Article

pubs.acs.org/JPCC

Monodisperse Colloidal Gold Nanorings: Synthesis and Utility for

Surface-Enhanced Raman Scattering
Yue Hu,† Tsengming Chou,† Hongjun Wang,*,‡ and Henry Du*,†
†
Department of Chemical Engineering and Materials Science and ‡Department of Chemistry, Chemical Biology, and Biomedical
Engineering, Stevens Institute of Technology, Hoboken, New Jersey 07030, United States
*
S Supporting Information

ABSTRACT: Highly monodisperse colloidal Au nanorings (Au NRs) were synthesized

via galvanic replacement reaction of 1D chain assembly of Co nanoparticles (Co NPs) in
HAuCl4. The Au NRs exhibited tunable localized surface plasmon resonance (LSPR)
wavelengths ranging from 651 to 760 nm as the aspect ratio increased from 3.8 ± 0.5 to
7.1 ± 1.8, consistent with calculations using the finite-difference time domain (FDTD)
method. The FDTD calculations indicated intense field enhancement within the cavity
of well-separated Au NRs as well as the presence of hot spots between closely situated
Au NRs. The Au NRs are individually active for surface-enhanced Raman scattering
(SERS). We show that the steric hindrance of densely packed poly(vinylpyrrolidone)
(PVP) stabilizer at the particle junctions of the 1D chain assembly of Co NPs to AuCl4−
diffusion is of critical importance for Au NR formation. We further demonstrate that
whether an analyte experiences the hot-spot effect or not depends strongly on its ability
to enter the junction points and thus its affinity to PVP on the surface of Au NRs in our
system of study.

1. INTRODUCTION on-wire lithography,33 anodized aluminum oxide (AAO)

Localized surface plasmon resonance (LSPR) arises from
collective oscillation of electrons in the conduction band of
nanostructured metal upon light irradiation. The resultant
electromagnetic field enhancement is a key enabling feature for
a multitude of applications, ranging from sensing and imaging
to cancer therapy.1−7 It is well established that LSPR strongly
depends on the size, shape, composition, interparticle spacing,
and dielectric environment.8,9 For example, Au nanostructures
in the form of nanoshells,10−12 nanorices,13 nanorods,14,15 and
nanocages16−18 have exhibited plasmon resonance wavelengths
spanning across the visible and near-infrared (NIR) range,19
affording significant opportunities for spectroscopic20−22 and
biological exploitations.23−27 These nanostructures are pro-
duced mainly via wet chemistry, leading to stable colloidal
solutions readily available for further explorations.
Compared to the solid nanoparticles with limited shift in
LSPR through variation in particle diameter,28 nanorings are of
particular interest because they allow significant tunability of
plasmon resonance wavelengths associated with variable
longitudinal and transverses axes.29 The LSPR tuning can be
achieved by keeping the outer diameter fixed while changing
the inner diameter, or the aspect ratio, of the nanorings. This
feature is especially attractive for cellular uptake in biological
applications where transport of large particles through cellular
membranes will be difficult.30 Meanwhile, a large surface-to-
volume ratio of nanorings reduces radiation damping and
further yields intense local electromagnetic field enhancements
in surface-enhanced Raman scattering (SERS).31 To date,
nanoring structures have been fabricated via nanolithography,32
growth template,34 colloidal lithography,31,35 nanosphere-
templated wet-chemical synthesis,36 and self-assembly of
metallic particles.37 While serving important purposes in
demonstrating the promise of nanorings and the suitability
for targeted use, these synthesis approaches not only involve
more sophisticated process steps but also lead to nanorings
anchored to solid support with limited feasibility for
postfabrication surface modification and subsequent utilization.
Clearly, there is a compelling need to develop a cost-effective
and straightforward approach to fabricate free-standing,
monodisperse nanorings in stable colloidal suspensions to
greatly expand the field of investigation and application of the
nanoring structures.
Here, we report a novel one-pot method to directly
synthesize colloidal Au NRs with high monodispersity in
aqueous solution using a galvanic replacement reaction. Cobalt
nanoparticles (Co NPs) coated with poly(vinylpyrrolidone)
(PVP) were used as sacrificial template and galvanically
replaced with Au to form Au NRs. By varying the size of Co
NPs and the concentration of Au salt, the dimensions of Au
NRs can be adjusted, leading to tunable LSPR. This capability
allows for systematically tailoring the plasmonic properties of
Au NRs. We identify the critical process parameters leading to
the formation of Au NRs and reveal the corresponding
mechanism. In addition, we combine the finite-difference
Received: April 29, 2014
Revised: June 30, 2014
Published: July 1, 2014

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The Journal of Physical Chemistry C
Figure 1. (a−d) TEM images of Au NRs at various tilt angles: 0°, 15°, 30°, and 45°. (e) TEM images of Au NRs of a large area. (f, g) HRTEM
images of Au NRs with fringe spacing of 0.14 nm indexed to {220} reflection of the face centered cubic (fcc). (h) EDX spectrum of Au NRs. (i)
Elemental mapping of Au NRs.
time domain (FDTD) modeling and SERS experiments to
study the plasmonic behavior of these nanostructures and
reveal the presence of concentrated near-field electromagnetic
field inside the individual Au NR cavity and the development of
hot spots between neighboring Au NRs in close proximity.
2. EXPERIMENTAL DETAILS
Materials. Cobalt chloride hexahydrate (CoCl2·6H2O
99.99%), sodium borohydride (NaBH4 99%), gold(III)
chloride solution (30 wt % of HAuCl4 in diluted HCl),
poly(vinylpyrrolidone) (PVP, Mw = 2500, 10 000, or 55 000),
poly(allylamine hydrochloride) (PAH, Mw = 15 000), trans-1,2-
bis(4-pyridyl)ethylene (BPE), and Rhodamine 123 (R123)
were purchased from Sigma-Aldrich (St. Louis, MO). Sodium
citrate trihydrate was procured from Fisher Scientific
(Pittsburgh, PA). Milli-Q ultrapure water (no less than 18.2
MΩ) was used for the synthesis experiments.
Synthesis of Au NRs. 100 μL of 0.4 M CoCl2·6H2O mixed
with 400 μL of 0.1 M sodium citrate trihydrate was added to
100 mL of 18.2 MΩ Milli-Q water in a 500 mL three-necked
round-bottom flask. The solution was deaerated by vacuuming
for 40 min under continuous argon flow. Then, 1 mL of 0.1 M
freshly prepared NaBH4 and 200 μL of 1 wt % PVP (Mw =
2500) were injected into the solution at the same time under
vigorous stirring. The color of the solution turned from pale
pink into brown in seconds, indicating the formation of Co
NPs. The solution was further vigorously stirred for 40 min
under argon flow protection until complete hydrolysis of the
borohydride. Subsequently, 150 μL of 0.1 M HAuCl4 was
added into the cobalt solution dropwise and allowed stirring for
another 30 min. Upon completion of the reaction, the solution
was exposed to lab ambient to oxidize the nonreacted cobalt.
Characterization of Au NRs. The size and distribution,
crystal structure, and LSPR of the resultant Au NRs were
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measured with a transmission electron microscope (TEM,
Philips CM20), a high-resolution transmission electron micro-
scope (HRTEM, JEOL 2100F), energy-dispersed X-ray
spectrometry (EDX, Philips CM20), and a UV−vis absorption
spectroscope (Synergy HT multidetection microplate reader,
BioTek Instruments, Inc. Winooski, VT). All the images were
analyzed using Image-J 1.46 software (NIH). In order to
examine Co NPs and Au NRs using TEM, HRTEM, and EDX,
these nanostructures were immobilized onto copper grids
(Electron Microscopy Sciences, Hatfield, PA). We designed an
in situ sampling protocol, in which poly(allylamine hydro-
chloride) (PAH)-modified TEM grids were used to capture the
nanostructures via electrostatic interaction during the synthesis
process.38 Briefly, the grids coated with 300-mesh holey carbon
were incubated with an aqueous solution of poly(allylamine
hydrochloride) (PAH, 2 mg/mL) at pH 9 for 20 min to
functionalize the surface. Upon rinsing with Milli-Q water to
remove any free or loosely bound PAH, the grids were quickly
dipped into the colloid solution to capture a small droplet, and
the water was immediately drained with filter paper. The
nanostructrues were immobilized onto the PAH-functionalized
grid surface through the electrostatic interaction with PAH as
well as via the binding affinity between nanostructures and
amino groups of PAH.
FDTD Simulation. For the simulation of plasmonic
properties of gold nanorings, Lumerical FDTD solution of
version 8.6.3 was used. The desired particle size and shape in
3D were built using the Cartesian coordinate system. Boundary
conditions and perfectly matched layer (PML) were defined in
the draw mode. The dielectric function of Au NRs is taken
from measurements by Johnson and Christy.39 The surround-
ing medium was set to be air, the refractive index of which is
1.0. A simulation area of 10003 nm3 surrounded by 12 perfectly
matched layers (PMLs) proved to be sufficient. The mesh gird
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Scheme 1. Schematic Illustration of the Possible Mechanism To Form Au NRs Using Co NPs as Sacrificial Templates under
Continuous External Stirring
size is 0.5 nm. For the ring dimers, the quartz substrate is
considered. The dimension of quartz substrate is 110 nm × 110
nm × 16 nm.
Surface-Enhanced Raman Measurement. In all experi-
ments Au NRs (Au NR I in Figure 4) were deposited on thin
quartz substrate (Electron Microscopy Sciences, Hatfield, PA)
to achieve SERS-active substrate for measurements of trans-1,2-
bis(4-pyridyl)ethylene (BPE) and Rhodamine 123 (R123). The
quartz surface was first modifed with a monolayer of positively
charged PAH. Immobilization was achieved by electrostatic
attraction between PAH and slightly negatively charged Au
NRs (ζ-potential of −5 mV in Milli-Q water) as well as by the
binding affinity of Au to amino groups in PAH. The absorption
spectra of SERS samples were measured by a PerkinElmer UV/
vis spectrometer Lambda 40, Waltham, MA. SERS measure-
ments were conducted at 785 nm excitation wavelength using
custom-built Raman spectrometer.28 Laser power is ∼25 mW.
Integration time is 20 s. The SERS data were processed using
Origin 8.5 software. Analytical SERS enhancement factors
(EFs) were calculated using EF = (ISERS/CSERS)/(INR/CNR),
where ISERS and INR are the integrated intensities of a
characteristic band from SERS and from normal Raman and
CSERS and CNR are concentrations of analytes used in SERS and
normal Raman experiments, respectively. Both ISERS and INR
were collected under the same conditions, and the loading
volume of the analyte solution was the same. Intensities of the
BPE peak (∼1619 cm−1) and R123 peak (∼1209 cm−1) were
used to calculate the EFs.
3. RESULTS AND DISCUSSION
Monodisperse Colloidal Au NRs. In order to facilely
fabricate colloidal Au NRs, we first synthesized the colloidal
magnetic Co NPs as a sacrificial template. This provides a
robust way to yield Au NRs directly in the aqueous solution.
Briefly, highly monodisperse Co NPs were obtained using
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NaBH4 as reducer and sodium citrate and PVP as stabilizers
under continuous stirring.40 High quality and monodisperse Co
NPs were obtained and subsequently used for template-guided
synthesis of Au NRs. Aqueous HAuCl4 solution was injected
gently to initiate the galvanic replacement of sacrificial Co NPs
at room temperature. Au NRs with high monodispersity were
obtained upon completion of the reaction. The replacement
reaction was robust since there exists a large differential
standard reduction potential between AuCl4−/Au (0.935 V vs
SHE) and Co2+/Co (−0.277 V vs SHE), which facilitated rapid
exchange between Co and AuCl4− with the latter being reduced
into Au0.41
Transmission electron microscopy (TEM) images in Figure
1a−d show that the as-fabricated Au NRs with outer diameter
of 39.7 ± 2.3 nm, wall thickness of 9.5 ± 1.6 nm, and sidewall
height of 15.6 ± 3.2 nm at different tilting angles. The high-
resolution transmission electron microscopy (HRTEM) images
(Figure 1f,g) reveal a lattice spacing of 0.14 nm, indexing to
{220} planes of face-centered-cubic (fcc) gold according to the
JCPDS No. 65-2870. Energy-dispersive X-ray (EDX) analysis
performed involving a large number of Au NRs suggests that
Au is the only constituent element in the nanorings (Figure
1h). This observation is consistent with the element mapping
of individual Au NRs (Figure 1i), indicating effective removal of
Co during galvanic replacement.
Discussion of the Formation Mechanism of Colloidal
Au NRs. The spatial organization of sacrificial Co NPs
assembly was found to be one of the key factors in determining
the final Au nanostructures. Scheme 1 schematically illustrates
the correlation between Co NPs assembly and resultant Au
nanostructures. Co NPs with magnetic dipole (N and S) field
exhibit 1D chain-like assembly along the external force line
under continuous stirring,42 as shown in Figure 2a. In contrast,
Co NPs exist as well-dispersed, discrete nanoparticles in a
stable colloidal solution in the absence of stirring, as
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Figure 2. (a) TEM images of chain-like Co nanoparticles and the final
products of Au NRs. (b) TEM images of discrete Co nanoparticles and
the final products of Au NSs.
demonstrated by the sample harvested from the solution
terminating stirring for 10 min (Figure 2b). This results from
the steric hindrance of surface-adsorbed stabilizer of PVP,
which prevents the Co NPs dipole−dipole interactions.43,44
Importantly, Au NRs were only obtained when Co NPs
appeared in 1D chain-like assembly. In the case of individually
dispersed Co NPs, gold nanoshells (Au NSs) were formed
instead (Figure 2b). Clearly, the state of Co NPs assembly in
the colloidal solution during the galvanic reaction plays a critical
role in determining the final shape of Au nanostructures.
Galvanic replacement was immediately initiated upon the
addition of HAuCl4 into the colloidal solution containing chain-
like Co NPs under continuous stirring. Note that the density of
PVP in the contact regions of the 1D linked Co NPs is up to
twice of that away from these sites, making the contact regions
of Co NPs kinetically less accessible by AuCl4− than the center
portion for preferential galvanic replacement. Upon completion
of the galvanic reaction, the remaining Co caps at the contact
region as well as the remnant Co cores are simply oxidized and
precipitated out in the aqueous solution, leaving individually
dispersed Au NRs. A very small fraction of bowl-like
nanostructures was also found in the synthesized Au NRs
(Figure S1 in the Supporting Information), coming from the
Figure 3. (a, b) TEM images of Au NRs obtained with PVP (Mw = 2500). (c, d) TEM images of Au NRs obtained with PVP (Mw = 10 000). (e, f)
TEM images of Au NRs obtained with PVP (Mw = 55 000).
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Co NPs located at the very ends of the chain-like structures,
which further confirms the illustrated mechanism in Scheme 1.
The molecular weight of PVP is another key factor affecting
the formation of Au NRs. Two additional PVPs with higher
molecular weight, Mw 10 000 and Mw 55 000, were chosen as a
control, following the same synthesis protocol as Mw 2500.
Interestingly, the resultant Au NRs displayed a chain-like
arrangement (Figure 3c−f), different from those of Mw 2500
(Figure 3a,b). Meanwhile, the average ring height of Au NRs in
the chains seems to decrease with the increase of Mw of PVP
(Figure 3d,f). This correlation further suggests that the density
of PVP in the particle contact regions plays a crucial role in
determing the final geometry of Au NRs. The increase of PVP
Mw, that is the length of PVP chain, can increase the
entanglement45 and the extensive bridging of adsorbed PVP
molecules on neighboring Au NRs, resulting in the formation of
permanently chained 1D assembly of Au NRs. Molecular
weight of PVP can thus be used to control Au NR
monodispersity and assembly.
LSPR Measurements and FDTD Simulation of Au NRs.
The synthesized colloidal Au NRs exhibit size-dependent LSPR
with highly tunable wavelength from visible to NIR regions. Au
NRs with three different geometries in Table 1, Figure 4, and
Figure S2 in the Supporting Information showed markedly
different LSPR characteristics. The main LSPR wavelength
exhibited a strong dependence on the outer diameter/shell
thickness aspect ratio (Figure 4a). As the aspect ratio increases
from 3.8 ± 0.5 (Au NR III) to 7.1 ± 1.8 (Au NR I), the LSPR
wavelength is progressively red-shifted from 651 nm (Au NR
III) to 760 nm (Au NR I). The heights of the three Au NRs
vary from 15.4 ± 4.2 nm (Au NR I) to 9.2 ± 1.8 nm (Au NR
III) as shown in Figure S2 in the Supporting Information,
depending on the size of the Co NPs and dictated by the
aforementioned synthesis mechanism. Besides a prominent
band, a lower intensity shoulder is also present in the UV−vis
spectrum of various Au NRs.
To obtain more quantitative insights into the LSPR behavior
of Au NRs, we performed FDTD calculations of the Au NRs.
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Table 1. Outer Diameter, Shell Thickness, Height, Aspect Ratio (Outer Diameter-to-Shell Thickness Ratio), Experimental SPR
Position, and FDTD Simulation SPR Peak Position of Three Different Au NRs
Au NRs outer diam (nm) shell thickness (nm) height (nm) aspect ratio exp SPR (nm) FDTD SPR (nm)
Au NR I 41.6 ± 1.7 6.2 ± 1.4 15.4 ± 4.2 7.1 ± 1.8 760 750
Au NR II 33.0 ± 1.2 5.9 ± 1.0 14.1 ± 2.6 5.8 ± 1.2 682 683
Au NR III 25.4 ± 1.1 6.6 ± 0.5 9.2 ± 1.8 3.8 ± 0.5 651 657

Figure 4. (a) Experimental and (b) simulated absorption spectra of three different Au NRs in Table 1. TEM images and electric field intensity
distributions in the cross section and middle planes of Au NRs: (c) Au NR I, (d) Au NR II, and (e) Au NR III. The red point/arrow and white arrow
are the propagation direction (k vector) and the polarization (E field vector), respectively. The scale bar is 20 nm. The color bar represents the value
of |E|/|E0|. The coordinate directions are as indicated.

The outer diameters of Au NR I, Au NR II, and Au NR III for
the simulation are 40, 30, and 25 nm, respectively, with the
same shell thickness of 5 nm. The heights of Au NR I, Au NR
II, and Au NR III are 15, 14, and 9 nm, respectively, close to the
experimental values. The peak positions of FDTD calculated
absorption spectra (Figure 4b) show excellent agreement with
the corresponding main LSPR wavelengths in Figure 4a (also
see Table 1). As the height of Au NRs in the same group is not
exactly the same, we carried out additional calculations to
ascertain the effect of changing heights on LSPR for the three
types of Au NRs. As shown in Figure S2 in the Supporting
Information, the effect on the resonance wavelength is relatively
small for the range of the height value investigated. Such
variations likely contributed to the broadening of the
experimental UV−vis spectra. Considering the presence of a
small fraction of bowl-like Au nanostructures, we further carried
out calculations for the bowl structure using the same
dimensions as the Au NRs (Table 2 and Figure S3 in the
Supporting Information). The calculated peak positions are also
consistent with those shoulder bands in the experimental UV−
vis spectra. Taken together, both LSPR measurement and
FDTD simulation suggest that our synthesis method leads to a
Table 2. Geometry and Characteristics of Three Au Bowls
Au bowls outer diam (nm) inner diam (nm) FDTD SPR (nm)
Au bowl I 40 30 625
Au bowl II 30 20 581
Au bowl III 25 15 557
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colloidal solution of predominantly Au NRs mixed with a small
quantity of Au nanobowls, in agreement with the TEM results
and in support of the mechanism of Au NR formation.
We have further used FDTD to calculate the electromagnetic
enhancement of Au NRs. Figure 4c−e shows the horizontal and
vertical cross-sectional views of the calculated near-field
electromagnetic distribution of Au NRs with different aspect
ratios at 785 nm excitation. The maximum enhancement (|E|2/|
E0|2), located at the upper and lower rim of the rings denoted
by the point monior, increased from ∼450 to ∼1270 as the
aspect ratio varied from 5 to 8 (Figure 4c−e). The calculated
fields are lower than the true surface field, as reported
elsewhere.46 Meanwhile, a relatively uniform intense field
enhancement is found inside the ring cavity rather than the
outside of the ring, which rapidly decays from the ring wall.
These resluts are qualitatively consistent with previously DDA
results in the gold nanorings.31 Also, Au NRs with a larger
surface-to-volume ratio can further reduce the retardation
effects.47 Combined with the tunability of LSPR through
different aspect ratios, the high field enhancement suggests that
the inner surface and the cavity of Au NRs itself can be utilized
to benefit field-enhanced phenomena such as SERS-based
sensing and detection.
SERS Measurements. The Au NRs were further assessed
for their utility in SERS. We chose two different analytes or
their mixture, trans-1,2-bis(4-pyridyl)ethylene (BPE) and
Rhodamine 123 (R123), in our studies. BPE has a high affinity
with the PVP while R123 preferentially binds with citrate ion
via the electostatic interation due to the ζ-potential of Au NRs
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Figure 5. (a) SERS spectra of 2 ppm BPE−R123 mixture (upper spectrum), 2 ppm BPE (middle spectrum), and 2 ppm R123 (lower spectrum)
obtained using Au NRs with coverage density ∼75 particles/μm2. Spectra were acquired at 785 nm (25 mW, 20 s). The characteristic bands for BPE
at ∼1619 and ∼1652 cm−1 correspond to δ(C−N), ν(C−C), δ(C−H), and ν(CN). The characteristic bands for R123 at ∼1209 and ∼1609 cm−1
correspond to ν(C−O−C) and external phenyl ring stretching. (b) SERS intensities of each BPE/R123 characteristic band as a function of Au NRs
coverage density for single analyte measurements. (c) SERS intensity area of BPE band at 1348 cm−1 and R123 band at 1372 cm−1 as a function of
Au NRs coverage density for dual-analyte measurements. (d) Measured absorptions spectra of SERS samples with different Au NRs coverage density
(CD). FDTD calculations of the absorption spectra (e) and electrical field intensity distribution (f) in the cross section and middle planes of two Au
NRs located on the quartz substrate with interspacing distance of 2, 5, 10, and 20 nm, respectively. The red point/arrow and white arrow are the
propagation direction (k vector) and the polarization (E field vector), respectively. The scale bar is 20 nm. The color bar represents the value of |E|/|
E0|. The coordinate directions are as indicated.

(−5 mV in Milli-Q water).48 Figure 5a shows the typical SERS
spectra of BPE, R123, and BPE−R123 mixture absorbed onto
Au NRs. We evaluated the dependence of SERS intensity on
the coverage density of Au NRs in each case. BPE is more
sensitive as measured than R123 (Figure 5b). The enhance-
ment factor (EF) of BPE reaches 8.85 × 106, which is ∼1 order
higher than R123. Importantly, both BPE and R123 followed a
linear intensity−coverage correlation up to ∼60 Au NRs/μm2
(Figure S4a−d in the Supporting Information). The trend
rapidly diverged for BPE beyond this coverage, exhibiting an
exponential dependence, while R123 continued its linear
correspondence. The observed linear intensity−coverage
correlation strongly indicates that Au NRs are individually
SERS-active. The exponential increase in the intensity of BPE
beyond ∼60 Au NRs/μm2 results from the formation of dimers
and trimers of Au NRs when the coverage density increases.
This experimental finding is consistent with our FDTD field
calculations of dimers of Au NRs (Figure 5f), where significant
field enhancement occurs in the junction. Figure 5f presents
examples of electric field profiles corresponding to different
interspacing distances of two Au NRs at a wavelength of 785
nm. The coupling mode of ring dimers is typical dipole−dipole
mode since the polarization direction of the incident light is
parallel to the ring dimer axis.49 The electric field inside
individual Au NR rapidly decayed when the distance decrease
from 20 to 2 nm, while the hot spot in the junction exhibit a
maximum electric field intensity distribution with an
exponential increase. Also, the measured absorption spectra
of SERS samples with different surface coverage densities show
a slightly red-shift with the inducing spaces (Figure 5d). The
experimental observations are in good agreement with the
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simulations, the plasmon resonance peaks of which show a red-
shift with decreasing the inter distance (Figure 5e). This can be
explained by the dipolar interaction model. The plasmon
frequency will be decreased when two dipolar plasmonic
particles experience stronger attraction with reduced separa-
tion.50,51 However, R123 seemed to be insensitive to the hot
spot effect of the Au NR clusters. To further probe the
divergence, a solution mixture of BPE and R123 was used for
the similar SERS measurements. To avoid the overlap of
characteristic bands (Figure 5a), for comparison, we focused
our analysis on two distinct bands, ∼1348 cm−1 for BPE and
∼1372 cm−1 for R123, and conducted peak deconvolution
(Figure S4e in the Supporting Information) to resolve the
spectral details as shown in Figure 5c. BPE and R123 from the
mixture also followed a similar trend as in the single analyte
measurements. We extended these measurements and analyses
to a higher coverage ranging from ∼90 to ∼130 Au NRs/μm2,
with the same general outcome (Figure S5 in the Supporting
Information). The plausible interpretation is that BPE has
stronger affinity with PVP than R123 at neutral pH,52 and the
dense PVP at the junction, therefore, further hinders the
adsorption of R123 onto Au NRs. The far more sensitive SERS
response to BPE than R123 was also attributed to the strong
affinity of BPE to PVP, which effectively brings BPE closer to
the Au NRs surface for electromagnetic as well as chemical
enhancement.
4. CONCLUSIONS
In conclusion, through controlled 1D assembly of Co NP
chains as template and via galvanic replacement reaction, we
dx.doi.org/10.1021/jp504190d | J. Phys. Chem. C 2014, 118, 16011−16018
The Journal of Physical Chemistry C
have achieved the synthesis of free-standing, stable, mono-
disperse Au NRs colloidal solutions. The geometrical
dimension of Au NRs can be tailored by changing the size of
Co NPs and the concentration of gold salt, leading to tunable
LSPR with intense electromagnetic field enhancements. FDTD
calculations show that a relatively uniform intense field
distributes inside the discrete individual Au NRs but hot
spots form when the Au NRs are brought to close proximity.
SERS measurements reveal that the Au NRs are individually
SERS-active, with analyte-dependent Raman intensity−Au NR
coverage correlation. Compared to other types of Au
nanostructures, the easy access to inside the Au NRs with
relatively uniform field intensity enhancement potentially opens
many new opportunities to explore and exploit Au nano-
plasmonics for sensing, imaging, and photomedicine. Our work
has led to the development of a novel and effective synthesis
strategy for free-standing Au NRs, an important category of the
fascinating Au nanostructures.
■
ASSOCIATED CONTENT
*
S Supporting Information
Experimental details and additional figures noted in the text,
including TEM images of bowl-like Au nanostructures, FDTD
calculations of Au NRs with different heights, TEM images of
three types Au NRs, FDTD calculations of Au nanobowls, SEM
images of different immobilized Au NRs substrates for SERS
measurements, peak deconvolution analysis on the SERS
spectra, and Raman intensity of characteristic bands as a
function of Au NR coverage density using the mixture of
analytes. This material is available free of charge via the Internet
at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail hdu@stevens.edu (H.D.).
*E-mail hongjun.wang@stevens.edu (H.W.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank the Center for Functional Nanomaterials at
Brookhaven National Laboratory for the use of their high-
resolution transmission electron microscope (HRTEM, JEOL
2100F). Y.H. is financially supported by a teaching assistantship
from Stevens Institute of Technology.
■
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