Electrically tunable quantum confinement of neutral excitons.

Confining particles to distances below their de Broglie wavelength discretizes their motional state. This fundamental effect is observed in many physical systems, ranging from electrons confined in atoms or quantum dots1,2 to ultracold atoms trapped in optical tweezers3,4. In solid-state photonics, a long-standing goal has been to achieve fully tunable quantum confinement of optically active electron-hole pairs, known as excitons. To confine excitons, existing approaches mainly rely on material modulation5, which suffers from poor control over the energy and position of trapping potentials. This has severely impeded the engineering of large-scale quantum photonic systems. Here we demonstrate electrically controlled quantum confinement of neutral excitons in 2D semiconductors. By combining gate-defined in-plane electric fields with inherent interactions between excitons and free charges in a lateral p-i-n junction, we achieve exciton confinement below 10 nm. Quantization of excitonic motion manifests in the measured optical response as a ladder of discrete voltage-dependent states below the continuum. Furthermore, we observe that our confining potentials lead to a strong modification of the relative wave function of excitons. Our technique provides an experimental route towards creating scalable arrays of identical single-photon sources and has wide-ranging implications for realizing strongly correlated photonic phases6,7 and on-chip optical quantum information processors8,9.

Freeform Electronic and Photonic Landscapes in Hexagonal Boron Nitride.

Atomically smooth hexagonal boron nitride (hBN) flakes have revolutionized two-dimensional (2D) optoelectronics. They provide the key substrate, encapsulant, and gate dielectric for 2D electronics while offering hyperbolic dispersion and quantum emission for photonics. The shape, thickness, and profile of these hBN flakes affect device functionality. However, researchers are restricted to simple, flat flakes, limiting next-generation devices. If arbitrary structures were possible, enhanced control over the flow of photons, electrons, and excitons could be exploited. Here, we demonstrate freeform hBN landscapes by combining thermal scanning-probe lithography and reactive-ion etching to produce previously unattainable flake structures with surprising fidelity. We fabricate photonic microelements (phase plates, grating couplers, and lenses) and show their straightforward integration, constructing a high-quality optical microcavity. We then decrease the length scale to introduce Fourier surfaces for electrons, creating sophisticated Moiré patterns for strain and band-structure engineering. These capabilities generate opportunities for 2D polaritonics, twistronics, quantum materials, and deep-ultraviolet devices.

Modification of Enzyme Activity by Vibrational Strong Coupling of Water.

Vibrational strong coupling (VSC) has recently emerged as a completely new tool for influencing chemical reactivity. It harnesses electromagnetic vacuum fluctuations through the creation of hybrid states of light and matter, called polaritonic states, in an optical cavity resonant to a molecular absorption band. Here, we investigate the effect of vibrational strong coupling of water on the enzymatic activity of pepsin, where a water molecule is directly involved in the enzyme's chemical mechanism. We observe an approximately 4.5-fold decrease of the apparent second-order rate constant kcat /Km when coupling the water stretching vibration, whereas no effect was detected for the strong coupling of the bending vibration. The possibility of modifying enzymatic activity by coupling water demonstrates the potential of VSC as a new tool to study biochemical reactivity.

Coherent Coupling of WS2 Monolayers with Metallic Photonic Nanostructures at Room Temperature.

Room temperature strong coupling of WS2 monolayer exciton transitions to metallic Fabry-Pérot and plasmonic optical cavities is demonstrated. A Rabi splitting of 101 meV is observed for the Fabry-Pérot cavity. The enhanced magnitude and visibility of WS2 monolayer strong coupling is attributed to the larger absorption coefficient, the narrower line width of the A exciton transition, and greater spin-orbit coupling. For WS2 coupled to plasmonic arrays, the Rabi splitting still reaches 60 meV despite the less favorable coupling conditions, and displays interesting photoluminescence features. The unambiguous signature of WS2 monolayer strong coupling in easily fabricated metallic resonators at room temperature suggests many possibilities for combining light-matter hybridization with spin and valleytronics.

High-Efficiency Second-Harmonic Generation from Hybrid Light-Matter States.

We report a novel approach to modify the second order nonlinear optical (NLO) susceptibility of organic nanofiber crystals by hybridization with the optical modes of microcavities in the strong coupling regime. The wavelength dependence of the SHG efficiency displays two intense peaks corresponding to the so-formed light-matter hybrid states. Our results demonstrate an enhancement of the resonant SHG efficiency of the lower polariton by 2 orders of magnitude for the collectively coupled molecules as compared to that of the same material outside the microcavity. This study is a proof of principle that opens a new direction for NLO of organic materials in subwavelength resonators.

Energy Transfer between Spatially Separated Entangled Molecules.

Light-matter strong coupling allows for the possibility of entangling the wave functions of different molecules through the light field. We hereby present direct evidence of non-radiative energy transfer well beyond the Förster limit for spatially separated donor and acceptor cyanine dyes strongly coupled to a cavity. The transient dynamics and the static spectra show an energy transfer efficiency approaching 37 % for donor-acceptor distances ≥100 nm. In such systems, the energy transfer process becomes independent of distance as long as the coupling strength is maintained. This is consistent with the entangled and delocalized nature of the polaritonic states.

Multiple Rabi Splittings under Ultrastrong Vibrational Coupling.

From the high vibrational dipolar strength offered by molecular liquids, we demonstrate that a molecular vibration can be ultrastrongly coupled to multiple IR cavity modes, with Rabi splittings reaching 24% of the vibration frequencies. As a proof of the ultrastrong coupling regime, our experimental data unambiguously reveal the contributions to the polaritonic dynamics coming from the antiresonant terms in the interaction energy and from the dipolar self-energy of the molecular vibrations themselves. In particular, we measure the opening of a genuine vibrational polaritonic band gap of ca. 60 meV. We also demonstrate that the multimode splitting effect defines a whole vibrational ladder of heavy polaritonic states perfectly resolved. These findings reveal the broad possibilities in the vibrational ultrastrong coupling regime which impact both the optical and the molecular properties of such coupled systems, in particular, in the context of mode-selective chemistry.

Non-Radiative Energy Transfer Mediated by Hybrid Light-Matter States.

We present direct evidence of enhanced non-radiative energy transfer between two J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity. Excitation spectroscopy and femtosecond pump-probe measurements show that the energy transfer is highly efficient when both the donor and acceptor form light-matter hybrid states with the vacuum field. The rate of energy transfer is increased by a factor of seven under those conditions as compared to the normal situation outside the cavity, with a corresponding effect on the energy transfer efficiency. The delocalized hybrid states connect the donor and acceptor molecules and clearly play the role of a bridge to enhance the rate of energy transfer. This finding has fundamental implications for coherent energy transport and light-energy harvesting.

Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field.

The ground-state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero-point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si-C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC-MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.

Quantum control of exciton wave functions in 2D semiconductors.

Excitons-bound electron-hole pairs-play a central role in light-matter interaction phenomena and are crucial for wide-ranging applications from light harvesting and generation to quantum information processing. A long-standing challenge in solid-state optics has been to achieve precise and scalable control over excitonic motion. We present a technique using nanostructured gate electrodes to create tailored potential landscapes for excitons in 2D semiconductors, enabling in situ wave function shaping at the nanoscale. Our approach forms electrostatic traps for excitons in various geometries, such as quantum dots, rings, and arrays thereof. We show independent spectral tuning of spatially separated quantum dots, achieving degeneracy despite material disorder. Owing to the strong light-matter coupling of excitons in 2D semiconductors, we observe unambiguous signatures of confined exciton wave functions in optical reflection and photoluminescence measurements. This work unlocks possibilities for engineering exciton dynamics and interactions at the nanometer scale, with implications for optoelectronic devices, topological photonics, and quantum nonlinear optics.

Layered metals as polarized transparent conductors.

The quest to improve transparent conductors balances two key goals: increasing electrical conductivity and increasing optical transparency. To improve both simultaneously is hindered by the physical limitation that good metals with high electrical conductivity have large carrier densities that push the plasma edge into the ultra-violet range. Technological solutions reflect this trade-off, achieving the desired transparencies only by reducing the conductor thickness or carrier density at the expense of a lower conductance. Here we demonstrate that highly anisotropic crystalline conductors offer an alternative solution, avoiding this compromise by separating the directions of conduction and transmission. We demonstrate that slabs of the layered oxides Sr2RuO4 and Tl2Ba2CuO6+δ are optically transparent even at macroscopic thicknesses >2 µm for c-axis polarized light. Underlying this observation is the fabrication of out-of-plane slabs by focused ion beam milling. This work provides a glimpse into future technologies, such as highly polarized and addressable optical screens.

Large optical nonlinearity enhancement under electronic strong coupling.

Nonlinear optical responses provide a powerful way to understand the microscopic interactions between laser fields and matter. They are critical for plenty of applications, such as in lasers, integrated photonic circuits, biosensing and medical tools. However, most materials exhibit weak optical nonlinearities or long response times when they interact with intense optical fields. Here, we strongly couple the exciton of cyanine dye J-aggregates to an optical mode of a Fabry-Perot (FP) cavity, and achieve an enhancement of the complex nonlinear refractive index by two orders of magnitude compared with that of the uncoupled condition. Moreover, the coupled system shows an ultrafast response of ~120 fs that we extract from optical cross-correlation measurements. The ultrafast and large enhancement of the optical nonlinar coefficients in this work paves the way for exploring strong coupling effects on various third-order nonlinear optical phenomena and for technological applications.

Selective crystallization via vibrational strong coupling.

The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational modes of solvents to cavity vacuum fields can influence the chemical reaction kinetics of dissolved solutes. This suggests that vibrational strong coupling might also effect other important solution-based processes, such as crystallization from solution. Here we test this hitherto unexplored notion, investigating pseudopolymorphism in the crystallization from water of ZIF metal-organic frameworks inside optical microcavities. We find that ZIF-8 crystals are selectively obtained from solution inside optical microcavities, where the OH stretching vibration of water is strongly coupled to cavity vacuum fields, whereas mixtures of ZIF-8 and ZIF-L are obtained otherwise. Moreover, ZIF crystallization is accelerated by solvent vibrational strong coupling. This work suggests that cavity vacuum fields might become a tool for materials synthesis, biasing molecular self-assembly and driving macroscopic material outcomes.

Conductivity and Photoconductivity of a p-Type Organic Semiconductor under Ultrastrong Coupling.

During the past decade, it has been shown that light-matter strong coupling of materials can lead to modified and often improved properties which has stimulated considerable interest. While charge transport can be enhanced in n-type organic semiconductors by coupling the electronic transition and thereby splitting the conduction band into polaritonic states, it is not clear whether the same process can also influence carrier transport in the valence band of p-type semiconductors. Here we demonstrate that it is indeed possible to enhance both the conductivity and photoconductivity of a p-type semiconductor rr-P3HT that is ultrastrongly coupled to plasmonic modes. It is due to the hybrid light-matter character of the virtual polaritonic excitations affecting the linear response of the material. Furthermore, in addition to being enhanced, the photoconductivity of rr-P3HT shows a modified spectral response due to the formation of the hybrid polaritonic states. This illustrates the potential of engineering the vacuum electromagnetic environment to improve the optoelectronic properties of organic materials.

Quantum Strong Coupling with Protein Vibrational Modes.

In quantum electrodynamics, matter can be hybridized to confined optical fields by a process known as light-matter strong coupling. This gives rise to new hybrid light-matter states and energy levels in the coupled material, leading to modified physical and chemical properties. Here, we report for the first time the strong coupling of vibrational modes of proteins with the vacuum field of a Fabry-Perot mid-infrared cavity. For two model systems, poly(l-glutamic acid) and bovine serum albumin, strong coupling is confirmed by the anticrossing in the dispersion curve, the square root dependence on the concentration, and a vacuum Rabi splitting that is larger than the cavity and vibration line widths. These results demonstrate that strong coupling can be applied to the study of proteins with many possible applications including the elucidation of the role of vibrational dynamics in enzyme catalysis and in H/D exchange experiments.

Ultra-strong coupling of molecular materials: spectroscopy and dynamics.

We report here a study of light-matter strong coupling involving three molecules with very different photo-physical properties. In particular we analyze their emission properties and show that the excitation spectra are very different from the static absorption of the coupled systems. Furthermore we report the emission quantum yields and excited state lifetimes, which are self-consistent. The above results raise a number of fundamental questions that are discussed and these demonstrate the need for further experiments and theoretical studies.

Quantum Yield of Polariton Emission from Hybrid Light-Matter States.

The efficiency of light-matter strong coupling is tuned by precisely varying the spatial position of a thin layer of cyanine dye J-aggregates in Fabry-Perot microcavities, and their photophysical properties are determined. Placing the layer at the cavity field maximum affords an interaction energy (Rabi splitting) of 503 meV, a 62% increase over that observed if the aggregates are simply spread evenly through the cavity, placing the system in the ultrastrong coupling regime. The fluorescence quantum yield of the lowest polaritonic state P- integrated over k-space is found to be ∼10(-2). The same value can be deduced from the 1.4 ps lifetime of P- measured by femtosecond transient absorption spectroscopy and the calculated radiative decay rate constant. Thus, the polariton decay is dominated by nonradiative processes, in contrast with what might be expected from the small effective mass of the polaritons. These findings provide a deeper understanding of hybrid light-molecule states and have implications for the modification of molecular and material properties by strong coupling.