Transition metal dichalcogenides (TMDs) are emerging as promising two-dimensional (2D) semiconductors for optoelectronic and flexible devices. However, a microscopic explanation of their photophysics, of pivotal importance for the understanding and optimization of device operation, is still lacking. Here, we use femtosecond transient absorption spectroscopy, with pump pulse tunability and broadband probing, to monitor the relaxation dynamics of single-layer MoS2 over the entire visible range, upon photoexcitation of different excitonic transitions. We find that, irrespective of excitation photon energy, the transient absorption spectrum shows the simultaneous bleaching of all excitonic transitions and corresponding red-shifted photoinduced absorption bands. First-principle modeling of the ultrafast optical response reveals that a transient bandgap renormalization, caused by the presence of photoexcited carriers, is primarily responsible for the observed features. Our results demonstrate the strong impact of many-body effects in the transient optical response of TMDs even in the low-excitation-density regime.

Optical harmonic generation occurs when high intensity light (>10 W m) interacts with a nonlinear material. Electrical control of the nonlinear optical response enables applications such as gate-tunable switches and frequency converters. Graphene displays exceptionally strong light-matter interaction and electrically and broadband tunable third-order nonlinear susceptibility. Here, we show that the third-harmonic generation efficiency in graphene can be increased by almost two orders of magnitude by controlling the Fermi energy and the incident photon energy. This enhancement is due to logarithmic resonances in the imaginary part of the nonlinear conductivity arising from resonant multiphoton transitions. Thanks to the linear dispersion of the massless Dirac fermions, gate controllable third-harmonic enhancement can be achieved over an ultrabroad bandwidth, paving the way for electrically tunable broadband frequency converters for applications in optical communications and signal processing.

Unveiling the nature of the bosonic excitations that mediate the formation of Cooper pairs is a key issue for understanding unconventional superconductivity. A fundamental step toward this goal would be to identify the relative weight of the electronic and phononic contributions to the overall frequency (Ω) dependent bosonic function, Π(Ω). We perform optical spectroscopy on Bi2Sr2Ca0.92Y0.08Cu2O 8+δ crystals with simultaneous time-and frequency-resolution; this technique allows us to disentangle the electronic and phononic contributions by their different temporal evolution. The strength of the interaction (λ∼1.1) with the electronic excitations and their spectral distribution fully account for the high critical temperature of the superconducting phase transition. [7]. Inelastic neutron and X-ray scattering experiments found evidence for both QP-phonon anomalies [8] and bosonic excitations attributed to spin fluctuations [7,9] and loop currents [10]. Dip features in tunnelling experiments have been used to alternatively support the scenarios of dominant electron-phonon interactions [11] or antiferromagnetic spin fluctuations [12]. The frequency-dependent dissipation of the Drude optical conductivity, σ (ω), measured by equilibrium optical spectroscopies, has been interpreted [13][14][15] as the coupling of electrons to bosonic excitations, in which the separation of the phononic and electronic contributions is impeded by their partial coexistence on the same energy scale (<90 meV).We disentangle the electronic and phononic contributions to Π(Ω) through a non-equilibrium optical spectroscopy, in which the femtosecond time-resolution is combined with an energy-resolution smaller than 10 meV, over a wide photon energy range (0.5-2 eV). Our approach is based on the widely-used assumption [16,17] that, after the interaction between a superconductor and a short laser pulse (1.55 eV photon energy), the effective electronic temperature (T e ) relaxes toward its equilibrium value through energy exchange with the different degrees of freedom that linearly contribute to Π(Ω). In a more formal description, the total bosonic function is given by Π(Ω)=Π be (Ω)+Π SCP (Ω)+Π lat (Ω) where Π be refers to the bosonic excitations of electronic origin at the effective temperature T be , Π SCP to the small fraction of strongly-coupled phonons (SCPs) at T SCP [16] and Π lat to all other * Electronic address: s.f.p.dalconte@tue.nl † Electronic address: claudio.giannetti@unicatt.it

Hybrid semiconductor-metal nanoparticles are interesting materials for use as photocatalysts due to their tunable properties and chemical processibility. Their function in the evolution of hydrogen in photocatalytic water splitting is the subject of intense current investigation. Here, the effects of the surface coatings on the photocatalytic function are studied, with Au-tipped CdS nanorods as a model hybrid nanoparticle system. Kinetic measurements of the hydrogen evolution rate following photocatalytic water reduction are performed on similar nanoparticles but with different surface coatings, including various types of thiolated alkyl ligands and different polymer coatings. The apparent hydrogen evolution quantum yields are found to strongly depend on the surface coating. The lowest yields are observed for thiolated alkyl ligands. Intermediate values are obtained with L-glutathione and poly(styrene-co-maleic anhydride) polymer coatings. The highest efficiency is obtained for polyethylenimine (PEI) polymer coating. These pronounced differences in the photocatalytic efficiencies are correlated with ultrafast transient absorption spectroscopy measurements, which show a faster bleach recovery for the PEI-coated hybrid nanoparticles, consistent with faster and more efficient charge separation. These differences are primarily attributed to the effects of surface passivation by the different coatings affecting the surface trapping of charge carriers that compete with effective charge separation required for the photocatalysis. Further support of this assignment is provided from steady-state emission and time-resolved spectral measurements, performed on related strongly fluorescing CdSe/CdS nanorods. The control and understanding of the effect of the surface coating of the hybrid nanosystems on the photocatalytic processes is of importance for the potential application of hybrid nanoparticles as photocatalysts.

We study the exciton valley relaxation dynamics in single-layer MoS 2 by a combination of two nonequilibrium optical techniques: time-resolved Faraday rotation and time-resolved circular dichroism. The depolarization dynamics, measured at 77 K, exhibits a peculiar biexponential decay, characterized by two distinct time scales of 200 fs and 5 ps. The fast relaxation of the valley polarization is in good agreement with a model including the intervalley electron-hole Coulomb exchange as the dominating mechanism. The valley relaxation dynamics is further investigated as a function of temperature and photoinduced exciton density. We measure a strong exciton density dependence of the transient Faraday rotation signal. This indicates the key role of exciton-exciton interactions in MoS 2 valley relaxation dynamics.

The understanding of how the sub-nanoscale exchange interaction evolves in macroscale correlations and ordered phases of matter, such as magnetism and superconductivity, requires to bridging the quantum and classical worlds. This monumental challenge has so far only been achieved for systems close to their thermodynamical equilibrium. Here we follow in real time the ultrafast dynamics of the macroscale magnetic order parameter in the Heisenberg antiferromagnet KNiF3 triggered by the impulsive optical generation of spin excitations with the shortest possible nanometre wavelength and femtosecond period. Our magneto-optical pump–probe experiments also demonstrate the coherent manipulation of the phase and amplitude of these femtosecond nanomagnons, whose frequencies are defined by the exchange energy. These findings open up opportunities for fundamental research on the role of short-wavelength spin excitations in magnetism and strongly correlated materials; they also suggest that nanospintronics and nanomagnonics can employ coherently controllable spin waves with frequencies in the 20 THz domain.

In strongly correlated systems the electronic properties at the Fermi energy (EF) are intertwined with those at high-energy scales. One of the pivotal challenges in the field of high-temperature superconductivity (HTSC) is to understand whether and how the high-energy scale physics associated with Mott-like excitations (|E−EF|>1 eV) is involved in the condensate formation. Here, we report the interplay between the many-body high-energy CuO2 excitations at 1.5 and 2 eV, and the onset of HTSC. This is revealed by a novel optical pump-supercontinuum-probe technique that provides access to the dynamics of the dielectric function in Bi2Sr2Ca0.92Y0.08Cu2O8+δ over an extended energy range, after the photoinduced suppression of the superconducting pairing. These results unveil an unconventional mechanism at the base of HTSC both below and above the optimal hole concentration required to attain the maximum critical temperature (Tc).

Graphene nanoribbons display extraordinary optical properties due to one-dimensional quantum-confinement, such as width-dependent bandgap and strong electron–hole interactions, responsible for the formation of excitons with extremely high binding energies. Here we use femtosecond transient absorption spectroscopy to explore the ultrafast optical properties of ultranarrow, structurally well-defined graphene nanoribbons as a function of the excitation fluence, and the impact of enhanced Coulomb interaction on their excited states dynamics. We show that in the high-excitation regime biexcitons are formed by nonlinear exciton–exciton annihilation, and that they radiatively recombine via stimulated emission. We obtain a biexciton binding energy of ≈250 meV, in very good agreement with theoretical results from quantum Monte Carlo simulations. These observations pave the way for the application of graphene nanoribbons in photonics and optoelectronics.