Ag nanocluster functionalized glasses for efficient photonic conversion in light sources, solar cells and flexible screen monitors.

An ever growing demand for efficient energy conversion, for instance in luminescent lamps, flexible screens and solar cells, results in the current significant growth of research on functionalized nanomaterials for these applications. This paper reviews recent developments of a new class of optically active nanostructured materials based on glasses doped with luminescent Ag nanoclusters consisting of only a few Ag atoms, suitable for mercury-free white light generation and solar down-shifting. This new approach, based solely on Ag nanocluster doped glasses, is compared to other alternatives in the field of Ag and rare-earth ion co-doped materials.

Polarization memory of white luminescence of Ag nanoclusters dispersed in glass host.

A mechanism for white luminescence of Ag nanoclusters dispersed in oxyfluoride glass host has been revealed by studying a temperature dependence of its polarization memory. The spectral dependence of the polarization memory indicates the presence of a variety of Ag nanoclusters, particularly emitting in the blue, green and red. Temperature activated intercluster energy transfer has been found responsible for white luminescence. The means for increasing luminescence quantum yield have been suggested. This efficient white luminescence may be used in highly demanded devices, such as luminescent lamps, displays, color phosphors for LEDs, photovoltaic devices based on down shifting of solar spectrum.

Energy level diagram and kinetics of luminescence of Ag nanoclusters dispersed in a glass host.

A site-selective spectroscopy study of Ag nanoclusters dispersed in oxyfluoride glass hosts has been carried out. The nano- to millisecond, essentially non-exponential, luminescence kinetics of Ag nanoclusters has been detected in the spectral range from 450 to 1000 nm, when excited at discrete wavelengths in the range 250 to 450 nm. Based on these experimental observations, the energy level configuration coordinate diagram for the involved ground and excited singlet/triplet states of the Ag nanoclusters has been proposed and confirmed by the density functional theory (DFT). The sites for the Ag nanoclusters are argued to be multiple. The structure/geometry of the involved Ag nanoclusters has been suggested to involve spin-paired dimers Ag²âº, or tetramers Ag4²âº, with a varying elongation/distortion along the tetramer diagonals.

Quantum cutting in Li (770 nm) and Yb (1000 nm) co-dopant emission bands by energy transfer from the ZnO nano-crystalline host.

Li-Yb co-doped nano-crystalline ZnO has been synthesized by a method of thermal growth from the salt mixtures. X-ray diffraction, transmission electron microscopy, atomic absorption spectroscopy and optical spectroscopy confirm the doping and indicate that the dopants may form Li-Li and Yb(3+)-Li based nanoclusters. When pumped into the conduction and exciton absorption bands of ZnO between 250 to 425 nm, broad emission bands of about 100 nm half-height-width are excited around 770 and 1000 nm, due to Li and Yb dopants, respectively. These emission bands are activated by energy transfer from the ZnO host mostly by quantum cutting processes, which generate pairs of quanta in Li (770 nm) and Yb (1000 nm) emission bands, respectively, out of one quantum absorbed by the ZnO host. These quantum cutting phenomena have great potential for application in the down-conversion layers coupled to the Si solar cells.

Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters.

Bulk oxyfluoride glasses doped with Ag nanoclusters have been prepared using the melt quenching technique. When pumped in the absorption band of Ag nanoclusters between 300 to 500 nm, these glasses emit a very broad luminescence band covering all the visible range with a weak tail extending into the near infrared. The maximum of the luminescence band and its color shifts to the blue with a shortening of the excitation wavelength and an increasing ratio of oxide to fluoride components, resulting in white color luminescence at a particular ratio of oxide to fluoride; with a quantum yield above 20%.

Cathodo- and photoluminescence in Yb(3+)-Er(3+) co-doped PbF(2) nanoparticles.

We have prepared and studied the PbF(2):(Yb(3+),Er(3+)) co-doped nanoparticles, with chemical formula (Yb-Er)(x)Pb(1-x)F(2+x), where x = 0.29, Yb(3+)/Er(3+) = 6, and estimated the energy efficiency for their cathodoluminescence, mostly of Yb(3+), and up-conversion photoluminescence of Er(3+) to reach more than 0.5% and 20%, respectively, which may be the highest to date for rare-earth doped nanoparticles. Electron beam induced temperature rise in the nanoparticles has been estimated by measuring the ratio of green emission bands of Er(3+). These high efficiencies are due to high doping level of nanoparticles and due to low phonon energy of the PbF(2) host.

Optical nanoheater based on the Yb3+-Er3+ co-doped nanoparticles.

Yb(3+)-Er(3+) co-doped fluoride nanoparticles have been prepared. When pumped by 975 nm laser diode into absorption band of Yb(3+), the laser-induced temperature rise up to 800 degrees C has been detected in the nanoparticles by measuring the ratio of the intensities of the thermalised up-conversion luminescence bands (2)H(11/2)-->(4)I(15/2) and (4)S(3/2)-->(4)I(15/2) of Er(3+). These results show that a controlled optical heating of the nanoparticles and their surrounding nano-volumes can be realised, while the location and temperature rise of the nanoparticles and heated nano-volumes can be detected distantly by means of luminescence.

Measurement of quantum yield of up-conversion Luminescence in Er(3+)-doped nano-glass-ceramics.

A measurement of quantum yield of up-conversion luminescence has been done for the Er(3+)-doped transparent oxyfluoride glass-ceramics 32(SiO,)9(AlO1.5)31.5(CdF2)18.5(PbF2)5.5(ZnF2): 3.5(ErF3) mol%, where most of Er3+ dopants partition in 8 nm diameter nano-crystals Er10Pb25F65. The yield was found by newly proposed method using the pump power dependence of the resonant luminescence. The result of the measurement points out that a theoretical maximum of 50% may be reached for the up-conversion luminescence yield in this material. This high yield is shown to be due to low phonon energy and short inter-dopant distances in the nano-crystals.

Preparation and up-conversion luminescence of 8 nm rare-earth doped fluoride nanoparticles.

Free-standing, 8 nm diameter, rare-earth doped nanoparticles Re(10)Pb(25)F(65) have been prepared, where Re stands for either single rare-earth ion, such as Er(3+), Yb(3+), Eu(3+), Dy(3+), Ho(3+), Tm(3+) or combinations of those ions. The nanoparticles have been extracted by chemical etching from the oxyfluoride nano-glass-ceramics template and analyzed by transmission electron microscope with energy dispersion spectroscopy. The nanoparticles show durable up-conversion photoluminescence, which is neither concentration nor impurity quenched after 6 months ageing in ambient atmosphere. High doping levels in these nanoparticles ensure high, up to 15%, quantum yield of up-conversion luminescence.

Broadband telecommunication wavelength emission in Yb(3+)-Er(3+)-Tm(3+) co-doped nano-glassceramics.

Transparent Yb(3+), Er(3+) and Tm(3+) co-doped nano-glass-ceramics 3(SiO(2)2)9(AlO(1.5))31.5(CdF(2))18.5(PbF(2))5.5(ZnF(2)):3.5(Yb-Er-TmF(3)), mol%, have been prepared where co-dopants mostly partition in nano-crystals Pb(1-x) (Yb(3+),Er(3+),Tm(3+))(x)F(2+x) embedded in the glass network. The Yb(3+) ensures high absorption at 980 nm telecommunication pump wavelength and further phonon-mediated energy transfer to Er(3+) and Tm(3+) co-dopants. Er(3+) and Tm(3+) radiate overlapping emission bands from their lowest energy levels, with similar lifetime of about 9 ms, which cover the range between 1.50 to 1.70 mum. The lifetime of all higher levels of Er(3+) and Tm(3+) dopants is shorter than 70 mus due to short inter-dopant distances in the nano-crystals resulting in fast energy transfer to their lowest levels.

Photoinduced anisotropy of photoconductivity in amorphous As50Se50 films.

We show that photoinduced optical anisotropy in amorphous As50Se50 films is accompanied by photoinduced anisotropy of photoconductivity while both photoinduced effects are optically reversible. We suggest that microanisotropic fragments which are the feature of amorphous chalcogenide films do affect not only the light absorption but also the transport of nonequilibrium charge carriers.