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.     

Ce3+,Tb3+共掺BaYF5微晶玻璃的光学特性

采用高温熔融法制备了一种新型的Ce3 +/Tb3+共掺BaYF5微晶玻璃.测试了微晶玻璃的X射线衍射图(XRD)谱、激发光普和发射光谱.研究发现:660℃热处理2h后的玻璃基质中析出BaYF5纳米晶相,根据XRD结果用Scherrer公式计算得到晶粒大小约为27 nm;在近紫外光(338 nm)激发下,观察到BaYF5...     

Superficial defects induced by argon and oxygen bombardments on (110) TiO2 surfaces

Compositional and chemical changes of titanium dioxide monocrystalline surfaces induced by bombardment with 4 keV argon and oxygen ions have been studied by AES, XPS and AFM. Argon ion bombardment induced strong changes in the composition and chemical state of the surface: loss of oxygen due to preferential sputtering occurred, and, related to this, Ti⁴⁺ species were reduced to Ti³⁺ and Ti²⁺. During oxygen bombardment, competition between preferential sputtering of oxygen ions of the oxide surface and oxygen implantation was observed. This phenomenon was found to be strongly dependent upon the incidence angle of the oxygen ions. Moreover, an oxygen bombardment with normal incidence of the surface that had been previously submitted to an argon ion bombardment led to a restoichiometrization of the surface: no further Ti³⁺ or Ti²⁺ was found by XPS, only Ti⁴⁺.     

Magnetic and microstructural properties of the Ti-doped Barium hexaferrite

A study of the magnetic and microstructural properties of the M-type Ti⁴⁺-doped Barium hexaferrite according to the stoichiometric formulation BaFe_{(12−(4/3)x)}Ti_xO₁₉ with x=0, 0.6, 0.8 and 1.0, has been reported. The XRD and magnetic analysis show a variation of the host lattice parameters and a decrease in the values of remnant magnetization and magnetic anisotropy with Ti⁴⁺ content. The behavior of magnetic properties of materials is explained by the combined effect of the coherent rotation of the magnetic domains and the replacements of Fe³⁺ by Ti⁴⁺ ions in the octahedral and tetrahedral sites.     

Oxygen ion conductivity of yttria-niobia mixed oxide with fluoride related structure

The oxygen ion conductivity of Y₂O₃---Nb₂O₅ with a fluorite-like structure was studied. Substitutional solid solutions of Nb₂ O₅ in Y₂O₃ lattice formed the defect fluorite phase and remarkably enhanced the oxygen ion conductivity. Doping with tetravalent cations, especially Ti⁴⁺ or Ce⁴⁺, in yttria-niobia oxide is effective in enhancing the oxygen ion conductivity. Although the n-type semiconducting property appeared below P_O2 = 10⁻¹⁸ atm at 1243 K, the yttria-niobia mixed oxide doped with Ce⁴⁺, Ti⁴⁺, and Zr⁴⁺ stably exhibited oxygen-ion conduction in the wide range of oxygen partial pressures studied.     

碱金属离子,Gd3+,Ce3+共掺杂的Lu3Al5O12陶瓷粉体的光学性能

用高温固相法制备了(Gd_xM_yLu_0.99-x-y)₃Al₅O₁₂:1%Ce³⁺(x=0,0.01,0.25,0.5,0.75,y=0,0.005,0.01,0.02,0.05,0.1,M=Li⁺,Na⁺,K⁺,Cs⁺)系列陶瓷粉体。X射线衍射仪对合成粉末微结构进行表征,FLS920光谱仪测量样品的激发光谱、发射光谱和荧光寿命,CIE色度系统分析合成材料的色坐标。X射线衍射仪结果显示,不同浓度碱金属离子、Gd³⁺、Ce³⁺共掺杂Lu₃Al₅O₁₂样品仍为立方晶相,但随着碱金属离子、Gd³⁺、Ce³⁺掺杂浓度的增加,合成样品衍射峰稍有向小角度偏移。在350 nm激发下,与Lu_2.97Al_5O₁₂:1%Ce³⁺样品相比,共掺杂Gd³⁺后的样品在511 nm附近发射强度降低且出现明显红移,随着Gd³⁺浓度增加,Ce³⁺能级寿命逐渐减小,范围为35~60 ns。与掺杂1%Ce³⁺,1%Gd³⁺样品比较,分别共掺杂2%的Li⁺、Na⁺、K⁺和1%的Cs⁺后样品发光强度提高了5.1倍,2.93倍,1.79倍,1.28倍,同时样品中Ce³⁺寿命继续减小。分别在λ=254.0 nm和λ=365.0 nm紫外灯照射下,随着Gd³⁺掺杂浓度的增加,观察到合成样品从深黄绿色变化为暗红色,色坐标显示样品发光由黄绿光区逐渐移动到红光区域,且共掺杂碱金属离子后,粉体的发光更亮。     

Surface chemical disorder and lattice strain of GaN implanted by 3-MeV Fe10+ ions

Chemical disorder on the surface and lattice strain in GaN implanted by Fe¹⁰⁺ ions are investigated. In this study, 3-MeV Fe¹⁰⁺ ions fluence ranges from 1×10¹³ ions/cm² to 5×10¹⁵ ions/cm² at room temperature. X-ray photoelectron spectroscopy, high-resolution x-ray diffraction, and high-resolution transmission electron microscopy were used to characterize lattice disorder. The transition of Ga-N bonds to oxynitride bonding is caused by ion sputtering. The change of tensile strain out-of-plane with fluence was measured. Lattice disorder due to the formation of stacking faults prefers to occur on the basal plane.     

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。     

Surface and interface properties of epitaxial Fe3O4 films studied by Mössbauer spectroscopy

Stoichiometric Fe₃O₄ films have formed epitaxially on -Al₂O₃ and MgO single-crystal substrates by a reactive vapor deposition method. In order to apply conversion electron Mössbauer spectroscopy depth-selectively, a 5–7 Åthick probe layer containing ⁵⁷Fe was formed at various depths in inactive ⁵⁶Fe₃O₄ matrix films. At the topmost surfaces and also at the interfaces, the essential electronic features of bulk Fe₃O₄ are retained, including a rapid electron hopping between the Fe²⁺ and Fe³⁺ ions at B sites. Minor depth-dependent changes are confined to a few outermost atomic layers, and the changes depend on the orientation and the lattice mismatch with the substrate. For (111) growth on -Al₂O₃, the surface layer seems to be strongly relaxed to reduced the electric polarization, while a high density of defects seems to be concentrated at the interface with -Al₂O₃. For (001) growth on MgO, the surface retains the spinel lattice though slightly oxidized, while the interface with MgO has good crystallinity and stoichiometry. An enhanced thermal fluctuation of the Fe³⁺-spins in contact with the MgO substrate and in the topmost surface layer can be seen in their reduced magnetic hyperfine field at 300 K.     

碱土金属离子对红色长余辉材料Y2O2S：Eu3+, M2+（M=Mg,Ca,Sr,Ba）,Ti4+纳米阵列发光性能的影响

采用溶胶凝胶模板法制备红色长余辉发光材料Y₂O₂S：Eu³⁺,M²⁺（M=Mg,Ca,Sr,Ba）,Ti⁴⁺纳米阵列,利用X射线衍射、扫描电子显微镜和荧光分光光度计、照度计分别研究了不同二价离子掺杂下所合成样品的物相、形貌及发光性能。结果表明：样品排列整齐有序,管径大小统一;不同的二价离子种类没有改变晶体结构和发射峰的位置,但对余辉性能有较大的影响。用324 nm波长光激发样品,由于Eu³⁺的⁵D₀→⁷F₂跃迁,最强的红色发射峰位于626 nm处;不同离子掺杂样品的余辉性能按Ba²⁺、Ca²⁺、Sr²⁺、Mg²⁺的顺序递加,其中二价离子为Mg²⁺ 时,余辉时间长达287 s（≥1 mcd/m²）,表现出最佳的余辉性能。     

Field-induced insulator-metal-insulator transitions in low-energy H_2~+ ion-irradiated epitaxial La_(2/3)Ca_(1/3)MnO_3 thin films

Epitaxial La 2/3 Ca 1/3 MnO 3 thin films grown on LaAlO 3 (001) substrates were irradiated with low-energy 120-keV H 2 + ions over doses ranging from 10 12 ions/cm 2 to 10 17 ions/cm 2 . The irradiation suppresses the intrinsic insulator-metal (I-M) transition temperature and increases the resistance by reducing the crystallographic symmetry of the films. No irradiation-induced columnar defects were observed in any of the samples. The specific film irradiated at a critical dose around 8 × 10 15 ions/cm 2 is in a threshold state of the electric insulator where the I-M transition is absent. In an external field of 4 T or higher, the I-M transition is restored and thus an enormous magnetoresistance is observed, while a negative temperature coefficient resumes as the temperature is reduced further. Magnetic relaxation behavior is confirmed in this and other heavily irradiated samples. The results are interpreted in terms of the displacement of oxygen atoms provoked by ion irradiation and the resulting magnetic glassy state, which can be driven into a phase coexistence of metallic ferromagnetic droplets and the insulating glass matrix in a magnetic field.     

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.     

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。     

Dy3+对Tb3+激活硅酸盐氟氧闪烁玻璃发光性能的影响

采用高温熔融法制备了Dy3+或Tb3+单掺和Dy3+/Tb3+共掺硅酸盐氟氧闪烁玻璃。通过对傅里叶变换红外光谱、透射光谱、光致激发和发射光谱、X射线激发发射光谱及荧光衰减曲线的分析,研究Dy3+与Tb3+之间的能量传递关系以及Dy3+对Tb3+激活硅酸盐氟氧闪烁玻璃发光性能的影响。实验结果表明：Dy3+/Tb3+共掺硅酸盐氟氧闪烁玻璃具有较高的密度和良好的可见区透过率,玻璃的网络结构是由[SiO₄]四面体和[AlO₄]四面体连接构成。在紫外光激发时,Dy3+单掺玻璃的发光源于Dy3+的4F_9/2→6H_15/2(483 nm),6H_13/2(576 nm)的跃迁发射,而Tb3+单掺玻璃的发光则源于Tb3+的5D₄→7F₆(489 nm),7F₅(544 nm),7F₄(586 nm)和7F₆(623 nm)的跃迁发射。对于Dy3+/Tb3+共掺玻璃,发射光谱则主要由Tb3+的荧光发射组成。通过对不同波长紫外光激发的发射光谱分析发现,Dy3+/Tb3+共掺闪烁玻璃中存在多种形式的能量传递。在以Dy3+的特征激发452 nm为激发波长时,Tb3+单掺玻璃的发光很弱。但随着Dy3+的引入,通过4F_9/2(Dy3+)→5D₄(Tb3+)的能量传递,Tb3+发光得到敏化增强。Dy3+/Tb3+共掺玻璃的发光强度随着Dy₂O₃含量的增多而增强,Dy₂O₃含量为1 mol%时达到最大,更高Dy₂O₃含量的样品由于Dy3+的浓度猝灭,减少了向Tb3+的能量传递,发光强度减弱。当激发波长减小到350 nm时,Dy3+和Tb3+均被激发到更高的能级6P_7/2(Dy3+)和5L₉(Tb3+),此时除了4F_9/2(Dy3+)→5D₄(Tb3+)的能量传递外,还出现了5D₄(Tb3+)→4F_9/2(Dy3+)的能量回传。Dy3+掺杂浓度较低时,Dy3+→Tb3+能量传递作用较强,Tb3+发光得到敏化增强。随着Dy₂O₃含量的增多,Tb3+→Dy3+能量传递作用增强。当Dy₂O₃含量超过0.4 mol%时,Tb3+→Dy3+能量传递强于Dy3+→Tb3+能量传递,减少了Tb3+的辐射跃迁发光,因此Dy3+/Tb3+共掺玻璃的发光强度开始减弱。由于Gd3+向Dy3+或Tb3+均可进行有效的能量传递,因此在以Gd3+的特征激发274 nm为激发光时,Dy3+/Tb3+共掺玻璃中出现了Dy3+和Tb3+对Gd3+传递能量的竞争。随着Dy₂O₃含量的增多,Tb3+所获得的能量不断减少,同时伴随着Tb3+→Dy3+能量回传和Dy3+之间的无辐射交叉弛豫作用,Dy3+/Tb3+共掺玻璃的发光强度不断减弱。对Dy3+/Tb3+共掺闪烁玻璃中Tb3+的5D₄→7F₅荧光衰减曲线分析还发现,随着Dy₂O₃含量的增多,Tb3+的荧光寿命从2.24 ms缩短到1.15 ms,曲线从单指数形式变为双指数形式,进一步证明玻璃中存在5D₄(Tb3+)→4F_9/2(Dy3+)的能量回传。X射线激发发射光谱显示,Dy3+的引入对Tb3+激活闪烁玻璃的辐射发光具有很强的负面影响,而这种负面影响不足以通过Dy3+→Tb3+能量传递来弥补,因此Dy3+/Tb3+共掺玻璃的辐射发光强度随着Dy₂O₃含量的增多而不断减弱。由此可见,在Tb3+激活硅酸盐氟氧闪烁玻璃中,不宜将Dy3+作为敏化剂,用于增强Tb3+的发光。     

Sm3+掺杂对CaMoO4:Eu3+红色荧光粉结构和发光性质的影响

采用共沉淀法制备了CaMoO4:Eu3,Sm3+纳米荧光粉材料.系统研究了Sm3+离子的引入对CaMoO4:Eu3+材料的结构和发光性质的影响.结果表明:纳米材料的尺寸随着Sm3+离子掺杂浓度的增加而变小.Sm3+的引入,可实现Sm3+和Eu3+之间的能量传递,使Eu3+在近紫外405 nm处的激发增强,进而使Eu3+...     

Luminescent properties of Dy-doped and Dy–Tmco-doped phosphate glasses

Phosphate glasses doped with Dy³⁺ ions and co-doped with Dy³⁺–Tm³⁺ ions are successfully prepared in the present work. Their photoluminescence properties have been studied by absorption, excitation and emission spectra. A combination of blue and yellow emissions has emerged in the glasses, which allows the observation of white light when the glasses are excited by the ultraviolet light. The emission intensity of Dy³⁺ is influenced by the system ionicity, while the intensity ratio of yellow to blue emissions from Dy³⁺ can be tuned by varying both the concentration of Tm³⁺ ion and the glass matrix composition.     

Ho3+掺杂的Ba0.8Sr0.2TiO3厚膜的发光特性

用丝网印刷法在氧化铝衬底上制备了Ho3+掺杂的Ba0.8Sr0.2TiO3(BST)厚膜.XRD谱表明,随着Ho3+掺杂摩尔分数从0.5%增加到2.0%,BST厚膜的晶格尺寸先增大后减小.在514 nm的氩离子激光激发下,样品均出现了中心波长为549,650,753 nm的发光带,分别对应于Ho3+离子的(5F4,5S...     

在BaYF5中Eu2+和Ho3+的荧光和能量传递

在脉冲N₂分子激光激发下,研究了在BaYF,中Eu²⁺和Ho³⁺的发射光谱,激发光谱和荧光寿命,以及Ho³⁺的超灵敏跃迁(⁵I₈→⁵G₆)。在Ho³⁺发射光谱中,⁵S₂→⁵I₈跃迁占主导地位。从Eu²⁺ 关键词：     

稀土离子掺杂LaAlO3:RE3+(RE=Eu,Tb,Sm,Tm)荧光粉的发光性能

采用溶胶凝胶法合成La_1-xAlO₃：xRE³⁺（RE=Eu,Tb,Sm,Tm）荧光粉,对样品进行热重差热（TGA-DTA）、X射线粉末衍射（XRD）、透射电镜（TEM）以及荧光光谱（PL）等表征,探讨样品的合成温度及稀土离子掺杂浓度对样品发光性能的影响。研究结果表明,当煅烧温度为800~1 200℃时,所合成样品为三方晶体结构。在紫外光激发下,掺杂离子均表现出特征的f-f电子跃迁发射,在一定掺杂浓度范围内,当Eu³⁺、Tb³⁺、Sm³⁺和Tm³⁺的掺杂浓度x值分别为0.02,0.04,0.005和0.005时,样品发光强度最大,在一定波长激发下,样品分别发射出红光、绿光、橙黄光和蓝光,Eu³⁺-Tb³⁺、Eu³⁺-Sm³⁺和Eu³⁺-Tm³⁺共掺杂有可能获得白光。     

铥、铽及铕离子掺杂的BaAl2O4膜的阴极射线发光特性

利用喷雾热解法合成了Tm、Tb及Eu离子掺杂的铝酸钡(BaAl₂O₄)发光膜,研究了合成条件对其结构和发光特性的影响.在退火温度达到700℃时,生成了BaAl₂O₄膜.Tm³⁺和Tb³⁺掺杂的BaAl₂O₄膜分别发蓝光和绿光,而Eu³⁺掺杂的BaAl₂O₄膜的发光既有Eu²⁺的特征发射——宽的蓝光发射带,也有Eu³⁺的特征发射——窄的红光发射峰.BaAl₂O₄:Tm³⁺的发射主峰位于462nm,在电压为5kV和电流密度为57μA/cm²的条件下,其阴极射线发光(CL)亮度可达25cd/m²,效率可达0.11lm/W.BaAl₂O₄:Tb³⁺的发射主峰位于549nm,在相同的条件下,其阴极射线发光亮度可达120cd/m²,效率可达0.55lm/W.BaAl₂O₄:Eu³⁺的发射主峰位于616nm,其阴极射线发光亮度为50cd/m²,效率为0.23lm/W.BaAl₂O₄:Eu²⁺发蓝光,峰值位于452nm,其阴极射线发光亮度为640cd/m²,效率为2.93lm/W.