Recently we studied the possibility to photostimulate living cells through functional interfaces based on organic semiconductors, polymers or molecules. After a brief review of the work done using thin films, I will describe in more details the recent use of polythiophene nanoparticles that shown the ability to recover visual acuity in lab models affected by the degeneration of photoreceptors according to Retinis Pigmentosa. The Photophysics of the nanoparticles will be presented together with a model of the interface that suggests a possible mechanism of photo-stimulation. As a last development in this research, I will report on the use of photochromic molecules as phototransducers in similar degenerated retina. The mechanism of stimulation will be described, and the recent results in vivo will be reported.
The overarching goal of our research is to manipulate the light-bio-matter interaction to obtain control over the functioning of living systems. Light can control cell activity, with high space and time resolution and a virtually infinite number of configurations, free from wiring constrains. We develop and study non-genetic cell opto-stimulation techniques based on artificial light actuators that establish functional abiotic-biotic interfaces able to transduce a light signal into a biological stimulus. This talk reports on the state of our research regarding organic bio interfaces for inducing light sensitivity in cells, both in vitro and in vivo. Light actuators comes in different shapes: planar patches, nanoparticle, intra-membrane probes. Their coupling mechanism is still far from being understood and attempts to shed light will be introduced. The research aims at a new technological platform for application in life enhancing technologies or new cyborg technologies. One of the most appealing application of this emerging technology is rescue vision in blind people.
Hybrid plasmonic photonic structures combine the plasmonic response with the photonic band gap, holding promise for utilization as optical switches and sensors. Here, we demonstrate the active modulation of the optical response in such structures with two different external stimuli, e.g. laser pulses and bacteria. First, we report the fabrication of a miniaturized (5 x 5 mm) indium tin oxide (ITO) grating employing femtosecond laser micromachining, and we show the possibility to modulate the photonic band gap in the visible via ultrafast photoexcitation in the infrared part of the spectrum. Note that the demonstrated time response in the picosecond range of the spectral modulation have an industrial relevance. Moreover, we manufacture one-dimensional photonic crystals consisting of a solution-processed dielectric Bragg stack exposing a top-layer of bio-active silver. We assign the bacterial responsivity of the system to polarization charges at the Ag/bacterium interface, giving rise to an overall blue shift of the photonic band gap.
Here we report on low-threshold blue lasing from fully-transparent nanostructured porous silicon (PSi) monolithic microcavities (MCs) infiltrated with a polyfluorene derivative, namely poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO). Single-mode blue lasing is achieved at the resonance wavelength of 466 nm, with line width of ~1.3 nm, lasing threshold as low as 5 nJ (i.e. fluence of 15 μJ/cm2), and good stability under operation (i.e. 40% decay in intensity after about 7 ×105 pulses at 50 nJ).
Organic semiconductors in different shapes and composition can be interfaced with living cells. This provides a new, exciting route towards optical control of physiological functions or the restoring of natural functions. In this talk I will present a number of experiments that show the effective abiotic-biotic coupling of organic semiconductors with cells and small animals, suggesting the potential of organic light actuators for geneless opto stimulation. Investigated systems are all based on polythiophene as photoactive layer, in planar films, nanostructured layers or nanoparticles. Spectroscopy, photo-electrochemistry and photo-electrophysiology are exploited to carry out the experimental investigations. While the mechanism explaining such coupling is still unknown, it is appering that thermal, capacitive, faradaic or chemical coupling are all options to be carefully evaluated.
To conclude the succesful use of an organic retina implant for restoring visual acuity in blind animals will be reported.
Organic semiconductors in different shapes and composition can be interfaced with living cells. This provides a new, exciting route towards optical control of physiological functions or the restoring of natural functions, e.g. vision. In this talk I will present a number of experiments that show the effective abiotic-biotic coupling of organic semiconductors with cells and small animals, suggesting the potential of organic light actuators for geneless opto stimulation. Investigated systems are all based on polythiophene as photoactive layer, in planar films, nanostructured layers or nanoparticles. Spectroscopy, photo-electrochemistry and photo-electrophysiology are exploited to carry out the experimental investigations. We report on photoluminescence in vivo of nanoparticles and other light actuators. While the mechanism explaining such coupling is still unknown, it is appearing that thermal, capacitive, faradaic or chemical coupling are all options to be carefully evaluated.
We describe different types of photonic structures that allow tunability of the photonic band gap upon the application of external stimuli, as the electric or magnetic field. We review and compare two porous one-dimensional (1-D) photonic crystals: in the first one, a liquid crystal has been infiltrated in the pores of the nanoparticle network, whereas in the second one, the optical response to the electric field of metallic nanoparticles has been exploited. Then, we present a 1-D photonic crystal made with indium tin oxide (ITO) nanoparticles, and we propose this system for electro-optic tuning. Finally, we describe a microcavity with a defect mode that is tuned in the near-infrared by the magnetic field, envisaging a contact-less magneto-optic switch. These optical switches can find applications in information and communications technologies and electrochromic windows.
We report a study on the excited state dynamics of two symmetric squaraine dyes, carrying different side-groups attached to the squaric ring. By means of UV-VIS absorption and time-resolved fluorescence spectroscopies, we found that the photodynamic of these functional molecules depends strongly on both the steric and electro-donating properties of the side-group.
We report the fabrication and validation of a microfluidic chip for fluorescence detection, which incorporates in the same glass substrate the microfluidic network, the excitation, the filtering, and the collection elements. The device is fabricated in a hybrid approach combining different technologies, such as femtosecond laser micromachining and RF sputtering, to increase their individual capabilities. The validation of the chip demonstrates a good wavelength selective light filtering and a limit of detection of a 600-nM concentration of Oxazine 720 perchlorate dye.
We report the realization and characterization of porous nanostructures where a periodic refractive index modulation is
achieved by stacking layers with different nano-architectures. One multilayer photonic crystal has been fabricated
starting from colloidal dispersion of silicon dioxide and zirconium dioxide using spin coating technique. Improved
efficiency of Bragg reflectivity (up to 85%) has been obtained by a new bottom-up fabrication technique of photonic
hierarchical nanostructures based on self-assembly from the gas-phase at low temperature whit a very thin (≈ 1 μm)
photonic crystal devices. Due to the high porosity, these systems can be infiltrated with nematic liquid crystals leading to
tuning of the Bragg reflection band by applying low voltages to the structure.
Charge generation at donor/acceptor interface is a highly debated topic in the organic photovoltaics (OPV)
community. The primary photoexcited state evolution happens in few femtosecond timescale, thus making very
intriguing their full understanding. In particular charge generation is believed to occur in < 200 fs, but no clear picture
emerged so far. In this work we reveal for the first time the actual charge generation mechanism following in real time
the exciton dissociation mechanism by means of sub-22 fs pump-probe spectroscopy. We study a low-band-gap polymer:
fullerene interface as an ideal system for OPV. We demonstrate that excitons dissociation leads, on a timescale of 20-50
fs, to two byproducts: bound interfacial charge transfer states (CTS) and free charges. The branching ratio of their
formation depends on the excess photon energy provided. When high energy singlet polymer states are excited, well
above the optical band gap, an ultrafast hot electron transfer happens between the polymer singlet state and the
interfacial hot CTS* due to the high electronic coupling between them. Hot exciton dissociation prevails then on internal
energy dissipation that occurs within few hundreds of fs. By measuring the internal quantum efficiency of a prototypical
device a rising trend with energy is observed, thus indicating that hot exciton dissociation effectively leads to a higher
fraction of free charges.
Photochromic materials reversibly change their colour due to a photochemical reaction that takes place when the material
is irradiated with photons of suitable energy. This peculiar feature has been extensively exploited to develop smart
sunglasses, filters and inks. With a proper molecular design it is possible to enable modulation not only of colour but also
of other properties such as refractive index, dipole moment, nonlinear optical properties or conductivity by a
photoswitching of the molecular structure. The approach herein developed consists in modifying, upon irradiation, the
properties of a molecular component coupled with the photochromic molecule. In particular, the switching features of
photochromic systems are matched with the intriguing peculiar properties of carbon nanotubes (CNTs). A photochromic
polyester has been properly synthesised to be used as switching polymer matrix coupled with a network of CNTs.
Irradiation of the polymer/CNTs blend results into a light-triggered conductance switching. The reversible
electrocyclization of the polymer under UV-vis illumination results into a modification of the inter-tube charge mobility,
and accordingly, of the overall resistance of the blend. Solution techniques allow us to obtain blended films with sheet
resistance modulation larger than 150%, good thermal stability and fatigue resistance at room conditions, in an easier,
faster and scalable way as respect to the single-molecule approach.ÿ
Conjugated luminescent polymers have been shown to exhibit stimulated emission under optical pumping. Dilution in
polymethylmethacrylate (PMMA) leads to an enlargement, towards longer wavelengths, of the gain region. In addition,
ultrafast optical switching is observed when a second pulse is applied during excited state lifetime. These two properties
are of high importance for optical communications and can bring to the plastic optical fibres (POFs) the equivalent of
erbium amplification in silica fibres. In this communication we report on the gain and switching properties of PMMA
films and POFs doped with conjugated oligomers and polymers, prepared by blending or copolymerisation. The dopants
were functionalised with polar side groups to improve their solubility in MMA and/or with reactive methacrylate groups
so they can be copolymerised with MMA.
We study excitation energy and charge transfer in small aggregates of chirality enriched carbon nanotubes by transient
absorption spectroscopy. Ground state photobleaching is used to monitor exciton population dynamics with sub-10 fs
time resolution. Upon resonant excitation of the first exciton transition in (6,5) tubes, we find evidence for energy
transfer to (7,5) tubes within our time resolution (< 10 fs). After pumping at high pump energies, free charge carriers are
produced via exciton scattering into the underlying continuum bands. We obtain clearly distinguished photoinduced
features in the visible spectral range, that allow for real-time tracing of charge carrier dynamics in carbon nanotubes on a
sub-picosecond time scale.
Femtosecond laser based micromachining technologies have the inherent capability of producing elements in 3D. Their
ability of rapid prototyping can be exploited to develop novel Optofluidics devices. Microfluidic channels were
fabricated and integrated with optical waveguides using a single femtosecond laser. Optically pumping the microchannel
filled with polyfluorene solution and by dispersing nanoparticles in the solution, random lasing in the microchannel is
obtained. We demonstrate a novel approach to organic photonic devices, where the unique properties of a conjugated
polymer in solution are exploited in a microfluidic configuration in order to produce easy-to-integrate photonic devices.
In this work modulation of laser emission from polymer
nano-structured lasers was explored
through three different optical techniques.
We show all optical control of polymer distributed feedback lasers based on polyfluorenes (PFO
and F8BT) by applying a gating pulse, which completely switch-off emission in the sub-ps time
scale. The switching mechanism is assigned to photo-injection of charge carriers induced by the
gate transition. This is a resonant non-linear process, that might work at high bit-rate, paving the
way toward plastic, large-scale integrated, ultrafast optical logic.
New opportunities may also be offered by two other techniques:
Two-photon two-color pumping
allows lasing action only in presence of two different pulses, one in the visible and one in the IR,
resonant with the second telecommunication window. This may allow to convert
telecommunication signal from a fiber to visible range and thus to Plastic Optical Fibers for organic
photonics. Another technique we explored uses a blend of F8BT and a photochromic material,
(1,2-bis-(5-phenyl-2-methyl-3-tienyl) perfluocyclopentene))(C4). With a UV pulse we are able to
change C4 structure, thus overlapping its absorption spectrum with F8BT emission and modulating
yellow ASE emission.
Using femtosecond pump probe spectroscopy with sub-20 fs resolution, we probe fundamental properties of the E11
exciton in (6,5) single walled carbon nanotubes, prepared by density gradient ultracentrifugation. From the initial
photobleaching signal, measured faster than any relaxation process, we obtain the one-dimensional size of the excitonic
wavefunction along the nanotube. Exciton decay is found pump-intensity dependent only at elevated pump intensities.
Numerical modelling of decay kinetics yields an exciton diffusion coefficient of about 0.1 cm^2/s. Anisotropy
measurements in highly purified samples show that there is virtually no depolarisation of the E11 bleach over 40 ps. A
photoinduced absorption (PA) band, blueshifted against the E11 bleach, shows only weak anisotropy.
We haven been exploring polymethylmethacrylate, PMMA, doped with conjugated luminescent polymers for
applications in plastic optical fibers (POFs) showing gain. In order to control loading and dispersion of the conjugated
polymers in the PMMA matrix, new polyfluorene- PMMA copolymers were synthesised. In this communication we
report on the optical properties of these copolymers, both in solution and in solid state. Furthermore, the properties of
POFs fabricated with such copolymers are presented and compared with the properties of POFs based on PMMApolyfluorene
blends.
We fabricated polymer optical fiber (POF) amplifiers operating between 440 and 480 nm, using POFs doped with a series of fluorene oligomers, including tri-, penta-(9,9-dioctylfluorene) and hepta-(9,9-dihexylfluorene). The gain properties of pure oligofluorene films demonstrate gain coefficients on the order of 250 dB/cm and amplified spontaneous emission thresholds between 1 and 8 µJ cm-2, significantly lower than other fluorene gain media. The optical and morphological characteristics of PMMA thin films doped with the oligomers demonstrate that the oligomers are largely isolated within the PMMA. The optical and gain properties of POFs produced using an adapted preform-drawing technique and doped with the oligofluorenes provide gain values on the order of 0.07 dB for 2 mm of doped POF. The oligofluorenes are largely isolated within the POFs, paving the way for all optical gain-switching.
KEYWORDS: Sensors, Cones, Retina, Color vision, Multispectral imaging, Visual system, Human vision and color perception, Resolution enhancement technologies, Machine vision, Human subjects
In principle, an artificial retina should mimic as much as possible the spectral sensitivities of the real retina.
For technological reasons, building such an artificial device can lead to spectral approximations in comparison
with the real sensitivities. To understand if possible discrepancies can determine big differences in the final
perception, the whole visual system should be taken into consideration, not only the retinal input signal difference.
This paper aims at investigate how retinal sensitivity differences should affect the final perception. However,
answering to this question is a very complex problem related to the whole visual system, that we do not want
to extensively address in this paper. We only want to investigate the relationship between the spatial aspects
of color perception and the spectral differences among cone sensitivities. Moreover, a personal interdifference
has been observed in cone spatial distribution between human subjects, without any corresponding significant
difference in final color sensation. It is likely that spatial compensation, performed by human observers, strongly
decreases this subjectivity in color signal. We aim at address if a similar principle should be considered in
artificial vision. In this paper we analyze the interdifference among integrated values obtained using different
organic-based artificial sensors with different spectral sensitivities. Experiments show a significant decrease of
the effect of spectral sensitivity sensor differences when a spatial color correction is applied.
Single-walled carbon nanotubes dispersed in a polymer matrix are studied via cw photomodulation spectroscopy. The spectrum is dominated by a modulation of the absorption lineshape, which we assigned to electro-absorption caused by local electric fields arising from trapped photoinduced charges. The lack of selectivity in the excitation and the dominance of the contribution by low energies point to an efficient migration of the photoexcited states, either the singlet excitons or the charges resulting from their dissociation.
Using ultrafast pump-probe and pump-push-probe spectroscopy we highlight evidence of monodimensional photophysics coming from isolated chains of poly(9,9-dioctylfluorene) (PFO). We identify a large gain band with peak value of 2600 db/cm.
By exploiting the peculiar one-dimensional physics of the isolated chain, we envisage a novel principle for ultrafast all-optical gain switching. Experiments suggest that the expected maximum rate of on-off switching over a broad wavelengths range (around 100 nm) can be as high as 300 GHz with large modulation depth.
We report on the photoinduced absorption spectra of polycarbazolydiacetylenes polyDCHD and its soluble analogous polyDCHD-S in a broad time domain ranging from femtosecond to millisecond. Both the blue and red forms of polyDCHD-S are investigated and the results are compared with those of blue polyDCHD. In the blue form of the two polymers charged states are detected in the ms domain in addition to triplet excitons. In the red form of polyDCHD-S only triplets are detected. Femtosecond pump and probe measurements allow us to interpret the generation mechanism of the triplet states as due to singlet excitons fission.
We demonstrate the use of a color center laser in a pump- and-probe correlation technique which enables us to extend the probe spectral range into the infrared. As a result, we find strong photoinduced infrared absorption in several (pi) -conjugated polymers and oligomers. We associate this absorption with optical transitions in the singlet exciton manifold.
The ultrafast excited state dynamics of Hexamethylsexithiophene are investigated by femtosecond time-resolved photoluminescence. The spontaneous recombination lifetime of the singlet excited state is measured to be in the order of 400 ps. A photoluminescence (PL) risetime of approximately 1 ps and temporal spectra redshift is observed. These effects are attributed to planarization of the oligomer backbone in the excited state via vibrational and torsional relaxation which increases the effective conjugation length of the oligomer. The rapid vibrational and torsional relaxation gave rise to the PL risetime. The change in oligomer bandgap energy due to a longer effective conjugation length which is manifested in the transient spectral redshift.
Guenther Leising, Olov Ekstroem, Wilhelm Graupner, Farideh Meghdadi, Markus Moser, Gerald Kranzelbinder, Thomas Jost, Stefan Tasch, Berthold Winkler, Laurence Athouel, Gerard Froyer, Ullrich Scherf, Klaus Muellen, Guglielmo Lanzani, Mauro Nisoli, Sandro De Silvestri
We present efficient blue electroluminescence devices based on pure soluble poly(paraphenylene) polymers and poly(phenylene) oligomers. Highly efficient green and red emission light is produced with a new color conversion technique by pumping fluorescent dye layers with blue organic light-emitting diodes. The high intrachain order of the laddertype poly(paraphenylene) allows us to observe stimulated emission in the blue-green spectral regions, which does not compete with dissipative processes, like in other conjugated polymers. We discuss the state of the art situation to realize an optically pumped homopolymer solid state laser.
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