Valter Kiisk

Spectral narrowing of self-trapped exciton emission in anatase thin films

Self-trapped excition (STE) emission of TiO2 (anatase) thin films grown by atomic layer deposition technique on single crystal α-Al2O3 (0 1 2) substrates were studied at temperatures 5–120 K. An in-plane preferential orientation of anatase crystallites was detected in the films by using the dependence of the emission polarisation on the observation angle. The STE emission recorded in the direction perpendicular to the film surface had a wide spectrum with the maximum at approximately 2.3 eV. The spectrum recorded from a cleaved edge in the direction nearly parallel to the film surface, showed two sharp peaks (spectral width as low as 0.03 eV) on the top of the broad STE emission band. The beam divergence determined at the wavelengths of these peaks was 6–10°. The effect was interpreted as a constructive interference of the emission leaving the film at the angle that is close to the angle of total internal reflection.

Spectroscopic and crystal field study of Sm3+ in different phases of TiO2

A systematic study of the photoluminescence spectra of samarium-doped crystalline TiO2 was conducted within the temperature range 10–300 K in order to reveal the energy levels of the trivalent impurity ion in different phases of titania. The sol–gel route was used to prepare Sm-doped TiO2 powders. The nanocrystalline anatase phase was obtained by annealing up to 800 °C, whereas the rutile phase was developed by annealing above 1000 °C. Crystal field calculations of Sm3+ energy levels in the two phases of TiO2 (anatase and rutile) were performed for the first time. The obtained set of energy levels assuming positioning of the Sm3+ ions in regular TiO2 lattice sites was consistent with the experimental results. The effect of the different phases of titania on the impurity is discussed.

Influence of ambient gas on the photoluminescence of sol-gel derived TiO2:Sm3+ films

Photoluminescence (PL) of TiO2:Sm3+ thin films was studied at RT. The films were prepared by the sol-gel spin-coating technique or by atomic layer deposition (ALD) followed by ion implantation. The PL was excited with a Nd:YAG pulse laser emitting at 355 nm. The spectrum of PL consists of intense Sm3+-specific emission lines with a well-pronounced fine structure. The influence of different gaseous environments (air, oxygen, nitrogen) or vacuum on the Sm3+ emission was investigated. In the case of a permanent irradiation of sol-gel films in an oxygen-containing environment, the PL intensity increased. The increase was significantly large but slow. The subsequent evacuation of the measurement chamber led to a rapid decrease of the emission below the detection limit. When the oxygen-containing gas was without any intermediate evacuation replaced by nitrogen, the PL intensity descended to an almost vacuum level. The subsequent exposure to oxygen led to a rather fast emission recovery. The ALD-prepared films exhibited a similar but markedly slower response. The fast response observed was attributed to the adsorption of oxygen on the surface, and the slower one, to the diffusion of oxygen vacancies taking place under the irradiation in the bulk.

Luminescent materials based on thin metal oxide films doped with rare earth ions

Luminescent films of TiO2: Sm were prepared by the sol-gel method using the spray pyrolysis technique. Various techniques (including IR absorption, Raman, AFM, XPS, photoluminescence) were used to characterize the samples. After a thermal treatment up to 750°C, intense Sm3+ luminescence with a well-resolved fine structure was observed under optical excitation within the fundamental absorption band of the TiO2 host. After further thermal treatments up to 950°C, the luminescence was quenched, although no anataseto-rutile phase transformation was observed. This behavior is attributed to nanocrystallinity and segregation of Sm ions in the surface layer.

Alkoxide-based precursors for direct drawing of metal oxide micro- and nanofibres

Abstract The invention of electrospinning has solved the problem of producing micro- and nanoscaled metal oxide fibres in bulk quantities. However, until now no methods have been available for preparing a single nanofibre of a metal oxide. In this work, the direct drawing method was successfully applied to produce metal oxide (SnO2, TiO2, ZrO2, HfO2 and CeO2) fibres with a high aspect ratio (up to 10 000) and a diameter as small as 200 nm. The sol–gel processing includes consumption of precursors obtained from alkoxides by aqueous or non-aqueous polymerization. Shear thinning of the precursors enables pulling a material into a fibre. This rheological behaviour can be explained by sliding of particles owing to external forces. Transmission (propagation) of light along microscaled fibres and their excellent surface morphology suggest that metal oxide nanofibres can be directly drawn from sol precursors for use in integrated photonic systems.

Afterglow and thermoluminescence of ZrO2 nanopowders

A careful study of the phosphorescence afterglow and the thermoluminescence (TL) of sol-gel-prepared m-ZrO2 nanocrystalline powders in an extended temperature range −100 to 300 °C was carried out. Wavelength-resolved TL proved the existence of a single active luminescence centre in this temperature range. A TL method based on various heating rates was used to derive more reliable trap depths of 0.75, 0.95, 1.25, 1.46 and 1.66 eV whereas deconvolution methods provided somewhat lower values. The most intense room-temperature afterglows (that were easily observable beyond 1000 s) were obtained from samples annealed at 1250 and 1500 °C, and were attributed mainly to depopulation of the 1.25 eV traps.

Optical study of local strain related disordering in CVD-grown MoSe2 monolayers

We present temperature dependent micro-photoluminescence and room temperature photoreflectance spectroscopy studies on aged MoSe2 monolayers with high surface roughness. A0 and B0 exciton bands were detected at 1.512 eV and 1.72 eV, respectively, which are 50–70 meV lower than those commonly reported for high-quality samples. It is shown that the difference can be accounted for using a model of localized excitons for disordered MoSe2 monolayers where the optical band gap energy fluctuations could be caused by random distribution of local tensile strain due to surface roughness. The density of localized exciton states is found to follow the Lorentzian shape, where the peak of this distribution is about 70 meV from the energy of delocalized states.

Confocal detection of Rayleigh scattering for residual stress measurement in chemically tempered glass

A new optical method is presented for evaluation of the stress profile in chemically tempered (chemically strengthened) glass based on confocal detection of scattered laser beam. Theoretically, a lateral resolution of 0.2 μm and a depth resolution of 0.6 μm could be achieved by using a confocal microscope with high-NA immersion objective. The stress profile in the 250 μm thick surface layer of chemically tempered lithium aluminosilicate glass was measured with a high spatial resolution to illustrate the capability of the method. The confocal method is validated using transmission photoelastic and Na+ ion concentration profile measurement. Compositional influence on the stress-optic coefficient is calculated and discussed. Our method opens up new possibilities for three-dimensional scattered light tomography of mechanical imaging in birefringent materials.

Angular shaping of fluorescence from synthetic opal-based photonic crystal

Spectral, angular, and temporal distributions of fluorescence as well as specular reflection were investigated for silica-based artificial opals. Periodic arrangement of nanosized silica globules in the opal causes a specific dip in the defect-related fluorescence spectra and a peak in the reflectance spectrum. The spectral position of the dip coincides with the photonic stop band. The latter is dependent on the size of silica globules and the angle of observation. The spectral shape and intensity of defect-related fluorescence can be controlled by variation of detection angle. Fluorescence intensity increases up to two times at the edges of the spectral dip. Partial photobleaching of fluorescence was observed. Photonic origin of the observed effects is discussed.

Gilded nanoparticles for plasmonically enhanced fluorescence in TiO2:Sm3+ sol-gel films

Silica-gold core-shell nanoparticles were used for plasmonic enhancement of rare earth fluorescence in sol-gel-derived TiO2:Sm3+ films. Local enhancement of Sm3+ fluorescence in the vicinity of separate gilded nanoparticles was revealed by a combination of dark field microscopy and fluorescence spectroscopy techniques. An intensity enhancement of Sm3+ fluorescence varies from 2.5 to 10 times depending on the used direct (visible) or indirect (ultraviolet) excitations. Analysis of fluorescence lifetimes suggests that the locally stronger fluorescence occurs because of higher plasmon-coupled direct absorption of exciting light by the Sm3+ ions or due to plasmon-assisted non-radiative energy transfer from the excitons of TiO2 host to the rare earth ions.PACS78; 78.67.-n; 78.67.Bf