Surface plasmons in metallic nanoparticles:

fundamentals and applications

M A Garcia

To cite this version:

M A Garcia. Surface plasmons in metallic nanoparticles: fundamentals and applications. Jour-
nal of Physics D: Applied Physics, IOP Publishing, 2011, 44 (28), pp.283001. �10.1088/0022-
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 M.A. García
Surface Plasmons in metallic nanoparticles

Surface Plasmons in metallic nanoparticles: Fundamentals and

applications.

M. A. Garcia,
Dpt. Electroceramics, Institute for Ceramic and Glass, CSIC, C/Kelsen 5, 28049 Madrid, Spain &
IMDEA Nanociencia, Madrid 28049, Spain
[email protected]

Index
1. Introduction

2. Fundamentals of SP in nanoparticles
2.1 SP in nanoparticles
2.2 Models and calculations of SP.
2.3 Size effects
2.4 Shape effects
2.5 Media effects
2.6 NPs Interaction effects

3. Applications of SP
3.1 Biomedical: Diagnosis and treatment
3.2 Energy: Photo-energies
3.3 Environmental Photocatalysis
3.4 Information technologies

4. Outlook and challenges

5. Acknowledgments

6. References

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Abstract

The excitation of surface plasmons in metallic nanoparticles induces optical properties hardly
achievable in other optical materials, yielding a wide range of applications in many fields. This
review presents an overview of surface plasmons in metallic nanoparticles. The concept of
surface plasmons in nanoparticles is qualitatively described using a comparison with simple linear
oscillators. The mathematical models to carry on calculations on surface plasmons are presented
as well as the most common approximations. The different parameters governing the features of
surface plasmons and their effect on the optical properties of the materials are reviewed. Finally,
applications of surface plasmons in different fields as biomedicine, energy, environment
protection and information technology are revised.

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1. Introduction

Surface Plasmons (SP) resonance is the most outstanding optical property of metallic
nanostructures. It consists of a collective oscillation of conduction electrons excited by the
electromagnetic field of light. SP resonance is in the origin of optical properties hardly achievable
with other physical processes [1,2,3]. In the case of metallic nanoparticles (NPs), where the
electrons are confined in the three dimensions, the electron oscillations induce an electric field
around the NP that can be much larger than the incident light one. SP are one of the best
examples that things are different at the nanoscale. When the size of a metallic particle is
reduced to the few nanometre range, the optical properties are dramatically modified by the
appearance of SP and its behaviour results completely different than the bulk metal one. SP open
the possibility to amplify, concentrate and manipulate light at the nanoscale, overcoming the
diffraction limit of traditional optics and increasing resolution and sensitivity of optical probes [4].
Consequently, the SP can be used in a wide range of fields, including biomedical [5,6,7,8],
energy [9,10,11], environment protection [12,13,14], sensing [15] and information technology
[3,4,16] applications. Nowadays, there are well established applications of SP that increases
rapidly with the development of our capabilities to fabricate and manipulate nanomaterials.
In this review the fundamentals of SP are surveyed. It does not pretend to be a presentation of
the proper and exact formalism required to describe SP but an attempt to explain what are SP in
an accessible way to most readers with different background. To this purpose, analogies with
simple systems as linear oscillators are used. After describing the physical basis of SP, the
theories that provide exact mathematical solutions and the usual approximations to carry on
proper calculations on SP are summarised. The main parameters affecting the SP excitation
processes are also revised. Finally, some applications of SP on different fields are surveyed. It
should be impossible to review here the huge number of applications of SP reported in the
literature. Thus, when selecting just some of them I do not pretend to neglect the researchers in
the field the credit they merit but just to highlight some applications to illustrate the capabilities of
SP.
The synthesis of metallic NPs in not addressed here. There are excellent reviews of this topic that
the reader is referred to [17,18,19,20,21,22,23]. Moreover, NPs are not the only metallic
nanostructures exhibiting SP. Films, wires and patterned media exhibit also SP [2,24,25]. In the
case of NPs, the confinement of electrons leads to localised SP, while other structures with large
dimensions compared with light wavelength (wires and films) hold extended SP that propagate

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along the interface between the metal and the dielectric medium. There is a third case
corresponding to mesoscopic systems, with dimensions comparable to wavelength. In this case
SP modes can also be excited [2,3]. We will only treat here the case of localised SP in NPs.

2. Fundamentals of SP in NPs
The scientific study of SP started in early XX century when Gustav Mie published his pioneer
work explaining the surprising optical properties of metallic colloids [26]. However, SP in NPs
have been empirically used for a long time, particularly for glass colouring. Glasses from the final
bronze age (1000-1200 BC) found in Fratessina di Rovigo (Northern Italy) were coloured by the
presence of metallic Cu NPs [27]. The Lygurcus cup (400 AC) is probably the most famous
example of the use of SP in the ancient times, exhibiting different coloration when observed upon
illumination inside or outside of the cup [28,29]. Actually many Roman mosaics used metallic NPs
to achieve red coloration [30,31]. At that time, Maya civilization also used metallic NPs to develop
blue paints exploding SP [32]. There are also evidence of the ancient use of metallic NPs in glass
and pottery from Egyptian dynasties [33], Celtic enamels [34], Japanese [35] and Chinese
glasses [36].
In the Middle Ages, the development of glass manufacturing processes induced outstanding
advances on stained glasses fabrication [37,38]. The variety of metallic NPs for glass colouring
increased substantially as we can observe in many church windows from that period. The
development of glass chemistry during Renaissance [39] and modern age [40], provided better
tuning of coloration effects based on the SP of metallic NPs. Excellent revisions of the historical
use of SP in metallic NPs for glass and pottery colouring are presented in ref. [31,41].
All these developments were empirically achieved without knowing the real origin of the surprising
optical effects appearing when metallic atoms were introduced in the glass. After Mie’s work in
early XX century, the origin of the optical properties of metallic NP was understood, but further
exploitation was limited by the capabilities to synthesise and manipulate NPs in a controlled way.
It was not until the development of nanotechnology at the end of XX century that the applications
of SP spread quickly on many fields.

2. 1 SP in NPs
As above indicated, SP correspond to an interaction between matter and the electromagnetic
field of the light. Thus, the exact analysis of SP implies solving the Maxwell equations with the
appropriate boundary conditions [1]. The solution of these equations is only possible for certain
conditions and even in this case, the results are mathematical series that do not explain what are

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SP. However, a simplified classical picture can be more useful to understand the physical
meaning of SP. A metallic NP can be described as a lattice of ionic cores with conduction
electron moving almost freely inside the NP (the Fermi sea) as figure 1 illustrates. When the
particle is illuminated, the electromagnetic field of the light exerts a force on these conduction
electrons moving them toward the NP surface. As these electrons are confined inside the NP,
negative charge will be accumulated in one side and positive charge in the opposite one, creating
an electric dipole. This dipole generates an electric field inside the NP opposite to that of the light
that will force the electrons to return to the equilibrium position (figure 1). The larger the electron
displacement, the larger the electric dipole and consequently the restoring force. The situation is
similar to a linear oscillator with a restoring force proportional to the displacement from the
equilibrium position. If the electrons are displaced from the equilibrium position and the field is
later removed, they will oscillate with a certain frequency that is called the resonant frequency; in
the case of SP it is named the plasmonic frequency. Actually, the electron movement inside the
NP exhibits some damping degree. The ionic cores and the NP surface partially damp the
electron oscillations. Thus, the system is similar to linear oscillator with some damping.

Figure 1. Scheme of the light interaction with a metallic NP. The electric field of the light induces the
movement of conduction electrons which accumulate at the NP surface creating an electric dipole. This
charge accumulation creates an electric field opposite to that of the light.

When an alternating force is applied to a linear oscillator, the system oscillates with the same
frequency than the external force but the amplitude and phase will depend on both the force and
the intrinsic parameters of the oscillator. In particular, the oscillating amplitude will be maxima for
the resonant frequency (figure 2a). It is quite straightforward to understand that, if the frequency
of the external force is the same that the plasmonic frequency of the NP, it will be easy to make
the electrons oscillate, but as we move far way from this frequency the movement of electrons will
be more difficult, i.e., with reduced amplitude.

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We can not observe directly the electrons movement to determine their oscillating amplitude.
However, we can determine this amplitude indirectly. The electronic oscillation implies an
increase of kinetic and electrostatic energies associated to the electric fields of the dipole. As
energy must be conserved, this increase of energy must be provided by the illuminating light.
Therefore, the light extinguishes partially when exciting SP inside the NP. The larger the electron
oscillations, the larger the light extinction, so the optical absorption spectrum allows to detect the
excitation of SP. The resonant frequency for these oscillations in metallic NPs corresponds
typically to UV-Vis light and consequently, the SP arise absorption bands in this region of the
spectrum as figure 2b illustrates.

Absorption (arb. units)

a
(a) (b)b
Amplitude

350 400 450 500 550

ωR
Frequency Wavelength (nm)

Figure 2. (a) Oscillation amplitude for a linear oscillator as a function of the external force frequency (b)
Optical absorption spectrum corresponding to 10 nm silver NPs embedded in a silica glass.

At this stage, SP can be considered as another electronic process in which light is absorbed to
promote electrons from the ground level to an excited one. What makes the SP unique are the
numbers of these processes. The absorbing efficiency of a particle is given by its absorption
cross section. Classically it corresponds to the geometrical section of an ideal opaque particle
absorbing the same number of photons than the studied particle. As figure 3 illustrates, we could
replace the absorbing NP by a perfect opaque one (absorbing any photon reaching its surface)
that will absorb the same number of photons that our real particle. The section of this ideal
particle represents the absorption cross section of the NP. For instance, if we have a NP
absorbing half of the photons reaching its surface, the absorption cross section will be half of its
geometrical section. Besides absorption, light interacting with matter can be scattered, changing
the propagation direction and eventually also energy and moment. For this process, we can
define also the scattering cross section as the geometrical section of an ideal scattering particle
(that scatters any photon reaching its surface) with the same scattering efficiency than the real
particle.

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Figure 3. (left) Illustration of absorption cross section concept. (right) Picture describing transmission,
absorption and scattering processes.

The sum of absorption and scattering cross section is defined as the extinction cross section that
represents the efficiency of the particle to remove photons from an incident beam (by both,
absorption or scattering processes). For perfect opaque particles the extinction cross section can
be at maximum the particle section (π·R2). However, for few nm NPs, extinction cross sections
larger to 10% of the geometrical section are scarcely found for other processes different to SP
excitation [42,43].
Figure 4 present the resonant wavelength and the extinction cross section for 10nm size metallic
NPs. It is found that for noble metal NPs the extinction cross section can be up to 10 times their
geometrical section; that is, the NP is capable of absorbing and scattering photon even away
from its physical position. Somehow, the excitation of the SP is equivalent to concentrate the light
passing by the NP to induce a huge extinction. It is worth noting that the light absorption has an
exponential dependence on the absorption cross section. A light beam propagating across a
medium with metallic NPs decay in intensity as:
I( x) = I0· e − C· σ· x (1)

being I0 the initial intensity, C the concentration of NPs per unit volume, σ their extinction cross
section and x the travelled distance. Therefore, a moderate increase in the extinction cross
section can lead to a huge enhancement of light absorption. As an example, if we have a
dielectric matrix containing 1020 NPs per cm3 with 10 nm size (1% in volume) and their extinction
cross section is equal to the geometrical section (π·R2) , the light transmitted across 1μm of the
material will be 45%; if the extinction cross section of the NPs is increased a factor of 10, the
transmitted light is reduced to 0.04% (i.e., 3 orders of magnitude). These numbers make SP
unique, since the cross section values found here are fairly larger than other optical processes as
electronic transitions in semiconductors (band to band transitions), rare earths atoms, defect
related absorption process in solid, or electronic excitations in molecules.

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700 Mg Li
600
Au

σext (nm )
500

2
400 Rb
300
K
Ag
200 Li
Ca
100 Pd Eu
Pt Y Cu
0
200 300 400 500 600 700
Wavelength (nm)

Figure 4. Resonant frequency and extinction cross section for metallic NPs with 10 nm size in air.

A more direct example of the huge extinction in metallic NPs due to SP excitation is provided by a
comparison with interband transitions. Besides SP, there are other possible electronic excitations
in metallic NPs. In a metallic material, valence and conduction bands overlap forming a
continuous spectrum of available states. However, some inner levels do not split enough to
overlap these bands so the system may exhibit interband transitions similar to those in
semiconductors [44]. Transitions between these inner levels and the conduction band induce an
absorption edge similarly to the case of semiconductors. Actually, some metals present a weak
luminescence emission due to electron decay between these bands. For bulk materials these
transitions are very unlikely and optical absorption and emission associated with these transitions
result very weak. For instance, a weak photoluminescence associated to interband transitions
has been measured for bulk gold [45] corresponding to transitions between the 3d level and the
conduction band. However, for NPs with a reduced number of atoms, energy bands are not so
well formed because of the limited number of atoms and interband transitions become more
prominent.
Figure 5 shows the optical absorption spectrum of Ag and Au NPs. In the case of Ag, both SP
band and interband transition absorption edge are well resolved. For Au NPs, both absorptions
overlap. This overlapping is important when analysing the shape of the SP. In particular, the width
of the SP band (related to the NP size) must be determined separating the contribution of the
interband transitions. We may observe how the SP absorption is fairly larger than that of the
interband transitions despite the fact that the absorbing centre is the same for both processes.

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40
Ag NPs 50 Au NPs
40 nm diameter 40 nm diameter SP band
SP band
30 40
Absorption (%)

Absorption (%)
20 (a) 30 Interband (b)
transitions
Interband 20
transitions
10
10

0 0
200 300 400 500 600 400 500 600 700 800
Wavelength (nm) Wavelength (nm)

Figure 5. Optical absorption spectra for (a) Ag and (b) Au NPs with 40 nm size (embedded in a silica
matrix with ε=2.25). For Au NPs, the contributions to the optical absorption of interband transitions and SP
are resolved.

The reason for this surprising behaviour can be qualitatively explained with the same classical
picture of SP. When the incident light reaches the NP, the conduction electrons move resulting in
a charge accumulation at the NP surface. This charge creates a field inside the NPs (the
restoring field) but also out of the NP. The large electron density and mobility in the metallic NP
produces a large charge accumulation at the NP surface and consequently intense fields in a
region fairly larger than NP size. As figure 6 illustrates, there are wide regions were the electric
field created by the particle is opposite to that of the light, so the interference results destructive,
leading to light extinction beyond the NP volume [46]. For other regions, the result of the
interference between both electric fields is a net field with other propagating direction, hence
inducing light scattering. This mechanism explains qualitatively the huge extinction cross section
of metallic NPs when SP are excited. Actually, the excitation of SP with laser sources can even
yield a modification of the NP shape by local increase of the temperature associated to the huge
absorption [47,48,49,50].

Figure 6. Illustration of electric fields of incident light and that created by the electron oscillations near the
NP.

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2.2 Models and calculations of SP

While the above classical description can be useful to illustrate and understand what are SP, it is
too simple to carry on numerical analyses. An accurate calculation of the SP and the associated
light absorption requires solving the Maxwell equations at the NP region using the proper
boundary conditions. The analytic solution can be obtained only for certain geometries and it was
developed by Gustav Mie in the early 1900 [1,26]. The Mie theory provides an exact solution for
spherical NPs assuming that they are non-interacting (i.e., the distance between the NPs is large
enough so we may assume that the electric field created by a NP does not affects to the rest of
them). In this case, Maxwell equations can be solved analytically and the extinction cross section
is given by:
2π ∞
σex = ∑ (2 L + 1)·Re[aL + bL ]
k 2 L=1
(2)

being

mΨL (mx )·ΨL' (x ) − ΨL' (mx )·ΨL (x ) ΨL (mx )·ΨL' (x ) − mΨL' (mx )·ΨL (x )
aL = bL =
mΨL (mx )·η L' (x ) − ΨL' (mx )·η L (x ) ΨL (mx )·η L' (x ) − mΨL' (mx )·η L (x )
;

Where k is the light wavevector in the dielectric medium, x=|k|·R, R is the NP radius, , m=n/nm
being n and nm the refraction index of the metal (complex) and that of the surrounding dielectric
medium respectively , and ΨL and ηL are the cylindrical Bessel-Ricatti functions. These
equations are not easy to handle, although there are codes available to carry on calculations.
There is a large list of theories that allow calculating the light absorption associated with SP for
specific size ranges or when NPs are not spherical or they are interacting. An excellent review of
these theories is given in [1]. We survey here just the most common ones.

The dipolar approximation

The dipolar approximation offers simple equations to calculate light absorption of metallic NPs
provided that the NP size is fairly smaller than the light wavelength (besides the hypothesis of Mie
theory). As the SP resonance band falls at the visible part of the spectrum (~360-720 nm), the
condition of small NPs is usually achieved for NPs diameter below ~50 nm. In this case, the
electric field inside the NP can be considered as uniform (see figure 7) and the particle can be
described by an electric dipole. Mathematically, this approximation is achieved assuming that x is

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small enough, so, in equation (2) we can just consider the first term L=1. (Note that the term L=0
corresponding to the total electric charge of the NPs is zero).

Light
--
++

Light --
++ -
+
- +
-- + +

Figure 7. Electric field and charge distribution at the NPs surface for size (top) much smaller and (down)
comparable to the light wavelength.

Within this approximation, the absorption cross section is given by:

3
24π 2R 3ε m2 ε2
σ ext = (3)
λ (ε 1 + 2ε m )2 + ε 22

As the NPs size increases, the approximation is not valid anymore, since the electric field inside
the NP can not be considered uniform. In that case, more multipolar terms (i.e. more terms in
equation 2) must be considered as discussed below.

The Effective Dielectric Function Theories

Another approach to calculate the optical properties of metallic NPs consist on replacing the
heterogeneous system formed by the NPs (described by a complex dielectric function ε1+iε2) and
the surrounding media (εm) by a homogeneous medium with an effective dielectric function
εeff1+iεeff2). These theories are known as effective medium theories. There are a large number of
these theories depending on the exact conditions that are imposed to the homogeneous medium
[1]. The first approach was proposed by Newton [1,51] defining an effective dielectric function as
an average of the NPs and medium dielectric function weighted by their volume.

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However, the best approach within the framework of effective medium theories was developed by
Maxwell-Garnett [52,53,54,55] proposing to replace the NPs-dielectric medium system by an
homogenous material exhibiting the same dielectric polarization upon light illumination. With this
condition, the complex effective dielectric function is given by:
ε eff − εm ε − εm
= f (4)
ε eff + 2εm ε + 2εm

and the extinction cross section of the material is then given by:

8.88·10 7
α(cm−1 ) = − ε1ef + ε12eff + ε22eff (5)
λ (nm)

being λ the light wavelength. For the case of spherical, small and isolated NPs, this model leads
to the same result that the dipolar approximation. An interesting advantage of the Maxwell-
Garnett model is that it can be modified to take into account interparticle interactions [56,57] or
the presence of non-spherical NPs [1,58, 59].

2.3 Size effects

NPs size has a dramatic effect on the SP resonance processes and consequently on the optical
properties of the NPs. Actually, there are different mechanisms inducing size dependence of the
SP properties. The predominant one will depend on the NP size range we consider. As a general
approach, we may distinguish two regimes corresponding to small NPs (fairly smaller than the
light wavelength) and large ones with size comparable to the wavelength.

Small NPs (up to ~50 nm)

For this size range, we may assume that the NP is properly described by a dielectric dipole. The
size dependence of the SP affects mainly the width and the intensity of the resonance band while
the effect on the resonance wavelength is quite reduced [60]. Dealing with size effects in this
range, we can distinguish between intrinsic and extrinsic size effects.
The intrinsic effects are related to the damping of the electron oscillations. When SP are excited,
the electrons are damped in their movement by the scattering with the ionic cores and with the
surface. The damping constant for the electron oscillations is given by:
VF
γ = γ0 + A (6)
R

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The first term (γ0) describes the damping due the scattering of the oscillating electrons with the
ionic cores. It is size independent and its value is given by γ0=vF/l∞, being vF the velocity of the
conduction electrons (Fermi velocity) and l∞ the electron mean free path in the metal. This term
depends just on the nature of the metal and the crystal structure. For Au at 300 K we have
vF=1.4·106 m·s-1 and l∞=30 nm leading to γ0=4.6·1013 s-1 and for Ag we have vF=1.39·106 m·s-1
and l∞=52 nm leading to γ0=2.6·1013 s-1.
The second term corresponds to the scattering of oscillating electrons with the particle surface. A
is a material dependent constant that takes into account the features of the surface scattering. It
is commonly considered as a phenomenological parameter although it is well established that it
depends on the surface features as crystal quality, facets, capping species, strain, etc [1,60]. The
electrons in a certain shell close to the NP surface will scatter this surface when they oscillate.
The larger the velocity of the oscillating electrons (which is about the Fermi velocity), the larger
the number of electrons scattering the surface during their movement (i.e., the thickness of the
shell of electrons scattering the surface during oscillations). As the particle size increases, the
fraction of electrons in the shell close to the surface decreases and therefore the total damping is
reduced. Therefore, the surface damping results proportional to the Fermi velocity in the metal
and inversely proportional to the particle radius.
It is well known that the resonance of a linear oscillator reduces its intensity and increases the
width with the damping constant, while the effect on the resonance frequency is very limited (a
slight shift toward smaller frequencies, i.e. larger wavelengths). Experimentally, it is observed that
the full-width-at half maximum (FWHM) of the SP resonance band is given by:

b
Γ = a+ (7)
R

Figure 8 presents the optical absorption spectra of silver NPs embedded in silica (n=1.5) with
different size. The resonance absorption intensity increases with particle size while the resonance
peak slightly moves. The dependence of the FWHM of the resonance peak with the particle size,
shown in figure 8 follows the inversely proportional law of eq. 7 for radius below 25 nm (inset in
figure 8).

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0.75
0,75
0.020 Ag NPs

FWHM (eV)
a b
Absorbance (arb. units)
20 nm 0.75
0,75 0.50
0,50
nm=1.5 0.25

FWHM (eV)
0,25
0.015

FWHM (eV)
0,00
10 nm 0.50
0,50 0.25 0,50
0,25 0.50 0,75
0.75 1,00
1

0.010 5 nm 1/R (nm-1)

0.25
0,25
0.005
2 nm

0,00
0.000 0 0 5 10 15 20 25 30
350 400 450 500
Wavelength (nm) NP Radius
Radio (nm)
(nm)

Figure 8 (a) Optical absorption spectrum for Ag NPs with different size calculated according to the Mie theory. (b)
FWHM as a function of the particle radius; inset shows the linear relationship between FWHM and the inverse of the
radius.

Besides this intrinsic effect of the NPs size on the SP, it has been reported that the dielectric
function of small NPs is also size dependent [1,61]. At this scale, the energy bands are not so
well defined as in a bulk solid, and consequently contribution of the interband transitions to the
dielectric function results size dependent. Consequently there is an additional dependence of the
SP on the NPs size through the dependence of its dielectric function. This effect is also
appreciable for NPs below 5 nm size and the value of the dielectric function can be calculated
from the bulk one [61 ].

Large NPs (above ~50 nm)

NPs with radius larger than 50 nm can not be considered anymore much smaller than the light
wavelength inside the metal. Thus, the particle is no more described by a dipole (figure 7) and
further multipolar terms are required. As a consequence, the resonance band splits into several
peaks: two peaks for quadrupole, three peaks for a octopole, etc [60]. Figure 9 shows the
contribution of the different terms in equation 2 to the extinction cross section of Au NPs.
For Au NP with radius below 60 nm, the quadrupolar term (L=2) is negligible and the multipolar
effects must be taken into account.

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R=40 nm L=1 L=2 L=3 L=4

Absorption Coeff.

R=60 nm L=1 L=2 L=3 L=4

R=80 nm L=1 L=2 L=3 L=4

R=100 nm L=1 L=2 L=3 L=4

400 500 600 700 800 400 500 600 700 800 400 500 600 700 800 400 500 600 700 800 400 500 600 700 800

Wavelength (nm)
Figure 9. Optical absorption spectrum for Au NP with different size calculated according to the Mie theory
for nm=1.5 and the contribution of the different multipolar terms

If the NP size is further increased, NPs can not be considered anymore as multipoles and the SP
become propagating waves with well defined modes or dispersion relations [2]. These are named
itinerant SP and represent a quite different kind of phenomenology [3].

Size dispersion
Although synthesis methods for metallic NPs improved substantially in the last years, the result is
always a set of NPs with certain size dispersion. Consequently, the experimentally measured
optical absorption spectrum of a material containing metallic NPs, will be a weighted average of
the absorption spectra corresponding to the NPs present in the sample.
The size dispersion induces a broadening of the absorption band. As figure 10 illustrates, the
larger the size dispersion, the wider the absortion band. In particular, we found that for a set of Ag
NPs with average size of 10 nm and a dispersion ±4.2nm, the FWHM of the SP absorption band
is three times smaller than that for 10 nm Ag NPs with a size dispersion ±8.5nm. Thus, it is not
possible to determine the size of the NPs just from the FWHM of the absorption band, as it
depends on two parameters: average size and size distribution width.

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Absortion coefficient (arb. units)

a
0.8
b
0 3 6 9 12 15

Radius (nm) 0.4

b 0.0
300 400 500 600

Wavelength (nm)
0 5 10 15 20 25

Radius (nm)

Figure 10 (left ) size distributions and (right) optical absorption spectra for Ag NPs both with 10 nm
average size but different size dispersion calculated according Mie theory and using nm=1.5. For size
distribution (a)

2.4 Shape effects

The resonance of SP is strongly affected by the particle shape. Since the restoring force for SP is
related to the charge accumulated at the particle surface, it will be influenced by the particle
geometry. The most clear example of these shape effect are the nanorods [59,62]. As figure 11
illustrates, for a nanorod, the charge accumulation at the NP surface will be different for electron
oscillations along the rod axis (longitudinal plasmons) and or along perpendicular direction
(transversal plasmons). In particular, the charge accumulation will be maximum for this later and
minimum for electron displacement along the rod axis. The restoring force is proportional to this
charge accumulation, and therefore, for electrons oscillating along the rod axis we should expect
smaller forces and consequently smaller resonance frequencies (i.e., larger resonant
wavelengths). For nanorods, the resonant frequency of transversals plasmons falls at about the
same position that for spherical NPs (actually, at wavelengths slightly smaller) while the
resonance of longitudinal plasmons shifts toward larger wavelengths when the nanorod aspect
ratio increases, as illustrated in figure 11b. This behaviour provides a method to tune the
resonance of the SP at the desired wavelength by controlling the aspect ratio, which is especially
useful for biomedical purposes as explained in section 3.1.
Using polarised light it is possible to excite separately the longitudinal or transversal SP of a
nanorod. However, if the rods are not macroscopically oriented (as it is the case for colloidal

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suspensions or solutions) we will always observe an average over the possible orientation with
both, longitudinal and transversal resonance bands in the spectrum as in figure 11b.
Other geometries as triangular prisms, nanocubes or nanocages give rise to more complicated
effects, but in general [59], deviation from sphericity shifts the resonance toward larger
wavelengths.

(a)

Resonance Intensity (arb. units)

--- Absortion Coef. (arb. units)
5
12 1200

(b) 4
(c)

Resonance Peak (nm)

+++++++++++

-----------

10
1000
3
8

1 2 6 800

4
600

2
+++ 400 600 800 1000 1200 1400 0 1 2 3 4 5 6

Wavelength (nm) Aspect Ratio

Figure 11. (a) Illustration of charge accumulation for longitudinal and transversal SP (b) Calculated
absorption spectra for Au nanorods with different aspect ratio indicated in the figure. (c) Resonant position
and intensity of the longitudinal SP as a function of the nanorod aspect ratio.

Calculations for non spherical NPs are rather complicated. Actually the Maxwell equations can be
solved analytically only for spherical nanoshells or ellipsoids. The Gans theory [1,58,59] provides
a method to calculate the SP spectra of non spherical NPs within the dipolar approximation
framework by approximating the nanostructure to an ellipsoid.
For other geometries, calculation of the SP spectra can be addressed by the so-called discrete
dipole approximation [59,63]. Within this method, the nanostructure is replaced by an ensemble
of nanospheres fairly smaller than the nanostructure. Each nanosphere is described by a
polarization factor (than can be derived from Maxwell-Equations since they are assumed to be
spherical) and the field at the nanosphere position is that of the incident light plus the field created
by the rest of NPs. With this method, any geometry can be in principle addressed.

2.5 Surrounding media

The excitation of SP does not depend only on the NPs features but it is also significantly modified
by the surrounding medium. It has two clear effects on the SP excitation process. On the one
hand, the dielectric function of the surrounding medium determines the light wavelength at the
vicinity of the NP hence altering the geometry of the electric field at the NPs surface.

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But the most important effect is related to the polarization of the medium. During SP excitation,
the charge accumulation creates an electric field in the vicinity of the NPs (beside that of the
incident light). This field induces the polarization of the dielectric medium, resulting in a charge
accumulation at the edges of the medium (i.e., at the interface between the dielectric and the
metallic NPs) that will partially compensate the charge accumulation due to the conduction
electrons movement. This reduction of charge will depend on the dielectric function of the media;
the larger εm, the larger the polarization charge, and hence, the larger the effect on the SP.
Reducing the net charge at the NP surface implies a reduction of the restoring force. For an
oscillator, it is well known that reducing the restoring force leads to smaller resonant frequency.
Thus, increasing the dielectric constant of the surrounding media will shift the SP resonant band
toward larger wavelengths (i.e., smaller frequencies).
Figure 12 shows the absorption spectra for 10nm size Au NPs embedded in media with different
dielectric functions. The surrounding medium has a limited effect on the bandwidth (measured in
eV), that is mainly related to the particle size. The resonance intensity also increases with the
dielectric function of the medium. This is the expected behaviour for a forced oscillator: when the
resonance frequency decreases, the amplitude at resonance increases. This is mathematically
3
reflected in eq. 3, where the absorption cross section is proportional to ε m2 .
Optical absorption (arb. units)

1
1.5
2
2.5
3
3.5

450 500 550 600 650 700 750 800

Wavelength (nm)

Figure 12 Optical absorption spectra for Au NPs with 10 nm size in a dielectric medium with
different dielectric function calculated according to Mie theory.

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NPs obtained by chemical routes are commonly capped with organic molecules to prevent
agglomeration. These capping agents have a significant effect on the SP features since they
represent the very first environment of the NP. Moreover, the strength of the bonds between the
NP and the molecules induces an extra effect [1,64,65]. The modification of the NP electronic
configuration due to surface bonds modifies the conditions for electron oscillation, yielding to
variations in the SP spectrum that can be used to investigate the characteristics of these bonds
[66].

2.6 NPs interactions effects.

As detailed above (see figure 6), the excitation of SP induces an electric field in the vicinity of the
NPs. If the NPs are close enough, the net applied field at the NPs positions will be that of the
incident light plus the field created by the rest of NPs. Therefore, the resonant conditions will be
modified. In general, interparticles interaction red-shift the resonance band increasing the FWHM
as illustrated in figure 13a [56,57,67,68]. When NPs are arranged in particular geometries it is
possible to create controlled interferences that allow additional tuning of the SP excitation band
(figure 13b). These effects can be achieved when the NPs are created by film deposition and
patterning or by self-assembly processes.
Extintion coeff. (arb. units)

(a) K=100 (b)

Ext. Coeff. (arb. units)

Ag NPs

K=50 R=20 nm

K=0

400 600 800 400 600 800

Wavelength (nm) Wavelength (nm)

Figure 13. (a) Optical absorption spectra for Au NPs with dipolar interactions. Parameter K represents the
intensity of the electric field created at a NP position by the rest of the NP as described in [57] (b) Optical
absorption spectrum of arrays of 20 nm Ag NPs with different geometries. Adapted from [1].

The field created by a NP quickly decays with distance and therefore, the main effect is due to
adjacent NPs while those far away have a very weak effect (note that for a dipole, the electric
field decreases as 1/r2) . Due to this fast decay, the electric field created at a NP position by other

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NPs close enough, will not be uniform but it will exhibit significant amplitude variations in the NP
volume. As SP resonance is a resonant process, it is required that all the electrons receive the
same electric field; otherwise the electrons movement will be heterogeneous leading to charge
accumulation inside the NP volume that rise electric forces, resulting on a extra damping of the
oscillations.

3. Applications
The high absorption coefficient associated with the excitation of SP opens a wide range of
potential applications of metallic NPs in many fields. The possibility to concentrate, amplify and
manipulate light at the nanoscale through SP, provides a method to improve optical effects or
activate processes in a controlled way. There are hundreds of potential applications of SP in
different fields that have been thoroughly reported in literature impossible to review here. We will
just highlight some of them in order to illustrate capabilities of SP in four selected fields:
biomedicine, energy, environment protection and information technologies.

3.1 Biomedicine
Biomedical applications are certainly the most developed SP potential uses. Besides the
possibility to explode SP, noble metal NPs exhibit additional features that make them specially
useful for this field [59,69,70]. NPs have the biological size, comparable to entities as virus, DNA
chains, cells or bacteria. Hence, it is possible the NPs to interact individually with these
organisms increasing efficiency and specificity of medical treatments. Moreover, noble metal NPs
are highly biocompatibility and easy to functionalize (mainly through thiol chains that create
strong bonds with NPs surface and may act as linkers with larger organic molecules). Thus, in
vitro applications of metallic NP exploding SP are well established while in vivo ones (always
slower to develop due to the requirements of long term effect essays) show certainly promising
results.

DNA sequencing
Noble metal NPs are nowadays used for DNA sequencing, replacing the dyes based technology
[71,72]. The use of dyes causes some problems as photobleaching and instability in certain
environments that limit their applications [72,73]. Moreover, the spatial resolution and sensitivity
required to carry out thousands of test compel to use confocal microscopy leading to complex
and expensive devices [74]. The use of metallic NPs may overcome these limitations as noble

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metals are highly stable and the huge absorption cross section associated with SP resonance
allows the easy detection of small quantities of NPs.
Figure 14 illustrates the strategy for the development of DNA sequencers. The target DNA chain
to be analyzed is attached to a metallic NP (gold NPs are the most commonly used ones)
creating a NP/DNA complex (figure 14a) by polymerase chain reaction or through thiol chains
[72,75]. A sensing surface is functionalized with patterns of oligonucleotides (short nucleic acid
chain, typically with fifty or fewer bases) to be used as probes (figure 14b). These
oligonucleotides are able to form self-assembled monolayers prompting the formation of
geometrical dense patterns. Finally, the solution containing the target NP/DNA complex is placed
over the sensing surface. DNA strands spontaneously bind to oligonucleotides containing the
complementary chain [76]. Therefore, the target DNA/NP complexes will accumulate over the
surface functionalised with oligonucleotides with chains complementary to the target DNA one
(figure 14c). Illuminating the sensing surface with light at the plasmonic frequency of the gold
NPs, it is possible to detect the regions where the DNA/NPs complexes are accumulated. The
large scattering due to SP excitation allows detecting small amounts of NPs in small regions
using an optical microscope (figure 15). Sensing surfaces with a large number of oligonucleotides
can be automatically analysed with a digital camera, allowing a quick identification of the
sequences present in the target DNA [72] as illustrated in figure 15.

Figure 14. Scheme of the DNA labelling process with NPs.(a) Target DNA chains are attached to metallic
NPs. (b) A sensing surface is prepared with regions of oligonucleotides (ON) with specific sequences to
be detected. (c) When the solution containing DNA/NPs complexes is placed on the sensing surface,
these complexes will bind to the oligonucleotides with the sequences complementary to the target DNA;
the SP allows the spatial detection of the NPs identifying the sequences present in the target DNA.

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Figure 15. (left) Optical reflection image of NP–labelled DNA chip; the regions with NPs appear brighter
due to the reflection of incident light. (right) Zoom of one square by scanning force microscopy reveals
individual NPs. Reproduced with permission from [72].

Cell labelling
Following a very similar strategy, it is possible to use SP for cell labelling. To this purpose, NPs
are functionalized with biomolecules exhibiting affinity for certain species and/or particular cell
features and introduced into cell cultures. This technology is particularly useful to identify cancer
cells [77,78,79,80,81]. NPs functionalized with molecules having higher affinity for these cancer
cells than for normal ones, will concentrate around these cancer cells that can be then detected
by optical microscopy.
Au NPs can be used to label malignant epithelial cells as demonstrated by El-Sayed et al [80].
Non-functionalised NPs tend to accumulate within the cell cytoplasm providing anatomic labelling
information of the cell. The NPs exhibit the same affinity for malignant and non malignant cells.
However, if the NPs are functionalized with monoclonal anti-epidermal growth factor receptor
antibodies, the affinity for malignant cells is 6 times larger than for non-malignant ones. The NPs
accumulation is detectable with optical microscopy at SP wavelength due to the high scattering
cross section, providing a method to identify malignant cells specifically (figure 16). In addition, a
spectroscopic study have shown that the SP absorption band for the NPs accumulated at the
surface of malignant cells results sharper and red shifted [80], which may be an additional
method for cell labelling using smaller quantities of NPs and more reliable than intensity contrast.

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Figure 16. Light scattering images of HaCaT non-cancerous cells (left), HOC cancerous cells (middle),
and HSC cancerous cells (column) after incubation with anti-EGFR antibody conjugated gold NPs. The
conjugated NPs bind specifically to the surface of the cancer cells (right). Reproduced with permission
from [80].

Similar works have demonstrated selective labelling using Au NPs functionalized for ductar
carcinoma cells (ATCC: Hs 578T) [79], human epidermal growth factor receptor 2 (HER2) [82],
cervical epithelial cancer cells (SiHa) [83] human oral squamous carcinoma cells (HOC) [84] and
others [85,86]. Outstanding results have been also achieved by using combined techniques in
which the excitation of SP is used to amplify or trigger other optical processes as photoacustic
imaging [87] SERS [88,89] or dye fluorescence [90].

In vivo labelling and imaging

Development of in vivo imaging and labelling techniques are quite limited because the absorption
band of SPR is almost identical to that of haemoglobin, the main protein of human blood as
shown in figure 17. Therefore, it is very difficult to detect or energize gold NPs in the bloodstream.
2.5
Nanoparticles
Nanorods
Coef. Abs. (cm )

2.0
-1

Blood
1.5

1.0

0.5 10 nm

0.0
500 600 700 800 900
Wavelength (nm)

Figure 17. Optical absorption spectrum of Au NPs and nanorods. Inset shows a TEM image of the
nanorods. Absorption spectrum of human blood is also shown for comparison. While the SP band of NPs
and the transversal SP of nanorods falls in the same region of the spectrum that the blood, the longitudinal
SP band is located at the Near-IR, where biological tissue scarcely absorbs.

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The strategy to overcome this limitation is the use of non-spherical NPs such as nanorods,
nanocubes, nanocages [59,74,81,91]. Among these geometries nanorods are the most
commonly used ones since controlling their aspect ratio it is possible to tune the SP resonance
position to the “biological window” between 800 and 110 nm where the blood and tissues scarcely
absorbs (see figure 17). Nevertheless, even with the use of nanorods, it is very complicated to
observe directly scattered or transmitted light across biological tissue due to the large number of
scattering bodies in the bloodstream (erythrocytes, leukocytes, thrombocytes, etc). Thus, the best
results in this line up to now have been achieved by using nanorods combined with other
techniques as SERS [92] or photoacoustic imaging.
For the combined use of SP resonance and photoacoustic technique, gold nanorods
functionalised with the appropriated biomolecules are injected in the tissue. The tissue is later
illuminated with pulses of light at the SP resonance wavelength in the NIR. The strong absorption
cross section of the nanorods leads to a local increase of temperature during laser pulse. This
heat is quickly dissipated to the adjacent tissue which undergoes a thermoplastic expansion
creating an acoustic wave that propagates through the tissue and can be mechanically detected
at the surface. Using this technique, Eghtedari et al recently detected Au nanorods in mice [93].
The experiment is illustrated in figure 18. Au nanorods where chemically synthesised controlling
the aspect ratio to exhibit the maximum absorption of longitudinal SP at about 750 nm. The
nanorods were injected in the mouse that was placed onto an acoustic transducer to detect
acoustic waves and convert them into an electrical signal. The mouse was illuminated with an
alexandrite laser (757 nm wavelength) emitting 75 ns pulses with an average energy per pulse of
6 mJ/cm. The laser beam scanned the mouse recording the signal on the transducer after each
pulse. Regions with high concentration of Au nanorods presented enhanced light absorption and
consequently produced more intense acoustic waves after the laser pulse, that were detected
with the acoustic transducer few microseconds after the laser pulse. The images of
photoacoustic waves intensity obtained upon scanning the mouse with the laser beam before and
after gold nanorods injection are shown in figure 18. The region where the nanorods were
injected results brighter demonstrating the capability of the method to detect gold nanorods into a
living organism.

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Figure 18. (left) Schematics of in vivo experiment to detect injected gold nanorods by optoacoustic
imaging. (right) A typical optoacoustic image of a nude mouse before (a) and after (b) subcutaneous
injection of Au nanorods in the abdominal area. Injected NPs were brightly visible in the optoacoustic
image (b). Drawing in (a) depicts the approximate position of the nude mouse during experiment.
Reproduced with permission from [93].

Hyperthermia
In addition to the possibility to detect, image and label biological entities, the SP offer the
possibility to activate processes in a controlled way, so they can also be used for therapy. The
intense light absorption and electromagnetic field enhancement allow energizing the NPs to
trigger events locally as desired.
Hyperthermia is a non-invasive technique for cancer treatment consisting of heating the biological
tissues to temperatures slightly (~5-10 ºC) over the normal one to promote the selective
destruction of abnormal cells [94]. This increase of temperature may induce denaturalization of
proteins, disruption of the organized biomolecular assemblies in the nucleus and cytoskeleton,
and increase the membrane permeability [95]. A further step is the selective hyperthermia,
consisting of a controlled heating of malignant cells. This strategy can provide advantages in
cancer treatments as the normal tissue remains unaffected promoting the replacement of
malignant cells with healthy ones, although the long term impact on patients is still undetermined.
The light absorption associated to SP excitation produces a local heating that can be exploded for
selective hyperthermia. To this purpose, nanorods are functionalized to bind specifically
malignant cells (as in the imaging techniques described above). When the tissues are illuminated
with NIR laser at the SP wavelength, the energy absorbed by the nanorods is partially converted

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into heat, increasing locally the temperature. Due to the high absorption efficiency of nanorods it
is possible to increase their temperature several degrees. As the functionalization of the nanorods
promote their accumulation around malignant cells, these later will be selectively heated,
favouring their elimination with a reduced effect on healthy cells.
Recently, Wei et al [,95,96,97] shown in vitro selective elimination of adherent human KB cells (a
tumour cell line derived from oral epithelium) using gold nanorods to perform localized
hyperthermia. Adherent KB cells cultive were exposed to gold nanorods conjugated to promote
the binding to the cell membrane (see figure 19).

(a) before (b) after

(c) before (d) after

Figure 19. Photothermolysis mediated by folate-conjugated nanorods. (a, b) KB cells with membrane-
bound nanorods (red) exposed to fs-pulsed near-infrared laser irradiation experienced membrane damage
and blebbing. The loss of membrane integrity was indicated by ethidium bromide nuclear staining (yellow).
(c, d) NIH-3T3 cells were unresponsive to nanorods and did not suffer photoinduced damage under the
same irradiation conditions. Reproduced with permission from [96].

A laser working at 815 nm (where the NR exhibited a high absorption due to excitation of SP) with
femtosecond pulses was used to irradiate the cultive. The irradiation induced a local heating of
the nanorods (and consequently of the malignant cells) leading to a severe damage of the
membrane. The membrane blebbing was optically confirmed by using a dye (ethidium bromide)
as indicator of the membrane permeability. As figure 18 illustrates, in absence of nanorods, the
cell did not suffer appreciable effects. Therefore, with the proper functionalization of the nanorods
to bind specifically malignant cells, it is possible to perform selective hyperthermia on these cells,
while normal ones do no suffer significant damage. Positive results have been found also

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functionalizing Au nanorods with CTAB and folate that promotes nanorods uptake and
internalization by the KB cells instead of accumulating at the membrane [95].

Drug delivery
This heat dissipation and local increase of temperature associated with SP excitation can be also
used for drug delivery. This is particularly useful for certain drugs that are highly aggressive and
may induce undesired secondary effects on normal tissues. Controlled drug delivery leads to
higher efficiency reducing these secondary effects. Commonly, the strategies of drug delivery are
based on covering the drug with a coating that avoids interaction with non-targeted cells [98].
Once the drug reaches the target cell, the coating is removed releasing the drug to act at the
desired region. Moreover, releasing rate can be also controlled to improve effectiveness. Metallic
NPs holding SP can be used to this purpose [99,100,101,102]. A controlled release of the drug
can be achieved by exciting SP: the light concentration around the NP can provide the energy
required to activate the drug release process. Figure 20 presents an example of SP controlled
drug delivery [98]. The drug is coated with a shell consisting on a polymer with embedded gold
NPs and functionalized on the outer side with antibodies for specific cells. Once the ensemble
reaches the target cells, the region is irradiated with light at the SP wavelength. The excitation of
SP at the NPs induces a local heating and melting of the polymer shell, releasing the drug at the
desired region and time. The heating efficiency of the metallic NPs can be optimized with different
methods [103].

Polymer conjugate with

gold nanoparticles
Antibodies

Figure 20. (a) Drug is coated with a polymer shell containing gold NPs and antibodies for specific uptake.
(b). When the drug reachs the target, SP are excited with a laser beam, the dissipated heat melts the
polymer and (c) release the drug at the desired region. Reproduced with permission from [98].

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3.2 Energy
The nowadays energy problem impels to search for energy sources different to traditional ones
based on fossil fuels. In this search, the sun appears as a clean source of energy with lifetime
over 5000 million years releasing daily 4000 times the earth electric energy consumption. The
use of solar energy can be addressed by different techniques including photovoltaic
[104,105,106,107], photochemical [108,109,110] or photothermal [111,112,113] ones. The main
limitation of these technologies relays on the efficiency of the light absorption and conversion
processes that make them hardly viable from an economical point of view. The capabilities to
concentrate and locally amplify the light electric field by means of SP offer new methods to
increase the efficiency of photoenergetic process, overcoming the efficiency limitation required for
the massive implantation of these technologies.
Photovoltaic devices represent the most exploded way to harvest solar energy. While there are
several generations of photovoltaic devices [106], all of them are based on junctions where
electron-holes pairs created by light absorption are separated, leading to charge accumulation
that produces electric voltage, i.e., electric energy, as figure 21a illustrates. The main limitation in
the development and implantation of photovoltaic devices is their efficiency. Photovoltaic devices
result economically viable with cost below ~1$/Watt [114], a value scarcely achievable by last
generation solar cells [106]. A key problem in improving efficiency of photovoltaic devices is that
large thicknesses are required to absorb most of the incoming light, especially for silicon based
solar cells, due to the indirect gap nature of silicon. However, these larger thicknesses enhance
the electron-hole recombination probability increasing looses and requires larger amount of
material (i.e., larger production costs). Thus, the efficiency of solar cells still is an open question:
nowadays, the most efficient devices cells reach 25% of energy conversion efficiency [106].
The incorporation of metallic NPs in solar cells can increase the efficiency of charge separation
by several physical processes [115,116,117]. As figure 21 illustrates, if we place metallic NPs at
the device surface, upon light illumination, the large scattering cross section associated with SP
can scatter the normal incident light beams. Hence, the effective path across the active
absorption layer in increased. Moreover, with a proper architecture, this scattering may be used
to promote total reflection inside the layer trapping the photons until they are finally absorbed
(figure 21b). Another method to improve efficiency exploding SP, consists of placing the NPs at
the junction interface (figure 21c). The light concentration and local amplification in the vicinity of
the NP when SP are excited increases the absorption efficiency. Stuart and Harris [118]

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demonstrated an increase up to a factor 20 in the photocurrent of a silicon photodetector by

placing silver NPs on the surface.

(a)
e n

p
* recomb.
h

(b) (c)

Figure 21 (top) Scheme of photovoltaic cell. Light absorption at the p-n junction induces charge
separation. If the absorption takes place far from the junction, recombination results more likely, reducing
the cell efficiency; (bottom) Illustration of processes improving photovoltaic efficiency by (a) light
scattering and (b) local amplification. Reproduced with permission from [115].

Increases of photovoltaic cells efficiency of the order of 10-15% have been achieved by
incorporating Au and Ag NPs on the cell surface [119,120,121,122,123]. The efficiency in this
kind of devices has a complex dependence on the NPs size, shape and spatial distribution, since
interacting effects play a different role on the light scattering and absorption processes [116]. The
impact of both mechanisms in the final improvement is not easy to disentangle although most
recent results points toward the scattering process as the key one. Actually, some outstanding
results have been achieved by using non-resonant silica NPs [124]. The use of SP has been
explored not only in silicon based solar cells, but also in third generation organic devices
[125,126,127] with efficiency enhancement up to a factor 2.

(a) (b)

Figure 22. Improvement of efficiency on (a) silicon and (b) organic photovoltaic cells by incorporation of
silver NPs. Reproduced with permission from [123] and [126] respectively.

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Photothermal technology is an alternative to photovoltaics especially when the energy is used for
heating [128]. In typical photothermal devices, a fluid absorbing light increases its temperature
and is submitted to a thermal cycle releasing energy. The efficiency of thermal cycles is limited by
the temperature difference between the hot and cold focus. Thus, reducing the mass that absorbs
the solar light will increase its temperature and consequently improve the efficiency of the device.
The huge extinction cross section of SP provides a method to achieve intense ligh absorption by
small masses. Moreover, the tunability of SP resonance band allows the design of selective
absorbers that reduces energy looses due to blackbody radiation [129].
Besides the pure physical methods, SP can also be used to catalyse reactions for energy
harvesting using chemical paths, for instance the water decomposition for hydrogen generation
as described in the next section.
In general, any photoenergetic process addresses the problem to explode the wide solar
spectrum. As most of optical transitions in bulk materials exhibit well defined absorption bands, it
is difficult to design materials capable to absorb efficiently over a large part of the solar spectrum.
SP are not an exception, but, as described above, it is possible to tune the SP band in a wide
range, something not straightforward with other absorbing materials as dyes or semiconductors.
This tunability rends SP especially advantageous for wide spectrum photo-energetic processes

3.3 Environment
The development of technological societies requires a progressive increase of the industrial
activity. Many industrial processes result in hazardous products for humans and environment
[130]. Reaction of these products to be transformed in inert ones is mandatory in order to ensure
a secure and sustainable development of our society. This problem has got particular importance
with the recent incorporation to the first world of new regions that increased exponentially their
industrial activity in the last years. Catalysis provides a pathway to eliminate these hazardous
products quickly, hence reducing their potential danger. Among the different catalytic processes,
photocatalysis exhibits particular importance since it is a clean process that can use solar light
and mimets other biological processes [131,132,133].
Metallic NPs exhibit catalytic activity [134] that can be improved upon light illumination to excite
SP [135]. However, the most exploded use of SP in photocatalysis is the enhancement of
photocatalytic efficiency in transition metal oxides by incorporation of metallic NPs. The principle
of photocatalysis in these material [136,137] is illustrated in figure 23. Transition metal oxides (as
TiO2) exhibit an energy gap in the UV-VIS part of the spectrum. Thus, upon illumination, electrons

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can be promoted to the conduction band. The excited electrons are available to participate in the
oxidation of the products that are absorbed on the catalytic surface. Similarly, holes created in the
valence band allow the donation of an electron from the absorbed products yielding their
reduction. It is straightforward to understand that the efficiency of the catalytic surface (measured
as the number of reaction that takes place per unit area and time) will depend critically on the
light absorption process that governs the number of active electrons/holes in the material.
Ph
oto
-re
du
ctio
n O2- M+ (aq.)
Photon
CB e
M (s)
O2

Egap H2O CO2

h H2O- Org. Comp.
VB
n
atio H2O
id
-ox
o to
Ph
Figure 23. Scheme of the photocatalysis processes in transition metal oxides.

The incorporation of metallic NPs have been used in the past since they act as electron traps
retarding electron-hole recombination and therefore increasing the process efficiency
[138,139,140]. However, the use of NPs exhibiting SP resonance by the photocatalytic surface
generates and additional increase of light absorption efficiency by the local electric field
amplification and scattering processes as in the photovoltaic devices above described.
Awazu et al [141] demonstrated the increase of photocatalytic efficiency of a TiO2 layer by
embedding Ag NPs near the surface as shown in figure 24a. The mechanism of efficiency
improvement is basically the same above described for photovoltaic devices (figure 21). The light
scattering at the silver NPs increases the effective optical path of photons leading to a higher
absorption rate, while the local electric field enhancement also assists the absorption processes.
With this arrangement, they found an increase above one order of magnitude in the
decomposition rate of methylene blue under near-UV irradiation (figure 24b). Similarly the
catalysis of carbon monoxide is substantially improved by the combined use of Au and Fe2O3
NPs [142] as shown in figure 24d. While separated use of Au or Fe2O3 NPs leads to almost
negligible photocatalytic efficiency, their combined use shows outstanding results activity as the

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excitation of SP in Au NPs enhances the photocatalysis of Fe2O3. SP enhancement

photocatalysis of TiO2 have been demonstrated for other reaction as methanol dehydrogenation,
acetic acid decomposition and propanol oxidation and others [143,144,145,146].
The incorporation of metallic NPs holding SP in photocatalytic materials may have additional
advantages. A key problem in some photocatalyst as ZnO is the photo-instability in aqueous
solution due to photocorrosion upon UV illumination [147]. It has been reported that incorporation
of Ag NPs onto ZnO films leads to an increase of photocatalytic efficiency and higher stability of
ZnO preventing the photocorrosion [148]. As figure 24c evidences, the presence of Ag NPs avoid
the photodegradation upon UV illumination.
SP can be also used to probe catalytic reactions. Larsson et al [149] could monitor CO and H2
oxidation on Pt, and NOx conversion to N2 on Pt/BaO reaction by following changes in the SP
resonance of Au NPs incorporated in the photocatalytic surface. The high sensitivity of SP to the
local environment dielectric properties induces a shift in the SP resonant position when the
catalytic process takes place as illustrated in figure 24e. With this method, they were able to
detect surfactant coverage with sensitivity below 10-3 monolayers.

(a)

(c)
(b)

(d) (e)

Figure 24 (a) TEM images of TiO2 film on Si with Ag NPs and (b) decomposition rate of methylene blue
upon UV irradiation on the TiO2 surface without (black) and with (red&blue) Ag NPs with different
geometry. (c) Durability of ZnO photocatalysts for the photodegradation of crystal violet under UV
irradiation with and without Ag NPs. (d) Photocatalytic CO decomposition activity using Fe2O3 and Au NPs.
(e) Shift in the SPR peak of Au NPs during the photo-oxidation of NOx→NO2 on BaO photocatalyst.
Reproduced with permission from [141] (a&b), [148] (c), [142] (d) and [149] (e).

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A particularly interesting case of photocatalysis is the photo-assisted hydrogen fuel generation.

Water decomposition (2H2O→2H2+O2) provides the possibility to store hydrogen to be used as
fuel [150,151]. The endothermic decomposition process (that takes place spontaneously at
temperatures at about 2500 K [152]) may be activated by several methods, that increase locally
the temperature or catalyse the reaction including chemical, electrical, thermal and optical ones.
Thus, solar light can be used to promote water splitting [152,153] using a fully clean and
environmental friendly method. As in the abovementioned processes, SP have demonstrated
their capabilities to improve the efficiency of the process [154,155,156 ]. Liu et al [156] recently
found an increase in a factor of 66 on the water splitting photocatalysis by TiO2 when
incorporating of Au NPs.
It is worthy mentioning that an indirect improvement of catalytic efficiency using SP may be due to
the increase of temperature induced by light absorption. The local enhancement of the
temperature associated to SP excitation may help the catalysis process that should be a
photothermal assisted catalysis rather than a real photocatalytic one.

3.4 Information technology

Optical signals are essential for information technology due to the fast propagation along
communication lines and absence of ohmic losses. Light manipulation is commonly achieved by
dielectric materials while metals are scarcely used due the short light penetration depth.
However, with dielectric materials, it is impossible to focus a beam below λ/2 due to the diffraction
at the aperture edges [157]. An additional key problem of optical information storage is the
difficulty in obtaining re-usable memories since rewritable optical devices stable and mechanically
solid are not easy to develop. These restrictions have represented a serious problem for the
development of information technology where miniaturization has achieved the nanometric scale.
Magnetic memories uses areas below 100 nm size for bit writing/recording, values that can not be
used in traditional optical ones.
Most of the plasmonic applications in this field are achieved with itinerant SP [2,3] but there are
also some outstanding examples of localised SP applications for information technologies. The
use of nanometals holding SP arises new methods for light manipulating, reading and writing
information in sizes significantly smaller than the light wavelength, while the huge absorption and
scattering cross sections allows detection of very small signals [158,159]. Thus, SP can be used
to design subwavelength optical devices as antennas, lenses and resonators for extreme light
concentration and manipulation [160,161].

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The electric field amplification around a metallic NP when SP are excited, make these elements
to act as nanoantennas with very low power consumption and large amplification factors
[1,2,3,162]. Moreover, patterns of NPs with specific geometries provide methods for selective
frequency antennas with even larger amplification [2,3,163,164] and to fabricate subwavelength
light waveguides with decay length of the order of 500 μm [165,166]. Photodetectors with
improved performance can also be developed exploding SP [167] similarly to the case of
photovoltaic cells. The incorporation of metallic NPs in photodetectors increases their efficiency
allows to reduce their size [158,168] leading to faster devices with reduced power consumption.
The dependence of SP resonance on factors as size, shape and orientation permits the design
of new devices that represent a breakthrough with conventional ones. Recently, Zijlstra et al [169]
designated a 5-dimension storage device based on the use of Au NPs and nanorods. Besides the
two dimensions of the storage surface, they included the NPs size, aspect ratio and orientation as
new ones.

(a)

(b)
(c)

Figure 25 (a) Illustration of the laser induced reshaping of nanorods and (b) TEM images and optical
absorption spectra of the nanorods. (c) Images recorded at the same position observed with different light
wavelength and polarization. Reproduced with permission from [169].

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In this device, the information is written using the thermal reshaping of the NPs: When SP are
excited with a laser, the local increase of temperature induces a melting that allows to reshape
the particles obtaining nanorods with controlled orientation and aspect ratio that depend on the
laser wavelength, intensity and polarization [47,48,49,50]. Moreover, as the SP band position
depends on the NP geometry (figure 25b) it is possible to reshape selectively NPs with certain
geometry into other one. Hence, the population of nanorods and their geometrical features can be
tuned optically (figure 25a). The information is read using different wavelengths and light
polarization to excite selectively some nanorods depending on their morphology. Consequently, it
is possible to store several bits of information in the same physical space. With 5 different
wavelengths and two different light polarizations they were able to write and read 6 different
images in the same area as figure 25c illustrates with a potential information density of
1Tby/cm2.
Another example of the potential use of SP for the information technology is the extraordinary
light transmission [170,171,172,173]. When a uniform light beam reaches an opaque surface with
nanometric holes, the light transmission is limited by the diffraction laws. Such a limit can be
overcome when dealing with metallic films with holes and SP are excited. The excitation of SP
produces a charge accumulation at the holes edge. This lead to a non-uniform wavefront that
concentrates the light at the hole region increasing the light transmission.
Excitation of SP can be also used to enhance the sensitivity of Raman spectroscopy by
concentrating and locally amplifying the light electric field yielding to much better sensitivity of the
technique [62,174,175,176,177]. The performance of Scanning Near Field Optical Microscopy
(SNOM) is also improved by placing metallic NPs at the tip that concentrates the light [178,158].

4. Outlook and challenges.

The excitation of SP in metallic NPs allows exploring regions prohibited for the traditional optics,
overcoming the diffraction limit and allowing local light amplification of orders of magnitude.
Therefore, potential uses of SP are as ubiquitous as the optics is. These applications include
completely new approaches to problems not yet solved and improvement of well established
optical processes. Future basic research on SP will certainly prompt new potential applications.
However, the nowadays knowledge is solid enough to develop a vast range of applications, some
of them already achieved, other in development and some other to be addressed.
The milestone for further development of these applications relays on our ability to process and
manufacture nanomaterials. In the case of biomedical applications where economical cost is not
a key issue, the challenge is a perfect control of NP size and shape dispersion, as well as

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functionalization. The recent advances in colloidal chemistry pushed the field substantially in the
last years to be the most developed among SP applications. For energy and environmental
sectors, processing large amounts of NPs with a relatively good control of morphology and size
dispersion at competitive costs is the key to promote a widespread use of SP technology. Finally,
for information technology, the advances on designing and understanding SP of complex
structures and NPs ensembles as well as improvement of lithography methods will drive future
advances.

Acknowledgements
I would like to acknowledge Prof. J. Llopis for lectures and fruitful discussions about surface
plasmons during many years. Jose de la Venta is acknowledged for critical reading of the
manuscript and valuable comments. This work has been partially supported by Spanish Ministry
of Science and innovation through the projects FIS-2008-06249, MAT2010-C21088-C03 and
Comunidad de Madrid, project NANOBIOMAGNET (S2009/MAT-1726).

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