surface plasmon resonance (SPR)

History
The SPR(surface plasmon resonance) is the century-old technique from the finding of the Wood’s
anomaly for the reflected light from the diffraction gratings. After Otto’s demonstration for the
surface plasmon excitation by light with attenuated total- reflection(ATR) coupler, the SPR method
applied to the organic filmsor the detection of antigen-antibody reaction[6]. The SPR theory is also
well established and the recent advance in the measurements can be reported in the reviews In the
SPR method the dielectric constant change in the sub-nm region from the surface can be measured
and the method can be easily applied to the adsorption phenomena in the electrochemical
environment where the capacitance can be measured simultaneously and get the complementary
information of the change in the dielectric properties on the electrode surface.

In the surface plasmon resonance (SPR) measurement we can detect the change of the film thickness
(refractive index change) in the sub-nonometer scale using a low-cost home-made apparatus (He-Ne
laser, rotating stage, photo-diode detector, prism, machine oil, and 50 nm gold films on a glass plate.
In this sense SPR is widely used, in particular, as the immunoassay to detect label-free antigen-
antibody reaction. When light is irradiated to the optical prism |thin metallic film (usually 50 nm gold
film is used)| sample system, the reflectivity of the light becomes almost zero at the angle of
incidence where the surface plasma wave of gold surface can couple to the part of the incident light. 1
This angle is called SPR angle and is very sensitive to the film thickness (refractivity) of the sample.
In the usual automated SPR measurement analysis routine one can get the SPR angle shift and the
change of the film thickness (and/or refractivity), thereby the measurement may be one of the ”black-
box”. However I think it is important to know the principle for the people to do something new by an
detailed analysis of the measurements. From the name ”plasmon” one may misunderstand that the
quantum mechanical understanding is required for SPR principles, but the phenomena can be
understood from the classical optics (or electromagnetic theory) which explain the light reflection,
transmission, and absorption for the multi-layer medium. In the famous book by Raether the principle
of SPR was written completely, but at least for me it is not easy to understand because the book may
be for specialist. This note is written for my self-study of SPR principle in order to analyze the SPR
curves,
Surface plasma oscillations
The electronic charges on metal boundary can perform coherent fluctuations which are
called surface plasma oscillations. The fluctuations are confined at the boundary and
vanishes both sides of the metal surface. This plasmon waves have p-character because the surface
charge induce the discontinuity of the electric field in the surface normal z-direction, but s-waves has
only Ey component (no Ez component).

Or
Plasma oscillation is the phenomena that free electrons in the metal oscillate cooperatively from
their equilibrium position where the positive charge of metal (atomic nucleus or jellium that the
positive charges are averaged) bind the ensemble of the free electrons . ”Plasmon” means the
quasi-particle representation of plasma frequency. The surface plasmon is the plasma oscillation
that localize at the surface or interface.

In sort  (SPR) is the collective oscillation of electrons in a solid or liquid stimulated by incident light.

The resonance condition is established when the frequency of light photons matches the natural
frequency of surface electrons oscillating against the restoring force of positive nuclei.

SPR in nanometer-sized structures is called localized surface plasmon resonance.

SPR is the basis of many standard tools for measuring adsorption of material onto planar metal
(typically gold and silver) surfaces or onto the surface of metal nanoparticles. It is the fundamental
principle behind many color-based biosensor applications and different lab-on-a-chip sensors.
Details of Phenomenon:

Surface plasmon polaritons are surface electromagnetic waves that propagate in a direction parallel to

the metal/dielectric (or metal/vacuum) interface. Since the wave is on the boundary of the metal and
the external medium (air or water for example), these oscillations are very sensitive to any change of
this boundary, such as the adsorption of molecules to the metal surface.

To describe the existence and properties of surface plasmon polaritons, one can choose from various
models (quantum theory, Drude model, etc.). The simplest way to approach the problem is to treat
each material as a homogeneous continuum, described by a frequency-dependent relative
permittivity between the external medium and the surface. This quantity, hereafter referred to as the
materials' "dielectric constant," is complex permittivity. In order for the terms which describe the
electronic surface plasmons to exist, the real part of the dielectric constant of the metal must be
negative and its magnitude must be greater than that of the dielectric. This condition is met in the IR-
visible wavelength region for air/metal and water/metal interfaces (where the real dielectric constant of
a metal is negative and that of air or water is positive).

LSPRs

(Localized SPRs) are collective electron charge oscillations in metallic nanoparticles that are excited
by light. They exhibit enhanced near-field amplitude at the resonance wavelength. This field is highly
localized at the nanoparticle and decays rapidly away from the nanoparticle/dieletric interface into the
dielectric background, though far-field scattering by the particle is also enhanced by the resonance.
Light intensity enhancement is a very important aspect of LSPRs and localization means the LSPR
has very high spatial resolution (subwavelength), limited only by the size of nanoparticles. Because of
the enhanced field amplitude, effects that depend on the amplitude such as magneto-optical effect are
also enhanced by LSPRs.

In order to excite surface plasmons in a resonant manner, one can use an electron or light
beam (visible and infrared are typical). The incoming beam has to match its momentum to that of the
plasmon. In the case of p-polarized light (polarization occurs parallel to the plane of incidence), this is
possible by passing the light through a block of glass to increase the wave number (and
the momentum), and achieve the resonance at a given wavelength and angle. S-polarized light
(polarization occurs perpendicular to the plane of incidence) cannot excite electronic surface
plasmons. Electronic and magnetic surface plasmons obey the following dispersion relation:

where   is the dielectric constant, and   is the magnetic permeability of the material.