Exploring the Charge Density Wave Phase of 1T-TaSe_{2}: Mott or Charge-Transfer Gap?

1T-TaSe_{2} is widely believed to host a Mott metal-insulator transition in the charge density wave (CDW) phase according to the spectroscopic observation of a band gap that extends across all momentum space. Previous investigations inferred that the occurrence of the Mott phase is limited to the surface only of bulk specimens, but recent analysis on thin samples revealed that the Mott-like behavior, observed in the monolayer, is rapidly suppressed with increasing thickness. Here, we report combined time- and angle-resolved photoemission spectroscopy and theoretical investigations of the electronic structure of 1T-TaSe_{2}. Our experimental results confirm the existence of a state above E_{F}, previously ascribed to the upper Hubbard band, and an overall band gap of ∼0.7 eV at Γ[over ¯]. However, supported by density functional theory calculations, we demonstrate that the origin of this state and the gap rests on band structure modifications induced by the CDW phase alone, without the need for Mott correlation effects.

Phototoxicity induced in living HeLa cells by focused femtosecond laser pulses: a data-driven approach.

Nonlinear optical microscopy is a powerful label-free imaging technology, providing biochemical and structural information in living cells and tissues. A possible drawback is photodamage induced by high-power ultrashort laser pulses. Here we present an experimental study on thousands of HeLa cells, to characterize the damage induced by focused femtosecond near-infrared laser pulses as a function of laser power, scanning speed and exposure time, in both wide-field and point-scanning illumination configurations. Our data-driven approach offers an interpretation of the underlying damage mechanisms and provides a predictive model that estimates its probability and extension and a safety limit for the working conditions in nonlinear optical microscopy. In particular, we demonstrate that cells can withstand high temperatures for a short amount of time, while they die if exposed for longer times to mild temperatures. It is thus better to illuminate the samples with high irradiances: thanks to the nonlinear imaging mechanism, much stronger signals will be generated, enabling fast imaging and thus avoiding sample photodamage.

Coherent anti-Stokes Raman spectroscopy of single and multi-layer graphene.

Spontaneous Raman spectroscopy is a powerful characterization tool for graphene research. Its extension to the coherent regime, despite the large nonlinear third-order susceptibility of graphene, has so far proven challenging. Due to its gapless nature, several interfering electronic and phononic transitions concur to generate its optical response, preventing to retrieve spectral profiles analogous to those of spontaneous Raman. Here we report stimulated Raman spectroscopy of the G-phonon in single and multi-layer graphene, through coherent anti-Stokes Raman Scattering. The nonlinear signal is dominated by a vibrationally non-resonant background, obscuring the Raman lineshape. We demonstrate that the vibrationally resonant coherent anti-Stokes Raman Scattering peak can be measured by reducing the temporal overlap of the laser excitation pulses, suppressing the vibrationally non-resonant background. We model the spectra, taking into account the electronically resonant nature of both. We show how coherent anti-Stokes Raman Scattering can be used for graphene imaging with vibrational sensitivity.

Hyperspectral imaging with a TWINS birefringent interferometer.

We introduce a high-performance hyperspectral camera based on the Fourier-transform approach, where the two delayed images are generated by the Translating-Wedge-Based Identical Pulses eNcoding System (TWINS) [Opt. Lett. 37, 3027 (2012)], a common-path birefringent interferometer that combines compactness, intrinsic interferometric delay precision, long-term stability and insensitivity to vibrations. In our imaging system, TWINS is employed as a time-scanning interferometer and generates high-contrast interferograms at the single-pixel level. The camera exhibits high throughput and provides hyperspectral images with spectral background level of -30dB and resolution of 3 THz in the visible spectral range. We show high-quality spectral measurements of absolute reflectance, fluorescence and transmission of artistic objects with various lateral sizes.

Versatile Control of

We demonstrate quantum control of ^{9}Be^{+} ions directly implemented by an optical frequency comb. Based on numerical simulations of the relevant processes in ^{9}Be^{+} for different magnetic field regimes, we demonstrate a wide applicability when controlling the comb's spectral properties. We introduce a novel technique for the selective and efficient generation of a spectrally tailored narrow-bandwidth optical frequency comb near 313 nm. We experimentally demonstrate internal state control and internal-motional state coupling of ^{9}Be^{+} ions implemented by stimulated-Raman manipulation using a spectrally optimized optical frequency comb. Our pulsed laser approach is a key enabling step for the implementation of quantum logic and quantum information experiments in Penning traps.

Robust singlet fission in pentacene thin films with tuned charge transfer interactions.

Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

Raman spectroscopy of graphene under ultrafast laser excitation.

The equilibrium optical phonons of graphene are well characterized in terms of anharmonicity and electron-phonon interactions; however, their non-equilibrium properties in the presence of hot charge carriers are still not fully explored. Here we study the Raman spectrum of graphene under ultrafast laser excitation with 3 ps pulses, which trade off between impulsive stimulation and spectral resolution. We localize energy into hot carriers, generating non-equilibrium temperatures in the ~1700-3100 K range, far exceeding that of the phonon bath, while simultaneously detecting the Raman response. The linewidths of both G and 2D peaks show an increase as function of the electronic temperature. We explain this as a result of the Dirac cones' broadening and electron-phonon scattering in the highly excited transient regime, important for the emerging field of graphene-based photonics and optoelectronics.

Mottness at finite doping and charge-instabilities in cuprates.

The influence of the Mott physics on the doping-temperature phase diagram of copper oxides represents a major issue that is subject of intense theoretical and experimental effort. Here, we investigate the ultrafast electron dynamics in prototypical single-layer Bi-based cuprates at the energy scale of the O-2p→Cu-3d charge-transfer (CT) process. We demonstrate a clear evolution of the CT excitations from incoherent and localized, as in a Mott insulator, to coherent and delocalized, as in a conventional metal. This reorganization of the high-energy degrees of freedom occurs at the critical doping pcr ≈0.16 irrespective of the temperature, and it can be well described by dynamical mean field theory calculations. We argue that the onset of the low-temperature charge instabilities is the low-energy manifestation of the underlying Mottness that characterizes the p < pcr region of the phase diagram. This discovery sets a new framework for theories of charge order and low-temperature phases in underdoped copper oxides.

Ultrafast spin-polarized electron dynamics in the unoccupied topological surface state of Bi2Se3.

The three-dimensional topological insulator Bi2Se3 presents two cone-like dispersive topological surface states centered at the [Formula: see text] point. One of them is unoccupied in equilibrium conditions and located 1.8 eV above the other one lying close to the Fermi level. In this work we employ time- and angle-resolved photoemission spectroscopy with circularly polarized pump photons to selectively track the spin dynamics of the empty topological states. We observe that spin-polarized electrons flow along the topological cone and recombine towards the unpolarized bulk states on a timescale of few tens of femtoseconds. This provides direct evidence of the capability to trigger a spin current with circularly polarized light.

Spin-Hall Voltage over a Large Length Scale in Bulk Germanium.

We exploit the spin-Hall effect to generate a uniform pure spin current in an epitaxial n-doped Ge channel, and we detect the electrically induced spin accumulation, transverse to the injected charge current density, with polar magneto-optical Kerr microscopy at a low temperature. We show that a large spin density up to 400 µm^{-3} can be achieved at the edges of the 100-µm-wide Ge channel for an applied electric field lower than 5 mV/µm. We find that the spin density linearly decreases toward the center of the Ge bar, due to the large spin diffusion length, and such a decay is much slower than the exponential one observed in III-V semiconductors, allowing very large spin accumulations over a length scale of tens of micrometers. This lays the foundation for multiterminal spintronic devices, where different spin voltages can be exploited as inputs for magnetologic gates on the same Ge platform.

Dissecting charge relaxation pathways in CdSe/CdS nanocrystals using femtosecond two-dimensional electronic spectroscopy.

Exciton relaxation dynamics of CdSe and quasi-type-II CdSe/CdS core/shell nanocrystals were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The use of 2DES allowed for determination of structure-specific and state-resolved carrier dynamics for CdSe nanocrystals formed with five, or fewer, CdS passivation monolayers (ML). For CdSe and CdSe/CdS nanocrystals formed with one through three MLs of CdS, excitation using broad bandwidth femtosecond visible laser pulses generated electron-hole pairs among the |X1〉 = 2.14 eV and |X2〉 = 2.27 eV exciton states. For both excitations, the electron is promoted to the lowest energy excited (1Se) conduction-band state and the hole is in the 1S3/2 (X1) or 2S3/2 (X2) valence-band state. Therefore, the relaxation dynamics of the hot hole were isolated by monitoring the-time-dependent amplitude of 2DES cross peaks. The time constant for hot hole relaxation within the CdSe valence band was 150 ± 45 fs. Upon passivation by CdS, this hole relaxation time constant increased to 170 ± 30 fs (CdSe/CdS-3ML). This small increase was attributed to the formation of a graded, or alloyed, interfacial region that precedes the growth of a uniform CdS capping layer. The small increase in hole relaxation time reflects the larger nanocrystal volume of the CdSe/CdS system with respect to the CdSe nanocrystal core. In contrast, the dynamics of larger core/shell nanocrystals (≥4ML CdS) exhibited a picosecond buildup in 2DES cross-peak amplitude. This time-dependent response was attributed to interfacial hole transfer from CdS to CdSe valence-band states. Importantly, the 2DES data distinguish CdSe exciton relaxation from interfacial carrier transfer dynamics. In combination, isolation of structurally well-defined nanocrystals and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.

Fourier transform spectroscopy in the vibrational fingerprint region with a birefringent interferometer.

We introduce a birefringent interferometer for Fourier transform (FT) spectroscopy in the mid-infrared, covering the vibrational fingerprint region (5-10 µm, 1000-2000 cm-1), which is crucial for molecular identification. Our interferometer employs the crystal calomel (Hg2Cl2), which combines high birefringence (ne-no≈0.55) with a broad transparency range (0.38-20 µm). We adopt a design based on birefringent wedges, which is simple and compact and guarantees excellent delay accuracy and long-term stability. We demonstrate FTIR spectroscopy, with a frequency resolution of 3 cm-1, as well as two-dimensional IR (2DIR) spectroscopy. Our setup can be extended to other spectroscopic modalities such as vibrational circular dichroism and step-scan FT spectroscopy.

Narrowband carrier-envelope phase stable mid-infrared pulses at wavelengths beyond 10 µm by chirped-pulse difference frequency generation.

We report on the generation of narrowband carrier-envelope phase stable mid-infrared (MIR) pulses between 10 and 15 µm. High pulse energies and narrow bandwidths are required for the selective nonlinear excitation of collective modes of matter that is not possible with current sources. We demonstrate bandwidths of <2% at 12.5 µm wavelength through difference frequency generation between two near-infrared (NIR) pulses, which are linearly chirped. We obtain a reduction in bandwidth by one order of magnitude, compared to schemes that make use of transform-limited NIR pulses. The wavelength of the narrowband MIR pulse can be tuned by changing the optical delay between the two chirped NIR pulses.

Direct observation of subpicosecond vibrational dynamics in photoexcited myoglobin.

Determining the initial pathway for ultrafast energy redistribution within biomolecules is a challenge, and haem proteins, for which energy can be deposited locally in the haem moiety using short light pulses, are suitable model systems to address this issue. However, data acquired using existing experimental techniques that fail to combine sufficient structural sensitivity with adequate time resolution have resulted in alternative hypotheses concerning the interplay between energy flow among highly excited vibrational levels and potential concomitant electronic processes. By developing a femtosecond-stimulated Raman set-up, endowed with the necessary tunability to take advantage of different resonance conditions, here we visualize the temporal evolution of energy redistribution over different vibrational modes in myoglobin. We establish that the vibrational energy initially stored in the highly excited Franck-Condon manifold is transferred with different timescales into low- and high-frequency modes, prior to slow dissipation through the protein. These findings demonstrate that a newly proposed mechanism involving the population dynamics of specific vibrational modes settles the controversy on the existence of transient electronic intermediates.

Macrospin dynamics in antiferromagnets triggered by sub-20 femtosecond injection of nanomagnons.

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.

Below-gap excitation of semiconducting single-wall carbon nanotubes.

We investigate the optoelectronic properties of the semiconducting (6,5) species of single-walled carbon nanotubes by measuring ultrafast transient transmission changes with 20 fs time resolution. We demonstrate that photons with energy below the lowest exciton resonance efficiently lead to linear excitation of electronic states. This finding challenges the established picture of a vanishing optical absorption below the fundamental excitonic resonance. Our result points towards below-gap electronic states as an intrinsic property of semiconducting nanotubes.

Stimulated Raman gas sensing by backward UV lasing from a femtosecond filament.

We perform a proof-of-principle demonstration of chemically specific standoff gas sensing, in which a coherent stimulated Raman signal is detected in the direction anticollinear to a two-color laser excitation beam traversing the target volume. The proposed geometry is intrinsically free space as it does not involve back-scattering (reflection) of the signal or excitation beams at or behind the target. A beam carrying an intense mid-IR femtosecond (fs) pulse and a parametrically generated picosecond (ps) UV Stokes pulse is fired in the forward direction. A fs filament, produced by the intense mid-IR pulse, emits a backward-propagating narrowband ps laser pulse at the 337 and 357 nm transitions of excited molecular nitrogen, thus supplying a counter-propagating Raman pump pulse. The scheme is linearly sensitive to species concentration and provides both transverse and longitudinal spatial resolution.

Optical stark effects in j-aggregate-metal hybrid nanostructures exhibiting a strong exciton-surface-plasmon-polariton interaction.

We report on the observation of optical Stark effects in J-aggregate-metal hybrid nanostructures exhibiting strong exciton-surface-plasmon-polariton coupling. For redshifted nonresonant excitation, pump-probe spectra show short-lived dispersive line shapes of the exciton-surface-plasmon-polariton coupled modes caused by a pump-induced Stark shift of the polariton resonances. For larger coupling strengths, the sign of the Stark shift is reversed by a transient reduction in normal mode splitting. Our studies demonstrate an approach to coherently control and largely enhance optical Stark effects in strongly coupled hybrid systems. This may be useful for applications in ultrafast all-optical switching.

Size and nanocrystallinity controlled gold nanocrystals: synthesis, electronic and mechanical properties.

The influence of nanocrystallinity on the electronic and mechanical properties of metal nanoparticles is still poorly understood, due to the difficulty in synthesizing nanoparticles with a controlled internal structure. Here, we report on a new method for the selective synthesis of Au nanoparticles in either a single-domain or a polycrystalline phase maintaining the same chemical environment. We obtain quasi-spherical nanoparticles whose diameter is tunable from 6 to 13 nm with a resolution down to ≈0.5 nm and narrow size distribution (4-5%). The availability of such high-quality samples allows the study of the impact of the particle size and nanocrystallinity on a number of parameters, such as plasmon dephasing time, electron-phonon coupling, period and damping time of the radial breathing modes.

Tracking the primary photoconversion events in rhodopsins by ultrafast optical spectroscopy.

Opsins are a broad class of photoactive proteins, found in all classes of living beings from bacteria to higher animals, which work either as light-driven ion pumps or as visual pigments. The photoactive function in opsins is triggered by the ultrafast isomerization of the retinal chromophore around a specific carbon double bond, leading to a highly distorted, spectrally red-shifted photoproduct. Understanding, by either experimental or computational methods, the time course of this photoisomerization process is of utmost importance, both for its biological significance and because opsin proteins are the blueprint for molecular photoswitches. This paper focuses on the ultrafast 11-cis to all-trans isomerization in visual rhodopsins, and has a twofold goal: (i) to review the most recent experimental and computational efforts aimed at exposing the very early phases of photoconversion; and (ii) discuss future advanced experiments and calculations that will allow an even deeper understanding of the process. We present high time resolution pump-probe data, enabling us to follow the wavepacket motion through the conical intersection connecting excited and ground states, as well as femtosecond stimulated Raman scattering data allowing us to track the subsequent structural evolution until the first stable all-trans photoproduct is reached. We conclude by introducing computational results for two-dimensional electronic spectroscopy, which has the potential to provide even greater detail on the evolution of the electronic structure of retinal during the photoisomerization process.