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Article history: This paper is to investigate numerically the photothermal response of the most common size of gold
Received 2 October 2014 nanoshell (AuNS) in an aqueous medium for biomedical applications. Three types of laser light irradiate
Received in revised form 16 May 2015 the particle; a continuous-wave (CW), short (nanosecond) and ultrashort (femtosecond) pulse laser. The
Accepted 16 May 2015
spatiotemporal evolution of the temperature profile inside and around the AuNS is computed using a
numerical framework based on the finite element method (FEM). For CW and nanosecond (ns) pulse laser
where the AuNS’s electrons and lattice are at thermal equilibrium, the ordinary heat diffusion equation is
Keywords:
used to describe the heat transfer to the surrounding water. For femtosecond (fs) pulse laser, due to the
Modeling and numerical simulation
Finite element method
inexistence of the thermal equilibrium, a two-temperature model (TTM) is used to describe the heat
Continuous wave transfer processes occurring in the AuNS and the normal heat diffusion equation is used for the heat flux
Short and ultra-short pulse laser calculation at the particle/water interface. For each case, the influence of laser intensity on the maximum
Hollow gold nanoshell and plasmonic temperature reached at the particle/water interface is studied. The aim of this study is to provide a
photothermal therapy description for the fundamentals of heat release of AuNSs and useful insights for the development of
these particles for biomedical applications such as drug delivery, photothermal cancer therapy and opto-
poration of cells.
Ó 2015 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijheatmasstransfer.2015.05.071
0017-9310/Ó 2015 Elsevier Ltd. All rights reserved.
A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871 867
require an enduring, moderate increase in temperature, such as surface of the AuNS. The absorption, scattering and extinction
hyperthermia and photothermal release of molecules. In this case, cross-section are defined as rabs ¼ Q abs =I0 , rscatt ¼ Q scatt =I0 and
AuNSs dissipate the absorbed energy into their surrounding envi- rext ¼ rabs þ rscatt , respectively. Here, I0 ¼ ð1=2Þe0 nw E20 represents
ronment without a substantial increase of their temperature the intensity of the incident laser beam of amplitude E0 in the sur-
[22,23]. Some applications such as photoacoustic imaging of cells rounding medium.
and gene silencing by transfection, necessitate a much higher
energy density in the vicinity of the AuNSs [24]. Further reducing 2.2. Thermal evolution
of the pulse width up to fs regime enables a very high-localized
temperature increase, more efficient energy deposition allowing The equation governs the thermal evolution of the AuNS and
the cleavage of bonds to link molecules to the AuNS surface [25]. surrounding water strongly depends on the irradiation
In recent years, there has been few research interests to time-regime. Comparison the pulse laser time width to the
advance fundamental understanding of plasmon-assisted pho- electron-lattice thermalization time 0.5–1 ps [32] plays a key role
tothermal phenomena around AuNS [26,27]. The main objective to choose thermal evolutional equations. For CW irradiation and ns
of this paper is to investigate the spatiotemporal photothermal pulses, the pulse width is much longer than electron-lattice ther-
response of the most common size of AuNS (40 nm diameter and malization time, therefore, the gold electrons and lattice are heated
3 nm shell thickness) for biomedical applications [28]. The particle in relative equilibrium. In this case the AuNS and water tempera-
is irradiated by CW, ns and fs laser pulses in water medium at a ture evolution are calculated from the usual heat diffusion equa-
wavelength of 800 nm where scattering in biological tissue is very tion [33]:
low. It has been found that such a AuNS around this size anneals
into solid particles within hours at 523 K [29], therefore, we @Tðr; tÞ
restrict the maximum temperature increase calculation to be in
qðrÞcðrÞ ¼ r ðkðrÞrTðr; tÞÞ þ Q ðr; tÞ; ð3Þ
@t
the same range. For each irradiation regime we show the maxi-
in above equation, T(r, t) is the local temperature, r is the posi-
mum temperature increase dependency and rate to laser intensity.
tion with the origin fixed at the particle center and t is the
It is worth to mention here that although we performed the calcu-
time. Three material parameters: cðrÞ; qðrÞ and kðrÞ are the heat
lations for a particular sized AuNS, however, upon request the
capacity, mass density and thermal conductivity, respectively.
developed tools are capable of doing the same calculation for any
metallic configuration and shape. Q ðr; tÞ ¼ h~
jðr; tÞ ~
Eðr; tÞi is the local heat generation density result-
t
ing from the electric current density ~ jðr; tÞ in the shell. In the case
2. Methods of pulse laser, the local field intensity calculated in Eq. (1) is modu-
lated by the Gaussian time profile of the incident laser pulse. The
The modeled system consists of AuNS with water core of radius intensity of the ns and fs pulse lasers are modeled by a Gaussian
of 17 nm and a gold layer with a thickness of 3 nm. The AuNS is curve, as following:
!
immersed in water since this medium has proven to be adequate
FL ½t t 0 2
for the modeling of laser processes occurring in a cellular medium. IðtÞ ¼ pffiffiffiffiffiffiffi exp ð4Þ
2pt r 2t 2r
The time-dependent distribution of the electromagnetic field and
thermal response of the AuNS is modeled by a system of partial dif- pffiffiffiffiffiffiffiffiffiffiffiffi
in the above equation, t r ¼ t l =2 2 ln 2 is the pulse width, where tl is
ferential equations (PDE). The system is solved in three-dimensional
the laser pulse width defined as the full with at half maximum of
(3D) using the finite element method (FEM) provided by the com-
the Gaussian temporal profile, t0 is the position of the center of
mercial software COMSOL 4.3 (www.comsol.com).
the peak and FL is the incident laser energy density (fluence).
Absorption of radiation in the core and in the surrounding
2.1. Electromagnetic field distribution
medium is neglected. In our calculations, the following thermal
characteristics of water and gold are used: cw = 4182 J kg1 K1,
Assuming time-harmonic electric field, the electric field distri-
qw = 103 kg m3, kw = 0.6 W K1 m1, cAu = 130 J kg1 K1, qAu =
bution ~
Eðr; tÞ is computed using the Helmholtz equation [13]: 19.3 103 kg m3 and kAu = 300 W K1 m1.
To study fs pulsed laser and AuNS interaction mechanisms, we
~ 2 r ~
r ðl1
r r EÞ k0 er j E¼0 ð1Þ consider the case where tl is much smaller than the characteristic
xe0
time constants of the transient non-equilibrium photothermal
where er is relative permittivity. For gold shell this quantity is a effects. These characters are electron–lattice interactions and pho-
complex, frequency dependant number and interpolated from non–phonon interactions at the surface of the particle. For this
Johnson and Christy [30]. For water er is set to be 1.77. The relative time regime the TTM can be used in which the electrons and lattice
permeability lr is taken as unity and k0 is the wave number. The remain at different temperatures (Te and Tl). This is due to the fact
other parameters in Eq. (1) are given in the reference [13]. This that the heat conduction in the lattice is small compared to that in
equation is solved in a spherical domain 10 times larger than the the electrons. Also the electron relaxation time is shorter than tens
AuNS with an outer perfectly matched layers (PML) shell and a scat- of fs for gold. In the water, considering laser fluences well below
tering type boundary condition that emulates an infinite domain. the optical breakdown, direct absorption is neglected and the usual
Assuming a non-dissipative host medium, the absorbed and one temperature heat diffusion equation applies. However,
scattered energies by the AuNS are obtained as [31]: because of the phonon mismatch factor, discontinuity between
ZZ the water and shell temperature appears at the interface. We solve
1 ~ ~scat ~
Q scat ¼ Re Escat H nds ð2-aÞ the following set of thermal evolutional equations for the electrons
2 s
and the lattice for AuNS and water [34]:
ZZ
1 ~ ~tot ~
Q abs ¼ Re Etot H nds ð2-bÞ
2 s
@T e ðr; tÞ
C e ðT e Þ ¼ r ðke rTðr; tÞÞ G ½T e ðr; tÞ T l ðr; tÞ þ SðtÞ
@t
where ~E and H~ represent the electric and magnetic field vectors,
ð5-aÞ
respectively. ~
n is an outward-pointing unit vector normal to the
868 A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871
@T l ðr; tÞ 2
C l ðT l Þ ¼ r ðkl rT l ðr; tÞÞ þ G ½T e ðr; tÞ T l ðr; tÞ F Absorption
@t 1.8 Scattering
ð5-bÞ Extiction
1.6
250 100 a single pulse with FL = 20 mJ/cm2. The laser peak intensity is
80
60
I = 3.75 MW/cm2. The maximum temperature increase
I = 5 MW/cm2
200
40 DTmax = 68 K is shown to occur 1 ns after the peak intensity.
20
0
0 50 100 150 200
Distance (nm)
3.3. Femtosecond pulse laser illumination
150
Intensity (MW/cm2)
60 3
Temperature increase (K)
1.4
40 2
100 1.2
20 1 Tl (Lattice temperature)
200 1
0 0
0 10 20 30 40 50 10 0.8
Time (ns)
70
150
Temperature increase (K)
60 0.6
50
40
1 Tm (Medium temperature) 0.4
100
30
0.2
20
8 ns 10 ns
50 10 0.1 0
0 0.1 1 10 100 1000 10000
Slope=3.4 Kcm2/mJ 0 10 20 30 40 50 60 70 80
Distance (nm) Time (ps)
0
0 20 40 60 80 100 350 6000
Laser fluence (mJ/cm2)
Maximum lattice & medium temperature increase (K)
(b)
Fig. 3. Maximum temperature increases variation on the surface of AuNS embed- 300
5000
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