Considerations for Electromagnetic Simulations for a Quantitative Correlation of Optical Spectroscopy and Electron Tomography of Plasmonic Nanoparticles
Mees Dieperink, Alexander Skorikov, Nathalie Claes, Sara Bals, Wiebke Albrecht
The optical cross sections of plasmonic nanoparticles are intricately linked to the morphology of the particle. If this connection can be made accurately enough, it would become possible to determine a particles shape solely from its measured optical cross sections. For that, electromagnetic simulations can be used to bridge the morphology and optical properties assuming that they can be performed in an accurate manner. In this paper, we study key factors that influence the accuracy of electromagnetic simulations. First, we compare several standard electromagnetic simulation methods and discuss in detail the effects of the meshing accuracy, choice of dielectric function and inclusion of a substrate for the boundary element method. To help the boundary element methods complex parametrization, we develop a workflow including reconstruction, meshing and mesh simplification steps to be able to use electron tomography data as input for these simulations. In particular, we analyze how the choice of reconstruction algorithm and the intricacies of image segmentation influence the simulated optical cross sections and correlate it to induced shape errors, which can be minimized in the data processing pipeline. In our case, optimal results could be obtained by using the Total Variation Minimization (TVM) reconstruction method in combination with Otsu thresholding and slight smoothing, which was important to create a reliable and watertight surface mesh using the marching cubes algorithm, especially for more complex shapes.
Optical properties of colloidal plasmonic titanium nitride nanoparticles are examined with an eye on their photothermal via transmission electron microscopy and optical transmittance measurements. Single crystal titanium nitride cubic nanoparticles with an average size of 50 nm exhibit plasmon resonance in the biological transparency window. With dimensions optimized for efficient cellular uptake, the nanoparticles demonstrate a high photothermal conversion efficiency. A self-passivating native oxide at the surface of the nanoparticles provides an additional degree of freedom for surface funct…
Bimetallic plasmonic nanoparticles enable tuning of the optical response and chemical stability by variation of the composition. The present numerical simulation study compares Ag-Au alloy, Ag@Au core-shell, and Au@Ag core-shell bimetallic plasmonic nanoparticles of both spherical and anisotropic (nanotriangle and nanorods) shapes. By studying both spherical and anisotropic (with LSPR in the near-infrared region) shapes, cases with and without interband transitions of Au can be decoupled. Explicit comparisons are facilitated by numerical models supported by careful validation and examination o…
Spatial confinement of matter in functional nanostructures has propelled these systems to the forefront of nanoscience, both as a playground for exotic physics and quantum phenomena and in multiple applications including plasmonics, optoelectronics, and sensing. In parallel, the emergence of monochromated electron energy loss spectroscopy (EELS) has enabled exploration of local nanoplasmonic functionalities within single nanoparticles and the collective response of nanoparticle assemblies, providing deep insight into the associated mechanisms. However, modern synthesis processes for plasmonic …
Anomalous resonances in properly shaped plasmonic nanostructures can in principle lead to infinite absorption/gain efficiencies over broad bandwidths. By developing a closed-form analytical solution for the fields scattered by conjoined semicircles, we outline the fundamental physics behind these phenomena, associated with broadband adiabatic focusing of surface plasmons at the nanoscale. We are able to justify the apparent paradox of finite absorption/gain in the limit of infinitesimally small material loss/gain, and we explore the potential of these phenomena in nonlinear optics, spasing, en…
Self-organized monocrystalline Au nanoparticles with potential applications in plasmonics are grown in a SrTiO$_3$ matrix by a novel two-step deposition process. The crystalline preferred orientation of these Au nanoparticles is investigated by synchrotron hard x-ray diffraction. Nanoparticles preferentially align with the (111) direction along the substrate normal (001), whereas two in-plane orientations are found with $[110]_{SrTiO_3} \: || \: [110]_{Au}$ and $[100]_{SrTiO_3} \: || \: [110]_{Au}$. Additionally, a smaller diffraction signal from nanoparticles with the (001) direction parallel…
We present a quantum mechanical approach to calculate broadening of plasmonic resonances in metallic nanostructures due to collisions of electrons with the surface of the structure. The approach is applicable if the characteristic size of the structure is much larger than the de Broglie electron wavelength in the metal. The approach can be used in studies of plasmonic properties of both single nanoparticles and arrays of nanoparticles.
We theoretically investigate equilibrium behaviors and photothermal effects of a flexible plasmonic metamaterial composed of aramid nanofibers and gold nanoparticles. The fiber matrix is considered as an external field to reconfigure a nanoparticle assembly. We find that the heating process tunes particle-particle and fiber-particle interactions, which alter adsorption of nanoparticles on fiber surfaces or clustering in pore spaces. Thus, it is possible to control the nanoparticle self-assembly by laser illumination. Gold nanoparticles strongly absorb radiations and efficiently dissipate absor…
We analyze the plasmonic modes of a metal nanoparticle circular array. Closed form solutions to the eigenmode problem are given. For each polarization, the plasmonic mode with the highest quality is found to be an antiphase mode. We found that the significant suppression in radiative loss can be understood as the cancellation of the dipolar radiation term in the radiative linewidth. The remaining finite radiative linewidth decreases exponentially as the number of particle increases.
We review the basic physics behind light interaction with plasmonic nanoparticles. The theoretical foundations of light scattering on one metallic particle (a plasmonic monomer) and two interacting particles (a plasmonic dimer) are systematically investigated. Expressions for effective particle susceptibility (polarizability) are derived, and applications of these results to plasmonic nanoantennas are outlined. In the long-wavelength limit, the effective macroscopic parameters of an array of plasmonic dimers are calculated. These parameters are attributable to an effective medium corresponding…
Plasmonic nanoparticles from unconventional materials can improve or even bring some novel functionalities into the disciplines inherently related to plasmonics such as photochemistry or (spectro)electrochemistry. They can, for example, catalyze various chemical reactions or act as nanoelectrodes and optical transducers in various applications. Silver amalgam is the perfect example of such an unconventional plasmonic material, albeit it is well-known in the field of electrochemistry for its wide cathodic potential window and strong adsorption affinity of biomolecules to its surface. In this st…
We present analytical expressions for the resonance frequencies of the plasmonic modes hosted in a cylindrical nanoparticle within the quasistatic approximation. Our theoretical model gives us access to both the longitudinally and transversally polarized dipolar modes for a metallic cylinder with an arbitrary aspect ratio, which allows us to capture the physics of both plasmonic nanodisks and nanowires. We also calculate quantum mechanical corrections to these resonance frequencies due to the spill-out effect, which is of relevance for cylinders with nanometric dimensions. We go on to consider…
For plasmonic nanoparticles, we investigate the influence of surface roughness inherent to top-down fabrication on the optical properties, and find that it has a surprisingly small influence on the position and width of the plasmon peaks. Our experimental observation is supported by simulations based on the boundary element method approach. Using a perturbation approach, suitable for metallic nanoparticles with a moderate degree of surface roughness, we demonstrate that the reason for this lies in motional narrowing where the plasmon averages over the random height fluctuations. Surface roughn…
We present a rigorous theoretical model for the optical interaction between a nitrogen-vacancy (NV) centre in diamond and a plasmonic metal nanoparticle (MNP), accompanied by a computationally efficient procedure to solve the evolution. The proposed model enables us to successfully explain existing optical emission measurements of NV centres both in the presence and absence of a metal nanoparticle. We show that the NV-plasmon interaction provides a versatile new avenue to enhance and control the optical emission of an NV centre. Changes to the MNP type and size, NV-MNP centre separation, subme…
We utilize experimental tools such as conductive atomic force microscopy and electrostatic force microscopy on photo-excited arrays of gold nanoparticles on indium tin oxide substrate. The nanoparticles are partially covered by a thin semiconductor polymer. The change in the current and potential profiles of the composite metal-semiconductor sample after excitation at plasmonic resonance frequency of metallic nanoparticles is analyzed.
While plasmonic particles can provide optical resonances in a wide spectral range from the lower visible up to the near-infrared, often symmetry effects are utilized to obtain particular optical responses. By breaking certain spatial symmetries, chiral structures arise and provide robust chiroptical responses to these plasmonic resonances. Here, we observe strong chiroptical responses in the linear and nonlinear optical regime for chiral L-handed helicoid III nanoparticles and quantify them by means of an asymmetric factor, the so-called g-factor. We calculate the linear-optical g-factors for …
Plasmonic nanoarrays which support collective surface lattice resonances (SLRs) have become an exciting frontier in plasmonics. Compared with the localized surface plasmon resonance (LSPR) in individual particles, these collective modes have appealing advantages such as angle-dependent dispersions and much narrower linewidths. Here, we investigate systematically how the geometry of the lattice affects the SLRs supported by metallic nanoparticles. We present a general theoretical framework from which the various SLR modes of a given geometry can be straightforwardly obtained by a simple compari…
We study emission of photoelectrons from plasmonic nanoparticles into surrounding matrix. We consider two mechanisms of the photoelectric effect from nanoparticles - surface and volume ones, and use models of these two effects which allow us to obtain analytical results for the photoelectron emission rates from nanoparticle. Calculations have been done for the step potential at surface of spherical nanoparticle, and the simple model for the hot electron cooling have been used. We highlight the effect of the discontinuity of the dielectric permittivity at the nanoparticle boundary in the surfac…
Gallium is a plasmonic material offering ultraviolet to near-infrared tunability, facile and scalable preparation, and good stability of nanoparticles. In our contribution, we experimentally demonstrate the link between the shape and size of individual gallium nanoparticles and their optical properties. To this end, we utilize scanning transmission electron microscopy combined with electron energy loss spectroscopy. Lens-shaped gallium nanoparticles with a diameter between 10 nm and 200 nm were grown directly on a silicon nitride membrane using an in-house developed effusion cell operated at u…
We investigate an array of metal nanoparticles as a channel for nanophotonic quantum communication and the generation of quantum plasmonic interference. We consider the transfer of quantum states, including single-qubits as plasmonic wavepackets, and highlight the necessity of a quantum mechanical description by comparing the predictions of quantum theory with those of classical electromagnetic theory. The effects of loss in the metal are included, thus putting our investigation into a practical setting and enabling the quantification of the performance of realistic nanoparticle arrays as plas…
Non-equilibrium quantum plasmonics in nanoparticle-on-mirror nanocavities
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China（电子科技大学前沿科学技术研究院）；Photonics Research Centre, Universiti Malaya（马来亚大学光子研究中心）；Nanophotonics Centre, Cavendish Laboratory, Department of Physics, University of Cambridge（剑桥大学物理系卡文迪许实验室纳米光子学中心）
We analyze nonlinear effects in optically driven arrays of nonlinear metallic nanoparticles. We demonstrate that such plasmonic systems are characterized by a bistable response, and they can support the propagation of dissipative switching waves (or plasmonic kinks) connecting the states with different polarization. We study numerically the properties of such plasmonic kinks which are characterized by a subwavelength extent and a tunable velocity.
For all applications of plasmonics to technology it is required to tailor the resonance to the optical system in question. This chapter gives an understanding of the design considerations for nanoparticles needed to tune the resonance. First the basic concepts of plasmonics are reviewed with a focus on the physics of nanoparticles. An introduction to the finite element method is given with emphasis on the suitability of the method to nanoplasmonic device simulation. The effects of nanoparticle shape on the spectral position and lineshape of the plasmonic resonance are discussed including retar…
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…
We demonstrate scaffolding of plasmonic nanoparticles by topological defects induced by colloidal microspheres to match their surface boundary conditions with a uniform far-field alignment in a liquid crystal host. Displacing energetically costly liquid crystal regions of reduced order, anisotropic nanoparticles with concave or convex shapes not only stably localize in defects but also self-orient with respect to the microsphere surface. Using laser tweezers, we manipulate the ensuing nanoparticle-microsphere colloidal dimers, probing the strength of elastic binding and demonstrating self-asse…
We demonstrate an efficient eigen-decomposition method for analyzing the guided modes in metal nanoparticle chains. The proposed method has the advantage of showing the dispersion relation and mode quality simultaneously. It can also separate the material and geometrical properties, so its efficiency does not depend on the complexity of the material polarizability. The method is applied to analyze the guided modes of a single and a pair of metal chains. The more accurate dynamic dipole polarizability typically gives a red-shift compared with the results obtained with the broadly used quasistat…
Efficient manipulation and long distance transport of single-photons is a key component in nanoscale quantum optics. In this letter, we study the emission properties of an individual light emitter placed into a nanofiber and coupled to a metallic nanoparticle. We find that plasmonic field enhancement together with the nanofiber optical confinement uniquely and synergistically contribute to an overall increase of emission rates as well as quantum yields.
In the last years there have been multiple proposals in nanophotonics to mimic topological condensed matter systems. However, nanoparticles have degrees of freedom that atoms lack of, like dimensions or shape, which can be exploited to explore topology beyond electronics. Elongated nanoparticles can act like projectors of the electric field in the direction of the major axis. Then, by orienting them in an array the coupling between them can be tuned, allowing to open a gap in an otherwise gapless system. As a proof of the potential of the use of orientation of nanoparticles for topology, we st…
Transport properties of a single plasmon interacting with a hybrid system composed of a semiconductor quantum dot (SQD) and a metal nanoparticle (MNP) coupled to one-dimensional surface plasmonic waveguide are investigated theoretically via the real-space approach. We considered that the MNP-SQD interaction leads to the formation of a hybrid exciton and the transmission and reflection of a single incident plasmon could be controlled by adjusting the frequency of the classical control field applied to the MNP-SQD hybrid nanosystem, the kinds of metallic nanoparticles and the background media, r…
Nanoparticle (NP) arrays of noble metals strongly absorb light in the visible to infrared wavelengths through resonant interactions between the incident electromagnetic field and the metal's free electron plasma. Such plasmonic interfaces enhance light absorption and photocurrent in solar cells. We report a cost effective and scalable room temperature/pressure spin-coating route to fabricate broadband plasmonic interfaces consisting of silver NPs. The NP interface yields photocurrent enhancement (PE) in thin film silicon devices by up to 200% which is significantly greater than previously repo…
Nanoparticles made of non-noble metals such as gallium have recently attracted significant attention due to promising applications in UV plasmonics. To date, experiments have mostly focused on solid and liquid pure gallium particles immobilized on solid substrates. However, for many applications, colloidal liquid-metal nanoparticle solutions are vital. Here, we experimentally demonstrate strong UV plasmonic resonances of eutectic gallium-indium (EGaIn) liquid-metal alloy nanoparticles suspended in ethanol. We rationalise experimental results through a theoretical model based on Mie theory. Our…
Spatial modulation microscopy is a technique originally developed for quantitative spectroscopy of individual nano-objects. Here, a parallel implementation of the spatial modulation microscopy technique is demonstrated based on a line detector capable of demodulation at kHz frequencies. The capabilities of the imaging system are shown using an array of plasmonic nanoantennas and dendritic cells incubated with gold nanoparticles.
We investigate the scattering and absorption properties of anisotropic metal-dielectric core-shell nanoparticles. It is revealed that the radially anisotropic dielectric layer can accelerate the evanescent decay of the localized resonant surface modes, leading to Q-factor and absorption rate enhancement. Moreover, the absorption cross section can be maximized to reach the single resonance absorption limit. We further show that such artificial anisotropic cladding materials can be realized by isotropic layered structures, which may inspire many applications based on scattering and absorption of…
Chemiphores are entities, which exhibit wide-band light emission without any external light source but just due to the chemical reaction resulting in the chemiluminescence effect. Since the chemiphores usually have low quantum efficiency, chemiluminescence is a weak optical effect. We found that plasmonic nanoparticles can efficiently enhance the peculiar effect of chemiluminescence due to the acceleration of the radiative decay of the chemiphore excited state which, in turn, enlarges the chemiluminescence yield. Correspondingly, plasmonic nanoparticles are nanoparticles with sub-wavelength si…
We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) are achieved by tuning either the dipolar or quadrupolar particle resonance to the rare earth ions excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmo…
It is challenging to strongly localize temperature in small volumes because heat transfer is a diffusive process. Here we show how to overcome this limitation using electrodynamic hot spots and interference effects in the regime of continuous-wave (CW) excitation. We introduce a set of figures of merit for the localization of temperature and for the efficiency of the plasmonic photo-thermal effect. Our calculations show that the temperature localization in a trimer nanoparticle assembly is a complex function of the geometry and sizes. Large nanoparticles in the trimer play the role of the nano…
Photoelectric properties of metamaterials containing non-centrosymmetric, similarly oriented metallic nanoparticles embedded in a homogeneous semiconductor matrix are theoretically studied. Due to the asymmetric shape of the nanoparticle boundary, photoelectron emission acquires a preferred direction, resulting in a photocurrent flow in that direction when nanoparticles are uniformly illuminated by a homogeneous plane wave. This effect is a direct analogy of the photogalvanic (or bulk photovoltaic) effect known to exist in media with non-centrosymmetric crystal structure, such as doped lithium…
The strong-field control of plasmonic nanosystems opens up new perspectives for nonlinear plasmonic spectroscopy and petahertz electronics. Questions, however, remain regarding the nature of nonlinear light-matter interactions at sub-wavelength spatial and ultrafast temporal scales. Addressing this challenge, we investigated the strong-field control of the plasmonic response of Au nanoshells with a SiO$_2$ core to an intense laser pulse. We show that the photoelectron energy spectrum from these core-shell nanoparticles displays a striking transition between the weak and strong-field regime. Th…
The heat-shielding properties of random metasurface, composed of spherical or spheroidal nanoparticles with random displacements and/or random deformation, were theoretically investigated using the finite difference time domain method. The effective coverage was defined using the total area of nanoparticles in the metasurface, and the robustness of the near-infrared light reflection against randomness was investigated. When the effective coverage was high, the near-infrared light reflection was reduced by at least 20% in both nanoparticle arrangement and shape randomness compared to the hexago…
Here we demonstrate the gas sensing ability of cavity-coupled metallic nanoparticle systems, comprising gold nanoparticles separated from a gold mirror with a polymer spacer. An increase in relative humidity (RH) causes the spacer to expand, which induces a significant reduction of nanoparticle scattering intensity, as the scattering is highly dependent on the cavity-nanoparticle coupling that closely relates to the nanoparticle-mirror distance. This lithography-free structure enables a remarkable averaging sensitivity at 0.12 dB/% RH and 0.25 dB/% RH over RH range (45-75%), possessing an esti…
Films of close-packed Au nanoparticles are coupled electrodynamically through their collective plasmon resonances. This collective optical response results in enhanced light-matter interactions, which can be exploited in various applications. Here, we demonstrate their application in sensing volatile organic compounds, using methanol as a test-case. Ordered films over several cm2 were obtained by interfacial self-assembly of colloidal Au nanoparticles (~10 nm diameter) through controlled evaporation of the solvent. Even though isolated nanoparticles of this size are inherently non-scattering, …
We have used a gold nanohole array to trap single polystyrene nanoparticles, with a mean diameter of 30 nm, into separated hot spots located at connecting nanoslot regions. A high trap stiffness of approximately 0.85 fN/(nmmW) at a low incident laser intensity of ~0.51 mW/um2 at 980 nm was obtained. The experimental results were compared to the simulated trapping force and a reasonable match was achieved. This plasmonic array is useful for lab-on-a-chip applications and has particular appeal for trapping multiple nanoparticles with predefined separations or arranged in patterns in order to stu…
It is a generally accepted idea that the particle size distribution strongly affects the optical spectra of colloidal plasmonic nanoparticles. It is often quoted as one of the main reasons while explaining the mismatch between the theoretical and experimental optical spectra of such nanoparticles. In this work, these aspects are critically analyzed by means of a bottom up statistical approach that considers variables such as mean, standard deviation and skewness of the nanoparticle size distribution independently from one another. By assuming normal and log-normal distributions of the particle…
We derive envelope equations which generate the Maxwell-Lorentz model and describe the interaction of optical pulses with plasmonic oscillations in metal nanoparticle composites. A family of solitary wave solutions is found which is analogous to self-induced transparency in Maxwell-Bloch. The evolution of incident optical pulses is studied numerically as are the collision dynamics of the solitary waves. These simulations reveal that the collision dynamics vary from near perfectly elastic to highly radiative depending on the relative phase of the initial pulses.
In this work, we present a novel technique to directly measure the phase shift of the optical signal scattered by single plasmonic nanoparticles in a diffraction-limited laser focus. We accomplish this by equipping an inverted confocal microscope with a Michelson interferometer and scanning single nanoparticles through the focal volume while recording interferograms of the scattered and a reference wave for each pixel. For the experiments, lithographically prepared gold nanorods where used, since their plasmon resonances can be controlled via their aspect ratio. We have developed a theoretical…
Plasmon-assisted hot carrier processes in metal nanoparticles can be described either classically or using the full strength of quantum mechanics. We reconfirm that from the practical applications point of view, when it comes to description of the decay of plasmons in nanoparticles, classical description is sufficiently adequate for all but the smallest of the nanoparticles. At the same time, the electron temperature rise in nanoparticles is discrete (quantized) and neglecting this fact can lead to significant underestimating of hot carrier assisted effects, such as photo-catalysis.
Ultrafast pump-probe measurements of plasmonic nanostructures probe the non-equilibrium behavior of excited carriers, which involves several competing effects obscured in typical empirical analyses. Here we present pump-probe measurements of plasmonic nanoparticles along with a complete theoretical description based on first-principles calculations of carrier dynamics and optical response, free of any fitting parameters. We account for detailed electronic-structure effects in the density of states, excited carrier distributions, electron-phonon coupling, and dielectric functions which allow us…
We investigated the plasmonic modes in a two-dimensional quasicrystalline array of metal nanoparticles. The polarization of the modes is in the array plane. A simplified eigen-decomposition method is presented with the help of rotational symmetry. Two kinds of anti-phase ring modes with radial and tangential polarizations are of highest spatial localizations among all of plasmonic modes. For the leaky characteristic of the anti-phase ring modes, the highest fidelity mode is found to be tangential polarized mode in the quasicrystal array, whereas normal-to-plane polarized mode in the solo ring.…
Multiple surface plasmon-polariton (SPP) waves excited at the interface of a homogeneous isotropic metal and a chiral sculptured thin film (STF) impregnated with silver nanoparticles were theoretically assessed for the multiple-SPP-waves-based sensing of a fluid uniformly infiltrating the chiral STF. The Bruggemann homogenization formalism was used in two different modalities to determine the three principal relative permittivity scalars of the silver-nanoparticle-impregnated chiral STF infiltrated uniformly by the fluid. The dynamic sensitivity increased when silver nanoparticles were present…
We numerically investigate the optical response of slowly scaling linear chains of mismatched silver nanoparticles. Hybridized plasmon chain resonances manifest unusual local field distributions around the nanoparticles that result from symmetry breaking of the geometry. Importantly, we find localization patterns characterized by bright hot-spots alternated by what we term \textit{dark} spots. A dark spot is associated to dark plasmons that have collinear and antiparallel dipole moments along the chain. As a result, the field amplification in the dark interjunction gap is extinguished for inci…
