The resonant wave modes in monomodal and multimodal planar Surface Plasmon Resonance (SPR) sensors and their response to a bidimensional array of gold nanoparticles (AuNPs) are analyzed both theoretically and experimentally, to investigate the parameters that rule the correct nanoparticle counting in the emerging metal nanoparticle-amplified surface plasmon resonance (PA-SPR) spectroscopy. With numerical simulations based on the Finite Element Method (FEM), we evaluate the error performed in the determination of the surface density of nanoparticles σ when the Maxwell-Garnett effective medium theory is used for fast data processing of the SPR reflectivity curves upon nanoparticle detection. The deviation increases directly with the manifestations of non-negligible scattering cross-section of the single nanoparticle, dipole-dipole interactions between adjacent AuNPs and dipolar interactions with the metal substrate. Near field simulations show clearly the set-up of dipolar interactions when the dielectric thickness is smaller than 10 nm and confirm that the anomalous dispersion usually observed experimentally is due to the failure of the effective medium theories. Using citrate stabilized AuNPs with a nominal diameter of about 15 nm, we demonstrate experimentally that Dielectric Loaded Waveguides (DLWGs) can be used as accurate nanocounters in the range of surface density between 20 and 200 NP/µm2, opening the way to the use of PA-SPR spectroscopy on systems mimicking the physiological cell membranes on SiO2 supports.
The influence of a dielectric shell on metallic spherical nanoparticles [core-shell nanoparticles (CSNps)] in the resonant modal response of a surface plasmon resonance (SPR)-type sensor is presented. The planar multilayer sensor structure, based on the Kretschmann and surface plasmon coupled emission (SPCE) configurations, is coupled to a periodic array of these nanoparticles. In the first configuration, the CSNps are considered as a homogeneous layer with effective permittivity given by the Clausius-Mossotti mixing formula and polarizability of a core shell for a quasi-static scattering regime. In the second configuration, it performed an evaluation via the discrete complex image method (DCIM). Electromagnetic wave propagation is evaluated by the generalized reflection coefficient for multilayer structures. The analytical results are validated by numerical simulations performed via finite element method and also by experimental data. We observed that the dielectric shell thickness affects considerably the sensibility of the sensor when analyzing the change in other parameters of the CSNps array.Resonance 186
An
alternative approach to classical surface plasmon resonance
spectroscopy is dielectric-loaded waveguide (DLWG) spectroscopy, widely
used in the past decades to investigate bio-interaction kinetics.
Despite their wide application, a successful and clear approach to
use the DLWGs for the one-step simultaneous determination of both
the thickness and refractive index of organic thin films is absent
in the literature. We propose here, for the first time, an experimental
protocol based on the multimodal nature of DLWGs to be followed in
order to evaluate the optical constants and thickness of transparent
thin films with a unique measurement. The proposed method is general
and can be applied to every class of transparent organic materials,
with a resolution and accuracy which depend on the nature of the external
medium (gaseous or liquid), the geometrical characteristics of the
DLWG, and the values of both the thickness and dielectric constant
of the thin film. From the experimental point of view, the method
is demonstrated in a nitrogen environment with an accuracy of about
3%, for the special case of electroluminescent thin films of Eu3+β-diketonate complexes, with an average thickness of
about 20 nm. The high value of the refractive index measured for the
thin film with the Eu(btfa)3(t-bpete) complex was confirmed
by the use of a spectroscopic model based on the Judd–Ofelt
theory, in which the magnetic dipole transition 5D0 → 7F1 (Eu3+) for
similar films containing Eu3+ complexes is taken as a reference.
The DLWGs are finally applied to control the refractive index changes
of the organic thin films under UVA irradiation, with potential applications
in dosimetry and monitoring light-induced transformation in organic
thin films.
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