Li+,Zn2+共掺杂对Gd2O3:Eu3+纳米粉结构和发光性能的影响

采用燃烧法制备出Li^＋,Zn^2＋掺杂的Gd2O3：Eu^3＋纳米荧光粉,研究了掺杂离子对Gd2O3：Eu^3＋的结晶性能、晶粒形貌和光致发光特性的影响.以X射线衍射（XRD）、透射电子显微镜（TEM）、发射光谱和衰减时间谱等手段表征材料性能.结果表明,Li^＋,Zn^2＋掺杂可显著提高Gd2O3：Eu^3＋纳米粉在611 nm处的发光强度,最大可达到未掺杂时的2.5倍.发光增强的主要原因可归结为3个方面： （1）使晶粒由单斜相向更利于发光的立方相转变; （2）氧空位的敏化剂作用; （3）掺杂离子的助熔剂效应,使晶粒的结晶性能提高、粒径增大,从而降低表面态引起的发光猝灭.     

白光LED用荧光材料Ba3Gd（BO3）3∶Eu^（3＋）的发光性能研究

用高温固相反应法制备了稀土离子Eu^3＋掺杂的三元稀土硼酸盐Ba3Gd（BO3）3发光材料,通过X射线衍射（XRD）、荧光光谱和扫描电镜（SEM）等测试手段对Ba3Gd（BO3）3∶Eu^3＋荧光粉的制备条件、发光性能以及形貌进行了研究。XRD结果表明,在1000℃时可得到Ba3Gd（BO3）3纯相。扫描电镜照片显示颗粒基本为球形,粒径约为200-400 nm。发光光谱测试表明,Ba3Gd（BO3）3∶Eu^3＋荧光粉在近紫外区（UV）（396 nm）和蓝光区（466 nm）可以被有效地激发,分别用255和396 nm的紫外光激发样品时,以Eu3＋的5D0-7F2（611和616 nm）超灵敏跃迁为主要发射峰。当Eu3＋的掺杂浓度为10%（摩尔分数）时,Ba3Gd（BO3）3∶Eu3＋在611和616 nm处的发光强度最大。因此,这种荧光粉是一种可能应用在白光LED上的红色荧光材料。     

Sr1-xZnxY2S4∶Er^3＋,Eu^2＋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∶Er^3＋,Sr1-xZnxY2S4∶Eu^2＋和Sr1-xZnxY2S4∶Er^3＋,Eu^2＋红色荧光粉。XRD图谱表明,Zn^2＋掺杂量x〈0.2 mol时,粉末样品为CaFe2O4型正交晶体。Zn^2＋离子在Sr1-xZnxY2S4∶Er^3＋,Eu^2＋中的固溶量（xmol）对荧光粉的发射强度影响很大。随着Zn^2＋离子掺杂浓度的增加,Sr1-xZnxY2S4∶Er^3＋,Eu^2＋（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Zn^2＋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∶0.24Er^3＋,0.006Eu^2＋是一种潜在的白光LED用红色荧光粉。     

白光LED用红色荧光粉CaWO_4:Eu~(3+),Li~+,Bi~(3+)的制备与表征

采用预先球磨、再二次热处理的高温固相合成法,制备了一系列白光LED用红色荧光粉CaWO4:Eu3+,L i+,B i3+,利用XRD,SEM和荧光光谱测试对其进行表征。XRD分析表明,所合成的样品为单一的四方晶系CaWO4,Eu3+,L i+,B i3+离子的先后掺杂使基质的部分衍射峰峰位向小角度移动;SEM照片显示,经过预先球磨制备的样品颗粒比较均一,尺寸约为0.5~3μm范围,结晶性好;荧光光谱测试发现这一系列荧光粉不仅可以被紫外光(254 nm)激发,还能被近紫外光(393 nm)和蓝光(465 nm)有效激发,其主发射峰值位于616 nm(Eu3+离子的5D0→7F2跃迁)的红光;另外详细研究了预先球磨的效果、加入H3BO3做助熔剂的质量分数以及Eu3+,L i+,B i3+离子单掺或多掺时的浓度对该体系荧光粉发光特性的影响。     

KLa(MoO_4)_2∶Eu~(3+)红色荧光粉的合成和发光性能

采用高温固相法制备了KLa(MoO4)2∶Eu3+红色荧光粉,对其物相结构、光谱性质进行了分析,研究了Eu3+的不同掺杂浓度对荧光粉的发光性能的影响,同时对其色坐标进行了分析.结果表明,KLa(MoO4)2为体心对称的单斜相;KLa(MoO4)2∶Eu3+荧光粉中Eu3+的最佳掺杂浓度为9%,当掺杂浓度大于9%出现浓度猝灭现象,出现这一现象的主要原因是由于交换作用导致Eu3+之间能量的转移.     

Eu3+掺杂YPO4的合成、结构及发光特性研究

以Eu^3＋掺杂YPO4为研究对象,通过简单水热法在200℃下制备了不同Eu^3＋掺杂浓度的YPO4纳米颗粒。采用X射线粉末衍射、透射电镜和荧光光谱对样品进行了表征,研究了Eu^3＋掺杂浓度对相结构、发光性能的影响。实验结果表明,通过调节掺杂Eu^3＋离子的浓度可以对样品的相结构进行调控。随着Eu^3＋掺杂浓度的提高,样品发生了从四方相到六方相,最后到单斜相的转变。因此通过不同Eu^3＋离子浓度的掺杂可以实现相结构的调控。荧光光谱测量发现所有发射均为Eu^3＋的f-f能级之间的特征跃迁,并且确定掺杂浓度为10％的样品具有最强的发光强度。     

LaF3:Eu3+纳米粒子的水热法制备及发光性质研究

用水热法制备了LaF3及Eu^3＋掺杂的LaF3纳米粒子, 通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）和荧光光谱（FS）对样品进行了表征. 结果表明： 所得的纳米粒子粒度均匀、结晶完好, 呈规则的六边形形状;研究了反应温度和时间对LaF3纳米粒子形成的影响, 初步探讨了纳米粒子的生长机制. 研究了掺杂Eu^3＋后的发光性质, 发现纳米粒子经高温煅烧后, 荧光强度有明显下降, 适宜的煅烧条件为600 ℃/6 h, Eu^3＋的掺杂量在5%（摩尔分数）时, 纳米粒子的荧光强度最强, 更高的掺杂浓度将导致荧光猝灭.     

镨和镱掺杂Ba2SiO4∶Eu^2＋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∶nEu^2＋（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。Pr^3＋和Yb3＋的掺入并未改变Ba2SiO4∶Eu^2＋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Pr^3＋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Eu^2＋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。     

YAG：Ce^3＋荧光粉的合成及α-Al2O3籽晶对相形成的促进作用

用聚丙烯酰胺凝胶法来合成YAG：Ge^3＋荧光粉，用XRD对煅烧过程粉体的结构进行了跟踪测定。结果发现，当直接煅烧凝胶时，可观察到θ-Al2O3，YAM和YAP等中间相的形成，而当煅烧含有α-Al2O3，YAM和YAP的形成，加速其与Y203的反应而在较低温度下直接生成YAG相。合成YAG：Ce^3＋荧光粉的发射峰为处于550nm的宽峰，其激发光谱有两个主要的吸收峰，主峰位于460nm，可以与GaN LED的蓝色发射相匹配而用于白光LED的组装。一些助熔剂可以提高荧光粉的光致发光特性，这归因于助熔剂对YAG结晶过程的改进作用和对YAG：Ce^3＋中三价铈离子的稳定作用。     

一类新的红色荧光粉MYzS4：Er^3＋（M=Srz＋，Ba^2＋）的合成与表征

Eu^2＋激活的CaS：Eu^[1],Eu^3＋和Sm^3＋激活的硫氧化物^[2]，Pr^3＋激活的Ca0.8Zn0.2Ti03^[3]以及Eu^2＋和Mn^2＋掺杂的SrY2S4^[4]都是重要的红色发光材料。然而，这些红色荧光粉的发射峰波长都短于650nm，对于农用日光转换材料^[5]，红色发射峰波长达到660nm才能与叶绿素的红区吸收相吻合。     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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Mit 2 Abbildungen     

γ-Nitro-γ-butyrolacton

γ-Nitro-γ-butyrolactone By oxidation of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) with KMnO₄, besides 3-(1′-nitro-2′-oxocyclohexyl)pripionic acid ( 2 ), the complete hydrolysis product 4-oxononanedioic acid ( 4 ) and the oxidized semi-hydrolysis product 5-(2-nitro-5-oxotetrahydro-2-furyl)pentanoic acid ( 3 ) were formed. The crystalline 3 decomposes at r.t. forming 4 and nitrous gases; its structure was established by X-ray determination.     

Synthesis of γγγ-trifluorocarbonyl compounds

γγγ-Trifluorocarbonyl compounds are easily obtained in a good yield by introduction of the 1,1,1-trifluoroethyl moiety (CF₃-CH₂-) on the -methylene group of a ketone.     

3x-pyrrolizin-3-ones

Condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groups, in the KOH-DMSO system, was used to prepare previously unknown 1-alkylthio-3H pyrrolizin-3-ones. The latter, treated with secondary amines, are readily converted to the corresponding 1-amino derivatives.     

3-H-pyrrolizin-3-ones

Previously unknown 1-alkylthio-3H-pyrrolizin-3-ones have been obtained by the condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groupings in the KOH-DMSO system. On treating the products with secondary amines they are readily converted into the corresponding 1-amino derivatives.Irkutsk Branch of the Russian Academy of Sciences, Irkutsk 664033. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–924, July, 1996. Original article submitted May 2, 1996.     

K3BiSe3, Rb3BiSe3 und Cs3BiSe3 – Substitutionsvarianten des Th3P4-Typs

K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ – Derivatives of the Th₃P₄ Structure Type The compounds K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ were synthesized by heating mixtures of Bi₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 850°C. Thin crystals of the compounds appear red in transmitted light. They crystallize isostructural with Na₃AsS₃, space group P2₁3, lattice constants a = 9.771(5) Å, a = 10.161(3) Å, and a = 10.587(5) Å for K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃, respectively. The Na₃AsS₃ structure type is a derivative of the Th₃P₄ structure type.     

Die Akzeptoreigenschaften von AsCl3, AsBr3, asJ3, SbCl3, SbBr3 und SbJ3

Zusammenfassung Es wurden die Enthalpien der Reaktionen von AsCl₃, AsBr₃, AsJ₃, SbCl₃, SbBr₃ und SbJ₃ mit Tributylphosphat, N,N-Dimethylacetamid und Hexamethylphosphorsäuretriamid bestimmt. Das Verhalten der Addukte bei Gegenwart eines Überschusses der Donoren wird beschrieben.

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Acceptor properties of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃, and SbI₃

The enthalpies of the reactions of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃ and SbI₃ with tributylphosphate, N,N-dimethylacetamide and hexamethylphosphoric acid triamide were measured. The behavior of the adducts in the presence of excess donor molecules is described.

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Mit 5 Abbildungen     

Freezing the polarization of CH3NH3PbI3 and CH3NH3PbI3-xClx perovskite films

Thin films of methylammonium lead halides, CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, were deposited onto symmetrical microstructured electrode arrays of gold or platinum on Si/SiO₂ wafers. Polarization studies were carried out on perovskite films under vacuum in the dark. For poling, a constant voltage was applied to the samples while the temperature was cycled between 295 K and 4 K. The measured current densities depending on the temperature showed distinct characteristics relating strongly to the crystal phase and the dielectric properties of the perovskite films. Voltage sweeps were carried out at different scan rates at specific temperature intervals after poling. The polarization of the films due to the migration of iodide vacancies in direction of the blocking perovskite/metal interface was frozen almost up to room temperature. Charge carriers were only able to cross the blocking barrier and contribute to the current where the ions have accumulated during poling. All J-V curves showed hysteresis: inverted and regular hysteresis at room temperature and below, respectively. Inverted hysteresis originates from the slow accumulation of ions at the blocking barrier, while regular hysteresis arises from a distortion in the adjacent crystals which will be discussed.