Optical Properties and Upconversion Luminescence of BaTiO3 Xerogel Structures Doped with Erbium and Ytterbium.

Erbium upconversion (UC) photoluminescence (PL) from sol-gel derived barium titanate (BaTiO3:Er) xerogel structures fabricated on silicon, glass or fused silica substrates has been studied. Under continuous-wave excitation at 980 nm and nanosecond pulsed excitation at 980 and 1540 nm, the fabricated structures demonstrate room temperature PL with several bands at 410, 523, 546, 658, 800 and 830 nm, corresponding to the 2H9/2 → 4I15/2, 2H11/2 → 4I15/2, 4S3/2 → 4I15/2, 4F9/2→ 4I15/2 and 4I9/2→ 4I15/2 transitions of Er3+ ions. The intensity of erbium UC PL increases when an additional macroporous layer of strontium titanate is used beneath the BaTiO3 xerogel layer. It is also enhanced in BaTiO3 xerogel films codoped with erbium and ytterbium (BaTiO3:(Er,Yb)). For the latter, a redistribution of the intensity of the PL bands is observed depending on the excitation conditions. A multilayer BaTiO3:(Er,Yb)/SiO2 microcavity structure was formed on a fused silica substrate with a cavity mode in the range of 650-680 nm corresponding to one of the UC PL bands of Er3+ ions. The obtained cavity structure annealed at 450 °C provides tuning of the cavity mode by 10 nm in the temperature range from 20 °C to 130 °C. Photonic application of BaTiO3 xerogel structures doped with lanthanides is discussed.

Symmetry Breaking in an Excited Quadrupolar Acridine-Dione Derivative Driven by Hydrogen Bonding.

An acridine-dione derivative (3,3,11,11-tetramethyl-8,16-diphenyl-3,4,8,10,11,12,13,16-octahydroacridino[4,3-c]acridine-1.9(2H,5H)dion) with quadrupolar motif has been synthesized and its stationary and transient spectra have been measured. Stationary absorption and fluorescence spectra as well as nonstationary spectra show no signs of symmetry breaking (SB) in aprotic solvents, even of high polarity. The specific features of SB are revealed in alcohol solvents through a considerable red shift of stationary fluorescence spectra and the appearance of a new excited state absorption band in transient absorption spectra. SB is due to the formation of asymmetric strong hydrogen bonds, mainly on one side of the molecule. An unexpected regularity of symmetry breaking is found in mixtures of aprotic dimethylformamide and protic methanol, where methanol acts as a fluorescence quencher. It is revealed that there is no quenching as long as the methanol concentration is less than the critical value of 9 M. This leads to the conclusion that SB in such mixtures is possible only if the concentration of the protic solvent exceeds a certain threshold value.

UV-Vis absorption spectra and electronic structure of merocyanines in the gas phase.

Gas-phase absorption spectra of a merocyanine vinylogous series have been studied for the first time. In vapour, their long-wavelength absorption bands were found to be considerably shifted hypsochromically, broader, more symmetrical, less intense, and their vinylene shift much smaller than even in low-polarity n-hexane. This indicates that in the gas phase their electronic structure closely approaches the nonpolar polyene limiting structure. The TDDFT calculations of the long-wavelength electronic transitions in the studied merocyanines in vacuo demonstrated good-to-excellent correlation - depending on the functional used - with the obtained experimental data. For comparison, the solvent effects was accounted for using the polarizable continuum model (PCM) with n-hexane and ethanol as low-polarity and high-polarity media, and compared with the UV-Vis spectral data in these solvents. In this case, the discrepancy between theory and experiment was much greater, increasing at that with the polymethine chain length.