Experiment No: 3

Surface Plasmon–Coupled Emission

Surface Plasmon Resonance (SPR) is a physical process that can occur when plane-polarized light hits a thin
metal film under total internal reflection conditions. At a certain angle of incidence, a portion of the light
energy couples through the metal coating with the electrons in the metal surface layer, which then move due
to excitation. The electron movements are called Plasmon, and they propagate parallel to the metal surface.
The Plasmon oscillation in turn generates an electromagnetic field whose range is around 300 nm from the
boundary between the metal surface and dielectric medium. These EM field decays evanescently into both the
metal and dielectric medium, the majority of the field is present in the dielectric medium due to increased
damping in the metal.

Thus the resonant oscillation of conduction electrons at the interface between metal film and dielectric
medium stimulated by incident light is called Surface Plasmon Resonance.

Since the wave is on the boundary of the conductor and the dielectric medium these oscillations are very
sensitive to any change of this boundary, such as the adsorption of molecules to the conducting surface.

Figure 1: The oscillations of conduction electrons at the metal-dielectric interface

There are two configurations which are used to excite Surface plasmon waves.

Otto Configuration: The light illuminates the wall of a glass block, typically a prism, and is totally internally
reflected. A thin metal film (for example gold) is positioned close enough to the prism wall so that an
evanescent wave can interact with the plasma waves on the surface and hence excite the plasmons.

Kretschmann configuration: The metal film is evaporated onto the glass block. The light again illuminates the
glass block, and an evanescent wave penetrates through the metal film. The plasmons are excited at the outer
side of the film. This configuration is used in most practical applications.
 Figure 2: Otto and Kretschmann configuration

Surface Plasmon Resonance Sensors

The fundamental principle of SPR thus provides highly sensitive spectroscopic tool that is increasingly being
used for label-free detection studies. SPR are widely used in color-based biosensor applications and different
lab-on-a-chip sensors.

The angle at which the minimum intensity of the reflected light is achieved is called ‘‘SPR angle’’. The SPR angle
is dependent on the refractive index of the material near the metal surface. Consequently, when there is a
small change in the reflective index of the sensing medium, plasmon cannot be formed. Detection is thus
accomplished by measuring the changes in the reflected light obtained on a detector. Different factors such as
nature of the metal layer, angle of SPR, refractive index at the metal-dielectric interface, wavelength of the
incident light, etc. regulate the magnitude of surface Plasmon resonance.

In SPR measurement the sensorgram indicates the changes in reflection intensity with respect to incident angle
before and after binding of the target molecule.

SPR technology is used widely as a transducer for affinity-based biosensors. An SPR-based affinity biosensor is
composed of a recognition element or ligand immobilized on the metal surface of a SPR transducer. An
example of a ligand–analyte pair is antibody–antigen. When the target molecules, species, or the analytes in
solution phase bind to the ligand, the solution refractive index at the interface changes, and consequently the
SPR takes place at a different angle. This change in SPR angle can be used to obtain information such as the
binding amount (how many analytes bind to surface-immobilized ligands), the association and dissociation rate
constants, and the apparent association constant by measuring the time relationship of refractive index
changes at various analyte concentrations.
 Figure 3: Sample sensogram of SPR

Fluorescence
Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation.
It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore lower
energy, than the absorbed radiation. The most striking example of fluorescence occurs when the absorbed
radiation is in the ultraviolet region of the spectrum, and thus invisible to the human eye, while the emitted
light is in the visible region, which gives the fluorescent substance a distinct color that can only be seen when
exposed to UV light. Fluorescent materials cease to glow nearly immediately when the radiation source stops,
unlike phosphorescence, where they continue to emit light for some time after.

Surface Plasmon–Coupled Emission

Surface plasmon–coupled emission (SPCE) arose from the integration of fluorescence and SPR. Excited surface
plasmons in the metal film create highly enhanced evanescent fields penetrating the fluorophores (dielectric)
above the metal surface up to several hundred nanometers into the sample. Conversely, excited fluorophores
present within this distance from the surface create an electromagnetic field that may strongly interact with
free charges in the metal film inducing surface plasmons. The frequency of these plasmons corresponds to the
emission frequency of the fluorophores. As a result, we observe a strong directional emission, which we call
Surface Plasmon Coupled Emission (SPCE) (Fig. 17.2). The resulting SPCE exhibits the same spectral shape as the
fluorophore emission, but is highly polarized with a sharply defined emission angle back into the glass
substrate.
 Figure 4: Surface Plasmon–Coupled Emission
On the basis of prism coupling measurements, two modes of SPCE can be used (9); the fluorophores can be
excited with light incident from either the prism side or the sample side. In the first mode (through the prism),
the incident light at the SPR angle can induce the oscillation of surface plasmons to excite the nearby
fluorophores. In this mode, the device operates similarly to SPR and is known as the Kretschmann (KR)
configuration. In the second mode (through the sample), the incident light can directly excite the fluorophores
so that the dipoles in the near field couple to surface plasmons, thereby inducing directional emission through
the prism. This mode is known as the reverse Kretschmann (RK) configuration. In the KR configuration, the
excited field is greatly enhanced in a resonance with an evanescent field, so the SPCE intensity is much higher
than in the RK configuration. However, the direct incidence in RK configurations means that these devices are
easier to create.

References
(1) Nguyen and Park et al; Surface Plasmon Resonance: A Versatile Technique for Biosensor Applications;
Sensors 2015, 15, 10481-10510.
(2) Cao and Cai et al; Surface Plasmon–Coupled Emission: What Can Directional Fluorescence Bring to the
Analytical Sciences; AnnuRev-Anchem; Vol. 5:317-336
(3) Joseph R. Lakowicz; Surface plasmon-coupled directional emission; Anal Biochem; 2004 Jan 15; 324(2):
153–169.
(4) Brongersma M.L., Kik P.G.; Surface Plasmon Nano photonics. Springer Series in Optical Sciences, vol 131.
Springer, Dordrecht.