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Surface diffusion dewetting of thin solid films: Numerical method and application to Si/ SiO2
J. Eymery
Équipe mixte CEA-CNRS-UJF, Nanophysique et Semiconducteurs, CEA/DRFMC/SP2M, 17, rue des Martyrs,
38054 Grenoble cedex 9, France
共Received 18 October 2005; revised manuscript received 30 January 2006; published 27 March 2006兲
A method has been developed to calculate and use a surface chemical potential which is valid in the large
curvature regime for any surface energy function. It is applied to the solid-phase dewetting of a finite film with
an initial rectangular profile and considers the surface diffusion mechanism. For an isotropic surface energy,
the film aspect ratio and the adhesion energy between the film and the substrate are shown to be the main
parameters that quantify the retraction, the breaking time, and the number of agglomerates. Moreover, it is
found that mild surface energy anisotropy with an energy minimum in the horizontal plane postpones the mass
detachment. Simple models of the ␥-plots for the surface energy illustrate the influence of cusp points on the
retraction profiles. Finally, the smooth and facetted experimental surfaces, that are observed in the Si/ SiO2
system after 900 ° C annealing under H2, are explained by a quite small anisotropy of the ␥-plot.
Jជ = −冉 冊
D s ជ
k BT
· ⵜ S , 共1兲
i = 0 + lim
␦i→0
冉 ␦Gi共␦i兲
␦Vi共␦i兲
冊, 共4兲
再冉 冊冎
b1,i + b2,i
冊冉
ture areas兲.
The infinitesimal increment of matter ␦N is expressed by ␥i−1 ␥i b2,i␥i⬘ b1,i␥i−1
⬘
⫻ h0,i + + − . 共5兲
the matter conservation law ᐉi−1 ᐉi ᐉi ᐉi−1
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再 冎
and 0.5%, respectively. The temporal convergence was ob-
2 ␥0 b␥⬘ tained by decreasing the time step dt until the breakup time tc
0 = 0 + ⫻ h0,0 − 0 − 共␥sub − ␥sub/film兲 共6兲 differed by less than 0.2% using dt and dt / 2 time steps.
b ᐉ0 ᐉ0
The code has been checked with three time-dependent
Furthermore, this procedure facilitates simulation of film problems described in the literature. First, an initial rectan-
motion with ␥sub − ␥sub/film = ± ␥0 corresponding to null or gular profile in free air converges at large times for any
180° contact angles. This point is difficult to implement with ␥-plot 共isotropic or not兲 to the thermodynamic equilibrium
other numerical methods when the contact angle is directly shape given by the Wulff’s construction where 兰s␥dS is
imposed as a boundary condition. minimum.21 Second, an initially sinusoidal profile, with
共ii兲 The flux of matter given by Eq. 共1兲 is simply calcu- small amplitude compared to its period, conserves its sinu-
lated by a finite-difference method along a segment between soidal shape and decreases its amplitude exponentially with
two consecutive points. For a 1D surface, the matter incre- time in agreement with the analytical solution z共x , t兲
ment ␦Ni attributed to the point M i 共i ⫽ 0 and i ⫽ n兲 is the = A exp关−B共2 / 兲4t兴sin共2x / 兲 关where A and are constant
algebraic sum of the fluxes along the two segments ending with A Ⰶ , and B is given by Eq. 共3兲兴 discussed by
on M i multiplied by the time step dt. The triangle Mullins,14 Lançon,23 and Cahn.24 Third, the retraction of an
共M i−1 , M i , M i+1兲 will then grow or shrink depending on the isotropic semi-infinite film step on a substrate is reproduced
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TABLE I. zmin and xzmin 共see Fig. 1兲 carried out from the aniso-
tropic cases of Fig. 10, for different 0 compared to the isotropic
case. When the surface energy of the 共0 , x , y兲 plane is a minimum
共0 = / 8兲, the hollow is shallower, and inversely for 0 = 0. When
0 = / 16, the plane disoriented by − / 16 from 共0 , x , y兲 is a mini-
mum of energy and the peak tends to develop this plane, so the
valley moves away from the first peak compared to the isotropic
case, and inversely for 0 = 3 / 16.
zmin xzmin
FIG. 12. 共Color online兲 Image: 1 m ⫻ 1 m AFM image 共tap-
0 = 0 ⬍ ⬇ ping mode兲 of the Si on SiO2 retraction after a 2 min annealing at
0 = / 16 ⬇ ⬎ 900 ° C 共the initial film thickness is 13.0 nm兲. The peak is facetted
0 = / 8 ⬎ ⬇ and reaches 52 nm high. No dip appears behind the 共113兲 plane.
0 = 3 / 16 ⬇ ⬍ Curve: Profile along 共0 , x兲. It is similar to the retraction simulations
with an anisotropic surface energy model.
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冉 冊
the 关0.94, 1.03兴 range. This is in agreement with the experi-
p l sin共兲 q l sin共兲
= cos共兲 − and = . 共8兲 mental profile given in Fig. 12. The dense planes observed in
a a tan共12兲 b b sin共12兲 the simulation depend on the surface energy ratio and can be
The energy of the P plane of length l is given by directly compared to the Wulff’s construction. From the
usual Wulff’s construction, it can be shown that the four
␥共兲l = ␥ P1 p + ␥ P2q. 共9兲 dense plane families are present in the equilibrium shape for
It gives the expression of the surface energy per unit length ␥c1 ⬍ ␥113 ⬍ ␥c2 with
of a plane with disorientation 苸 关0 , 12兴 ␥c1 = 3/冑11 ⬇ 0.9045, 共12兲
␥共兲 = ␥ P1 冉 cos共兲 −
sin共兲
tan共12兲
冊
+ ␥ P2
sin共兲
sin共12兲
. 共10兲
冉
cos
1
+ arccos共冑2/3兲 − arccos共冑2/11兲 冊
For that particular ␥-plot, only dense plane orientations 4 2
冉 冊
␥c2 = ⬇ 1.125.
appear on the Wulff’s construction. It can be demonstrated 1 冑
cos − arccos共 2/3兲
that this type of ␥-plot is formed of portions of circles going 4 2
through the origin. To the first order, this ␥-plot is equivalent
共13兲
to the one generally developed for a vicinal surface with a
step-free energy  given by 共where h is the step height兲29 Below ␥c1, the planes 兵001其 are unstable and above ␥c2 the
 ␥ P2 ␥ P1 planes 兵113其 do not appear in the Wulff’s construction any-
= − . 共11兲 more. In Fig. 14, all four dense planes are developed for ␥113
h sin共12兲 tan共12兲
in the 关0.94, 1.03兴 range, in agreement with the stability do-
The ␥-plot used to simulate the experimental dewetting of mains. The relative facet extensions directly depend on the
共001兲 silicon on SiO2 共see the inset of Fig. 14兲 is defined by ratio of the surface energy of the dense planes. For example,
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as ␥113 increases, the 共001兲 plane becomes larger in the occur. During the diffusion motion of a finite film, two re-
Wulff’s construction and appears larger on the top of the gimes can be clearly identified. At the beginning, the behav-
peak during dewetting. Moreover, the dip can be drastically ior of the film profile is similar to the semi-infinite geometry.
favored or almost vanished depending on ␥113. As ␥113 in- Then, edge-coupling effects due to surface diffusion may be
creases, the dip is shallower and larger, and the pinch off is observed if the film is short enough. The aspect ratio as well
postponed. A small variation of ␥113 yields large modification as the energy of the contact line largely influences the break-
of the breakup time and phenomenology. For ␥113 = 0.94, the ing time and the phenomenology. An empirical law is pro-
breakup time is comparable to the isotropic case. For posed, predicting the fragmentation of the film defined only
␥113 艌 0.97, it is more than fifteen times larger than the iso- by these two parameters.
tropic case whereas for ␥113 = 0.905, it is more than sixty Experimental measurements have shown that annealing of
times lower. In the range ␥113 苸 关␥c1 , 1.00兴, the breakup time different thin silicon patterns on amorphous silicon oxide
varies over three orders of magnitude. Even for ␥113 ⬎ ␥c2, a within similar experimental conditions 共thermal annealing
very shallow dip is still observed but the 共111兲 plane is de- from 900 ° C to 950 ° C under H2 atmosphere兲 can lead to a
veloped on the right of the peak instead of 共113兲. For smooth or facetted dewetting profile. The experimental fac-
␥113 艌 1.10, ␣ = 90°, and F = 500, the film does not breakup etted profiles have been fitted qualitatively by a ␥-plot with
and rearranges itself in a single agglomerate. For ␥113 ⬍ ␥c1, cusp points and small anisotropy. The simulated and experi-
the peak does not exhibit a 共001兲 plane anymore which is in mental profiles of Figs. 14 and 12 are in qualitative good
agreement with stability domains, and the rest of the film agreement for a ␥-plot following Eq. 共10兲 and plane energies
set around 1.00. For a slightly modified ␥-plot, the phenom-
develops microfacets with 共1̄1̄3兲 and 共113兲 planes. For dif-
enology and the breaking time can be very different. For
ferent ␣, the phenomenology and the breaking time are also
example, changing the surface energy at a cusp point by less
drastically modified by a very small variation of ␥113. In
than 7% can introduce a variation of the breaking time over
consequence, an accurate description of the ␥-plot features is
three orders of magnitude. So, to be able to use this to pre-
needed to predict the facet morphologies. This study also
dict film behavior, a very high accuracy of the ␥-plot de-
indicates that surface tension anisotropy can favor the film
scription is needed. Nevertheless, for a mildly anisotropic
stability from the pinch off point of view. However, the film
␥-plot with ␥001 being a minimum, the pinch off is post-
retraction x0 is comparable 共within 20%兲 to the isotropic case
poned. It can even be annihilated with ␥-plots having cusp
共see Figs. 10 and 14兲. Indeed, the value and speed of retrac-
points. Therefore, from the mass detachment point of view,
tion seem to be mainly governed by the contact line equilib-
the stability domain can be extended thanks to surface en-
rium, and not by anisotropy effects.
ergy anisotropy. At any given adhesion energy, our simula-
tions show that the retraction quantity x0 slightly depends on
V. DISCUSSION AND CONCLUSION the ␥-plot. The contact line retraction speed is not affected
by the surface energy anisotropy which mainly affects the
A numerical method for the calculation of surface chemi-
pinch off phenomenology. It appears from this study that the
cal potential has been developed that goes beyond the usual
best way to decrease the retraction speed of the film is to
surface potential developed by Herring22 which is limited to
increase the adhesion energy. The anisotropy of surface dif-
small curvature and cannot be applied to a severe anisotropy
fusion coefficients has not been discussed in this paper, and it
where faceting is expected. This method accommodates ev-
could be interesting in future work to study the interplay
ery anisotropic feature of the surface energy 共or diffusion兲
between the faceting imposed by the surface energy and the
and can be applied to a large number of physical problems
surface diffusion coefficient anisotropies. Elastic energy
such as hole opening, and thermal grooving as well as to
could also be taken into account to simulate strained films
nonuniform substrate interfaces 共nonplanar geometry and/or
that are currently used in microelectronics. Finally, 3D simu-
nonconstant interface energy兲. The surface energy is de-
lations could be performed with the same numerical method
scribed by a so called ␥-plot where cusp points may occur. In
共including anisotropy and/or strain effects兲 to get better un-
this paper, the retraction of finite thin films defined by their
derstanding of the highly symmetric experimental patterns
aspect ratio has been analyzed considering only the surface
obtained during solid-state thin film retraction.6
diffusion mechanism. The contact line between the film and
the substrate is defined by its energy, and the contact angle ACKNOWLEDGMENTS
results from local equilibrium conditions. This is a natural
result from the simulation and no numerical artifact constrain We wish to acknowledge O. Cueto, D. Jamet, and B.
the simulation in any way. For every ␥-plot, the film is sta- Mathieu for advice in numerical computation. We are grate-
bilized in its equilibrium shape given by the Wulff’s con- ful to F. Lançon and J. Villain for many useful scientific
struction or by the analytic procedure given by Khare.31 discussions. We thank Y. Campidelli and Y. Bogumilowicz
The surface diffusion mechanism produces a minimum of for technical assistance with the AFM instrumentation. Our
the surface thickness below its initial value. As this mini- gratitude is also extended to J-M. Hartmann for the time
mum deepens, the film may break up and mass shedding may spent supporting the annealing experiments.
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83, 3162 共2003兲. Surfaces, edited by M. G. Lagally 共Plenum Press, New York,
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