Guglielmo Lanzani

Hot exciton dissociation in polymer solar cells

The standard picture of photovoltaic conversion in all-organic bulk heterojunction solar cells predicts that the initial excitation dissociates at the donor/acceptor interface after thermalization. Accordingly, on above-gap excitation, the excess photon energy is quickly lost by internal dissipation. Here we directly target the interfacial physics of an efficient low-bandgap polymer/PC(60)BM system. Exciton splitting occurs within the first 50 fs, creating both interfacial charge transfer states (CTSs) and polaron species. On high-energy excitation, higher-lying singlet states convert into hot interfacial CTSs that effectively contribute to free-polaron generation. We rationalize these findings in terms of a higher degree of delocalization of the hot CTSs with respect to the relaxed ones, which enhances the probability of charge dissociation in the first 200 fs. Thus, the hot CTS dissociation produces an overall increase in the charge generation yield.

Tetrapod-Shaped Colloidal Nanocrystals of II−VI Semiconductors Prepared by Seeded Growth

We report a general synthetic approach to tetrapod-shaped colloidal nanocrystals made of various combinations of II-VI semiconductors. Uniform tetrapods were prepared using preformed seeds in the sphalerite structure, onto which arms were grown by coinjection of the seeds and chemical precursors into a hot mixture of surfactants. By this approach, a wide variety of core materials could be chosen (in practice, most of the II-VI semiconductors that could be prepared in the sphalerite phase, namely, CdSe, ZnTe, CdTe); in contrast, the best materials for arm growth were CdS and CdTe. The samples were extensively characterized with the aid of several techniques.

A hybrid bioorganic interface for neuronal photoactivation

A key issue in the realization of retinal prosthetic devices is reliable transduction of information carried by light into specific patterns of electrical activity in visual information processing networks. Soft organic materials can be used to couple artificial sensors with neuronal tissues. Here, we interface a network of primary neurons with an organic blend. We show that primary neurons can be successfully grown onto the polymer layer without affecting the optoelectronic properties of the active material or the biological functionality of neuronal network. Moreover, action potentials can be triggered in a temporally reliable and spatially selective manner with short pulses of visible light. Our results may lead to new neuronal communication and photo manipulation techniques, thus paving way to the development of artificial retinas and other neuroprosthetic interfaces based on organic photodetectors.

A polymer optoelectronic interface restores light sensitivity in blind rat retinas

Interfacing organic electronics with biological substrates offers new possibilities for biotechnology due to the beneficial properties exhibited by organic conducting polymers. These polymers have been used for cellular interfaces in several fashions, including cellular scaffolds, neural probes, biosensors and actuators for drug release. Recently, an organic photovoltaic blend has been exploited for neuronal stimulation via a photo-excitation process. Here, we document the use of a single-component organic film of poly(3-hexylthiophene) (P3HT) to trigger neuronal firing upon illumination. Moreover, we demonstrate that this bio-organic interface restored light sensitivity in explants of rat retinas with light-induced photoreceptor degeneration. These findings suggest that all-organic devices may play an important future role in sub-retinal prosthetic implants.

Ultrafast electron-hole dynamics in core/shell CdSe/CdS dot/rod nanocrystals.

Colloidal semiconductor nanocrystals are nanoscale materials whose optical, electronic and transport properties, due to their strong dependence on size and shape, can be finely tuned by advanced chemical synthesis approaches. Among various types of semiconductor nanocrystals, core-shell nanostructures comprised of a semiconductor core that is covered by a thin shell of another type of semiconductor material have been extensively investigated.

Plasmon dynamics in colloidal Cu₂-xSe nanocrystals.

The optical response of metallic nanostructures after intense excitation with femtosecond-laser pulses has recently attracted increasing attention: such response is dominated by ultrafast electron-phonon coupling and offers the possibility to achieve optical modulation with unprecedented terahertz bandwidth. In addition to noble metal nanoparticles, efforts have been made in recent years to synthesize heavily doped semiconductor nanocrystals so as to achieve a plasmonic behavior with spectrally tunable features. In this work, we studied the dynamics of the localized plasmon resonance exhibited by colloidal Cu(2-x)Se nanocrystals of 13 nm in diameter and with x around 0.15, upon excitation by ultrafast laser pulses via pump-probe experiments in the near-infrared, with ∼200 fs resolution time. The experimental results were interpreted according to the two-temperature model and revealed the existence of strong nonlinearities in the plasmonic absorption due to the much lower carrier density of Cu(2-x)Se compared to noble metals, which led to ultrafast control of the probe signal with modulation depth exceeding 40% in transmission.

Amplified spontaneous emission and efficient tunable laser emission from a substituted thiophene-based oligomer

We investigated gain and lasing in spin-coated films of a soluble substituted oligothiophene. With increasing excitation power, the photoluminescence spectra show a clear line narrowing due to amplified spontaneous emission. We measure a low threshold (20 μJ cm−2) for line narrowing and a large gain cross section (6×10−16 cm2), indicating that this molecule is a promising active material for organic solid-state lasers. As a demonstrator, we realize a transverse electromagnetic (TEM00) single-mode laser with tunable emission from the yellow to the red (a range of 37 nm), with a pump threshold as low as 18 μJ cm−2 and efficiency of 1.9%. These results are among the best so far reported for organic lasers.

Suppression of biexciton auger recombination in CdSe/CdS dot/rods: role of the electronic structure in the carrier dynamics.

We studied carrier dynamics in semiconductor nanocrystals consisting of a small CdSe dot embedded in an elongated, rod-shaped CdS shell, using the ultrafast pump-probe technique. We found clear evidence of a substantial suppression of the Auger nonradiative recombination in the biexciton regime. Moreover, a simple model of the dynamics in which biexcitons show no Auger recombination, and only holes are localized in the dot, fits well the differential transmission observed at all pump densities. The long biexciton lifetime results into an observed long-living gain having a peak that is red shifted with respect to the lowest energy absorption peak. We argue that the origin of the large relative gain observed at large fillings is related to the peculiar structure of the electronic levels, and in particular, to delocalization of electrons in the rod.

Pump‐Probe Spectroscopy in Organic Semiconductors: Monitoring Fundamental Processes of Relevance in Optoelectronics

In this review we highlight the contribution of pump-probe spectroscopy to understand elementary processes taking place in organic based optoelectronic devices. The techniques described in this article span from conventional pump-probe spectroscopy to electromodulated pump-probe and the state-of-the-art confocal pump-probe microscopy. The article is structured according to three fundamental processes (optical gain, charge photogeneration and charge transport) and the contribution of these techniques on them. The combination of these tools opens up new perspectives for assessing the role of short-lived excited states on processes lying underneath organic device operation.

Full temporal resolution of the two-step photoinduced energy–electron transfer in a fullerene–oligothiophene–fullerene triad using sub-10 fs pump–probe spectroscopy

Abstract The intramolecular photoinduced energy and electron transfer in a fullerene–oligothiophene–fullerene triad with nine thiophene units (C60–9T–C60) has been investigated with sub-10 fs pump–probe spectroscopy in solvents of different polarity. Photoexcitation of the oligothiophene moiety results in an ultrafast singlet-energy transfer reaction to create the fullerene singlet-excited state with a time constant of 95 fs, irrespective of the polarity of the medium. In a polar solvent, the ultrafast singlet-energy transfer is followed by intramolecular electron transfer from the oligothiophene to the fullerene with a time constant of 10 ps, resulting in a charge-separated state (CSS) with a lifetime of 80 ps.