Porous silica nanoparticles are considering good systems for drug cargo and liquid separation. In this work we studied the release of rhodamine 6G (Rh6G) from solid and porous silica nanoparticles. Solid and porous SiO2 spheres were prepared by sol-gel method. Nanoporous channels were produced by using a surfactant that was removed by chemical procedure. Rh6G was incorporated into the channels by impregnation. The hexagonal structure of the pores was detected by XRD and confirmed by HRTEM micrographs. Rh6G released from the particles by stirring them in water at controlled speed was studied as function of time by photoluminescence. Released ratio was faster in the solid nanoparticles than in the porous ones. In the last case, a second release mechanism was observed. It was related with rhodamine coming out from the porous.
Rare earths in confined systems are studied because their possible imaging applications. In this work we studied the optical properties of Eu3+ inside nanoporous spheres. Their properties were compared with these from europium in solid SiO2 spheres prepared by sol-gel method. Nanoporus channels were produced by using a surfactant. The last one was removed by chemical procedure. Then, europium was incorporated into the channels. XRD reveals the hexagonal structure of the pores. That was confirmed by HRTEM that shows the channels, clearly. N2 adsorption- desorption isotherm Type IV, characteristic of mesoporous materials, was obtained by BET. The I(5D0→7F2)/I(5D0→7F1) asymmetry ratio from Eu3+ transitions was obtained by photoluminescence. It had a value of 2.65 in the solid spheres and 1.65 in the nanoporous ones. That means Eu3+ is in an asymmetric site in both systems, and asymmetry is bigger in the solid spheres. Because the differences, we can use this parameter to distinguish between both systems, easily. Photoluminescence lifetimes were obtained for the 5D0 → 7F2 emission. It was shorter in the solid spheres than in the nanoporous ones, confirming there is a more asymmetric site for the rare earth in the first case. IR spectra shows Eu3+ is not incorporated as part of the SiO2 network.
Films made of Polymethylmetacrylate (PMMA) and doped with dipolar second order nonlinear optical chromophores
were studied by UV-visible spectroscopy and transmitted resonant Second Harmonic Generation technique. The
chromophores were non-centrosymmetrically oriented by a Corona poling field. The UV-visible spectra were measured
in poled films at normal incidence as function of their poling temperatures (60, 80 and 100°C) and they were analyzed in
terms of the Second Order Parameter (A2). The Second Harmonic Generation (SHG) signals in the films were measured
in-situ as function of the poling time at several incidence angles for each poling temperature. The stability of the SHG
signal was also determined, by turning off the Corona field but leaving the films at their original poling temperature. The
films were of two different kinds: amorphous and nanostructured. All the films doped simultaneously with chromophores
and surfactants showed long-range ordered nanostructures. Two kinds of surfactants were used during the synthesis of
the films: ionic and neutral, both of them induced long-range order in the structure of the PMMA, but only some of the
nanostructured films exhibited enough large SHG signals. The second order nonlinear optical response of the
nanostructured films was compared with the corresponding response of the amorphous films. The long-range order in the
films was detected by X-Ray Diffraction (XRD).
Two and three dimensional structures with micron and submicron resolution have been achieved in commercial resists,
polymeric materials and sol-gel materials by several lithographic techniques. In this context, silicon-based sol-gel
materials are particularly interesting because of their versatility, chemical and thermal stability, amount of embeddable
active compounds. Compared with other micro- and nano-fabrication schemes, the Two Photon Induced Polymerization
is unique in its 3D processing capability. The photopolymerization is performed with laser beam in the near-IR region,
where samples show less absorption and less scattering, giving rise to a deeper penetration of the light. The use of
ultrashort laser pulses allows the starting of nonlinear processes like multiphoton absorption at relatively low average
power without thermally damaging the samples.
In this work we report results on the photopolymerization process in hybrid organic-inorganic films based
photopolymerizable methacrylate-containing Si-nanobuilding blocks. Films, obtained through sol-gel synthesis, are
doped with a photo-initiator allowing a radical polymerization of methacrylic groups. The photo-initiator is activated by
femtosecond laser source, at different input energies. The development of the unexposed regions is performed with a
suitable solvent and the photopolymerized structures are characterized by microscopy techniques.
Amorphous, PMMA: DR1: surfactant and PMMA:DR1:TEOS thin films were prepared by dip-coating. All films were
calcined at 70 °C for 3 hours. For nanostructured thin films two ionic surfactants were used, Sodium Dodecyl Sulfate
(SDS) and Cetyltrimethyl ammonium bromide (CTAB) to obtain two different nanostructures of the PMMA matrix:
lamellar, and hexagonal, respectively. X-ray diffraction studies were performed to determine the long-order structure
tailored in the films. The measurements of the optical absorption and the second harmonic generation (SHG) intensity
were carried out at different orientation arrangements of the chromophores embedded in the films. The chromophore
orientation distributions were obtained by means of the corona technique. These distributions depend on the corona
poling time. We physically modeled the optical absorption and the second harmonic generation experimental results as
function of the corona poling time, employing only one fitting parameter related to the matrix-chromophore interactions.
The physical model and the experimental results were in an excellent agreement. The experimental results fitted by the
model are shown in plots of order parameter against corona poling time and SHG intensity against corona poling time.
The amorphous films provide a larger SHG intensity values than those obtained from the nanostructured films. Thin
films with lamellar structure have a SHG intensity bigger than those from hexagonal and PMMA:TEOS thin films.
Amorphous and nanostructured SiO2:DR1 sol-gel films were prepared by dip-coating. X-ray diffraction studies were
performed to determine the long-order structure obtained in the films. The optical absorption (AO) measurements were
done in three different nanostructures of the SiO2 network: lamellar, hexagonal and mixed. The AO measurements and
the second harmonic generation (SHG) intensity were carried out at different orientation steps of the chromophores
embedded in the films. These chromophore orientation distributions were obtained by means of the corona technique,
and they depend on the corona poling time. We physically model the optical absorption and the second harmonic
generation experimental results as function of the corona poling time, employing only one fitting parameter related to the
matrix-chromophore interactions. The physical model and the experimental results were in an excellent agreement. The
experimental results fitted by the model are shown in plots of order parameter against corona poling time and SHG
intensity against corona poling time. The lamellar structure provides a larger order parameter values than those obtained
for the other structures. A minimum value for the order parameter was detected by means of the optical absorption
measurements at short poling times. For the SHG measurements, four different chromophore concentrations were used.
As the concentration increases the measured SHG intensity increases too, but the increment is limited by the electrostatic
interactions among the chromophores, which is also considered in our model.
We report on the physical modelling of the photoconductive response of nanostructured sol-gel films in function of the silver nitrate concentration (ions and colloids). This model considers several factors as the silver nitrate concentration and the transport parameters obtained. The model is compared with others commonly used. 2d-hexagonal nanostructured sol-gel thin films were prepared by dip-coating method using a non-ionic diblock copolymer Brij58 (surfactant) to produce channels into the film. Silver colloids (metallic Ag0 nanoparticles ) were obtained by spontaneous reduction process of Ag+ ions to Ag0. These nanoparticles were deposited into the channels formed by the surfactant. The structure was identified by X-ray diffraction and TEM. An absorption band located at 430 nm was detected by optical absorption; it corresponds to the plasmon surface. Fit to this band with modified Gans theory is presented. Photoconductivity studies were performed on films with silver ions and films with silver colloids to characterized their mechanisms of charge transport in the darkness and under illumination at 420, 633 nm wavelengths. Transport parameters were calculated. The films with silver colloids exhibit a photovoltaic effect stronger than the films with silver ions. While, the last ones possesses a photoconductivity behaviour.
2d-hexagonal nanostructured sol-gel thin films were prepared by dip-coating method. A neutral surfactant Brij58 was used as template to produced channels into the film. The structure was identified by X-ray diffraction and TEM. Silver nanoparticles were obtained by spontaneous reduction process of Ag+ ions to Ag0 at room temperature. A broad band located at 430 nm was detected by optical absorption; it corresponds to the surface plasmon. Photoconductivity studies were performed on films with ions and with silver nanoparticles to characterize their mechanisms of charge transport in the darkness and under illumination at 420 and 633 nm wavelengths. Straight lines showing an ohmic behavior fit the experimental data. Films without colloids possess normal photoconductivity behavior. But films with colloids present an abnormal response. Transport parameters were calculated. The films with silver nanoparticles exhibit a photovoltaic effect stronger than the films without nanoparticles, except to high concentrations. A theoretical model is proposed to predict these processes as function of the silver concentration.
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