Assemblies of closely separated gold nanoparticles exhibit a strong collective plasmonic response due to coupling of the plasmon modes of the individual nanostructures. In the context of self-assembly of nanoparticles, closed packed 2D clusters of spherical nanoparticles present an important composite system that promises numerous applications. The present study probes the collective plasmonic characteristics and resulting photothermal behavior of closed packed 2D Au nanoparticle clusters in order to delineate the effects of cluster size, inter-particle distance and particle size. Smaller nanoparticles (20 nm and 40 nm in diameter) that exhibit low individual scattering and high absorption were considered for their relevance to photothermal applications. In contrast to typical literature studies, the present study compares the optical response of clusters of different sizes ranging from a single nanoparticle up to large assemblies of 61 nanoparticles. Increasing the cluster size induces significant changes to the spectral position and opto-physical characteristics. Based on the model outcome, an optimal cluster size for maximum absorption per nanoparticle is also determined for enhanced photothermal effects. The effect of particle size and inter-particle distance is investigated in order to elucidate the nature of interaction in terms of near-field and far-field coupling. The photothermal effect resulting from absorption is compared for different cluster sizes and inter-particle distances considering a homogeneous water medium. A strong dependence of the steady state temperature of the nanoparticles on the cluster size, particle position in the cluster, incident light polarization and inter-particle distance provides new physical insight in local temperature control of plasmonic nanostructures.
We present theoretical and experimental studies of the optical response of L-shaped silver nanoparticles. The scattering spectrum exhibits several plasmon resonances that depend sensitively on the polarization of the incident electromagnetic field. The physical origin of the resonances is traced to different plasmon phenomena. In particular, a high energy band with unusual properties is interpreted in terms of volume plasmon oscillations arising from the asymmetry of a nanoparticle.
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 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…
In this work, we proposed new shape nanoparticles in the name of supershape nanoparticles by manipulation in the morphology of a disk nanoparticle. The electric field distribution of supershape nanoparticles were investigated at resonance wavelength of particle plasmons. The effects of dispersed medium and different sensory materials on particle plasmons were reported. The obtained results showed that there exist the multiple plasmonics modes in supershape nanoparticles. We found that the high sensitivity factor is available in the supershape nanoparticles. This study can be a base for the cha…
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…
We predict the simultaneous occurrence of two fundamental phenomena for metal nanoparticles possessing sharp corners: First, the main plasmonic dipolar mode experiences strong red shift with decreasing corner curvature radius; its resonant frequency is controlled by the apex angle of the corner and the normalized (to the particle size) corner curvature. Second, the split-off plasmonic mode experiences strong localization at the corners. Altogether, this paves the way for tailoring of metal nano-structures providing wavelength-selective excitation of localized plasmons and a strong near-field e…
A novel theoretical approach to the dynamics analysis of excitation of plasmon modes in nanoparticles is presented. This approach is based on the biorthogonal plasmon mode expansion and it leads to the predictions of time-dynamics of excitation of specific plasmon modes as well as their steady state amplitude and their decay. Temporal characteristics of plasmon modes in nanoparticles are expressed in terms of their shapes, permittivity dispersion relations and excitation conditions. In the case of the Drude model, analytical expressions for time-dynamics of plasmon modes are obtained.
We report on the manipulation of magnetization by femtosecond laser pulses in a periodic array of cylindrical nickel nanoparticles. By performing experiments at different wavelength, we show that the excitation of collective surface plasmon resonances triggers demagnetization in zero field or magnetic switching in a small perpendicular field. Both magnetic effects are explained by plasmon-induced heating of the nickel nanoparticles to their Curie temperature. Model calculations confirm the strong correlation between the excitation of surface plasmon modes and laser-induced changes in magnetiza…
We show that, when a gold nanoparticle is coated by a thin layer of nematic liquid crystal, the deformation produced by the nanoparticle surface can enhance the splitting of the nanoparticle surface plasmon. We consider three plausible liquid crystal director configurations in zero electric field: boojum pair (north-south pole configuration), baseball (tetrahedral), and homogeneous. From a calculation using the Discrete Dipole Approximation, we find that the surface plasmon splitting is largest for the boojum pair, intermediate for the homogeneous, and smallest for the baseball configuration. …
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…
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…
We report on a photoconductive gain effect in two-dimensional arrays of gold nanoparticles, in which alkane molecules are inserted. The nanoparticle arrays are formed by a self-assembly process from alkanethiol-coated gold nanoparticles, and subsequently they are patterned on a Si/SiO2 chip by a microcontact printing technique. We find that the photoconductance of the arrays is strongly enhanced at the frequency of the surface plasmon of the nanoparticles. We interpret the observation as a bolometric enhancement of the conductance of the nanoparticle arrays upon excitation of the surface plasm…
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…
Understanding and controlling properties of plasmon-induced hot carriers is a key step towards next-generation photovoltaic and photocatalytic devices. Here, we uncover a route to engineering hot-carrier generation rates of silver nanoparticles by designed embedding in dielectric host materials. Extending our recently established quantum-mechanical approach to describe the decay of quantized plasmons into hot carriers we capture both external screening by the nanoparticle environment and internal screening by silver d-electrons through an effective electron-electron interaction. We find that h…
Plasmonic core-shell nanoparticles (PCSNPs) can function as nanoantennas and improve the efficiency of dye-sensitized solar cells (DSSCs). To achieve maximum enhancement, the morphology of PCSNPs need to be optimized. Here we precisely control the morphology of Au@TiO2 PCSNPs and systematically study its influence on the plasmonic enhancement effect. Enhancement mechanism was found to vary with the thickness of TiO2 shell. PCSNPs with thinner shell enhance the current due to plasmonic effect, whereas particles with thicker shell improve the voltage due to increasing semiconducting character. W…
The optical and morphological properties of hollow gold nanoparticles (HGNPs) can be finely modified by employing Poly-L-Lysine hydrobromide (PLL), an homo poly aminoacid of the L-lysine, used as reducer and stabilizer. We investigate locally the plasmonic response of these nanostructures by electron energy loss spectroscopy (EELS). The plasmon excitations are interpreted by discrete dipolar approximation (DDA) simulations. We demonstrate that this controlled top-down morphological modification a fine tuning of the optical response is possible. Unlike the traditional lithographic techniques, t…
Harnessing hot electrons and holes resulting from the decay of localized surface plasmons in nanomaterials has recently led to new devices for photovoltaics, photocatalysis and optoelectronics. Properties of hot carriers are highly tunable and in this work we investigate their dependence on the material, size and environment of spherical metallic nanoparticles. In particular, we carry out theoretical calculations of hot carrier generation rates and energy distributions for six different plasmonic materials (Na, K, Al, Cu, Ag and Au). The plasmon decay into hot electron-hole pairs is described …
We study the distance dependence of the rate of electronic excitation energy transfer from a dye molecule to a metal nanoparticle. Using the spherical jellium model, we evaluate the rates corresponding to the excitation of l = 1, 2, and 3 modes of the nanoparticle. Our calculation takes into account both the electron-hole pair and the plasmon excitations of the nanoparticle. The rate follows conventional R^-6 dependence at large distances while small deviations from this behavior are observed at shorter distances. Within the framework of the jellium model, it is not possible to attribute the e…
The adsorption of hydrogen on Au nanoparticles (NPs) of size of the order of 10 nm has been investigated by use of localised surface plasmon resonances (LSPR) in the NPs. The samples, formed by Au NPs obtained by oblique angle deposition on glass substrates, display a strong optical dichroism due to two different plasmon resonances dependent on the polarisation of light. This ensured the use of Transmittance Anisotropy Spectroscopy, a sensitive derivative optical technique, which permitted one to measure shifts of the LSPR as small as 0.02 nm upon H adsorption, which is not accessible by conve…
The present paper deals with the systematic growth of plasmonic gold nanoparticles (Au NPs) on molybdenum disulphide (MoS$_2$) nanosheets as well as the effect of Au NPs on the optical and magnetic properties. The crystalline nature of the nanocomposites is confirmed by X-ray diffraction and transmission electron microscopic techniques. The optical properties are characterized using absorption and Raman spectroscopic techniques. The electron paramagnetic resonance technique is used to study the magnetic response of the nanocomposites. The paper attempts to gain a fundamental understanding of t…
Ultrafast demagnetization in magnetic nanoparticles using pulsed laser has attracted considerable attention because of its potential applications in spintronics, such as data storage. In such applications, it is necessary to control magnetization using low energy laser pulses, however, this poses the problem of increasing the amount of energy from the excitation laser pulses to the spin subsystem. We take advantage of the phenomenon known as localized surface plasmon resonance (LSPR) to enhance the energy transfer from laser pulses to the spin subsystem. To induce LSPR, hybrid nanoparticles co…
The technology problems of fabricating different, nanometers sized gold particles in the layered composites like light-sensitive chalcogenide glass/gold nanoparticles/transparent substrate or titanium/titanium oxide/gold nanoparticles were investigated in our work. Combination of ion implantation, plasma deposition with annealing processes results physical routes for creation of gold nanoparticles in the mentioned structures, which possess plasmon effects. These functionalized structures are planned to use for investigations of optical recording processes, biocompatibility of titanium implants…
Flat TiO$_2$ layers are deposited by magnetron sputtering on Ti/Si wafers. The TiO$_2$ surfaces are then sputter-coated with thin Au films of a nominal thickness of 0.5-10 nm that are converted by solid-state dewetting into Au nanoparticles of tuneable size and spacing; the Au nanoparticle size can be tuned over a broad range, i.e. ca. 3-200 nm. The Au-decorated TiO$_2$ surfaces enable plasmonic photo-electrochemical water splitting under visible light illumination (450-750 nm). The water splitting performance reaches a maximum for TiO$_2$ layers decorated with ~ 30 nm-sized Au particles. As e…
We present an approach to master the well-known challenge of calculating the contribution of d-bands to plasmon-induced hot carrier rates in metallic nanoparticles. We generalise the widely used spherical well model for the nanoparticle wavefunctions to flat d-bands using the envelope function technique. Using Fermi's golden rule, we calculate the generation rates of hot carriers after the decay of the plasmon due to transitions from either a d-band state to an sp-band state or from an sp-band state to another sp-band state. We apply this formalism to spherical silver nanoparticles with radii …
The effect of smooth shape changes of metallic nanoparticles on localized surface plasmon resonances is assessed with a boundary integral equation method. The boundary integral equation method allows compact expressions of nanoparticle polarizability which is expressed as an eigenmode sum of terms that depends on the eigenvalues and eigenfunctions of the integral operator associated to the boundary integral equation method. Shape variations change not only the eigenvalues but also their coupling weights to the electromagnetic field. Thus, rather small changes in the shape may induce large vari…
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…
Shifting of the surface plasmon resonance wavelength induced by the variation of the thickness of insulating spacer between single layer graphene and Au nanoparticles is studied. The system demonstrates a blue shift of 29 nm as the thickness of the spacer layer increases from 0 to 15 nm. This is due to the electromagnetic coupling between the localized surface plasmons excited in the nanoparticles and the graphene film. The strength of the coupling decays exponentially with a decay length of d/R=0.36, where d is the spacer layer thickness and R is the diameter of the Au nanoparticles. The resu…
Formation of surface plasmon modes in sodium nanoclusters containing 20-300 atoms was studied using the GW method. It is shown that in the small Na nanoparticles up to 2 nm in size, the loss function $Im[ε^{-1}]$ is dominated by a single peak corresponding to localized surface plasmon resonance (LSPR). For particles of 2 nm and more, a resonance corresponding to surface plasmon polariton (SPP) oscillations begins to form, as well as a resonance corresponding to volume plasmon (VP) excitations. Considering the above, the linear size of a particle in the range of 0.7-3.7 nm can be estimated as t…
Anisotropic plasmon coupling in closely-spaced chains of Ag nanoparticles was visualized using the electron energy loss spectroscopy in a scanning transmission electron microscope. For dimers as the simplest chain, mapping the plasmon excitations with nanometers' spatial resolution and 0.27 eV energy resolution intuitively identified two coupling plasmons. The in-phase mode redshifted from the ultraviolet region as the inter-particle spacing was reduced, reaching the visible range at 2.7 eV. Calculations based on the discrete dipole approximation confirmed its optical activeness, where the lon…
We have investigated the effects of tuning the localized surface plasmon resonances (LSPRs) of silver nanoparticles on the fluorescence intensity, lifetime, and Raman signal from nearby fluorophores. The presence of a metallic structure can alter the optical properties of a molecule by increasing the excitation field, and by modifying radiative and non-radiative decay mechanisms. By careful choice of experimental parameters we have been able to decouple these effects. We observe a four-fold increase in fluorescence enhancement and an almost 30-fold increase in decay rate from arrays of Ag nano…
The incorporation of noble metal nanoparticles, displaying localized surface plasmon resonance, in the active area of donor-acceptor bulk-heterojunction organic photovoltaic devices is an industrially compatible light trapping strategy, able to guarantee better absorption of the incident photons and give an efficiency improvement between 12% and 38%. In the present work, we investigate the effect of Au and Ag nanoparticles blended with P3HT: PCBM on the P3HT crystallization dynamics by synchrotron grazing incidence X-ray diffraction. We conclude that the presence of (1) 80nm Au, (2) mix of 5nm…
Metal nanoparticles are attractive for plasmon-enhanced generation of hot carriers, which may be harnessed in photochemical reactions. In this work, we analyze the coherent femtosecond dynamics of photon absorption, plasmon formation, and subsequent hot-carrier generation through plasmon dephasing using first-principles simulations. We predict the energetic and spatial hot-carrier distributions in small metal nanoparticles and show that the distribution of hot electrons is very sensitive to the local structure. Our results show that surface sites exhibit enhanced hot-electron generation in com…
We present theoretical calculations for the absorption properties of protein-coated gold nanoparticles on graphene and graphite substrates. As the substrate is far away from nanoparticles, numerical results show that the number of protein bovine serum molecules molecules aggregating on gold surfaces can be quantitatively determined for gold nanoparticles with arbitrary size by means of the Mie theory and the absorption spectra. The presence of graphitic substrate near protein-conjugated gold nanoparticles substantially enhances the red shift of the surface plasmon resonances of the nanoparticl…
We report the investigation of the generation and detection of GHz coherent acoustic phonons in plasmonic gold nanoparticles superlattices (NPS). The experiments have been performed from an optical femtosecond pump-probe scheme across the optical plasmon resonance of the superlattice. Our experiments allow to estimate the collective elastic response (sound velocity) of the NPS as well as an estimate of the nano-contact elastic stiffness. It appears that the light-induced coherent acoustic phonon pulse has a typical in-depth spatial extension of about 45 nm which is roughly 4 times the optical …
We describe the process of Foerster transfer between semiconductor nanoparticles in the presence of a metal subsystem (metal nanocrystals). In the presence of metal nanocrystals, the Foerster process can become faster and more long-range. The enhancement of Foerster transfer occurs due to the effect of plasmon-assisted amplification of electric fields inside the nanoscale assembly. Simultaneously, metal nanocrystals lead to an increase of energy losses during the Foerster transfer process. We derive convenient equations for the energy transfer rates, photoluminescence intensities, and energy d…
Design of nanoscale structures with desired nanophotonic properties are key tasks for nanooptics and nanophotonics. Here, the correlative relationship between local nanoparticle geometries and their plasmonic responses is established using encoder-decoder neural networks. In the im2spec network, the correlative relationship between local particle geometries and local spectra is established via encoding the observed geometries to a small number of latent variables and subsequently decoding into plasmonic spectra; in the spec2im network, the relationship is reversed. Surprisingly, these reduced …
