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MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

ANALYSIS OF THERMAL DIFFUSION IN MULTI-LAYER THIN FILMS

BY A RESPONSE FUNCTION METHOD

T. Baba and N. Taketoshi

National Research Laboratory of Metrology

Tsukuba, Ibaraki, 305-8563, Japan

When the picosecond thermoreflectance technique is applied to multi-layer thin films, the
surface temperature response is distorted after heat diffuses across the interface between the
layers because of the difference of thermal effusivity. An algorithm is presented to derive the
thermal diffusivity and the effusivity ratios of the successive layers from the surface temper-
ature response based on the response function method. This algorithm is applied to analyze
experimental data of several kinds of thin films such as aluminum thin films on silicon and
glass substrate measured with the picosecond thermoreflectance system developed in the Na-
tional Research Laboratory of Metrology.

1. INTRODUCTION
Thermophysical properties of thin films are the essential information in order to carry out
thermal design of large-scale integrated circuits like CPU and high-density storage media like
MO disk or DVD. It is difficult to measure thermophysical properties of submicrometer thin
film free from the effect of substrate with using conventional thermophysical property mea-
surement techniques. This problem can be solved by the picosecond thermoreflectance me-
thod which can measure thermal diffusivity of the submicrometer thin films in several hun-
dreds picosecond before the heat absorbed at the film surface diffuses into the substrate [1].
The National Research Laboratory of Metrology (NRLM), Japan, has been developing a pi-
cosecond thermoreflectance technique in order to measure thermophysical properties of sub-
micrometer thin films [2,3]. First, the surface is irradiated by a laser pulse of a few picose-
cond duration and the temperature of the surface layer as thin as 10 nm is heated by the order
of 10 K. Then, the surface temperature decreases over the time scale from 10 ps to several
hundreds ps because of thermal diffusion towards inside of the film. The cooling rate of the
surface temperature depends on the thermal diffusivity of the film and the initial temperature
distribution in the surface layer. Ultra fast change of the surface temperature is observed by
the change in the reflection intensity of the probe picosecond pulse arriving at the surface
with controlled delay time from the heating picosecond pulse.
This technique is applicable to metal films because most metals absorb visible to near infrared
light in a layer of the order of 10 nm and the reflectivity of metal surface changes dependent
on the surface temperature. The initial temperature distribution is determined by the absorp-
tion coefficient of the film surface to the picosecond laser pulse measured with ellipsometry.
The details of the picosecond thermoreflectance measurement system developed in NRLM

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MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

are described in our previous reports [2,3].

The picosecond thermoreflectance technique can be applied to measure thermophysical prop-
erties of film/substrate systems [3]. Surface temperature response of a film/substrate system is
distorted when heat diffuses across the film/substrate interface because of thermal effusivity
difference as shown in Fig.1. When the film is thick enough to be considered as semi-infinite
and heat does not reach the substrate within the observing time of several hundreds of pico-
seconds, the temperature of the film surface changes following the dashed curve in Fig.1. If
the film and the substrate have the same thermal effusivity, the surface temperature change
also follows the dashed curve either.
When the thermal diffusivity of the substrate is negligibly small compared with the film, the
film/ substrate interface is considered as the adiabatic boundary condition and the film surface
temperature changes along the dotted curve in Fig.1.
The ratio of the substrate thermal effusivity, bs , to the film thermal effusivity, b f , is defined
as β = bs b f . When 0 < β < 1 , the film surface temperature changes along the solid curve
in Fig.1. The deviation from the dashed curve starts when heat reaches the film/substrate in-
terface and is blocked by smaller thermal effusivity of the substrate. Thus, the shape of the
solid curve is determined by the thermal diffusion time τ f from the film surface to the
film/substrate interface and the thermal effusivity ratio β .
Aluminum thin films of different thickness of 50 nm, 100 nm, and 500 nm synthesized on
glass substrate and silicon substrate have been systematically measured with the picosecond
thermoreflectance method in NRLM [3]. In our previous analysis, we have derived an analyt-
ical solution for thermal diffusion in the film/substrate two layer model under the approxima-
tion when the thermal diffusion time
across the film τ f is negligibly small
compared with the characteristic thermal
diffusion time into the substrate τ f [3]. 1
Temperature rise (normalized)

Thermal effusivity
This analysis has been successfully applied bf > bs
to the aluminum films on glass substrate
since thermal effusivity of the glass is
much smaller than the aluminum film. Adiabatic bs = 0
Based on this analysis, the thermal effu-
sivity ratio of the glass substrate to the
aluminum film and the ratio of the film
thickness to the penetration depth of the
heating laser beam were calculated. Semi-infinite bf = bs
0
However, the assumption of this analysis
is not valid for the aluminum thin films on
the silicon substrate since the thermal ef-
0 50 100 150
fusivity of silicon is larger than one tenth
Time (arbitrary)
of the thermal effusivity of aluminum.
Here, we present the analytical solution to Figure 1. Temperature history curves of the
express one-dimensional thermal diffusion thin film surface on a substrate af-
in multi-layer thin films after a pulse heat- ter picosecond pulse heating de-
ing at the film surface. This analysis is ap- pendent on the substrate thermal
effusivity compared with the film.

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MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

plied to the temperature history curves of the aluminum films on the silicon substrate ob-
served by the picosecond thermoreflectance.

2. RESPONSE FUNCTION METHOD

The temperature response of the semi-infinite solid material after an impulse heating of unit
intensity to the solid surface at time, t ′ , is represented by the following Green’s function [4].
1 ⎛ x2 ⎞
G ( x, t | 0, t ' ) = exp⎜⎜ − ⎟⎟ (1),
b π (t − t ′) ⎝ 4α (t − t ′) ⎠
where x is the distance of the observing position from the solid surface, t is the time of
observation. The thermophysical properties of the solid material are represented as α is the
thermal diffusivity, b the thermal effusivity defined as b = λcρ = cρ α , λ is the ther-
mal conductivity, c is the specific heat capacity, and ρ is the density.
When a front surface of a parallel plate is pulse-wise heated, transient temperature distribu-
tion across the plate is given by the following Green’s function.
1 ⎡ ∞
nπx ⎡ t − t ′ ⎤⎤
G ( x, t | 0, t ' ) = ⎢
cρd ⎣
1 + 2 ∑
n =1
cos
d
・exp ⎢− n 2π 2
⎣ τ ⎥⎦ ⎥⎦
(2),

where the definition of x, t , t ′, c, ρ , α are same as the equation (1), d is the thickness of
the plate, τ is the characteristic time of thermal diffusion across the plate defined as
τ = d2 α .
The temperature response of the point x at the time t by the arbitrary function f (t ) is ex-
pressed by the following convolution integral.
t
T ( x, t ) = ∫ G ( x, t | 0, t ′) f (t ′)dt ′ (3).
−∞

When the steady state temperature of a parallel plate is constant, T0 , the temperature re-
sponse at the both faces at time t are represented by the following equations under incoming
heat flux density q f (t ) to the front face and q r (t ) to the rear face [5].
t
T (t ) = T0 + ∫ R (t − t ′)q (t ′)dt ′ (4),
0

⎡T ⎤ ⎡T (t )⎤ ⎡R ff (t ) R fr (t )⎤ ⎡q (t )⎤
T0 = ⎢ 0 ⎥, T (t ) = ⎢ f ⎥, R (t ) = ⎢ ⎥ , q (t ) = ⎢ f ⎥ ,
⎣T0 ⎦ ⎣ Tr (t ) ⎦ ⎣ R fr (t ) R rr (t ) ⎦ ⎣ q r (t ) ⎦
where R (t ) is the impulse response function matrix of a parallel plate adiabatic to the envi-
ronment and the element R ij (t ) is the temperature rise at the face “ i ” at time “ t ” after the
unit impulse heating to the face “ j ” at time “0”. The subscript i or j represents either
front face “ f " or rear face “ r ”.
T f (t ) = T0 + ∫ (R ff (t − t ′)q f (t ′) + R fr (t − t ′)q f (t ′) ) dt ′
t
(5),
0

Tr (t ) = T0 + ∫ (R rf (t − t ′)q f (t ′) + R rr (t − t ′)q r (t ′) ) dt ′
t
(6).
0

The initial temperature T0 can be assumed to zero for simplicity without losing generality.
These equations are simplified in the Laplace transformed space. The Laplace transform of
f (t ) is expressed as f (ξ ) defined by the following equation with Laplace parameter ξ .
~

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MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

∫
~
f (ξ ) = exp( −ξt ) f (t )dt
0
(7).
Laplace transform of the
equation(4) is,
~ ~
T (ξ ) = R(ξ ) ⋅ q~ (ξ )
(8),
~ ~
~ ⎡ R (ξ ) R fr (ξ )⎤
R (ξ ) = ⎢ ~ ff ~ ⎥
⎢⎣ R rf (ξ ) R rr (ξ )⎥⎦
(9),
Figure 2. Four elements of response function matrix of ~
a parallel plate. where R (ξ ) is called as
the transfer matrix.

2.1 Uniform single layer

Since Green’s function of a uniform single layer is expressed by the equation (2), the ele-
ments of the impulse response matrix are expressed as follows,
1 ⎡ ∞
⎛ t ⎞⎤
R ff (t ) = R rr (t ) = ⎢
cρd ⎣
1 + 2 ∑
n =1
exp⎜ − n 2π 2 ⎟⎥
⎝ τ ⎠⎦
(10),

1 ⎡ ∞
⎛ t ⎞⎤
R fr (t ) = R rf (t ) = ⎢
cρd ⎣
1 + 2 ∑
n =1
(−1) n exp⎜ − n 2π 2 ⎟⎥
⎝ τ ⎠⎦
(11).

Laplace transformation of the equation (10) and (11) are

1 ⎡1 ⎤
( )
∞
~ ~ 1 1
R ff (ξ ) = R rr (ξ ) = ⎢ + 2∑ ⎥= coth ξτ (12),
cρd ⎣ξ n =1 ξ + n π / τ ⎦
2 2
b ξ
1 ⎡1 (−1) n ⎤
( )
∞
~ ~ 1
R fr (ξ ) = R rf (ξ ) = ⎢
cρd ⎣ ξ
+ 2 ∑ ⎥=
n =1 ξ + n π / τ ⎦
2 2
b ξ
cosech ξτ (13).

2.2 Four-pole matrix

Explicit expression of the equation (8) is
~ ~ ~
⎡T f (ξ )⎤ ⎡R ff (ξ ) R fr (ξ )⎤ ⎡q~ f (ξ )⎤
⎢~ ⎥ = ⎢~ ~ ⎥⎢ ~ ⎥ (14).
⎣ Tr (ξ ) ⎦ ⎣⎢ R rf (ξ ) R rr (ξ ) ⎦⎥ ⎣ q r (ξ ) ⎦
This equation is transformed to a four-pole matrix expression which relates the pair of the
heat flux density at the front face to the same pair at the rear surface as follows.
~
⎡− q~r (ξ )⎤ ~ ⎡q f (ξ )⎤
⎢ T~ (ξ ) ⎥ = S (ξ ) ⎢T~ (ξ ) ⎥ (15),
⎣ r ⎦ ⎣ f ⎦
⎡ cosh τξ ( ) ( )
− b ξ ⋅ sinh τξ ⎤
S(ξ ) = ⎢⎢ 1 ⎥
~
− ( )
⋅ sinh τξ cosh τξ( ) ⎥
(16),
⎢⎣ b ξ ⎥⎦
where the four-pole matrix S(ξ ) is the function of thermal diffusivity b and the thermal
~

288
MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

diffusion time τ = d 2 α [5]. It should be noted that q~ f (ξ ) and − q~r (ξ ) are the vectors of
the same direction as defined in Fig.2.

2.3 Film/substrate two layer model

A thin film synthesized on a semi-infinite substrate is illustrated in Fig.3. The parameters to
specify this film/substrate two-layer system are thickness of the film d f , thermal diffusivity
of the film α f , thermal effusivity of the film b f , thermal diffusivity of the substrate α s ,
and he thermal effusivity of the substrate bs [3]. Temperature response of the film substrate
interface, T s (t ) , is calculated as convolution integral of the heat flux density diffusing into
the substrate, q s (t ) , and the Green’s function of the semi-infinite substrate as shown in the
equations (1) and (3).
t 1
Ts (t ,0) = ∫ q s (t ′)dt ′ (17).
0
bs π (t − t ′)
Laplace transform of this equation is
~ 1
Ts (ξ ) = ⋅ q~s (ξ ) (18).
bs ξ
The pair of q s (t ) and T s (t ) is related to the pair of the heat flux density onto the film
surface, q f (t ) , and the temperature at the film surface, T f (t ) , via the four-pole matrix of the
~
film, S f (ξ ) , as the equation (15).
⎡q~s (ξ )⎤ ~ ⎡q~ f (ξ )⎤
⎢T~ (ξ ) ⎥ = S f (ξ ) ⋅ ⎢T~ (ξ ) ⎥ (19).
⎣ s ⎦ ⎣ f ⎦
Substituting q f (t ) = δ (t ) , the delta function at time “0”, the simutaneous equations (18) and
(19) are solved and T f (t ) is expressed as follows.
~ 1 coth( ξ τ f ) + β
T f (ξ ) =
bs ξ coth( ξτ f ) + β −1
Film Substrate (20),
where the thermal diffusion
bf bs β = bs b f time across the film is defined
(τ s → ∞)
Pulse
τf as τ f = d f α f
2
Infinite and the
heating
thermal effusivity ratio of the
q~ f (ξ ) = 1
q~s (ξ ) substrate to the film is defined
as β = bs bf [3].
S f (ξ ) T s (ξ ) = ⋅ q~s (ξ )
~ ~ 1
bs ξ The equation (20) is expressed
as the function of exp(− 2 ξτ f )
T f (ξ ) T s (ξ )
~ ~
by substituting
1 + exp(− 2x )
coth( x ) = as,
Figure 3. Temperature response, heat flux 1 − exp(− 2x)
density, and thermophysical proper-
ties in a film/substrate system.

289
MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

T f (ξ ) =
~ 1 (
1 + γ exp − 2 ξτ f ) = 1 ⎛1 + 2 γ
∞
( )⎞
ξ 1 − γ exp (− 2 ) b ξ ⎜⎝ ∑ exp − 2n ξτ f ⎟
n
(21),
bf ξτ f f n =1 ⎠
where γ = (b f − bs ) (b f + bs ) = (1 − β ) (1 + β ) .
The surface temperature is obtained by Inverse Laplace transformation of the equation (21).
1 ⎛⎜ ∞
⎛ 2 τ f ⎞⎞
T f (t ) = 1 + 2 ∑ γ n
exp⎜⎜ − n ⎟⎟ ⎟ (22).
b f πt ⎜⎝ n =1 ⎝ t ⎠⎠
⎟
This equation corresponds to the temperature response induced by infinite series of virtual
heat sources of intensity γ n located periodically with the separation of twice of the film
thickness as shown in Fig.4. If the temperature response is analyzed from the impulse heating
time, the temperature changes following the equation T (t ) = 1 /(b f πt ) （corresponding to
the term of n = 0 in the equation (22)） free from the effect of substrate in the beginning.
Later, the contribution of the higher order terms ( n ≥1) in the equation (22) are superimposed.
Since the contribution of n = 1 term is much larger than the contribution of the n ≥ 2 term,
the equation (22) is approximated by the following equation.
1 2γ ⎛ τf ⎞
T f (t ) = + exp⎜⎜ − ⎟⎟ (23).
b f πt b f πt ⎝ t ⎠
This approximation corresponds to considering only the nearest couple of virtual heat sources
in addition to the original impulse heat source in Fig.4.

3. ANALYSIS OF EXPERIMENTAL RESULTS

Figure 5 shows the surface temperature change of the aluminum thin films synthesized on the
silicon substrate measured with the picosecond thermoreflectance measurement system de-
veloped by NRLM. In the case of the 500 nm thick film, the surface temperature changes fol-
lowing the first term of the equation (23) all over the observation period as shown in broken
2d f curve in Fig.5 since heat does not
(Substrate) reach the film/substrate interface
within 150 ps.
In the case of the aluminum thin
films of 50 nm thick and 100 nm
thick, heat diffuses to the
Film
film/substrate interface and temper-
ature decrease is suppressed because
of lower thermal effusivity of the
silicon substrate. Thus, temperature
change is deviated from the first
term of the equation (23) by the
γ 2
γ 1 γ γ 2 contribution of the higher terms.
These deviations are plotted in the
b − b lower part of Fig.5. Considering the
Virtual Heat
γ =
f s
dominant n = 1 terms only, the
Sources b f + bs
deviation curves are least square fit-
Figure 4. Mirror images of impulse heating as virtual
heat sources to temperature rise in the
ted by the second term in the equa-

290
 MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

tion (23) with adjusting the parameters τ f and γ . Then, the thermal diffusivity of the film,
α f , and the thermal effusivity of the substrate, bs , are determined if the film thickness, d f ,
and the thermal effusivity of the film, b f , are known. Table 1 shows the thermophysical
properties of the aluminum thin films on the silicon substrate and the glass substrate
calculated from this procedure compared with the literature values for bulk materials [6, 7].

4. CONCLUSION
A universal algorithm is introduced in order to represent thermal diffusion penetrating mul-
ti-layer thin films. The temperature response expressed by the Green’s function in a
semi-infinite uniform media is distorted by a film/film interface with thermal effusivity mis-
match. The distortion of the temperature response is represented by virtual heat sources (or
heat sinks when thermal effusivity of the second layer is larger than the first layer) whose
amplitude is proportional to the discrepancy
of the thermal effusivity between the first
layer and the second layer. Temperature re-
1 sponse induced by infinite series of the virtual
Temperature rise /Max.

heat sources is represented by infinite summa-

50nm tion of the Green’s functions. Contribution of
the first and the second nearest terms are ob-
100nm servable from the surface temperature re-
sponse curve deviating from the ideal temper-
500nm ature response of the semi-infinite uniform
media since their contribution is much larger
0 than the higher order terms.
Both thermal diffusion time across the first
layer and the thermal effusivity ratio of the
0 50 100 150
second layer to the first layer are determined
Time /ps
as fitting parameters to the observed tempera-
ture response curves of Aluminum thin films
Bias from 500nmt Al-film
of different thickness synthesized on glass
Temperature deviation

0.5
substrates and silicon substrates. The thermal
effusivity of the second layer obtained by this
50nm method is consistent with that obtained by the
response function method presented in our
previous paper [3].
100nm
Thus, surface temperature response of mul-
ti-layer thin films after picosecond pulse
0.0 heating are systematically analyzed by the
virtual heat source method and the response
0 50 100 150 function method, independently and consis-
Time /ps tently. These analysis are generally applied to
Figure 5. Surface temperature response analysis of thermal diffusion penetrating
of aluminum thin films on sili- across media of multi-layer structure over the
con substrate (upper) and their time scale ranging from picoseconds to longer
temperature deviation from 500 than seconds including the laser flash method.
nm thick aluminum film (lower).

291
 MICROSCALE FEAT TRANSFER Edited by J. B. Saulnier, D. Lemonnier, and J.-P. Bardon
EUROTHERM Seminar No. 57, 8-9-10 July 1998 (Poitiers, France).

Table 1 Thermophysical properties of films and substrates calculated from the picosecond ther-
moreflectance measurements based on the response function method. They are com-
pared with literature values

Aluminum Thermal Thermal

Thermal
film thick- diffusivity of diffusivity Thermal ef- Literature
Substrate diffusion
ness aluminum of bulk fusivity ratio value
time
(nominal) film aluminum
d f nm τ f ps αf m 2 s −1 αb m 2 s −1 β = bs b f β = bs b f

glass 100 144 6.9×10-5 9.98×10-5 0.033 0.049

50 55 4.5×10-5 0.153
silicon 9.98×10-5 0.65
100 128 7.8×10-5 0.096

NOMENCLATURE ρ : Density
t, t ′ : Time τ = d α : Characteristic time
2

ξ : Laplace parameter R (t ) : Impulse response function matrix

x : Position ~
R (ξ ) : Transfer function matrix
n : Integer
S (ξ )
~
: Four-pole matrix
T (t ) : Temperature
G ( x, t | x ′, t ′) : Green's function
T (ξ ) : Laplace transform of T (t )
~
β = bs b f : Thermal effusivity ratio
q (t ) : Heat flux density
γ = (b f − bs ) (b f + bs ) = (1− β ) (1+ β )
q (ξ )
~ : Laplace transform of q (t )
d : Thickness
α : Thermal diffusivity Subscripts
b : Thermal effusivity f : Film, film surface
c : Specific heat capacity s : Substrate, film/substrate boundary

References
[1] C.A.Paddock, G.L.Eesley: “Transient thermoreflectance from thin metal films,” Journal of
Applied Physics, 60 (1986) 285-290.
[2] N.Taketoshi, T.Baba, A.Ono: “Development of a thermal diffusivity measurement system
with a picosecond thermoreflectance technique”, High Temperatures - High Pressures, 29
(1996) 59-66.
[3] N.Taketoshi, T.Baba, A.Ono: “Picosecond thermoreflectance measurements of thermal
diffusion in film/substrate two-layer systems”, to be published in Proceedings of 24th In-
ternational Thermal Conductivity Conference, (Pittsburgh, 1997).
[4] H.S.Carslaw, J.C.Jaeger, “Conduction of Heat in Solids (2nd ed.)” Oxford (1959) p.361.
[5] T.Baba: “Introduction of a Response Function Method for Analysis of Functionally Gra-
dient Materials”, Japan Journal of Thermophysical Properties 7 (1993) 14-19.
[6] Y.S.Touloukian, R.W.Powell, C.Y.Ho, and P.G.Klemens, “Thermophysical Properties of
Matter 2: Thermal conductivity” (1978).
[7] K.Kobayashi (ed.): "Thermophysical Properties Handbook", Yokendo (1990).

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