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The insulator-to-metal transition in Mott insulators is the key mechanism for a novel class of electronic devices, belonging to the Mottronics family. Intense research efforts are currently devoted to the development of specific control protocols, usually based on the application of voltage, strain, pressure and light excitation. The ultimate goal is to achieve the complete control of the electronic phase transformation, with dramatic impact on the performance, for example, of resistive switching devices. Here, we investigate the simultaneous effect of external voltage and excitation by ultrashort light pulses on a single Mottronic device based on a V$_2$O$_3$ epitaxial thin film. The experimental results, supported by finite-element simulations of the thermal problem, demonstrate that the combination of light excitation and external electrical bias drives a volatile resistivity drop which goes beyond the combined effect of laser and Joule heating. Our results impact on the development of protocols for the non-thermal control of the resistive switching transition in correlated materials.

It is shown that the Raman signal can be enhanced using BaTiO 3 microspheres beyond that obtained by the highest numerical aperture objective available on a standard Raman microscope. This research is aimed at understanding the basis of the light interaction at the nanoscale level, with implications for photodynamic processes on bio-objects.

One-color transient reflectivity measurements are carried out on two different samples of vertically aligned single-wall carbon nanotube bundles and compared with the response recently published on unaligned bundles. The negative sign of the optical response for both samples indicates that the free electron character revealed on unaligned bundles is only due to the intertube interactions favored by the tube bending. Neither the presence of bundles nor the existence of structural defects in aligned bundles is able to induce a free-electron like behavior of the photoexcited carriers. This result is also confirmed by the presence of non-linear excitonic effects in the transient response of the aligned bundles. (C) 2013 Elsevier B.V. All rights reserved.

High-resolution time resolved transmittivity measurements on horizontally aligned free-standing multi-walled carbon nanotubes reveal a different electronic transient behavior from that of graphite. This difference is ascribed to the presence of discrete energy states in the multishell carbon nanotube electronic structure. Probe polarization dependence suggests that the optical transitions involve definite selection rules. The origin of these states is discussed and a rate equation model is proposed to rationalize our findings.

The specific mechanisms which leads to the formation of fractal nanostructures by pulsed laser deposition remain elusive despite intense research efforts, motivated mainly by the technological interest in obtaining tailored nanostructures with simple and scalable production methods. Here we focus on fractal nanostructures of titanium dioxide, $TiO_2$, a strategic material for many applications, obtained by femtosecond laser ablation at ambient conditions. We model the fractal formation through extensive Monte Carlo simulations based on a set of minimal assumptions: irreversible sticking and size independent diffusion. Our model is able to reproduce the fractal dimensions and the area distributions of the nanostructures obtained in the experiments for different densities of the ablated material. The comparison of theory and experiment show that such fractal aggregates are formed after landing of the ablated material on the substrate surface by a diffusive mechanism. Finally we discuss the role of the thermal conductivity of the substrate and the laser fluence on the properties of the fractal nanostructures. Our results represent an advancement towards controlling the production of fractal nanostructures by pulsed laser deposition., Comment: 21 pages

The crystallization behavior of two new stable glasses belonging to the BaO−K2O−Na2O−Nb2O5−SiO2 system, synthesized by the melt-quenching technique, was studied with the aim to obtain nanostructured glasses based on tungsten−bronze phases. Nanostructured samples with valuable second harmonic generation (SHG) activity were obtained starting from 8BaO·15Na2O·27Nb2O5·50SiO2 glass after suitable heat treatments performed in the glass transition range, by means of the bulk nucleation mechanism. The influence of the devitrification mechanism on the SHG efficiency was clarified with particular reference to the effect of structural modifications on the transparency of the nanostructured glasses. These samples are formed by Ba2NaNb5O15 nanocrystals (about 15 nm in size) randomly dispersed in a phase-separated amorphous matrix. Their SHG efficiency is partially impaired by the Rayleigh scattering originated by the nanocrystals. These nanostructured glasses can be useful when the generation efficiency is not an issue, as in the diagnostics for ultrafast lasers, due to the independence of the second harmonic generation from the polarization state of the laser light and no need for preferential material orientation.

Unveiling the nature of the bosonic excitations that mediate the formation of Cooper pairs is a key issue for understanding unconventional superconductivity. A fundamen- tal step toward this goal would be to identify the relative weight of the electronic and phononic contributions to the overall frequency (\Omega) dependent bosonic function, \Pi(\Omega). We perform optical spectroscopy on Bi2212 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 ({\lambda}~1.1) with the electronic excitations and their spectral distribution fully account for the high critical temperature of the superconducting phase transition., Comment: 9 pages, 4 figures

Using time-resolved reflectivity measurements on unaligned and aligned bundled single-wall carbon nanotubes with a pump energy of 1.55 eV, quasi-resonant with the second Van Hoye singularity of semiconducting tubes, a positive sign of the transient reflectivity is detected in unaligned nanotubes. In contrast a negative sign is detected in aligned nanotubes. This discovery addresses a long-standing question showing that in unaligned nanotubes the stronger intertube interactions favor the formation of short-lived free charge carriers in semiconducting tubes. A detailed analysis of the transient reflectivity spectral response shows that the free carriers in the photo-excited state of semiconducting tubes move towards metallic tubes in about 400 fs. (C) 2011 Elsevier Ltd. All rights reserved.

The response of the torsional modes of a thermally excited cantilever across the jump-to-contact transition shows a modification of the oscillation amplitude, frequency, and damping. The measurement of these parameters is important because their analysis provides nanoscale information on the physical, chemical, and topographic properties of the sample. The tip-surface interaction potential is usually reconstructed by Fourier analysis of the cantilever oscillations around its equilibrium position. However, Fourier analysis can be correctly interpreted only in the case of stationary systems. The wavelet transform analysis overcomes these limitations, revealing the temporal evolution of the spectral content of a temporal trace. The one-dimensional time signal from the photodiode is converted into a two-dimensional time-frequency topography, which simultaneously exhibits the time and frequency behavior of the cantilever thermal fluctuations. In the present study, we show preliminary data obtained using wavelet transforms to analyze thermally excited torsional cantilever modes during jump-to-contact transition on a highly oriented pyrolitic graphite surface in air. [DOI: 10.1380/ejssnt.2011.228]

Transparent glasses having molar composition (23-x)K{sub 2}O.xNa{sub 2}O.27Nb{sub 2}O{sub 5}.50SiO{sub 2} (x=0, 5, 10, 15 and 23) have been synthesized by the melt-quenching technique and their devitrification behaviour has been investigated by DTA and XRD. Depending on the composition, the glasses showed a glass transition temperature in the range 660-680 deg. C and devitrified in several steps. XRD measurements showed that the replacement of K{sub 2}O by Na{sub 2}O strongly affects the crystallization behaviour. Particularly, in the glasses with only potassium or low sodium content the first devitrification step is related to the crystallization of an unidentified phase, while in the glass containing only sodium, NaNbO{sub 3} crystallizes. For an intermediate sodium content (x=10 and 15) a potassium sodium niobate crystalline phase, belonging to the tungsten-bronze family, is formed by bulk nucleation. This system looks promising to produce active nanostructured glasses as the tungsten-bronze type crystals have ferroelectric, electro-optical and non-linear optical properties. Preliminary measurements evidenced SHG activity in the crystallized glasses containing this phase. - Graphical abstract: Synthesis of glasses (23-x)K{sub 2}O.xNa{sub 2}O.27Nb{sub 2}O{sub 5}.50SiO{sub 2} (x=0, 5, 10, 15 and 23) from which SHG active phases crystallize by bulk nucleation for non-linear optical nanostructured glasses.

The way organic thin films properties are affected by molecular interactions at surfaces is an important research topic because thin molecular films constitute a model system for biological research and have applications ranging from light-emitting diodes and solar cells to chemical sensors. In this work, the formation of thin films of Methylene Blue in aqueous solution at a fused quartz surface was investigated with evanescent wave absorption spectroscopy, using a continuum spectrum generated in a non-linear fiber by short laser pulses.

The use of femtosecond laser pulses to impulsively excite thermal and mechanical transients in matter has led, in the last years, to the development of picosecond acoustics. Recently, the pump-probe approach has been applied to nano-engineered materials to optically generate and detect acoustic waves in the GHz-THz frequency range. In this paper, we review the latest advances on ultrafast generation and detection of thermal gradients and pseudo-surface acoustic waves in two-dimensional lattices of metallic nanostructures. Comparing the experimental findings to the numeric analysis of the full thermo-mechanical problem, these materials emerge as model systems to investigate both the mechanical and thermal energy transfer at the nanoscale. The sensitivity of the technique to the nanostructures mass and shape variations, coupled to the phononic crystal properties of the lattices opens the way to a variety of applications ranging from hypersonic waveguiding to mass sensors with femtosecond time-resolution.ens the way to a variety of applications ranging from hypersonic waveguiding to mass sensors with femtosecond time-resolution., Comment: 20 pages, 6 figures. Published on IEEE Photonics Journal

In this review we describe the development of ultrafast non-linear photoemission spectroscopy on metals from the first historic observations in the sixties to state-of-the-art experiments. We present an account that is focused on electron spectroscopy experiments that use short laser pulses to investigate the non-equilibrium response of electrons in metals. Several examples of the application of non-linear spectroscopy to the investigation of many-body effects and highly non-equilibrium processes will be illustrated. Furthermore, we give a brief overview of the wide spectrum of experimental methods based on non-linear photoemission spectroscopy.

Angle resolved non-linear photoemission induced by short laser pulses is used to investigate both the occupied surface state and the unoccupied image potential states on Cu(1 1 1). The image potential state effective mass measured at zero parallel momentum with a non-resonant photon energy between the surface state and the image potential state is significantly different from the effective mass measured at resonance in the same conditions. The surface state effective mass shows no variation with photon energy. To explain the modification of the image potential state effective mass in the non-resonant excitation, the influence of the high energy electron population in the bulk bands near the image potential state must be taken into account.

The non-linear photoelectron spectra obtained by short laser pulses from a Ag(100) surface show a high-energy electron emission due to an athermal electron distribution created by the laser pulse. By comparing the photoemission at normal and non-normal emission geometry it is possible to evidence the independence of the hot electron photoemission on the parallel momentum and on different final-state configurations. A photoemission correlation measurement evidences that non-photoelectric effects, as tunneling or thermally assisted photoemission, do not contribute to the electron yield. Various theoretical models are discussed on the basis of the present data.

Image potential states are populated through indirect, scattering-mediated multiphoton absorption induced by femtosecond laser pulses and revealed by single-photon photoemission. The measured effective mass is significantly different from that obtained with direct, resonant population. These features reveal a strong coupling of the electrons residing in the image potential state, outside the solid, with the underlying hot electron population created by the laser pulse. The coupling is mediated by a many-body scattering interaction between the image potential state electrons and bulk electrons in highly excited states.

A novel apparatus devoted to time-resolved photoemission experiments in the sub-picosecond regime will be presented. The system is composed of a Ti:sapphire laser source and a time of flight (TOF) electron energy analyzer mounted in a UHV experimental chamber. The laser source is characterized by a pulse duration of 150 fs at a wavelength of 790 nm (1.57 eV) and operates at a repetition rate of 1 kHz. To perform photoemission measurements, UV radiation up to 6.28 eV is produced with sequential steps of frequency conversion by employing crystals with a second order nonlinearity. Photoelectrons are collected by a TOF spectrometer designed to analyze electrons from tenths of eV up to 5 eV. It can be operated in two different angular resolution modes switching on and off an electrostatic collection optics: the high angular resolution mode (Deltaalpha = +/-2.7degrees) and the low angular resolution mode (Deltaalpha = +/-5.6degrees). Single photon photoemission spectra from the Ag(100) clean surface have been recorded at room temperature using the fourth harmonic light (lambda = 200 nm and hv = 6.28 eV). The Fermi edge profile convoluted with a Gaussian-shaped energy transmission function of the TOF spectrometer sets an upper limit for the energy resolution which is about 65 meV (FWHM) at 2 eV of electron energy.

The investigation of surface chemical reactions in biological samples, avoiding sample preparation treatments, is important to access the complex chemical machinery of living cells. Many cell functions depend on surface ligand-receptor complexes or surface chemical reactions and many kind of tumors start from the first cellular layer inside hollow organs. Therefore, non-invasive techniques that allow in vivo study of chemical processes located at surfaces are fundamental tools to develop and test biological models and target diseases. Optical spectroscopy techniques, tailored to image surface molecular complexes, are a possible answer to these issues. Keywords—optical spectroscopy, time resolved techniques, molecules at surfaces. We describe a multimodal approach based on evanescent wave spectroscopy and picosecond photo-acustics using ultrafast lasers, thus exploiting time-resolved techniques on nanoscale objects. Short light pulses are used in an evanescent wave configuration between two transparent interfaces as surface sensitive optical probes [1,2]. Following optical excitation by a pump pulse, evanescent-wave probes allow to retrieve the time evolution of the absorbance of the molecular species residing on the surface. This gives a selective fingerprint in terms of the temporal response after the excitation (the relaxation time) as well as subwavelenght spatial localization in the dimension normal to the surface. It is foreseen that application in fluorescence resonance energy transfer (FRET) should give interesting insights, especially in situations where donor and acceptor chromophores reside on surfaces. In recent years, the use of femtosecond laser pulses to excite thermal and mechanical transients in matter led to the development of picosecond acoustics, that will develop into a useful tool for material science and biotechnology. Recently, we applied this approach to optically generate and detect acoustic modes in the gigahertz–terahertz frequency range in ordered nanostructures [2,3,4]. The frontier of this intriguing research field is the characterization of both the mechanical and thermal energy transfer of a single nanoparticle. Such informations are of interest for the thermodynamics of single biomolecules, receptor aggregates and in drug delivery issues. The future goal is to relate the parameters measured with these techniques to theoretical models, thus characterizing the response of the system with a multimodal approach. Our main purpose in presenting this talk is to seek collaborations with scientists working in bio-related areas, thus fulfilling the interdisciplinary scope of our laboratories. [1] G. Malegori, D. Nardi, F. Banfi, C. Giannetti, G. Ferrini, " Optical and Mechanical Investigations of Nanostructures for Biomolecular Detection," in Nanomedicine and cancer therapies, Volume 2 of the Advances in Nanoscience and Nanotechnology book series, M. Sebastian, N. Ninan, E. Elias, Eds. (2012). Apple Academic press. [2] G. Ferrini, L. De Carlo, C. Giannetti, and F. Parmigiani, "Evanescent wave spectroscopy of methylene blue solutions at surfaces using a continuum generated by a nonlinear fiber," Optics and Spectroscopy 107, 464 (2009). [3] D. Nardi, E. Zagato, G. Ferrini, C. Giannetti, and F. Banfi, "Design of a surface acoustic wave mass sensor in the 100 GHz range", Appl. Phys. Lett. 100, 253106 (2012). [4] D. Nardi, M. Travagliati, M. E. Siemens, Q. Li, M. M. Murnane, H. C. Kapteyn, G. Ferrini, F. Parmigiani, F. Banfi, "Probing Thermomechanics at the Nanoscale: Impulsively Excited Pseudosurface Acoustic Waves in Hypersonic Phononic Crystals," Nano Lett. 11, 4126 (2011). This work has been partially supported by the Universita Cattolica del Sacro Cuore through D.2.2 grants and the Fondazione Cariplo through grant ID 20110387 Controlled Nanostructures.

Photoemission from image potential states on Ag(100) is investigated using angle resolved multiphoton photoemission induced by 150 fs laser pulses. For the first time we demonstrate that image potential states populated by indirect transitions can be observed with light polarized parallel to the plane of incidence and light polarized normal to the plane of incidence. The latter is a process normally forbidden by the dipole transition selection rules. These findings are related to the creation of a hot-electron population whose properties largely remains to be understood.

Ultrafast broadband transient reflectivity experiments are performed to study the interplay between the nonequilibrium dynamics of the pseudogap and the superconducting phases in Bi(2)Sr(2}Ca(0.92)Y(0.08)Cu(2)O(8+δ). Once superconductivity is established, the relaxation of the pseudogap proceeds ~2 times faster than in the normal state, and the corresponding transient reflectivity variation changes sign after ~0.5 ps. The results can be described by a set of coupled differential equations for the pseudogap and for the superconducting order parameter. The sign and strength of the coupling term suggest a remarkably weak competition between the two phases, allowing their coexistence.

Since their invention scanning tunneling microscopy (STM, (Binnig et al., 1982)) and atomic force microscopy (AFM, (Binnig et al., 1986)) have emerged as powerful and versatile techniques for atomic and nanometer-scale imaging. In this review we will focus on AFM, whose methods have found applications for imaging, metrology and manipulation at the nanometer level of a wide variety of surfaces, including biological ones (Braga & Ricci, 2004; Garcia, 2010; Jandt, 2001; Jena & Horber, 2002; Kopniczky, 2003; Morita et al., 2009; 2002; Yacoot & Koenders, 2008). Today AFM is regarded as an essential tool for nanotechnology and a basic tool for material science in general.

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-E$_{F}$|>1 eV) is involved in the condensate formation. Here we show 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, which provides access to the dynamics of the dielectric function in Bi$_2$Sr$_2$Ca$_{0.92}$Y$_{0.08}$Cu$_2$O$_{8+{\delta}}$ 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 (T$_c$)., Comment: Text and Supplementary Information

In this letter we demonstrate the possibility to determine the temporal and spectral structure (spectrogram) of a complex light pulse exploiting the ultrafast switching character of a non-thermal photo-induced phase transition. As a proof, we use a VO2 multi-film, undergoing an ultrafast insulator-to-metal phase transition when excited by femtosecond near-infrared laser pulses. The abrupt variation of the multi-film optical properties, over a broad infrared/visible frequency range, is exploited to determine, in-situ and in a simple way, the spectrogram of a supercontinuum pulse produced by a photonic crystal fiber. The determination of the structure of the pulse is mandatory to develop new pump-probe experiments with frequency resolution over a broad spectral range (700-1100 nm)., Comment: 4 pages, 3 figures, letter

We present the experimental evidence of the interplay between the variation of the linewidth and effective mass of electrons in image potential states on a Cu(1 1 1) surface induced by a selective alteration of the hot-electron gas density generated by ultra-short laser pulse excitations. (C) 2008 Elsevier B.V. All rights reserved.

The ultrafast thermal and mechanical dynamics of a two-dimensional lattice of metallic nano-disks has been studied by near infrared pump-probe diffraction measurements, over a temporal range spanning from 100 fs to several nanoseconds. The experiments demonstrate that, in these systems, a two-dimensional surface acoustic wave (2DSAW), with a wavevector given by the reciprocal periodicity of the array, can be excited by ~120 fs Ti:sapphire laser pulses. In order to clarify the interaction between the nanodisks and the substrate, numerical calculations of the elastic eigenmodes and simulations of the thermodynamics of the system are developed through finite-element analysis. At this light, we unambiguously show that the observed 2DSAW velocity shift originates from the mechanical interaction between the 2DSAWs and the nano-disks, while the correlated 2DSAW damping is due to the energy radiation into the substrate., 13 pages, 10 figures

Quantum Efficiency (QE) measurements of single photon photoemission from a Cu(111) single crystal and a Cu polycrystal photocathodes, irradiated by 150 fs-6.28 eV laser pulses, are reported over a broad range of incidence angle, both in s and p polarizations. The maximum QE (\simeq 4\times10^{-4}) for polycrystalline Cu is obtained in p polarization at an angle of incidence {\theta} = 65deg. We observe a QE enhancement in p polarization which can not be explained in terms of optical absorption, a phenomenon known as vectorial photoelectric effect. Issues concerning surface roughness and symmetry considerations are addressed. An explanation in terms of non local conductivity tensor is proposed., Comment: 3 pages, 3 figures

Nonlinear photoemission from a silver single crystal is investigated by femtosecond laser pulses in a perturbative regime. A clear observation of above-threshold photoemission in solids is reported for the first time. The ratio between the three-photon above-threshold and the two-photon Fermi edges is found to be 10^{-4}. This value constitutes the only available benchmark for theories aimed at understanding the mechanism responsible for above-threshold photoemission in solids., Comment: 5 pages, 4 figures

Pump and probe electron photoemission, induced by 150 fs–790 nm laser pulses on polycrystalline molybdenum, is used to investigate the non-linear photoemissive regime. The analysis of these experimental data evidences third and fourth order thermally assisted currents that contribute to the electron yield. In addition, partial yield measurements at very low pulse intensities confirm the above analysis, evidencing a change in the logarithmic slope as predicted by the theory.

The ultrafast thermal and mechanical dynamics of a two‐dimensional lattice of metallic nanodisks has been studied by near‐infrared pump‐probe diffraction measurements over a temporal range spanning from 100 fs to several nanoseconds. The experiments demonstrate that in these systems a surface acoustic wave (SAW), with a wave vector given by the reciprocal periodicity of the two‐dimensional array, can be excited by 120 fs Ti:sapphire laser pulses. We unambiguously show that the observed SAW velocity shift originates from the mechanical interaction between the SAWs and the nanodisks, while the correlated SAW damping is due to the energy radiation into the substrate. In order to clarify the interaction between the nanodisks and the substrate, numerical calculations of both the elastic eigenmodes and the time‐dynamics of the system, following the impulsive heating excitation by the laser, are performed. Simulations based on finite‐elements analysis, together with a wavelet analysis of our experimental data, ...

Nonlinear photoelectric emission from Cu and W is investigated by subpicosecond laser pulses. Using a pump and probe technique, total-yield correlation measurements are obtained without space-charge saturation. The effects of the heating of the conduction electrons induced by the laser pulses are shown, considering the peak to background contrast ratio of the experimental correlation trace. The present analysis clarifies the consequences of a transient nonequilibrium temperature difference between electrons and the lattice on the correlation trace, confirming for W the presence of a thermally assisted photoemission mechanism. @S0163-1829~97!05628-2#

The total charge emitted from a polycrystalline Mo surface by 500 fs-264 nm laser pulses has been measured. Though a one-photon photoelectric effect is expected, a non-linear increase of the photoelectric yield was observed as a function of laser peak intensity, confirming earlier observations on Au, W and Zr. The threshold intensity for this non-linearity is 2 between 0.1 and 0.2 GW/ cm . The linear and non-linear regimes were clearly discerned in the experimental data. The non-equilibrium heating of the conduction electrons is considered as the cause of the observed non-linear behaviour. © 1999 Elsevier Science B.V. All rights reserved.

The total charge emitted from a polycrystalline Mo sample by 500 fs laser pulses at normal incidence is measured as a function of the laser peak intensity. Total yield data are taken at wavelengths of 527 and 264 nm. In both cases, a nonlinearity higher than expected is measured. A thermally enhanced regime is clearly observed when using 264 nm pulses for laser peak intensity larger than 0.1--0.2 ${\mathrm{G}\mathrm{W}/\mathrm{c}\mathrm{m}}^{2}$. This effect is interpreted on the basis of the nonequilibrium heating of the conduction electrons. Pump and probe photoemission data at 527 nm show a significant enhancement of the photoelectric sensitivity when the probe pulse is delayed by 1 ps from the pump. This enhancement is related to the growth of the available electron density induced by the nonequilibrium heating. Single pulse photoemission at this wavelength is not properly explained by a thermally assisted photoemission regime. This may indicate that other processes have a role in determining the photoemission yield.

The total yield photoemission of a polycrystalline molybdenum sample irradiated by 790 nm–150 fs laser pulses is measured in the absence of space charge saturation. The extracted charge versus the laser intensity, measured over three decades of the extracted charge, which represents a significant extension of the previous experiments, gives us the opportunity to test the so-called thermally assisted non-linear photoemission model. The present results show non-linear photoemission behavior that can be explained, as expected, by a thermally assisted 3-photon emission. However a pure 4-photon emission could not be discarded. To take aim at clarifying this question the related non-linear coefficients are calculated and a scaling law for the probability of different multiphoton orders is proposed.