Francisco Gallego-Gómez

Near-infrared sensitivity enhancement of photorefractive polymer composites by pre-illumination

Among the various applications for reversible holographic storage media, a particularly interesting one is time-gated holographic imaging (TGHI). This technique could provide a noninvasive medical diagnosis tool, related to optical coherence tomography. In this technique, biological samples are illuminated within their transparency window with near-infrared light, and information about subsurface features is obtained by a detection method that distinguishes between reflected photons originating from a certain depth and those scattered from various depths. Such an application requires reversible holographic storage media with very high sensitivity in the near-infrared. Photorefractive materials, in particular certain amorphous organic systems, are in principle promising candidate media, but their sensitivity has so far been too low, mainly owing to their long response times in the near-infrared. Here we introduce an organic photorefractive material—a composite based on the poly(arylene vinylene) copolymer TPD-PPV—that exhibits favourable near-infrared characteristics. We show that pre-illumination of this material at a shorter wavelength before holographic recording improves the response time by a factor of 40. This process was found to be reversible. We demonstrate multiple holographic recording with this technique at video rate under practical conditions.

Water-Dependent Photonic Bandgap in Silica Artificial Opals

Some characteristics of silica--based structures-like the photonic properties of artificial opals formed by silica spheres--can be greatly affected by the presence of adsorbed water. The reversible modification of the water content of an opal is investigated here by moderate heating (below 300 °C) and measuring in situ the changes in the photonic bandgap. Due to reversible removal of interstitial water, large blueshifts of 30 nm and a bandgap narrowing of 7% are observed. The latter is particularly surprising, because water desorption increases the refractive index contrast, which should lead instead to bandgap broadening. A quantitative explanation of this experiment is provided using a simple model for water distribution in the opal that assumes a nonclose-packed fcc structure. This model further predicts that, at room temperature, about 50% of the interstitial water forms necks between nearest-neighbor spheres, which are separated by 5% of their diameter. Upon heating, dehydration predominantly occurs at the sphere surfaces (in the opal voids), so that above 65 °C the remaining water resides exclusively in the necks. A near-close-packed fcc arrangement is only achieved above 200 °C. The high sensitivity to water changes exhibited by silica opals, even under gentle heating of few degrees, must be taken into account for practical applications. Remarkably, accurate control of the distance between spheres--from 16 to 1 nm--is obtained with temperature. In this study, novel use of the optical properties of the opal is made to infer quantitative information about water distribution within silica beads and dehydration phenomena from simple reflection spectra. Taking advantage of the well-defined opal morphology, this approach offers a simple tool for the straightforward investigation of generic adsorption-desorption phenomena, which might be extrapolated to many other fields involving capillary condensation.

Nanoscale morphology of water in silica colloidal crystals

We show a simple method to visualize the morphology of water adsorbed within the pore network of colloidal crystals made of submicrometer silica spheres. Water is replicated into silica by modified silicon tetrachloride hydrolysation under standard ambient conditions, making it visible to standard electronic microscopy and thus allowing one to discern the original water distribution. Different distribution patterns are identified depending on the water content, surface condition, and spheres arrangement. The dimension and shape of wetting layers (covering the submicrometer spheres) and capillary bridges (joining them) are measurable at the nanoscale. We finally use these findings to demonstrate proof-of-principle of fabrication of isolated and freestanding silica nanorings by using hydrophobic polymeric templates and selective etching.

High-performance reflection gratings in photorefractive polymers

To date highest external diffraction efficiency and two-beam coupling gain at moderate applied fields (about 30% and 260cm−1, respectively, at 60V∕μm) are obtained in photorefractive reflection gratings with grating periods of about 0.2μm using a standard low-glass-temperature polyvinylcarbazole based composite. Reflection gratings exhibit five times faster growth/erasure rates than conventional transmission gratings. Further, their performance is very sensitive to changes in the saturation field. This allows a reliable calculation of the photorefractive trap density, which shows a significant enhancement with the field. Finally, the theoretical analysis reveals the geometry-dependent competition between the birefringence and electro-optic contributions.

Exploration and Exploitation of Water in Colloidal Crystals

Water on solid surfaces is ubiquitously found in nature, in most cases due to mere adsorption from ambient moisture. Because porous structures have large surfaces, water may significantly affect their characteristics. This is particularly obvious in systems formed by separate particles, whose interactions are strongly influenced by small amounts of liquid. Water/solid phenomena, like adsorption, condensation, capillary forces, or interparticle cohesion, have typically been studied at relatively large scales down to the microscale, like in wet granular media. However, much less is known about how water is confined and acts at the nanoscale, for example, in the interstices of divided systems, something of utmost importance in many areas of materials science nowadays. With novel approaches, in-depth investigations as to where and how water is placed in the nanometer-sized pores of self-assembled colloidal crystals have been made, which are employed as a well-defined, versatile model system with useful optical properties. In this Progress Report, knowledge gained in the last few years about water distribution in such nanoconfinements is gathered, along with how it can be controlled and the consequences it brings about to extract new or enhance existing material functionalities. New methods developed and new capabilities of standard techniques are described, and the water interplay with the optical, chemical, and mechanical properties of the ensemble are discussed. Some lines for applicability are also highlighted and aspects to be addressed in the near future are critically summarized.

Three Regimes of Water Adsorption in Annealed Silica Opals and Optical Assessment

Physisorbed and structurally bound (surface and internal) water in silica opals are distinguished and quantified by thermogravimetry. By controlled dehydroxylation with thermal annealing, we correlate these forms of water with the silica chemistry. In particular, we find that the silica capability to physically adsorb water from ambient moisture exhibits three regimes, associated with the distinct condensation behavior of bonded and unbonded surface silanols. Features in both opal IR absorbance and photonic band gap reproduce the physisorbed water regimes. This allows direct assessment of the water content and its evolution just by routine optical spectroscopy, being a useful tool for local and nondestructive analysis of colloidal silica. Besides, this provides a simple recipe for accurate tuning of the opal photonic band gap (about 10% in position and width) by just selecting the annealing temperature.

Light Emission from Nanocrystalline Si Inverse Opals and Controlled Passivation by Atomic Layer Deposited Al2O3

This work was partially supported by EU FP7 NoE Nanophotonics 4 Energy grant No. 248855; the Spanish MICINN CSD2007-0046 (Nanolight.es), CSD2008-00023 (FUNCOAT), CSD2009-00013 (Imagine), MAT2009-07841 (GLUSFA), TEC2008-06756-C03-02/TEC, CSIC PIF08-016 (Intramural Frontera), MAT2010-18432 and the Comunidad de Madrid S2009/MAT-1756 (PHAMA) projects. F. G. G. was supported by the JAE Postdoctoral Program from the CSIC. M. I. is a Ramon y Cajal researcher.

Bipolar charge transport in an organic photorefractive composite

The authors report on tuning the near-infrared holographic recording speed in a poly(N-vinylcarbazole) based photorefractive composite by illuminating it at a wavelength of very strong absorption. Due to the small penetration depth of the light under these conditions this approach allows to flood the material with charge carriers from the side of the sample. Even at light levels much stronger than the write beams, this additional illumination does allow for grating recording. However, under these conditions competition between positive and negative charges leads to sign inversion of the two-beam coupling gain coefficient during recording. An improvement of the recording speed is demonstrated.

Colloidal crystals and water: Perspectives on liquid-solid nanoscale phenomena in wet particulate media.

Solid colloidal ensembles inherently contain water adsorbed from the ambient moisture. This water, confined in the porous network formed by the building submicron spheres, greatly affects the ensemble properties. Inversely, one can benefit from such influence on collective features to explore the water behavior in such nanoconfinements. Recently, novel approaches have been developed to investigate in-depth where and how water is placed in the nanometric pores of self-assembled colloidal crystals. Here, we summarize these advances, along with new ones, that are linked to general interfacial water phenomena like adsorption, capillary forces, and flow. Water-dependent structural properties of the colloidal crystal give clues to the interplay between nanoconfined water and solid fine particles that determines the behavior of ensembles. We elaborate on how the knowledge gained on water in colloidal crystals provides new opportunities for multidisciplinary study of interfacial and nanoconfined liquids and their essential role in the physics of utmost important systems such as particulate media.

Photoinduced Local Heating in Silica Photonic Crystals for Fast and Reversible Switching

Fast and reversible photonic-bandgap tunability is achieved in silica artificial opals by local heating. The effect is fully reversible as heat rapidly dissipates through the non-irradiated structure without active cooling and water is readsorbed. The performance is strongly enhanced by decreasing the photoirradiated opal volume, allowing bandgap shifts of 12 nm and response times of 20 ms.