Francesco Quochi

Third-order nonlinearities in silicon at telecom wavelengths

The two-photon absorption coefficient and Kerr coefficient of bulk crystalline silicon are determined near the telecommunication wavelengths of 1.3 and 1.55 μm using femtosecond pulses and a balanced Z-scan technique. A phase shift sensitivity of the order of 1 mrad is achieved, enabling the accurate measurement of third-order nonlinear coefficients at fluences smaller than 100 μJ/cm2. From the two-photon absorption coefficient (β∼0.8 cm/GW) and the Kerr coefficient (n2∼4×10−14 cm2/W) at a wavelength λ=1.54 μm, a value F∼0.35 for the nonlinear figure of merit for all-optical switching is determined.

Correlated electron–hole plasma in organometal perovskites

Organic-inorganic perovskites are a class of solution-processed semiconductors holding promise for the realization of low-cost efficient solar cells and on-chip lasers. Despite the recent attention they have attracted, fundamental aspects of the photophysics underlying device operation still remain elusive. Here we use photoluminescence and transmission spectroscopy to show that photoexcitations give rise to a conducting plasma of unbound but Coulomb-correlated electron-hole pairs at all excitations of interest for light-energy conversion and stimulated optical amplification. The conductive nature of the photoexcited plasma has crucial consequences for perovskite-based devices: in solar cells, it ensures efficient charge separation and ambipolar transport while, concerning lasing, it provides a low threshold for light amplification and justifies a favourable outlook for the demonstration of an electrically driven laser. We find a significant trap density, whose cross-section for carrier capture is however low, yielding a minor impact on device performance.

Gain amplification and lasing properties of individual organic nanofibers

We study gain and lasing processes in individual self-assembled organic nanofibers grown on mica substrates. The gain-induced response of the nanofibers is found to depend sensitively on the fiber structure. In homogeneous fibers where no coherent optical feedback is present, high net optical gain (of up to 103cm−1) results in spectral narrowing at the material gain peaks. In the case of strong optical feedback, which occurs in long nanofibers with randomly distributed scattering centers, gain is in turn responsible for low-threshold coherent random laser action.

Random laser action in self-organized para-sexiphenyl nanofibers grown by hot-wall epitaxy

We report on the observation of amplified spontaneous emission and random lasing in self-organized crystalline para-sexiphenyl nanofibers. Using subpicosecond excitation, a lasing threshold is observed on the 0–1 emission band near 425 nm at excitation fluences as low as 0.5 μJ/cm2 (6×1016 cm−3 equivalent density), near the onset of density-dependent recombination processes. The dependence of the nonlinear emission spectrum on both the pump intensity and position of the excitation area are attributed to the interplay between random lasing and amplified spontaneous emission occurring along the nanofibers.

Exciton-Exciton Interaction and Optical Gain in Colloidal CdSe/CdS Dot/Rod Nanocrystals.

Exciton-exciton interaction in dot/rod CdSe/CdS nanocrystals has proved to be very sensitive to the shape of nanocrystals, due to the unique band alignment between CdSe and CdS. Repulsive exciton-exciton interaction is demonstrated, which makes CdSe/CdS dot/rods promising gain media for solution-processable lasers, with projected pump threshold densities below 1 kW cm(-2) for continuous wave lasing.

Absorption F-Sum Rule for the Exciton Binding Energy in Methylammonium Lead Halide Perovskites

Advances of optoelectronic devices based on methylammonium lead halide perovskites depend on understanding the role of excitons, whether it is marginal as in inorganic semiconductors, or crucial, like in organics. However, a consensus on the exciton binding energy and its temperature dependence is still lacking, even for widely studied methylammonium lead iodide and bromide materials (MAPbI3, MAPbBr3). Here we determine the exciton binding energy based on an f-sum rule for integrated UV-vis absorption spectra, circumventing the pitfalls of least-squares fitting procedures. In the temperature range 80-300 K, we find that the exciton binding energy in MAPbBr3 is EB = (60 ± 3) meV, independent of temperature; for MAPbI3, in the orthorhombic phase (below 140 K) EB = (34 ± 3) meV, while in the tetragonal phase the binding energy softens to 29 meV at 170 K and stays constant up to 300 K. Implications of binding energy values on solar cell and LED workings are discussed.

Near infrared light emission quenching in organolanthanide complexes

We investigate the quenching of the near infrared light emission in Er3+ complexes induced by the resonant dipolar interaction between the rare-earth ion and high frequency vibrations of the organic ligand. The nonradiative decay rate of the lanthanide ion is discussed in terms of a continuous medium approximation, which depends only on a few, easily accessible spectroscopic and structural data. The model accounts well for the available experimental results in Er3+ complexes, and predicts an ∼100% light emission quantum yield in fully halogenated systems.

Optical properties of strained antimonide-based heterostructures

The optical properties of strained GaAsSb/GaAs quantum wells grown by molecular beam epitaxy were investigated by photoluminescence spectroscopy as a function of excitation intensity and temperature. Photoluminescence spectra exhibit strong blue shifts of the emission peak with increasing excitation intensity, ascribed to the interplay between band tail filling at low carrier densities and electrostatic band bending at high carrier concentrations. Spectroscopic data are consistent with a type II band alignment, with a small conduction band offset (ΔEc∼100 meV), and gain spectra are blue shifted with respect to the low excitation luminescence. The large material gain and fast carrier recombination lifetimes demonstrate the viability of this material system for the fabrication of 1.3 μm lasers.

Excited state properties of hybrid perovskites

Metal halide perovskites have come to the attention of the scientific community for the progress achieved in solar light conversion. Energy sustainability is one of the priorities of our society, and materials advancements resulting in low-cost but efficient solar cells and large-area lighting devices represent a major goal for applied research. From a basic point of view, perovskites are an exotic class of hybrid materials combining some merits of organic and inorganic semiconductors: large optical absorption, large mobilities, and tunable band gap together with the possibility to be processed in solution. When a novel class of promising semiconductors comes into the limelight, lively discussions ensue on the photophysics of band-edge excitations, because just the states close to the band edge are entailed in energy/charge transport and light emission. This was the case several decades ago for III-V semiconductors, it has been up to 10 years ago for organics, and it is currently the case for perovskites. Our aim in this Account is to rationalize the body of experimental evidence on perovskite photophysics in a coherent theoretical framework, borrowing from the knowledge acquired over the years in materials optoelectronics. A crucial question is whether photon absorption leads to a population of unbound, conductive free charges or instead excitons, neutral and insulating bound states created by Coulomb interaction just below the energy of the band gap. We first focus on the experimental estimates of the exciton binding energy (Eb): at room temperature, Eb is comparable to the thermal energy kBT in MAPbI3 and increases up to values 2-3kBT in wide band gap MAPbBr3 and MAPbCl3. Statistical considerations predict that these values, even though comparable to or larger than thermal energy, let free carriers prevail over bound excitons for all levels of excitation densities relevant for devices. The analysis of photophysics evidence confirms that all hybrid halide perovskites behave as free-charge semiconductors. Thanks to such property, in combination with band gap energies covering the entire solar spectrum, perovskites represent a promising materials platform for highly efficient, single and multijunction solar cells. Concerning the use of perovskites as color-tunable materials in light emitting devices, free-charges are not the preferred species, as they recombine radiatively through a bimolecular process that is inefficient at the charge-injection levels typical of LED operation. Strategies to overcome this limit, and thus extend the use of perovskite materials beyond solar energy conversion, could be borrowed from inorganic semiconductor optoelectronics and include the fabrication of nanostructures with reduced dimensionality to alter the electronic density of states, as well as engineering composite materials.

Light-Induced Charged and Trap States in Colloidal Nanocrystals Detected by Variable Pulse Rate Photoluminescence Spectroscopy

Intensity instabilities are a common trademark of the photoluminescence of nanoemitters. This general behavior is commonly attributed to random fluctuations of free charges and activation of charge traps reducing the emission yield intermittently. However, the actual physical origin of this phenomenon is actively debated. Here we devise an experiment, variable pulse rate photoluminescence, to control the accumulation of charges and the activation of charge traps. The dynamics of these states is studied, with pulse repetition frequencies from the single-pulse to the megahertz regime, by monitoring photoluminescence spectrograms with picosecond temporal resolution. We find that both photocharging and charge trapping contribute to photoluminescence quenching, and both processes can be reversibly induced by light. Our spectroscopic technique demonstrates that charge accumulation and trap formation are strongly sensitive to the environment, showing different dynamics when nanocrystals are dispersed in solution or deposited as a film.