Plasmonics (2014) 9:623–630
DOI 10.1007/s11468-014-9673-8
Photothermal Enhancement in Core-Shell Structured
Plasmonic Nanoparticles
Qiang Li & Weichun Zhang & Ding Zhao & Min Qiu
Received: 8 November 2013 / Accepted: 22 January 2014 / Published online: 6 February 2014
# Springer Science+Business Media New York 2014
Abstract Plasmonic nanoparticles (NPs) with photothermal
effects can be exploited as efficient heat sources in various
applications. Here, the photothermal properties in core-shell
structured plasmonic NPs, including metal/silica NP, silica/
metal NP, and metal/silica/metal NP, are investigated. Com-
pared with bare metal NPs, the core-shell plasmonic NPs not
only exhibit extremely agile tunability in the surface plasmon
resonances but also show considerably enhanced
photothermal effects in terms of the maximum temperature
rise. For metal/silica NPs and metal/silica/metal NPs, the SiO2
shells function as effective thermal-protective layers for en-
hanced photothermal effect. For silica/metal NPs, the SiO2
core and the metal shell show uniform temperature rise. These
findings are essential for applying the core-shell structured
plasmonic NPs on photothermal imaging, nanofluidics, etc.
Keywords Plasmonics . Core-shell nanoparticle .
Photothermal effect
Introduction
Metallic nanoparticles (NPs) with vivid optical, thermal,
electronic, and catalytic properties have aroused keen
interest due to their potential applications in various
Q. Li (*) : W. Zhang : D. Zhao : M. Qiu (*)
State Key Laboratory of Modern Optical Instrumentation,
Department of Optical Engineering, Zhejiang University,
Hangzhou 310027, China
e-mail: qiangli@zju.edu.cn
e-mail: minqiu@zju.edu.cn
M. Qiu
School of Information and Communication Technology, Royal
Institute of Technology, Electrum 229, 16440 Kista, Sweden
interdisciplinary areas [1]. One distinguished feature of
a metallic NP lies in its surface plasmon resonance
(SPR), which is collective oscillation of conduction
electrons excited by an electromagnetic field. For bare
metal NPs, the resonance tunability is somewhat limited.
For example, the 530-nm resonance of a gold NP with a
size of 5 nm in water shifts only 25 nm at an increased
size in 100 nm, thus restricting its application around
the gold plasma frequency. The core-shell structured NP
[1], whose SPR can be readily varied via changing the
shell thickness, has emerged as a particularly fascinating
solution. In this way, the SPR can be tuned to match
the laser wavelength, fluorescence molecule excitation
wavelength, human-tissue transparency window, etc. to
achieve the optimal performance. Thus far, several core-
shell structured plasmonic NPs with SPRs have been
demonstrated: (1) metal/silica core-shell NP, where the
metal NP is encapsulated with a silica shell. The silica
shell provides not only enhanced SPR tunability and
colloidal stability in water but also a means to control
the distances between metal particles within assemblies.
Au@SiO2 NPs with various silica thicknesses (from 1
to 120 nm) have been synthesized [1]. (2) Silica/metal
core-shell NP consists of a silica core covered with a
metallic layer. The optical resonance of such NP ex-
hibits highly agile tunability spanning from near-
ultraviolet to the near-infrared region since its SPR
depends dramatically on the relative size between the
core and the shell. Typical examples include SiO2@Au
NPs [1], with various silica radii and metal thicknesses.
(3) Metal/silica/metal core-shell1-shell2 NP composed of
a silica-coated metal core surrounded by a metal shell.
For this type of NP, the metal core and shell can be of
the same material (Au@SiO2@Au) or of different ma-
terials, and the coupling between the metal core and
shell is determined by controlling the thickness of the
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Fig. 1 Schematic of the plasmonic NPs. a metal NP, b metal/silica core-shell NP, c silica/metal core-shell NP, and d metal/silica/metal core-shell1-shell2
NP. The gold and gray regions denote metal, and the blue regions are silica (Color figure online)
dielectric spacer [1]. Such NPs also possess a highly
geometrically tunable optical resonance.
Since the inevitable absorption by the lossy metal
leads to the dissipation of light into resistive thermal
energy, optically excited plasmonic NPs can thereby be
exploited as efficient heat sources in a set of applica-
tions [2–11]. These applications range from biomedical
therapy [2], photothermal imaging [3], optical data stor-
age [4], nanofluidics [5], nanotweezers [6], photonic
switch [7], material processing [8], plasmon ruler [9],
etc. For plasmonic NPs, previous research into
photothermal effects has mainly concentrated on the
bare Au NP of various morphologies, including gold
spheres, gold ellipsoids/disks/rings, gold rods, gold
sphere dimers, gold sphere chains, gold nanostars, and
gold spheres in ice [12–14]. For the core-shell struc-
tured plasmonic NP, while a lot of experimental works
on its applications in biomedical have been done [15],
the tunable photothermal properties of the core-shell
structured NPs and the role of shell in the thermal
response are still yet to be explored. Given the promis-
ing applications of core-shell structured plasmonic NPs
as efficient heat sources, it is of vital importance to
unveil their photothermal properties.
To a d d r e s s t h i s i s s u e , w e i n v e s t i g a t e t h e
photothermal properties in core-shell structured
Fig. 2 Absorption spectrum for 30 nm Au@SiO2 core-shell NPs for
different SiO2 shell thicknesses. (Color figure online)
Plasmonics (2014) 9:623–630
plasmonic NPs in this paper. Three kinds of typical
core-shell structured plasmonic NPs are taken into
consideration: metal/silica core-shell NP, silica/metal
core-shell NP, and metal/silica/metal core-shell1-shell2
NP. Gold with excellent SPR properties is considered
as the metal material.
Structure and Simulation
Structural Model of the NPs
The schematic diagrams of a bare plasmonic NP and core-
shell structured plasmonic NPs are depicted in Fig. 1: (a) metal
NP, (b) metal/silica core-shell NP, (c) silica/metal core-shell
NP, and (d) metal/silica/metal core-shell1-shell2 NP. r0 desig-
nates the core radius and t the shell thickness. The plasmonic
NPs are surrounded by water, which is analogous to the
biological environment.
Optical Simulation
The simulations of optical and thermal properties are
performed based on commercially available finite ele-
ment method solver (Comsol Multiphysics 4.2a). The
core-shell structured plasmonic NP in a water matrix is
illuminated by a plane wave traveling from the negative
x direction with a z-polarized electric field, as is shown
in Fig. 1. The illumination light has an intensity of
1 mW/μm 2 and a wavelength corresponding to the
SPR peak wavelength in all cases except specified.
The geometrical sizes of the NPs used in the simulation
correspond to the typical sizes of chemically synthesized
core-shell structured plasmonic NPs [1].
As has been reported previously [16], the use of bulk
dielectric functions of metal can lead to an unjustified de-
crease in the SPR width. For a thin metal shell (or metal core),
when its thickness becomes comparable with the mean free
path of conductive electrons, the deviation in the density from
that existing in the bulk metal has a considerable effect on the
dielectric functions. Accordingly, the dielectric function of
metal shell should be corrected to incorporate the size-
limiting effects for the sub-100-nm NPs considered here.
Plasmonics (2014) 9:623–630 625

Fig. 3 Cross sections of the normalized electric field and heat power density around a 30 nm Au@10 nm SiO2 core-shell NP in water when it is excited
at 540 nm z-polarized illumination from x direction. (Color figure online)

The frequency-dependent dielectric function of metal film damping constant of bulk metal, and υF is the Fermi velocity.
with a thickness of t can be described by [16] A0 is 1 for simple Drude theory and isotropic scattering. The
values of Γ∞, υF, and ωp for Au are 11×1013 Hz, 1.4×106 m/s,
ω2p ω2p and 2π×2.195×1015 Hz, respectively [17]. The experimental-
εðωÞ ¼ εbulk ðωÞ þ − ð1Þ ly obtained Johnson and Christy dielectric function for metal
ω2 þ iΓ ∞ ω ω2 þ iΓ ðt Þω
is adopted for the bulk value [17].

Thermal Simulation
where εbulk is the bulk dielectric function, ω is the angular
frequency of light, ωp is the bulk plasma frequency; Γ(Γ∞ + The absorption of light by the core-shell structured plasmonic
A0υF/t) is the size-dependent damping constant, Γ∞ is the NP leads to the generation of heat. The heat power density

Fig. 4 a Temperature rise distribution for a 30 nm Au@10 nm SiO2 core-shell NP. b Maximum temperature rise versus SiO2 shell thickness. The Au
core radius is 30 nm. (Color figure online)
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Fig. 5 Spatial distribution of temperature rise in radial direction of 30 nm
Au@SiO2 core-shell NP for different SiO2 shell thicknesses. The gray
dots denote the core-shell interfaces (Color figure online)
(resistive loss) q can be expressed in terms of the metal loss
and the electric field distribution in the NP [13]. q=ε0ωε″mm|-
E|2/2, where ε0 is the permittivity in vacuum, ε″m is the imag-
inary part of the dielectric function, and E is the electric field.
Due to a strong boundary scattering effect, a reduced
thermal conductivity can be expected for a thin material
film, and the bulk value is thus not valid for describing
the thermal conductive behavior in the core-shell struc-
tured plasmonic NPs. Qiu and Tien’s model [18, 19],
which combines both the surface and grain-boundary
scattering effects, is used to describe this size effect.
k(t)=kbulk /(1+3L/8t+7α/5), where kbulk is the bulk ther-
mal conductivity and L is the electron’s mean free path
in bulk material. α=(L/D)(R/1−R), where D is the av-
erage in-plane grain diameter and R is the reflection
coefficient at the grain boundaries. The ratio D/t is
assumed to be 0.2 [18, 19]. The L, R, and kbulk for
Au are 42 nm [20], 0.17 [19], and 317 W/(m K) [21],
respectively. For a silica film, the thermal conductivity k
is related to the bulk value kbulk and the film thickness t
by k = k bulk /(1 + (k bulk × 3.4 × 10 − 8 [m 2 K W − 1 ]/t)) [22],
where the bulk value for silica is 1.44 W/(m K).
Photothermal Properties of Metal/Silica Core-Shell NP
Metal/Silica Core-Shell NP
Figure 2 shows the absorption spectrum for the bare Au
NP and the Au@SiO2 core-shell NP with a core radius
of 30 nm. The bare Au NP exhibits a characteristic SPR
at 532 nm. For the Au@SiO2 core-shell NP, there is a
redshift and an intensity increase in the SPR peak due
to an increase in the local refractive index around the
Au NPs. A maximum redshift of 12 nm can be
Plasmonics (2014) 9:623–630
observed after an 80-nm silica shell is coated. The
position of the SPR peak is no longer sensitive to the
shell thickness when the thickness is above 80 nm.
Figure 3 depicts the electric field and heat power density
around a 30 nm Au@10 nm SiO2 core-shell NP in water when
it is excited at 540 nm. Since the radius of the gold NP is only
30 nm, a nearly uniform electric field distribution inside the
gold core can be seen, thus leading to a nearly uniform heat
power density.
Figure 4a shows the temperature rise distribution for
the 30 nm Au@ 10 nm SiO2 core-shell NP. The tem-
perature is uniform inside the Au NP owing to its large
thermal conductivity, and the temperature rise is 71.4 K.
For the SiO2 surface, the temperature rise is 38.4 K.
The sharp temperature decline of 33 K is attributed to
its comparatively small thermal conductivity. Figure 4b
plots the maximum temperature rise (ΔTmax) versus the
SiO2 shell thickness for Au@SiO2 core-shell NP. ΔTmax
decreases as the SiO2 shell thickness increases. Two
factors contribute to the maximum temperature rise:
the absorption power and the SiO2 thermal conductivity.
The thermal conductivity of SiO2 shell increases signif-
icantly as the SiO2 shell thickness increases, which
efficiently exhausts the heat out of the sources and
alleviates ΔTmax to a great extent. The SiO2 thermal
conductivity takes a prominent role and thereby leads to
a decrease in ΔTmax.
For a bare Au NP with a radius of 30 nm, ΔTmax is
45.1 K. Therefore, the ΔTmax for the bare Au NP is
smaller than that (71.4 K) for the Au@SiO2 NP; how-
ever, this value is higher than the shell surface temper-
ature (38.4 K) for the Au@SiO2 NP. For such applica-
tions as thermal imaging and data storage, ΔTmax is a
critical parameter while the NP surface temperature
plays a prominent role in applications such as
Fig. 6 Absorption spectrum for SiO2/Au core-shell NPs for different Au
shell thicknesses. The SiO2 core radius is 50 nm. (Color figure online)
Plasmonics (2014) 9:623–630 627

Fig. 7 Cross sections of a the normalized electric field and b the heat power density around a 50 nm SiO2@7.5 nm Au core-shell NP when it is excited at
830 nm. (Color figure online)

nanofluids. When the SiO2 shell thickness is smaller
than 36.3 nm, the thermal conductivity of SiO 2 is
smaller than that of water; therefore, a thin coating of
SiO2 shell actually blocks the thermal diffusion and
leads to an increase in ΔTmax and a decrease in the
surface temperature. Therefore, the use of Au@SiO2 NP
for enhanced photothermal effects depends on specific
applications.
The radial temperature distributions for the Au@SiO2 core-
shell NP for different SiO2 shell thicknesses are shown in Fig. 5.
The temperature decreases far more quickly in the SiO2 shell
than in the water for the SiO2 shell thickness below 36.3 nm, in
which case the thermal conductivity of SiO2 is smaller than that
of water. The SiO2 shell thus functions as an effective thermal
protective layer for enhanced photothermal effect.
Silica/Metal Core-Shell NP
Figure 6 shows the absorption spectrum for the SiO2@Au core-
shell NPs for different Au shell thicknesses. In sheer contrast to
the limited tunability of Au@SiO2 NP, the optical resonance of
such NPs depends dramatically on the relative size between the
core and the shell and shows highly agile tunability. The SPR
peak shifts from 1,190 to 730 nm when the Au shell thickness
varies from 2.5 to 12.5 nm. The absorption power rises and then
decreases with the increase of the Au shell thickness. As the Au

Fig. 8 a Temperature distribution for a 50 nm SiO2@7.5 nm Au core-shell NP. b Maximum temperature rise versus Au shell thickness. The SiO2 core
radius is 50 nm. (Color figure online)
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Fig. 9 Spatial distribution of temperature rise in the radial direction of
SiO2@Au core-shell NP for different shell thicknesses. The radius of the
SiO2 core is 50 nm. The gray dots denote the core-shell interfaces. (Color
figure online)
shell thickness increases, more field concentrates in the metal
shell and the absorption power increases consequently. How-
ever, when the shell thickness increases further above 7.5 nm,
the absorption power decreases so as the metal becomes less
lossy at higher thickness.
The electric field and heat power density around a 50 nm
SiO2@7.5 nm Au core-shell NP in water at 830-nm illumina-
tion are depicted in Fig. 7. Around the gold shell, the electric
field is strong in the z direction, where the excitation electric
field is polarized. Contrarily, the electric field in the z direction
is smaller than that in the x and y directions inside the gold
shell, leading to a low heat power density in this direction.
Figure 8a shows the temperature rise distribution for a
50 nm SiO2@7.5 nm Au core-shell NP. The temperature is
uniform inside the SiO2 core and the Au shell, and the value is
97.4 K, higher than that for the Au@SiO2 NPs shown in
Fig. 10 Absorption spectrum for Au@SiO2@Au three-layered NPs for
different silica shell thicknesses. The gold core radius and the gold shell
thickness are 30 nm and 10 nm, respectively. (Color figure online)
Plasmonics (2014) 9:623–630
“Metal/Silica Core-Shell NP” section. Even if there is no heat
generation in the SiO2 core, no temperature decrease in the
SiO2 core can be produced since it is fully surrounded by the
Au heat source. Figure 8b shows ΔTmax versus the Au shell
thickness. The ΔTmax rises as the Au shell thickness increases
first and then decreases with an increasing shell thickness. The
ΔTmax for the silica@metal core-shell NP is mainly decided
by the absorption power.
The radial temperature distributions for the 50 nm
SiO2@Au core-shell NP for different Au shell thicknesses
are shown in Fig. 9. A uniform temperature rise can be seen
in the SiO2 core and the Au shell.
Metal/Silica/Metal Core-Shell1-Shell2 NP
Figure 10 shows the tunable absorption spectrum for
Au@SiO 2 @Au core-shell1-shell2 NPs. Similar to the
SiO2@Au NPs, the optical resonance of such NPs also ex-
hibits extremely large tunability in the near-infrared region.
The coupling between the Au core and Au shell is mediated
through the SiO2 spacer, which can thus be easily controlled in
the NP synthesis.
Figure 11 provides the normalized electric field and the
heat power density around a 30 nm Au@10 nm SiO2@10 nm
Au core-shell1-shell2 NP when it is excited at 900 nm. A large
local field enhancement in the SiO2 spacer is a characteristic
of such three-layered plasmonic NP.
Figure 12a shows the temperature rise distribution for a
30 nm Au@10 nm SiO2@10 nm Au three-layered NP. The
temperature is uniform inside the Au core (143 K) and the Au
shell (74 K). These values are much higher than those for bare
Au (45.1 K), demonstrating enhanced photothermal effects
with core-shell NPs. The 10-nm thickness SiO2 layer func-
tions as a thermal spacer between the Au core and the Au
shell. Figure 12b plots the ΔTmax versus the SiO2 shell thick-
ness for Au@SiO2@Au NP. The maximum temperature rise
increases with the SiO2 shell thickness varying from 5 to
15 nm because of the increase in the absorption power, as is
shown in Fig. 10.
The radial temperature distributions for the 30 nm
Au@SiO2@10 nm Au core-shell1-shell2 NP for different
SiO2 shell thicknesses are shown in Fig. 13. The Au core
and the Au shell show a uniform temperature rise. A signifi-
cant temperature decline in the SiO2 shell can be seen. The
reduced temperature in the SiO2 shell increases with the
increasing SiO2 shell thickness.
Conclusion
The photothermal properties in three kinds of core-shell struc-
tured plasmonic NPs are investigated in this paper, including
metal/silica NP, silica/metal NP, and metal/silica/metal NP.
Plasmonics (2014) 9:623–630 629

Fig. 11 Cross sections of a the normalized electric field and b the heat power density around a 30 nm Au@10 nm SiO2@10 nm Au three-layered NP
when it is excited at 900 nm. (Color figure online)

When excited at the SPR resonance, the maximum
temperature rise for a bare 30 nm Au NP is only
45.1 K. For the 30 nm Au@10 nm SiO2 core-shell
NP, the temperature is uniform inside the Au NP, and
the maximum temperature rise is 71.4 K. While for the
SiO2 shell surface, the temperature rise is 38.4 K. A
thin coating of SiO2 shell blocks the thermal diffusion and
leads to an increase in the core temperature and a decrease
in the surface temperature. For the 50 nm SiO2@7.5 nm Au
core-shell NP, the temperature is uniform inside both the
SiO2 core and the Au shell, and the maximum temperature
rise is 97.4 K. For the 30 nm Au@10 nm SiO2@10 nm Au
three-layered NP, the temperature is uniform inside the Au
core (143 K) and the Au shell (74 K). The core-shell NPs
not only exhibit extremely agile tunability in the SPR but
also show considerably enhanced photothermal effect
compared with the bare metal NPs. It can be expected
that the photothermal effect can be further enhanced
using a collection of core-shell NPs. Compared with
other morphologies, the core-shell structured NPs pos-
sess highly tunable optical resonance and photothermal
effect by changing the shell thickness.

Fig. 12 a Temperature distribution for a 30 nm Au@10 nm SiO2@10 nm Au core-shell1-shell2 NP. b Maximum temperature rise versus SiO2 shell
thickness for Au@SiO2@Au core-shell1-shell2 NP. The Au core radius is 30 nm and the Au shell2 thickness is 10 nm. (Color figure online)
630
Fig. 13 Spatial distribution of temperature rise in radial direction of
Au@SiO2@Au three-layered NPs for different SiO2 shell thicknesses.
The Au core radius is 30 nm and the Au shell2 thickness is 10 nm. The
dashed line denotes the core/shell1, shell1/shell2, and shell2/H2O bound-
aries. (Color figure online)
The findings presented are essential for applying the core-
shell structured plasmonic NPs on photothermal imaging,
nanofluidics, etc.
Acknowledgments This work is supported by the National Natural
Science Foundation of China (grant nos. 61275030, 61205030, and
61235007), the Qianjiang River Fellow Fund of Zhejiang Province, the
Scientific Research Foundation for the Returned Overseas Chinese
Scholars from the State Education Ministry, the Opened Fund of State
Key Laboratory of Advanced Optical Communication Systems and Net-
works, the Fundamental Research Funds for the Central Universities,
Doctoral Fund of Ministry of Education of China (grant no
20120101120128), the Swedish Foundation for Strategic Research
(SSF), and the Swedish Research Council (VR).
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