Colloids and Surfaces A: Physicochem. Eng.

Aspects 436 (2013) 1069–1075

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Synthesis and characterization of hollow gold nanoparticles using

silica spheres as templates
S. Narjes Abdollahi a,∗ , Malek Naderi a , Ghassem Amoabediny b,c
a
Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran
b
Department of Chemical Engineering, School of Engineering, University of Tehran, Tehran, Iran
c
Research Center for New Technologies in Life Science Engineering, University of Tehran, Tehran, Iran

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Using optimum amount of

Na3 C6 H5 O7 prevents agglomeration
of hollow spheres.
• The morphology of gold shell
depends on the concentration of the
etchant.
• The SPR peak shows the red shift to
near IR region upon etching of the
cores.
• Hollow gold particles show optical
response to NIR range rather than vis-
ible.

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, we report preparation and characterization of monodispersed hollow gold nanoparticles
Received 3 June 2013 with the average thickness of about 25 nm through the template method. The formation of these hollow
Received in revised form 4 August 2013 nanostructures involves three subsequent steps: preparation and functionalization of silica nanospheres,
Accepted 6 August 2013
formation of a thick gold shell around the templates and following selective etching of silica particles
Available online 26 August 2013
by HF solution. In order to obtain monodispersed hollow particles, the optimum amount of trisodium
citrate was used as stabilizing agent. The results show that although for both concentrated and diluted
Keywords:
HF solution, pure gold nanoparticles were obtained, but the 10 volume percent HF solution destroys the
Silica-gold nanoshells
Hollow gold nanoparticles
hollow structures and just agglomerated gold particles were generated. Furthermore, by investigation
Selective etching the optical response of the synthesized metallic nanoparticles consisting gold nanoparticles, silica-gold
nanoshells and hollow gold nanoparticles, it can be inferred that the hollow structures are capable to
absorb wavelengths mainly within near infrared region. Hence, this paper introduces a new strategy to
produce the metallic nanostructures with optical response within NIR range which may provide new
opportunities for their applications in variety of fields such as photoelectronics, catalysis and cancer
therapy.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction oscillation of the conduction electrons in response to the opti-

In the past decade, considerable efforts have been devoted to
design and synthesis of plasmonic metal nanostructures because
of their attractive optical properties originating from the collective
∗ Corresponding author. Tel.: +98 21 64542978.
E-mail address: foroozan1516@aut.ac.ir (S.N. Abdollahi).
cal excitation. Their unique optical properties depend on their
shape and size. Hence, controlling the optical properties of metallic
nanostructures through manipulating their shape and size accord-
ing to the desire applications is possible [1,2]. For example, the
surface plasmon resonance (SPR) band of spherical monodispersed
gold nanocolloids can only be tuned around 520 nm as much
as ∼50 nm by changing their average diameter [3]. Halas and
coworkers have demonstrated that the SPR band of gold nanoshells

0927-7757/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.08.028
1070 S.N. Abdollahi et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 1069–1075
containing silica cores are capable to absorb or emit different wave-
lengths from the visible region to the near infrared by varying their
core diameter to shell thickness ratio [4].
One of the most important issues for biomedical researchers
is to introduce the best treatments for cancer therapy. Although,
surgery, chemotherapy, high intensity ultrasound are some of the
common treatments, but often there is a high risk for damaging
the surrounding tissues [5]. Photothermal ablation therapy (PTA)
has been investigated for cancer treatment in recent years. Pho-
tothermal ablation therapy is a therapeutic strategy in which the
radiated light converts into heat to damage and destroy cancer cells
[2,5]. The near infrared range extending from 700 nm to 1400 nm
also known as “tissue optical window” or “therapeutic window”
can penetrate relatively deep into biological soft tissues while
the wavelengths in the visible region are greatly absorbed by tis-
sue pigments such as hemoglobin, melanin and tissue water [6].
Therefore, using near IR region for PTA is more preferable than
visible due to deeper penetrating of the light [5]. Using metallic
nanoparticles as a photothermal agent helps to generate localized
heat in the target tissue increasing efficiently of the treatment
[7]. Ideal metallic nanostructures for PTA should be capable to
absorb wavelengths in the near IR region [2]. The SPR band of
gold nanoparticles and gold nanoshells can be tuned in the vis-
ible and from the visible to NIR, respectively. Hence, using gold
nanoshells for PTA gained more attention than gold nanoparti-
cles because of relatively better optical response of nanoshells to
NIR wavelengths [8]. However, researchers are still looking for the
nanostructures with the more appropriate optical properties in NIR
range for PTA leading to introducing new metallic nanoparticles
[2,7].
Recently, monodisperse hollow metallic spheres have attracted
considerable interest due to their unique structural and opti-
cal properties, including high surface area, low density, tunable
SPR features and wide range of potential applications such as
encapsulation of products (for the controlled release of drugs,
cosmetics, inks, enzymes and proteins), biomedical diagnostics
and hyperthermia [9–11]. Their SPR band strongly depends on
the particles size, the shell thickness, the interior void and the
dielectric constant of the surrounding environment [11]. Two
main methods known as the galvanic replacement and the hard
template method have been employed to prepare metallic hol-
low spheres. Simplicity in preparation, narrow size distribution
and availability in a wide range of particles size are the most
important benefits to use the hard template method for synthe-
sizing metallic hollow nanostructures [10]. The most commonly
employed hard templates include metal colloids (silver and cobalt
nanocolloids), silica nanoparticles, polystyrene particles and car-
bon spheres [12].
In this paper, we investigate the fabrication and characteriza-
tion of hollow gold nanoparticles using hard template method and
the effect of the etchant solution concentration on morphology of
obtained nanostructures. First, silica spheres were synthesized and
were modified with 3-aminopropyltriethoxysilane (APTES). The sil-
ica spheres were coated with gold through two subsequent steps:
seeding gold nanocolloids on the cores and shell growth. At the last
step, hollow spheres were produced via chemically etching of silica
spheres with hydrofluoric acid solution. Field emission scanning
electron microscopy (FE-SEM), transmission electron microscopy
(TEM), high resolution transmission electron microscopy (HR-TEM)
and UV–vis spectroscopy were further used to characterize synthe-
sized nanoparticles. Our results indicate the tunability of hollow
gold nanoparticles to near IR region. According to our results as
well as considering low toxicity and biocompatibility of the gold
nanoparticles [2], monodispersed hollow gold nanoparticles can be
considered as one of the most promising candidates for the medical
applications.
2. Experimental
2.1. Materials
Ammonium hydroxide (25%), ethanol absolute, hydrochloric
acid (37%), hydrofluoric acid (40%), potassium carbonate, tetraethy-
lorthosilicate (TEOS) (99%) and trisodium citrate dihydrate were
purchased from Merck. 3-Aminopropyltriethoxysilane and nitric
acid (65%) were purchased from Sigma–Aldrich. Sodium borohy-
dride (98%) and formaldehyde solution (37%) were purchased from
Acros and Applichem, respectively. All chemicals were used as
received.
2.2. Synthesis of silica-gold nanoshells
Silica-gold nanoshells were synthesized by seed growth method
as described in our previous work [13]. Briefly, monodis-
persed silica spheres were prepared by stirring 100 ml ethanol,
5 ml deionized water, 8.5 ml ammonium hydroxide and 1.5 ml
tetraethylorthosilicate at 40 ◦ C for 3 h. Then, silica spheres
were functionalized by APTES and the modified particles were
separated by centrifugation and were dispersed in deionized
water.
In order to synthesize gold nanoparticles, 1 ml of 1% HAuCl4
solution, 2 ml of 1% trisodium citrate and 1 ml of fresh 0.075% NaBH4
in 1% trisodium citrate were added into 100 ml room temperature
deionized water and the mixture was stirred for about 10 min. Here,
sodium borohydride and trisodium citrate dihydrate were used as
reducing agent and capping agent, respectively. The red colored
solution containing gold nanospheres was kept at 4 ◦ C for further
use.
At the seeding step, 10 ml functionalized silica spheres and
100 ml gold nanocolloids were mixed together. The solution con-
taining gold decorated silica particles was centrifuged and the
deposited pellet was redispersed in deionized water.
Finally, at the shell growth step, 1 ml of gold seeded silica
solution and 80 ␮l formaldehyde were added into 20 ml of gold
hydroxide solution which was obtained from mixing 1.5 ml of 1%
HAuCl4 solution and 100 ml of 2 mM potassium carbonate aqueous
solution. The obtained dark blue solution was centrifuged and the
deposited solid was redispersed in deionized water.
2.3. Synthesis of hollow gold nanoparticles
Hollow gold nanoparticles were prepared based on chemical
etching of the silica templates. First, the solution containing gold
nanoshells was sonicated for 3 min. 14 ml of 5 vol% HF solution was
added into 20 ml of sonicated solution and the mixture was stirred
magnetically for 5 min in presence of trisodium citrate (about
0.01–0.015 g) in a plastic beaker. Gradually, the color of solution
changed to light blue which is a characteristic of selective etching
of silica spheres. Finally, the solution was centrifuged and the pel-
let was redispersed in deionized water. In order to investigate the
influence of HF concentration, the same procedure was repeated
for a 10 vol% HF solution.
2.4. Characterization
The UV–vis absorption spectra were obtained using a T80+ dou-
ble beam spectrophotometer (PG Instrument). The X-ray diffraction
patterns of the samples were recorded in an X’pert Pro diffrac-
tometer (PANalytical) using Cu K␣ radiation ( = 1.5418 A◦ ). The
surface morphology and the components of the synthesized
nanostructures were characterized using S-4160 field emission
scanning electron microscope (Hitachi) and energy dispersive X-
ray spectrometer (Oxford Instrument) coupled with the S-4160,
 S.N. Abdollahi et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 1069–1075 1071

Fig. 1. (a) TEM image of bare silica particles, (b and c) FE-SEM and TEM images of gold seeded silica spheres, (d and e) FE-SEM and TEM images of silica-gold nanoshells.

respectively. Samples were dropped on a cylinder, were dried in an
oven at 30 ◦ C, and were covered with a thin gold layer. TEM images
were taken through EM 208 electron microscope (Philips) operat-
ing at a bias voltage of 100 kV. HR-TEM images and the selected area
electron diffraction (SAED) pattern were obtained using CM 30 elec-
tron microscope (Philips) working at 150 kV. Samples for TEM and
HR-TEM were obtained by dropping a small droplet of the synthe-
sized nanostructures onto a carbon-coated copper grid and drying
at ambient atmosphere. The particle size measurements were done
using Digimizer image analysis software (version 4.1.1.0, MedCalc
Software, Belgium).
3. Results and discussion
Fig. 1a presents TEM image of the monodispersed silica spheres
with an average diameter of 130 nm which were synthesized
according to Stöber method [14].
In order to increase the affinity between silica particles and
negatively charged gold colloids, the cores were functionalized
with APTES resulting positively charged modified silica spheres.
When modified silica particles were mixed with citrate-capped
gold nanospheres, the nanosized gold particles were immobilized
onto the surface of the silica spheres. FE-SEM and TEM images
1072 S.N. Abdollahi et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 1069–1075
Fig. 2. (a and b) FE-SEM images of hollow gold nanoparticles obtained using the 5 vol% HF solution. (c) EDS pattern of the hollow nanostructures.
of gold decorated silica particles are shown in Fig. 1b and c. The
images demonstrate that the gold nanoparticles were deposited
onto substrate separately due to repulsive interparticle Coulomb
interactions between gold colloids inhibiting attachment of further
particles. Hence, in order to increase the degree of silica surface
coverage with gold or in fact to obtain a complete shell, a subse-
quent reduction step of gold hydroxide on surface of immobilized
gold colloids was applied. Fig. 1d and e demonstrate that a uniform
and complete crystalline gold shell about 25 nm was obtained after
shell growth step (the XRD pattern of gold nanoshells which is an
evidence for crystalline structure of gold shell was presented in our
previous paper [13]).
During etching step, the silica spheres were dissolved by treat-
ment with HF dilute solution according to following reaction [15]:
SiO2 + 4HF = SiF4 + 2H2 O
Our experimental observations reveal that the hollow gold
nanoparticles were agglomerated gradually during etching step
may be due to decreasing surface charge of these particles. Hence,
we used trisodium citrate as a stabilizing agent [16] during selective
etching of silica cores to prevent hollow particles from aggrega-
tion as much as possible. Although, using trisodium citrate prevents
agglomeration, but excessive amount of trisodium citrate prevents
the separation and the collection of obtained particles through
centrifugation. Therefore, an optimum amount of stabilizing agent
should be used. Furthermore, the dissolution step mixing time
should not be less than 3 min nor more than 5 min. A short mixing
time does not provide enough time to complete dissolution reac-
tion. On the other hand, if the mixing time exceed more than 5 min,
the hollow particles tend to agglomerate even in the presence of
trisodium citrate. So, the mixing time is an important parameter to
prevent agglomeration of hollow nanostructures.
Fig. 2a and b presents FE-SEM images of products obtained from
mixing gold nanoshells with the 5 vol% HF solution. The images
show that the obtained nanostructures are hollow spherical gold
shells with the average thickness of 25 nm. Hence, it can be inferred
that the gold shell was permeable to the acid and the silica spheres
were dissolved selectively with HF solution without collapsing the
gold shell. EDS pattern of hollow gold particles (Fig. 2c) shown in
Fig. 2b indicates that hollow gold nanoparticles are pure gold and
the silica spheres were etched completely.
HR-TEM images of hollow gold nanoparticles obtained from this
procedure are shown in Fig. 3a and b. In these images, the con-
trast between the dark edge and the light center indicates the
selective etching of silica particles and formation of hollow gold
nanospheres.
The SAED pattern of hollow gold particles is presented in Fig. 3c.
The SAED pattern shows the diffraction rings corresponding to the
(1 1 1), (2 0 0), (2 2 0), (3 1 1) and (2 2 2) planes of the face centered
 S.N. Abdollahi et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 1069–1075
Fig. 3. (a and b) HR-TEM images of hollow gold nanoparticles. (c) SAED pattern of hollow gold nanoparticles.
cubic structure of gold [17]. The pattern demonstrates the poly-
crystalline nature of the hollow nanoparticles. Furthermore, the
ring-type dotted pattern may be due to irregular attachment of gold
nanoparticles onto the surface of silica nanospheres or irregular
gold shell growth [18].
Upon increasing the HF concentration to 10 vol%, the structure of
obtained products was completely different. As shown in FE-SEM
and HR-TEM images (Fig. 4a–d), during etching step, the hollow
structure was destroyed and the particles were broken into smaller
pieces, producing large aggregates of irregular shapes. The EDS
pattern of obtained nanostructures is presented in Fig. 4e. The pat-
tern demonstrates that the nanoparticles are pure gold same as
the hollow gold particles and there is no impurity in it. So, it can
be concluded that although the concentrated solution of HF does
not change the components of products compared to the diluted
solution, but the morphology of products depends on the HF con-
centration.
Fig. 5 shows UV–vis absorption spectra of synthesized nanopar-
ticles consisting gold nanoparticles, gold decorated silica particles,
gold nanoshells and hollow gold nanoparticles which were nor-
malized at their maximum absorption for comparison. As shown in
Fig. 5, curve a, the surface plasmon resonance of synthesized gold
nanospheres is about 525 nm.
As shown in Fig. 5, in the case of gold nanoshells, it can
be inferred that the SPR peak of core–shell nanostructures is
shifted from about 540 nm for gold seeded silica particles (curve
b) to longer wavelengths (about 650 nm) for silica-gold nanoshells
(curve c). Furthermore, a second peak at shorter wavelengths
(about 385 nm) is shown up. The red shift of SPR peak to 650 nm is
due to stronger plasmon coupling between gold particles aggre-
gated on silica spheres [19]. Besides, according to hybridization
model presented by Halas et al., the SPR band of nanoshells is the
1073
consequence of an interaction between plasmon response from a
nanosphere and a nanocavity. The interaction between these two
plasmons leads to hybridization of plasmon resonance into anti-
symmetric mode and symmetric mode. The strength of plasmon
coupling determines the position of the SPR for nanoshells [20,21].
Hence, the red shift of SPR band observed for synthesized gold
nanoshells can be described by hybridization model.
In case of gold nanoshells, as the shell growth proceeds, the
higher order multipole mode (i.e. quadrupolar plasmon resonance)
becomes more dominant for the advent of SPR band which was
initially due to dipolar plasmon resonance. The higher order mul-
tipole mode resonance gives rise to a secondary peak to the left of
the SPR band [22]. This justifies the appearance of the second peak
observed at curve c, at 385 nm. Moreover, increasing interparticle
interactions leads to the broadening of absorption spectrum of gold
nanoshells [23] which is observed in curve c.
According to UV–vis spectrum of obtained hollow gold nanopar-
ticles shown in Fig. 5, curve d, it can be understood that by removing
silica spheres, the SPR peak showed a red shift into the near-IR
region and the plasmon bandwidth was increased.
In this research, upon selective etching of silica particles, the
produced central void of the hollow nanostructures was fulfilled
with water (the embedding medium). Hence, the dielectric con-
stant of the core was decreased from ∼2.04 for silica particles to
∼1.77 for water, while the dielectric constant of the surround-
ing medium is still ∼1.77 (the surrounding medium for both
silica-gold nanoshells and hollow gold nanoparticles is water). Liu
et al. investigated the effect of the dielectric core and embed-
ding medium on optical properties of core–shell nanostructures.
They theoretically demonstrated that the SPR band of the silica-
gold nanoshells (shell thickness = 10 nm, total diameter = 60 nm)
shows a redshift to longer wavelengths by increasing the dielectric
1074 S.N. Abdollahi et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 1069–1075

Fig. 4. (a and b) FE-SEM and (c and d) HR-TEM images of the nanoparticles produced using the 10 vol% HF solution. (e) EDS pattern of aggregated nanoparticles.

constant of core and medium due to polarizability of the dielec-
tric material. However, the sensitivity of the SPR band position to
changing the dielectric core is less than dielectric medium [24].
But, as in our work, the SPR band was shifted to longer wave-
lengths upon etching silica particles and decreasing the dielectric
constant, our result is in contrast to what Liu et al. theoret-
ically illustrated. This difference may be due to the following
reasons.
It is mentioned before in the manuscript that selective etching
of the cores enhanced aggregation of the products, so the distance
between the metallic nanoparticles was decreased. Decreasing the
distances leads to stronger plasmon coupling between neighboring
gold nanoparticles, hence, a red shift to longer wavelengths is the
consequence [25,26]. Furthermore, the position of SPR band of the
hollow nanoparticles depends on their aspect ratio (outer diame-
ter to shell thickness ratio). Increasing the particle size of hollow
nanoparticles at a constant shell thickness leads to the red shift
of SPR band [26,27]. Therefore, in this research, the observed red
shift of SPR upon removing silica spheres may be due to aggrega-
tion of gold nanoparticles and strong plasmon coupling between
 S.N. Abdollahi et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 1069–1075
Fig. 5. Normalized UV–vis spectra of (a) gold nanoparticles, (b) gold seeded silica
nanoparticles, (c) silica-gold nanoshells and (d) hollow gold nanoparticles.
obtained particles as well as the high aspect ratio of synthesized
hollow nanostructures.
On the other hand, increasing the plasmon bandwidth of
spectrum after removing silica spheres is due to aggregation of
nanoparticles and the introduction of new multipole modes [26]
as well as polydispersity in particle size or shape of products
[28]. Hence, based on our results it can be inferred that among
these synthesized nanoparticles, hollow particles are almost the
only nanostructures which show optical response to wavelengths
within near IR range rather than visible range.
4. Conclusions
The main purpose of our present work has been to present
an effective procedure to produce polycrystalline hollow gold
nanoparticles. Since, silica nanoparticles are inexpensive, easily
obtainable and controllable in size; we employed them as the hard
templates to produce hollow nanostructures. In this paper, it has
been demonstrated that using silica spheres as templates and sub-
sequent selective etching of the cores provides a successful route
to synthesize such nanostructures. In conclusion, the amount of
trisodium citrate using as a stabilizing agent and the mixing time
are two important issues must be considered at dissolution step in
order to prevent agglomeration and obtain monodispersed prod-
ucts. Furthermore, the concentration of HF solution as etchant is
the determinative factor to obtain hollow nanoparticles without
collapsing or destroying the structures.
Moreover, we studied the optical properties of obtained nanos-
tructures. The results reveal that gold nanospheres are capable
to absorb the wavelengths of visible region. For the silica-gold
nanoshells, the absorption spectrum was shifted to longer wave-
lengths in the visible region. But, in the case of hollow nanoparticles,
the particles absorb the wavelength in near-IR region rather than
the visible. Hence, tunability of hollow gold nanoparticles into near-
IR region made them more attractive than gold nanoshells for the
applications that require nanostructures with maximum absorp-
tion in the near-IR range such as photothermal therapy of cancer
cells through irradiation hollow nanoparticles with infrared laser.
Acknowledgements
Authors would like to thank staff members of Research Center
for New Technologies in Life Science Engineering and Department
1075
of Mining and Metallurgical Engineering of Amirkabir University of
Technology (Tehran Polytechnic) for supporting this research.
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