arXiv subjects

Rakesh Arul

Publications and source records attributed to Rakesh Arul.

14 recordsLinked to original sources

arXiv2026

Accessing both electrochemical SEIRA and SERS with ultrasensitive metamaterials for enhanced molecular identification

Surface-enhanced IR absorption (SEIRA) and surface-enhanced Raman spectroscopy (SERS) are complementary techniques that allow for ultrasensitive chemical fingerprinting. Non-invasive optical sensing would be significantly improved by a robust implementation of a reusable substrate that combines these techniques. Here, we present an electrochemically-cleanable metamaterial that enables combined real-time SEIRA and SERS in flow. This metamaterial facilitates the study of surface-adsorbed species and diffusion layers, elicits spectral shifts from changes in nanogap refractive index of 1400 nm/RIU, and delivers ultrasensitive analyte detection. Combining SERS and SEIRA clarifies molecular (electro)chemical transformations and tracks changes in selection rules and symmetry breaking at the analyte-electrode interface. This development in enhanced multimodal spectro-electrochemistry is suited for multiple domains, including understanding charge transport mechanisms and interfacial dynamics at electrodes, and is capable of real-time flow monitoring for a wide range of molecular processes.

physics.optics↗

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

Coherent room-temperature dipole synchronization in nanocavity sheets

Plasmonic nanocavities enable the synchronization of spatially distant emissive dipoles through strong near-field coupling in sub-nm gaps. We report formation of a room-temperature synchronized dipole state in locally-ordered plasmonic nanogap 2D arrays under non-resonant continuous-wave pumping. Unlike lasers, photonic Bose-Einstein condensates, or exciton-polariton condensates, this system exhibits spatial coherence across the dipoles, while rapid radiative and non-radiative emission suppresses temporal photon coherence. A change of behaviour is observed with increasing pumping, marked by the spatial spread of g(1) coherence, but without spectral narrowing or directional emission. This driven-dissipative system exhibits fast temporal coherence decay and complex spatial correlations, offering a new platform for studying synchronization at room temperature. Combining ultralow mode volumes, high Purcell enhancement, and scalable ambient operation, it opens pathways for novel photonic and quantum technologies.

cond-mat.mes-hall↗

arXiv2025

Tracking and controlling monolayer water in gold nanogaps using extreme plasmonic spectroscopy

Nanogaps are ubiquitous across science, confining molecules and thus changing chemistries which influence many areas such as catalysis, corrosion, photochemistry, and sensing. However in ambient conditions, it is unclear how water solvates nanogaps and even if nominally dry, what water structure persists. Despite its low Raman cross-section, surface-enhanced Raman spectroscopy (SERS) enables study of water at coinage metal surfaces. Using multi-layer aggregates of close-packed gold nanoparticles with sub-nanometre gaps precisely defined by organic spacer molecules, we achieve consistent and large SERS enhancements, enabling systematic study of water within these confined spaces. Ostensibly dry facets in air evidence water monolayer coatings, with hydrogen-bonding only reappearing upon immersion in solution. Under negative applied potentials, surface water is seen to re-orient at the metal facets with distinct spectral shifts among the quartet of vibrational peaks which correspond to those expected from water dimers. Comparing nanogaps in deuterated water also reveals how individual water molecules bind onto organic spacer molecules in such nanogaps. Realistic models of water dressing will enable better understanding of catalytic and contact chemistries.

physics.optics↗

arXiv2024

Efficient short-wave infrared upconversion by self-sensitized holmium-doped nanoparticles

Photon upconversion, combining several low-energy photons to generate one high-energy photon is of wide interest for biomedical, catalytic and photonic applications. Lanthanide-doped nanoparticles (LnNP) are a unique type of upconversion nanoconverter, which can realize ultralarge anti-Stokes shift (>1000 nm) and high photostability, without photo-bleaching and photo-blinking. The excitation wavelength of LnNPs has been limited to the second near-infrared window (1000-1700 nm), mainly sensitized by erbium ions with absorption centered around 1.5 $μ$m. Here, we demonstrate novel self-sensitized holmium (Ho)-doped nanoconverters to further expand the sensitization range to the short-wave infrared at 2 $μ$m and achieve efficient upconversion to 640 nm. We show that this upconversion is a 4-photon conversion process with an underlying energy transfer upconversion mechanism. Via careful control of dopant concentration and shelling we achieve a relative upconversion-to-downconversion efficiency up to 15.2%, more than half the theoretical maximum. The placement of the Ho doped LnNPs into a plasmonic nanocavity device enables large gains in emission intensity (up to 32-fold), due to the dramatic shortening of the emission lifetime of Ho from 29 $μ$s to <1 ns, indicating a high Purcell-enhancement factor of 3x10$^4$. These results open new possibilities at the frontier of short-wave infrared upconversion and the nanoplasmonic enhancement of LnNP emission, with potential applications in detection, theranostics, photonics and optoelectronics.

physics.optics↗

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↗

arXiv2023

Anti-Stokes Photoluminescence in Monolayer WSe$_2$ Activated by Plasmonic Cavities through Resonant Excitation of Dark Excitons

Anti-Stokes photoluminescence (PL) is light emission at a higher photon energy than the excitation, with applications in optical cooling, bioimaging, lasing, and quantum optics. Here, we show how plasmonic nano-cavities activate anti-Stokes PL in WSe$_2$ monolayers through resonant excitation of a dark exciton. The tightly confined plasmonic fields excite the out-of-plane transition dipole of the dark exciton, leading to light emission from the bright exciton at higher energy. Through statistical measurements on hundreds of plasmonic cavities, we show that coupling to the dark exciton is key to achieving a near hundred-fold enhancement of the upconverted PL intensity. This is further corroborated by experiments in which the laser excitation wavelength is tuned across the dark exciton. Finally, we show that an asymmetric nanoparticle shape and precise geometry are key for consistent activation of the dark exciton and efficient PL upconversion. Our work introduces a new excitation channel for anti-Stokes PL in WSe$_2$ and paves the way for large-area substrates providing optical cooling, anti-Stokes lasing, and radiative engineering of excitons.

cond-mat.mes-hall↗

arXiv2023

Direct Linearly-Polarised Electroluminescence from Perovskite Nanoplatelet Superlattices

Polarised light is critical for a wide range of applications, but is usually generated by filtering unpolarised light, which leads to significant energy losses and requires additional optics. Herein, the direct emission of linearly-polarised light is achieved from light-emitting diodes (LEDs) made of CsPbI3 perovskite nanoplatelet superlattices. Through use of solvents with different vapour pressures, the self-assembly of perovskite nanoplatelets is achieved to enable fine control over the orientation (either face-up or edge-up) and therefore the transition dipole moment. As a result of the highly-uniform alignment of the nanoplatelets, as well as their strong quantum and dielectric confinement, large exciton fine-structure splitting is achieved at the film level, leading to pure-red LEDs exhibiting a high degree of linear polarisation of 74.4% without any photonic structures. This work unveils the possibilities of perovskite nanoplatelets as a highly promising source of linearly-polarised electroluminescence, opening up the development of next-generation 3D displays and optical communications from this highly versatile, solution-processable system.

physics.optics↗

arXiv2022

Accelerated Molecular Vibrational Decay and Suppressed Electronic Nonlinearities in Plasmonic Cavities through Coherent Raman Scattering

Molecular vibrations and their dynamics are of outstanding importance for electronic and thermal transport in nanoscale devices as well as for molecular catalysis. The vibrational dynamics of <100 molecules are studied through three-colour time-resolved coherent anti-Stokes Raman spectroscopy (trCARS) using plasmonic nanoantennas. This isolates molecular signals from four-wave mixing (FWM), while using exceptionally low nanowatt powers to avoid molecular damage via single-photon lock-in detection. FWM is found to be strongly suppressed in nm-wide plasmonic gaps compared to plasmonic nanoparticles. The ultrafast vibrational decay rates of biphenyl-4-thiol molecules are accelerated ten-fold by a transient rise in local non-equilibrium temperature excited by enhanced, pulsed optical fields within these plasmonic nanocavities. Separating the contributions of vibrational population decay and dephasing carefully explores the vibrational decay channels of these tightly confined molecules. Such extreme plasmonic enhancement within nanogaps opens up prospects for measuring single-molecule vibrationally-coupled dynamics and diverse molecular optomechanics phenomena.

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

Theory of strong coupling between molecules and surface plasmons on a grating

The strong coupling of molecules with surface plasmons results in hybrid states which are part molecule, part surface-bound light. Since molecular resonances may acquire the spatial coherence of plasmons, which have mm-scale propagation lengths, strong-coupling with molecular resonances potentially enables long-range molecular energy transfer. Gratings are often used to couple incident light to surface plasmons, by scattering the otherwise non-radiative surface plasmon inside the light-line. We calculate the dispersion relation for surface plasmons strongly coupled to molecular resonances when grating scattering is involved. By treating the molecules as independent oscillators rather than the more typically-considered single collective dipole, we find the full multi-band dispersion relation. This approach offers a natural way to include the dark states in the dispersion. We demonstrate that for a molecular resonance tuned near the crossing point of forward and backward grating-scattered plasmon modes, the interaction between plasmons and molecules gives a five-band dispersion relation, including a bright state not captured in calculations using a single collective dipole. We also show that the role of the grating in breaking the translational invariance of the system appears in the position-dependent coupling between the molecules and the surface plasmon. The presence of the grating is thus not only important for the experimental observation of molecule-surface-plasmon coupling, but also provides an additional design parameter that tunes the system.

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

Understanding the chemical mechanism behind photo-induced enhanced Raman spectroscopy

Photo-Induced Enhanced Raman Spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with an order-of-magnitude Raman signal enhancement of adsorbed analytes over that of typical SERS substrates. Despite the impressive PIERS enhancement factors and explosion in recent demonstrations of its utility, the detailed enhancement mechanism remains undetermined. Using a range of optical and X-ray spectroscopies, supported by density functional theory calculations, we elucidate the chemical and atomic-scale mechanism behind the PIERS enhancement. Stable PIERS substrates with enhancement factors of 10^6 were fabricated using self-organized hexagonal arrays of TiO2 nanotubes that were defect-engineered via annealing in inert atmospheres, and silver nanoparticles were deposited by magnetron sputtering and subsequent thermal dewetting. We identified the key source of the enhancement of PIERS vs. SERS in these structures as an increase in the Raman polarizability of the adsorbed probe molecule upon photo-induced charge transfer. A balance between crystallinity, which enhances charge transfer due to higher electron mobility in anatase-rutile heterostructures but decreases visible light absorption, and oxygen vacancy defects, which increase visible light absorption and photo-induced electron transfers, was critical to achieve high PIERS enhancements.

cond-mat.mtrl-sci↗

arXiv2020

LIPSS-Sticks: Laser induced double self organization enhances the broadband light harvesting of TiO2 nanotube arrays

Sub-wavelength laser induced periodic surface structures (LIPSS-Sticks) created by ultrashort pulsed laser irradiation on the surface of titanium are used for the first time to template the electrochemical growth of titanium dioxide nanotube arrays. This is an example of a double self-organized process, as both LIPSS formation and electrochemical anodization involve spontaneous generation of order from initially non-ordered precursors. LIPSS-Sticks have a 2x greater visible to near infrared light (400 - 1400 nm) collection efficiency compared to flat titanium dioxide due to the enhanced light scattering from grating-like structures. The growth of nanostructures with time was modelled electrostatically to explain the features of a templated anodization process that differ from the usual anodization of flat surfaces. This new templated growth method is general and can also be applied to Cu, W, Fe, Ti alloys and Al for the fabrication of hierarchically nanostructured surfaces using two complementary fabrication techniques: ultrashort pulsed laser ablation and electrochemical anodization.

physics.app-ph↗