Experimental Surface Plasmon Resonance in a Thin Gold Film

Sebastian Duque1
1

Grupo de Fsica At
omica y Molecular, Instituto de Fsica, Facultad de Ciencias Exactas y Naturales,
Universidad de Antioquia UdeA; Calle 70 No. 52-21, Medelln, Colombia.
(Dated: October 2, 2014)
By shining monochromatic light into a thin gold metal film through a prism the surface plasmon
resonance curve is pretended to be observed. In this write-up the experimental progress up to the
date is described.
INTRODUCTION

Surface plasmons are a collective oscillations of electrons in a solid (or liquid) excited by photons incident on
the metal-glass interface. Surface plasmons are a quantum phenomena, however, they are well described by
classical electromagnetic theory as waves traveling along
the interface of two different media [1]. Surface plasmon
resonance (SPR) is an experimental technique for measuring changes in the index of refraction and is widely
use for studying binding interactions of biomolecules including antigen/antibody, complementary DNA probes,
enzyme/substrate and receptor/ligand interactions.
Although SPR is theoretically observable in any conducting metal, silver and gold are the metals of choice
because its plasma resonance is observed in the visible
part of the electromagnetic spectrum [2].
The dispersion relation for surface waves propagating
along the interface semi-infinite dielectric bounded by
vacuum is

1/2

()
kx =
(1)
c () + 1
with  the complex dielectric function of the medium [1].
This surface plasmons cannot be excited directly by light
beams since light propagating in vacuum wont match
the frequency and wave vector of them. An increase on

the magnitude of the free propagating light wave vector

can be achieved by passing the incident light through a
medium, such as glass, allowing some of the incident light
to excite the surface plasmon (see figure 1). This coupling
scheme is known as attenuated total internal reflection
and involves tunneling of the fields of the excitation beam
to the interface where surface plasmon excitation takes
place [3]. Since this kind of surface plasma waves consist
only of evanescent waves, they dont emit light, hence are
called non-radiative surface plasma waves [4].
This report is organized as follows: first the underlying
theory of surface plasmon resonance effect is reviewed.
After the possible schemes of optical excitation of the
surface plasmons are commented and using the S-matrix
formulation the reflectivity is calculated. Last, experimental observation of Surface Plasmon is presented discussing
the sample preparation, the experimental set-up and experimental results.

THEORY

A Surface Plasmon (SP) is a surface-bound electromagnetic wave that propagates along the interface of a metal
and a dielectric. SP are charge density fluctuations (see
fig. 2) in the free electron gas (plasma), meaning that
SP excitation is only achieved in metals well described
by the free electron gas model. The resonance width of
thin silver films is smaller than for gold leading to higher
sensitivity but the inertness and ease of functionalization
of gold makes it the most aplicable metal.
Electromagnetic waves propagating in media are described by Maxwells equations. These equations can
be combined to yield wave equations for B and E with
plane waves as solution. The wave equation imposes a
constraint (known as the dispersion relation) between the
magnitude of the wave vector k and the frequency . For
example, for waves propagating in vacuum
k2 =

FIG. 1.

2
 .
c2

(2)

In nonmagnetic materials the permeability = 1; in

a dielectric material, such as glass, the permittivity 
usually varies with the frequency .
In a more complicated situation, such as a plane bound-

2
(light). Since this plasma waves dont propagate in vacuum they are called non-radiative. However, if light pass
by a medium, such as glass, the magnitude of the wave
vector is increased and the dispersion curves (light and
plasmon curves) will intersect. Experimentally a prism
is used to couple light and plasmons. The wave-vector
component of the incident light parallel to the boundary
is matched to the surface plasmon wave vector by changing the incidence angle i relative to the normal of the
glass/metal-film interface (see figure 3) by means of

FIG. 2.

ary between a region (z > 0) with dielectric constant 1

real and positive and a region (z < 0) with dielectric
constant 2 that can be complex (as depicted in figure 2),
there are a set of solutions called surface waves which
exist at the boundary between medium 1 and 2 propagating along the surface z = 0. In this case the constraint
from the dispersion relation is
kz2 = 

2
kx2 .
c2

(3)

Notice that kz must be real, meaning that kz itself is

either real, implying wave propagation in the z direction,
or is imaginary, implying an exponential decay of the field
in the z direction. From the boundary conditions the next
condition must be fulfilled
p
p
1 kx2 2 2 /c2 = 2 kx2 1 2 /c2 .
(4)
Only if 2 < 0 the condition above can be fulfilled. Solving
for , the dispersion relation for surface waves:


1
1
2
2
= (ckx )
+
.
(5)
1
2

kglass sin i = kplasmon .

(8)

When the critical angle for plasmon excitation is achieved

then energy of the beam is taken by the plasmon and a
deep in the reflectivity is seen.
Fresnels theory relates the amplitude of the surface
plasmon with the amplitude of the incident radiation
using the electromagnetic boundary conditions at the
interfaces [? ]. However, the S-matrix method uses the
fact that there are only boundary conditions at those
interfaces and the wave propagation can be derived as a
simple matrix operation if the incident field is known [?
]. In fact, on biosensing applications there are more than
three media involved modifying the plasmon resonance
and solving analytically Maxwells equations becomes a
tedious task; on the other hand, S-matrix formulation can
be employed to solve for an arbitrary number of layers [?
].
Consider a stack of N + 1 smooth and perfectly parallel
layers with varying thicknesses dj , and complex refractive index nj . The incident layer and the last layer are
considered as non-absorbing. The relation between the

The above equation implies that 2 < 0 and |2 | > |1 |.
If the interface is formed by air 1 1 and a metal well
described by the free electron model
2 () = 1

 2
p

(6)

where p is the plasma frequency, the dispersion relation

for surface waves between a metal and air is


1
2 = (ckx )2 1 +
.
(7)
1 (p /)2
With all of the above one can notice that for all values
of kx > 0 the dispersion curve for surface plasmons propagating the metal-air boundary lies to the right of the
dispersion curve for electromagnetic waves in air, = ckx
(see fig. 1). Because the dispersion curve for propagation
in vacuum does not intersect the disperson curve for surface plasmons, it is not possible to match the frequency
and wave vector of the surface plasmons to the frequency
and wave vector of incident electromagnetic radiation

FIG. 3.
Prism coupling and surface plasmon dispersion
relation. Figure taken from [3].

3
2.2 Stratified medium matrix model

electric field vectors at two points z1 and z2 is given by

 +

 +

E (z1 )
E (z2 )
=M
(9)
E (z1 )
E (z2 )
where M denotes the scattering matrix. When the points
are located within the same layer the relation can be
written as
 +

 +

E (z1 )
E (z2 )
= Lj
(10)
E (z1 )
E (z2 )
wherein Lj is the layer matrix of j-th layer, given by
 i

e j
0
Lj =
,
(11)
0
eij

15

Incident light

Reflected light
E||

E
x
y

0th layer, (; n0)

1st layer, (d1; n1+ik1)

2nd layer, (d2; n2+ik2)

jth layer, (dj; nj+ikj)

Nth layer, (; nN)

Figure 2.3: Layer stack in the stratified medium model. The 0th and Nth layers are
semi-infinite
and have
real refractive
indices.
Thesurface
incident wave
is p- (TM,
k) or s- (TE,
FIG. 4.
Prism
coupling
and
plasmon
dispersion
?) polarized.
TheFigure
planes show
the from
interfaces,
relation.
taken
[3].Iij .

describing the phase shift undergone upon propagation.

p, T M or k) or perpendicular- (denoted s , T E or ?) polarized. The Cartesian
The phase shift is given by
matrix
elements
coordinate
system
in Figure 2.3 defines the z-direction as parallel to the plane of
6/16/2014 2:43:39 PM
incidence
with the
positive direction into theSample:
layer stack.
Project:
2014-06-16
Au Electric fields will be su2dj
Au
M21
1
j =
nj cos j
(12) perscripted
+ for
positive and
- for negative z-direction
to refracted
Owner:
INCA
Type: Default
r=
,
= corresponding
.
(19)

Site: Site
of Interest
1M11 For our purposes
ID:
and reflected
waves
respectively.
it is M
convenient
(although not
11
where nj is the complex refractive index of the layer, dj necessary) to consider all layers isotropic, hence all fields are independent of x or
y. Just as before, it is assumed that the permeability = 0 for all layers.
Spectrum processing :
is the layer thickness and j is the incidence angle. If the
No peaks omitted
two points are located within two adjacent layers then
EXPERIMENTAL SURFACE PLASMON
Derivation
Processing option : All elements analyzed (Normalised)
 +

 +

RESONANCE
Number of iterations = 3
E (z1 )
E (z2 )
Since there is no dependence on x or y, we have for the total electric field amplitude
=
I
(13)
ij
E (z1 )
E (z2 )
Standard :
at a certain distance along the z-axis:
Sample preparationTwo gold samples (10 nm and
C CaCO3 1-Jun-1999 12:00 AM
O SiO2 1-Jun-1999 12:00 AM
100
nm) were prepared
using
the
sputtering technique.
Etot
E+
(2.25)
where
the
interface
matrix
I
is
given
by
z =
z +E
z
ij
Na Albite 1-Jun-1999 12:00 AM
The
main
purpose
of
using
two
samples
is
to
observe
the
Mg MgO 1-Jun-1999 12:00 AM


Where the subscript indicates the z-dependence. Eqn. 2.25 holds for both TM1 1 rij
Al Al2O3 1-Jun-1999 12:00 AM
influence of the thickness and oxidation in the surface
I
=
(14) polarized and TE-polarized light respectively. For the relation between the electric
ij
Si SiO2 1-Jun-1999 12:00 AM
r
1
resonance.
Figure
shows the 10 nm gold sample

ij
ij
field plasmon
vectors at two
points, z1 and
z2 we5have:
K MAD-10 Feldspar 1-Jun-1999 12:00 AM
spectra taken
using
a
Scanning
Electron
Microscope. It
Ca Wollastonite 1-Jun-1999 12:00 AM
+

+
+
Au Au 1-Jun-1999
AM rij the transmission and reflection Fresnel
with ij12:00
and
M11 peaks,
M12
Ez other peaks
Ez come from
z
is easy to Esee
the
Au
all
=
=M
(2.26)
Ez
M21 M22
Ez
Ez
coefficients
the substrate
(glass).
Element
App
Intensity
Weight%
Weight%
Atomic%
Conc.
Corrn.
Sigma
SimulationUsing
S-matrix
formalism described in
From
the German word senkrecht,the
meaning
orthogonal.
nj cos
n17.03
i cos j
CK
0.62
0.2795 r 9.15
3.97 i
,
(15)
ij =
Sec.
the
Surface
Plasmon
Resonance
curve is calculated
OK
4.89
0.6382
31.81 nj cos
1.89i + n44.44
i cos j
within the model presented in fig. 6. The reflectance is
Na K
1.62
0.9650
6.94
0.53
6.74
2ni cos
i
Mg K
0.33
0.7749
1.76
0.26
1.62
ij0.78=
.
(16)
Al K
0.16
0.8651
0.20
0.64
n
cos

+
n
cos j
j
i
i
Si K
7.04
0.9435
30.80
1.58
24.51
KK
Ca K
Au M
Totals

0.23

0.9494

0.99

0.20

0.56

In1.22
the general
z1 and 3.05
z2 are separate within
0.9208 case
5.47 where
0.42
1.91
0.6430 layers
12.29
1.32
1.39
non-adjacent
100.00

 +

E+ (z1 )
E (z2 )
=M
(17)
E (z1 )
E (z2 )
where

M=

N
1
Y

Comment:

j=1

I(j1)j Lj I(N 1)N .

(18)

With all of the above, the reflection r = E (0)/E+ (0)

and transmission = E+ (N )/E+ (0) coefficients of the
layer stack can be expressed in terms of the scattering
FIG. 5.

18

RR0
1.0

Total internal reflection

0.8

dgold = 100 nm
0.6

Critical Angle
0.4

dgold = 10 nm

Plasmon Resonance

0.2

0.0
0.0

0.2

0.4

1.0

aHradL

[1] H. J. Simon, D. E. Mitchell, and J. G. Watson, American

Journal of Physics 43 (1975).
[2] C. Rhodes, S. Franzen, J.-P. Maria, M. Losego, D. N.
Leonard, B. Laughlin, G. Duscher, and S. Weibel, Journal
of Applied Physics 100, 054905 (2006).

1000

0.6
0.7
0.7
0.7
0.8

800

0.8
0.7
0.9
0.7

(nm)

600

0.6
0.4
400

0.8
0.1
0.5
0.2
0.3
0.8

Prism

Glass prism
dair = 300
nmfilm
Airelectron
Free
metal
Adsorbate
layer
Gold
Ambient
Glass

1
= 0.467 + 2.415i 2
3
= 1.5

nglass

0.1

however, dierent for dierent states of polarization.

k

rij =

n
j cos
n
j cos

n
i cos

ni cos j
i +

0.7

Figure 2.4: Four layer model of an SPR biosensor. In the most simple case an SPR
sensor can be modeled as a four
layer 6.
stratified medium where the constituents are a glass
FIG.
prism, coated with a thin metal film, to which the organic sensing layer is adsorbed. The
semi-infinite ambient layer is typically aqueous buer.

2.41 are,

1.4

optimization programs and along with simulations, the

dielectric constant of materials and layer thickness can
be measured.
AcknowledgementsI specially acknowledge Juan

Serna from Grupo de Optica

y Fotonica for advising
the present project, for his patience and interesting dis
cussion. I also thanks Grupo de Optica
y Fotonica for
allowing me to use their working space and equipment.

200

nair = 1

sion coefficients, Eqn.

1.2

FIG. 7.

ngold

0.8

Surface plasmon resonance

= 633 nm
nprism = 1.52

0.6

dair

given by


 r01 (1 + r12 r23 e2i2 ) + e2i1 (r12 + r23 e2i2 ) 2

R = 
1 + r01 e2i1 (r12 + r23 e2i2 ) + r12 r23 e2i2 
(20)
where j is given by equation 12 and rij , ij are the
reflection and transmission coefficients.
The results are plotted in figure 7 showing that gold
film thickness modify strongly the plasmon resonance
angle and deep. In fact, we supposed a 300 nm thick
air layer but due to experimental limitations it cannot
be controlled. Figure 8 shows how plasmon resonance
angle is modified and suppressed as a function of the air
layer thickness. An optimal gold and air layer thickness
should be found in order to improve the experimental
measurement of the plasmon resonance.
Set-upFor the experimental realization a = 633
laser were used. A pupil and filters clean-up the laser
spot for measurement and a polarizer ensures the correct
polarization to excite the plasmon. A lock-in with a light
chopper clean up the signal of any undesired noise. The
prism and the sensor were mounted in a rotary stage to
vary the light incidence angle. The experimental set-up
is shown in figure 9.
ResultsThe results obtained for a 10 nm gold film
along with the simulation (supposing a 800 nm thick air
layer) are shown in figure 10. It may seems that the
simulation and the experimental measurement coincides
but this is not a complete proof of the experimental
excitation of the plasmon.
For a 100 nm film a detailed measurement were not
performed, but the angle of total internal reflection were
found and a interesting behavior appears around the total
internal reflection angle (figure 11). Results are shown
along the simulation supposing again a 800 nm thick air
layer.
DiscussionAlthough non-trivial effects due to the
presence of the gold film are evident it is not yet stablished
if they really correspond to surface plasmon resonance.
One of the main problems of our experiment is the distance
between the prism and the gold film (the thickness of the
air layer), since we were not able to control it we are
not sure if the measure was perform within the regime of
existence of plasmon resonances (see fig. 8).
PerspectivesIf the experimental technique is improved
then a characterization device can be built so, using

0.0

0.5

1.0
a

FIG. 8.

(rad)

1.5

5
Film
Prism and
rotary stage
Polarizer
Light
chopper

Sensor and
rotary stage

[3] S. A. Maier, Plasmonics: Fundamentals and Applications

(SpringerScience+BusinessMedia, New York, 2007).
[4] A. Otto, Zeitschrift fur Physik 216, 398 (1968).

Filters
Pupil
Aligning
mirrors
FIG. 9.
Intensity
1.6"
(a.u.)

2.5"
Intensity
(a.u.)
2.45"

1.4"

2.4"

1.2"
2.35"

1"

2.3"
RR0
1.0

2.25"

RR0
1.0

0.8"

0.8

2.2"

0.8

0.6"
0.6

0.6

2.15"

d = 800 nm

0.4

0.4"

0.4

2.1"
0.2

2.05"

0.2

0.2"

10 nm film

2"
320"

322"

324"

0.0
0.0

326"

328"

Data
1
Serie1"

0.2

330"

Data
2
Serie2"

FIG. 10.

0.4

332"

Data
Serie3" 3

0.6

0.8

334"

Average
Serie4"

1.0

1.2

336"

1.4

338"

aHradL

340"
Degrees

0.0
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

100 nm film

aHradL

0"
45"

47"

49"

51"

53"

55"

Serie1"
Data 1

Serie2" 2
Data

FIG. 11.

57"
Serie3"
Average

59"

61"

63"

Degrees65"