Single-Molecule Ultrafast Fluorescence-Detected Pump-Probe Microscopy.

We introduce fluorescence-detected pump-probe microscopy by combining a wavelength-tunable ultrafast laser with a confocal scanning fluorescence microscope, enabling access to the femtosecond time scale on the micrometer spatial scale. In addition, we obtain spectral information from Fourier transformation over excitation pulse-pair time delays. We demonstrate this new approach on a model system of a terrylene bisimide (TBI) dye embedded in a PMMA matrix and acquire the linear excitation spectrum as well as time-dependent pump-probe spectra simultaneously. We then push the technique toward single TBI molecules and analyze the statistical distribution of their excitation spectra. Furthermore, we demonstrate the ultrafast transient evolution of several individual molecules, highlighting their different behavior in contrast to the ensemble due to their individual local environment. By correlating the linear and nonlinear spectra, we assess the effect of the molecular environment on the excited-state energy.

Plasmonic wavelength-dependent optical switch.

We design and experimentally demonstrate an optical switch based on the interference of plasmonic modes in whispering gallery mode (WGM) antennas. Simultaneous excitation of even and odd WGM modes, enabled by a small symmetry breaking via non-normal illumination, allows switching the plasmonic near field between opposite sides of the antenna, depending on the excitation wavelength used in a wavelength range of 60 nm centered around 790 nm. This proposed switching mechanism is experimentally demonstrated by combining photoemission electron microscopy (PEEM) with a tunable wavelength femtosecond laser source in the visible and infrared.

Coherent 2D electronic spectroscopy with complete characterization of excitation pulses during all scanning steps.

Coherent two-dimensional (2D) electronic spectroscopy has become a standard tool in ultrafast science. Thus it is relevant to consider the accuracy of data considering both experimental imperfections and theoretical assumptions about idealized conditions. It is already known that chirped excitation pulses can affect 2D line shapes. In the present work, we demonstrate performance-efficient, automated characterization of the full electric field of each individual multipulse sequence employed during a 2D scanning procedure. Using Fourier-transform spectral interferometry, we analyze how the temporal intensity and phase profile varies from scanning step to scanning step and extract relevant pulse-sequence parameters. This takes into account both random and systematic variations during the scan that may be caused, for example, by femtosecond pulse-shaping artifacts. Using the characterized fields, we simulate and compare 2D spectra obtained with idealized and real shapes obtained from an LCD-based pulse shaper. Exemplarily, we consider fluorescence of a molecular dimer and multiphoton photoemission of a plasmonic nanoslit. The deviations from pulse-shaper artifacts in our specific case do not distort strongly the population-based multidimensional data. The characterization procedure is applicable to other pulses-shaping technologies or excitation geometries, including also pump-probe geometry with multipulse excitation and coherent detection, and allows for accurate consideration of realistic optical excitation fields at all inter-pulse time-delays.

Space- and time-resolved UV-to-NIR surface spectroscopy and 2D nanoscopy at 1 MHz repetition rate.

We describe a setup for time-resolved photoemission electron microscopy with aberration correction enabling 3 nm spatial resolution and sub-20 fs temporal resolution. The latter is realized by our development of a widely tunable (215-970 nm) noncollinear optical parametric amplifier (NOPA) at 1 MHz repetition rate. We discuss several exemplary applications. Efficient photoemission from plasmonic Au nanoresonators is investigated with phase-coherent pulse pairs from an actively stabilized interferometer. More complex excitation fields are created with a liquid-crystal-based pulse shaper enabling amplitude and phase shaping of NOPA pulses with spectral components from 600 to 800 nm. With this system we demonstrate spectroscopy within a single plasmonic nanoslit resonator by spectral amplitude shaping and investigate the local field dynamics with coherent two-dimensional (2D) spectroscopy at the nanometer length scale ("2D nanoscopy"). We show that the local response varies across a distance as small as 33 nm in our sample. Further, we report two-color pump-probe experiments using two independent NOPA beamlines. We extract local variations of the excited-state dynamics of a monolayered 2D material (WSe2) that we correlate with low-energy electron microscopy (LEEM) and reflectivity measurements. Finally, we demonstrate the in situ sample preparation capabilities for organic thin films and their characterization via spatially resolved electron diffraction and dark-field LEEM.

Spatial Variations in Femtosecond Field Dynamics within a Plasmonic Nanoresonator Mode.

Plasmonic resonators can be designed to support spectrally well-separated discrete modes. The associated characteristic spatial patterns of intense electromagnetic hot-spots can be exploited to enhance light-matter interaction. Here, we study the local field dynamics of individual hot-spots within a nanoslit resonator by detecting characteristic changes of the photoelectron emission signal on a scale of ∼12 nm using time-resolved photoemission electron microscopy (TR-PEEM) and by excitation with the output from a 20 fs, 1 MHz noncollinear optical parametric amplifier (NOPA). Surprisingly, we detect apparent spatial variations of the Q-factor and resonance frequency that are commonly considered to be global properties for a single mode. By using the concept of quasinormal modes we explain these local differences by crosstalk of adjacent resonator modes. Our findings are important in view of time-domain studies of plasmon-mediated strong light-matter coupling at ambient conditions.

Fluorescence-Detected Two-Quantum and One-Quantum-Two-Quantum 2D Electronic Spectroscopy.

We demonstrate two-quantum (2Q) coherent two-dimensional (2D) electronic spectroscopy using a shot-to-shot-modulated pulse shaper and fluorescence detection. Broadband collinear excitation is realized with the supercontinuum output of an argon-filled hollow-core fiber, enabling us to excite multiple transitions simultaneously in the visible range. The 2Q contribution is extracted via a three-pulse sequence with 16-fold phase cycling and simulated employing cresyl violet as a model system. Furthermore, we report the first experimental realization of one-quantum-two-quantum (1Q-2Q) 2D spectroscopy, offering less congested spectra as compared with the 2Q implementation. We avoid scattering artifacts and nonresonant solvent contributions by using fluorescence as the observable. This allows us to extract quantitative information about doubly excited states that agree with literature expectations. The high sensitivity and background-free nature of fluorescence detection allow for a general applicability of this method to many other systems.

Angular momentum-induced delays in solid-state photoemission enhanced by intra-atomic interactions.

Attosecond time-resolved photoemission spectroscopy reveals that photoemission from solids is not yet fully understood. The relative emission delays between four photoemission channels measured for the van der Waals crystal tungsten diselenide (WSe2) can only be explained by accounting for both propagation and intra-atomic delays. The intra-atomic delay depends on the angular momentum of the initial localized state and is determined by intra-atomic interactions. For the studied case of WSe2, the photoemission events are time ordered with rising initial-state angular momentum. Including intra-atomic electron-electron interaction and angular momentum of the initial localized state yields excellent agreement between theory and experiment. This has required a revision of existing models for solid-state photoemission, and thus, attosecond time-resolved photoemission from solids provides important benchmarks for improved future photoemission models.