Spectroscopy in Nanoscopic Cavities: Models and Recent Experiments.

The ability of nanophotonic cavities to confine and store light to nanoscale dimensions has important implications for enhancing molecular, excitonic, phononic, and plasmonic optical responses. Spectroscopic signatures of processes that are ordinarily exceedingly weak such as pure absorption and Raman scattering have been brought to the single-particle limit of detection, while new emergent polaritonic states of optical matter have been realized through coupling material and photonic cavity degrees of freedom across a wide range of experimentally accessible interaction strengths. In this review, we discuss both optical and electron beam spectroscopies of cavity-coupled material systems in weak, strong, and ultrastrong coupling regimes, providing a theoretical basis for understanding the physics inherent to each while highlighting recent experimental advances and exciting future directions.

Dynamic Ultrastrong Coupling in a 2 nm Gap Plasmonic Cavity at the Sub-Picosecond Scale.

Localized surface plasmon resonances (LSPRs) can enhance the electromagnetic fields on metallic nanostructures upon light illumination, providing an approach for manipulating light-matter interactions at the sub-wavelength scale. However, currently, there is no thorough investigation of the physical mechanism in the dynamic formation of the strongly coupled LSPRs on sub-5 nm plasmonic cavities at the sub-picosecond scale. In this work, through femtosecond broadband transient absorption spectroscopy, we reveal the dynamic ultrastrong coupling processes in a nanoparticle-in-trench (NPiT) structure containing 2 nm gap cavities, and demonstrate a coherent motional coupling between vibrating AuNPs and the nanogaps. We achieve a maximum Rabi splitting energy of ∼660 meV in the sub-picosecond hot-electron relaxation time scale under the resonant excitation of the nanogap cavity's LSPR, reaching the ultrastrong coupling regime. This leads to a change of global vibration modes for the 2 nm gap cavity, potentially related to the dynamical Casimir effect with nanogap resonators.

Ultrastrong Coupling Enhancement with Squeezed Mode Volume in Terahertz Nanoslots.

Metallic nanogaps have emerged as a versatile platform for realizing ultrastrong coupling in terahertz frequencies. Increasing the coupling strength generally involved reducing the gap width to minimize the mode volume, which presents challenges in fabrication and efficient material coupling. Here, we propose employing terahertz nanoslots, which can efficiently squeeze the mode volume in an extra dimension alongside the gap width. Our experiments using 500 nm wide nanoslots integrated with an organic-inorganic hybrid perovskite demonstrate ultrastrong phonon-photon coupling with a record-high Rabi splitting of 48% of the original resonance (Ω = 0.48ω0), despite having a gap width 5 times larger than previously reported structures with Ω = 0.45ω0. Mechanisms underlying this effective light--matter coupling are investigated with simulations using coupled mode theory. Moreover, bulk polariton analyses reveal that our results account for 68% of the theoretical maximum Rabi splitting, with the potential to reach 82% through further optimization of the nanoslots.

Electrical Detection of Ultrastrong Coherent Interaction between Terahertz Fields and Electrons Using Quantum Point Contacts.

Light-matter interaction in the ultrastrong coupling regime is attracting considerable attention owing to its applications to coherent control of material properties by a vacuum fluctuation field. However, electrical access to such an ultrastrongly coupled system is very challenging. In this work, we have fabricated a gate-defined quantum point contact (QPC) near the gap of a terahertz (THz) split-ring resonator (SRR) fabricated on a GaAs two-dimensional (2D) electron system. By illuminating the system with external THz radiation, the QPC shows a photocurrent spectrum which exhibits significant anticrossing that arises from coupling between the cyclotron resonance of the 2D electrons and the SRR. The observed photocurrent signal can be explained by energy-selective transmission/reflection of the quantum Hall edge channels at the QPC. Furthermore, at the same gate voltage and magnetic field conditions under which the anticrossing signal was observed, the QPC exhibits anomalous conductance modulation even in the dark environment.

Mid-Infrared Intersubband Cavity Polaritons in Flexible Single Quantum Well.

Strong and ultrastrong coupling between intersubband transitions in quantum wells and cavity photons have been realized in mid-infrared and terahertz spectral regions. However, most previous works employed a large number of quantum wells on rigid substrates to achieve coupling strengths reaching the strong or ultrastrong coupling regime. In this work, we experimentally demonstrate ultrastrong coupling between the intersubband transition in a single quantum well and the resonant mode of photonic nanocavity at room temperature. We also observe strong coupling between the nanocavity resonance and the second-order intersubband transition in a single quantum well. Furthermore, we implement for the first time such intersubband cavity polariton systems on soft and flexible substrates and demonstrate that bending of the single quantum well does not significantly affect the characteristics of the cavity polaritons. This work paves the way to broaden the range of potential applications of intersubband cavity polaritons including soft and wearable photonics.

Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling.

We simulate vibrational strong coupling (VSC) and vibrational ultrastrong coupling (V-USC) for liquid water with classical molecular dynamics simulations. When the cavity modes are resonantly coupled to the O-H stretch mode of liquid water, the infrared spectrum shows asymmetric Rabi splitting. The lower polariton (LP) may be suppressed or enhanced relative to the upper polariton (UP) depending on the frequency of the cavity mode. Moreover, although the static properties and the translational diffusion of water are not changed under VSC or V-USC, we do find the modification of the orientational autocorrelation function of H2O molecules especially under V-USC, which could play a role in ground-state chemistry.

Dicke-Cooperativity-Assisted Ultrastrong Coupling Enhancement in Terahertz Metasurfaces.

A system of N two-level atoms cooperatively interacting with a photonic field can be described as a single giant atom coupled to the field with interaction strength ∝N. This enhancement, known as Dicke cooperativity in quantum optics, has recently become an indispensable element in quantum information technology. Here, we extend the coupling beyond the standard light-matter interaction paradigm, enhancing Dicke cooperativity in a terahertz metasurface with N meta-atoms. The cooperative enhancement is manifested through the hybridization of the localized surface plasmon resonance in individual meta-atoms and surface lattice resonance due to the periodic array. Furthermore, through engineering of the capacitive split-gap in the meta-atoms, we were able to enhance the coupling rate into the ultrastrong coupling regime by a factor of N. Our strategy can serve as a new platform for demonstrating effective control of fermionic systems by weak pumping, superradiant emission, and ultrasensitive sensing of molecules.

Direct Visualization of Ultrastrong Coupling between Luttinger-Liquid Plasmons and Phonon Polaritons.

Ultrastrong coupling of light and matter creates new opportunities to modify chemical reactions or develop novel nanoscale devices. One-dimensional Luttinger-liquid plasmons in metallic carbon nanotubes are long-lived excitations with extreme electromagnetic field confinement. They are promising candidates to realize strong or even ultrastrong coupling at infrared frequencies. We applied near-field polariton interferometry to examine the interaction between propagating Luttinger-liquid plasmons in individual carbon nanotubes and surface phonon polaritons of silica and hexagonal boron nitride. We extracted the dispersion relation of the hybrid Luttinger-liquid plasmon-phonon polaritons (LPPhPs) and explained the observed phenomena by the coupled harmonic oscillator model. The dispersion shows pronounced mode splitting, and the obtained value for the normalized coupling strength shows we reached the ultrastrong coupling regime with both native silica and hBN phonons. Our findings predict future applications to exploit the extraordinary properties of carbon nanotube plasmons, ranging from nanoscale plasmonic circuits to ultrasensitive molecular sensing.

Terahertz Light-Matter Interaction beyond Unity Coupling Strength.

Achieving control over light-matter interaction in custom-tailored nanostructures is at the core of modern quantum electrodynamics. In strongly and ultrastrongly coupled systems, the excitation is repeatedly exchanged between a resonator and an electronic transition at a rate known as the vacuum Rabi frequency ΩR. For ΩR approaching the resonance frequency ωc, novel quantum phenomena including squeezed states, Dicke superradiant phase transitions, the collapse of the Purcell effect, and a population of the ground state with virtual photon pairs are predicted. Yet, the experimental realization of optical systems with ΩR/ωc ≥ 1 has remained elusive. Here, we introduce a paradigm change in the design of light-matter coupling by treating the electronic and the photonic components of the system as an entity instead of optimizing them separately. Using the electronic excitation to not only boost the electronic polarization but furthermore tailor the shape of the vacuum mode, we push ΩR/ωc of cyclotron resonances ultrastrongly coupled to metamaterials far beyond unity. As one prominent illustration of the unfolding possibilities, we calculate a ground state population of 0.37 virtual photons for our best structure with ΩR/ωc = 1.43 and suggest a realistic experimental scenario for measuring vacuum radiation by cutting-edge terahertz quantum detection.

Few-Electron Ultrastrong Light-Matter Coupling at 300 GHz with Nanogap Hybrid LC Microcavities.

Ultrastrong light-matter coupling allows the exploration of new states of matter through the interaction of strong vacuum fields with huge electronic dipoles. By using hybrid dipole antenna-split ring resonator-based cavities with extremely small effective mode volumes Veff/λ03 ≃ 6 × 10-10 and surfaces Seff/λ02 ≃ 3.5 × 10-7, we probe the ultrastrong light-matter coupling at 300 GHz to less than 100 electrons located in the last occupied Landau level of a high mobility two-dimensional electron gas, measuring a normalized coupling ratio of ΩR/ωc = 0.36. Effects of the extremely reduced cavity dimensions are observed as the light-matter coupled system is better described by an effective mass heavier than the uncoupled one. These results open the way to ultrastrong coupling at the single-electron level in two-dimensional electron systems.

Spatially Uniform and Quantitative Surface-Enhanced Raman Scattering under Modal Ultrastrong Coupling Beyond Nanostructure Homogeneity Limits.

We developed a substrate that enables highly sensitive and spatially uniform surface-enhanced Raman scattering (SERS). This substrate comprises densely packed gold nanoparticles (d-AuNPs)/titanium dioxide/Au film (d-ATA). The d-ATA substrate demonstrates modal ultrastrong coupling between localized surface plasmon resonances (LSPRs) of AuNPs and Fabry-Pérot nanocavities. d-ATA exhibits a significant enhancement of the near-field intensity, resulting in a 78-fold increase in the SERS signal for crystal violet (CV) compared to that of d-AuNP/TiO2 substrates. Importantly, high sensitivity and a spatially uniform signal intensity can be obtained without precise control of the shape and arrangement of the nanoscale AuNPs, enabling quantitative SERS measurements. Additionally, SERS measurements of rhodamine 6G (R6G) on this substrate under ultralow adsorption conditions (0.6 R6G molecules/AuNP) show a spatial variation in the signal intensity within 3%. These findings suggest that the SERS signal under modal ultrastrong coupling originates from multiple plasmonic particles with quantum coherence.

Ultralong-Range Energy Transport in a Disordered Organic Semiconductor at Room Temperature Via Coherent Exciton-Polariton Propagation.

Amorphous molecular solids are inherently disordered, exhibiting strong exciton localization. Optical microcavities containing such disordered excitonic materials have been theoretically shown to support both propagating and localized exciton-polariton modes. Here, the ultrastrong coupling of a Bloch surface wave photon and molecular excitons in a disordered organic thin film at room temperature is demonstrated, where the major fraction of the polaritons are propagating states. The delocalized exciton-polariton has a group velocity as high as 3 × 107 m s-1 and a lifetime of 500 fs, leading to propagation distances of over 100 µm from the excitation source. The polariton intensity shows a halo-like pattern that is due to self-interference of the polariton mode, from which a coherence length of 20 µm is derived and is correlated with phase breaking by polariton scattering. The demonstration of ultralong-range exciton-polariton transport at room temperature promises new photonic and optoelectronic applications such as efficient energy transfer in disordered condensed matter systems.

Ultrastrong coupling of plasmons and excitons in a nanoshell.

The strong coupling regime of hybrid plasmonic-molecular systems is a subject of great interest for its potential to control and engineer light-matter interactions at the nanoscale. Recently, the so-called ultrastrong coupling regime, which is achieved when the light-matter coupling rate reaches a considerable fraction of the emitter transition frequency, has been realized in semiconductor and superconducting systems and in organic molecules embedded in planar microcavities or coupled to surface plasmons. Here we explore the possibility to achieve this regime of light-matter interaction at nanoscale dimensions. We demonstrate by accurate scattering calculations that this regime can be reached in nanoshells constituted by a core of organic molecules surrounded by a silver or gold shell. These hybrid nanoparticles can be exploited for the design of all-optical ultrafast plasmonic nanocircuits and -devices.