FULL PAPER

DOI: 10.1002/adfm.200800706

Influence of Iodide Ions on the Growth of Gold Nanorods: Tuning

Tip Curvature and Surface Plasmon Resonance**
By Marek Grzelczak, Ana Sánchez-Iglesias, Benito Rodrı´guez-González, Ramón Alvarez-Puebla,
Jorge Pe´rez-Juste,* and Luis M. Liz-Marzán*

This paper describes morphological and optical changes induced by seed-mediated growth of gold nanorods in the presence of
iodide ions. Addition of small amounts of iodide to the growth solution results in the growth of nanoparticles with dumbbell-like
structure, meaning that gold salt reduction takes place preferentially at the rod tips. However, when excess iodide is added,
homogeneous rod growth is observed, and therefore the original shape is retained. By controlling the experimental conditions,
the position of the longitudinal plasmon band of grown nanorods can be shifted up to as much as 250 nm. These optical effects
were also simulated by means of the boundary element method (BEM), achieving an excellent agreement with the experimental
spectra. X-ray photoelectron spectroscopy (XPS) and surface enhanced Raman spectroscopy (SERS) analysis of the gold
nanorods before and after iodide addition revealed the presence of AuI and AgI at the particles surface. A growth mechanism is
proposed on the basis of preferential iodide adsorption at the tips {111} facets, leading to the formation of AgI, followed by
reduction of gold salt precursor due to a decrease in the surface redox potential.

1. Introduction
Gold nanorods attract enormous attention because of their
extremely interesting, surface-plasmon based optical proper-
ties,[1] which render them ideal candidates for a large number
of applications, in particular for medical uses in diagnosis and
therapy.[2–4] The optical response of nanorods typically
involves two surface plasmon modes, associated with the
oscillation of conduction electrons, either parallel (long-
itudinal surface plasmon, LSP) or perpendicular (transverse
surface plasmon, TSP) to the rod long axis. One of the most
attractive features of nanorods is the exquisite dependence of
the LSP frequency with small variations in the aspect ratio,
with no need to significantly vary the overall dimensions.
However, in order to achieve a narrow plasmon band in the
near-IR (the water optical window, suited for medical
applications),[5] considerably longer rods are required, which
are often more polydisperse.[6] Therefore, synthetic methods
are still required for tuning the morphology of gold rods in such
[*] Prof. L. M. Liz-Marzán, Dr. J. Pérez-Juste, Dr. M. Grzelczak,
A. Sánchez-Iglesias, Dr. B. Rodrı́guez-González, Dr. R. Alvarez-Puebla
Departamento de Quı́mica Fı́sica and Unidad Asociada CSIC
Universidade de Vigo
Vigo 36310 (Spain)
E-mail: juste@uvigo.es; lmarzan@uvigo.es
[**] The authors thank Prof. F. Javier Garcı́a de Abajo (CSIC) for providing
the BEM software and assisting with modeling. This work was
supported by the Spanish MEC (MAT2007-62696; Consolider-Ingenio
Nanobiomed) and Xunta de Galicia (PGIDIT06TMT31402PR). Sup-
porting Information is available online from Wiley InterScience or
from the author.
a way that the LSP can be tailored with no need to make very
long rods.
Although various methods have been proposed for the
reproducible and controlled synthesis of gold nanorods,
nowadays almost exclusively the seeded growth method is
used for both scientific studies and practical applications. This
method, based on the reduction of a gold salt on pre-made
small seeds by a weak reducing agent (ascorbic acid), in the
presence of a cationic surfactant (most frequently cetyl-
trimethylammonium bromide, CTAB), has been optimized
along the present decade to produce nanorods with a wide
range of aspect ratios and dimensions.[7–9] Additionally,
variations of the method have been found to result in a
variety of other morphologies, such as cubes,[10] plates,[11]
stars,[10] or dog bone-like nanoparticles.[12,13] While the precise
mechanism involved in these morphological changes is not
completely understood, and several possibilities have been
proposed, including electric field-directed preferential reduc-
tion at the tips,[14] preferential adsorption of CTAB on certain
crystallographic faces,[15] or underpotential deposition of a
small amount of silver,[8] we still see every now and then new
reports which do not really fit with these models, and thus a
further insight in the growth mechanism is still required.
Recently,[11] the presence of iodide ions during seeded
growth on small seeds has been shown to lead to the formation
of uniform gold nanoplates. The authors claimed that for-
mation of the planar structure was due to growth inhibition of
the {111} facets by strongly bound iodide ions, accompanied by
preferential gold reduction on the more curved edges, which
are less protected by CTAB. In this work, we explored the role
of iodide ions on rod growth, when using pre-grown gold

3780 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2008, 18, 3780–3786
M. Grzelczak et al. / Tuning Tip Curvature in Gold Nanorods
nanorods as seeds, on which additional gold salt was reduced,
in the presence of different amounts of iodide. The results
demonstrate that by changing iodide concentration different
morphologies can be obtained, ranging from thicker nanorods
(uniform growth) to well-defined, dumbbell-like particles,
which was confirmed by electron tomography. As expected, all
these morphological changes result in notable variations of the
LSP band position, providing us with a simple tool to tune the
optical properties, through controlled morphological changes,
but with no need to strongly affect the global dimensions of
the original rods. Detailed X-ray photoelectron spectroscopy
(XPS) and surface enhanced Raman spectroscopy (SERS)
studies provide important information related to the role of
iodide during growth.
2. Results and Discussion
The results reported here are related to the seeded growth
on pre-formed gold nanorods. All experiments were carried
out using the same amount of rods as seeds, as well as the same
concentrations of ascorbic acid and CTAB, as described in
Section 4. Since we were interested in studying the effect of
iodide ions on the growth of Au nanorods, we first carried out a
systematic variation of the amount of KI present during growth
(measured as [KI]/[Au0] molar ratio, [Au0] being the molar
concentration of Au metal in the nanorod seed solution), for a
constant [Au0]/[Au3þ] (¼ 0.6) molar ratio, so that the same
total volume increase were achieved. The UV–Vis–NIR
spectra of the corresponding final colloids are displayed in
Figure 1. It is immediately apparent from this figure that the
presence of low ([KI]/[Au0] < 1) and high ([KI]/[Au0] > 1)
amounts of KI lead to gradual red-shift and blue-shift of the
longitudinal plasmon band, respectively, as compared to the
spectrum of the starting rod (seed) solution, while intermediate
concentrations resulted in intermediate band positions. A
a seed solution =223 nm
1.0 [KI]/[Au0]
b 0.0
c 3.66
Norm. Absorbance
0.8 d 2 presence of various iodide concentrations are shown in the inset
e 0.8
f 0.33
0.6
g 0.038
0.4
0.2 b between experimental and calculated band positions (see
a Supporting Information, Fig. S2), the agreement is excellent
0.0
400 600 800 1000
Wavelength (nm)
Figure 1. UV–Vis–NIR spectra of gold nanorods before (a) and after
growth in the presence of different amounts of KI (see labels), keeping
the same Au0/Au3þ and ascorbic acid/Au3þ molar ratios.
Adv. Funct. Mater. 2008, 18, 3780–3786
FULL PAPER
closer look at the transverse plasmon band (see Figs. S1 and S2,
Supporting Information) also reveals an increase in the
intensity of the band with increasing the size of the tips. For
both the longitudinal and transverse plasmon bands, the largest
red-shift was observed at a ratio as low as 0.04, producing an
LSP shift of 122 nm.
According to the well-known correlation between aspect
ratio and plasmon band position, the observed shifts seem to
indicate an increase in aspect ratio for low [KI] and a decrease
for high [KI]. However, TEM observation of the corresponding
nanoparticles (see Fig. 2) does not really confirm this
prediction. While in the presence of high iodide concentration,
the rods were indeed observed to grow uniformly, with the
expected decrease in aspect ratio, smaller amounts of added KI
induced preferential growth at the rod tips, while the central
part of the rods remained almost unaltered (at least for the
lowest KI concentration). The dumbbell (or peanut-like)
morphology of the final particles was confirmed by electron
tomography, which allowed us to obtain 3D representations of
the particles, as that shown in Figure 2h, and even rendering
movies that show rotation of the particle (see example in the
Supporting Information).
A summary of the dimensions and aspect ratios of the initial
rods and those obtained after growth in the presence of
different [KI]/[Au] ratios, is provided in the plots shown in
Figure 3 (see also Fig. S4 and Table S1 in the Supporting
Information). While the total length of all grown rods is of the
same order, the thickness values strongly depend on whether
they have been measured at the center of the rod or near the
tips. Accordingly, the values of aspect ratio can become very
different, depending on which thickness is considered.
Because of the morphological changes observed in the TEM
images, modeling of the optical response of these rods required
the use of a numerical method that allowed us to design different
shapes resembling the experimentally measured nanoparticles.
The boundary element method (BEM)[16,17] is well suited for
this, since it allows fast computation of the optical spectra when
the particles have a rotation axis, which can be assumed for the
different morphologies obtained in our experiments, since in this
way, only the outer edge needs to be parametrized. The models
for the different geometries of the particles grown in the
of Figure 4, and should be compared with the TEM images in
Figure 2. Using these models, complete UV–Vis–NIR spectra
could be calculated, which are plotted in Figure 4. Comparison of
these plots with the experimental spectra shown in Figure 1
indicates that the obtained agreement is very good, even for
these simple geometrical models. Apart from small deviations
and confirms that the plasmon resonance can be easily
1200 manipulated through iodide-mediated growth. It should be
stressed that, even though the three spectra corresponding to
dumbbell-like nanoparticles that have the same nominal aspect
ratio, small changes in the extent and curvature of the tips lead to
LPB shifts of up to 130 nm.
ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.afm-journal.de 3781
 M. Grzelczak et al. / Tuning Tip Curvature in Gold Nanorods
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Again, dumbbell-like particles

were only obtained for low [KI],
regardless of the number of
seeds, while for high [KI], uni-
form growth is consistently
observed. In both cases, when
lower concentrations of seeds
were used, bigger particles were
obtained. It is clear thus that the
dominating parameter defining
the final shape is the amount of
iodide related to the number of
seed nanorods, which is likely to
be related to the preferential
adsorption of iodide ions on
{111} faces, as compared to
Figure 2. TEM micrographs presenting the initial gold rods (a), and rods grown in the absence (b), and in the {110} and {100}. In this way,
presence (c–g) of KI, with the amount of KI decreasing from (c) to (g). Electron tomography 3D-reconstruction low amounts of iodide would
(h) of a single Au dumbbell from the sample shown in (g). inhibit growth mainly at the
lateral sides and the very tip
A second set of experiments was carried out, in which the ends (top and bottom faces of the rod), while growth would
added amount of seeds was varied, while maintaining a take place at the rounding part of the tips, resulting in
constant [KI]/[Au] ratio. In order to perform a more dumbbell formation. When the amount of iodide is increased,
exhaustive analysis, two series of samples were prepared, with adsorption must necessarily become more homogeneous and
the higher and lower [KI] defined in Figures 1–4, which thereby growth takes place progressively closer to homo-
produced very different morphologies. Representative TEM geneous growth, as observed both in the absence of KI and in
images of the resulting nanoparticles are shown in Figure 5. the presence of a large KI concentration. It should be clear
that, inhibition of Au growth on iodide-containing surfaces
does not mean that there is no growth, but rather that it takes
90 Length
place at a slower rate.
80 The UV–Vis–NIR spectra of these series of samples (Fig. S3,
Supporting Information) reveals a gradual blue-shift of the
70 longitudinal plasmon band for high iodide content, which is
nm

X consistent with a larger increase of the rod thickness as

60 compared to length (decrease of aspect ratio), as the amount of
seeds is decreased, while for low iodide content, the dumbbell
Width morphology is retained but the initial red-shift observed for the
25

20 tip
middle
15
X
Aspect ratio

5 X

3
0 1 2 3 4
0
[KI]/[Au ]

Figure 3. Values of length, width, and aspect ratio for grown gold nanor-
ods, as a function of [KI]/[Au] molar ratio. These measurements are based Figure 4. Calculated (BEM) extinction spectra of Au rods and dumbbells
on the TEM images shown in Figure 2. The crosses correspond to the initial with similar morphologies to those obtained experimentally (Fig. 2). Inset:
gold nanorods. Schematic drawing of the geometries used for BEM spectral simulation.

3782 www.afm-journal.de ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2008, 18, 3780–3786
M. Grzelczak et al. / Tuning Tip Curvature in Gold Nanorods
Figure 5. TEM images of nanoparticles resulting from the growth of Au
nanorods for two [KI]/[Au] ratios: 3.6 (left) and 0.083 (right). The relative
amount of seeds employed for the growth decreases from top to bottom,
so that larger particles are obtained.
selective growth at the tips, is reverted when the particles get
thicker and the aspect ratio is globally reduced.
Following on the effort to propose a mechanism that accounts
for the iodide-induced change in tip curvature of gold nanorods,
we need to focus on the crystalline structure and the surface
chemistry of the rods, both before and after iodide addition. The
initial rods are enclosed within eight {110} and {100} alternating
lateral facets, their tips being terminated by {100}, {110}, and
{111} facets.[18] For similar nanorods, elemental analysis carried
out by Orendorff and Murphy[19] showed that the gold nanorods
indeed contain silver, in a percentage that can vary from 2.5 up to
4.3%, depending on the experimental conditions. These authors
suggested that silver metal is mostly distributed on the surface of
the particles, in accordance with the underpotential deposition
model proposed by Liu and Guyot-Sionnest[8] for gold nanorod
growth. We carried out surface characterization of the nanorods
by means of XPS and SERS. The XPS survey spectrum of the
initial nanorods (Fig. S5, Supporting Information) shows the
presence of bromide and clearly demonstrates the presence of
silver. Quantification of the percentage of silver compared to
gold reveals a higher percentage of silver of around 9%, as
compared to the values previously reported from elemental
analysis. This confirms that a higher percentage of silver atoms is
present at or close to the surface of the particles. Additionally, as
will be shown below, the silver content remains constant after KI
Adv. Funct. Mater. 2008, 18, 3780–3786 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
addition, while bromide ions are completely removed and
replaced by iodide. For the initial rods (Fig. S5B, Supporting
Information) the characteristic energy for gold (Au-4f7/2),
usually at 83.8 eV,[20] was found to be slightly shifted to 83.48 eV.
This shift may be attributed to the formation of Au-Br species at
the surface of the particles, which is consistent with the
observation of a smaller shift in the Au-4f7/2 band after the
addition of KI (83.54 eV), because of the increase in the covalent
character of the gold halide bond.[21] The characteristic silver
peaks (Ag-3d5/2) were also shifted toward lower energies, from
their normal energy of 368 eV[22] to 367.34 and 367.49 eV for Ag-
Br and Ag-I, respectively (Fig. S5C, Supporting Information). In
this case, deconvolution of the complex signal is safer than for
gold, since silver remains as a minority component, around 9%
(related to gold), in both materials. Figures S5D and E in the
Supporting Information show that Ag-3d5/2 bands comprise two
contributions: one at 368 eV, with lower intensity and a binding
energy common to both samples, which is ascribed to metallic
silver; whereas the second, with higher intensity, is located at
367.34 eV for Ag-Br and 367.54 eV for Ag-I components,
respectively. Conclusive evidence of the presence of bromide
and iodide ions bonded to the metallic surface of the rods was
obtained by careful deconvolution of their Br-3d5/2 and I-3d5/2
characteristic bands, as well as by SERS (Fig. 6). Deconvolution
of Br-3d5/2 bands (Fig. 6A) shows the presence of two
contributions at 67.7 and 67.3 eV for gold and silver bromides,
respectively.[23] In the case of iodide (Fig. 6B), the I-3d5/2 peak
also shows two contributions at 620.1 and 619.4 eV, which can be
unambiguously assigned to gold and silver iodide, respec-
tively.[24,25] Notably, the silver halide signal is in both cases much
larger than that of gold, suggesting that Ag ions are concentrated
at the surface.
Additional evidence of the presence of Ag and Au halides
on the surface of the rods was gained through SERS
spectroscopy. SERS measurements were performed on the
different rod samples and on citrate reduced gold and silver
colloids, which were previously exposed to 10
3 M solutions of
KBr or KI (Fig. 6C). SERS spectra of Au nanoparticles display
broad and intense peaks at 196 and 160 cm
1, which are
attributed to Au-Br and Au-I stretchings. In the case of silver,
both SERS spectra show complex peaks at 152 and 121 cm
1,
assigned to Ag-Br and Ag-I. In both cases, the obtained SERS
results agree well with published data[26,27] and show that the
halides are coordinated to the metallic surface. Spectra for
both nanorod samples (before and after KI addition) show
patterns corresponding to the combination of the correspond-
ing halides. Additionally, after KI addition, no Br signals
remain. This absence of Br ions on the sample treated with
KI is very likely related to the higher stability of gold or
silver iodides over their respective bromides, in full agree-
ment with their solubility products, Ks(AgI) ¼ 3.90  10
17,
Ks(AgBr) ¼ 2.71  10
13,[25] Ks(AuI) ¼ 10
16, and Ks(AuBr) ¼
10
12.[28]
Based on this characterization, and assuming the single
crystalline structure of the nanorods we can propose a growth
mechanism based on the following points:
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 M. Grzelczak et al. / Tuning Tip Curvature in Gold Nanorods
FULL PAPER

adsorbed, replacing bromide, which in

their case would favor the reduction of
cytochrome C.
Based on these findings we suggest that
when a small amount of KI is present in
solution, the exchange of bromide by iodide
takes place at the tips, where {111} facets are
present due to the higher affinity of iodide ions
to these facets, as compared to {110} and {100}.
Therefore, the tips enclosed by {111} facets
contain AgI and AuI on their surface, while in
the lateral faces bromide ions remain
adsorbed. Subsequently, when ascorbic acid
is added, the nanorods are cathodically
polarized and gold ions get catalytically
reduced at the surfaces where the surface
redox potential is lower,[29] that is, AgI coated
surfaces at the tips, leading to dumbbell
formation. Conversely, from the results
Figure 6. High resolution XPS characteristic bands and their deconvoluted gold and silver
obtained with excess KI present in solution,
contributions for (A) Br 3d (in the initial rods) and (B) I 3d (after KI addition). (C) SERS spectra
of the initial rods, and after treatment with KI. For comparison, an analytical blank was prepared full overcoating would result from complete
by adding either KI or KBr solutions to regular gold or silver citrate reduced nanospheres. Note adsorption of iodide on the whole surface of
that in both cases the rods show a complex signal that is composed of contributions from both the nanorods, i.e., equal surface redox poten-
silver and gold halides.
tial at the tips and the sides of the nanorods.
Although this seems to contradict the
– Silver is present mostly on the surface of the gold nanorods, results presented by Ha et al.,[11] where preferential adsorption
as demonstrated by elemental analysis,[19] XPS and SERS of iodide on {111} gold facets was claimed to block growth in this
(Fig. 6). direction and end up with triangular shapes, we need to point out
– Iodide ions have higher binding affinity to gold than bromide that the seeds used in that case were Ag-free, while there is Ag
ions. This was also confirmed by XPS and SERS analysis. present at the surface of our gold nanorod seeds. The influence of
– Iodide ions have different binding affinity to different gold silver on tip growth was confirmed through a control experiment
crystalline facets. Iodide ions adsorb preferentially onto in which penta-twinned gold nanorods (grown in the absence of
{111} facets.[11] silver ions[14]) were used as seeds. These rods have {111} facets on
– The surface redox potential of gold nanorods is affected by the tips and {100} facets on the sides.[30] Growth experiments on
adsorption of AgI(UPD) or AgBr(UPD). Chumanov and these new seeds were carried out, both in the presence and in the
coworkers[29] have reported a decrease in the surface redox absence of KI, observing in both cases a blue-shift of the LSP
potential of silver nanoparticles when iodide ions were band (see Fig. 7), which suggests a decrease of the aspect ratio.
Interestingly, in the presence of KI, the shift is considerably
larger (ca. 100 nm) than in the absence of KI (40 nm), while TEM
analysis shows that no dumbbell shapes were formed in either
0.8
B-No KI case (Fig. S6, Supporting Information). Statistical analysis of the
dimensions show that, while the thickness increased in a similar
C-With KI
extent in both cases (from 24 up to 32 nm), the length
Absorbance

0.6
A-Rod Initial increased when no KI was present (from 109 up to 114 nm),
however it remained basically constant in the presence of KI.
0.4 This indicates again that iodide ions block {111} facets at the tips,
as expected for Ag-free rod seeds.
0.2

0.0 3. Conclusions
450 600 750 900 1050
Wavelength [nm] The growth of gold nanorods can be notably modified
through the presence of tiny amounts of iodide, in such a way
Figure 7. UV–Vis–NIR spectra of gold nanorods prepared without silver
nitrate (A) and further overgrowth by gold shell in the absence (B) and that tip growth can be greatly enhanced, resulting in the
presence (C) of KI. formation of well-defined dumbbell morphologies. Our results

3784 www.afm-journal.de ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2008, 18, 3780–3786
M. Grzelczak et al. / Tuning Tip Curvature in Gold Nanorods
indicate that iodide can readily replace bromide ions from the
rod surface, and this replacement is more favorable at {111}
facets, which are only present at the tips. This simple procedure
becomes a solid strategy for tuning nanorod morphology, and
in turn the optical response of the system. Optical spectroscopy
characterization of the different morphologies indicates that
growth of dumbbell structures leads to strong shifts of the
longitudinal plasmon resonance (and smaller shifts of the
transverse resonance), which were found to be in good
agreement with numerical modeling based in the BEM.
Applications can be foreseen in various fields, but importantly
in LSPR biosensor design, SERS, and development of probes
for hyperthermia, since the longitudinal plasmon can be driven
to the NIR region without the need for largely increasing
particle size or aspect ratio.
4. Experimental
Gold nanorods were prepared through the well-known seeded
growth method [7,8], based on the reduction of HAuCl4 with ascorbic
acid on CTAB-stabilized Au nanoparticle seeds (<3 nm), in the
presence of CTAB (0.1 M), HCl (pH 2–3), and AgNO3 (0.12 mM).
Upon synthesis, the gold nanorod solution (10 mL) was centrifuged
(8000 rpm, 30 min) to remove excess silver salt, ascorbic acid and HCl,
and redispersed in CTAB solution (2 mL, 0.1 M), so that the
concentration of the gold nanorods in the seed solution used for
further growth was 2.5 mM.
For the growth of gold nanorods in the presence of KI, an
appropriate volume of 0.1 M CTAB (calculated for a total volume of
10 mL) was mixed with HAuCl4 (0.05 mL, 0.05 M) and stored for 5 min
at 27 8C to allow for complexation of gold salts, followed by addition of
0.01 M KI (5.7, 50, 120, 300, 550 mL) and ascorbic acid (0.04 mL, 0.1 M).
Finally, a gold nanorod seed solution (0.6 mL, 2.5 mM) was added
under stirring.
To examine the influence of gold nanorod seed concentration (at
constant [KI] / [Au] molar ratio), different growth solutions were
prepared with identical concentrations of CTAB (0.1 M) and HAuCl4
(0.25 mM), but different KI concentrations chosen to fit the selected
[KI]/[Au] molar ratios (3.6 and 0.083). To each of these solutions
(10 mL), ascorbic acid (0.04 mL, 0.1M) was added, followed by
different amounts of gold nanorods (1, 0.6, 0.3, 0.1 mL; [Au] = 2.5 mM).
Optical characterization was carried out by UV–Vis–NIR spectro-
scopy with a Cary 5000 spectrophotometer, using 10 mm path length
quartz cuvettes. Transmission electron microscopy (TEM) images
were obtained with a JEOL JEM 1010 transmission electron
microscope operating at an acceleration voltage of 100 kV. For the
electron tomography measurements, data were acquired with a JEOL
JEM 2010F microscope, operating at 200 kV, using a Gatan 912 ultra
high tilt tomography holder. Image acquisition was carried out with
multiscan Gatan camera and the Digital Micrograph software. The
total tilt angle was 1258 (from
578 to þ 688), taking 125 images, one
every 18. Image alignment was performed manually using Midas
software, while for reconstruction the TOMOJ package was used. XPS
analysis of the samples was performed using a VG Escalab 250 iXL
ESCA instrument (VG Scientific), equipped with aluminum Ka1.2
monochromatic radiation at 1486.92 eV X-ray source. SERS was
measured with a LabRam HR system (Horiba-Jobin Yvon), equipped
with a confocal optical microscope, high resolution gratings
(1800 g mm
1) and a Peltier CCD detector. For the sample excitation,
a near-infrared laser line (785 nm) and low power at the sample (7 mW)
and collection times (1 s) were used to avoid halide decomposition.
Analytical blanks for SERS were prepared by adding either KBr or KI
(10 mL, 10
2 M) to gold or silver nanospheres (1 mL, prepared by
Adv. Funct. Mater. 2008, 18, 3780–3786 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
citrate reduction), giving rise to final halide concentrations of 10
4 M.
SERS spectra of the different rod and blank samples were directly
collected from the liquid suspensions by using a macrosampling
accessory attached directly to the microscope. Simulation of optical
spectra was based on the BEM. In the BEM, scalar and vector
potentials f and A are used and they are expressed inside each
homogeneous region of space (e.g., region j) as the sum of an external
field contribution (i.e., the potentials corresponding to the incident
light plane wave, for which the scalar potential can be chosen as zero)
and surface integrals involving the noted equivalent boundary charges
sj and currents hj, defined on the boundary of region j, Sj. For water, the
index of refraction was taken constant and equal to 1.333, the value at
600 nm, while for gold tabulated, frequency-dependent dielectric
functions were used [31]). The particles were described by axially
symmetric shapes capturing the main physical aspects of their response
to external illumination. Geometrical models were devised on the basis
of nanoparticles’ shape observed in the TEM images. The circular
edges are rounded, in order to avoid sharp corners that can cause
numerical problems. Convergence to the point where differences in
numerical results cannot be resolved on the scale of the figures when
changing the number of parametrization points N has been achieved
for N ¼ 150.
Received: May 22, 2008
Published online: September 9, 2008
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