Sub-nanometre control of the coherent interaction between a single molecule and a plasmonic nanocavity
Yao Zhang, Qiushi Meng, Li Zhang, Yang Luo, Yunjie Yu, Ben Yang, Yang Zhang, Rubén Esteban, Javier Aizpurua, Yi Luo, Jinlong Yang, Zhen‐Chao Dong, Jian Hou
The coherent interaction between quantum emitters and photonic modes in cavities underlies many of the current strategies aiming at generating and controlling photonic quantum states. A plasmonic nanocavity provides a powerful solution for reducing the effective mode volumes down to nanometre scale, but spatial control at the atomic scale of the coupling with a single molecular emitter is challenging. Here we demonstrate sub-nanometre spatial control over the coherent coupling between a single molecule and a plasmonic nanocavity in close proximity by monitoring the evolution of Fano lineshapes and photonic Lamb shifts in tunnelling electron-induced luminescence spectra. The evolution of the Fano dips allows the determination of the effective interaction distance of ∼1 nm, coupling strengths reaching ∼15 meV and a giant self-interaction induced photonic Lamb shift of up to ∼3 meV. These results open new pathways to control quantum interference and field-matter interaction at the nanoscale.
The coherent interaction between quantum emitters and photonic modes in cavities underlies many of the current strategies aiming at generating and controlling photonic quantum states. A plasmonic nanocavity provides a powerful solution for reducing the effective mode volumes down to nanometre scale, but spatial control at the atomic scale of the coupling with a single molecular emitter is challenging. Here we demonstrate sub-nanometre spatial control over the coherent coupling between a single molecule and a plasmonic nanocavity in close proximity by monitoring the evolution of Fano lineshapes and photonic Lamb shifts in tunnelling electron-induced luminescence spectra. The evolution of the Fano dips allows the determination of the effective interaction distance of ∼1 nm, coupling strengths reaching ∼15 meV and a giant self-interaction induced photonic Lamb shift of up to ∼3 meV. These results open new pathways to control quantum interference and field-matter interaction at the nanoscale.
Abstract In the light–matter strong coupling regime, the excited state of quantum emitters is inextricably linked to a photonic mode, leading to hybrid states that are part light and part matter. Recently, there has been a huge effort to realize strong coupling with nanoplasmonics, since it provides a versatile environment to study and control molecules in ambient conditions. Among the most promising designs are plasmonic nanocavities that confine light to unprecedentedly small volumes. Such nanocavities, though, support multiple types of modes, with different field profiles and radiative decay rates (bright and dark modes). Here, we show theoretically that the different nature of these modes leads to mode beating within the nanocavity and the Rabi oscillations, which alters the spatiotemporal dynamics of the hybrid system. By specifically designing the illumination setup, we decompose and control the dark and bright plasmon mode excitation and therefore their coupling with quantum emitters. Hence, this work opens new routes for dynamically dressing emitters, to tailor their hybrid states with external radiation.
Using a scattered field interference mechanism, we theoretically demonstrate the quantum statistics control with a hybrid system comprised of a quantum emitter and a plasmonic multimode nanocavity. Enhanced through multimode interactions, destructive interference between scattered fields from the emitter and nanocavity is able to change the photon statistics from bunching to antibunching. This transition cannot be explained by treating the plasmonic nanocavity in the dipole approximation. In some specific regions, an effective single-mode model, which is equivalent to the multimode model, is derived by simply shifting the transition frequency and modifying decay rates of the nearby quantum emitter. Superior to the closed optical microcavity, this hybrid system can be used to control the photon statistics without the need for strong coupling, and may find applications in nanoscale refractive index sensing.
Quantum plasmonics extends cavity quantum electrodynamics (cQED) concepts to the nanoscale, benefiting from the strongly subwavelength confinement of the plasmon modes supported by metal nanostructures. In this work, we describe in detail collective strong coupling to a plasmonic nanocavity. Similarities and differences to cQED are emphasized. We notably observe that the Rabi splitting can strongly deviate from the standard NeΔΩ1 law, where Ne is the number of emitters and ΔΩ1 is the Rabi splitting for a single emitter. In addition, we discuss the collective Lamb shift and the role of quantum corrections to the emission spectra.
Strong light-matter coupling offers a powerful framework for modifying molecular structure, dynamics, and optical response, yet achieving this regime at the single-molecule level remains a central challenge. Scanning Tunneling Microscope Break Junctions (STM-BJ) provide a promising route by combining single-molecule addressability with extreme nanoscale field confinement. However, the metallic environment that enables such confinement also introduces substantial plasmonic and excitonic losses, raising the question of how strong coupling can be realized in a metal-molecule-metal junction. Here, we identify the voltage as the key control parameter. We show that the applied bias not only drives the formation of an interfacial exciton through resonant charge transport but also suppresses its coupling to metallic loss channels. Simultaneously, the plasmonic cavity retains extreme mode confinement while the availability of modes is moderately tuned by voltage. Together, these results establish voltage-driven STM-BJs as electrically tunable single-molecule plasmonic cavities and open new routes for using the powerful STM-BJ toolbox, including quantum transport, tracking chemical dynamics, optoelectronics, and molecular-scale quantum control under strong light-matter coupling.
Abstract Interactions between a single emitter and cavity provide the archetypical system for fundamental quantum electrodynamics. Here we show that a single molecule of Atto647 aligned using DNA origami interacts coherently with a sub-wavelength plasmonic nanocavity, approaching the cooperative regime even at room temperature. Power-dependent pulsed excitation reveals Rabi oscillations, arising from the coupling of the oscillating electric field between the ground and excited states. The observed single-molecule fluorescent emission is split into two modes resulting from anti-crossing with the plasmonic mode, indicating the molecule is strongly coupled to the cavity. The second-order correlation function of the photon emission statistics is found to be pump wavelength dependent, varying from g (2) (0) = 0.4 to 1.45, highlighting the influence of vibrational relaxation on the Jaynes-Cummings ladder. Our results show that cavity quantum electrodynamic effects can be observed in molecular systems at ambient conditions, opening significant potential for device applications.
Abstract Quantum state control of two‐level emitters is fundamental for many information processing, metrology, and sensing applications. However, quantum‐coherent photonic control of solid‐state emitters has traditionally been limited to cryogenic environments, which are not compatible with implementation in scalable, broadly distributed technologies. In contrast, plasmonic nano‐cavities with deep sub‐wavelength mode volumes have recently emerged as a path toward room temperature quantum control. However, optimization, control, and modeling of the cavity mode volume are still in their infancy. Here recent demonstrations of plasmonic tip‐enhanced strong coupling (TESC) with a configurable nano‐tip cavity are extended to perform a systematic experimental investigation of the cavity‐emitter interaction strength and its dependence on tip position, augmented by modeling based on both classical electrodynamics and a quasinormal mode framework. Based on this work, a perspective for nano‐cavity optics is provided as a promising tool for room temperature control of quantum coherent interactions that could spark new innovations in fields from quantum information and quantum sensing to quantum chemistry and molecular opto‐mechanics.