掺Er^3＋重金属氧氟硅酸盐玻璃的光谱性质与Judd—Ofelt理论分析

制备了掺Er^3 重金属氧氟硅酸盐玻璃，研究了玻璃的吸收光谱和荧光光谱性质，应用Judd-Ofelt理论计算了强度参数Ωt(t＝2，4，6)、Er^3 离子的振子强度、自发辐射跃迁几率、荧光分支比和辐射寿命等光谱参数。应用McCCumber理论，计算了能级^413/2→^4I15/2跃迁的受激发射截面。结果表明：掺Er^3 重金属氧氟硅酸盐玻璃具有较宽的荧光半高宽和较大的受激发射截面。对Er^3 离子在不同玻璃基质中带宽特性的比较发现，掺Er^3 重金属氧氟硅酸盐玻璃的带宽特性与碲酸盐和铋酸盐玻璃相当，大于磷酸盐、锗酸盐和硅酸盐玻璃。     

掺Er~(3+)重金属氧氟硅酸盐玻璃的光谱性质与Judd-Ofelt理论分析

制备了掺Er3+重金属氧氟硅酸盐玻璃,研究了玻璃的吸收光谱和荧光光谱性质,应用Judd Ofelt理论计算了强度参数Ωt(t=2,4,6)、Er3+离子的振子强度、自发辐射跃迁几率、荧光分支比和辐射寿命等光谱参数。应用McCumber理论,计算了能级4I13 2→4I15 2跃迁的受激发射截面。结果表明:掺Er3+重金属氧氟硅酸盐玻璃具有较宽的荧光半高宽和较大的受激发射截面。对Er3+离子在不同玻璃基质中带宽特性的比较发现,掺Er3+重金属氧氟硅酸盐玻璃的带宽特性与碲酸盐和铋酸盐玻璃相当,大于磷酸盐、锗酸盐和硅酸盐玻璃。     

GdF3∶Er^3＋,Yb^3＋的合成和上转换发光特性

采用水热法制备了Er^3＋离子浓度为3%,Yb^3＋离子浓度分别为10%,20%的GdF3∶Er^3＋,Yb^3＋。XRD结果表明：合成的样品均为正交结构的GdF3,Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品的晶粒尺寸分别为28和26nm。研究了980nm红外光激发的上转换发射光谱。结果表明：红光和绿光发射分别来自于Er^3＋离子的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁。样品的绿光发射强度较红光发射强。但绿光和红光发射的相对强度比例与Yb^3＋离子浓度有关。对Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品中可能的上转换发光机制进行了讨论。     

掺铒TeO2-WO3玻璃光谱性能

研究了掺铒TeO2-WO3玻璃的吸收光谱和荧光光谱性质.根据吸收光谱,应用Judd-Ofelt理论计算得到了3个强度参数Ωt(t=2,4,6),分别为Ω2=5.38×10-20cm2,Ω4=1.78×10-20 cm2,Ω6=0.75×10-20cm2.Er3 离子在TeO2-WO3玻璃中的Ω6小于磷酸盐、氟磷酸盐中的Ω6,而大于锗酸盐、硅酸盐和碲酸盐玻璃中的Ω6,说明Er-O键在TeO2-WO3玻璃中的共价性大于磷酸盐、氟磷酸盐中Er-O键的共价性而小于锗酸盐、硅酸盐和碲酸盐玻璃中Er-O键的共价性.4I13/2→4I15/2荧光光谱表明Er3 的荧光半高宽(FWHM)为66 nm,荧光寿命为3.2 ms;应用McCumber理论计算了Er3 的峰值发射截面σe为8.0×10-21cm2.对Er3 在不同基质玻璃中光谱参数比较发现,TeO2-WO3玻璃的FWHM×σe乘积较大,说明其带宽特性较好.     

Er3+单掺与Er3+/Yb3+双掺杂Bi2O3-GeO2-B2O3-ZnO玻璃的光谱研究

用高温融熔法制备了Er^3＋单掺与Er^3＋/Yb^3＋双掺杂的（60-x）Bi2O3-xGeO2-30B2O3-10ZnO （x=5,10, 20, 30）系统玻璃. 用差热曲线（DTA）研究了该玻璃系统的热稳定性. 结果表明, GeO2的掺入, 使得玻璃的软化温度与结晶起始温度的差增加, 玻璃的稳定性与料性增加. 测定了玻璃的吸收光谱. 应用McCumber理论计算了Er^3＋离子的受激发射截面及Er^3＋离子^4I13/2-^4I15/2发射光谱的荧光半高宽. 从吸收光谱特性出发, 应用J-O理论计算了玻璃中Er^3＋离子的强度参数（Ω2, Ω4, Ω6）, Er^3＋离子的自发跃迁几率、荧光分支比以及辐射寿命. 在970 nm波长的激发下, 研究了样品在红外波段的荧光光谱. Yb2O3的掺入, 大幅度地提高了970 nm波长的抽运效率以及在1.54 μm波段的发光强度.     

Tm3+/Yb3+共掺氧氯碲酸盐玻璃上转换发光研究

制备了Tm^3＋/Yb^3＋共掺氧氯碲酸盐玻璃, 研究了玻璃的热稳定性能、 Raman光谱和上转换发光光谱, 分析了上转换发光机制. 结果表明： 通过980 nm的激光二极管激发, 在室温下同时观察到强烈的蓝光（476 nm）和微弱的红光（649 nm）, 分别是Tm^3＋离子的1G4→3H6和1G4→3H4跃迁. 随氯化铅含量增加, 基质玻璃的热稳定性能增强, 基质玻璃的声子能量降低, 上转换蓝光和红光的强度增加. 表明Tm^3＋/Yb^3＋共掺氧氯碲酸盐玻璃是一种上转换蓝光激光器的潜在基质材料.     

Y2O2S∶Er3+，Yb3+的制备及Er3+离子在晶场中的能级分裂

采用沉淀法制备前驱体,通过不同温度合成了上转换发光材料Y2O2S∶Er3+,Yb3+,运用XRD,SEM和上转换发射光谱对其进行表征。结果表明,所合成的Y2O2S∶Er3+Yb3+属于六方晶系晶体,随着合成温度的升高,产物的粒径不断增大,上转换发射光强度逐渐增加。研究Y2O2S∶Er3+Yb3+的上转换发光过程,红光发射和绿光发射分别源于Er3+离子的4F9/2→4I15/2以及2H11/2→4I15/2,4S3/2→4I15/2能级跃迁。利用群论计算了晶场中Er3+离子的能级分裂数目。     

掺铒碲酸盐玻璃光谱特性研究

测试了样品(75-x)TeO2-xWO3-15ZnO-5La2O3-5Nb2O5(摩尔分数)-1%(质量分数)Er2O3(TWZ,x=0,4,8,12,15)和(75-y)TeO2-yB2O3-15ZnO-5La2O3-5Nb2O5(摩尔分数)-1%(质量分数)Er2O3(TBZ,y=0,4,8,12,15)玻璃的吸收光谱、荧光光谱、上转换光谱、能级寿命和热稳定性.应用J-O理论和McCumber理论分别计算了玻璃中Er3+离子光学跃迁强度参数Ωt(t=2,4,6)和受激发射截面.在975 nm激励下,该玻璃同时观察到了绿光(528和544 nm)和红光(660 nm)的上转换发光现象,分别对应于Er3+的.2Hu/2→4I15/2,4S3/2→4I15/2和 4F9/2→4I15/2跃迁.分析比较了玻璃中WO3和B2O3含量变化对光谱参数的影响.结果表明:随着WO3含量的增加,TWZ玻璃1.53μm波段荧光强度逐渐增大,上转换发光强度逐渐减弱,4I13/2能级寿命增加;随着B2O3含量的增加,TBZ玻璃1.53 μm波段荧光强度、上转换发光强度以及4I13/2能级寿命逐渐减弱.另外,TWZ和TBZ系列玻璃的热稳定性都有所提高.     

一种新型铒镱共掺碲硅酸盐玻璃的光谱性质及荧光俘获效应研究

用高温熔制法制备了系列Er^3＋／Yb^3＋共掺碲硅酸盐玻璃样品，测试和分析了玻璃样品的吸收光谱、荧光光谱、上转换发光光谱及热稳定性。结果表明：这种玻璃具有较宽的荧光半高宽、较大的受激发射截面，较好的热稳定性。970nm泵浦下该系列玻璃在可见光525，546和658nm这3处存在明显的上转换现象，它们分别由Er^3＋离子^2H11/2→^4 I15/2，4S3/2→^4 I15/2和^4 F9/2→^4 I15/2辐射跃迁产生。另外，测试和讨论了在不同样品厚度下玻璃的光谱特性，如荧光光谱、荧光寿命和上转换发光光谱等。结果表明，荧光俘获效应对Er^3＋离子1．5μm波段荧光及上转换发光都有着较大的影响，并随着玻璃厚度的增加而增大，导致测量值与实际值产生较大的偏差。     

Er3+/Yb3+共掺纳米In2O3的制备及上转换发光

用低温溶剂热法以乙二醇为溶剂合成了Er3+和Yb3+共掺的In2O3纳米晶。用X射线衍射(XRD)、透射电镜(TEM)、漫反射光谱和上转换发光光谱对样品进行了分析。XRD和TEM结果表明,产物为纯的立方相In2O3结构,粒径约为30 nm;漫反射光谱显示了In2O3∶Er3+,Yb3+纳米晶在522、653和975 nm附近有3个吸收带;在980 nm近红外光激发下,样品发射出中心波长为525及555 nm的绿光和662 nm的红光,分别对应于Er3+的2H11/2→4I15/2、4S3/2→4I15/2和4F9/2→4I15/2跃迁;研究了Er3+和Yb3+离子的不同掺杂浓度对发光强度的影响,确定了Yb3+和Er3+离子的最佳掺杂浓度均为3%;双对数曲线显示绿光和红光的发射过程均为双光子吸收过程,对样品的上转换发光机制进行了初步讨论。     

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     

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.     

K3SbSe3, Rb3SbSe3 und Cs3SbSe3 – Synthese und Kristallstruktur

K₃SbSe₃, Rb₃SbSe₃, and Cs₃SbSe₃ – Synthesis and Crystal Structure The compounds K₃SbSe₃, Rb₃SbSe₃ and Cs₃SbSe₃ were synthesized by heating mixtures of Sb₂O₃ and an alkalicarbonate in a stream of hydrogen saturated by selenium in a temperature range between 750 °C and 800 °C. The compounds crystallize isostructural with Na₃AsS₃. A comparison of atomic distances and bond angles with those of the isostructural arsenic and bismuth compounds shows the effect of lone pairs.     

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.     

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.     

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.     

Synthesis of some derivatives of 3-amino-3-desoxyerythrose and 3-amino-3-desoxy-D-3-erythrose

The synthesis of derivatives of 3-amino-3-deoxy-L-erythrose by LAH or LAD reduction of the oxime of 1,2-O-isopropylidene α-L -glycero-tetros-3-ulofuranose is described.     

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.