Interferometric Near-field Fano Spectroscopy of Single Halide Perovskite Nanoparticles.

Semiconducting halide perovskite nanoparticles support Mie-type resonances that confine light on the nanoscale in localized modes with well-defined spatial field profiles yet unknown near-field dynamics. We introduce an interferometric scattering-type near-field microscopy technique to probe the local electric field dynamics at the surface of a single MAPbI nanoparticle. The amplitude and phase of the coherent light scattering from such modes are probed in a broad spectral range and with high spatial resolution.

Ultrafast Coherent Exciton Couplings and Many-Body Interactions in Monolayer WS.

Transition metal dichalcogenides (TMDs) are quantum confined systems with interesting optoelectronic properties, governed by Coulomb interactions in the monolayer (1L) limit, where strongly bound excitons provide a sensitive probe for many-body interactions. Here, we use two-dimensional electronic spectroscopy (2DES) to investigate many-body interactions and their dynamics in 1L-WS at room temperature and with sub-10 fs time resolution. Our data reveal coherent interactions between the strongly detuned A and B exciton states in 1L-WS.

Full visible range two-dimensional electronic spectroscopy with high time resolution.

Two-dimensional electronic spectroscopy (2DES) is a powerful method to study coherent and incoherent interactions and dynamics in complex quantum systems by correlating excitation and detection energies in a nonlinear spectroscopy experiment. Such dynamics can be probed with a time resolution limited only by the duration of the employed laser pulses and in a spectral range defined by the pulse spectrum. In the blue spectral range (<500 nm), the generation of sufficiently broadband ultrashort pulses with pulse durations of 10 fs or less has been challenging so far.

Plasmon mediated coherent population oscillations in molecular aggregates.

The strong coherent coupling of quantum emitters to vacuum fluctuations of the light field offers opportunities for manipulating the optical and transport properties of nanomaterials, with potential applications ranging from ultrasensitive all-optical switching to creating polariton condensates. Often, ubiquitous decoherence processes at ambient conditions limit these couplings to such short time scales that the quantum dynamics of the interacting system remains elusive. Prominent examples are strongly coupled exciton-plasmon systems, which, so far, have mostly been investigated by linear optical spectroscopy.

Monolayer-Based Single-Photon Source in a Liquid-Helium-Free Open Cavity Featuring 65% Brightness and Quantum Coherence.

Solid-state single-photon sources are central building blocks in quantum information processing. Atomically thin crystals have emerged as sources of nonclassical light; however, they perform below the state-of-the-art devices based on volume crystals. Here, we implement a bright single-photon source based on an atomically thin sheet of WSe coupled to a tunable optical cavity in a liquid-helium-free cryostat without the further need for active stabilization.

Ultrafast Coupling of Optical Near Fields to Low-Energy Electrons Probed in a Point-Projection Microscope.

We report the first observation of the coupling of strong optical near fields to wavepackets of free, 100 eV electrons with <50 fs temporal resolution in an ultrafast point-projection microscope. Optical near fields are created by excitation of a thin, nanometer-sized Yagi-Uda antenna, with 20 fs near-infrared laser pulses. Phase matching between electrons and near fields is achieved due to strong spatial confinement of the antenna near field.

Tracking the Electron Transfer Cascade in European Robin Cryptochrome 4 Mutants.

The primary step in the mechanism by which migratory birds sense the Earth's magnetic field is thought to be the light-induced formation of long-lived magnetically sensitive radical pairs within cryptochrome flavoproteins located in the birds' retinas. Blue-light absorption by the non-covalently bound flavin chromophore triggers sequential electron transfers along a chain of four tryptophan residues toward the photoexcited flavin. The recently demonstrated ability to express cryptochrome 4a from the night-migratory European robin (), Cry4a, and to replace each of the tryptophan residues by a redox-inactive phenylalanine offers the prospect of exploring the roles of the four tryptophans.

Phonon-driven intra-exciton Rabi oscillations in CsPbBr halide perovskites.

Coupling electromagnetic radiation with matter, e.g., by resonant light fields in external optical cavities, is highly promising for tailoring the optoelectronic properties of functional materials on the nanoscale.

Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes.

Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S1 excited state are one-photon allowed, whereas the next higher S2 state can only be accessed by two-photon transitions.

Plasmon-Enhanced Exciton Delocalization in Squaraine-Type Molecular Aggregates.

Enlarging exciton coherence lengths in molecular aggregates is critical for enhancing the collective optical and transport properties of molecular thin film nanostructures or devices. We demonstrate that the exciton coherence length of squaraine aggregates can be increased from 10 to 24 molecular units at room temperature when preparing the aggregated thin film on a metallic rather than a dielectric substrate. Two-dimensional electronic spectroscopy measurements reveal a much lower degree of inhomogeneous line broadening for aggregates on a gold film, pointing to a reduced disorder.

Distinguishing between coherent and incoherent signals in excitation-emission spectroscopy.

The separation of incoherent emission signals from coherent light scattering often poses a challenge in (time-resolved) microscopy or excitation-emission spectroscopy. While in spectro-microscopy with narrowband excitation this is commonly overcome using spectral filtering, it is less straightforward when using broadband Fourier-transform techniques that are now becoming commonplace in, e.g.

Ultrafast Electron Tunneling Devices-From Electric-Field Driven to Optical-Field Driven.

The search for ever higher frequency information processing has become an area of intense research activity within the micro, nano, and optoelectronics communities. Compared to conventional semiconductor-based diffusive transport electron devices, electron tunneling devices provide significantly faster response times due to near-instantaneous tunneling that occurs at sub-femtosecond timescales. As a result, the enhanced performance of electron tunneling devices is demonstrated, time and again, to reimagine a wide variety of traditional electronic devices with a variety of new "lightwave electronics" emerging, each capable of reducing the electron transport channel transit time down to attosecond timescales.

Revealing generation, migration, and dissociation of electron-hole pairs and current emergence in an organic photovoltaic cell.

Using an innovative quantum mechanical method for an open quantum system, we observe in real time and space the generation, migration, and dissociation of electron-hole pairs, transport of electrons and holes, and current emergence in an organic photovoltaic cell. Ehrenfest dynamics is used to study photoexcitation of thiophene:fullerene stacks coupled with a time-dependent density functional tight-binding method. Our results display the generation of an electron-hole pair in the donor and its subsequent migration to the donor-acceptor interface.

Intermolecular conical intersections in molecular aggregates.

Conical intersections (CoIns) of multidimensional potential energy surfaces are ubiquitous in nature and control pathways and yields of many photo-initiated intramolecular processes. Such topologies can be potentially involved in the energy transport in aggregated molecules or polymers but are yet to be uncovered. Here, using ultrafast two-dimensional electronic spectroscopy (2DES), we reveal the existence of intermolecular CoIns in molecular aggregates relevant for photovoltaics.

Probing plasmonic excitation mechanisms and far-field radiation of single-crystalline gold tapers with electrons.

Conical metallic tapers represent an intriguing subclass of metallic nanostructures, as their plasmonic properties show interesting characteristics in strong correlation to their geometrical properties. This is important for possible applications such as in the field of scanning optical microscopy, as favourable plasmonic resonance behaviour can be tailored by optimizing structural parameters like surface roughness or opening angle. Here, we review our recent studies, where single-crystalline gold tapers were investigated experimentally by means of electron energy-loss and cathodoluminescence spectroscopy techniques inside electron microscopes, supported by theoretical finite-difference time-domain calculations.

Photoluminescence of InAs/GaAs quantum dots under direct two-photon excitation.

Self-assembled quantum dots grown by molecular beam epitaxy have been a hotbed for various fundamental research and device applications over the past decades. Among them, InAs/GaAs quantum dots have shown great potential for applications in quantum information, quantum computing, infrared photodetection, etc. Though intensively studied, some of the optical nonlinear properties of InAs/GaAs quantum dots, specifically the associated two-photon absorption of the wetting and barrier layers, have not been investigated yet.

Nonlinear plasmon-exciton coupling enhances sum-frequency generation from a hybrid metal/semiconductor nanostructure.

The integration of metallic plasmonic nanoantennas with quantum emitters can dramatically enhance coherent harmonic generation, often resulting from the coupling of fundamental plasmonic fields to higher-energy, electronic or excitonic transitions of quantum emitters. The ultrafast optical dynamics of such hybrid plasmon-emitter systems have rarely been explored. Here, we study those dynamics by interferometrically probing nonlinear optical emission from individual porous gold nanosponges infiltrated with zinc oxide (ZnO) emitters.

Coherent Real-Space Charge Transport Across a Donor-Acceptor Interface Mediated by Vibronic Couplings.

There is growing experimental and theoretical evidence that vibronic couplings, couplings between electronic and nuclear degrees of freedom, play a fundamental role in ultrafast excited-state dynamics in organic donor-acceptor hybrids. Whereas vibronic coupling has been shown to support charge separation at donor-acceptor interfaces, so far, little is known about its role in the real-space transport of charges in such systems. Here we theoretically study charge transport in thiophene:fullerene stacks using time-dependent density functional tight-binding theory combined with Ehrenfest molecular dynamics for open systems.

Far-Field Radiation of Three-Dimensional Plasmonic Gold Tapers near Apexes.

Three-dimensional plasmonic gold tapers are widely used structures in nano-optics for achieving imaging at the nanometer scale, enhanced spectroscopy, confined light sources, and ultrafast photoelectron emission. To understand their radiation properties further, especially in the proximity of the apex at the nanoscale, we employ cathodoluminescence spectroscopy with high spatial and energy resolution. The plasmon-induced radiation in the visible spectral range from three-dimensional gold tapers with opening angles of 13° and 47° is investigated under local electron excitation.

Ultrafast Charge Carrier Relaxation in Inorganic Halide Perovskite Single Crystals Probed by Two-Dimensional Electronic Spectroscopy.

Halide perovskites are promising optoelectronic materials. Despite impressive device performance, especially in photovoltaics, the femtosecond dynamics of elementary optical excitations and their interactions are still debated. Here we combine ultrafast two-dimensional electronic spectroscopy (2DES) and semiconductor Bloch equations (SBEs) to probe the room-temperature dynamics of nonequilibrium excitations in CsPbBr crystals.

Steering second-harmonic radiation through local excitations of plasmon.

We propose an approach of steering the second harmonic (SH) emission from a single plasmonic structure, through local excitations of plasmon. The proposed idea is confirmed experimentally, by adjusting the incident beam position at the fundamental frequency, on a single plasmonic antenna. A significant directivity change ( ± 52°) for the SH emission is observed with submicrometer adjustment ( ± 250 nm) of the excitation beam position, over broadband SH frequencies.

Vectorial near-field coupling.

The coherent exchange of optical near fields between two neighbouring dipoles plays an essential role in the optical properties, quantum dynamics and thus the function of many naturally occurring and artificial nanosystems. These interactions are challenging to quantify experimentally. They extend over only a few nanometres and depend sensitively on the detuning, dephasing and relative orientation (that is, the vectorial properties) of the coupled dipoles.

Observing charge separation in nanoantennas via ultrafast point-projection electron microscopy.

Observing the motion of electrons on their natural nanometer length and femtosecond time scales is a fundamental goal of and an open challenge for contemporary ultrafast science. At present, optical techniques and electron microscopy mostly provide either ultrahigh temporal or spatial resolution, and microscopy techniques with combined space-time resolution require further development. In this study, we create an ultrafast electron source via plasmon nanofocusing on a sharp gold taper and implement this source in an ultrafast point-projection electron microscope.