Journal of Quantitative Spectroscopy &

Radiative Transfer 89 (2004) 3742

Spontaneous emission enhancement near nanoparticles
L.A. Blanco

, F.J. Garc a de Abajo

Centro Mixto CSIC-UPV/EHU and Donostia International Physics Center (DIPC), Apartado 1072, 20080 San
Sebastian, Spain
Abstract
The effect of nanoparticles in the spontaneous emission from a nearby atom is studied by calculating the
emission probability and the distribution of the near eld for various nanoparticle shapes and positions of
the atom. For atoms near a gold sphere or in the region between two neighbouring spheres, a strong
enhancement of the emission takes place for transition energies near the plasmon resonances of the system.
Finally, the near eld associated to the emission is examined when the atom is located at the focus of a
dielectric ellipsoid, in which case a strong enhancement of the eld at the other focus is observed at certain
resonance energies, even when the dimension of the ellipsoid is comparable to the wavelength.
r 2004 Elsevier Ltd. All rights reserved.
Keywords: Spontaneous emission; Field enhancement; Nanoparticles
1. Introduction
Spontaneous photon emission from an atom in the presence of different environments has
received considerable attention over the last few years, with particular emphasis in geometries that
give rise to either strong enhancement or inhibition of the emission [19]. In particular, strong
enhancement has been reported for decay from atoms in photonic crystals [3,6,8], sometimes
accompanied by a pronounced angular focusing effect [8]. Inhibition of spontaneous emission
takes place when the emission lies in the gap of a photonic crystal [2,7]. Other geometries
including dielectric slabs [5] and optical cavities [4,10,11] have also been discussed. Strong features
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doi:10.1016/j.jqsrt.2004.05.009

Corresponding author. Tel.: +34-943015-421; fax: +34-943015-600.

E-mail address: swxbljil@sc.ehu.es (L.A. Blanco).
occur when the emission frequency is near the plasmon frequency of the nearby material, giving
rise to very intense enhancement [9].
In this work, we will focus on the enhancement of spontaneous emission by placing the atom
close to metallic nanoparticles when the emission resonates with plasmon modes of the particles.
The effect is similar to the properties of the spectra obtained in surface-enhanced Raman
spectroscopy (SERS) [12]. Also, we are reporting strong focusing of the near eld accompanying
the emission for atoms inside ellipsoidal dielectric nanoparticles.
2. Theory
The emission probability will be obtained using a semi-classical procedure consisting in solving
Maxwells equations with a source corresponding to the dipolar charge and current densities
associated to the atomic transition. The current density has the expression
jr i
e_
m
C
n
g
r
~
rC
e
r;
where C
g
r and C
e
r are the wavefunctions of the ground state and the excited state,
respectively. The charge density is related to the current density via the continuity equation:
rr
1
io
~
r jr:
With these currents one can build the electric eld as
Er
Z
dr
0
ik
c
Gr r
0
jr
0

1

~
r
r
Gr r
0
rr
0

;
where Gr expik
0
r=r is the Green function of the scalar Helmholtz equation, k o=c, and
k
0
k

p
. Analogously the magnetic eld can also be expressed in terms of the densities. Within
the dipole approximation (the emission wavelength is much bigger than the physical dimensions
of the atomic system), the rate of emission is related to the integral of the Poynting vector in the
far eld, and the only parameter that is needed to characterize the atom is the transition dipole
moment. This simple procedure permits recovering in particular the emission rate in vacuum,
G 32p
3
jdj
2
=3l
3
;
where G is the emission probability per unit time, d ehC
g
jrjC
e
i is the atomic transition dipole
moment and l is the wavelength.
The scattering between the electromagnetic eld created by the atom and the nanoparticles will
be studied in the framework of the boundary element method [13], which consists in solving
Maxwells equations by discretizing the interfaces that form the geometry. The eld of the atom
gives rise to surface charge and current densities at the interfaces between media with different
dielectric constants, and these densities are the sources of the induced eld. Then, the total eld
(i.e., the sum of this induced eld and the dipolar eld of the atom) must satisfy the customary
boundary conditions at the interfaces. The latter lead to a set of linear equations with the surface
charges and currents as the unknowns. Solving this system of linear equations, one can obtain the
latter, and therefore solve the problem.
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L.A. Blanco, F.J. Garca de Abajo / Journal of Quantitative Spectroscopy & Radiative Transfer 89 (2004) 3742 38
3. Results
We have investigated the enhancement of the emission probability induced by surface plasmons
near metallic particles (Fig. 1) and also near eld focusing effects in dielectric ellipsoids (Fig. 2).
Next, we will briey discuss on the results separately.
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400 800 1200 1600 2000
0
40000
80000
120000
160000
200000
d=0.5 nm
d=1 nm
(nm)
(nm)
400 800 1200 1600 2000
0
400
800
1200
d=0.5 nm
d=1 nm
E
m
i
s
s
i
o
n

P
r
o
b
a
b
i
l
i
t
y

n
o
r
m
a
l
i
z
e
d

t
o

v
a
c
u
u
m
E
m
i
s
s
i
o
n

P
r
o
b
a
b
i
l
i
t
y

n
o
r
m
a
l
i
z
e
d

t
o

v
a
c
u
u
m
d
d
(a)
(b)
Fig. 1. (a) Angle-integrated spontaneous emission probability for an atom located in the region between two Au spheres of radius
50 nm, normalized to the probability in the absence of the spheres, as a function of emission wavelength l. The atomic dipole moment
has been taken along the line that connects the sphere centres, and the atom is situated at the same distance d from each sphere. (b) The
same as (a), when there is only one Au sphere.
L.A. Blanco, F.J. Garca de Abajo / Journal of Quantitative Spectroscopy & Radiative Transfer 89 (2004) 3742 39
3.1. Metallic nanoparticles
It is well known that the near electromagnetic eld between two metallic surfaces placed at a
short distance presents a large enhancement in comparison to the value measured when only one
surface is present. We want to test if this behaviour is also present when considering the far eld,
as it happens in the total spontaneous emission probability, as stated above. Fig. 1 shows the
spontaneous emission enhancement (i.e., the ratio of the emission rate in the presence of metallic
surfaces to the rate in vacuum) for atoms located near Au nanoparticles of equal radius 50 nm.
The most salient characteristic of these spectra is that strong enhancement features show up at
specic emission wavelengths, which correspond to the plasmon resonances of the coupled system
under consideration.
The orientation of the atomic dipole moment is directed towards the sphere centres both in
Figs. 1(a) and (b). We have tried dipole moments oriented perpendicular to the vertical direction,
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-1 0
0
4
8
12
A
B
x/
z
/

z/

-0.5 0.0 0.5
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5

(,)/
direct
()
a/
0.2 0.6 1

(
d
e
g
r
e
e
s
)
120
60
180
0
(a)
S
q
u
a
r
e
d

e
l
s
c
t
r
i
c

f
i
l
l
e
d

(
a
r
b
.

u
n
i
t
s
)
B 1
(b) (c)
A
Fig. 2. Near and far electric eld distributions produced by spontaneous emission from an atom placed inside an ellipsoid of dielectric
constant 3, with semi-axes a b 0:75l and c 1:5l, where l is the wavelength. The emitting atom lies at one focus (1.3 l away
from the ellipsoid centre) and has an electric dipolar moment directed along the z axis. (a) Far eld as a function of polar emission
angle y and short-axis radius a. (b) Induced eld both inside and outside the ellipsoid. (c) Induced (solid line) and direct (dashed line)
squared electric eld for the same system as in (a), along the ellipsoid axial-symmetry axis. The direct eld is dened as the eld that
would be produced in an innite medium with 3.
L.A. Blanco, F.J. Garca de Abajo / Journal of Quantitative Spectroscopy & Radiative Transfer 89 (2004) 3742 40
but the enhancement in that case is even smaller than 1 at some wavelengths. Therefore, a dipole
moment oriented towards the sphere surfaces is able to create oscillating charges of dipolar origin
in the spheres, and this is what drives the strong enhancement shown in the gure. On the other
side, when the dipole is oriented tangentially to the surfaces these induced dipole charges cancel
out their contributions to the far eld and the emission is suppressed.
The emission enhancement decreases strongly with the distance to the sphere surfaces, and this
effect is particularly strong in the case of a single sphere. Furthermore, the position of the
resonance shifts towards smaller wavelengths with the distance between spheres in the two-sphere
case, and reaches actually the value of 460 nm when the two spheres are innitely separated, which
corresponds to the case considered in Fig. 1(b).
Notice that the actual value of the enhancement is two orders of magnitude larger in the two-
sphere case as compared with the case of one isolated sphere, and this provides a possible strategy
for constructing geometries where spontaneous emission can be made larger, consisting in putting
metallic surfaces in contact on localized spatial regions.
3.2. Focusing the near eld in ellipsoids
When an atom is placed in the focus of an ellipsoid, if the geometrical optics approximation
holds, it is expected that the electromagnetic eld at the other focus reaches its maximum value.
Nevertheless, when the dimension of the cavity is of the same order as the wavelength, geometrical
optics approximation is no longer valid and therefore the eld does not concentrate on the lower
focus for all conditions. Fig. 2 shows results for far and near elds associated to the spontaneous
emission in an ellipsoid whose shape is given by the equation x
2
=a
2
y
2
=b
2
z
2
=c
2
1, with
a b, c 2a. That is, the two foci of the ellipsoid are located in the points 0; 0;

3
p
a. We have
placed the emitter atom at the upper focus (see inset) and have studied the properties of the
electromagnetic eld. The far eld emission distribution [Fig. 2(a)] exhibits intensity fringes as a
result of complicated wave propagation patterns in the ellipsoidal cavity, as its dimensions are
comparable to l. In Fig. 2(b) we study the dependence of the value of the square of the induced
electric eld at the lower focus with the ratio a=l. There is one resonance in particular when this
ratio is 0.75. Fig. 2(b) shows a density plot of the squared electric eld in this case. There is a clear
focusing effect of the electric eld on the lower focus. One further application of this behaviour
would be the study of chaos in optical resonators [14].
Fig. 2(c) shows how that the direct eld (i.e. the dipolar eld from the atom in an innite
medium of the same material as in the ellipsoid with 3) is negligible at the position of the other
focus (dashed curve). That means that all the eld accumulated at the lower focus is due to
multiple scattering on the boundaries of the cavity. Notice that the system is fully scalable, so this
effect can be produced at any wavelength just by changing the size of the ellipsoid.
4. Conclusions
In summary, it has been shown that placing an atom between two metallic spheres produces a
strong enhancement of the spontaneous emission probability at wavelengths that are in resonance
with plasmon modes of the system, and the wavelength resonance depends on the distance
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L.A. Blanco, F.J. Garca de Abajo / Journal of Quantitative Spectroscopy & Radiative Transfer 89 (2004) 3742 41
between the spheres. Enhancements as large as 2 10
5
are predicted, which goes well beyond the
enhancement that is obtained for a single sphere, of the order of 10
3
. Moreover, the near eld
associated to the spontaneous emission can be focused in very small regions of space far from the
emitting atom, as shown for emission within dielectric ellipsoids, using their foci to concentrate
the near eld. Surprisingly, this effect works even when the dimension of the ellipsoid is
comparable to the wavelength, but only for specically chosen wavelengths.
Acknowledgements
This work has been supported in part by the Basque Departamento de Educacio n,
Universidades e Investigacio n, the University of the Basque Country UPV/EHU (Contract No.
00206.215-13639/2001), and the Spanish Ministerio de Ciencia y Tecnolog a (Contract No.
MAT2001-0946).
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