Eleonora Vella

Ultrafast Spectroscopy with Photocurrent Detection: Watching Excitonic Optoelectronic Systems at Work

While ultrafast spectroscopy with photocurrent detection was almost unknown before 2012, in the last 3 years, a number of research groups from different fields have independently developed ultrafast electric probe approaches and reported promising pilot studies. Here, we discuss these recent advances and provide our perspective on how photocurrent detection successfully overcomes many limitations of all-optical methods, which makes it a technique of choice when device photophysics is concerned. We also highlight compelling existing problems and research questions and suggest ways for further development, outlining the potential breakthroughs to be expected in the near future using photocurrent ultrafast optical probes.

Evidence of delocalized excitons in amorphous solids.

We studied the temperature dependence of the absorption coefficient of amorphous SiO2 in the range from 8 to 17.5 eV obtained by Kramers-Kronig dispersion analysis of reflectivity spectra. We demonstrate the main excitonic resonance at 10.4 eV to feature a close Lorentzian shape redshifting with increasing temperature. This provides a strong evidence of excitons being delocalized notwithstanding the structural disorder intrinsic to amorphous SiO2. Excitons turn out to be coupled to an average phonon mode of 83 meV energy.

Ultrafast decoherence dynamics govern photocarrier generation efficiencies in polymer solar cells

All-organic-based photovoltaic solar cells have attracted considerable attention because of their low-cost processing and short energy payback time. In such systems the primary dissociation of an optical excitation into a pair of photocarriers has been recently shown to be extremely rapid and efficient, but the physical reason for this remains unclear. Here, two-dimensional photocurrent excitation spectroscopy, a novel non-linear optical spectroscopy, is used to probe the ultrafast coherent decay of photoexcitations into charge-producing states in a polymer:fullerene based solar cell. The two-dimensional photocurrent spectra are interpreted by introducing a theoretical model for the description of the coupling of the electronic states of the system to an external environment and to the applied laser fields. The experimental data show no cross-peaks in the twodimensional photocurrent spectra, as predicted by the model for coherence times between the exciton and the photocurrent producing states of 20 fs or less.

Probing polaron excitation spectra in organic semiconductors by photoinduced-absorption-detected two-dimensional coherent spectroscopy

Abstract We report a theoretical description and experimental implementation of a novel two-dimensional coherent excitation spectroscopy based on quasi-steady-state photoinduced absorption measurement of a long-lived nonlinear population. We have studied a semiconductor-polymer:fullerene-derivative distributed heterostructure by measuring the 2D excitation spectrum by means of photoluminescence, photocurrent and photoinduced absorption from metastable polaronic products. We conclude that the photoinduced absorption probe is a viable and valuable probe in this family of 2D coherent spectroscopies.

Excitonic coupling dominates the homogeneous photoluminescence excitation linewidth in semicrystalline polymeric semiconductors

We measure the homogeneous excitation linewidth of regioregular poly(3-hexylthiophene), a model semicrystalline polymeric semiconductor, by means of two-dimensional coherent photoluminescence excitation spectroscopy. At a temperature of 8\,K, we find a linewidth that is always

Incoherent population mixing contributions to phase-modulation two-dimensional coherent excitation spectra

\gtrsim 110

Unraveling exciton dynamics in amorphous silicon dioxide: Interpretation of the optical features from 8 to 11 eV

\,meV full-width-at-half-maximum, which is a significant fraction of the total linewidth. It displays a spectral dependence and is minimum near the 0--0 origin peak. We interpret this spectral dependence of the homogeneous excitation linewidth within the context of a weakly coupled aggregate model.

Vacuum-ultraviolet absorption of amorphous SiO 2 : Intrinsic contribution and role of silanol groups

We present theoretical and experimental results showing the effects of incoherent population mixing on two-dimensional (2D) coherent excitation spectra that are measured via a time-integrated population and phase-sensitive detection. The technique uses four collinear ultrashort pulses and phase modulation to acquire two-dimensional spectra by isolating specific nonlinear contributions to the photoluminescence or photocurrent excitation signal. We demonstrate that an incoherent contribution to the measured line shape, arising from nonlinear population dynamics over the entire photoexcitation lifetime, generates a similar line shape to the expected 2D coherent spectra in condensed-phase systems. In those systems, photoexcitations are mobile such that inter-particle interactions are important on any time scale, including those long compared with the 2D coherent experiment. Measurements on a semicrystalline polymeric semiconductor film at low temperatures show that, in some conditions in which multi-exciton interactions are suppressed, the technique predominantly detects coherent signals and can be used, in our example, to extract homogeneous line widths. The same method used on a lead-halide perovskite photovoltaic cell shows that incoherent population mixing of mobile photocarriers can dominate the measured signal since carrier-carrier bimolecular scattering is active even at low excitation densities, which hides the coherent contribution to the spectral line shape. In this example, the intensity dependence of the signal matches the theoretical predictions over more than two orders of magnitude, confirming the incoherent nature of the signal. While these effects are typically not significant in dilute solution environments, we demonstrate the necessity to characterize, in condensed-phase materials systems, the extent of nonlinear population dynamics of photoexcitations (excitons, charge carriers, etc.) in the execution of this powerful population-detected coherent spectroscopy technique.