Dielectric and optical properties of organic photorefractive materials

The work presented in this thesis is derived from experimentation in the field of polymeric photorefractive materials. Low T(_g) polymeric composites were prepared, based on the well-known photoconductive polymer PVK (maximum 50% w/w), sensitized with TNF (2% w/w) and C(_60) (0.2% w/w), plasticized with ECZ (maximum 49.3% w/w) and doped with the nonlinear optical materials NPP (50% w/w), DAN (20% w/w), DED (5% w/w), DCNQI (0.5% w/w), ULTRA-DEMI (5% w/w) and DI-DEMI (2% w/w), and their dielectric, linear and non linear optical properties were investigated. All the materials, except DCNQI, exhibited good solubility and sample processibility. The dielectric properties of the composites at 1 KHz and 1 MHz were determined using a parallel-plate capacitance bridge. The dielectric constant and loss at 10 GHz were measured using a novel adaptation of the resonant cavity technique, which was designed for measurements at ambient and elevated temperatures. The method was used to measure of the dielectric constant and loss of two novel, high T(_g), electro-optic polymers at temperatures up to 100 ºC. The dielectric properties measured were typical of polymeric materials. The absorption coefficient and the refractive index at different wavelengths were measured using a spectrophotometer. For the refractive index, an interference fringe analysis was used. The nonlinear measurements consisted of second harmonic generation, to prove the nonhnearity of the composites, two-beam coupling measurements, to prove their photorefractivity and degenerate four-wave mixing to measure their diffraction efficiency. The NPP, DAN, DED and ULTRA-DEMI doped investigated composites exhibited second order nonlinearity with highest the one of ULTRA-DEMI, at 292 pm/V for 19 kV of corona poling field. The photorefractivity of the NPP, DAN and DED doped composites was proven at 632.8 nm, while ULTRA-DEMI doped composites photooxidized before any measurements were possible. The two-beam coupling coefficients measured were lower than 20 cm(^-3), while net gain was observed only in the NPP doped composite. The diffraction efficiencies of the NPP, DAN and DED doped composites were measured at 632.8 nm, and were found to be l0(^-5)-l0(^-6)

Additive Manufacturing: Applications and Directions in Photonics and Optoelectronics

The combination of materials with targeted optical properties and of complex, 3D architectures, which can be nowadays obtained by additive manufacturing, opens unprecedented opportunities for developing new integrated systems in photonics and optoelectronics. The recent progress in additive technologies for processing optical materials is here presented, with emphasis on accessible geometries, achievable spatial resolution, and requirements for printable optical materials. Relevant examples of photonic and optoelectronic devices fabricated by 3D printing are shown, which include light-emitting diodes, lasers, waveguides, optical sensors, photonic crystals and metamaterials, and micro-optical components. The potential of additive manufacturing applied to photonics and optoelectronics is enormous, and the field is still in its infancy. Future directions for research include the development of fully printable optical and architected materials, of effective and versatile platforms for multimaterial processing, and of high-throughput 3D printing technologies that can concomitantly reach high resolution and large working volumes

Advances in functional assemblies for regenerative medicine

The ability to synthesise bioresponsive systems and selectively active biochemistries using polymer-based materials with supramolecular features has led to a surge in research interest directed towards their development as next generation biomaterials for drug delivery, medical device design and tissue engineering

Bio-Interfaces Engineering Using Laser-Based Methods for Controlled Regulation of Mesenchymal Stem Cell Response In Vitro

The controlled interfacial properties of materials and modulated behaviours of cells and biomolecules on their surface are the requirements in the development of a new generation of high-performance biomaterials for regenerative medicine applications. Roughness, chemistry and mechanics of biomaterials are all sensed by cells. Organization of the environment at the nano- and the microscale, as well as chemical signals, triggers specific responses with further impact on cell fate. Particularly, human mesenchymal stem cells (hMSCs) hold a great promise in both basic developmental biology studies and regenerative medicine, as progenitors of bone cells. Their fate can be affected by various key regulatory factors (e.g. soluble growth factors, intrinsic, extrinsic environmental factors) that can be delivered by a fabricated scaffold. For example, when cultured on engineered environments that reproduce the physical features of the bone, hMSCs express tissue-specific transcription factors and consequently undergo an osteogenic fate. Therefore, producing smart bio-interfaces with targeted functionalities represents the key point in effective use of hierarchically topographical and chemical bioplatforms. In this chapter, we review laser-based approaches (e.g. Matrix-Assisted Pulsed Laser Evaporation (MAPLE), Laser-Induced Forward Transfer (LIFT), laser texturing and laser direct writing) used for the design of bio-interfaces aimed at controlling stem cell behaviour in vitro

Smart photochromic gratings with switchable wettability realized by green-light interferometry

We demonstrate the enhancement of the wetting properties of smart photochromic surfaces by a specifically developed, gentle interferometric patterning employing green light. We realized photochromic gratings with 2.5–10.0μm period by a blend consisting of a green-curable matrix and spiropyran molecules. The structured surfaces exhibit photocontrolled and reversible wettability, and enhanced hydrophilicity with respect to the native substrates. The dynamics of liquid spreading onto the gratings was also investigated, and the wetting behavior analyzed according to Wenzel's [Ind. Eng. Chem. 28, 988 (1936)] model for rough surfaces. These results indicate switchable gratings as promising functional components for microfluidics and modulation, and green-light interferometry as a reliable lithographic method for patterning organics without degradation or photochemical reactions

Force-displacement relationship in micro-metric pantographs: experiments and numerical simulations

International audienceIn this paper, we reveal that the mathematical discrete model of Hencky type, introduced in [1], is appropriate for describing the mechanical behavior of micro-metric pantographic elementary modules. This behavior does not differ remarkably from what has been observed for milli-metric modules, as we prove with suitably designed experiments. Therefore, we conclude that the concept of pantographic microstructure seems feasible for micro-metrically architected microstructured (meta)materials as well. These results are particularly indicative of the possibility of fabricating materials that can have an underlying pantographic microstructure at micrometric scale, so that its unique behavior can be exploited in a larger range of technological applications

Strong and Broadband Pure Optical Activity in 3D Printed THz Chiral Metamaterials

Optical activity (polarization rotation of light) is one of the most desired features of chiral media, as it is important for many polarization related applications. However, in the THz region, chiral media with strong optical activity are not available in nature. Here, we study theoretically, and experimentally a chiral metamaterial structure composed of pairs of vertical U-shape resonators of "twisted" arms, and we reveal that it demonstrates large pure optical activity (i.e. optical activity associated with negligible transmitted wave ellipticity) in the low THz regime. The experimental data show polarization rotation up to 25 (deg) for an unmatched bandwidth of 1 THz (relative bandwidth 80 %), from a 130 um-thickness structure, while theoretical optimizations show that the rotation can reach 45 (deg). The enhanced chiral response of the structure is analyzed through an equivalent RLC circuit model, which provides also simple optimization rules for the enhancement of its chiral response. The proposed chiral structures allow easy fabrication via direct laser writing and electroless metal plating, making them suitable candidates for polarization control applications.Comment: 17 pages, 7 figure

Graphene-doped photo-patternable ionogels: tuning of conductivity and mechanical stability of 3D microstructures

This work reports for the first time the development of enhanced conductivity, graphene- doped photo-patternable hybrid organic-inorganic ionogels and the effect of the subsequent materials condensation on the conductivity and mechanical stability of three- dimensional microstructures fabricated by multi-photon polymerisation (MPP). Ionogels were based on photocurable silicon/zirconium hybrid sol-gel materials and phosphonium (trihexyltetradecylphosphonium dicyanamide [P6,6,6,14][DCA] ionic liquid (IL). To optimise the dispersion of graphene within the ionogel matrices, aqueous solutions of graphene were prepared, as opposed to the conventional graphene powder approach, and employed as catalysts of hydrolysis and condensation reactions occurring in the sol-gel process. Ionogels were prepared via a two step process by varying the hydrolysis degree from 25 to 50%, IL content between 0-50 w/w%, and the inorganic modifier (zirconate complex) concentration from 30 to 60 mol.% against the photocurable ormosil and they were characterised via Raman, Electrochemical Impedance Spectroscopy and Transmission Electron Microscopy. MPP was performed on the hybrid ionogels, resulting in three- dimensional microstructures that were characterised using scanning electron microscopy. It is clearly demonstrated that the molecular formulation of the ionogels, including the concentration of graphene and the zirconate network modifier, play a critical role in the conductivity of the ionogels and influence the resulting mechanical stability of the fabricated three-dimensional microstructures. This work aims to establish for the first time the relationship between the molecular design and condensation of materials in the physico-chemistry and dynamic of ionogels

Split-cube-resonator-based metamaterials for polarization-selective asymmetric perfect absorption

Abstract: A split-cube-resonator-based metamaterial structure that can act as a polarization- and direction-selective perfect absorber for the infrared region is theoretically and experimentally demonstrated. The structure, fabricated by direct laser writing and electroless silver plating, is comprised of four layers of conductively-coupled split-cube magnetic resonators, appropriately rotated to each other to bestow the desired electromagnetic properties. We show narrowband polarization-selective perfect absorption when the structure is illuminated from one side; the situation is reversed when illuminating from the other side, with the orthogonal linear polarization being absorbed. The absorption peak can be tuned in a wide frequency range by a sparser or denser arrangement of the split cube resonators, allowing to cover the entire atmospheric transparency window. The proposed metamaterial structure can find applications in polarization-selective thermal emission at the IR atmospheric transparency window for radiative cooling, in cost-effective infrared sensing devices, and in narrowband filters and linear polarizers in reflection mode