LUMINESCENT PROPERTIES OF SILVER CLUSTERS FORMED BY ION EXCHANGE METHOD IN PHOTO-THERMO-REFRACTIVE GLASS

Subject of Study.The paper deals with novel research of ion exchange duration influence on spectral-luminescent properties of silver clusters formed in photo-thermo-refractive glass. Method. Photo-thermo-refractive matrix glass based on Na2O–Al2O3–ZnO–SiO2–F (% mol.) system doped with 0,002% mol. of Sb2O3 was synthesized for further research. Silver ions were introduced with low temperature ion exchange method. The glass samples were immersed in the mixture of sodium and silver nitrates 5AgNO3/95NaNO3 (% mol.) at the temperature of 320 °C. Ion exchange duration varied from 5 minutes to 21 hours. Luminescent silver clusters were formed in surface layers of photo-thermo-refractive glass by subsequent heat treatment at the temperature of 450 °C. Main Results. Embedding of silver ions in photo-thermo-refractive glass with ion exchange method led to long-wavelength shift of the UV edge of strong absorption. Location of the UV edge of strong absorption and emission peak of silver clusters depends on ion exchange duration and shifts to the greater wavelengthswith increasing the ion exchange process time. Quantum yield of luminescence decreases significantly according to Stern-Volmer equation with the rising of ion exchange duration. Practical Relevance. Research results can be used for developing white LEDs and down-convertors of solar radiation

Durability study of a fluorescent optical memory in glass studied by luminescence spectroscopy

Thermal stress at 100 °C for more than 3168 h of a fluorescent optical memory composed of laser written silver nano clusters embedded in glass has been performed. Measurements of luminescence spectra have been carried out at different times, showing a decreasing and an increasing evolution of the red and the blue part of the spectrum, respectively. This evolution has been attributed to the diffusion and the reorganization of different silver species inside the matrix, altering the internal electric field. Stark effect based modeling enables the degradation mode of the memory

Durability study of a fluorescent optical memory in glass studied by luminescence spectroscopy

Thermal stress at 100 °C for more than 3168 h of a fluorescent optical memory composed of laser written silver nano clusters embedded in glass has been performed. Measurements of luminescence spectra have been carried out at different times, showing a decreasing and an increasing evolution of the red and the blue part of the spectrum, respectively. This evolution has been attributed to the diffusion and the reorganization of different silver species inside the matrix, altering the internal electric field. Stark effect based modeling enables the degradation mode of the memory

Direct laser writing of a new type of optical waveguides and components in silver containing glasses

"Thèse en cotutelle, Doctorat en physique; Université Laval, Québec, Canada et Université de Bordeaux, Talence, France"L'inscription laser directe est un domaine de recherche en croissance depuis ces deux dernières décennies, fournissant un moyen efficace et robuste pour inscrire directement des structures en trois dimensions (3D) dans des matériaux transparents tels que des verres en utilisant des impulsions laser femtosecondes. Cette technique présente de nombreux avantages par rapport à la technique de lithographie, qui se limite à la structuration en deux dimensions (2D) et implique de nombreuses étapes de fabrication. Cela rend la technique d’inscription laser directe bien adaptée aux nouveaux procédés de fabrication. Généralement, l’inscription laser dans les verres induit des changements physiques tels qu'un changement permanent de l'indice de réfraction localisé. Ces modifications ont été classées en trois types distincts:(type I, type II et type III). Dans ce travail, nous présentons un nouveau type de changement d'indice de réfraction, appelé type A qui est basé sur la création d’agrégats d'argent photo-induits. En effet, dans des verres dans lesquels sont incorporés des ions argent Ag+, lors de leur synthèse, l’inscription laser directe induit la création d’agrégats d’argent fluorescents Agmx+ au voisinage du voxel d’interaction. Ces agrégats modifient localement les propriétés optiques comme la fluorescence, la non-linéarité et la réponse plasmonique du verre. Ainsi, différents guides d'ondes, un séparateur de faisceau 50-50, ainsi que des coupleurs optiques ont été inscrits en se basant sur ce nouveau type A et complétement caractérisés. D'autre part, une étude comparative entre les deux types de guides d'ondes (type A et type I) est présentée, tout en montrant qu’en ajustant les paramètres laser, il est possible de déclencher soit le type I soit le type A. Enfin, en se basant sur des guides d’ondes de type A inscrits proche de la surface du verre, un capteur d'indice de réfraction hautement sensible a été inscrit dans une lame de verre de 1 cm de long. Ce capteur miniaturisé peut présenter deux fenêtres de détection d’indice, ce qui constitue une première mondiale. Les propriétés des guides d'ondes inscrits dans ces verres massifs ont été transposées à des fibres en forme de ruban, du même matériau contenant de l'argent. Les résultats obtenus dans ce travail de thèse ouvrent la voie à la fabrication de circuits intégrés en 3D et de capteurs à fibre basés sur des propriétés optiques originales inaccessibles avec des guides d’onde de type I standard.Direct Laser Writing (DLW) has been an exponentially growing research field during the last two decades, by providing an efficient and robust way to directly fabricate three dimensional (3D) structures in transparent materials such as glasses using femtosecond laser pulses. It exhibits many advantages over the lithography technique, which is mostly limited to two dimensional (2D) structuring and involves many fabrication steps. This competitive aspect makes the DLW technique suitable for future technological transfer to advanced industrial manufacturing. Generally, DLW in glasses induces physical changes such as permanent local refractive index modifications that have been classified under three distinct types: (Type I, Type II & Type III). In silver containing glasses with embedded silver ions Ag+, DLW induces the creation of fluorescent silver clusters Agmx+ at the vicinity of the interaction voxel. In this work, we present a new type of refractive index change, called type A occurring in the low pulse energy regime that is based on the creation of the photo-induced silver clusters allowing the creation of new linear and nonlinear optical waveguides in silver containing glasses. Various waveguides, a 50- 50 Y beam splitter, as well as optical couplers, were written based on type A modification inside bulk glasses and further characterized. In addition, a comparitive study between type A and type I waveguides is presented, showing that finely tuning the laser parameters allows the creation of either type A or type I modifications inside silver containing glasses. Finally, based on type A near-surface waveguides, a highly sensitive refractive index sensor is created in a 1 cm glass chip, which could exhibit a pioneer demonstration of double sensing refractive ranges. The waveguiding properties observed and reported in the bulk of such silver containing glasses were transposed to ribbon shaped fibers of the same material. Those results pave the way towards the fabrication of 3D integrated circuits and fiber sensors with original fluorescent, nonlinear and plasmonic properties that are not accessible using the standard type I modification