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.     

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.     

Li+和Er3+掺杂对Ba2SiO4：Eu2+发光性能的影响

采用化学沉淀法一次煅烧工艺制备了Ba_1.99-x/2-2ySiO₄:Eu_0.01²⁺, Li_x+y²⁺, Eu_y³⁺绿色荧光粉, 用X射线衍射仪和荧光分光光度计对样品的晶体结构、发光性能进行表征. 结果表明: 少量Eu²⁺, Li⁺和Er³⁺的共掺杂没有改变晶体结构; 其激发光谱分布在270–440 nm波长范围, 谱峰位于288 nm, 360 nm处, 可以被InGaN 管芯产生的360–410 nm辐射有效激发; 在360 nm近紫外光激发下, 测得其发射光谱峰值在500 nm 处, 是Eu²⁺4f⁶5d¹→4f⁷跃迁的典型发射; 荧光粉发光强度随着Li⁺掺杂量的增大先增强, 后减弱, 当x=0.1时, 发光强度最大; 随着Li⁺, Er³⁺共掺杂量的增加(y=0.012), 出现位于530 nm和488 nm的发射峰, 对应于Er³⁺的²H_11/2→⁴I_15/2和⁴F_7/2→⁴I_15/2特征发射, 同时分析了Eu²⁺→Er³⁺的能量传递过程. 关键词： 化学沉淀法 2SiO₄：Eu²⁺,Li⁺,Er³⁺')" href="#">Ba₂SiO₄：Eu²⁺,Li⁺,Er³⁺ 能量传递 发光性能     

Red emission of PbWO4 crystals

Luminescence characteristics of a large number of undoped and doped PbWO₄ crystals, grown by the Czochralski or Bridgman method, as-grown or annealed in the nitrogen atmosphere or in air, were studied in the 4.2–300 K temperature range. Two types of red emission centres were found. The centres with the emission band, peaking at 4.2 K at 1.57 eV, were observed in most of the crystals studied. The centres with the emission band, peaking at 4.2 K at 1.48 eV, were observed only in the PbWO₄ : Mo⁶⁺, Y³⁺ crystal. It is suggested that incompletely compensated lead vacancies are responsible for the appearance of the red emission.     

Electronic states and transition probabilities of the Au center in KCl

The emission spectra and lifetimes of the Au^— center in KCl crystals were measured. The Au^— concentration was measured by counting the activity of a radioactive tagged sample to determine the oscillator strength of the electronic transitions. The lifetime of the A'emission is calculated from the oscillator strength and is close to the experimental value of 103 ns at 4 K. The lifetimes and intensities of the Au^— emission bands C', B', A' and were measured between 4 and 500 K. The A'emission consists of a fast and slow decaying component. Time-resolved emission spectroscopy improved the measurements of the emission. From the temperature dependence of the lifetimes and intensities it is found that the radiating states of the A' and emission ³T_1u and ³A_1u are coupled by radiationless transitions. These transitions and the radiationless transitions from the excited state of the B' emission must be described as transitions between weakly coupled states similar to the radiationless transitions in rare earth ions. The excited state of an absorption band at 236 nm is responsible for the C' emission. Both the C' emission and the 236 nm absorption are phonon-induced transitions. The most probable explanation for the C' excited state is that the C' as well as the B' excited states come from the atomic state ³P₂ which is split into ³T_2u and ³E_u by the crystal field. The splitting energy is 0.9 eV and implies that one should look for the same effect in other s² centers.     

Self-trapped excitons perturbed by Na in KCl crystal

The optical absorption and emission induced by electron irradiation of Na⁺-doped KCl was measured and new absorption and emission bands which decay at the same time constant were found and ascribed to the self-trapped exciton perturbed by Na⁺ impurity.     

Na+替位掺杂对Li2MnSiO4的电子结构以及Li+迁移过程的影响

在锂二次电池中, 硅酸锰锂作为正极材料得到广泛研究, 但其固有的电子和离子电导率较低, 直接影响着电池的功率密度和充放电速率. 本文建立了不同浓度的Na⁺离子替位掺杂Li⁺离子形成的Li_1-xNa_xMnSiO₄(x=0, 0.125, 0.25, 0.5)结构, 采用第一性原理的方法, 研究了掺杂前后硅酸锰锂的电子结构以及Li⁺离子的跃迁势垒. 发现在Li⁺位替代掺杂Na⁺, 导带底的能级向低能方向发生移动, 降低了Li₂MnSiO₄ 材料的禁带宽度, 有利于提升材料的电子导电性能. 随着掺杂浓度的升高, 禁带宽度逐渐变窄. CI-NEB结果表明, 在Li₂MnSiO₄体系中具有两条有效的Li⁺离子迁移通道, 掺杂Na⁺以后扩大了Li⁺ 离子在[100]晶向上的迁移通道, Li⁺离子的跃迁势垒由0.64 eV降低为0.48, 0.52和0.55 eV. 掺杂浓度为 x=0.125时, 离子迁移效果最佳. 研究表明Na⁺掺杂有利于提高Li₂MnSiO₄材料的离子和电子电导率.     

RAMAN STUDY ON $X_i^-$(Pb) CENTERS IN SINGLE CRYSTALS OF ALKALI HALIDES DOPED WITH LEAD

Low frequency modes were observed in a series of alkali halides doped with lead after X-irradiation at 77K. The peak positions of the Raman signals are at 34cm^-1 for NaCl:Pb²⁺, 30cm^-1 for KCl:Pb²⁺,28cm^-1 for RbCl:Pb²⁺ and 22cm^-1 for KBr:Pb²⁺. They are assigned to the inelastic light scattering caused by the local vibration of X^-_i (Pb⁺) center, which consists of an interstitial halogen ion stabilized by a substitutional ion Pb⁺ . Polarized Raman measurements and Behavior Typer(BT) analysis show that the symmetry of the X^-_i (Pb⁺) center belongs to the point group C_3v A structure model of the X^-_i (Pb⁺) center is proposed based on the Raman data and the result of BT analysis.     

Ce3+/Tb3+/Sm3+共掺CaO-B2O3-SiO2玻璃的光学性能调控

采用高温熔融法制备了Ce³⁺/Tb³⁺/Sm³⁺掺杂的CaO-B₂O₃-SiO₂（CBS）发光玻璃。通过傅利叶红外光谱仪、荧光光谱仪表征了该系列发光玻璃的微观结构和发光性质,并对Ce³⁺到Tb³⁺、Ce³⁺到Sm³⁺之间的能量传递机制进行了研究。结果表明,在339,378,407 nm激发下,单掺Ce³⁺、Tb³⁺和Sm³⁺的CBS玻璃分别发射紫蓝光、绿光和红光,恰好符合混合合成白光的条件。Ce³⁺/Tb³⁺和Ce³⁺/Sm³⁺双掺CBS玻璃的发射光谱以及Ce³⁺衰减寿命的变化证实了Ce³⁺→Tb³⁺和Ce³⁺→Sm³⁺之间存在能量传递,随Tb³⁺和Sm³⁺浓度增加,Ce³⁺的寿命减小,且传递效率由5.4%和5.7%分别增加至24.0%和27.1%。调节3种稀土离子的掺杂浓度并选择合适的激发波长,实现了发光颜色可调,并最终获得白光发射。     

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.     

Mn-Mg共掺杂AlON荧光粉制备及荧光性质

采用固相反应法成功合成了一系列Mn-Mg共掺的Al₂₃O₂₇N₅荧光粉。结果显示煅烧条件和Mn的掺杂浓度对Mn-Mg共掺的AlON荧光粉的制备和发光性质都有重要影响。获得纯相AlON的温度从未掺杂的1 900 ℃下降到10% Mn和10% Mg(摩尔分数)共掺杂的1 800 ℃。晶格参数随着Mn掺杂浓度升高而增加,说明Mn进入了AlON晶格中。未掺杂和Mg单掺以及10% Mn和10% Mg共掺杂样品的发射光谱都含有一个350～600 nm之间的宽带发射。绿光发射归属于Mn的3d电子之间的传输。蓝光发射可能与杂质或Al空位相关。     

Mn2+, Pb2+共掺杂ZnS纳米材料制备及光致发光

采用聚乙烯基吡咯烷酮(PVP)为表面包覆剂,在室温大气条件下的水溶液中制备了ZnS:Mn,Pb纳米晶。讨论了Mn²⁺和Pb²⁺掺杂量对ZnS纳米发光材料光致发光强度的影响,确定了Mn²⁺和Pb²⁺掺杂量相对于Zn²⁺的最佳的量的比,并对其发光机理进行了初步的探讨。     

KCdF3晶体中Cr3+-Li+中心局域结构研究

利用零场分裂参量与晶体结构之间的定量关系,研究了双掺杂晶体KCdF₃:Cr³⁺,Li⁺的局域结构。指出,对于KCdF₃:Cr³⁺,Li⁺晶体,四角晶场的形成包含两个方面:(1)由于电荷补偿而产生的等效电荷形成的四角对称晶场;(2)Cr³⁺的局域结构发生晶格畸变而产生的四角对称晶场。事实上,当Cr³⁺和Li⁺掺入KCdF₃晶体时,Cr³⁺代替了Cd²⁺离子;由于Cr³⁺离子与Cd²⁺离子的半径不同、电荷不同、质量不同,导致Cr³⁺的局域结构发生晶格畸变,由此而产生四角对称晶场;由于电荷补偿,Li⁺离子取代了[001]方向与Cr³⁺离子邻近的Cd²⁺离子,由此产生的等效电荷而形成的四角晶场。这样,Cr³⁺的局域结构由O_h对称变为C_4v点对称。文中建立了ZFS参量和晶体结构之间的定量关系。在考虑晶格畸变和等效电荷的基础上,研究了KCdF₃:Cr³⁺,Li⁺晶体的ZFS参量,理论结果和实验符合很好。得到了F^-离子向中心离子分别移动为ΔR₁=0.00268nm,ΔR₂=0.001nm,ΔR₃=0.00165nm。     

Li+离子掺杂对红色发光材料Y2(W,Mo)O6:Eu3+发光性能的影响

采用高温固相法制备了荧光粉Y2-x(W,Mo)O6:Eu3+,xLi+,利用X射线衍射仪和电子扫描显微镜对样品的结构和形貌进行了表征,并利用荧光光谱法分析了样品的光谱特性.首先在Y2WO6中掺入少量的Mo6+离子,掺入Mo6+后增加了原Y2WO6:Eu3+的激发光谱在近紫外光区的吸收,扩展了激发光谱的谱宽,但却使Y2W...     

Li~+,Zn~(2+),Mg~(2+)掺杂Lu_2O_3∶Er~(3+)荧光粉的制备及发光特性

用微波高温固相法合成了Er~(3+)单掺Lu_2O_3,Li~+与Er~(3+)共掺Lu_2O_3及Li~+,Zn~(2+),Mg~(2+)掺杂Lu_2O_3∶Er~(3+)的荧光粉。实验表明金属离子Li~+、Zn~(2+)、Mg~(2+)、Er~(3+)掺杂Lu_2O_3,不影响Lu_2O_3的立方晶相。扫描电子显微镜测量表明,Li~+掺杂可以有效改善粉体的分散性和形貌,Li~+,Zn~(2+),Mg~(2+)共掺杂获得的粉体颗粒分布更加均匀,粒径范围为80～100 nm。379 nm激发下,Li~+与Er~(3+)共掺样品发光较单掺Er~(3+)样品在565 nm处的发光增强了4.5倍,而Li~+、Zn~(2+)、Mg~(2+)与Er~(3+)共掺样品较其发光增强5.3倍。980 nm激发下,Li~+与Er~(3+)共掺样品,Li~+、Zn~(2+)、Mg~(2+)与Er~(3+)共掺样品的发光分别比单掺Er~(3+)样品在565 nm处发光增强23倍与39倍,在662 nm处发光强度分别增强20倍与43倍。379 nm激发下,较单掺Er~(3+)的样品,掺杂Li~+的样品和Li~+,Zn~(2+),Mg~(2+)和Er~(3+)共掺的样品荧光寿命均有所增加,而Zn~(2+)、Er~(3+)共掺及Mg~(2+)、Er~(3+)共掺样品的荧光寿命则有所缩短。     

Decay kinetics of the green emission in tungstates and molybdates

Luminescence characteristics of a number of undoped and variously doped PbWO₄ crystals were studied at 0.4–400 K by the time-resolved spectroscopy and compared with those of ZnWO₄,CdWO₄ and PbMoO₄ crystals. Two types of green emission centres are detected in PbWO₄ crystals. The centres of the first type are responsible for the low-temperature 2.3–2.4 eV emission observed under excitation around 3.90–3.95 eV. The structure and parameters of their relaxed excited states were determined. It was concluded that the origin of defects responsible for the green emission of the first type could vary for different crystals. The centres of the second type with the emission around 2.5 eV appear in crystals containing oxygen vacancies after the thermal destruction of Pb⁺-WO₃ centres at T>180 K. Decomposition of the exciton and various defect-related states was also studied, and activation energies of this process were calculated.     

绿色荧光粉NaCaPO4：Tb3+的制备与发光特性

采用高温固相法合成了适用于UVLED芯片激发的NaCaPO₄:Tb³⁺绿色荧光粉并对其发光性质进行了研究。该荧光粉的发射峰位于418,440,492,545,586,622nm,分别对应Tb³⁺的⁵D₃→⁷F₅、⁵D₃→⁷F₄、⁵D₄→⁷F₆、⁵D₄→⁷F₅、⁵D₄→⁷F₄、⁵D₄→⁷F₃能级跃迁。其中位于492,545nm的发射峰最强,样品发射很好的绿光。主要激发峰位于380~400nm之间,属于4f→4f电子跃迁吸收,与UVLED芯片的发射相匹配。考察了Tb³⁺掺杂浓度和Li⁺,Na⁺和K⁺作为电荷补偿剂对样品发光性能的影响:Tb³⁺的最佳掺杂浓度为10%,以Li⁺的补偿效果最好。NaCaPO₄:Tb³⁺是一种适用于白光LED的绿色荧光材料。     

近紫外激发具有颜色可调的Er3+/Eu3+共掺BiOCl荧光粉

本文采用固相法在500℃合成了Er³⁺/Eu³⁺共掺BiOCl 荧光粉, 并通过XRD, SEM, 吸收, 激发和发射光谱研究了其结构、形貌和发光特性. XRD 和SEM结果表明在500℃下即可成功合成纯四方相片层结构的Er³⁺/Eu³⁺共掺BiOCl荧光粉. 吸收光谱表明掺杂Er³⁺/Eu³⁺离子使BiOCl形成杂质能级; 激发光谱显示该荧光粉具有来自于基质BiOCl价带(VB)到导带(CB)跃迁的优异宽带近紫外激发特性. 在380 nm近紫外光激发下, 同时获得了Er³⁺离子和Eu³⁺离子的特征发射峰, 其中发光中心位于410 nm (²H_9/2→⁴I_15/2), 525 nm (²H_11/2→⁴I_15/2), 554 nm (⁴S_3/2→⁴I_15/2), 673 nm (⁴F_9/2→⁴I_15/2)的发射峰来自于Er³⁺离子的跃迁, 而581 nm(⁵D₀→⁷F₀), 594 nm (⁵D₀→⁷F₁), 622 nm (⁵D₀→⁷F₂), 653 nm (⁵D₀→⁷F₃), 699 nm (⁵D₀→⁷F₄)的发射峰则来自于Eu³⁺离子的跃迁. 值得注意的是, 与传统Er³⁺/Eu³⁺掺杂的材料不同, 该荧光粉还具有独特高效的紫光(Er³⁺)和长波红光(Eu³⁺)发射特性, 分析表明这与BiOCl的结构有关; 并且通过改变掺杂浓度, 实现了发光颜色由黄绿光→黄光→橙红光的调节. 研究结果表明Er³⁺/Eu³⁺共掺BiOCl荧光粉有望成为一种潜在的近紫外激发白光LED荧光粉.     

Li+离子掺杂Gd2O3：Sm3+纳米晶的发光增强

采用燃烧法制备了Gd₂O₃:Sm³⁺和Li⁺离子掺杂的Gd₂O₃:Sm³⁺纳米晶,根据X射线衍射图谱确定所得纳米样品为纯立方相。在室温下,用275 nm和980 nm激发光激发各样品时,可分别观测到Sm³⁺离子的强荧光发射和上转换特征发射,其主发射峰分别位于560,602,650 nm处,分别对应着Sm³⁺离子的⁴G_5/2→⁶H_5/2,⁴G_5/2→⁶H_7/2和⁴G_5/2→⁶H_9/2的电子跃迁,其中以⁴G_5/2→⁶H_7/2跃迁的光谱强度最大。实验表明Li⁺离子的掺入使得Sm³⁺离子的荧光发射强度显著增加。通过对样品的XRD、TEM和激发光谱、发射光谱的研究,分析了引起样品荧光强度变化的原因。     

Sr2SiO4:Ce3+,Li+蓝紫色荧光粉发光性能的研究

以MCM-41为硅源,采用共沉淀法制备Sr_2-xSiO₄:xCe³⁺(x=0.01~0.09,步长为0.01)和Sr_1.95-ySiO₄: 0.05Ce³⁺,yLi⁺(y= 0.01~0.07,步长为0.02)蓝紫色荧光粉。Sr_2-xSiO₄:xCe³⁺的发射光谱是一个不对称的宽带,最大峰值在410 nm左右。Ce³⁺的最佳掺杂量为5%。Ce³⁺离子倾向于占据九配位的Sr(Ⅱ)格位。共掺电荷补偿剂Li⁺可以有效地提高Sr_1.95SiO₄: 0.05Ce³⁺的发光强度,其中Li⁺离子对1 100 ℃煅烧样品的发光强度的提高程度比1 000 ℃的更高,Li⁺的最佳掺杂量为y=0.05。