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Rohit Chikkaraddy

Publications and source records attributed to Rohit Chikkaraddy.

At least 19 recordsLinked to original sources
arXiv2026

Extreme mid-infrared field enhancement and anapoles in high-index plasmonic metamaterials

High-refractive-index materials underpin a wide range of optical technologies, including communications, imaging, lasers, and integrated photonic systems. Here, we demonstrate a self-assembled metamaterial platform based on gold nanoparticle aggregates with nanometer-scale gaps exhibit remarkably high effective refractive indices exceeding 15 in the mid-infrared regime, while simultaneously producing gap-field enhancements of at least two-orders of magnitude. This combination of high refractive index and extreme field enhancement enables exceptionally strong light-matter interactions. We demonstrate this by designing a compact high-index metamaterial device supporting an anapole, which further enhances the nanogap field. By placing quantum emitters with terahertz transitions inside the plasmonic gaps, we show a stimulated-emission response enhanced by at least three orders of magnitude, highlighting applications in non-linear optics, frequency up-conversion and vibrational strong coupling.

physics.optics↗
arXiv2026

Near-Field Vibrational Energy Transfer for Mid-Infrared Upconversion in Plasmonic Nanogaps

F\"{o}rster energy transfer underpins modern photonics, yet establishing an analogous vibrational pathway in the mid-infrared (MIR) remains highly challenging, as sub-picosecond intramolecular vibrational redistribution (IVR) suppresses intermolecular coupling. Here we demonstrate vibrational donor--acceptor transfer in the MIR and subsequent upconversion to visible luminescence enabled by sub-2 nm plasmonic nanogaps. The extreme lateral field confinement in metal--molecule--metal ring cavities defined by self-assembled molecular spacers couples efficiently to in-plane molecular dipoles. Continuous-wave MIR excitation selectively populates $-\mathrm{C}\equiv\mathrm{N}$ vibrational donors, and plasmon-enhanced near-field coupling transfers this energy to nearby electronic acceptors, generating anti-Stokes visible emission under low power densities. Upconversion efficiencies exceeding $0.3\%$ are observed, limited by competition between the plasmon-mediated transfer rate and IVR. These results show that extreme plasmonic confinement can redirect molecular vibrational relaxation pathways, opening a route toward vibrational nanophotonics, intermolecular interactions for bioimaging, and room-temperature MIR detection based on molecular degrees of freedom.

physics.optics↗
arXiv2026

Mid-infrared Assisted THz Phonon Amplification in a 2D Semiconductor for Room Temperature Detection

Efficient and selective excitation of lattice vibrations is central to controlling energy flow at the nanoscale, yet remains challenging under conventional optical excitation. Here, we introduce a mid-infrared-assisted phonon amplification approach, termed MIRAPA, that enables efficient energy injection directly into vibrational bonds. Using surface-enhanced resonant Raman scattering in few-layer $\mathrm{MoS_2}$, we exploit strong exciton--phonon coupling to monitor phonon populations. When mid-infrared (MIR) light is introduced, it couples directly to out-of-plane lattice vibrations, leading to room-temperature phonon amplification exceeding $80\%$. Crucially, MIRAPA bypasses electronic excitation pathways, allowing the MIR power density to be nearly $300\times$ lower than that required for visible excitation to achieve comparable enhancement. The resulting phonon modulation is robust, persisting over more than $2800$ on/off cycles and exceeding $15$ hours of continuous-wave laser illumination without degradation. Quantitative analysis yields an effective noise-equivalent power of approximately $0.3\,\mathrm{nW}/\sqrt{\mathrm{Hz}}$ for MIR detection, highlighting the sensitivity of the approach. By combining vibrational selectivity, low-power operation, and long-term stability, MIRAPA provides a robust platform for probing and amplifying phonons in two-dimensional semiconductors. These results open new opportunities for nanoscale vibrational sensing, mid-infrared detection, and phonon-based coherent devices, including routes toward phonon lasing.

physics.app-ph↗
arXiv2023

Raman-probing the local ultrastrong coupling of vibrational plasmon-polaritons on metallic gratings

Strong coupling of molecular vibrations with light creates polariton states, enabling control over many optical and chemical properties. However, the near-field signatures of strong coupling are difficult to map as most cavities are closed systems. Surface-enhanced Raman microscopy of open metallic gratings under vibrational strong coupling enables the observation of spatial polariton localization in the grating near-field, without the need for scanning probe microscopies. The lower polariton is localized at the grating slots, displays a strongly asymmetric lineshape, and gives greater plasmon-vibration coupling strength than measured in the far-field. Within these slots, the local field strength pushes the system into the ultrastrong coupling regime. Models of strong coupling which explicitly include the spatial distribution of emitters can account for these effects. Such gratings form a new system for exploring the rich physics of polaritons and the interplay between their near- and far-field properties through polariton-enhanced Raman scattering (PERS).

physics.optics↗
arXiv2022

Boosting Optical Nanocavity Coupling by Retardation Matching to Dark Modes

Plasmonic nano-antennas can focus light to nanometre length-scales providing intense field enhancements. For the tightest optical confinements (0.5-5 nm) achieved in plasmonic gaps, the gap spacing, refractive index, and facet width play a dominant role in determining the optical properties making tuning through antenna shape challenging. We show here that controlling the surrounding refractive index instead allows both efficient frequency tuning and enhanced in/output-coupling through retardation matching as this allows dark modes to become optically active, improving widespread functionalities.

physics.optics↗
arXiv2022

Giant mid-IR resonant coupling to molecular vibrations in sub-nm gaps of plasmonic multilayer metafilms

Nanomaterials capable of confining light are desirable for enhancing spectroscopies such as Raman scattering, infrared absorption, and nonlinear optical processes. Plasmonic superlattices have shown the ability to host collective resonances in the mid-infrared, but require stringent fabrication processes to create well-ordered structures. Here, we demonstrate how short-range-ordered Au nanoparticle multilayers on a mirror, self-assembled by a sub-nm molecular spacer, support collective plasmon-polariton resonances in the visible and infrared, continuously tunable beyond 11 $μ$m by simply varying the nanoparticle size and number of layers. The resulting molecule-plasmon system approaches vibrational strong coupling, and displays giant Fano dip strengths, SEIRA enhancement factors ~10$^6$, light-matter coupling strengths g~100 cm$^{-1}$, Purcell factors ~10$^6$, and mode volume compression factors ~10$^8$. The collective plasmon-polariton mode is highly robust to nanoparticle vacancy disorder and is sustained by the consistent gap size defined by the molecular spacer. Structural disorder efficiently couples light into the gaps between the multilayers and mirror, enabling Raman and infrared sensing of sub-picolitre sample volumes.

physics.optics↗
arXiv2022

Single-molecule mid-IR detection through vibrationally-assisted luminescence

Room temperature detection of molecular vibrations in the mid-infrared (MIR, $λ$ =3-30$μ$m) has numerous applications including real-time gas sensing, chemical reactivity, medical imaging, astronomical surveys, and quantum communication [1,2]. However, MIR detection is severely hindered by thermal noise, hence current technologies rely on energy-intensive cooled semiconductor detectors (mercury cadmium telluride, MCT) [3,4,5]. One way to overcome this challenge is to upconvert the low-energy MIR light into high-energy visible wavelengths ($λ$ =500-800nm) where detection of single photons is easily achieved using silicon technologies [6,7]. This process suffers from weak cross sections and the mismatch between MIR and visible wavelengths, limiting its efficiency. Here, we exploit molecular emitters possessing both MIR and visible transitions from molecular vibrations and electronic states, coupled through Frank-Condon factors. By assembling molecules into a nanoscale cavity and continuously optically pumping them below the electronic absorption band, we show the transduction of MIR light absorbed by the molecular vibrations. The upconverted signal is observed as enhanced high-energy luminescence. Combining Purcell-enhanced visible luminescence with enhanced rates of vibrational pumping gives transduction efficiencies exceeding 10%. By down-scaling the cavity volume below $1nm^3$, we show MIR detection of single-molecular bonds, inaccessible to any previous detector.

physics.app-ph↗
arXiv2021

Mid-infrared-perturbed Molecular Vibrational Signatures in Plasmonic Nanocavities

Recent developments in surface-enhanced Raman scattering (SERS) enable observation of single-bond vibrations in real-time at room temperature. By contrast, mid-infrared (MIR) vibrational spectroscopy is limited to inefficient slow detection. Here we develop a new method for MIR sensing using SERS. This method utilizes nanoparticle-on-foil (NPoF) nanocavities supporting both visible and MIR plasmonic hotspots in the same nano-gap formed by a monolayer of molecules. Molecular SERS signals from individual NPoF nanocavities are modulated in the presence of MIR photons. The strength of this modulation depends on the MIR wavelength, and is maximized at the 6-12$μ$m absorption bands of SiO$_2$ or polystyrene placed under the foil. Using a single-photon lock-in detection scheme we time-resolve the rise and decay of the signal in a few 100ns. Our observations reveal that the phonon resonances of SiO$_2$ can trap intense MIR surface plasmons within the Reststrahlen band, tuning the visible-wavelength localized plasmons by reversibly perturbing the nanostructure crevices. This suggests new ways to couple nano-scale bond vibrations for optomechanics, with potential to push detection limits down to single-photon and single-molecule regimes.

physics.optics↗
arXiv2021

Accessing Plasmonic Hotspots using Nanoparticle-on-Foil Constructs

Metal-insulator-metal (MIM) nanogaps in canonical nanoparticle-on-mirror geometry (NPoM) provide deep-subwavelength confinement of light with mode volumes smaller than $V/V_0$ $<$ $10^{-6}$. However, access to these hotspots is limited by the impendence mismatch between the high in-plane $k_{//}$ of trapped light and free-space plane-waves, making the in- and out-coupling of light difficult. Here, by constructing a nanoparticle-on-foil (NPoF) system with thin metal films, we show the mixing of insulator-metal-insulator (IMI) modes and MIM gap modes resulting in MIMI modes. This mixing provides multi-channel access to the plasmonic nanocavity through light incident from both sides of the metal film. The red-tuning and near-field strength of MIMI modes for thinner foils is measured experimentally with white-light scattering and surface-enhanced Raman scattering from individual NPoFs. We discuss further the utility of NPoF systems since the geometry allows tightly confined light to be accessed simply and through different ports.

physics.optics↗
arXiv2021

Detecting mid-infrared light by molecular frequency upconversion with dual-wavelength hybrid nanoantennas

Coherent interconversion of signals between optical and mechanical domains is enabled by optomechanical interactions. Extreme light-matter coupling produced by confining light to nanoscale mode volumes can then access single mid-infrared (MIR) photon sensitivity. Here we utilise the infrared absorption and Raman activity of molecular vibrations in plasmonic nanocavities to demonstrate frequency upconversion. We convert λ~10 μm incoming light to visible via surface-enhanced Raman scattering (SERS) in doubly-resonant antennas that enhance upconversion by >10^10. We show >200% amplification of the SERS antiStokes emission when a MIR pump is tuned to a molecular vibrational frequency, obtaining lowest detectable powers ~1 μW/μm^2 at room temperature. These results have potential for low-cost and large-scale infrared detectors and spectroscopic techniques, and bring single-molecule sensing into the infrared

physics.optics↗
arXiv2020

Breaking the Selection Rules of Spin-Forbidden Molecular Absorption in Plasmonic Nanocavities

Controlling absorption and emission of organic molecules is crucial for efficient light-emitting diodes, organic solar cells and single-molecule spectroscopy. Here, a new molecular absorption is activated inside a gold plasmonic nanocavity, and found to break selection rules via spin-orbit coupling. Photoluminescence excitation scans reveal absorption from a normally spin-forbidden singlet to triplet state transition, while drastically enhancing the emission rate by several thousand fold. The experimental results are supported by density functional theory, revealing the manipulation of molecular absorption by nearby metallic gold atoms.

physics.optics↗
arXiv2019

Plasmonic nanocavity modes: From near-field to far-field radiation

In the past decade, advances in nanotechnology have led to the development of plasmonic nanocavities which facilitate light-matter strong coupling in ambient conditions. The most robust example is the nanoparticle-on-mirror (NPoM) structure whose geometry is controlled with subnanometer precision. The excited plasmons in such nanocavities are extremely sensitive to the exact morphology of the nanocavity, giving rise to unexpected optical behaviors. So far, most theoretical and experimental studies on such nanocavities have been based solely on their scattering and absorption properties. However, these methods do not provide a complete optical description of a NPoM. Here, the NPoM is treated as an open non-conservative system supporting a set of photonic quasinormal modes (QNMs). By investigating the morphology-dependent optical properties of nanocavities, we propose a simple yet comprehensive nomenclature based on spherical harmonics and report spectrally overlapping bright and dark nanogap eigenmodes. The near-field and far-field optical properties of NPoMs are explored and reveal intricate multi-modal interactions.

physics.optics↗
arXiv2018

Plasmofluidic Single-Molecule Surface Enhanced Raman Scattering from Dynamic Assembly of Plasmonic Nanoparticles

Single-molecule surface enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon-polariton assisted, reversible assembly of plasmonic nanoparticles at an unstructured metal-fluid interface. One of the unique features of our method is that we use a single evanescent-wave optical excitation for nanoparticle-assembly, manipulation and SM-SERS measurements. Furthermore, by utilizing dual excitation of plasmons at metal-fluid interface, we create interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures. Our work will have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms.

physics.optics↗
arXiv2018

Large-scale dynamic assembly of metal nanostructures in plasmofluidic field

We discuss two aspects of the plasmofluidic assembly of plasmonic nanostructures at the metal fluid interface. First, we experimentally show how three and four spot evanescent wave excitation can lead to unconventional assembly of plasmonic nanoparticles at the metal fluid interface. We observed that the pattern of assembly was mainly governed by the plasmon interference pattern at the metal fluid interface, and further led to interesting dynamic effects within the assembly. The interference patterns were corroborated by 3D finite difference time domain simulations. Secondly, we show how anisotropic geometry, such as Ag nanowires, can be assembled and aligned in unstructured and structured plasmofluidic fields. We found that by structuring the metal-film, Ag nanowires can be aligned at the metal fluid interface with a single evanescent wave excitation, thus highlighting the prospect of assembling plasmonic circuits in a fluid. An interesting aspect of our method is that we obtain the assembly at locations away from the excitation points, thus leading to remote assembly of nanostructures. The results discussed herein may have implications in realizing a platform for reconfigurable plasmonic metamaterials, and a test-bed to understand the effect of plasmon interference on assembly of nanostructures in fluids.

physics.optics↗
arXiv2017

Mapping nanoscale hotspots with single-molecule emitters assembled into plasmonic nanocavities using DNA origami

Fabricating nanocavities in which optically-active single quantum emitters are precisely positioned, is crucial for building nanophotonic devices. Here we show that self-assembly based on robust DNA-origami constructs can precisely position single molecules laterally within sub-5nm gaps between plasmonic substrates that support intense optical confinement. By placing single-molecules at the center of a nanocavity, we show modification of the plasmon cavity resonance before and after bleaching the chromophore, and obtain enhancements of $\geq4\times10^3$ with high quantum yield ($\geq50$%). By varying the lateral position of the molecule in the gap, we directly map the spatial profile of the local density of optical states with a resolution of $\pm1.5$ nm. Our approach introduces a straightforward non-invasive way to measure and quantify confined optical modes on the nanoscale.

physics.optics↗
arXiv2017

Strong-coupling of WSe2 in ultra-compact plasmonic nanocavities at room temperature

Strong-coupling of monolayer metal dichalcogenide semiconductors with light offers encouraging prospects for realistic exciton devices at room temperature. However, the nature of this coupling depends extremely sensitively on the optical confinement and the orientation of electronic dipoles and fields. Here, we show how plasmon strong coupling can be achieved in compact robust easily-assembled gold nano-gap resonators at room temperature. We prove that strong coupling is impossible with monolayers due to the large exciton coherence size, but resolve clear anti-crossings for 8 layer devices with Rabi splittings exceeding 135 meV. We show that such structures improve on prospects for nonlinear exciton functionalities by at least 10^4, while retaining quantum efficiencies above 50%.

physics.optics↗
arXiv2017

Suppressed Quenching and Strong Coupling of Purcell-Enhanced Single-Molecule Emission in Plasmonic Nanocavities

An emitter in the vicinity of a metal nanostructure is quenched by its decay through non-radiative channels, leading to the belief in a zone of inactivity for emitters placed within $<$10nm of a plasmonic nanostructure. Here we demonstrate that in tightly-coupled plasmonic resonators forming nanocavities "quenching is quenched" due to plasmon mixing. Unlike isolated nanoparticles, plasmonic nanocavities show mode hybridization which massively enhances emitter excitation and decay via radiative channels. This creates ideal conditions for realizing single-molecule strong-coupling with plasmons, evident in dynamic Rabi-oscillations and experimentally confirmed by laterally dependent emitter placement through DNA-origami.

physics.optics↗