Transverse and longitudinal surface plasmon resonances of a hexagonal array of gold

nanorods embedded in an alumina matrix

Brian G. McMillan, Léonard E. A. Berlouis, Francis R. Cruickshank, David Pugh, and Pierre-François Brevet

Citation: Applied Physics Letters 86, 211912 (2005); doi: 10.1063/1.1939070

View online: http://dx.doi.org/10.1063/1.1939070
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 APPLIED PHYSICS LETTERS 86, 211912 共2005兲

Transverse and longitudinal surface plasmon resonances of a hexagonal

array of gold nanorods embedded in an alumina matrix
Brian G. McMillan, Léonard E. A. Berlouis,a兲 Francis R. Cruickshank, and David Pugh
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street,
Glasgow G1 1XL, United Kingdom
Pierre-François Brevet
Laboratoire de Spectrométrie Ionique et Moléculaire, UMR CNRS 5579, Université Claude Bernard Lyon 1,
43 Boulevard du 11 Novembre 1918, F-69622 Villeurbanne Cedex, France
共Received 29 December 2004; accepted 19 April 2005; published online 19 May 2005兲
The specular reflectance from a hexagonal array of gold nanorods embedded in an alumina matrix
supported on an aluminum substrate is reported. The rods were grown by electrodeposition of gold
in an alumina template and were oriented with their long axis perpendicular to the film surface.
Optical reflectance measurements performed with an incident light beam of S polarization only
exhibited the transverse surface plasmon resonance whereas the measurements obtained with P
polarization exhibited both transverse and longitudinal resonances. A model for the reflectance from
a thin anisotropic film was developed and shown to be in agreement with the experimental data.
© 2005 American Institute of Physics. 关DOI: 10.1063/1.1939070兴

The properties of metal nanoparticles have received
considerable interest due to their wide range of applications
extending from surface sensitive spectroscopic analysis to
catalysis and microwave polarizers.1–6 To date, various meth-
ods for synthesizing these nanoparticles, both spheres and
rods, have been described.7,8 Present work concentrates on
the use of porous alumina as a template to produce a hex-
agonally ordered array of gold nanorods and the subsequent
characterization of the Au nanorods/alumina composites by
optical reflectance is discussed. A model describing the re-
flectance, including the anisotropic Au nanorods/alumina
film, is proposed.
The alumina template was formed following the method
of Masuda et al., Foss et al., and S.L. Pan et al.9–11 Essen-
tially, an electropolished aluminum sample underwent a two-
step anodization process in 0.3 M oxalic acid at 40 V—the
period of the second anodization being 30 min. Au elec-
trodeposition into the pores was carried out under ac condi-
tions 共6 V rms, 200 Hz兲 from 0.1 M KAu共CN兲2. The optical
characterization of gold nanorods has been extensively per-
formed for liquid suspensions where all possible orientations
of the rods with respect to the polarization state of the inci-
dent light occur.7,12–14 In this configuration, the absorbance
spectra exhibit both transverse and longitudinal surface plas-
mon resonances. The transverse resonance is located at
520 nm for aqueous suspensions of gold nanorods whereas
the longitudinal one is found at longer wavelengths, the ex-
act location depending, among other factors, on the aspect
ratio of the rods. For supported and aligned nanorods, the
description of the data must take due account of the polar-
ization state of the incident beam and the orientation of the
nanorods. Experiments reported on such aligned arrays have
thus been performed with the light at normal incidence either
to the nanorods’ short axes 共i.e., equivalent S and P polariza-
tion兲 or to their long axes in a wire-grid-type polarizer ar-
rangement. Models employed to account for the experimen-
tal data were based on a Maxwell-Garnett effective medium
a兲
Electronic mail: l.berlouis@strath.ac.uk
approach,15–19 extended to include the size dependence of the
depolarization factor. This could generate quite readily the
absorbance features of the metal nanorods/alumina compos-
ites as a function of the aspect ratio of the nanorods. On the
other hand, there has only been a limited study of these ar-
rays by specular reflectance instead of transmittance.20 This
approach required the evaluation of the reflection coefficients
from the ambient–metal/alumina and the metal/alumina–
aluminum substrate interfaces as well as the multiple reflec-
tions within the films. However, in that work, the composite
film was thought to incorporate spherical Au particles and
was assumed to have a nonuniform thickness, at least on the
order of the incident wavelength. Any interference patterns
arising from multiple reflections were therefore destroyed.
The reflectance curves experimentally obtained and calcu-
lated by these authors thus corresponded and showed the
presence of a minimum at 520 nm corresponding to the sur-
face plasmon frequency of the gold spherical particles.
The reflectance data, normalized with an aluminum mir-
ror, obtained from our Au nanorods/alumina composite film
on the aluminum substrate using P- and S-polarized light
over the wavelength range 400– 820 nm are shown in Fig. 1.
FIG. 1. Experimental reflectance curves obtained for the Au nanorods/
alumina composite system for S- and P-polarized waves at an angle of
incidence ␪0 = 30°.

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 211912-2 McMillan et al. Appl. Phys. Lett. 86, 211912 共2005兲

on the surface of the system, irrespective of its angle of

polarization, can be separated into two perpendicular S- and
P-polarized components. These two component waves then
experience separate reflectances given by:20

R␯ = 兩r̂␯兩2 , 共1兲
where ␯ represents either S or P polarization. The corre-
sponding reflection coefficient is then given by:
ˆ ˆ
␯ r␯01 + r̂12
␯ −2i␾
e ␯ −2i共␾+␦␯兲
+ r̂23 e ␯ ␯ ␯ −2i␦␯
+ r01 r̂12r̂23e
r̂ = ˆ ˆ , 共2兲
FIG. 2. Schematics of the three layer model used for the description of the 1 + r␯01r̂12
␯ −2i␾
e ␯ ␯ −2i共␾+␦␯兲
+ r01 r̂23e ␯ ␯ −2i␦␯
+ r̂12 r̂23e
data. The refractive indices of air and of the alumina/air layer are no and n1,
respectively. n̂2o and n̂2e are the ordinary and extraordinary refractive indi-
where r␯ij is the Fresnel coefficient for the interface between
ces, respectively, of the Au nanorods/alumina layer. The semilong and semi- layers i and j. The anisotropic character of layer 2 must be
short axes of the Au prolate ellipsoids are given by a and b, respectively. The introduced through the appropriate coefficients of reflection
refractive index of Al is n̂3. and transmission at an isotropic/anisotropic interface with
the appropriate angle of refraction.24 Layer 0 is the ambient
Interference patterns are observed in the spectra, testimony air medium. The phase shifts ␾ and ␦ˆ ␯ are introduced to
of the uniformity in the thickness of the alumina layer. account for the multiple reflections within layers 1 and 2,
Furthermore, two minima are observed in the data for respectively, and are given by:
P-polarized light at 520 and 700 nm whereas only one is
2␲d1
found at 520 nm for S polarization. This is significantly dif- ␾= n1 cos ␪1 , 共3兲
ferent from the reflectance data presented by Goad et al. 20 ␭
for spherical gold particles where only one single feature at where ␭ is the wavelength and ␪1 the incidence angle. Any
520 nm was reported. Our data are thus more in line with anisotropy in layer 1 is neglected and its refractive index, n1,
transmission measurements on liquid suspensions of gold can be derived from that of alumina.20 In the anisotropic Au
nanorods7,21 or polyethylene incorporated gold nanorods18 nanorods/alumina composite 共layer 2兲, the phase shift is ei-
where evidence of both transverse and longitudinal surface ther;
plasmons was found and also with recent transmittance ex-
periments on silver nanowires.18,22,23 The issue then was to 2␲d2
develop a model which could account for the presence of ␦ˆ S = n̂2o cos ␪2S , 共4兲
␭
both transverse and longitudinal plasmons in the reflectance
spectra of the gold nanorods/alumina composites, viz, reflec- where n̂2o and ␪2S are, respectively, the refractive index and
tance from a uniaxial anisotropic film.24,25 the refraction angle for the ordinary S-polarized wave, or
In general, any linearly polarized wave incident on a
uniaxial medium is reflected and refracted. The refracted 2␲d2
␦ˆ P = n̂2o cos ␪2P 共5兲
wave propagating in the anisotropic medium may be decom- ␭
posed, in principle, into the superposition of two waves, an
ordinary and an extraordinary one propagating in the film for the extraordinary P-polarized wave, with
with two orthogonal polarizations and two different propaga-
tion directions. These two directions of propagation are de-
冑共n̂2e2 − n21 sin2 ␪1兲
cos ␪2P = , 共6兲
fined by the exact orientation of the optic axis and the angle n̂2e
of incidence. In the present case of nanorods aligned with
n̂2e is the extraordinary refractive index and ␪2P is the com-
their long axis perpendicular to the plane of the film surface,
plex angle which depends on the direction of propagation of
the optic axis is parallel to the surface normal. The
the extraordinary wave in layer 2.25
S-polarized wave propagates within the film with its electric
By treating the Au nanorods as prolate ellipsoids, the
vector perpendicular to the plane of incidence and has a con-
ordinary and extraordinary refractive indices of layer 2 are
stant refractive index irrespective of its direction of propaga-
then obtained through the Maxwell-Garnett effective me-
tion. This is the ordinary wave. On the other hand, the inci-
dium approximation:26
dent P-polarized wave is refracted and propagates within the
film with its electric vector lying in the plane of incidence.
共1 − q兲␧m + q␤␧ˆ
This is the extraordinary wave experiencing an incident ␧ˆ f = , 共7兲
angle dependent refractive index. 1 − q + q␤
In order to account for the experimental data, the Au where ␧ˆ f , ␧ˆ , and ␧m are the dielectric constants of the layer,
nanorods/alumina composite films were modeled as a three- gold27 and alumina, respectively, q is the volume fraction of
layer system, see Fig. 2. The first layer is formed by an array the metal nanorods in the film and
of empty pores in an alumina layer of thickness d1 whereas
the second layer is formed by a Au nanorods/alumina com- ␧m
posite of thickness d2. Experimentally, it was indeed ob- ␤i = , 共8兲
␧m + Li共␧ˆ − ␧m兲
served that the deposited gold did not fill the pores up to the
top surface. The third layer is the aluminum substrate. The Where Li is the form factor for prolate ellipsoids with a
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overall reflection coefficient for any incident wave impinging semilong axis a and a semishort axis b. As such, the form
On: Tue, 09 Dec 2014 10:21:04
 211912-3 McMillan et al. Appl. Phys. Lett. 86, 211912 共2005兲

nanorods/alumina composite layer is treated as a uniaxial

film and the ordinary and extraordinary refractive indices are
derived from a Maxwell–Garnett effective medium approxi-
mation to yield a close match to the experimental data.
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