Surface Plasmon Resonance (SPR) Theory: Tutorial

Masahiro Yamamoto
Department of Energy and Hydrocarbon Chemistry, Kyoto University,
Kyoto-Daigaku-Katsura, Nishikyo-ku, 615-8510, JAPAN
This manuscript is modied on October 20, 2008 8 : 22 am

Introduction

In the surface plasmon resonance (SPR) measurement we can detect the change of
the lm thickness (refractive index change) in the sub-nonometer scale using a low-cost
home-made appratus (He-Ne laser, rotating stage, photo-diode detector, prism, maching
oil, and 50 nm gold lm on a glass plate, See Appendix). 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 lm (usually 50 nm gold
lm is used)| sample system, the reectivity 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
lm thickness (refractivity) of the sample. In the usual automated SPR measurementanalysis routine one can get the SPR angle shift and the the change of the lm 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 reection, 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. 2
This note is written for my self-study of SPR principle in order to analyze the SPR
curves, 3 . ,later was publish in Review of Polarography, 48, No3. 2002, 209 , and
posted the revised version at http://www.scl.kyoto-u.ac.jp/ masahiro/sprtheory.html.
(I am very happy that many people give me contacts and some comments.)
In this note on SPR theory I also describe the basics of the light reection, transmission, absorption at the surface of dielectrics or metal, then it is my pleasure that

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.
2
There are a lot of review or papers which describe the SPR principle, but almost all of them did
not describe the formulation and start from the equation of the SPR resonance condition. I want to
formulate the equation from scratch.
3
Tell me, and I forget. Teach me, and I may remember. Involve me , and I learn. Benjamin Franklin

those who are doing the photon-in/photon-out electrochemistry with the interface spectroscopy with evanescent wave, ellipsometry, nonlinear spectroscopy, have an interest in
this note.
The SPR(surface plasmon resonance)[1] is the century-old technique from the nding
of the Woods anomaly for the reected light from the diraction gratings[2]. After
Ottos demonstration[3] for the surface plasmon excitation by light with attenuatedtotal-reection(ATR) coupler[4], the SPR method applied to the organic lms[5] or the
detection of antigen-antibody reaction[6]. The SPR theory is also well established[7],
and the recent advance in the measurements can be reported in the reviews[8, 9, 10].
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[11, 12], where the capacitance can be
measured simultaneously and get the complementary information of the change in the
dielectric properties on the electrode surface.
In this note Theoretical Electromagnetics(Japanese, Kinokuniya, 1973) by S. Sunagawa, Principles of Optics (7th expanded edition) (Cambridge Univ. Press, 1999) by
M. Born and E. Wolf[13], and Optics(4th edition) (Addison Wesley, 2002) by E.
Hecht[14] are used for reference.

Maxwell Equation

The Maxwell equations are described

divD =

(1)

divB = 0

(2)

B
t
D
rotH = J +
t
rotE =

(3)
(4)

Here we use MKSA-SI unit. The electric eld E (Vm1 ) and magnetic eld H (Am1 )
are related to the electric displacement (or dielectric ux density or electric ux density)
D (Cm2 ) and magnetic-ux density (or magnetic induction) B (T:tesla = NA1 m1 )
D = 0 E

(5)

B = 0 H

(6)

The Maxwell equations have the beautiful mathematical form. We learned the physical meaning
of the equations in high school physics course and are mathematically extended to the 3-dimensional
case (or 4 dimension when time is included.) by vector analysis. divV V means the dierence
between the input of the vector eld V(r) to the innitesimal volume dr and the output from there,
and is called as divergence. In the vector analysis the meaning of rot is hard to understand, but
S. Naganuma gave us a method to understand the meaning of rotation in his book (Intuitive method
for phycal mathematics(Japanese) ) [The rotational velocity of the innitesimal water wheel in water
ow eld u. (The water ow of the right side of the wheel in the upper direction uy is faster than the
left side (uy /x > 0), the wheel rotates in the anticlockwise direction. In the same the water ow of
the upper side of the wheel in the right direction ux is slower than the lower side (ux /y < 0) the
wheel rotates in the anticlockwise direction. (rotu)z = uy /x ux /y) ] The Maxwell equations
say, roughly speaking, Eq.(1): The number of the electric ux line coming(entering) from the positive
(negative) charge is proportion to the amount of the charge. Eq.(2): magnet has always S and N pole.
Eq.(3): When a magnet approachs the coil, the inductive current is passed to reduce the magnetic
eld from the magnet. Eq.(4): A current generates the rotating magnetic eld in the direction of the
right-handed screw.

Here and 0 are the dielectric constant (with no dimension) and electric permittivity
of free space [8.854187817 1012 Fm1 (= CV1 m1 )], respectively. and 0 are
magnetic permeability (with no dimension) and magnetic permeability of free space
(4 107 NA2 ), respectively. We will assume the Ohms law for the relation between
the current J and the electric eld E
J = E

2.1

(7)

Energy Conservation and Poynting Vector

5

The equation of motion of point charges is

Z

mi ri =
P

If we apply (
X

i vi )

dr {ei (r ri (t))E + ei (r ri (t))ri B}

from the left, and the velocity is dened as vi = ri

XZ

mi vi v i =

dr ei (r ri (t))vi E + ei (r ri (t)) vi [vi B]

XZ

{z

=0

drei (r ri (t))vi E

(8)

From the denition of the current and the Eq.(4).

J =

ei r i (t)(r ri (t))

(9)

= rotH
Then

X d 1
i

dt

mi vi2

D
t

(10)

dr rotH

D
t

(11)

D
B
1
(E D + B H) = E
+H
2 t
t
t
D
= E
H rotE
t
!

Z
1
d X1
=
dr
mi vi2
(E D + B H)
dt
2
2 t
i

H
rotE{z+ E rotH}
|
=div(EH)

d
X 1
mi vi2 +

dt
2
i
|

{z

kinetic energy

1
2
|

dr(E D + B H)
{z

total energy of electromagnetic eld

dS

[E H]
| {z }

n (12)

Poynting vector

From above equations the Poynting vector S[= E H] means the energy ux going out
from the system.
5
The point charge, which is given by delta function, feel the Lorentz force from the electromagnetic
eld.

2.2

Wave Equations

From Eqs.(3) and (6)

rotE = 0

H
t

(13)

From Eqs.(4), (5), and (7)

E
t
If we apply to Eq.(13) and /t to Eq.(14) and using the relation
rotH = E + 0

E = rot x

Ex
"

Ez

Ey

Ez
y

(14)

Ey
z

Ex
z

Ez
x

Ey
x

Ex
y

2 Ey
2 Ex 2 Ez
2 Ez

+
+ j[..] + k[..]
2
2
xy
y
z
xz

Ex Ey
Ez

= i
+
+
+ j divE + k divE
x x
y
z
y
z
2
2
2
i Ex j Ey k Ez
= i

= grad(divE) 2 E

(15)

If we assume = 0, divE = 0 then

2 E = 0

2E
E
+ 0 0 2
t
t

(16)

2 H = 0

H
2H
+ 0 0 2
t
t

(17)

In the same way we can get

In the case that the electric eld has a plane wave form
E = E0 ei(krt)

(18)

where E0 is the polarization vector and the wavevector k is in the direction of the wave
propagation and the magnitude is given from Eq.(16)
k 2 = i0 + 0 0 2

(19)

In vacuum, = 1, = 1, = 0 and c/ = , c/ = /(2), k = 2/ = /c then

c = 1/ 0 0

(20)

The complex optical index n

may be given by
k=

2
= =

v
c

n
2 = k 2 c2 / 2 = + i
n
= n + i,

(21)

k=n
/c = (n + i)/c

(22)
(23)

where n and are the real and imaginary part of the complex optical index, respectively.
E(z, t) = E0 ei(kzt) = E0 ez/c ei(nz/ct)

2 2z/c

I(z) E E = |E0 | e

= I0 e

(24)

(Lambert s Law)

= 2/c
2

(25)

= = 1 + i2

1 = n ,
2

[ = 1, = 0 in Eq.(22)]

2 = 2n

(26)
(27)

Here is the absorption coecient, is the complex dielectric constant, 1 and 2 are
the real and imaginary part of the complex dielectric constant, respectively.
If we take divergence of the plane-wave electric led,

+i
+i
(E0x i + E0y j + E0z k)ei(kx x+ky y+kz zt)
x
y
z
= i(kx E0x + ky E0y + kz E0z ) = ik E0

=
=0
0

divE =

(28)
(29)
(30)

Then we can nd that the electric eld is transverse wave, i.e. k E0 .

If the magnetic-ux density B is written as
B=

k E0 i(krt)
e
,

(31)

then the magnetic-ux density satises Eq.(3), because

Ez
Ey

) + ..
y
z
= i(iky Ez ikz Ey ) + ..

rotE = i(

In vacuum

2.3

B
t

= ik E
k E0
=
(i)ei(krt)

= ik E

|E0 |
0
0
=
=
=
|H0 |
k
0 0

0
= 376.7
0

(32)
(33)
(34)
(35)
(36)

(37)

Boundary Conditions at a Interface Between Dierent Media

Now we think a interface which is at the boundary medium 1 and 2 as shown in Fig.1.
From Gauss law, we can get the following for the Gauss box which include the interface
inside the box,
Z
Z
V

dr
D} =
| {z

D dS

(38)

In the limit that the Gauss box is very thin (h 0)

Z
V

dr = Qbox = n [D1 D2 ]S

(39)

where vector n means the surface normal unit vector pointing from media 2 to 1.
n [D1 D2 ] = Qbox /S = 12
5

(40)

where 12 means the interface charge density. From B = 0

n [B1 B2 ] = 0
I

(41)

As shown in Fig. 2 for a general vector eld V(r), Stokes theorem gives
V dr = (I) + (II) + (III) + (IV)
= Vx (x0 , y0 )dx + Vy (x0 + dx, y0 )dy + Vx (x0 , y0 + dy)(dx) + Vy (x0 , y0 )(dy)
Vy
= Vx (x0 , y0 )dx + [Vy (x0 , y0 ) +
dx]dy
x
Vx
[Vx (x0 , y0 ) +
dy]dx Vy (x0 , y0 )dy
y

Vy
Vx
=

dxdy = (rotV)z dxdy

x
y

medium 1
n

t1

medium 2

t2

Figure 1: Gauss and Stokes box

y
(x0, y0+dy)

(III)

(x0+dx, y0+dy)

(IV)

(II)
(I)

(x0, y0)

(x0+dx, y0)
x

Figure 2: Stokes theorem

From Eq.(3) and Stokes theorem we can get
I

E dr =

rotE dS

B
bdS
S t
B
r[E1 t1 + E2 t2 ] =
brh 0
t
t = t1 = t2
=

t [E1 E2 ] = 0
6

(42)
(43)
(44)
(45)
(46)

Here b is the unit vector dened by b = n t. From Eq.(4)

I
C

H dr =

Z
S

rotH dS

(47)

D
bdS
t
S

D
r[H1 t1 + H2 t2 ] =
J+
brh J brh
t
t [H1 H2 ] = Js [ surface current density(Am1 )]
=

J+

(48)
(49)
(50)

Reection and Transmission

Now we dene the incident plane wave as

E = E0 ei(krt) ,

= (k),

B=

k E0 i(krt)
e

(51)

reected wave as

E = R0 ei(k r t) ,

= (k ),

B =

k R0 i(k r t)
e

(52)

transmitted wave as
E = T0 ei(k

r t)

= (k ),

B =

k T0 i(k r t)
e

Ep
Rp

Es

medium 1

Rs

x
medium 2

Tp

Ts
k

Figure 3: Reection and Transmission of Light

(53)

From Fig.3
k = (k sin , 0, k cos )

(54)

= (k sin , 0, k cos ),

i( )

= cos + i sin

(55)

= (k sin , 0, k cos )

(56)

The p-wave has the components of x and z, but s-wave has only the y component.

3.1

t [E1 E2 ] = 0

Condition I:

From Eq.(46) the tangential component of the electric eld become

Ep cos e

i(k sin xt)

i(k

+ Rp cos e

Ex + Ex = Ex

sin x t)

at z = 0

(57)

i(k sin x t)

= Tp cos e

(58)

For any x at z = 0 this condition should be satised, then

= =

(59)

(60)

because k = k

(61)

k sin = k sin = k sin

The magnitude of the wavevector is given by Eq.(21)
sin = sin = sin( ),

The incident angle equals to the reection angle, and

k sin = n
1

sin = k sin = n
2
sin
c
c

(62)

Then we can get Snells law because =

The Eq.(58) becomes

n
1 sin = n
2 sin

(63)

(Ep Rp ) cos = Tp cos

(64)

From Fig.3 we can get

Ep cos
Rp cos
Tp cos

Es
Rs
Ts
E0 =
, R0 =
, T0 =

Ep sin
Rp sin
Tp sin

(65)

For y-direction we can get the condition

Ey + Ey = Ey

at z = 0
i(k

(Es + Rs )ei(k sin xt) = Ts e

(Es + Rs ) = Ts
6

sin xt)

(66)
(67)
(68)

Light (electromagnetic) wave is the transverse wave and has the two polarization components. (If
you look at the the digital watch(almost linear polarized light!?) through the polarized sunglasses, you
can see the bright and dark light at every 90 degree if you rotate the watch.) s-wave (s polarized
light) is the component parallel to the reection plane, and p-wave (p polarized light) is the component
perpendicular to the paper plane. Because the electric component is perpendicular to the paper plane,
s-wave is called as TE (transverse electric) wave. Because the magnetic component is perpendicular to
the paper plane, p-wave is called as TM wave.

3.2

n (B1 B2 ) = 0

Condition II:

For the boundary condition in Eq.(41)

k E0

= k sin

Ep cos

j
k
0
k cos
Es Ep sin

= k[iEs cos + j(Ep cos2 + Ep sin2 ) + kEs sin ]

B = k E0 =

k R0

kEs cos

kEp

kEs sin

= k sin

Rp cos

(70)

j
k
0
k cos
Rs Rp sin

= k[iRs cos + j(Rp cos2 + Rp sin2 ) + kRs sin ]

B = k R0 =

k T0

kRs cos

kRp

kRs sin

= k sin

Tp cos

B = k T0

(71)
(72)

j
k
0 k cos
Ts Tp sin

= k [iTs cos + j(Tp cos2 + Tp sin2 ) + kTs sin ]

(69)

k Ts cos

k Tp

k Ts sin

(73)
(74)

The boundary condition Bz + Bz = Bz becomes

k sin
k sin

(Es + Rs )ei(k sin xt) =

Ts ei(k sin xt)

n1 (Es + Rs ) sin = n2 Ts sin

(75)
(76)

Es + Rs = Ts

(77)

We used Snells law in the last equation. This equation is the same as Eq.(68).

3.3

n (D1 D2 )

Condition III:

For the boundary condition in Eq.(40)

1 0 (Ez + Ez ) = 2 0 Ez + 12
1 0 (Ep sin Rp sin )e

i(k sin xt)

(78)

i(k sin xt)

= 2 0 (Tp sin )e
Z

12 (r, t) = (z)

dk

+ 12 (r, t)

d12 (k, )ei(kxt) (79)

In Eq.(79)
we used the Fourier transformed charge
density 12 (k, ). If we apply
RR
RR
x t)

2
i(k
2
(1/2)
dxdte
, then we use (1/4 )
dxdtei(k sin xk x) ei( )t = (k sin

k )( ) and the above equations are held at z = 0

1 0 (Ep sin Rp sin )(k sin k )( ) = 2 0 Tp sin (k sin k )

( ) +

Z Z

dk d 12 (k , )(k k )( ) (80)

12 (k sin , )
0
From Snell s law
12 (k sin , )
n1 (Ep + Rp ) = n2 Tp +
0 n1 sin

n1 2 (Ep + Rp ) sin = n2 2 Tp sin +

(81)
(82)
(83)

Here we can neglect the 12 (k sin , ) term 7 .

Condition IV: t [H1 H2 ] = Js

3.4

Hx + Hx = Hx + (Js )x
Hy +

Hy

Hy

+ (Js )y

Bx = 0 Hx , ......
Z Z

3.5

dkd[Js (k, )]x ei(kxt) , ..

[Js (r, t)]x =

kEs cos kRs cos i(k sin xt)

+
e
1 0
1 0
n1 cos
(Es Rs )
1

kRp
kEp
+
ei(k sin xt)
1 0 1 0
n1
(Ep + Rp )
1

(84)
(85)
(86)
(87)

k Ts cos i(k sin t)

e
+ [Js (r, t)]x
2 0
n2 cos
Ts + c0 [Js (k sin , )]x
(88)
2
k Tp i(k sin xt)
e
+ [Js (r, t)]y
(89)
2 0
n2
Tp + c0 [Js (k sin , )]y
(90)
2

=
=
=
=

Reection and Transmission Coecients

In the end we can obtain the following equation for p-wave

(Ep Rp ) cos = Tp cos
12 (k sin , )
n1 (Ep + Rp ) = n2 Tp +
0 n1 sin
n1
n2
(Ep + Rp ) =
Tp + c0 [Js (k sin , )]y
1
2

(91)

Es + Rs = Ts
n1 cos
n2 cos
(Es Rs ) =
Ts + c0 [Js (k sin , )]x
1
2

(94)

(92)
(93)

and for s-wave

(95)

7
Laser light(10 mW He-Ne, focused to 20 m, 1026 photons/s/m2 = I/(
h) I = c0 E02 /2 (J/m2 /s
= W/m2 ) c=299792458 m, E0 = 1.5 105 V/m ) Bright sunlight (average 480nm, 1018 photons/s/m2
E0 = 18V/m.) For electrochemical systems 12 (k sin
= 0, = 0) is the order of 10 C/cm2 = 0.1
2
C/m (fully dissociated 3-mercaptopropionic acid in the 3 3 structure on Au(111) surface = 0.74
C/m2 ). 12 /0 = (1 8) 1010 V/m. However, the surface charge at the electrode in the = 0 limit do
not couple to the photon eld at = photon .

10

3.5.1

Usual Solution: No Absorption in the Media 1 and 2.

Here we assume that 12 (k sin , ) = 0, Im(

n1,2 ) = 0 (later we will consider the case
that the optical constant is complex, i.e. the medium absorb the light.), 1 = 2 =
1, [Js (k sin , )]x = 0, [Js (k sin , )]y = 0. Then for p-wave we can get
(Ep Rp ) cos = Tp cos

(96)

n1 (Ep + Rp ) = n2 Tp

(97)

and for s-wave

Es + Rs = Ts

(98)

n1 cos (Es + Rs ) = n2 cos Ts

(99)

If we dene the amplitude reection coecient r and the amplitude transmission

coecient for s- and p-waves,
rp
tp
rs
ts

Rp
Ep
Tp
Ep
Rs
Es
Ts
Es

(100)
(101)
(102)
(103)

(1 rp ) cos = tp cos

(104)

n1 (1 + rp ) = n2 tp

(105)
(106)

and for s-wave

1 + rs = t s

(107)

n1 cos (1 rs ) = n2 cos ts

(108)

We nally get the Fresnel() equations

rp =
tp =
rs =
ts =

n1 cos + n2 cos
n1 cos + n2 cos
2n1 cos
n1 cos + n2 cos
n1 cos n2 cos
n1 cos + n2 cos
2n1 cos
n1 cos + n2 cos

(109)
(110)
(111)
(112)

The reectance R is dened as the ratio of the reected power (or ux)
to the incident power of the light
R=

I A cos
I
n1 R2 /(2c0 )
=
=
= r2
IA cos
I
n1 E 2 /(2c0 )
11

(113)

sin(/2 )

cos
A
S
S cos

Figure 4: Angle dependency of the intensity of light

The radiant ux density I (W/m2 ) is given by the averaged Poynting vector < EH >=
n
E 2 /(2c0 ). In the same way the transmittance T may be given by
T =

I A cos
vt t T 2 cos
n2 cos 2
=
=
t
IA cos
vi i E 2 cos
n1 cos

(114)

In Fig.4 and Fig.5 the r, t, R, and T are plotted for the air(1)|water(2) [airwater]
and water(1)|air(2) [waterair] interface, respectively. 8 In the both cases ts and tp are
always positive, and this means the phase shifts of transmitted wave are always zero.
For the case of air(1)|water(2) [airwater] rs is always negative and rp is positive for
< p,airwater and become negative for > p,airwater . These means that the phase
shift is for reected s wave and phase shift become 0 to at p,airwater . For the case of
water(1)|air(2) [waterair] rs is always positive and rp is negative for < p,waterair
and become positive for > p,waterair . These means that the phase shift is 0 for
reected s wave and phase shift become to 0 at p,waterair . In Appnedix the plot of
the phase shift of the reected s and p waves are shown. We also shown the condition
of the black lm formation in Appendix.
3.5.2

Brewster angle

In Figs.4 and 5, we can nd the point rp = Rp = 0

and this condition is given by

n1 cos + n2 cos = n1 cos

(cos sin cos sin ) =

sin
cos = 0
sin

(115)

ei + ei ei ei
ei + ei ei ei

2
2i
2
2i

8
From Fig.5 (right), intensity of the s-component of the reected wave from the water surface is
greater than the p-wave for all the reected angles. Then the polarized sunglass should has better
performance if the s-wave component is not transmitted. The s-wave has the electric eld vector in the
horizontal direction. Then, the polarized sunglass passes the light with the electric eld vector with the
vertical direction. If you try to see the light reected from the sea surface through the polarized sun
glass, the intensity of light is lowest and if you rotate the sunglass (or head if you like) 90 degree the
reected light becomes the strongest. And when you see the LCD(liquid crystal display) and the watch
with liquid crystal through the polarized sunglass, the display becomes totally black if you rotate the
glass to 45 degree in the clockwise direction. I think the displayed is designed we can see it even if you
wear the polarized sunglass.
For the reection from water to air interface as shown in Fig.6, total reection of light R = 1, T = 0
is observed from the angle 48.66 degree.
9
In the laser resonator silica plate is set at the Brewster angle, and the p-wave is transmitted but
s-wave is reected and decayed in the resonator.

12

Air(n1=1)|Water(n2=1.332) Interface :He-Ne Laser

Air(n1 =1)|Water(n2 =1.332) Interface: He-Ne Laser

1
0.8

0.6
0.4
0.2
0

0.8

tp

rp

-0.2
-0.4

0.6

R or T

ts

Tp

Ts

0.4

rs

-0.6
-0.8

0.2

-1

Rs

Rp

0
0

10

20

30
40
50
60
incident angle (degree)

70

80

90

10

20

30
40
50
60
70
incident angle (degree)

80

90

Figure 5: Reection and transmission of He-Ne laser light at air|water interface

Water(n1=1.332)|Air(n2=1) Interface :He-Ne Laser

Water(n1 =1.332)|Air(n2 =1) Interface: He-Ne Laser

2.5

Ts

Tp

Rs

Rp

0.8

2
ts

1
0.5

0.6

R or T

tp

1.5

0.4

rs

0.2

rp

0
-0.5

0
0

10

15 20 25 30 35
incident angle (degree)

40

45

50

10

15 20 25 30 35
incident angle (degree)

40

45

50

Figure 6: Reection and transmission of He-Ne laser light at water|air interface

=
=

e2i e2i
e2i e2i

4i
4i
2i sin(2 ) 2i sin(2)
=0
4i

Then

2
The angle between the reected light and the transmitted light is orthogonal.
=

n2 sin = n2 sin(/2 ) = n2 cos = n1 sin

(116)

(117)

n2
(118)
n1
From air to water reection, the Brewster angle is 53.10 degree, and from water to
air the angle is 36.90 degree.
Brewster = tan1

3.6

Total Internal Reection

Now we will consider the case that the angle between the transmitted wave and the
surface normal is 90 degree, i.e., sin c = (n1 /n2 ) sin c = 1. Here
n2
c = sin1
(119)
n1
13

and should n2 < n1 . For water to air reection c = 48.66 degree. In this situation the
transmitted light is along the surface parallel direction. What happens if > c ?
q

cos =

sin2

=i

sin2

1 = i (n1 /n2 )2 sin2 1

(120)

The transmitted wave can be written as

E = T0 ei(k

r t)

(121)

i(k sin x+k cos z t)

= T0 e

i(k

= T0 e

sin x t)

n sin
i 2 c
x

= T0 e

(n1 /n2

n2

ei t e

2n2

(122)
)2

sin2

1z

(n1 /n2 )2 sin2 1

z
c

(123)
(124)

(n1 /n2 )2 sin2 1

z
c
The transmitted light intensity decays as e
. The decay length is
the order of wavelength because c/ = /2. The Poynting vector S in the z direction
in the medium 2,

z S =
=
=

1
Re(E B ) z
20
1
Re[E (k E ) ] z
20
1

Re[k |E |2 E (k
E}) z
| {z
20

(125)
(126)
(127)

=0

1
Re(
20

z
| {zk }

|E |2 )

(128)

k cos =pure imaginary

= 0

(129)

direction in the medium 2 is zero. We call this exponentialThereby the energy ux to z

decay wave as evanescent wave, and is used for some interface spectroscopies to detect
species located at the evanescent eld.
3.6.1

Phase Shift of the Total Internal Reection Wave

For the total internal reection the amplitudes of the incident wave and the reected
wave are the same but there is a phase shift between them.
rp =

a2 b2 2iab
n2 cos n1 cos
a ib
=
=
= eip
n2 cos + n1 cos
a + ib
a2 + b2

(130)

a = n2 cos , b = n1 (n1 /n2 )2 sin2 1

2ab
tan(p ) =
2
a b2
n1 cos n2 cos
c id
c2 d2 2icd
rs =
=
=
= eis
n1 cos + n2 cos
c + id
c2 + d2

(131)
(132)
(133)

c = n1 cos ,
2cd
tan(s ) = 2
c d2

d = n2 (n1 /n2 )2 sin2 1

(134)
(135)

14

phase shift / pi

0.8

rp

0.6
rs
0.4
0.2
0
45

50

55

60
65
70
75
80
incident angle (degree)

85

90

Figure 7: Phase shift of the TIR wave (He-Ne laser) from water|air interface.

3.7

Metal Surface

For the metal surface the optical index becomes complex because some part of the light
is absorbed by the electronic transition of metallic electrons at Fermi level.
n
2 = n2 + i2 , k = n
2 /c = (n2 + i2 )/c

(136)

From the condition I,

n1 sin = n
2 sin = (n2 + i2 ) sin

(137)

Now is complex, and we dene[13]

n
2 cos u2 + iv2 ,
(u2 + iv2 )2

Here u2 and v2 are real.

n2
= n
22 cos2 = n
22 (1 21 sin2 ) = n
22 n21 sin2
n
2

(138)
(139)

For the real and imaginary parts of Eq.(139)

u22 v22 = n22 22 n21 sin 2
2u2 v2 = 2n2 2

(140)
(141)

Then we can get

u22 =
v22 =

n22 22 n21 sin2 +

(n22 22 n21 sin2 )2 + 4n22 k22

(n22 22 n21 sin2 ) +

q2

(n22 22 n21 sin2 )2 + 4n22 k22

2

(142)
(143)

For p wave,
n
2 cos n1 cos
n
22 cos n1 n
2 cos
=
n
2 cos + n1 cos
n
22 cos + n1 n
2 cos
(n22 22 + 2in2 2 ) cos n1 (u2 + iv2 )
(n22 22 + 2in2 2 ) cos + n1 (u2 + iv2 )

rp p eip =
=
2p

(n2 2 ) cos n u + i(2n cos n v ) 2

1 2
2 2
1 2
2
2
= 2

(n2 22 ) cos + n1 u2 + i(2n2 2 cos + n1 v2 )

15

(144)
(145)
(146)

[(n22 22 ) cos n1 u2 ]2 + (2n2 2 cos n1 v2 )2

[(n22 22 ) cos + n1 u2 ]2 + (2n2 2 cos + n1 v2 )2

(147)

tan p = {[(n22 22 ) cos + n1 u2 ](2n2 2 cos n1 v2 ) [(n22 22 ) cos n1 u2 ]

=
tp =
=
p2 =
tan p =

(2n2 2 cos + n1 v2 )}/[(n22 22 )2 cos2 n21 u22 + 4n22 22 cos n21 v22 ]
2n2 u2 2 (n22 k22 )v2
2n2 cos 2
(148)
(n2 + 22 )2 cos2 n21 (u22 + v22 )
2n1 cos
2n1 n
2 cos
p eip =
=
(149)

n1 cos + n
2 cos
n1 n
2 cos + n
22 cos
2n1 n2 cos + i2n1 2 cos
(150)
2
n1 u2 + (n2 22 ) cos + i(n1 v2 + 2n2 2 cos )
n22 + 22
4n21 cos2 =
(151)
[n1 u2 + (n22 22 ) cos ]2 + (n1 v2 + 2n2 2 cos )2
n1 2 u2 + 2 (n22 22 ) cos n1 n2 v2 2n22 2 cos
2n1 cos
(152)
2n2 cos [n21 u2 + n1 (n22 22 ) cos + n1 2 v2 + 2n2 22 cos ]

The tp in the book Born and Wolf, Principles of Optics (7th ed) p.575 Eqs.(14) and
(15)[13] may be wrong.
For s wave
n1 cos n
2 cos
n1 cos (u2 + iv2 )
=

n1 cos + n
2 cos
n1 cos + u2 + iv2

n1 cos u2 iv2 2
(n1 cos u2 )2 + v22

n cos + u + iv = (n cos + u )2 + v 2
1
2
2
1
2
2
2v2 n1 cos
n21 cos2 u22 v22
2n1 cos
2n1 cos
s eis =
=
n1 cos + n
2 cos
n1 cos + u2 + iv2
2

4n21 cos2
2n1 cos
=

n cos + u + iv
(n1 cos + u2 )2 + v22
1
2
2
2v2 n1 cos
v2
2
=
2
n1 cos + u2
2n1 cos + 2u2 n1 cos

rs = s eis =

(153)

2s =

(154)

tan s =
ts =
s2 =
tan s =

(155)
(156)
(157)
(158)

For He-Ne laser (632.8 nm) the reectance at the air|gold surface (n = 0.181, =
2.99) is shown in Fig.7. For IR light at 3100 nm the reectance at the air|gold surface
(n = 1.728, = 19.2) is shown in Fig. 8.
The intensities of light in the z- and y-component per unit area on the Au surface
becomes
(Ep /Ep )2 / cos |E0z + R0z |2 /Ep2 / cos = | Ep sin Rp sin |2 /Ep2 / cos
= | Ep sin rp Ep sin |2 /Ep2 / cos
= | Ep sin (p cos p + ip sin p )Ep sin p |2 /Ep2 / cos
= sin 2 (1 + 2p cos p + 2p )/ cos

(159)

(Es /Es )2 / cos |E0y + R0y |2 /Es2 / cos

= |Es + Rs |2 /Es2 / cos = |Es + rs Es |2 /Es2 cos
= (1 + 2s cos s + 2s )/ cos

(160)

These equations give the basics of the surface sensitivity of the RAIRS(Reection Absorption Infrared Spectroscopy) and Polarization-Modulation FTIR spectroscopy, and the
16

250
s-wave

0.98

phase shift (degree)

200

reflectance

0.96
0.94
0.92
Rp

0.9

150
p-wave

100
50

0.88
0.86

0
0

10

20

30 40 50 60 70
incident angle (degree)

80

90

10

20

30
40
50
60
70
incident angle (degree)

80

90

80

90

Figure 8: He-Ne laser (632.8 nm) reection from air|Au surface

1

200
Rs

0.98

180
phase shift (degree)

reflectance

s-wave

160

0.96
0.94
0.92
Rp

0.9
0.88
0.86

140
120
100
80
60
p-wave

40

0.84

20

0.82

0
0

10

20

30 40 50 60 70
incident angle (degree)

80

90

10

20

30
40
50
60
70
incident angle (degree)

Figure 9: IR light (3100 nm) reection from air|Au surface

angle dependence are shown in Fig.9. The 180 degree phase change of s-wave leads to
destructive interference and no interaction with surface dynamic dipoles from molecular vibrations. 10 For the surface normal component of the p-wave the interference is
constructive and it can excite the dynamic dipole perpendicular to the surface. The
excitation is ecient for a higher angle of incidence.

Surface Plasmon

The electronic charges on metal boundary can perform coherent uctuations which are
called surface plasma oscillations. The uctuations are conned 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 eld in the surface normal z-direction,
but s-waves has only Ey component (no Ez component).
Now we consider the air(medium 2)|metal(medium 1) surface where the electric elds
are dumped both side of the interface.
Using a pure imaginary kz2 the electric and magnetic eld in medium 2(air, z > 0)

10

The surface parallel x-component (not shown here) of p-wave is also negligible.

17

45
40
35
30
25
p-normal Eq.(159)

20
15
10
5

s-parallel Eq.(160)

0
0

10

20

30
40
50
60
incident angle (degree)

70

80

90

Figure 10: plots of (Ep /Ep )2 / cos and (Es /Es )2 / cos . The IR light is 3100 nm and

the IR light is reected from the air|Au surface. (Es /Es )2 / cos is negligible because
the phase shift is almost 180 degree between the incident wave and the reected wave.
can be given by

E2

(161)

= Hy2 ei(kx2 x+kz2 zt)

0

(162)

H2

Ex2

= 0 ei(kx2 x+kz2 zt)

Ez2

Using a pure imaginary kz1 the electric and magnetic eld in medium 1(metal, z > 0)
can be given by

E1

(163)

= Hy1 ei(kx1 xkz1 zt)

0

(164)

H1

Ex1

= 0 ei(kx1 xkz1 zt)

Ez1

From the Condition I, we can get

kx1 = kx2 = kx

(165)

Ex1 = Ex2

(166)

Ez1 = Ez2

(167)

From condition IV,

Hy1 = Hy2

(168)

here we assume (Js )y 0

(169)

From condition III,

1 0 Ez1 = 2 0 Ez2

(170)

here we assume
18

12 (kx , ) D1z , D2z

(171)

From Eq.4 and J 0

D
t
i

rotH =

x
0

rotH =

(172)

Hyi + k Hyi
z = i
z
x
0

Hyi

(173)

From the i component of the above equation,

ikz1 Hy1 = i0 1 Ex1

(174)

ikz2 Hy2 = i0 2 Ex2

(175)

kz1
kz2
Hy1 +
Hy2 = 0
0 1
0 2

(176)

kz1 kz2
+
=0
1
2

(177)

Ex1 = Ex2 then

Hy1 = Hy2 then

From Eqs.(21) and (26)

k

kx2

2
kzi

= i

(178)

2
kz1
c
2

2
= 2
kz2
c
2
2
2

kz1
= 2
c
1

kx2 = 1
kx2

(179)

(180)

From the last two equations Eqs.(179) and (180).

kx2

1 2
1 + 2

2
kz1

2
kz2

21
1 + 2
22
1 + 2

(181)

!
2

(182)

(183)

!
2

If we remind that 1 = 1 + i1 , 2 = 2
kx2 =

(1 + i1 )2
(1 + i1 ) + 2

1 (1 + 2 ) + 1 2 + i[1 ( 1 + 2 ) 1 1 ]

(1 + 2 )2 + 1 2

(184)

If we assume 1 < |1 |
Re(kx ) =

Im(kx ) =

1 2
1 + 2
1 2
1 + 2

19

1/2

(185)
3/2

212

(186)

The surface plasmon decay in x-direction can be evaluated from Im(kx ) because the
intensity decreased as exp[2Im(kx )x]. The decay length L12 may be obtained as
L12 = [2Im(kx )]1 =

1 2

1 + 2

3/2

12
1

(187)

For the water|metal interface the decay lengths L12 are 6.4 m for gold (16.6 m for air|gold
surface), 12.3 m for silver, and 5.5 m for aluminum. The decay length L12 is the key
parameter to carry out a SPR imaging measurements 11 . In addition there is a temporal
decay in , please refer the Raethers book for details[7].

The dispersion relation kx vs become close to the light line 2 /c at small kx ,

because in the limit that 0, 1 >> 2 . At large kx the denominator of Eq.(185)
becomes zero
1 + 2 = 0
(188)
For simple metals the dielectric constant is given by the plasma frequency p [16]

12

p2
(189)
2
From Eqs.(188) and (189) the surface plasma frequency sp may be obtained as
1 = 1

sp = p

1
1 + 2

(190)

In Fig.10 we plot the dispersion relation Eq.(185).

3.5
bulk plasmon energy
3

energy (eV)

2.5

surface plasmon energy

2
1.5
1
0.5
0
0

0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
kx (108 m-1)

Figure 11: Surface plasmon dispersion (kx ) on gold surface. The vertical axis is scaled

as h (eV). The straight solid line in the gure shows the light line kx = 2 /c. The
energy of bulk plasmon is 3.22 eV, and that of surface plasmon is 2.28 eV and shown as
the arrows in the gure.
In the z-direction the electric eld of the surface plasmon decays as Ez e|kzi ||z| .
If we assume 1 < |1 | again,

2
kz1

2
kz2

12
1 + 2
22

1 + 2

11

!
2

(191)

(192)

!
2

From this discussion the lateral resolution of SPR is more than micrometer size. Aluminium has
small L12 and living cell is observed with SPR imaging. [15]
12
If the energy loss of electron beam reected from the metal surface is measured, the plasma frequency
can be determined. Surface plasma frequency can be also measured in the same way.

20

1 + 2 < 0 then kzi is purely imaginary. For He-Ne laser light (632.8 nm) on the gold
surface
1/Re(kz1 )(metal) = 32 nm, 1/Re(kz2 )(air) = 285 nm
(193)
From the k component of rotH = D/t [cf. Eq.(173)]
Hy1
x
Hy2
x

= ikx1 Hy1 = i0 1 Ez1

(194)

= ikx2 Hy2 = i0 2 Ez2

(195)

From the i component of Eqs.(172-173) and Eq.(194)

Hy1 =
Ez1
Ex1
Hy2
Ez2
Ex2

0 1 Ex1
0 1 Ez1
=
kz1
kx1

kx1
kz1
0 2 Ex2
0 2 Ez2
=
=
kz2
kx2
kx2
=
kz2
=

(196)
(197)
(198)
(199)
(200)

5
5.1

Excitation of Surface Plasmon by Light

ATR (Attenuated Total Reection) Coupler Method

We will consider the situation that the light is reected from a metal surface covered
with a dielectric medium (pr > 1) , e.g. with a BK7 half cylinder glass prism (n=1.515
at 633 nm) or SF10 glass prism (n=1.723 at 643.8 nm). The x and z components of the
wavevector in the prism are given by

(201)
kxpr = pr sin pr = npr sin pr
c
c

(202)
kzpr = pr cos pr = npr cos pr
c
c
Here pr means the prism.
The resonance condition of the light in the prism with the surface plasmon
at metal(1)|air(2) interface (Kretschmann-Raether conguration) is 13
kxpr = kxsp

pr

sin pr =
c

1 2
1 + 2

(203)
(204)

Here we use Eq.(181) for kxsp .

13
In the ATR coupler there are two types, one is prism|metal lm|sample Kretschmann-Raether type
and the other is prism|thin sample(thickness is wavelength of light)|metal Otto type. In the Otto type the
controll of the thin gap is dicult, and then Kretschmann-Raether type is usually used. However, the Au
lm thickness should be controlled around 50 nm in the Kretschmann-Raether type, otherwise the SPR
resonance (T 0) become un-sharp. In the electrochemical environment the gold lm is not stably deposited on the glass plate when the potential is applied. Then (3-mercaptopropyl)trimethoxysilane(MPS)
is used for the binder between the glass and gold (see Appendix). Otto rst showed that light can excite
surface plasmon by the use of ATR coupler[3], but He claimed that the surface plasmon can not be
excited by the Kretschmann-Raether type ATR coupler and later it was found that his claim was wrong.
After that Otto never went mainstream in the SPR world!?

21

pr
pr

kxpr

d1

Figure 12: Schematic diagram of ATR coupler: Kretschmann-Raether type

5.1.1

Prisim|Metal|Medium Three-Layer Model

The reectivity Rpr|1|2 may be given by Frensels equations of the prism|metal|air threelayer system.

p
rik
=

n
k kkzii n
i kkzk
n
k cos i n
i cos k
k
=
=
kzk
kzi
n
k cos i + n
i cos k
n
k ki + n
i kk
kzi
n
2i
kzi
n
2i

kzk
n
2k
kzk
n
2k

n
k kzi c
n
i
n
k kzi c
n
i

kzi /
i kzk /
k
kzi /
i + kzk /
k

p
p
rki
= rik

n
i kzk c
n
k
n
i kzk c
n
k

(205)

(206)
(207)

For transmission
n
i
p
(1 + rik
)
n
k
n
k
n
k
p
p
=
(1 + rki
)=
(1 rik
)
n
i
n
i
p
p
= (1 + rik
)(1 rik
)

tpik =

(208)

tpki

(209)

tpik tpki

(210)

The total reection of the three-layer model becomes

R =

p
|rpr12
|2

p
p 2ikz1 d1 2
r
pr1 + r12 e

=
p
p 2ikz1 d1
1 + rpr1

r12
e

cos i /
ni cos k /
nk
n
k cos i n
i cos k
=
n
k cos i + n
i cos k
cos i /
ni + cos k /
nk
= n
1 sin 1 = n
2 sin 2

p
rik
=

npr sin pr

(211)
(212)

n
k cos k = n
k (1 sin2 k )1/2 = n
k (1 n2pr sin2 pr /
n2k )1/2 = (
n2k n2pr sin2 pr )1/2
p
rik
=
p
rpr1

k
i (
k n2pr sin2 pr )1/2 /
(
i n2pr sin2 pr )1/2 /
2
2
1/2
1/2
2
2
(
i npr sin pr ) /
i + (
k npr sin pr ) /
k

(213)

1
cos pr /npr (
1 n2pr sin2 pr )1/2 /
cos pr /npr + (
1 n2pr sin2 pr )1/2 /
1

(214)

22

The above equation for R can be understood by considering

p
rpr12

p
p 2ikz1 d1
rpr1
+ r12
e
p
p 2ikz1 d1
1 + rpr1 r12 e

(215)

p
p 2ikz1 d1
p
p 2ikz1 d1
p
p 2 4ikz1 d1
(rpr1
+ r12
e
)(1 rpr1
r12
e
+ (rpr1
)2 (r12
) e
....)
p
p 2ikz1 d1
p
p 2ikz1 d1
= rpr1
+ r12
e
(rpr1
)2 r12
e
p
p 2 4ikz1 d1
p
p 2 4ikz1 d1
rpr1
(r12
) e
+ (rpr1
)3 (r12
) e
+ ...
p
p
p 2ikz1 d1
p
p
p 2 4ikz1 d1
= rpr1
+ (1 rpr1
)2 r12
e
+ rpr1
[(rpr1
)2 1](r12
) e
+ ...
p
p
p
p
= rpr1
+ (1 + rpr1
)r12
(1 rpr1
) e2ikz1 d1

{z

p p
tppr1 r12
t1pr

p
p
p
p
p
+ (1 + rpr1
)r12
(rpr1
)r12
(1 rpr1
) e4ikz1 d1

{z

p p
p p
tppr1 r12
r1pr r12
t1pr

p
p p
p p
p p
= rpr1
+ tppr1 r12
t1pr e2ikz1 d1 + tppr1 r12
r1pr r12
t1pr e4ikz1 d1

phase factor

kz1 d1 = k1 (d1 cos 1 ) is optical path length.

n2pr

kz1 d1 = k1 d1 cos 1 = n
1 d1 1 2 sin2 pr
c
n
1

d1 (
1 n2pr sin2 pr )1/2
=
c

(216)
(217)

!1/2

(218)

1
0.9
0.8
reflectance

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
35

36

37

38 39 40 41 42
incident angle (degree)

43

44

45

Figure 13: SPR curve for SF10(n = 1.723)|gold(50nm, n

1 = 0.1726+i3.4218) |air(n =
1.0) for He-Ne laser light (633 nm).
The FORTRAN program to get the SPR curve by Eq.(211) is
c234567-- spr_angle_3layer.f --c
complex calculation
implicit real*8 (a-h,o-z)
complex*16 e1,rpr1,r12,rpr12,rpr12c,alpha,ref
complex*16 aaa,fukso,e2

23

c
c
c

c=2.99792458d8
hbar=6.5822d-16
pi=acos(-1.0d0)
------ air ---e2=dcmplx(1.0d0,0.0d0)
----- SF10 633 nm
enpr=1.723d0
----- gold 633 nm
e1n=0.1726d0
e1k=3.4218d0
e1r=e1n**2-e1k**2
e1i=2.0d0*e1n*e1k
e1=dcmplx(e1r,e1i)
---- gold thickness (m)
d1=50.0d-9

ramd=633.0d-9
omega=2.0d0*pi/ramd*c
fukso=dcmplx(0.0d0,1.0d0)
write (6,*) ramd,omega,hbar*omega
--------- angle scan ---------ang0=35.0d0
ang1=45.0d0
do i=1, 1001
theta=(ang0+dble(i-1)/1000.0d0*(ang1-ang0))/180.0d0*pi
rpr1=(cos(theta)/enpr &
sqrt(e1-enpr**2*sin(theta)**2)/e1)
&
/ (cos(theta)/enpr +
&
sqrt(e1-enpr**2*sin(theta)**2)/e1)

&
&
&

r12=( sqrt(e1-enpr**2*sin(theta)**2)/e1 sqrt(e2-enpr**2*sin(theta)**2)/e2 )

/ ( sqrt(e1-enpr**2*sin(theta)**2)/e1 +
sqrt(e2-enpr**2*sin(theta)**2)/e2 )
aaa=2.0d0*omega/c*d1*sqrt(e1-enpr**2*sin(theta)**2)
alpha=aaa*fukso
rpr12=(rpr1+ r12*exp(alpha))/(1.0d0+rpr1*r12*exp(alpha))
rpr12c=conjg(rpr12)
ref=rpr12*rpr12c
write (6,*) theta/pi*180.0d0,dble(ref)
enddo
end

The calculated results are shown in Fig. 12. At resonance or R = 0 the power of the
SPs is lost by internal absorption in the metal. This loss is compensated by the power
of the incoming light. Both have to be equal in the steady state.
If the reectivity R has lowest value, the intensity of the electromagnetic eld reaches
its maximum at the metal surface. For 600 nm light the maximum enhancement
of the electric eld intensity is ca. 200 for silver lm (60 nm thickness), 30 for gold
lm, 40 for aluminum lm, and 7 for copper lm, respectively[7].

24

5.2

General solution of N-layer model. [ F. Abel`

es, Ann. Phys. (Paris)
5, (1950) 596. W. N. Hansen, J. Opt. Soc. Amer. 58 (1968) 380. ]

z1
1

z3

z2
2

zN-2 zN-1

3 4 N-2 N-1 N

Figure 14: N-layer model for SPR measurement.

The tangential elds at the rst boundary z = z1 = 0 are related to those at the
nal boundary z = zN 1 by
"

U1
V1

"

= M2 M3 ...MN 1

UN 1
VN 1

"

=M

UN 1
VN 1

(219)

For p-wave at boundary k,

Uk = HyT + HyR
ExT

Vk =
and

"

Mk =

cos k
i sin k /qk
iqk sin k
cos k

ExR

(220)
(221)

Here qk = (k /k )1/2 cos k

k
= 1

(222)
(223)

(k n21 sin2 1 )1/2

qk
(224)
= (1/k )1/2 cos k =
k
2
2
n
k cos k (zk zk1 ) = (zk zk1 ) (
k n21 sin2 1 )1/2 (225)
k =
0
0
The reection and transmission coecient for p-wave (TM) is
rp =
Mij

(M11 + M12 qN )q1 (M21 + M22 qN )

(M11 + M12 qN )q1 + (M21 + M22 qN )

N 1
Y

Mk

k=2

i, j = 1, 2

rp

(228)

r
Rp1/2 eip
p

(229)

= arg(r )

tpH

tpE

Tp =
tp =

(227)

ij

Rp = |rp |2
rp =

(226)

(230)

2q1
(M11 + M12 qN )q1 + (M21 + M22 qN )
N n1 p
t
1 n
N H
N Re(
nN cos N /
n2N ) p 2
|tH |
1 n1 cos 1 /n21
arg(tpE )
25

(231)
(232)
(233)
(234)

For s-wave (TE) the above equations hold except

s

qk =

k
cos k
k

(235)

In this sense these equations are easy to calculate the multilayer optical problem.

1
0.9
0.8
reflectance

0.7
0.6
(I) Au

0.5
0.4

(II) SAM on Au

0.3
0.2
0.1
0
35

36

37

38 39 40 41 42
incident angle (degree)

43

44

45

Figure 15: SPR curves for (I) the SF10 glass prism(n=1.723)|Au(n + ik =
0.1726+i3.4218, 50nm)|Air(n=1.0) and (II) the SF10 prism|Au(50nm)|SAM(n=1.61245,
1nm)|Air systems.
The SPR resonance calculation FORTRAN program for N-layer system is given
in the following, and the results for the 4-layer system [ prism|gold|Self-AssmbledMonolayer(SAM, 1 nm thickness)|Air ] is shown in Fig. 14. The SAM lm thickness
of 1 nm is clearly seen as the shift of the SPR angle.
c234567-- spr_angle_Nlayer.f --c
1 | 2 | 3 ... N-2|N-1|N :N layer system
c
complex calculation
implicit real*8 (a-h,o-z)
parameter (nlay=10)
complex*16 e(nlay) , em(nlay,2,2) ,emtot(2,2)
complex*16 emtot1(2,2)
dimension en(nlay), ek(nlay), d(nlay)
complex*16 beta,q,rp,q1,qn,ref,tp,tra
complex*16 fukso
c=2.99792458d8
hbar=6.5822d-16
26

field enhancement

25
20
15
10
5

35

36

37

38

39

40

41

42

Figure
16:
Field
enhancement
factor
|tph |2
prism|Au(50nm)|SAM(n=1.61245, 1nm)|Air system.

c
c

c
c

43

incident angle (degree)

pi=acos(-1.0d0)
------- N layer ---nlayer=4
------ air ---en(4)=1.d0
ek(4)=0.0d0
er=en(4)**2-ek(4)**2
ei=2.0d0*en(4)*ek(4)
e(4)=dcmplx(er,ei)
----- SF10 633 nm
en(1)=1.723d0
ek(1)=0.0d0
er=en(1)**2-ek(1)**2
ei=2.0d0*en(1)*ek(1)
e(1)=dcmplx(er,ei)
----- gold 633 nm
en(2)=0.1726d0
ek(2)=3.4218d0
er=en(2)**2-ek(2)**2
ei=2.0d0*en(2)*ek(2)
e(2)=dcmplx(er,ei)
---- gold thickness (m)
d(2)=50.0d-9
------ SAM ----------en(3)=1.61245
ek(3)=0.0d0
er=en(3)**2-ek(3)**2
ei=2.0d0*en(3)*ek(3)
e(3)=dcmplx(er,ei)
----- SAM thickness ---

27

for

44

the

45

the

SF10

d(3)=1.0d-9
c

ramd=633.0d-9
omega=2.0d0*pi/ramd*c
fukso=dcmplx(0.0d0,1.0d0)
write (6,*) ramd,omega,hbar*omega
--------- angle scan ---------ang0=35.0d0
ang1=45.0d0
do i=1, 1001
theta=(ang0+dble(i-1)/1000.0d0*(ang1-ang0))/180.0d0*pi
q1=sqrt(e(1)-en(1)**2*sin(theta)**2)/e(1)
qn=sqrt(e(nlayer)-en(1)**2*sin(theta)**2)/e(nlayer)
do j=2, nlayer-1
beta=d(j)*2.0d0*pi/ramd*sqrt(e(j)-en(1)**2*sin(theta)**2)
q=sqrt(e(j)-en(1)**2*sin(theta)**2)/e(j)
em(j,1,1)=cos(beta)
em(j,1,2)=-fukso*sin(beta)/q
em(j,2,1)=-fukso*sin(beta)*q
em(j,2,2)=cos(beta)
enddo
emtot(1,1)=dcmplx(1.0d0,0.0d0)
emtot(2,2)=dcmplx(1.0d0,0.0d0)
emtot(1,2)=dcmplx(0.0d0,0.0d0)
emtot(2,1)=dcmplx(0.0d0,0.0d0)
do j=2, nlayer-1
emtot1(1,1)=em(j,1,1)
emtot1(1,2)=em(j,1,2)
emtot1(2,1)=em(j,2,1)
emtot1(2,2)=em(j,2,2)
emtot=matmul(emtot,emtot1)
enddo
rp=( (emtot(1,1)+emtot(1,2)*qn)*q1 (emtot(2,1)+emtot(2,2)*qn) )
/ ( (emtot(1,1)+emtot(1,2)*qn)*q1 +
(emtot(2,1)+emtot(2,2)*qn) )
tp=2.0d0*q1/( (emtot(1,1)+emtot(1,2)*qn)*q1 +
&
(emtot(2,1)+emtot(2,2)*qn) )
&
&
&

&
&
&
&

rp=( (emtot(1,1)+emtot(1,2)*qn)*q1 (emtot(2,1)+emtot(2,2)*qn) )

/ ( (emtot(1,1)+emtot(1,2)*qn)*q1 +
(emtot(2,1)+emtot(2,2)*qn) )
tp=2.0d0*q1/( (emtot(1,1)+emtot(1,2)*qn)*q1 +
(emtot(2,1)+emtot(2,2)*qn) )
ref=rp*conjg(rp)
enh=tp*conjg(tp)
tra=tp*conjg(tp)/cos(theta)*en(1)*dble(qn)
28

write (6,*) theta/pi*180.0d0,dble(ref),enh

write (6,*) theta/pi*180.0d0,dble(ref),dble(tra)
enddo
end

Acknowledgement

The author would like to thank for Mr. A. Shirakami for his great contribution to the
startup of the SPR study in our laboratory. The author also thank Prof. R. Corn, Prof.
T. Kakiuchi and Dr. D. Hobora for helpful discussions on this subject.

Appendix

In Fig.16 the phase shifts of the reected wave(He-Ne laser light) are shown in the case
of Air(n = 1) Water(n = 1.332)(top gure) and WaterAir(bottom gure). For the
case of WaterAir the critical angle for total reection is 48.66 degree and the phase
shift is shown in Fig.6.

References
[1] R. H. Ritchie. Plasma losses by fast electrons in thin lms. Phys. Rev., 106:874881, 1957.
[2] R. W. Wood. On a remarkable case of uneven distribution of light in a diraction grating
spectrum. Phil. Mag. Ser. 6, 4:396402, 1902.
[3] A. Otto. Excitation of surface plasma waves in silver by the method of frustrated total
reection. Z. Physik, 216:398410, 1968.
[4] H. Raether E. Kretschmann. Radaitive decay of non-radiative surface plasmons excited by
light. Z. Naturforsch., 23A:21352136, 1968.
[5] J. G. Gordon II and J. D. Swalen. The eect of thin organic lms on the surface plasma
resonace on gold. Opt. Commun., 22:374376, 1977.
[6] C. Nylander B. Liedberg and I. Lundstrom. Surface plasmon resonance for gas and biosensing. Sensers and Acutuators, 4:299304, 1983.
[7] H. Raether. Surface Plasmons on Smooth and Rough Surface and on Gratings. SpringerVerlag, Berlin, 1988.
[8] B. L. Frey R. Corn D. G. Hanken, C. E. Jordan. Surface plasmon reasonance measurements
of ultrathin organic lms at electrode surfaces. Electroanal. Chem., 20:141225, 1998.
[9] W. Knoll. Interfaces and thin lms as seen by bound electromagnetic waves. Annu. Rev.
Phys. Chem., 49:569638, 2000.
[10] R. Corn J. M. Brockman, B. P. Nelson. Surface plasmon reasonance imaging measurements
of ultrathin organic lms. Annu. Rev. Phys. Chem., 51:4163, 2000.
[11] D. M. Kolb. The study of solid-liquid interfaces by surface plasmon polariton excitation.
In V. M. Agranvich and D. L. Mills, editors, Surface Polaritons, chapter 8, pages 299329.
North-Holland, Amsterdam, 1982.
[12] V. Scheumann Z. Zizlsperger J. Mack G. Jung A. Badia, S. Arnold and W. Knoll. Probing
the elecrochemical deposition and/or desorption of self-assembled and electropolymerizable
organic thin lm by surface plasmon spectroscopy and atomic force microscopy. Sensors
and Actuators B, 54:145165, 1999.
[13] M. Born and E. Wolf. Principles of Optics (7th expanded edition). Cambridge University
Press, Cambridge, 1999.

29

[14] E. Hecht. Optics. Addison-Wesley, San Francisco, 2002.

[15] S. Herminghaus M. Riedel P. Leiderer U. Weiland K.-F. Giebel, C. Bechinger and M. Bastmeyer. Imaging of cell/substrate contacs of living cells with surface plasmon resonance
microscopy. BioPhys. J., 76:509516, 1999.
[16] C. Kittel. Introduction to Solid State Physics (7th edition). Wiley, New York, 1996.

30

180

rs

phase shift (degree)

150

120

90

air to water

rp

60

30

0
0

10

20

30
40
50
60
incident angle (degree)

70

80

90

180

150

phase shift (degree)

water to air
120

rp

90

60

30

rs
0
0

10

20
30
incident angle (dgree)

40

Figure 17: Phase shifts of the reected wave(He-Ne laser light) are shown in the case
of Air(n = 1) Water(n = 1.332)(top gure) and WaterAir(bottom gure). For the
case of WaterAir the critical angle for total reection is 48.66 degree and the phase
shift is shown in Fig.6.
In Fig.17 schematic diagram of light reection from black lm is shown. When the
incident angle is small, the phase shift of s wave is for OC and zero for OAB and the
phase shift of p wave is zero for OC and for OAB.(Please see Fig.16) If the lm
thickness d is much smaller than the wavelength/4, the interference between OC and
wave from B become destructive.(Please note that the formulation is shown in the inset
of Fig.17). Then we can see no light from thin lm like lipid bilayer or soap bubble.
31

Figure 18: Schematic diagram of light reection for black lm. When the incident angle
is small, the phase shift of s wave is for OC and zero for OAB and the phase shift of
p wave is zero for OC and for OAB.(Please see Fig.16) If the lm thickness d is much
smaller than the wavelength/4, the interference between OC and wave from B become
destructive. Please note that the formulation is shown in the inset. Then we can see no
light from thin lm like lipid bilayer or soap bubble.

32

Appendix
Home-made SPR Apparatus (by A. Shirakami)
He-Ne laser
628.3 nm

Beam splitter
ND filter

Rotating stage

Lens

Polarizer

PC

Lens
Detector

Lens
Detector
2

A/D converter

Electrochemical Cell for SPR

SF-10 hemicylindrical
prism
Working electrode

Glass slide
Gold layer

Potentiostat
Reference
electrode

Counter electrode

Details of the Sample Setup

SF10 glass Prism
n matching oil
SF10 slide glass
MPS
Au film (50nm)
SAM
Figure 19:
33