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.

Vibrational Coupling Infrared Nanocrystallography.

Coupling between molecular vibrations leads to collective vibrational states with spectral features sensitive to local molecular order. This provides spectroscopic access to the low-frequency intermolecular energy landscape. In its nanospectroscopic implementation, this technique of vibrational coupling nanocrystallography (VCNC) offers information on molecular disorder and domain formation with nanometer spatial resolution. However, deriving local molecular order relies on prior knowledge of the transition dipole magnitude and crystal structure of the underlying ordered phase. Here we develop a quantitative model for VCNC by relating nano-FTIR collective vibrational spectra to the molecular crystal structure from X-ray crystallography. We experimentally validate our approach at the example of a metal organic porphyrin complex with a carbonyl ligand as the probe vibration. This framework establishes VCNC as a powerful tool for measuring low-energy molecular interactions, wave function delocalization, nanoscale disorder, and domain formation in a wide range of molecular systems.

Nonlinear Nano-Imaging of Interlayer Coupling in 2D Graphene-Semiconductor Heterostructures.

The emergent electronic, spin, and other quantum properties of 2D heterostructures of graphene and transition metal dichalcogenides are controlled by the underlying interlayer coupling and associated charge and energy transfer dynamics. However, these processes are sensitive to interlayer distance and crystallographic orientation, which are in turn affected by defects, grain boundaries, or other nanoscale heterogeneities. This obfuscates the distinction between interlayer charge and energy transfer. Here, nanoscale imaging in coherent four-wave mixing (FWM) and incoherent two-photon photoluminescence (2PPL) is combined with a tip distance-dependent coupled rate equation model to resolve the underlying intra- and inter-layer dynamics while avoiding the influence of structural heterogeneities in mono- to multi-layer graphene/WSe2 heterostructures. With selective insertion of hBN spacer layers, it is shown that energy, as opposed to charge transfer, dominates the interlayer-coupled optical response. From the distinct nano-FWM and -2PPL tip-sample distance-dependent modification of interlayer and intralayer relaxation by tip-induced enhancement and quenching, an interlayer energy transfer time of τ ET ≈ ( 0 . 35 - 0.15 + 0.65 ) $\tau _{\rm ET} \approx (0.35^{+0.65}_{-0.15})$  ps consistent with recent reports is derived. As a local probe technique, this approach highlights the ability to determine intrinsic sample properties even in the presence of large sample heterogeneity.

Electrically Tunable Single Polaritonic Quantum Dot at Room Temperature.

Exciton-polaritons confined in plasmonic cavities are hybridized light-matter quasiparticles, with distinct optical characteristics compared to plasmons and excitons alone. Here, we demonstrate the electric tunability of a single polaritonic quantum dot operating at room temperature in electric-field tip-enhanced strong coupling spectroscopy. For a single quantum dot in the nanoplasmonic tip cavity with variable dc local electric field, we dynamically control the Rabi frequency with the corresponding polariton emission, crossing weak to strong coupling. We model the observed behaviors based on the quantum confined Stark effect in the strong coupling regime.

Tip-Enhanced Dark Exciton Nanoimaging and Local Strain Control in Monolayer WSe2.

Dark excitons in transition-metal dichalcogenides, with their long lifetimes and strong binding energies, provide potential platforms from photonic and optoelectronic applications to quantum information science even at room temperature. However, their spatial heterogeneity and sensitivity to strain is not yet understood. Here, we combine tip-enhanced photoluminescence spectroscopy with atomic force induced strain control to nanoimage dark excitons in WSe2 and their response to local strain. Dark exciton emission is facilitated by out-of-plane picocavity Purcell enhancement giving rise to spatially highly localized emission, providing for higher spatial resolution compared to bright exciton nanoimaging. Further, tip-antenna-induced dark exciton emission is enhanced in areas of higher strain associated with bubbles. In addition, active force control shows dark exciton emission to be more sensitive to strain with both compressive and tensile lattice deformation facilitating emission. This interplay between localized strain and Purcell effects provides novel pathways for nanomechanical exciton emission control.

Ultrafast Nanoimaging of Electronic Coherence of Monolayer WSe2.

Transition-metal dichalcogenides (TMDs) have demonstrated a wide range of novel photonic, optoelectronic, and correlated electron phenomena for more than a decade. However, the coherent dynamics of their excitons, including possibly long dephasing times and their sensitivity to spatial heterogeneities, are still poorly understood. Here we implement adiabatic plasmonic nanofocused four-wave mixing (FWM) to image the coherent electron dynamics in monolayer WSe2. We observe nanoscale heterogeneities at room temperature with dephasing ranging from T2 ≲ 5 to T2 ≳ 60 fs on length scales of 50-100 nm. We further observe a counterintuitive anticorrelation between FWM intensity and T2, with the weakest FWM emission at locations of longest coherence. We interpret this behavior as a nonlocal nano-optical interplay between spatial coherence of the nonlinear polarization and disorder-induced scattering. The results highlight the challenges associated with heterogeneities in TMDs limiting their photophysical properties, yet also the potential of their novel nonlinear optical phenomena.

Gate-Tuning Hybrid Polaritons in Twisted α-MoO3/Graphene Heterostructures.

Modulating anisotropic phonon polaritons (PhPs) can open new avenues in infrared nanophotonics. Promising PhP dispersion engineering through polariton hybridization has been demonstrated by coupling gated graphene to single-layer α-MoO3. However, the mechanism underlying the gate-dependent modulation of hybridization has remained elusive. Here, using IR nanospectroscopic imaging, we demonstrate active modulation of the optical response function, quantified in measurements of gate dependence of wavelength, amplitude, and dissipation rate of the hybrid plasmon-phonon polaritons (HPPPs) in both single-layer and twisted bilayer α-MoO3/graphene heterostructures. Intriguingly, while graphene doping leads to a monotonic increase in HPPP wavelength, amplitude and dissipation rate show transition from an initially anticorrelated decrease to a correlated increase. We attribute this behavior to the intricate interplay of gate-dependent components of the HPPP complex momentum. Our results provide the foundation for active polariton control of integrated α-MoO3 nanophotonics devices.

Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals.

Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s-SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins.

Electron-Phonon Coupling in a Magic-Angle Twisted-Bilayer Graphene Device from Gate-Dependent Raman Spectroscopy and Atomistic Modeling.

The importance of phonons in the strong correlation phenomena observed in twisted-bilayer graphene (TBG) at the so-called magic-angle is under debate. Here we apply gate-dependent micro-Raman spectroscopy to monitor the G band line width in TBG devices of twist angles θ = 0° (Bernal), ∼1.1° (magic-angle), and ∼7° (large-angle). The results show a broad and p-/n-asymmetric doping behavior at the magic angle, in clear contrast to the behavior observed in twist angles above and below this point. Atomistic modeling reproduces the experimental observations in close connection with the joint density of electronic states in the electron-phonon scattering process, revealing how the unique electronic structure of magic-angle TBGs influences the electron-phonon coupling and, consequently, the G band line width. Overall, the value of the G band line width in magic-angle TBG is larger when compared to that of the other samples, in qualitative agreement with our calculations.

Semi-empirical quantum optics for mid-infrared molecular nanophotonics.

Nanoscale infrared (IR) resonators with sub-diffraction limited mode volumes and open geometries have emerged as new platforms for implementing cavity quantum electrodynamics at room temperature. The use of IR nanoantennas and tip nanoprobes to study strong light-matter coupling of molecular vibrations with the vacuum field can be exploited for IR quantum control with nanometer spatial and femtosecond temporal resolution. In order to advance the development of molecule-based quantum nanophotonics in the mid-IR, we propose a generally applicable semi-empirical methodology based on quantum optics to describe light-matter interaction in systems driven by mid-IR femtosecond laser pulses. The theory is shown to reproduce recent experiments on the acceleration of the vibrational relaxation rate in infrared nanostructures. It also provides physical insights on the implementation of coherent phase rotations of the near-field using broadband nanotips. We then apply the quantum framework to develop general tip-design rules for the experimental manipulation of vibrational strong coupling and Fano interference effects in open infrared resonators. We finally propose the possibility of transferring the natural anharmonicity of molecular vibrational levels to the resonator near-field in the weak coupling regime to implement intensity-dependent phase shifts of the coupled system response with strong pulses and develop a vibrational chirping model to understand the effect. The semi-empirical quantum theory is equivalent to first-principles techniques based on Maxwell's equations, but its lower computational cost suggests its use as a rapid design tool for the development of strongly coupled infrared nanophotonic hardware for applications ranging from quantum control of materials to quantum information processing.

2D Vibrational Exciton Nanoimaging of Domain Formation in Self-Assembled Monolayers.

Order, disorder, and domains affect many of the functional properties in self-assembled monolayers (SAMs). However, carrier transport, wettability, and chemical reactivity are often associated with collective effects, where conventional imaging techniques have limited sensitivity to the underlying intermolecular coupling. Here we demonstrate vibrational excitons as a molecular ruler of intermolecular wave function delocalization and nanodomain size in SAMs. In the model system of a 4-nitrothiophenol (4-NTP) SAM on gold, we resolve coupling-induced peak shifts of the nitro symmetric stretch mode with full spatio-spectral infrared scattering scanning near-field optical microscopy. From modeling of the underlying 2D Hamiltonian, we infer domain sizes and their distribution ranging from 3 to 12 nm across a field of view on the micrometer scale. This approach of vibrational exciton nanoimaging is generally applicable to study structural phases and domains in SAMs and other molecular interfaces.

Nanocavity Clock Spectroscopy: Resolving Competing Exciton Dynamics in WSe2/MoSe2 Heterobilayers.

Transition-metal dichalcogenide heterostructures are an emergent platform for novel many-body states from exciton condensates to nanolasers. However, their exciton dynamics are difficult to disentangle due to multiple competing processes with time scales varying over many orders of magnitude. Using a configurable nano-optical cavity based on a plasmonic scanning probe tip, the radiative (rad) and nonradiative (nrad) relaxation of intra- and interlayer excitons is controlled. Tuning their relative rates in a WSe2/MoSe2 heterobilayer over 6 orders of magnitude in tip-enhanced photoluminescence spectroscopy reveals a cavity-induced crossover from nonradiative quenching to Purcell-enhanced radiation. Rate equation modeling with the interlayer charge transfer time as a reference clock allows for a comprehensive determination from the long interlayer exciton (IX) radiative lifetime τIXrad = (94 ± 27) ns to the 5 orders of magnitude faster competing nonradiative lifetime τIXnrad = (0.6 ± 0.2) ps. This approach of nanocavity clock spectroscopy is generally applicable to a wide range of excitonic systems with competing decay pathways.

Multidimensional Nano-Imaging of Structure, Coupling, and Disorder in Molecular Materials.

A hierarchy of intramolecular and intermolecular interactions controls the properties of biomedical, photophysical, and novel energy materials. However, multiscale heterogeneities often obfuscate the relationship between microscopic structure and emergent function, and they are generally difficult to access with conventional optical and electron microscopy techniques. Here, we combine vibrational exciton nanoimaging in variable-temperature near-field optical microscopy (IR s-SNOM) with four-dimensional scanning transmission electron microscopy (4D-STEM), and vibrational exciton modeling based on density functional theory (DFT), to link local microscopic molecular interactions to macroscopic three-dimensional order. In the application to poly(tetrafluoroethylene) (PTFE), large spatio-spectral heterogeneities with C-F vibrational energy shifts ranging from sub-cm-1 to ≳25 cm-1 serve as a molecular ruler of the degree of local crystallinity and disorder. Spatio-spectral-structural correlations reveal a previously invisible degree of highly variable local disorder in molecular coupling as the possible missing link between nanoscale morphology and associated electronic, photonic, and other functional properties of molecular materials.

In Liquid Infrared Scattering Scanning Near-Field Optical Microscopy for Chemical and Biological Nanoimaging.

Imaging biological systems with simultaneous intrinsic chemical specificity and nanometer spatial resolution in their typical native liquid environment has remained a long-standing challenge. Here, we demonstrate a general approach of chemical nanoimaging in liquid based on infrared scattering scanning near-field optical microscopy (IR s-SNOM). It is enabled by combining AFM operation in a fluid cell with evanescent IR illumination via total internal reflection, which provides spatially confined excitation for minimized IR water absorption, reduced far-field background, and enhanced directional signal emission and sensitivity. We demonstrate in-liquid IR s-SNOM vibrational nanoimaging and conformational identification of catalase nanocrystals and spatio-spectral analysis of biomimetic peptoid sheets with monolayer sensitivity and chemical specificity at the few zeptomole level. This work establishes the principles of in-liquid and in situ IR s-SNOM spectroscopic chemical nanoimaging and its general applicability to biomolecular, cellular, catalytic, electrochemical, or other interfaces and nanosystems in liquids or solutions.

Anisotropic Flow Control and Gate Modulation of Hybrid Phonon-Polaritons.

Light-matter interaction in two-dimensional photonic or phononic materials allows for the confinement and manipulation of free-space radiation at sub-wavelength scales. Most notably, the van der Waals heterostructure composed of graphene (G) and hexagonal boron nitride (hBN) provides for gate-tunable hybrid hyperbolic plasmon phonon-polaritons (HP3). Here, we present the anisotropic flow control and gate-voltage modulation of HP3 modes in G-hBN on an air-Au microstructured substrate. Using broadband infrared synchrotron radiation coupled to a scattering-type near-field optical microscope, we launch HP3 waves in both hBN Reststrahlen bands and observe directional propagation across in-plane heterointerfaces created at the air-Au junction. The HP3 hybridization is modulated by varying the gate voltage between graphene and Au. This modifies the coupling of continuum graphene plasmons with the discrete hBN hyperbolic phonon polaritons, which is described by an extended Fano model. This work represents the first demonstration of the control of polariton propagation, introducing a theoretical approach to describe the breaking of the reflection and transmission symmetry for HP3 modes. Our findings augment the degree of control of polaritons in G-hBN and related hyperbolic metamaterial nanostructures, bringing new opportunities for on-chip nano-optics communication and computing.

Purcell-Enhanced Spontaneous Emission of Molecular Vibrations.

Infrared (IR) spectroscopy of molecular vibrations provides insight into molecular structure, coupling, and dynamics. However, picosecond scale intermolecular and intramolecular many-body interactions, nonradiative relaxation, absorption, and thermalization typically dominate over IR spontaneous emission. We demonstrate how coupling to a resonant IR antenna can enhance spontaneous emission of molecular vibrations. Using time-domain nanoprobe spectroscopy we observe an up to 50% decrease in vibrational dephasing time T_{2,vib}, based on the coupling-induced population decay with T_{κ}≃550 fs and an associated Purcell factor of >10^{6}. This rate enhancement of the spontaneous emission of antenna-coupled molecular vibrations opens new avenues for IR coherent control, quantum information processing, and quantum chemistry.

Polarization Control with Plasmonic Antenna Tips: A Universal Approach to Optical Nanocrystallography and Vector-Field Imaging.

Controlling the propagation and polarization vectors in linear and nonlinear optical spectroscopy enables us to probe the anisotropy of optical responses providing structural symmetry selective contrast in optical imaging. Here, we present a novel tilted antenna-tip approach to control the optical vector-field by breaking the axial symmetry of the nanoprobe in tip-enhanced near-field microscopy. This gives rise to a localized plasmonic antenna effect with significantly enhanced optical field vectors with control of both in-plane and out-of-plane components. We use the resulting vector-field specificity in the symmetry selective nonlinear optical response of second-harmonic generation (SHG) for a generalized approach to optical nanocrystallography and imaging. In tip-enhanced SHG imaging of monolayer MoS2 films and single-crystalline ferroelectric YMnO3, we reveal nanocrystallographic details of domain boundaries and domain topology with enhanced sensitivity and nanoscale spatial resolution. The approach is applicable to any anisotropic linear and nonlinear optical response and enables the optical nanocrystallographic imaging of molecular or quantum materials.

Photoinduced Tip-Sample Forces for Chemical Nanoimaging and Spectroscopy.

Control of photoinduced forces allows nanoparticle manipulation, atom trapping, and fundamental studies of light-matter interactions. Scanning probe microscopy enables the local detection of photoinduced effects with nano-optical imaging and spectroscopy modalities being used for chemical analysis and the study of physical effects. Recently, the development of a novel scanning probe technique has been reported with local chemical sensitivity attributed to the localization and detection of the optical gradient force between a probe tip and sample surface via infrared vibrationally resonant coupling. However, the magnitude and spectral line shape of the observed signals disagree with theoretical predictions of optical gradient forces. Here, we clarify this controversy by resolving and analyzing the interplay of several photoinduced effects between scanning probe tips and infrared resonant materials through spectral and spatial force measurements. Force spectra obtained on IR-active vibrational modes of polymer thin films are symmetric and match the material absorption spectra in contrast to the dispersive spectral line shape expected for the optical gradient force response. Sample thickness dependence shows continuous increase in force signal beyond the thickness where the optical dipole force would saturate. Our results illustrate that photoinduced force interactions between scanning probe tips and infrared-resonant materials are dominated by short-range thermal expansion and possibly long-range thermally induced photoacoustic effects. At the same time, we provide a guideline to detect and discriminate optical gradient forces from other photoinduced effects, which opens a new perspective for the development of new scanning probe modalities exploiting ultrastrong opto-mechanical coupling effects in tip-sample cavities.

Near-Field Enhanced Photochemistry of Single Molecules in a Scanning Tunneling Microscope Junction.

Optical near-field excitation of metallic nanostructures can be used to enhance photochemical reactions. The enhancement under visible light illumination is of particular interest because it can facilitate the use of sunlight to promote photocatalytic chemical and energy conversion. However, few studies have yet addressed optical near-field induced chemistry, in particular at the single-molecule level. In this Letter, we report the near-field enhanced tautomerization of porphycene on a Cu(111) surface in a scanning tunneling microscope (STM) junction. The light-induced tautomerization is mediated by photogenerated carriers in the Cu substrate. It is revealed that the reaction cross section is significantly enhanced in the presence of a Au tip compared to the far-field induced process. The strong enhancement occurs in the red and near-infrared spectral range for Au tips, whereas a W tip shows a much weaker enhancement, suggesting that excitation of the localized plasmon resonance contributes to the process. Additionally, using the precise tip-surface distance control of the STM, the near-field enhanced tautomerization is examined in and out of the tunneling regime. Our results suggest that the enhancement is attributed to the increased carrier generation rate via decay of the excited near-field in the STM junction. Additionally, optically excited tunneling electrons also contribute to the process in the tunneling regime.

Mechanism of Electric Power Generation from Ionic Droplet Motion on Polymer Supported Graphene.

Graphene-based electric power generation that converts mechanical energy of flow of ionic droplets over the device surface into electricity has emerged as a promising candidate for blue-energy network. Yet the lack of a microscopic understanding of the underlying mechanism has prevented ability to optimize and control the performance of such devices. This requires information on interfacial structure and charging behavior at the molecular level. Here, we use sum-frequency vibrational spectroscopy to study the roles of solvated ions, graphene, surface moiety on substrate and water molecules at the aqueous solution/graphene/polymer interface. We discover that the surface dipole layer of the neutral polymer is responsible for ion attraction toward and adsorption at the graphene surface that leads to electricity generation in graphene. Graphene itself does not attract ions and only acts as a conducting sheet for the induced carrier transport. Replacing the polymer by an organic ferroelectric substrate could allow switching of the electricity generation with long durability. Our microscopic understanding of the electricity generation process paves the way for the rational design of scalable and more efficient droplet-motion-based energy transducer devices.