Excerpt from the Proceedings of the COMSOL Users Conference 2007 Taipei

Analysis of Heat Transfer and Phase Change in Laser-Assisted Direct Imprinting

Processes

F. K. Chung *,1 , Y. L. Wang 1 , C. H. Chen 1

1
Department of Mold and Die Engineering, National Kaohsiung University of Applied Sciences
*
Corresponding author: Department of Mold and Die Engineering, National Kaohsiung University of
Applied Sciences, Kaohsiung , Taiwan, cfk@cc.kuas.edu.tw

Abstract: In this study a model cast in
COMSOL multiphysics has been developed for
the analysis of heat transfer and phase change
during laser-assisted direct imprinting processes.
The features of this model include the
employment of temperature-dependent thermal
properties, the use of equivalent specific heat for
the treatment of latent heat of fusion,
automatically switching the thermal contact
resistance off once the near surface of the
substrate is melted and keeping it zero thereafter,
and prompt adjustments to reflectivity and
absorption coefficient depending upon the local
phase within the substrate. The reflectivity of
melted silicon under the irradiation of KrF
(249nm) excimer laser were estimated by
comparison of simulated results to available
experimental data in the literature. It is found
that the reflectivity of molten silicon varies with
the fluence of laser and is about 1.0 to 1.2 times
the reflectivity of solid silicon in the range of
fluence from 0.9 J/cm2 to 1.8 J/cm2 . For a
LADI process using XeCl (308nm) laser as the
heating source which has an energy density of
1.6 J/ cm2 and a pulse duration of 20ns, the
resulting molten depth ranges from 289.08 nm to
303.76 nm for different values of thermal contact
resistance up to 10 −3 m 2 ⋅ K/W as the reflectivity
is taken to be 0.5638 before melting and 0.6868
after melting.
Keywords: LADI, Phase Change, Thermal
Contact Resistance
1. Introduction
Laser-assisted direct imprinting (LADI)
technique was proposed by S. Y. Chou et al. [1]
in 2002. In this method, a quartz mold with
nanostructures on its surface is pressed against
the substrate at the start. A pulse excimer laser is
then triggered to penetrate the highly transparent
mold and radiate on the substrate. Heated by the
irradiating laser, the near-surface region of the
substrate is melted and the mold is pressed into
the molten layer. After the liquid layer solidifies,
the mold is then separated from the imprinted
substrate, leaving a nano patterns on the
substrate.
The melting duration and melted depth are
key issues for laser-assisted direct imprinting
technique. Early in 1981, Wood et. al. [2] had
investigated the temperature-distribution and
phase-change problem in the silicon substrate
under the direct irradiation of pulse laser. A
FDM-based software HEATING5 was employed
to analyze the variation of melting duration and
melted depth with the laser's characteristics and
the thermal properties of the substrate. Although
the absorption coefficient of the silicon substrate
should increase from a value of about
105 ~ 106 m −1 in solid state to about 108 m −1 as the
near-surface region of the substrate melts, it was
found that the melted depth decreases only
slightly with the increasing absorption
coefficient when its value is greater than
~ 2 ×106 m −1 . A series experiments on excimer
laser annealing of silicon substrate were
performed by Narayan et. al. [3, 4].
Microstructural changes as a function of laser
parameters were investigated by TEM and
concomitant changes in dopant profiles were
monitored by Rutherford backscattering
spectroscopy. The melting threshold for KrF
laser pulses at the pulse duration of 24ns in
amorphous and crystalline silicon layers were
determined to be 0.16 J/cm 2 and 0.75 J/cm 2 ,
respectively. Time-resolved reflectivity (TRR)
measurements on silicon and germanium under
the irradiation of KrF excimer laser were carried
out by Jellison et. al. [5]. From these
measurements, the change of reflectivities before
and after the melt, the melt duration, and the time
of the onset of melting could be determined.
Recently, Hsiao et. al. [6, 7] proposed a
mathematical model for predicting the required
thermal response for LADI fabrication. Both
analytical method and numerical method were
developed to solve the associated equations. The
analytic method [6] focused on the temperature
 Excerpt from the Proceedings of the COMSOL Users Conference 2007 Taipei

distribution within the substrate with the Note should be paid that when the near-surface
assumption of constant thermal properties. The region of the substrate melts, not only does the
moving boundary was treated as a moving heat reflectivity increase, the absorption coefficient
sink inside the substrate. The numerical method should increase to metallic values of about
[7] employed the explicit finite-difference 108 m −1 [2].
algorithm and both the temperature-dependent
thermal properties and the thermal contact
resistance at the interface between mold and
substrate were taken into consideration. The
present study is indeed an extension of the work
in Ref. [7]. Viewing that the tracking of melting
front in an explicit method may cause significant
deviation from that obtained by an implicit
method, a COMSOL model on the basis of
equivalent heat capacity method is employed in
the present work. Furthermore, thermal contact
resistance is switched off once the surface of the Fig.1 schematic diagram of the simplified LADI
substrate is melted and kept zero thereafter. model for heat-transfer analysis

2. Theoretical modelling Since phase change may take place in the

substrate, Eq.(2) may be reformulated by the use
The schematic diagram of the simplified LADI of equivalent heat capacity [8] as
model for heat-transfer analysis is shown in Fig.
1. The one-dimensional energy equations within ∂Ts ∂ ∂T
quartz mold and substrate can be written as ρ s ces = (k s s ) + g s (5)
∂t ∂x ∂x

∂Tq ∂ ∂Tq where the equivalent heat capacity is defined by

ρ q cq = (k q ) for x min < x < 0 and t > 0 (1)
∂t ∂x ∂x

∂hs ∂ ∂T
ces = cs + hLsδ (Ts − Tms ) (6)
ρs = ( k s s ) + g s for 0 < x < x max and t > 0
∂t ∂x ∂x (2)
The initial and boundary conditions are
expressed as following:
where ρ , c, k , and T represent density, specific
heat capacity, thermal conductivity, and Tq ( x,0) = T∞ ； Ts ( x,0) = T∞
temperature, respectively. The heat-generation ∂T q (7)
( x min , t ) = 0 ； Ts ( x max , t ) = T∞
term, g s , induced by the absorption of the ∂x
incident laser within the substrate can be
described as [6] The interfacial conditions at x = 0 are

g s ( x, t ) = α (1 − R ) e −αx I (t ) (3) ∂Tq Tq − Ts ∂Ts

− kq = = −k s (8)
∂x Rc ∂x
where the power density function, I (t ) , is
assumed to be Gaussian-shaped and can be where Rc stands for the thermal contact
expressed as resistance on the interface between mold and
substrate. Generally, the value of Rc is about
El (t − t m ) 2 10−4 ~ 10−5 m 2 ⋅ K/W . However, Rc approaches
I (t ) = exp[ − ] (4)
2π σ 2σ 2 zero as the surface of substrate melts.

3. Modelling in COMSOL
 Excerpt from the Proceedings of the COMSOL Users Conference 2007 Taipei

The variable liqv is used to adjust the

The existence of the thermal contact absorption coefficient α . In order to
resistance causes a temperature discontinuity monitor the phase on the mold-substrate
across the mold-substrate interface. Therefore, interface, a variable liqs is defined in
the employment of two heat-transfer modes is 「 Boundary Integration Variables 」 for
necessary. The dependent variables of the two global destination as
modes are named as Tq and Ts referring to the
liqs=liqv
temperatures in quartz mold and substrate,
respectively. Each mode has a subdomain and is The variable liqs is designed to monitor
active only in its own subdomain. whether the surface of the substrate is
Some important settings for the present melted so as to adjust the reflectivity R and
COMSOL model are listed as following: the thermal contact resistance Rc . When
(1) Treatment of latent heat of fusion
The singular dirac-delta function, δ (Ts − Tms ) ,
Rc becomes zero after the substrate has
been melted, a very small value, says
is replaced by Gaussian-pulse function
10 −12 m ⋅ K/W, should be adopted in order to
2
defined in 「Scalar Expressions」as
avoid the error of division by zero.
fgauss=exp(-(Ts-Tmelts)^2/deltaT^2)
/(sqrt(pi)*deltaT)
(4) Variables for postprocessing
where deltaT is chosen to be 1.0K.
A variable Tqs is defined in 「Subdomain
(2) Temperature-dependent thermal properties Expressions」 as
Tqs= ⎧
Temperature-dependent thermal properties, Tq, in the subdomain for quartz
including thermal conductivity and specific ⎨
⎩ Ts, in the subdomain for substrate
heat capacity, are stored in 「Interpolation With this variable Tqs, the temperature
Functions」. The properties for quartz and distributions in both subdomains may be
silicon used in this study are listed in Table displayed simultaneously. Another variable,
1. called Dmelted, is set from 「 Subdomain
Integration Variables」 with its destination
Material Quartz Silicon defined at the interfacial point. It is
Density (kg/m3) 2650 2420 expressed as
Melting temperature
2000 1690 Dmelted=liqv
(K)
Latant heat (J/kg) 1.802× 106 The variable Dmelted is employed to record
the melted depth during the whole LADI
300K 2 120
process. The information about melting
500K 2 63
Thermal duration may also be determined from the
1000K 4 27 records.
conductivity
1500K 5 20
(W/m ⋅ K )
1690K 6 17(solid) 4. Results and Discussion
Liquid 6 63
300K 710 700 As an application, the present model was
Specific 500K 900 790 used to estimate the reflectivity of melted silicon
heat 1000K 1200 970 irradiated directly by KrF (248nm) excimer laser.
capacity 1500K 1252 1080 From Ref.[9], the values of n and κ for solid
(J/kg ⋅ K ) 1690K 1270 1100(solid) crystalline silicon at 248nm are respectively 1.57
Liquid 1270 1100 and 3.565. The reflectivity and absorption
coefficient of solid silicon may be calculated to
(3) Liquid fraction in the substrate be R =0.6748 and α =0.1806 nm -1 . In the
Set liqv for the substrate in 「 Scalar absence of information about the reflectivity and
Expressions」as the absorption coefficient of molten silicon, we
liqv= flc1hs(Ts-Tmelts,deltaT) estimated their values by the trial and error
method so as to match the available experimental
 Excerpt from the Proceedings of the COMSOL Users Conference 2007 Taipei

data about molten depth or melting duration [4].

Since the absorption coefficient has little effect
on the molten depth [2], the absorption
coefficient for liquid silicon was chosen to be the
same as that for solid silicon, i.e., 0.1806 nm -1 .
With the data given in Table 2 for the reflectivity
of liquid silicon with respect to the KrF laser of
different fluences, the simulated molten depths
are in well agreement with the experimental data,
as shown in Fig.2. It implies that the reflectivity
of melted silicon varies with the fluence of the
laser and is about 1.0 to 1.2 times the reflectivity
of solid silicon in the range of fluence from 0.9
to 1.8 J/cm 2 . Fig. 3 The distribution of thermal conductivity in
silicon substrate at different time steps
Fluence(J/cm2) Reflectivity for molten Si under the irradiation of KrF laser at a
0.9 0.7211 fluence of 1.4 J/cm 2 and a pulse duration
1.0 0.7086 of 38ns.
1.2 0.6945
1.4 0.6805 Simulation of a LADI process as reported in
1.6 0.6839 Ref.[1] was performed. In this process, XeCl
1.8 0.6739 (308nm wavelength) excimer laser with a energy
Table 2. Estimated reflectivity of molten silicon density of 1.6 J/cm 2 and a pulse duration of 20ns
with respect to the KrF laser at different was employed to melt the silicon substrate. From
fluences Ref.[9], the refractive indexes for quartz and
500 solid silicon are nq =1.486, ns =5.013 and
Narayan et al.(1985)

κ s =3.689, which lead to R =0.4667 and

450
COMSOL Multiphysics
400

α =0.1505 nm -1 for solid silicon. The reflectivity

M olten depth (nm )

350

300

250
and the absorption coefficient for molten silicon
200 are chosen to be 0.5528 and 0.1505 nm -1
150 respectively. Fig. 4 shows the temperature
100
distribution in quartz mold and silicon substrate
50
with a thermal contact resistance of
0
0.9 1 1.2 1.4 1.6 1.8 10 −8 m 2 ⋅ K/W before melting. It can be observed
Laser fluence (J/cm2)
KrF(249nm)-pulse width 24ns that discontinuities of temperature exist at the
Fig.2 Comparison of molten depth between mold-substrate interface before the substrate is
simulated and experimental results melted. Once the surface of the substrate has
been melted, the thermal contact resistance
Because of the high temperature gradient in becomes zero and the temperature becomes
the silicon substrate, the consideration of continuous. It is worth noting that the maximum
temperature-dependent thermal properties is temperature occurs in the quartz region near
necessary. Fig. 3 shows the distribution of interface during the cooling stage. This is
thermal conductivity in silicon substrate at because the thermal conductivity of quartz is
different time steps under the irradiation of KrF much less than that of silicon.
laser at a fluence of 1.4 J/cm 2 and pulse duration
of 38ns. The variation of thermal conductivity
with position is significant and even
discontinuous.
 Excerpt from the Proceedings of the COMSOL Users Conference 2007 Taipei
Fig. 4 Temperature distribution in quartz mold
and silicon substrate with a thermal
contact resistance of 10−8 m 2 ⋅ K/W under
the irradiation of XeCl laser at 1.6 J/ cm 2
fluence and 20ns FWHM.
Relationship between melted depth and time
is shown in Fig. 5 by the plot of Dmelted vs.
time. Read from this figure, the melted depth is
443nm and the melting duration is 85ns.
According to the record in Ref. [1], the molten
silicon layer can be about 280~300nm deep and
the melting duration is about 220ns. There are
significant deviations between the simulated
results and the reported data.
Fig. 5 Relationship between melted depth and
time(XeCl laser at 1.6 J/ cm 2 fluence and
20ns FWHM)
As the XeCl laser shines directly on the solid
Si substrate, the theoretical value of reflectivity
would be 0.5638. As a numerical experiment, if
the reflectivity is taken to be 0.5638 before
melting and 0.6868 after melting, the resulting
melted depth would be in the range of 289.08 nm
to 303.76 nm for thermal contact resistance
varying from 0 to 10−3 m 2 ⋅ K/W , as listed in
Table 3. However, the melting duration obtained
by numarical simulation is about 64 ns for all
cases.
Rc ( m 2 ⋅ K/W) Melted depth(nm)
0 297.48
10 −9 303.76
10 −8 296.36
10 −7 291.2
10 −6 289.08
10 −5 297.45
10 −4 283.28
10 −3 300.28
Table 3. Melted depth when the reflectivity is
taken to be 0.5638 before melting and
0.6868 after melting
5. Conclusions
In this study a model cast in COMSOL
multiphysics has been developed for the analysis
of heat transfer and phase change during laser-
assisted direct imprinting processes. The features
of this model include the employment of
temperature-dependent thermal properties, the
use of equivalent specific heat for the treatment
of latent heat of fusion, automatically switching
the thermal contact resistance off once the near
surface of the substrate is melted and keeping it
zero thereafter, and prompt adjustments to
reflectivity and absorption coefficient depending
upon the local phase within the substrate.
Some conclusions may be drawn from the
simulated results:
1. Because of the high temperature gradients
in domains, the consideration of temperature-
dependent thermal properties is necessary.
Thermal conductivity of silicon changes abruptly
during phase transition, thus the distribution of
thermal conductivity in the silicon substrate may
be discontinuous.
2. The reflectivity of melted silicon could be
estimated from the available experimental data.
Under the irradiation of KrF (249nm) excimer
laser, the estimated reflectivity of liquid silicon
is about 1.0 to 1.2 times the reflectivity of solid
silicon in the range of fluence from 0.9 to 1.8
J/ cm2 .
 Excerpt from the Proceedings of the COMSOL Users Conference 2007 Taipei

3. Thermal contact resistance does affect the standard deviation of the Gaussian
thermal response of a LADI process. However
σ
function, FWHM/ 2 2 ln 2
the influence is not very significant. This is Subscripts
because thermal contact resistance will become 0 air
zero after the substrate has been melted, ∞ surroundings
therefore the time duration for which the thermal q quartz mold
contact resistance has its effect on is relatively s substrate
short as compared to the whole heating duration.
4. Applying this model to analyze a LADI
process, there are considerable deviations
7. References
1. S. Y. Chou, C. Keimel and J. Gu, Ultrafast
between the simulated results and the
and direct imprint of nanostructures in silicon,
experimental results. Further investigation is
Nature, Vol. 417, pp 835-837, 2002.
necessary.
2. R. F. Wood and G. E. Giles, Macroscopic
theory of pulsed-laser annealing. I. Thermal
6. Nomenclature
c transport and melting, Phys. Rev. B 23,
specific heat capacity
2923 – 2942, 1981.
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El fluence of pulse laser R. T. Young, Excimer laser annealing of ion-
pulse duration imprinted silicon, J. Appl. Phys. vol. 55,
FWHM pp.1125-1130, 1984.
(Full Width at Half Magnitude)
4. J. Narayan, C. W. White, M. J. Aziz, B.
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hL latent heat of melting Crystalline Silicon Layers, J. Appl. Phys. vol.
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n real part of the refractive index Mashburn, and R. F. Wood, 1986, Time-
overall reflectivity, resolved reflectivity measurements on silicon
R ( R1 + R2 − 2 R1 R2 )(1 − R1 R2 ) and germanium using a pulsed excimer KrF
Rc thermal contact resistance laser heating beam, Physical Review B Vol.
34(4), pp.2407-2415, 1986.
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Chuang, Y. C. Lee, C. P. Liu and H. J. Hsu,
( n0 − n q ) 2 /( n0 + n q ) 2 An analytical modeling of heat transfer for
reflectivity at the mold-substrate laser-assisted nanoimprinting processes,
R2 interface, Comput. Mech 37, pp. 173-181, 2006.
[( n q − n s ) 2 + κ s2 ] /[( n q + n s ) 2 + κ s2 ] 7. Fei-Bin Hsiao, Di-Bao Wang and Chun-Ping
t time Jen, Numerical Investigation of Thermal
the time with maximum power Contact Resistance between the Mold and
tm density, 3 σ Substrate on Laser-Assisted Imprinting
Fabrication, Numerical Heat Transfer, Part A,
T temperature
49：pp.669-682, 2006.
Tm melting temperature 8. 王儀嵐，"雷射輔助壓印製程的相變化與熱
x spatial coordinate 傳分析"，碩士論文，高雄應用科技大學，
α absorption coefficient, 4πκ s 2007
λ 9. Edward D. Palik, "Handbook of Optical
δ Dirac delta function Constants of Solids", 1985.
κ imaginary part of the refractive
index
λ wavelength of the laser
ρ density