4606 Langmuir 2007, 23, 4606-4611

Plasmon Coupling in Layer-by-Layer Assembled Gold Nanorod Films

Stéphanie Vial, Isabel Pastoriza-Santos, Jorge Pérez-Juste, and Luis M. Liz-Marzán*
Departamento de Quı́mica Fı́sica and Unidad Asociada CISC, UniVersidade de Vigo, 36310, Vigo, Spain

ReceiVed December 28, 2006. In Final Form: February 6, 2007

A systematic study of the optical effects derived from plasmon coupling in mono- and multilayers of gold nanorods
is presented. The monolayers were prepared using the standard polyelectrolyte-assisted layer-by-layer (LbL) method
and gold nanorods coated with either poly(N-vinyl pyrrolidone) or homogeneous silica shells. Such plasmon coupling
leads in general to extensive red-shift and broadening of the longitudinal plasmon bands, which are discussed on the
basis of recently reported theoretical modeling. Whereas for PVP-coated rods, strong interactions were observed for
high-density monolayers and closely spaced multilayers, increasingly efficient screening is observed for thicker silica
shells.

Introduction
Many practical applications of (coinage) metal nanoparticles
are directly related to their striking optical properties, arising
from localized surface plasmon resonances.1-4 Such applications
can be found in fields such as nonlinear optics, optical re-
cording, biolabeling, biosensing, or therapy and often require
the immobilization of nanoparticles on a transparent substrate.
For this reason, development of efficient immobilization tech-
niques and control over all parameters influencing the optical
response of deposited nanoparticles are crucial for an efficient
use of these systems within practical devices. In the context of
exploiting the optical response of metal nanoparticles, the main
parameters are particle size and shape, dielectric environment
(refractive index of medium/solvent and of coating shells), and
interparticle distance.4 Control over particle shape has been
dramatically improved over the past decade, with geometries
including spheres,5 single-crystal or penta-twinned rods,6-10
flat platelets,11-14 nanocages,15,16 polyhedrons,17,18 or even
nanostars,19,20 with better or worse success regarding simultan-
eous control over particle size. A number of studies have focused
* Corresponding author. E-mail: lmarzan@uvigo.es. Fax:
+34 986812556.
(1) Haes, A. J.; Stuart, D. A.; Nie, S.; Van Duyne, R. P. J. Fluoresc. 2004,
14, 355.
(2) Daniel, M.-C.; Astruc, D. Chem. ReV. 2004, 104, 293.
(3) Burda, C.; Chen, X.; Narayanan, R.; El-Sayed, M. A. Chem. ReV. 2005,
105, 1025.
(4) Liz-Marzán, L. M. Langmuir 2006, 22, 32.
(5) Rodrı́guez-Fernández, J.; Pérez-Juste, J.; Garcı́a, de Abajo, F. J.; Liz-
Marzán, L. M. Langmuir 2006, 22, 7007.
(6) Pérez-Juste, J.; Pastoriza-Santos, I.; Liz-Marzán, L. M.; Mulvaney, P. Coord.
Chem. ReV. 2005, 249, 1870.
(7) Johnson, C. J.; Dujardin, E.; Davis, S. A.; Murphy, C. J.; Mann., S. J.
Mater. Chem. 2002, 12, 1765.
(8) Chen, H.; Wang, J.; Yu, H.; Yang, H.; Xie, S.; Li, J. J. Phys. Chem. B 2005,
109, 2573.
(9) Wang, Z. L.; Mohamed, M. B.; Link, S.; El-Sayed, M. A. Surf. Sci. 1999,
440, L809.
(10) Sun, Y. G.; Xia, Y. AdV. Mater. 2002, 14, 833.
(11) Jin, R.; Cao, C. Y.; Hao, E.; Métraux, G.; Schatz, G. C.; Mirkin, C. A.
Nature 2003, 425, 487.
(12) Germain, V.; Li, J.; Ingert, D.; Wang, Z. L.; Pileni, M. P. J. Phys. Chem.
B 2003, 107, 8717.
(13) Pastoriza-Santos, I.; Liz-Marzán, L. M. Nano Lett. 2002, 2, 903.
(14) Lofton, C.; Sigmund, W. AdV. Funct. Mater. 2005, 15, 1197.
(15) Oldenburg, S. J.; Averitt, R. D.; Westcott, S. L.; Halas, N. J. Chem. Phys.
Lett. 1998, 288, 243.
(16) Chen, J.; Saeki, F.; Wiley, B.; Cang, H.; Cobb, M.; Li, Z.; Au, L.; Zhang,
H.; Kimmey, M.; Li, X.; Xia, Y. Nano Lett. 2005, 5, 473.
(17) Kim, F.; Connor, S.; Song, H.; Kuykendall, T.; Yang, P. Angew. Chem.,
Int. Ed. 2004, 43, 3673.
(18) Sánchez-Iglesias, A.; Pastoriza-Santos, I.; Pérez-Juste, J.; Garcı́a, de Abajo,
F. J.; Liz-Marzán, L. M. AdV. Mater. 2006, 18, 2329.
in turn, on the optical effects derived from changes in the dielectric
environment, either through dispersion (immersion) in different
solvents6 or through growth of (inorganic) shells around the
particles.21-24 However, detailed studies regarding the optical
changes due to interparticle interactions are much more rare and
basically restricted to spherical particles. For example, Brust et
al.25 have examined multilayer films made of small gold
nanoparticles where interparticle distance was dictated by the
length of hydrocarbon chains within dithiols used as linker
molecules, whereas Ung et al.26 studied interactions at longer
separation distances using silica shells with controlled thickness
as rigid interparticle spacers. Apart from a general observation
of red-shift and broadening of the plasmon band as the particles
come closer together and consequently the interactions increase,
these results also provide the idea that the range of dipolar coupling
is of the order of the diameter of the spheres, which readily
dictates a rule of thumb regarding the minimum separation within
a device for the metallic nanospheres to maintain their single-
particle response. However, there is a lack of experimental
systematic studies regarding interparticle interactions between
nonspherical particles, and this is a crucial point for practical
uses, since the efficiency of a device will improve by increasing
the density of nanoparticles on the support (for example in a
biosensor we can increase the density of recognition sites), but
one has to be aware that below a certain distance the single-
particle response will no longer be available, therefore affecting
the measurements. The most popular (and better characterized
until now) nonspherical metal nanoparticle systems are gold
nanorods,6 which display orientation-dependent optical responses,
with a tight control of the plasmon resonance frequencies, mainly
as a function of aspect ratio (length over thickness). The wet-
chemical synthesis for gold nanorods has been optimized over
the last few years, allowing the dimensions to be tailored, thus
offering a tool to fabricate nanoparticle-based devices operating
in a wide wavelength range. Another advantage is the sensitivity
(19) Yamamoto, M.; Kashiwagi, Y.; Sakata, T.; Mori, H.; Nakamoto, M. Chem.
Mater. 2005, 17, 5391.
(20) Nehl, C. L.; Liao, H.; Hafner, J. H. Nano Lett. 2006, 6, 683.
(21) Liz-Marzán, L. M.; Giersig, M.; Mulvaney, P. Langmuir 1996, 12, 4329.
(22) Liu, M.; Guyot-Sionnest, P. J. Mater. Chem. 2006, 16, 3942.
(23) Pastoriza-Santos, I.; Pérez-Juste, J.; Liz-Marzán, L. M. Chem. Mater.
2006, 18, 2465.
(24) Pastoriza-Santos, I.; Pérez-Juste, J.; Carregal-Romero, S.; Hervés, P.;
Liz-Marzán, L. M. Chem. Asian J. 2006, 1, 730.
(25) Brust, M.; Bethell, D.; Kiely, C. J.; Schiffrin, D. J. Langmuir 1998, 14,
5425.
(26) Ung, T.; Liz-Marzán, L. M.; Mulvaney, P. J. Phys. Chem. B 2001,105,
3441.

10.1021/la063753t CCC: $37.00 © 2007 American Chemical Society

Published on Web 03/17/2007
Plasmon Coupling in Gold Nanorod Films
of the nanorod longitudinal plasmon band toward environmental
changes, which renders them very attractive for sensing ap-
plications.27 Regarding interparticle coupling in gold nanorod
systems, large red-shifts of the longitudinal plasmon band were
reported for cases where end-to-end assembly was dominant,28-30
whereas El-Sayed and co-workers31 have recently reported that
blue-shifts arise from salt-induced aggregation in solution, where
side-to-side assembly is more probable. These authors carried
out computational modeling based in the discrete dipole
approximation (DDA),32 which explains both types of effects.
Another related paper has been published by Wang, Dong, and
colleagues,33 where the layer-by-layer method was applied to
build multilayer films of gold nanorods, where coupling-related
new bands are reported, but only briefly discussed, whereas
emphasis was laid on SERS effects.
We concentrate in this paper on a systematic investigation of
the optical effects resulting from an increase of nanorod density
on a glass support, either allowing very high densities and even
particle-particle contacts, or preventing such contacts through
assembly of silica-coated nanorods, so that minimum spacing is
determined by the shell thickness. The corresponding optical
effects are explained on the basis of the theoretical results reported
in ref 31.
Experimental Section
Materials. Tetrachloroauric acid (HAuCl4‚3H2O), sodium boro-
hydride, ascorbic acid, sodium chloride (NaCl), HCl, NH4OH (32%),
cetyltrimethyl ammonium bromide (CTAB), poly(allylamine hy-
drochloride) (PAH, Mw 15 000), and tetraethylorthosilicate (TEOS)
were purchased from Aldrich. Poly(vinylpyrrolidone) (PVP, MW
10 000, 40 000, and 360 000) was supplied by Fluka. Poly-
(styrenesulfonate) (PSS, MW 70 000) and poly(diallyldimethylam-
monium chloride) (PDDA, MW 200 000-350 000, 20 wt %) were
procured from Sigma. Poly(styrenesulphonate) (PSS, Mw 14 900)
was procured from Polysciences. All chemicals were used as received.
Pure grade ethanol and Milli-Q grade water were used to make up
all solutions.
Synthesis of Gold Nanorods. Gold nanorods were synthesized
according to the protocols described by Nikoobakht et al.34 and Liu
et al.35 First, a gold seed solution was prepared by borohydride
reduction of 0.25 mM HAuCl4 in an aqueous 0.1 M CTAB solution.
Subsequently, 24 µL of the seed solution was added to a growth
solution (10 mL) containing 0.1 M CTAB, 0.5 mM HAuCl4, 0.019
M HCl, 0.8 mM ascorbic acid, and silver nitrate (0.08 mM).
Prior to LbL assembly, the metal particles were coated with poly-
(vinylpyrrolidone) (PVP, Mw 40 000) by first centrifuging (8000
rpm, 20 min) and redispersing in Milli-Q water, followed by dropwise
addition of a PVP aqueous solution, previously sonicated during 15
min ([Au]/[PVP] ratio ) 1), under vigorous stirring. The mixture
was gently stirred overnight and then centrifuged (3500 rpm, 3h)
and redispersed in ethanol under sonication.
Silica Coating. Deposition of uniform silica shells on gold
nanorods was accomplished by use of a recently reported method,23
based on a combination of polyelectrolyte wrapping and hydrolysis
of tetraethoxysilane in an isopropanol-water mixture. In brief, after
removing excess surfactant by centrifugation (8000 rpm, 20 min),
(27) Wang, C.; Ma, Z.; Wang, T.; Su, Z. AdV. Funct. Mater. 2006, 16, 1673.
(28) Thomas, K. G.; Barazzouk, S.; Ipe, B. I.; Joseph, S. T. S.; Kamat, P. V.
J. Phys. Chem. B 2004, 108, 13066.
(29) Joseph, S. T. S.; Ipe, B. I.; Pramod, P.; Thomas, K. G. J. Phys. Chem.
B 2006, 110, 150.
(30) Correa-Duarte, M. A.; Pérez-Juste, J.; Sánchez-Iglesias, A.; Liz-Marzán,
L. M. Angew. Chem., Int. Ed. 2005, 44, 4375.
(31) Jain, P. K.; Eustis, S.; El-Sayed, M. A. J. Phys. Chem. B 2006, 110,
18243.
(32) Draine, B. T.; Goodman, J. Astrophys. J. 1993, 405, 685.
(33) Hu, X.; Cheng, W.; Wang, T.; Wang, Y.; Wang, E.; Dong, S. J. Phys.
Chem. B 2005, 109, 19385.
(34) Nikoobakht, B.; El-Sayed, M. A. Chem. Mater. 2003, 15, 1957.
(35) Liu, M.; Guyot-Sionnest, P. J. Phys. Chem. B 2004, 108, 5882.
Langmuir, Vol. 23, No. 8, 2007 4607
the particles were dispersed in Milli-Q water and added dropwise
under vigorous stirring to an aqueous solution of polystyrene-
sulphonate (PSS, Mw 14 900; 2 g/L, 6 mM NaCl). PSS adsorption
was allowed to proceed for 3 h. After a washing step to remove
excess PSS, the process was repeated with poly(allylamine hydro-
chloride) (PAH). PSS/PAH coated gold nanorods were then mixed
with PVP (Mw 10 000, 4 g/L) in water and stirred overnight. The
mixture was centrifuged at 2800 rpm for 3 h and the precipitate
redispersed in isopropanol (1.5 mL) in an ultrasonic bath. Aqueous
ammonia, and TEOS in isopropanol were then added dropwise under
vigorous stirring, followed by gentle stirring for 2 h. The shell
thickness was mainly determined through the nanorod and TEOS
concentrations. As an example, for a thickness of 12 nm, the final
concentrations were 0.85 mM Au, 10.55 M water, 0.2 M ammonia,
and 5.57 mM TEOS.
LbL Assembly. Microscope glass slides were used as substrates,
so as to allow UV-vis-NIR spectroscopy measurements. The
substrates were sonicated for 10 min in water and then in ethanol,
subsequently thoroughly cleaned using piranha solution (H2SO4:
H2O2)7:3), rinsed with deionized water, and dried under an air
stream. The slides were stored in water until use. For the assembly
of nanorods, the slides were first immersed in an aqueous solution
of positively charged PDDA (1 mg/mL in 0.5 M NaCl aqueous
solution) for 20 min, then in an aqueous solution of the polyanion
PSS (Mw 70 000, 1 mg/mL in 0.5 M NaCl aqueous solution) for
10 min, and finally in PDDA solution for 10 min. At this stage, the
slides are positively charged, favoring the electrostatic interactions
with negatively charged nanorods. To obtain a monolayer of gold
nanorods, the pretreated slides were immersed into the corresponding
colloid for a suitable period time (see below). Multilayer films were
prepared by sequential adsorption of PDDA (20 min) and Au nanorods
(1 h), denoted (PDDA/Au)n for n layers. After each adsorption step,
the substrates were rinsed with water and dried under an air stream.
Results and Discussion
The strategy used for the assembly of gold nanorods was the
well-known polyelectrolyte-assisted layer-by-layer assembly.36
This technique, mainly based on electrostatic interactions between
polyelectrolytes and nanoparticles, has been often applied for
the assembly of metal (among many others) nanoparticles,26,33,37
and renders random, uniform deposition derived from a strong
interaction and fast deposition. A modification of this technique,
where the polyelectrolytes were assembled on high aspect ratio
nanorods, rather than on the substrate was reported as well.38
Unless indicated, the results reported here were obtained using
Au nanorods with average length of 62 nm and average aspect
ratio of 3.3. Shown in Figure 1 are a representative TEM image
and the corresponding UV-vis-NIR spectra, for the CTAB-
stabilized nanorods in water and after exchange of CTAB for
PVP, both in water and ethanol. Exchange of CTAB for PVP
was required to generate a uniform negative charge on the
nanorods’ surface23 and thereby facilitate LbL assembly.
However, since the long-term stability of PVP capped nanorods
in water was compromised, they were transferred into ethanol.
From the spectra in Figure 1, it is clear that the exchange of
capping agent does not lead to aggregation, since basically no
changes can be seen when the particles are dispersed in water,
while a small red-shift of about 8 nm is observed upon transfer
into ethanol due to the change in solvent refractive index from
1.333 up to 1.359).6
1. Au-PVP Monolayers. Monolayers of gold nanorods were
hence formed by adsorption of the negatively charged particles
generated upon PVP capping, on a glass substrate covered by
(36) Kotov, N. A.; Dekany, I.; Fendler, J. H. J. Phys. Chem. 1995, 99, 13065.
(37) Gao, M. Y.; Richter, B.; Kirstein, S.; Möhwald, H. J. Phys. Chem. B 1998,
102, 4096.
(38) Gole, A.; Murphy, C. J. Chem. Mater. 2005, 17, 1325.
4608 Langmuir, Vol. 23, No. 8, 2007
Figure 1. Representative TEM image and UV-vis-NIR spectra
of gold nanorods (aspect ratio 3.3), stabilized with CTAB in water
(green), and with PVP in both water (red) and ethanol (blue).
Figure 2. UV-vis spectra of a monolayer of PVP-coated gold
nanorods on a PDDA-modified glass substrate, as a function of
deposition time.
the cationic polyelectrolyte PDDA, and UV-vis spectra were
recorded as a function of deposition time, as summarized in
Figure 2. Since the nanorod concentration in the ethanolic
dispersion was found to strongly influence the deposition rate,
the concentration of PVP coated gold nanorods was maintained
constant for all experiments ([Au] ) 0.5 mM). At the early
assembly stages, the UV-vis spectra invariably show two surface
plasmon bands centered at 513 and 715 nm, as compared to 514
and 771 nm for the same rods in water. The blue-shift of the
longitudinal surface plasmon band is due to the change in the
average refractive index of the environment after deposition on
Vial et al.
the glass slide and drying (from 1.333 down to almost 1, for the
rods in air but in contact with the glass support).6
When the deposition time was prolonged from 5 min up to
1 h, both plasmon bands remained basically at the same position,
though with a significant absorbance increase, indicating that a
larger number of particles were deposited on the substrate, but
still well separated from each other, so that plasmon coupling
was still negligible. However, when the deposition time reached
2 h, broadening and red-shift were observed, along with a further
absorbance increase of the longitudinal plasmon band, and these
effects became more and more evident for longer deposition
times (up to 14 h). According to what has been reported for Au
nanoparticles with other shapes,26,39 as well as calculations for
Au nanorod assemblies,31 these effects point to increasingly
stronger coupling between adjacent particles as the average
interparticle distance decreases, which was confirmed by scanning
electronic microscopy (see Figure 3).
From the SEM images, we can see that after 1h of assembly
time the gold nanorods are randomly distributed onto the substrate
and consistently well separated from each other, which results
in the absence of interparticle interactions, whereas for longer
times, as more nanorods are deposited (always filling up empty
surface, rather than on previously deposited nanorods, because
of the charge difference), the distance between rods gets smaller
and the number of contact points gradually increases, which are
indistinctly head-to-tail, side-to-side, or tip-to-side, leading to
increased broadening of the absorbance bands. Image analysis
reveals that for deposition times of 1, 3.5, and 14 h, the surface
coverage amounts to 6%, 13%, and 25%, respectively, revealing
that filling up a surface monolayer with randomly oriented
nanorods is very difficult, since additional rods hardly fit in
empty spaces and repulsion from like-charged rods screens
attraction to the oppositely charged substrate.
Interpretation of the optical effects can be made in the following
terms. If we consider a single monolayer of particles, the
interactions between neighboring nanorods can be classified into
head-to-tail, end-to-side, and side-to-side. Head-to-tail interactions
arise from coupling between longitudinal plasmons, producing
a red-shift of the longitudinal plasmon resonance, as has been
shown from both theory and experiments,28-31 with a longer
shift as interparticle distance decreases. On the other hand, side-
to-side interactions are attributed to the mutual coupling between
transverse and longitudinal plasmon resonances of the interacting
nanorods, thus affecting both resonances. Focusing on the effect
over the longitudinal plasmon band, the coupling leads in this
case to a blue-shifted resonance. Additionally, in both cases, an
increase in the number of assembled particles (dimers, trimers,
tetramers, etc.) enhances the magnitude of the respective shifts.
Finally, end-to-side interactions produce the coupling of the
longitudinal plasmon band of one nanorod with the transverse
plasmon of its neighbor, producing a red-shift of the longitudinal
plasmon resonance, as demonstrated by Jain et al.31 from DDA
simulations. From the relative orientation of neighboring rods
in the SEM images (Figure 3), one can see that end-to-side should
be the dominating interactions.
In our experimental results, we indeed see from Figures 2 and
3 that, as the density of particles within a monolayer increases,
a progressive broadening and red-shift in the position in the
longitudinal plasmon band occurs (from 712 nm up to 838 nm).
For clarification, we have normalized the absorption spectra at
the maximum of the longitudinal resonance (see Figure S1 in the
Supporting Information), which clearly reveals that the broadening
(39) Malikova, N.; Pastoriza-Santos, I.; Schierhorn, M.; Kotov, N. A.; Liz-
Marzán, L. M. Langmuir 2002, 18, 3694.
Plasmon Coupling in Gold Nanorod Films Langmuir, Vol. 23, No. 8, 2007 4609

Figure 3. Representative SEM images of LbL assembled nanorod monolayers on PDDA-covered glass slides, for selected deposition times,
as indicated in the labels. Three different magnifications are shown for each time, defined by scale bars on the top images, showing
homogeneous deposition and an increase of surface coverage for longer deposition times.

Figure 5. Normalized UV-vis-NIR spectra of one monolayer

Figure 4. UV-vis spectra of LBL-assembled Au nanorod mono-
layers (number of layers as labeled), separated by single PDDA
layers.
stems almost exclusively from red-shifting effects, indicating
that side-to-side interactions are hardly noticeable. This can be
due to a negligible contribution compared to other interactions
(as suggested from the relative intensities obtained in the
calculations reported in ref 31) or to the shorter interparticle
distances required for the onset of side-to-side interaction.
2. Au@PVP Multilayer Films. The build-up of multilayer
structures, even if they are not densely packed, is more likely
to involve interparticle interactions than in the case of single
after 1 h deposition time (black) and four Au nanorod monolayers
separated by: single PDDA monolayers (red), PDDA/PSS bilayers
(blue), and PDDA/PSS/PDDA/PSS multilayers (green).
monolayers, since contact between particles located in successive
layers is highly probable.26,33,39 In the present work, Au nanorod
multilayer films were built up using the LbL approach, through
alternate deposition of oppositely charged species (PDDA and
PVP-capped nanoparticles) onto glass substrates. To separately
account for interlayer interactions, rather than interparticle
interactions within single layers, each nanorod monolayer was
prepared allowing deposition to proceed for 1 h, which was
previously found to be the limit to avoid plasmon coupling within
4610 Langmuir, Vol. 23, No. 8, 2007
Figure 6. TEM images of LBL assembled multilayer Au nanorod films with four nanorod layers separated by: a single PDDA layer (a);
PDDA/PSS bilayers (b), and PDDA/PSS/PDDA/PSS multilayers (c).
a single monolayer, using 0.5 mM gold nanorod dispersions in
ethanol. This was combined with PDDA deposition (for 20 min)
to build up to four (PDDA/Au) bilayers, and the optical response
was investigated by UV-vis-NIR spectroscopy (Figure 4).
Although in principle the effects appear to be similar to those
described for denser nanorod monolayers (red-shift and broaden-
ing, along with absorbance increase), closer inspection reveals
that the absorbance band also becomes less symmetric after
deposition of the second layer, in such a way that a new band
seems to develop at higher wavelengths, while the original band
remains basically at the same position, but with a clear overlap
between them. The original longitudinal plasmon band still
remains because many particles within the different monolayers
do not suffer from any coupling, since in each monolayer the
particles are well separated, thus preserving their single-particle
optical response. This effect is in accordance with the trend
reported by Hu et al. for a similar system33 and was more clearly
observed when nanorods with higher aspect ratio were assembled
(see Figure S2 in the Supporting Information). If the density of
particles in each monolayer were higher, the initial longitudinal
band should disappear, as observed for the single monolayer
experiment at longer deposition times (Figure 2). In this case,
as we have also seen for Au rod monolayers, the optical response
of the films seems to originate mainly from head-to-tail and
head-to-side interactions, but now between neighboring mono-
layers.
The development of new bands from plasmon coupling has
been reported for Au nanoparticle multilayers with different
geometries, including nanoplates, in which case the assignment
to interlayer interactions was based on experiments where
coupling was screened by separating monolayers with thicker
spacing.39 We carried out similar experiments to gradually screen
the interactions between adjacent gold nanorod layers, just by
increasing the thickness of the polymeric spacing. Repeated
depositions of PDDA and PSS bilayers allowed a gradual increase
of the separation distance between successive gold nanorod layers,
since the thickness of a PDDA/PSS bilayer has been reported
to be 2-3 nm.40-42 The results are summarized in Figure 5,
where the spectrum of one monolayer after 1 h of deposition
time and the final spectra after deposition of four nanorod
monolayers are compared, for those cases where PDDA/PSS
bilayers and PDDA/PSS/PDDA/PSS multilayers were used as
spacers between successive nanorod monolayers. For the sake
of an easier comparison, the maximum absorbance was normal-
ized to 1, so that the broadening and position of the maximum
can be compared for the different samples. It is clear from this
plot that if the separating polymeric region is increased, the
(40) Lvov, Y.; Decher, G.; Mohwald, H. Langmuir 1993, 9, 481.
(41) Decher, G.; Schmitt, J. Prog. Colloid Polym. Sci. 1992, 89, 160.
(42) Caruso, F.; Niikura, K.; Furlong, D. N.; Okahata, Y. Langmuir 1997, 13,
3422.
Vial et al.
absorbance becomes noticeably less broadened, due to further
screening of interparticle interactions, in a similar way to what
has been previously reported for gold nanoplates.39 The increase
in monolayer separation distance seems to screen mainly the
weaker interparticle coupling, arising from interactions between
particles separated by longer distances. Therefore, only the more
intense coupling remains, which also leads to a red-shift in the
longitudinal plasmon band, as compared to the spectrum of a
single monolayer, but much narrower than that for closely spaced
multilayers.
The morphology of the multilayer films was characterized
using SEM, as shown in Figure 6. The images reveal that, with
a single separating polyelectrolyte layer, it is difficult to distinguish
the successive gold nanorod layers, thus confirming that the
particles are indeed very close to each other. On the contrary,
when 3 or 5 polyelectrolyte monolayers are deposited between
each subsequent gold rod layers, the contrast between them
gradually gets more blurred, revealing the increased separation
between neighboring layers, which contributes to screening of
interparticle interactions.
3. Au@ SiO2 Multilayer Films. From the results presented
in the previous section, we learn that increasing physical separation
between gold nanorods can efficiently screen plasmon coupling
and thus retain the optical response of single nanorods within
multilayer films. However, even when successive layers are
separated by five polyelectrolyte monolayers, some residual
broadening is observed (Figure 5), which suggests that an
alternative procedure is required for an efficient screening. Based
on our own experience with silica coating of metal nanopar-
ticles,21,23 and previous studies related to the study of plasmon
coupling in gold nanoparticle multilayer films,26 we decided to
carry out the construction of multilayer films through assembly
of gold nanorods coated with silica shells of various thickness.
The coating was performed through a recently reported proce-
dure,23 which allows a fine control of shell thickness, and LbL
assembly was used in the same way as for PVP-capped rods. The
colloidal stability of gold nanorods (no aggregation) during the
silica coating was monitored through UV-vis-NIR spectroscopy
and TEM (examples are shown in the Supporting Information,
Figure S3). As expected, growth of increasingly thick silica shells
was observed to promote a gradual red-shift of the longitudinal
surface plasmon band, due to the corresponding increase in local
refractive index around the particles, while the global shape of
the spectrum remains almost completely unaltered, except for a
relative absorbance increase at lower wavelengths due to the
contribution of Rayleigh scattering from the silica shell.21,23
For the sake of consistency, these experiments were also carried
out with gold nanorods of aspect ratio 3.3, so that a proper
comparison with the previous section can be made. Particles
were used with silica shell thicknesses of 4, 9, and 12 nm, so
as to evaluate plasmon coupling as a function of minimum
Plasmon Coupling in Gold Nanorod Films
Figure 7. (a) SEM image of a (PDDA/ Au@SiO2)4 nanorod
multilayer (silica shell thickness ) 9 nm). (b) Effect of silica shell
thickness (as indicated in the legend) on the evolution of longitudinal
surface plasmon band position during the construction of a multilayer
film with four nanoparticle layers.
interparticle distance (defined by twice the shell thickness).
Although the obtained multilayer structure was in all cases far
from compact (see a representative SEM image in Figure 7a),
the UV-vis-NIR spectra measured for the films confirm a
gradual screening of the coupling for increasing shell thickness,
as summarized in Figure 7b, where the maximum positions of
the respective longitudinal surface plasmon bands are plotted for
the first four monolayers of each sample. In this plot, we can see
that for the first (noncompact) monolayer, the plasmon band is
Langmuir, Vol. 23, No. 8, 2007 4611
more red-shifted for monolayers of nanorods coated with thicker
shells, due to the above-discussed local refractive index effect,
which is more obvious in the dry films than in solution, because
of the larger refractive index difference between silica and air
than between silica and water or ethanol. Additionally, although
in all films a red-shift is observed when the number of deposited
layers is increased, the slope is clearly smaller for thicker shells,
with only 4 nm shift for 12 nm thick silica shells, indicating that
interparticle interactions are almost fully suppressed for distances
of the order of the nanorod thickness.
Conclusions
The influence of average interparticle distance on the optical
response of gold nanorods was studied through the systematic
construction (via LbL assembly) and characterization of mono-
layers and multilayers on transparent glass substrates. The control
of nanorod density in monolayers was achieved by varying
deposition time, and interlayer separation in multilayer films
was varied through the assembly of an increasing number of
polyelectrolyte monolayers. Finally, well-defined interparticle
distances were imparted through homogeneous coating of the
nanorods with silica shells. In all cases, plasmon coupling (leading
to extensive red-shift and broadening of the longitudinal surface
plasmon band) could be efficiently screened by keeping the
particles separated at distances longer than the nanorod short
axis. These results, which are in agreement with previous results
for gold nanoparticles of different shapes, can be explained
through recently reported theoretical modeling, and should be
taken into account when designing devices based on gold nanorod
assemblies, if the single particle optical response is to be
maintained.
Acknowledgment. This work has been supported by the
Spanish Ministerio de Educación y Ciencia, through Grant Nos.
MAT2004-02991 and NAN2004-09133-C03-03. The authors
would like to thank Jacinto Pérez-Borrajo for assistance during
SEM measurements.
Supporting Information Available: Additional resources
including Figures S1-S4. This material is available free of charge via
the Internet at http://pubs.acs.org.
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