Upconversion luminescence in Er3+ doped Ga10Ge 25S65 glass and glass-ceramic excited in the near-infrared

The infrared-to-visible frequency upconversion was investigated in Er 3+-doped Ga10Ge25S65 glass and in the transparent glass-ceramic obtained by heat-treatment of the glass above its glass-transition temperature. Continuous-wave and pulsed lasers operating at 980 nm and 1480 nm were used as excitation sources. The green (2H 11/2 → 4I15/2; 4S3/2 → 4I15/2) and red (4F9/2 → 4I15/2) photoluminescence (PL) signals due to the Er3+ ions were characterized. The PL decay times were influenced by energy transfer among Er3+ ions, by cross-relaxation processes and by energy transfer from the Er3+ ions to the host material. The PL from the Er3+ ions hosted in the crystalline phase was distinguished only when the glass-ceramic was excited by the 1480 nm pulsed laser. The excitation pathways responsible for the green and red PL bands are discussed to explain the differences between the spectra observed under continuous-wave and pulsed excitation. © 2013 American Institute of Physics.

Visible to infrared energy conversion in Pr3+-Yb3+ co-doped fluoroindate glasses

Processes involving visible to infrared energy conversion are presented for Pr3+-Yb3+ co-doped fluoroindate glasses. The emission in the visible and infrared regions, the luminescence decay time of the Pr 3+:3P0 → 3H4 (482 nm), Pr3+:1D2 → 3H6 (800 nm), Yb3+:2F5/2 → 2F 7/2 (1044 nm) transitions and the photoluminescence excitation spectra were measured in Pr3+ samples and in Pr3+-Yb 3+ samples as a function of the Yb3+ concentration. In addition, energy transfer efficiencies were estimated from Pr3+: 3P0 and Pr3+:1D2 levels to Yb3+:2F7/2 level. Down-Conversion (DC) emission is observed due to a combination of two different processes: 1-a one-step cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) resulting in one photon emitted by Pr3+ (1G4 → 3H5) and one photon emitted by Yb3+ (2F7/2 → 2F5/2); 2-a resonant two-step first order energy transfer, where the first part of energy is transferred to Yb3+ neighbor through cross relaxation (Pr3+:3P0 → 1G4; Yb3+:2F7/2 → 2F5/2) followed by a second energy transfer step (Pr 3+:1G4 → 3H4; Yb3+:2F7/2 → 2F5/2). A third process leading to one IR photon emission to each visible photon absorbed involves cross relaxation energy transfer (Pr3+: 1D2 → 3F4; Yb 3+:2F7/2 → 2F5/2). © 2013 Elsevier B.V. All rights reserved.

Persistent luminescence mechanisms: human imagination at work

The present status and future progress of the mechanisms of persistent luminescence are critically treated with the present knowledge. The advantages to be achieved by a further need as well as the pitfalls of the excessive use of imagination are shown. As usual, in the beginning of the present era of persistent luminescence since the mid 1990s, the imagination played a more important role than the sparse solid experimental data and the chemical common sense and knowledge was largely ignored. Since some five years, the mechanistic studies seem to have reached the maturity and - perhaps deceivingly - it seems that there are only details to be solved. However, the development of red emitting nanocrystalline materials poses a challenge also to the more fundamental studies and interpretation. The questions still luring in the darkness include the problems how the increased surface area affects the defect structure and how the "persistent energy transfer" really works. There is still some light to be thrown onto these matters starting with agreeing on the terminology: the term phosphorescence should be abandoned altogether. The long lifetime of persistent luminescence is due to trapping of excitation energy, not to the forbidden nature of the luminescent transition. However, the technically well-suited term "afterglow" should be retained for harmful, short persistent luminescence. (C) 2012 Optical Society of America

Plasmonic Coupling in Er3+:Au Tellurite Glass

In this paper, we report on luminescence and absorbance effects of Er+3:Au-doped tellurite glasses synthesized by a melting-quenching and heat treatment technique. After annealing times of 2.5, 5.0, 7.5, and 10.0 h, at 300 A degrees C, the gold nanoparticles (GNP) effects on the Er+3 are verified from luminescence spectra and the corresponding levels lifetime. The localized surface plasmon resonance around 800 nm produced a maximum fluorescence enhancement for the band ranging from 800 to 840 nm, corresponding to the transitions H-4(11/2) -> aEuro parts per thousand I-4(13/2) (805 nm) and S-4(3/2) -> aEuro parts per thousand I-4(13/2) (840 nm), with annealing time till 7.5 h. The measured lifetime of the levels H-4(11/2) and S-4(3/2) confirmed the lifetime reduction due to the energy transfer from the GNP to Er+3, causing an enhanced photon emission rate in these levels.

Infrared-to-visible upconversion emission in Er3+ doped TeO2-WO3-Bi2O3 glasses with silver nanoparticles

The influence of silver nanoparticles (NPs) on the frequency upconversion luminescence in Er3+ doped TeO2-WO3-Bi2O3 glasses is reported. The effect of the NPs on the Er3+ luminescence was controlled by appropriate heat-treatment of the samples. Enhancement up to 700% was obtained for the upconverted emissions at 527, 550, and 660 nm, when a laser at 980 nm is used for excitation. Since the laser frequency is far from the NPs surface plasmon resonance frequency, the luminescence enhancement is attributed to the local field increase in the proximity of the NPs and not to energy transfer from the NPs to the emitters as is usually reported. This is the first time that the effect is investigated for tellurite-tungstate-bismutate glasses and the enhancement observed is the largest reported for a tellurium oxide based glass. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754468]

Novel porphyrin amino acids as building blocks for artificial photosynthetic reaction centers : photoinduced energy and electron transfer

This thesis reports on the synthesis and characterisation of trans-(M)AB2C meso-substituted porphyrin amino acid esters (PAr) (M = 2H or Zn) with tunable electron donating and electron withdrawing Ar substituents at B positions (Ar = 4-C6H4OnBu, 4-C6H4OMe, 2,4,6-C6H2Me3, 4-C6H4Me, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5). These porphyrins were used as key building blocks for photosynthetic LHC (LHC = light-harvesting antenna complex) and RC (RC = reaction center) model compounds.rnBased on free-base or zinc(II) porphyrin amino acid esters and porphyrin acids several amide linked free-base bis(porphyrins) PAr1-PAr2 (Ar1 = 2,4,6-C6H2Me3, C6F5 and Ar2 = 2,4,6-C6H2Me3, 4-C6H4F, 4-C6H4CF3, C6F5), mono metallated bis(porphyrin) PAr1-(Zn)PAr2 (Ar1 = 2,4,6-C6H2Me3 and Ar2 =4-C6H4F) and its doubly zincated complexes (Zn)PAr1-(Zn)PAr2 were prepared. In the fluorescence spectra of free-base bis(porphyrins) the porphyrin with the strongest electron donating power of Ar substituents at B positions is the light emitting unity. The emission of mono metallated bis(porphyrin) occurs only from the free-base porphyrin building block. This phenomenon is caused by an efficient energy transfer likely via the Dexter through-bond mechanism.rnLinking of anthraquinone (Q) as electron acceptor (A) to the N-terminus of porphyrin amino acid esters ((M)PAr) and aminoferrocene (Fc) as electron donor (D) to the C-terminus of the porphyrin resulting in Q-(M)PAr-Fc triads (M = 2H or Zn, Ar = 4-C6H4OnBu, 4-C6H4OMe, 2,4,6-C6H2Me3, 4-C6H4Me, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) with tunable electron density at the porphyrin chromophore. In these triads initial oxidative PET (Q←(M)PAr) and reductive PET ((M)PAr→Fc) (PET = photoinduced electron transfer) are possible. Both processes leads to an emission quenching of (M)PAr. The efficiency of the PET pathways occurring in the Marcus normal region is controlled by the specific porphyrin electron density.rnAmide-linked conjugates PAr-Fc (Ar = 2,4,6-C6H2Me3, C6F5) and Fmoc-Fc-PAr1 (N-Fmoc-Fc = N-Fmoc protected 1,1’-ferrocene amino acid; Ar1 = C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) as well as hinges PAr2-Fc-PAr1 (Ar1 = C6H5, 4-C6H4F and Ar2 = 2,4,6-C6H2Me3) were studied with respect to the reductive PET. The PET driving force (−GET) in dyads increases with the increasing electron withdrawing character of Ar substituents. Additionally, intramolecular energy transfer between porphyrins PAr1 and PAr2 is feasible in the hinges via the Förster mechanism.rn

Energy and charge transfer dynamics in DNA based light harvesting antennae

DNA can serve as a versatile scaffold for chromophore assemblies. For example, light-harvesting antennae have been realized by incorporating phenanthrene and pyrene building blocks into DNA strands. It was shown that by exciting at 320 nm (absorption of phenanthrene), an emission at 450 nm is observed which corresponds to a phenanthrene-pyrene exciplex. The more phenanthrenes are added into the DNA duplex, the higher is the fluorescence intensity with no significant change in quantum yield. This shows that phenanthrene acts as a donor and efficiently transfers the excitation energy to the pyrene. Up to now, the mechanism of this energy transfer and exciplex formation is not known. Therefore, we first aim at studying the photo-cycle of such DNA assemblies through transient absorption spectroscopy. Based on the results, we will explore ways to manipulate the energy transfer by application of intense THz fields. Ground as well as excited state Stark effect dynamics will be investigated.

Upconversion in Nd(3+)-doped glasses: Microscopic theory and spectroscopic measurements

In this work, we report a systematic investigation of upconversion losses and their effects on fluorescence quantum efficiency and fractional thermal loading in Nd(3+)-doped fluoride glasses. The energy transfer upconversion (gamma(up)) parameter, which describes upconversion losses, was experimentally determined using different methods: thermal lens (TL) technique and steady state luminescence (SSL) measurements. Additionally, the upconversion parameter was also obtained from energy transfer models and excited state absorption measurements. The results reveal that the microscopic treatment provided by the energy transfer models is similar to the macroscopic ones achieved from the TL and SSL measurements because similar gamma(up) parameters were obtained. Besides, the achieved results also point out the migration-assisted energy transfer according to diffusion-limited regime rather than hopping regime as responsible for the upconversion losses in Nd-doped glasses. (c) 2008 American Institute of Physics.

On the wake-induced vibration of tandem circular cylinders: the vortex interaction excitation mechanism

The mechanism of wake-induced vibrations (WIV) of a pair of cylinders in a tandem arrangement is investigated by experiments. A typical WIV response is characterized by a build-up of amplitude persisting to high reduced velocities; this is different from a typical vortex-induced vibration (VIV) response, which occurs in a limited resonance range. We suggest that WIV of the downstream cylinder is excited by the unsteady vortex-structure interactions between the body and the upstream wake. Coherent vortices interfering with the downstream cylinder induce fluctuations in the fluid force that are not synchronized with the motion. A favourable phase lag between the displacement and the fluid force guarantees that a positive energy transfer from the flow to the structure sustains the oscillations. If the unsteady vortices are removed from the wake of the upstream body then WIV will not be excited. An experiment performed in a steady shear flow turned out to be central to the understanding of the origin of the fluid forces acting on the downstream cylinder.

Europium luminescent polymeric microspheres fabricated by spray drying process

The spray drying method was used to prepare luminescent microspheres. These microspheres were prepared by spraying an aqueous solution of dextrin and an europium(III) complex with subsequent drying in a hot medium. The spray dried powder was characterized by scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). Particle size distribution was estimated from SEM images. The ultrasonic spray drying technique was successfully applied to yield a microparticulated and red luminescent powder composed by the [Eu(dpa)(3)](3-) stop (dpa = dipicolinic acid) complex incorporated in dextrin microspheres.

Non-equilibrium energy and momentum accommodation coefficients of Ar atoms scattered from Ni(001) in the thermal regime: A molecular dynamics study

Molecular dynamics simulations are used to study energy and momentum transfer of low-energy Ar atoms scattered from the Ni(001) surface. The investigation concentrates on the dependence of these processes on incident energy, angles of incidence and surface temperature. Energy transfer exhibits a strong dependence on the surface temperature, at incident energies below 500 meV, and incident angles close to specular incidence. Above 500 meV, the surface temperature dependence vanishes, and a limiting value in the amount of energy transferred to the surface is attained. Momentum exchange is investigated in terms of tangential and normal components. Both components exhibit a weak surface temperature dependence, but they have opposite behaviours at all incidence angles. In each component, momentum can be lost or gained following the interaction with the surface. (C) 1997 Elsevier Science B.V.

Energy evaporation: the new concept of indoor systems for WPT and EH embedded into the floor

This work introduces a novel idea for wireless energy transfer, proposing for the first time the unit-cell of an indoor localization and RF harvesting system embedded into the floor. The unit-cell is composed by a 5.8 GHz patch antenna surrounded by a 13.56 MHz coil. The coil locates a device and activate the patch which, connected to a power grid, radiates to wirelessly charge the localized device. The HF and RF circuits co-existence and functionality are demonstrated in this paper, the novelty of which is also in the adoption of low cost and most of all ecofriendly materials, such as wood and cork, as substrates for electronics.

Silicon nanocluster sensitization of erbium ions under low-energy optical excitation

The sensitizing action of amorphous silicon nanoclusters on erbium ions in thin silica films has been studied under low-energy (long wavelength) optical excitation. Profound differences in fast visible and infrared emission dynamics have been found with respect to the high-energy (shortwavelength) case. These findings point out to a strong dependence of the energy transfer process on the optical excitation energy. Total inhibition of energy transfer to erbium states higher than thefirst excited state (4I13/2) has been demonstrated for excitation energy below 1.82 eV (excitation wavelength longer than 680 nm). Direct excitation of erbium ions to the first excited state (4I13/2)has been confirmed to be the dominant energy transfer mechanism over the whole spectral range of optical excitation used (540 nm¿680 nm).