Influence of Oxygen Vacancies on the Luminescence Spectra of Y2O3 Thin Films

Luminescence spectra of Y₂O₃ thin films annealed in air and in vacuum are investigated. It is established that the presence of oxygen vacancies leads to a decrease in the intensity of the luminescence band with a maximum at 3.4 eV (related to emission of selflocalized Frenkel excitons describing the excited state of a molecular ion (YO₆)^9–) and of the luminescence band with a maximum at 2.9 eV (related to the anion sublattice). It is revealed that the oxygen vacancies also lead to a decrease in the luminescence intensity in the 2.60, 2.35, 2.10. 1.90, and 1.70 eV bands that are related to radiative recombination in the donor–acceptor Y³⁺–O^2– pairs. The donor–acceptor distances are calculated.     

Quantitative Modelization of Hydrogen-Bonding in Polyoxometalate Chemistry

The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to polyoxometalate chemistry. Using the Ca₂(H₃O)₂[V₁₀O₂₈]16H₂O crystal structure, it was shown that the relative affinity for protons of the various oxygen sites may be quantitatively determined. The charge distribution was also found to be in good agreement with ¹⁷O and ⁵¹V NMR measurements. The H-bond energy in this kind of compound was found to be about –17 kJmol^–1, i.e., about 20% lower than in hexagonal ice. Finally, the 57 H-atom coordinates characterizing this structure were successfully recovered from a crystal structure optimization in the solid-state through electrostatic balance minimization. The importance of considering neutral clusters for a good modelization was demonstrated not only in the case of the decavanadate structure, but also in polysilicate chemistry. For the first time a clear picture emerges explaining the widespread occurrence of four- and five-membered rings in zeolite and silicate chemistry. The possibility of forming much larger polyanions with transition metal cations, is well explained using the crystal structure of the superfullerene keplerate [Mo₁₃₂O₃₇₂(HCO₂)₃₀(H₂O)₇₂]^42– as a benchmark compound. The possibility of performing an ab-initio retrosynthetic analysis of this cage is demonstrated.     

Structural analysis of tris(tetra-n-butylammonium) hexakisisothiocyanatoyttrate(III)

The structural analysis of [(n-C₄H₉)₄N]₃[Y(NCS)₆] (I) using single-crystal diffraction data and full-matrix least squares refinement has been carried out. The hexaisothiocyanate complex crystallizes in the centrosymmetric triclinic space group P (No. 2) with unit cell constants of a = 12.431(1), b = 12.866(1), c = 22.750(2) Å, = 90.78(1), = 92.05(1), = 96.67(1)°, and Z = 2. The molecular unit consists of three separate cationic tetra-n-butylammonium groups and an independent hexakisisothiocyanatoyttrate anionic group in which the six thiocyanate ligands are octahedrally coordinated through the N atom to the Y central ion. Selected bond distances and angles are presented as well as the synthesis and peripheral studies of (I).     

Thin ORMOSIL Films with Different Organics

Structural, optical and electrical properties of silicate films modified by structure fragments containing different organic groups were studied. The ORMOSILs were produced by a cohydrolysis of tetraethoxysilane with different types of alkyl (aryl) substituted alkoxysilanes. Film structure and its evolution during heat treatment were studied by ellipsometry and IR spectroscopy. For methyl- and phenyl-modified silicate films the shrinkage is lower than for silicate ones in the range of annealing temperature from 200 to 500°C. The shrinkage of phenyl-modified silicate film is more than three times lower than of methyl- and trimethyl-modified ones. The presence of single or double C=C bonds in the organic chain leads to an increase in the film shrinkage due to the thermodestruction of the bond as it is confirmed by IR data. In the case of phenyl- and methyl-modified silicate films this process starts from 500°C and it is accompanied by abrupt film shrinkage. The dielectric constant and the loss tangent of methyl and phenyl groups decrease due to reduction of hydroxyl content and film density. Other groups are not effective due to their thermodestruction at lower temperatures.     

掺Yb3+氧化镧钇透明激光陶瓷的光谱特性

采用传统陶瓷烧结工艺,在无压还原气氛下低温制备出透明性良好的掺Yb3+氧化镧钇透明激光陶瓷,测试了其在室温下的吸收光谱、发射光谱和荧光寿命.结果表明,掺Yb3+氧化镧钇透明激光陶瓷的吸收系数随着Yb3+掺杂浓度的增加而增大,最强吸收峰974nm处的吸收截面为0.90～1.12×10－20 cm2;主发射峰1 032 nm和1 075 nm处的发射截面分别为1.05×10－20 cm2和0.87×10－20 cm2; Yb3+掺杂浓度为5at.%时荧光寿命为1.38 ms,并随Yb3+掺杂浓度的增加而减小;当Yb3+掺杂浓度超过10at.%时,样品中存在严重的浓度猝灭.产生浓度猝灭的原因是高掺杂时离子间存在合作上转换和能量转移.