激发黄色荧光粉Ba3Y4O9：Dy3+的制备及发光特性

通过高温固相法合成了一系列Ba₃Y_4-xO₉：xDy³⁺荧光粉材料。利用X射线粉末衍射、荧光光谱和荧光寿命对样品进行了表征。实验表明,样品的激发光谱由一系列线状峰组成,峰值分别位于328,355,368,386,427,456,471 nm。在355 nm激发下,荧光粉在490 nm（⁴F_9/2→⁶H_15/2）和580 nm（⁴F_9/2→⁶H_13/2）处有很强的发射,发射光谱的色坐标位于黄光区域。研究了不同Dy³⁺掺杂浓度对样品发光性质的影响,发现样品的发光随着Dy³⁺浓度的增大而增强,但光谱形状基本保持不变,表明Dy³⁺占据了基质中低对称性的Y³⁺格位。当Dy³⁺摩尔分数x=0.08时出现发光强度猝灭现象,浓度猝灭机理为电偶极-电偶极相互作用。样品的发光寿命随着Dy³⁺浓度的增大逐渐减小,进一步证明了Dy³⁺离子之间存在着能量传递现象。Ba₃Y₄O₉：Dy³⁺荧光粉的发光位于黄光区域,有较好的热稳定性,是潜在的白光LED用荧光粉材料。     

Electronic structure and photoluminescence property of a novel white emission phosphor Na_3MgZr(PO_4)_3:Dy~(3+) for warm white light emitting diodes

To explore suitable single-phase white emission phosphors for warm white light emitting diodes, a series of novel phosphors Na_3MgZr(PO_4)_3:xDy~(3+)(0 ≤ x ≤ 0.03) is prepared, and their phase purities as well as photoluminescence properties are discussed in depth via x-ray diffraction structure refinement and photoluminescence spectrum measurement.The electronic structure properties of the Na_3MgZr(PO_4)_3host are calculated. The results reveal that Na_3MgZr(PO_4)_3 possesses a direct band gap with a band gap value of 4.917 e V. The obtained Na_3MgZr(PO_4)_3:Dy~(3+) phosphors are all well crystallized in trigonal structure with space group Rc, which has strong absorption around 365 nm and can generate warm white light emissions peaking at 487, 576, and 673 nm upon ultraviolet excitation, which are attributed to the transitions from ~4F_(9/2) to ~6H_(15/2),~6H_(13/2), and ~6H_(11/2) of Dy~(3+) ions, respectively. The optimal doping content, critical distance, decay time, and Commission International de L'Eclairage(CIE) chromaticity coordinates are investigated in Dy~(3+) ion-doped Na_3MgZr(PO_4)_3. The thermal quenching analysis shows that Na_3MgZr(PO_4)_3:Dy~(3+) has a good thermal stability, and the thermal activation energy is calculated. The performances of Na_3MgZr(PO_4)_3:Dy~(3+) make it a potential single-phase white emission phosphor for warm white light emitting diode.     

Shaped crystal growth and scintillating properties of Yb:(Gd,Lu)3Ga5O12 solid solutions

Shaped single crystals of (Lu_xGd_1−x)₃Ga₅O₁₂ (0.0x1.0) and (Yb_0.05Lu_xGd_0.95−x)₃Ga₅O₁₂ (0.0x0.9) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃Ga₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect-host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.