多氟代季戊四芳醚的合成及其在低介电薄膜中的应用

合成了六个多氟代季戊四芳醚类化合物,并且对部分化合物掺杂于SiO~2薄膜的介电性质进行了研究。当氟原子掺杂浓度(F/Si)为1%时,薄膜介电常数K值小于3。     

Y_2O_3∶Eu~(3+)薄膜的制备及发光性能的研究

以稀土氧化物为原料,用溶胶-凝胶法制备前驱液,加入适量的聚乙烯醇做成膜物质,用浸渍拉提法在石英玻璃表面上得到均匀的薄膜,然后经过适当的干燥和热处理得到Y2O3∶Eu3+发光薄膜.讨论了Eu3+的掺杂浓度和热处理温度对薄膜发光性能的影响.试验表明:Eu3+的最佳掺杂浓度为8%(摩尔分数),薄膜的发光性能随热处理温度提高而增强,当热处理温度达到700℃后,薄膜的发光性能基本上稳定.同时用原子力显微镜和X射线衍射分析了薄膜的表面形貌和结构.     

铒偏析与沉淀对掺铒硅1.54 μm光发射的影响

用金属蒸气真空弧离子源(MEVVA)制备高浓度掺铒硅发光薄膜, 研究高浓度Er掺杂发光薄膜中Er的偏析与沉淀现象对1.54 μm光发射的影响. RBS分析表明, Er的掺杂浓度可达～10%(原子分数), 即Er原子体浓度为1×1021 cm-3. XRD分析掺铒硅薄膜的物相结构发现, Er在薄膜中的存在形式与离子注入参数有关. Er的偏析、沉淀以及辐照损伤等因素会影响掺铒硅薄膜的1.54 μm光发射.     

YVO_4:Eu~(3+),Al~(3+)荧光粉的制备及荧光性能研究

用高温固相法制备了Al3+掺杂的YVO4:Eu3+荧光粉。采用X射线粉末衍射(XRD)、环境扫描电镜(SEM)、荧光光谱(FL)等对样品进行了表征。分析了Al3+掺杂对YVO4:Eu样品晶体结构、晶胞参数和荧光性能的影响,并探讨了烧结温度对光谱性能的影响。研究结果表明:当Eu3+的浓度x(摩尔百分比)为4%,Al3+的浓度为1.5%时,在1100℃下烧结的样品其荧光性能最好,5D0→7F2处的发光强度约为未掺Al3+的2.5倍。由于Eu3+的7F2→5L6跃迁吸收,YVO4:Eu3+,Al3+荧光粉可在395 nm被有效激发。因此,YVO4:Eu3+,Al3+可以作为近紫外激发的白光LED红色荧光粉。     

镨和镱掺杂Ba2 SiO4:Eu2+荧光材料的合成与发光性能

采用高温固相反应法分别合成了变价稀土镨和镱离子掺杂的绿色荧光粉[Ba(2-n-1.5x)REx]SiO4:nEu2+ (n=0.03, RE=Pr, Yb;x=0, 0.02,0.05,0.10).结果表明: 所有合成荧光粉的激发峰均为250～400 nm的宽峰, 与近紫外LED的发射光波长相匹配.发射峰位于450～550 nm之间, 是Eu2+的5d-4f跃迁的典型发射.Pr3+和Yb3+的掺入并未改变Ba2SiO4:Eu2+的相组成, 但对荧光强度的影响大, 且与掺杂元素、掺杂量和煅烧温度相关.当掺杂Pr3+和Yb3+的量为x=0.02时, 经1150 ℃煅烧所得荧光粉的发光强度分别是未掺杂时的595%和168%.证明三价稀土离子掺杂可以导致基质中的电荷缺陷而敏化Eu2+离子的发光, 而变价稀土离子的掺杂可以大大提高电荷缺陷, 导致荧光强度的进一步提高.     

KSrBP2O8:RE(RE=Eu2+,Tb3+,Eu3+)荧光粉的制备与发光性能研究

采用高温固相反应法制备了KSrBP2O8:RE(RE=Eu2+,Tb3+,Eu3+)系列荧光粉。利用X射线衍射仪对样品的物相结构进行了分析,结果表明:稀土离子的掺入没有改变荧光粉的主晶相。利用荧光光谱仪对样品的发光性能进行了测试,发现在近紫外光激发下掺杂Eu2+离子的样品具有宽带发射峰,最强发射位于450 nm左右,对应于Eu2+离子的4f65d1→4f7辐射跃迁。随着Eu2+掺杂量的增加,发射光从蓝光逐渐转变到蓝白光。另外,KSrBP2O8:Tb3+和KSrBP2O8:Eu3+能够在近紫外光激发下分别发射出绿光和红光,其最佳掺杂浓度分别为0.04%和0.08%(摩尔分数)。     

退火温度对PLD法制备ZnO:Eu3+,Li+薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)法在Si(111)衬底上制备了Eu3+,Li+共掺杂的ZnO薄膜,分别在450,500,550和600℃条件下进行退火,退火气氛为真空。利用X射线衍射(XRD)仪和荧光分光光度计研究了退火温度对薄膜结构和光致发光(PL)的影响。研究结果表明,Eu3+,Li+共掺杂的ZnO薄膜具有c轴择优取向,Eu3+,Li+没有单独形成结晶的氧化物,均以离子形式掺入ZnO晶格中。PL谱中有较宽的ZnO基质缺陷发光,ZnO基质与稀土Eu3+之间存在能量传递,但没有有效的能量传递。随着退火温度的增加,薄膜发光先增强后减弱,退火温度为550℃时发光最强。当用395 nm的激发光激发样品时,仅观察到稀土Eu3+在594 nm附近的特征发光峰,但发光强度随退火温度变化不明显。     

固体电解质Ce_(0.9)Er_(0.1-x)Pr_xO_(1.95+δ)的微观结构及电性能

采用柠檬酸溶胶-凝胶法制备了固体电解质Ce0.9Er0.1-xPrxO1.95+δ(x=0.02~0.08),利用X射线粉末衍射(XRD)、原子力显微镜(AFM)、拉曼光谱(Raman)、X射线光电子能谱(XPS)和交流阻抗谱研究了样品的微观结构和电性能.XRD结果表明,800℃煅烧的所有样品均形成了单相立方萤石结构;Raman光谱结果表明,Ce0.9Er0.05Pr0.05O1.95+δ具有氧缺位的立方萤石结构;XPS分析表明,Ce0.9Er0.05Pr0.05O1.95+δ存在氧缺位,Pr3+离子和Pr4+离子共存;AFM观测结果表明,1300℃下烧结的样品比1400℃下烧结的样品致密;交流阻抗谱结果表明,Pr掺杂量x=0.05时,Ce0.9Er0.05Pr0.05O1.95+δ的电导率最高(σ600℃=1.34×10-2S/cm,Ea=0.90 e V),比未掺杂Pr的Ce0.9Er0.1O1.95(σ600℃=8.81×10-3S/cm,Ea=0.92 e V)提高了52%,说明在Ce0.9Er0.1O1.95中适量掺杂Pr可提高材料的电导率,降低活化能.     

Sr1-x Znx Y2 S4:Er3+,Eu2+荧光粉的合成与发光特性的研究

采用碳酸盐前躯体高温分解法合成了Sr1-xZnxY2S4:Er3+, Sr1-xZnxY2S4:Eu2+和Sr1-xZnxY2S4:Er3+, Eu2+红色荧光粉. XRD图谱表明, Zn2+掺杂量x<0.2 mol 时, 粉末样品为CaFe2O4型正交晶体. Zn2+离子在Sr1-xZnxY2S4:Er3+, Eu2+中的固溶量(x mol)对荧光粉的发射强度影响很大. 随着Zn2+离子掺杂浓度的增加, Sr1-xZnxY2S4:Er3+, Eu2+(SZYSEE)紫外区激发峰(200～413 nm)发生红移, 并与可见光激发带(413～600 nm)形成一个连续的宽带谱, 与紫外和GaN基LED芯片辐射都有良好的匹配性. 当Zn2+掺杂量为0.1 mol时, SZYSEE的发光强度达到最大, 其发光强度比未掺Zn2+的增强10.7倍. Sr0.9Zn0.1Y1.76S4:0.24Er3+, 0.006Eu2+是一种潜在的白光LED用红色荧光粉.     

非晶红色荧光粉Cd3AlSi3O12:Eu3+的制备及发光性能

使用溶胶-凝胶法制备了Cd3Al2Si3O12:Eu3+非晶体系红色荧光粉,并对其发光性质进行了研究.该荧光粉在Eu3+的位于394 nm的5L6能级和464 nm的5D2能级的激发下能够产生强的5D0→7F的红光特征发光,最佳掺杂摩尔分数为25％.Cd3Al2Si3O12:Eu3+荧光粉与传统的Y2O3:Eu3+相比较,其发光强度是Y2O3:Eu3+的2.4倍左右(在394和464 nm的激发下).Cd3Al2Si3O12:Eu3+的热稳定性好,比已经商业化的YAG:Ce3+的热猝灭影响要小得多.所有这些结果表明Cd3A12Si3O12:Eu3+可作为暖白光LED用红色荧光粉.     

Significant suppression of leakage current in (Ba x ,Sr1-x )TiO3/MgO heterostructured thin films by thin MgO layers insertion

The leakage behavior and dielectric property of BST80/MgO heterostructured thin films deposited on LaNiO₃ (LNO)/Si substrates by sol-gel were investigated. The dielectric constant and the leakage current are modified by MgO insertion. The dramatic reduction in the leakage current effectively increased the charge retention of the capacitors consisted of heterostructured thin films as compared to the pure BST films. The significant reduction in the leakage current can be attributed to the minute solid solubility of MgO in the BST lattice and the potential barrier built in the interface between BST and MgO layers in the heterostructured thin films.     

Dielectric Characteristics of Sol-Gel-Derived BST/BSLaT/BST Multilayer

BST/BSLaT/BST multiplayer (ML) films were prepared by sol-gel method on the Pt/Ti/SiO₂/Si substrate. X-ray diffraction analysis and atomic force microscopy showed that dopant La causes decreased grain size of BST thin films obviously, and ML films were similar to BST films in size. The dielectric constant versus temperature curve of ML films becomes sharper comparing with that of BST films near the phase transition point, which indicated that the pyroelectric coefficient is propitious to be enhanced. The ML films also improve the leakage current characteristics of BST thin films and the linear relationship of the log J versus E^1/2 curves shows in a good agreement with the Schottky thermionic emission model. This work clearly reveals the highly promising potential of BST/BSLaT/BST multiplayer films compared with BST films for application in uncooled infrared focal plane arrays system.     

Facile preparation of vanadium oxide thin films on sapphire(0001) by sol–gel method

The Ba_0.6Sr_0.4TiO₃ (BST60) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel method. The thickness of CeO₂, serving as a buffer layer, was varied from 0 to 75 nm, in order to optimize the dielectric tunable property. X-ray patterns analysis indicates that all the thin films exhibit good crystalline quality with a pure perovskite phase and insertion of the CeO₂ buffer layer does not change the crystal structure of BST60. Dielectric properties of the thin films were investigated as a function of both temperature and direct current electric field. The results show that dielectric constant and loss are modified by insertion of the CeO₂ buffer layer. The BST60 thin films with 25 nm thickness CeO₂ buffer layer have the highest figure of merit, low dielectric loss, and suitable dielectric constant, which render them attractive for the tunable microwave device applications.     

Eu0.5RE0.5Fe0.5Mn0.5O3的57Fe Msosbauer谱研究

利用固相反应合成了Eu0.5RE0.5Fe0.5Mn0.5O3(RE=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Y)等化合物。测量了其XRD谱及57FeMssbauer谱。实验发现,随着RE原子序数的增加,样品的晶胞体积减小,Fe在化合物中处于Fe3+的高自旋状态,57Fe的四极裂矩与样品的畸变参数D成线性关系。     

Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．5）O_3的~（57）Fe Msosbauer谱研究

利用固相反应合成了Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｙ）等化合物。测量了其ＸＲＤ谱及~（５７）ＦｅＭｓｓｂａｕｅｒ谱．实验发现，随着ＲＥ原子序数的增加，样品的晶胞体积减小，Ｆｅ在化合物中处于Ｆｅ~（３＋）的高自旋状态，~（５７）Ｆｅ的四极裂矩与样品的畸变参数Ｄ成线性关系。     

YAG∶Ce体系中稀土离子掺杂对Ce3+的光谱性能的影响

采用高温固相法合成了一系列的(Y0.95Ln0.01Ce0.04)3Al5O12(简称YAG∶Ce,Ln), 系统地研究了此体系中的Ln3+对Ce3+的发光强度的影响. 结果表明, 在YAG∶Ce的体系中, La3+, Gd3+, Lu3+等光学透明离子的少量掺杂对Ce3+的发光强度的影响不大; 掺入少量的Pr3+, Sm3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+等稀土离子, 由于它们的能级与Ce3+的能级有交叠, 使它们之间存在着竞争吸收或能量转移, 对Ce3+的发光有较明显的变化, 其中, Pr3+和Sm3+的掺入使其在红光区有发射峰, 可以增加YAG∶Ce的红色成分以提高显色性; Nd3+, Eu3+和Yb3+对Ce3+的发光有严重的猝灭作用.     

Distribution of Europium Ions in Ion-Exchanged NaX and NaY Zeolites

The chemical environments of europium-exchanged NaX (Si/Al =1.16) and NaY (Si/Al = 2.29) zeolites have been investigated by means of ¹²⁹Xe NMR and isotherm measurements of adsorbed xenon. EuNaX and EuNaY samples with varied concentrations of Eu cations were subjected to diverse chemical and thermal treatments, namely dehydration, reduction, oxidation, and re-reduction. Thermal analyses of hydrated EuNaX and EuNaY samples indicate that both the structural stability and the saturation concentration of water increase with increasing Eu content. For dehydrated EuNaY zeolites, the Eu³⁺ cations tend to replace Na⁺ ions at S2 sites and tend to be located in framework supercages; similar behavior is found for Eu²⁺ ions after reduction. After subsequent oxidation, Eu³⁺ ions migrate from supercages into small sodalite and/or D6R cages; similar results were deduced for samples after re-reduction. In contrast to the behavior observed in EuNaY, Eu³⁺ ions tend to exchange for Na⁺ ions in the sodalite and/or D6R cages in dehydrated EuNaX zeolites, regardless of the thermal treatment; this behavior is ascribed to the existence of unlocalized S3 Na⁺ in EuNaX samples.     

Potentiometric study of reactions of rare-earth elements with 3-allylpentanedione in a water-dioxane medium

Reactions of the ions of La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, and Lu with 3-allylpentanedione (HL) in a water-dioxane (50 vol%) medium were studied by pH-metric titration. Stability constants of LnL²⁺ and LnL ₂ ⁺ complexes and pH range where these compounds are mainly formed were determined. The dependence of the stability constants on the atomic number of an element has a characteristic break on the gadolinium ion and shows that the stability of the complexes increases as the size of Ln³⁺ ions decreases.     

Syntheses, structures and properties of seven isomorphous 1D Ln3+complexes Ln(BTA)(HCOO)(H2O)3 (H2BTA = bis(tetrazoly)amine, Ln = Pr, Gd, Eu, Tb, Dy, Er, Yb) and two 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr, Nd)

Seven isomorphous 1D chain Ln3+ complexes Ln(BTA)(HCOO)(H2O)3 (Ln = Pr (1), Gd (2), Eu (3), Tb (4) Dy (5), Er (6) and Yb (7)), and two formate coordinating and bridging 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr (8) and Nd (9)) have been synthesized and characterized by single crystal X-ray diffraction analysis. Although the Ln3+ ions in 1-7 have different radius, the trivalent lanthanide ions in 1-7 show the same coordinated environment. The well-defined single crystal structures of 8 and 9 are first samples for formate-bridged Ln3+ metallic complexes. The luminescent properties of solid samples of 2-5 at room temperature and the magnetic property of 2 have been also reported and discussed in this paper.