Antenna-coupled infrared nanospectroscopy of intramolecular vibrational interaction.

Many photonic and electronic molecular properties, as well as chemical and biochemical reactivities are controlled by fast intramolecular vibrational energy redistribution (IVR). This fundamental ultrafast process limits coherence time in applications from photochemistry to single quantum level control. While time-resolved multidimensional IR-spectroscopy can resolve the underlying vibrational interaction dynamics, as a nonlinear optical technique it has been challenging to extend its sensitivity to probe small molecular ensembles, achieve nanoscale spatial resolution, and control intramolecular dynamics. Here, we demonstrate a concept how mode-selective coupling of vibrational resonances to IR nanoantennas can reveal intramolecular vibrational energy transfer. In time-resolved infrared vibrational nanospectroscopy, we measure the Purcell-enhanced decrease of vibrational lifetimes of molecular vibrations while tuning the IR nanoantenna across coupled vibrations. At the example of a Re-carbonyl complex monolayer, we derive an IVR rate of (25±8) cm-1 corresponding to (450±150) fs, as is typical for the fast initial equilibration between symmetric and antisymmetric carbonyl vibrations. We model the enhancement of the cross-vibrational relaxation based on intrinsic intramolecular coupling and extrinsic antenna-enhanced vibrational energy relaxation. The model further suggests an anti-Purcell effect based on antenna and laser-field-driven vibrational mode interference which can counteract IVR-induced relaxation. Nanooptical spectroscopy of antenna-coupled vibrational dynamics thus provides for an approach to probe intramolecular vibrational dynamics with a perspective for vibrational coherent control of small molecular ensembles.

Understanding attosecond streaking.

This tutorial provides an overview on the theory of attosecond streaking, a pump-probe scheme to extract timing information of ionization processes that has been widely used in the past decade. Emphasis is put on the origin of the Coulomb-laser-coupling (CLC) term, which is crucial in the interpretation of streaking delays. Having gained a proper understanding of how the CLC terms in various publications relate to each other, we will be able to analyze in which regime the streaking delay can be split into a measurement-induced CLC term and a 'pure' ionization delay and under which conditions this splitting may break down. Thus we address the long-standing question of the validity of the widely applied interpretation of the streaking delay as a sum of the CLC term and a 'pure' ionization delay.

Cavity Catalysis of an Enantioselective Reaction under Vibrational Strong Coupling.

Strong light-matter interaction is emerging as an exciting tool for controlling chemical reactions. Here, we demonstrate an L-proline-catalyzed direct asymmetric Aldol reaction under vibrational strong coupling. Both the reactants (4-nitrobenzaldehyde and acetone) carbonyl bands are coupled to an infrared photon and react in the presence of L-proline. The reaction mixture is eluted from the cavity, and the conversion yields and enantiomeric excess are quantified using NMR and chiral HPLC. The conversion yields increase by up to 90 % in ON-resonance conditions. Interestingly, a large increase in the conversion yield does not affect the enantiomeric excess. Further control experiments were carried out by varying the temperature, and we propose that the rate-limiting step may not be the deciding factor in enantioselectivity. Whereas the formation of the enamine intermediate is modified by cavity coupling experiments. For this class of enantioselective reactions, strong coupling does not change the enantiomeric excess, possibly due to the large energy difference in chiral transition states. Strong coupling can boost the formation of enamine intermediate, thereby favouring the product yield. This gives more hope to test polaritonic chemistry based on enantioselective reactions in which the branching ratios can be controlled.

An All-Dielectric Polaritonic Metasurface with a Giant Nonlinear Optical Response.

Enhancing the efficiency of second-harmonic generation using all-dielectric metasurfaces to date has mostly focused on electromagnetic engineering of optical modes in the meta-atom. Further advances in nonlinear conversion efficiencies can be gained by engineering the material nonlinearities at the nanoscale, however this cannot be achieved using conventional materials. Semiconductor heterostructures that support resonant nonlinearities using quantum engineered intersubband transitions can provide this new degree of freedom. By simultaneously optimizing the heterostructures and meta-atoms, we experimentally realize an all-dielectric polaritonic metasurface with a maximum second-harmonic generation power conversion factor of 0.5 mW/W2 and power conversion efficiencies of 0.015% at nominal pump intensities of 11 kW/cm2. These conversion efficiencies are higher than the record values reported to date in all-dielectric nonlinear metasurfaces but with 3 orders of magnitude lower pump power. Our results therefore open a new direction for designing efficient nonlinear all-dielectric metasurfaces for new classical and quantum light sources.

Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry.

Energy transfer in terms of excitation or charge is one of the most basic processes in nature, and understanding and controlling them is one of the major challenges of modern quantum chemistry. In this work, we highlight that these processes as well as other chemical properties can be drastically altered by modifying the vacuum fluctuations of the electromagnetic field in a cavity. By using a real-space formulation from first principles that keeps all of the electronic degrees of freedom in the model explicit and simulates changes in the environment by an effective photon mode, we can easily connect to well-known quantum-chemical results such as Dexter charge-transfer and Förster excitation-transfer reactions, taking into account the often-disregarded Coulomb and self-polarization interaction. We find that the photonic degrees of freedom introduce extra electron-electron correlations over large distances and that the coupling to the cavity can drastically alter the characteristic charge-transfer behavior and even selectively improve the efficiency. For excitation transfer, we find that the cavity renders the transfer more efficient, essentially distance-independent, and further different configurations of highest efficiency depending on the coherence times. For strong decoherence (short coherence times), the cavity frequency should be in between the isolated excitations of the donor and acceptor, while for weak decoherence (long coherence times), the cavity should enhance a mode that is close to resonance with either donor or acceptor. Our results highlight that changing the photonic environment can redefine chemical processes, rendering polaritonic chemistry a promising approach toward the control of chemical reactions.

Direct Excitation of Triplet State of Molecule by Enhanced Magnetic Field of Dielectric Metasurfaces.

Efficient excitation of a triplet (T1 ) state of a molecule has far-reaching effects on photochemical reaction and energy conversion systems. Because the optical transition from a ground singlet (S0 ) to a T1 state is spin-forbidden, a T1 state is generated via intersystem crossing (ISC) from an excited singlet (S1 ) state. Although the excitation efficiency of a T1 state can be increased by enhancing ISC utilizing a heavy atom effect, energy loss during S1 →T1 relaxation is inevitable. Here, a general approach to directly excite a T1 state from a ground S0 state via magnetic dipole transition, which is boosted by enhanced magnetic field induced by a dielectric metasurface, is proposed. As a dielectric metasurface, a hexagonal array of silicon (Si) nanodisks is employed; the nanodisk array induces a strongly enhanced magnetic field on the surface due to the toroidal dipole (TD) resonance. A proof-of-concept experiment is performed using ruthenium (Ru) complexes placed on a metasurface and demonstrates that the phosphorescence is 35-fold enhanced on a metasurface when the TD resonance is tuned to the wavelength of the direct S0 →T1 transition. These results indicate that photon energy necessary to excite the T1 state can be reduced by more than 400 meV compared to the process involving the ISC. By combining optical measurements with numerical simulations, the mechanism of the phosphorescence enhancement is quantitatively discussed.

Highly Enhanced Light-Matter Interaction in MXene Quantum Dots-Monolayer WS2 Heterostructure.

Since the Ti3 C2 was discovered in 2011, the family of MXenes has attracted much attention. MXenes offer great potential in the tuning of many fundamental properties by the synthesis of new structures. The synthesis methods of MXene mainly require steps including immersing a MAX phase in hydrofluoric acid (HF) and processing at high temperatures. However, the HF may be hard to acquire in many countries and processing at high temperatures may cause risk issues. In this article, a simple and cost-effective synthesis of Ti3 C2 Tx quantum dots (QDs) via chemical solution method that follows the long-time magnetic stirring process-initiated etching of Al atoms from commercial Ti3 AlC2 powder at room temperature is introduced. With WS2 monolayer sitting over the MXenes QD arrays, a higher level of photoluminescence (PL) enhancement is found in the heterostructure with increasing laser power at room temperature and a few novel quasi-particles species in the heterostructure at -190 °C. The observations show that the possible plasmonic behavior initiated by QD arrays and the suspension state of WS2 may coplay the roles to trigger multiple quasi-particles species. This study can be an important benchmark for the extensive understanding of quasi-particles species, and their dynamics.

Bose-Einstein Condensation of Exciton-Polaritons in Organic Microcavities.

Bose-Einstein condensation describes the macroscopic occupation of a single-particle mode: the condensate. This state can in principle be realized for any particles obeying Bose-Einstein statistics; this includes hybrid light-matter excitations known as polaritons. Some of the unique optoelectronic properties of organic molecules make them especially well suited for the realization of polariton condensates. Exciton-polaritons form in optical cavities when electronic excitations couple collectively to the optical mode supported by the cavity. These polaritons obey bosonic statistics at moderate densities, are stable at room temperature, and have been observed to form a condensed or lasing state. Understanding the optimal conditions for polariton condensation requires careful modeling of the complex photophysics of organic molecules. In this article, we introduce the basic physics of exciton-polaritons and condensation and review experiments demonstrating polariton condensation in molecular materials.

Plasmon-Enhanced Near-Field Chirality in Twisted van der Waals Heterostructures.

It is shown that chiral plasmons, characterized by a longitudinal magnetic moment accompanying the longitudinal charge plasmon, lead to electromagnetic near-fields that are also chiral. For twisted bilayer graphene, we estimate that the near-field chirality of screened plasmons can be several orders of magnitude larger than that of the related circularly polarized light. The chirality also manifests itself in a deflection angle that is formed between the direction of the plasmon propagation and its Poynting vector. Twisted van der Waals heterostructures might thus provide a novel platform to promote enantiomer-selective physio-chemical processes in chiral molecules without the application of a magnetic field or external nanopatterning that break time-reversal, mirror plane, or inversion symmetry, respectively.

Near-Unity Light Absorption in a Monolayer WS2 Van der Waals Heterostructure Cavity.

Excitons in monolayer transition-metal-dichalcogenides (TMDs) dominate their optical response and exhibit strong light-matter interactions with lifetime-limited emission. While various approaches have been applied to enhance light-exciton interactions in TMDs, the achieved strength have been far below unity, and a complete picture of its underlying physical mechanisms and fundamental limits has not been provided. Here, we introduce a TMD-based van der Waals heterostructure cavity that provides near-unity excitonic absorption, and emission of excitonic complexes that are observed at ultralow excitation powers. Our results are in full agreement with a quantum theoretical framework introduced to describe the light-exciton-cavity interaction. We find that the subtle interplay between the radiative, nonradiative and dephasing decay rates plays a crucial role, and unveil a universal absorption law for excitons in 2D systems. This enhanced light-exciton interaction provides a platform for studying excitonic phase-transitions and quantum nonlinearities and enables new possibilities for 2D semiconductor-based optoelectronic devices.

Surface Plasmon-Enhanced Switching Kinetics of Molecular Photochromic Films on Gold Nanohole Arrays.

Diarylethene molecules are discussed as possible optical switches, which can reversibly transition between completely conjugated (closed) and nonconjugated (open) forms with different electrical conductance and optical absorbance, by exposure to UV and visible light. However, in general the opening reaction exhibits much lower quantum yield than the closing process, hindering their usage in optoelectronic devices. To enhance the opening process, which is supported by visible light, we employ the plasmonic field enhancement of gold films perforated with nanoholes. We show that gold nanohole arrays reveal strong optical transmission in the visible range (∼60%) and pronounced enhancement of field intensities, resulting in around 50% faster switching kinetics of the molecular species in comparison with quartz substrates. The experimental UV-vis measurements are verified with finite-difference time-domain simulation that confirm the obtained results. Thus, we propose gold nanohole arrays as transparent and conductive plasmonic material that accelerates visible-light-triggered chemical reactions including molecular switching.

Photonic hypercrystals for control of light-matter interactions.

Photonic crystals (PCs) have emerged as one of the most widely used platforms for controlling light-matter interaction in solid-state systems. They rely on Bragg scattering from wavelength-sized periodic modulation in the dielectric environment for manipulating the electromagnetic field. A complementary approach to manipulate light-matter interaction is offered by artificial media known as metamaterials that rely on the average response of deep-subwavelength unit cells. Here we demonstrate a class of artificial photonic media termed "photonic hypercrystals" (PHCs) that combine the large broadband photonic density of states provided by hyperbolic metamaterials with the light-scattering efficiency of PCs. Enhanced radiative rate (20×) and light outcoupling (100×) from PHCs embedded with quantum dots is observed. Such designer photonic media with complete control over the optical properties provide a platform for broadband control of light-matter interaction.

A Spin-Photon Interface Using Charge-Tunable Quantum Dots Strongly Coupled to a Cavity.

Charged quantum dots containing an electron or hole spin are bright solid-state qubits suitable for quantum networks and distributed quantum computing. Incorporating such quantum dot spin into a photonic crystal cavity creates a strong spin-photon interface in which the spin can control a photon by modulating the cavity reflection coefficient. However, previous demonstrations of such spin-photon interfaces have relied on quantum dots that are charged randomly by nearby impurities, leading to instability in the charge state, which causes poor contrast in the cavity reflectivity. Here we demonstrate a strong spin-photon interface using a quantum dot that is charged deterministically with a diode structure. By incorporating this actively charged quantum dot in a photonic crystal cavity, we achieve strong coupling between the cavity mode and the negatively charged state of the dot. Furthermore, by initializing the spin through optical pumping, we show strong spin-dependent modulation of the cavity reflectivity, corresponding to a cooperativity of 12. This spin-dependent reflectivity is important for mediating entanglement between spins using photons, as well as generating strong photon-photon interactions for applications in quantum networking and distributed quantum computing.

Simultaneous Surface-Enhanced Resonant Raman and Fluorescence Spectroscopy of Monolayer MoSe2: Determination of Ultrafast Decay Rates in Nanometer Dimension.

The fact that metallic nanostructures are an excellent light receiver and transmitter connects the underlying principles of two widely applied optical processes: surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). A comparative study of SERS and SEF can eliminate the typical unknown quantities of the system and reveal important parameters that cannot be accessed by conventional techniques. Here, we use this simultaneous SERS and SEF technique in a monolayer MoSe2 coupled plasmonic nanocavity. After optimizing the spatial and the spectral overlaps between excitonic and plasmonic resonances, the SERS and SEF enhancement factors can exceed 107 and 6000, respectively, at the same time on the same nanocube. The comparison of the SERS and SEF enhancements allows the estimation of the ultrafast total decay rate of the bright exciton in monolayer MoSe2 in the nanocavity down to tens of femtoseconds, which is otherwise hard to realize using time-resolved techniques.

Reaction microscope endstation at FLASH2.

A reaction microscope dedicated to multi-particle coincidence spectroscopy on gas-phase samples is installed at beamline FL26 of the free-electron laser FLASH2 in Hamburg. The main goals of the instrument are to follow the dynamics of atoms, molecules and small clusters on their natural time-scale and to study non-linear light-matter interaction with such systems. To this end, the reaction microscope is combined with an in-line extreme-ultraviolet (XUV) split-delay and focusing optics, which allows time-resolved XUV-XUV pump-probe spectroscopy to be performed.

Deterministic Positioning of Colloidal Quantum Dots on Silicon Nitride Nanobeam Cavities.

Engineering an array of precisely located cavity-coupled active media poses a major experimental challenge in the field of hybrid integrated photonics. We deterministically position solution-processed colloidal quantum dots (QDs) on high quality (Q)-factor silicon nitride nanobeam cavities and demonstrate light-matter coupling. By lithographically defining a window on top of an encapsulated cavity that is cladded in a polymer resist, and spin coating the QD solution, we can precisely control the placement of the QDs, which subsequently couple to the cavity. We show rudimentary control of the number of QDs coupled to the cavity by modifying the size of the window. Furthermore, we demonstrate Purcell enhancement and saturable photoluminescence in this QD-cavity platform. Finally, we deterministically position QDs on a photonic molecule and observe QD-coupled cavity supermodes. Our results pave the way for precisely controlling the number of QDs coupled to a cavity by engineering the window size, the QD dimension, and the solution chemistry and will allow advanced studies in cavity enhanced single photon emission, ultralow power nonlinear optics, and quantum many-body simulations with interacting photons.

Kohn-Sham approach to quantum electrodynamical density-functional theory: Exact time-dependent effective potentials in real space.

The density-functional approach to quantum electrodynamics extends traditional density-functional theory and opens the possibility to describe electron-photon interactions in terms of effective Kohn-Sham potentials. In this work, we numerically construct the exact electron-photon Kohn-Sham potentials for a prototype system that consists of a trapped electron coupled to a quantized electromagnetic mode in an optical high-Q cavity. Although the effective current that acts on the photons is known explicitly, the exact effective potential that describes the forces exerted by the photons on the electrons is obtained from a fixed-point inversion scheme. This procedure allows us to uncover important beyond-mean-field features of the effective potential that mark the breakdown of classical light-matter interactions. We observe peak and step structures in the effective potentials, which can be attributed solely to the quantum nature of light; i.e., they are real-space signatures of the photons. Our findings show how the ubiquitous dipole interaction with a classical electromagnetic field has to be modified in real space to take the quantum nature of the electromagnetic field fully into account.

Transversely Divergent Second Harmonic Generation by Surface Plasmon Polaritons on Single Metallic Nanowires.

Coherently adding up signal wave from different locations are a prerequisite for realizing efficient nonlinear optical processes in traditional optical configurations. While nonlinear optical processes in plasmonic waveguides with subwavelength light confinement are in principle desirable for enhancing nonlinear effects, so far it has been difficult to improve the efficiency due to the large momentum mismatch. Here we demonstrate, using remotely excited surface plasmon polaritons (SPPs), axial collimated but transversely divergent second harmonic (SH) generation in a single silver nanowire-monolayer molybdenum disulfide hybrid system. Fourier imaging of the generated SH signal confirms the momentum conservation conditions between the incident and reflected SPPs and reveals distinct features inherent to the 1D plasmonic waveguides: (i) the SH photons are collimated perpendicular to the nanowire axis but are divergent within the perpendicular plane; (ii) the collimation (divergence) is inversely proportional to the length of the active region (lateral confinement of the SPPs); and (iii) the SH emission pattern resembles that of an aligned dipole chain on top of the substrate with an emission peak at the critical angle. Our results pave the way to generate and manipulate SH emission around subwavelength waveguides and open up new possibilities for realizing high efficiency on-chip nonlinear optics.

Enabling enhanced emission and low-threshold lasing of organic molecules using special Fano resonances of macroscopic photonic crystals.

The nature of light interaction with matter can be dramatically altered in optical cavities, often inducing nonclassical behavior. In solid-state systems, excitons need to be spatially incorporated within nanostructured cavities to achieve such behavior. Although fascinating phenomena have been observed with inorganic nanostructures, the incorporation of organic molecules into the typically inorganic cavity is more challenging. Here, we present a unique optofluidic platform comprising organic molecules in solution suspended on a photonic crystal surface, which supports macroscopic Fano resonances and allows strong and tunable interactions with the molecules anywhere along the surface. We develop a theoretical framework of this system and present a rigorous comparison with experimental measurements, showing dramatic spectral and angular enhancement of emission. We then demonstrate that these enhancement mechanisms enable lasing of only a 100-nm thin layer of diluted solution of organic molecules with substantially reduced threshold intensity, which has important implications for organic light-emitting devices and molecular sensing.

Quantum control of polariton emission in a microcavity-quantum well system under magnetic field.

In this work, a quantum dissipative model is employed to investigate the influence of a perpendicular magnetic field on the photoluminescence (PL) spectrum of a quantum well embedded within a microcavity. This model incorporates both the exact electron-hole interaction within the semiconductor and the light-matter coupling between the fundamental photonic mode and the fermionic particles. The loss and pumping mechanisms are described using the quantum master equation, and the PL spectrum is determined via the quantum regression theorem. Our findings demonstrate that the magnetic field acts as a control mechanism in the polariton emission energy, the emission linewidth and the intensity distribution along the emission line. Finally, it is observed that the magnetic field can redistribute the density matrix occupations leading to modifications in the average number of polaritons in the system.