Materials and Engineering B101 (2003) 181
/185

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Effect of Sb on Si/Si and Ge/Si growth process

A. Portavoce a,b, I. Berbezier a,*, A. Ronda a
a
CRMC2-CNRS, Case 913, Campus de Luminy, 13288 Marseilles Cedex 9, France
b
L2MP Faculté des Sciences de St Jérôme, Case 511, 13397 Marseilles Cedex, France

Received 6 November 2002; accepted 23 November 2002

Abstract

In this paper, we investigate the surfactant effect of Sb on the growth of Ge on Si(1 1 1) and on Si(1 0 0). We show that Sb has
mainly two effects: first it delays the 2D
/3D growth mode transition and consequently permits to produce thicker flat Ge layers;
second Sb promotes the layer by layer 2D nucleation growth mode. The latter effect can be used to considerably reduce the lateral
size of Ge islands at 550 8C on both Si(1 1 1) and Si(0 0 1). In order to understand the fundamental role of Sb on the growth
processes, we have determined the microstructure and the growth mode of Ge layers deposited on Si and on one monolayer Sb/Si
surfaces by atomic force microscopy and reflection high-energy electron diffraction (RHEED). We show that the growth mode
changes induced by Sb at 350 and 550 8C (thicker 2D wetting layer and smaller islands, respectively) are explained by the
conjugated effects of thermodynamics (decrease of the surface energy) and of kinetics (decrease the surface diffusion length) induced
by Sb. We finally suggest that partial desorption of Sb is responsible for the formation of islands at 550 8C.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Sb; Surfactant-mediated growth; Ge; Si(1 1 1); Molecular beam epitaxy

1. Introduction surfactant-mediated growth. We show that the different

The use of Sb as surfactant in order to modify the
growth of Ge on Si substrate (Stranski
/Krastanov
growth mode) has been shown to be very attractive for
different applications. Indeed first Sb allows the epitaxy
of highly concentrated Si1x Gex flat layers (by pre-
venting the growth of 3D Ge islands) [1
/9]. Second, Sb
surfactant-mediated growth also permits to self-organize
Ge dots [10] and to produce smaller Ge islands [11
/14].
Finally, Sb can also be used to perform relaxed Ge
layers with very low bulk defects density and flat surface
[15
/18].
In a previous study [19], we have shown that Sb
favours the growth of flat Ge layers at 350 8C, and of
very small strained Ge islands with high surface density
at 550 8C on Si(0 0 1). In order to understand these
results, we investigate in this paper the influence of
substrate orientation and growth temperature on Sb
* Corresponding author. Tel.: /33-660-362-813; fax: /33-491-418-
916.
E-mail address: berbezier@crmc2.univ-mrs.fr (I. Berbezier).
0921-5107/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-5107(02)00710-9
growth morphologies obtained at 350 and 550 8C can
be understood by considering the Sb partial desorption
during Ge/Sb/Si growth. Finally, we conclude that the
effect of Sb on the growth of Ge/Si is explained by a
decrease of both the surface energy and the surface
diffusion.
2. Experimental
All the layers were grown in a Riber MBE system with
a base pressure typically B/10 11 Torr. Floating zone
silicon was evaporated thermally from an electron beam
evaporator. Ge and Sb were evaporated from effusion
cells. Si wafers of nominal orientation (miscut B/0.28)
were ex situ cleaned and protected by an oxide layer as a
final step. Subsequent in situ cleaning consisting in
thermal desorption of the oxide layer at temperature
about 900 8C was performed. A 50 nm thick Si buffer
layer was systematically grown to achieve reproducible
surfaces, whose cleanliness is qualitatively checked by
the streak’s intensity of the (7 /7) reconstruction
observed by reflection high-energy electron diffraction
182 A. Portavoce et al. / Materials and Engineering B101 (2003) 181
/185
(RHEED). Si or Ge (7 monolayers (ML) thick film) was
deposited at a rate about 0.3 and 0.063 Å s 1,
respectively, directly on Si(1 1 1) or after the deposition
of 1 ML of Sb. The Sb flux was calibrated using the
surface reconstruction change from the Si(1 0 0)
/(2 /1)
pattern to the (1 /1) pattern at 1 ML Sb coverage [20].
The 2D (flat layer)
/3D (islands) growth mode transition
was determined by measuring, during the growth, the
evolution of the FWMH of the RHEED streaks. The
presence and the absence of RHEED oscillations were
attributed to the growth regimes of nucleation and of
step flow, respectively. Morphological characterization
of the surfaces was also performed after growth by
atomic force microscopy (AFM).
3. Results
The typical variations of the RHEED oscillations
versus the growth temperature (Tc) during the growth of
Si on Si(1 1 1) are presented in Fig. 1. Three main
growth regimes can be distinguished. (1) Kinetic rough-
ening at low temperatures that is evidenced by an
important damping of the RHEED oscillations (Fig.
1a, Tc /325 8C). The damping coefficient of the
oscillations is directly related to the evolution of the
surface roughness during growth. This roughness is
induced by the low surface diffusion of Si adatoms at
this temperature. (2) Step flow at high temperatures that
is revealed by the total absence of RHEED oscillations
(Fig. 1c, Tc /590 8C). At this temperature, the surface
diffusion of Si adatoms is larger than the terrace length
and all Si adatoms stick the step edges. Growth proceeds
by advancement of the step edges. (3) Layer by layer 2D
nucleation at intermediate temperatures that is evi-
denced by RHEED oscillations without any damping
(Fig. 1b, Tc /460 8C).
As a comparison, the RHEED oscillations were
recorded during the growth of Si on 1 ML of Sb
predeposited on Si(1 1 1) (system Sb/Si(1 1 1)). Only two
main regimes can be distinguished. (1) Kinetic rough-
Fig. 1. RHEED oscillations during the growth of Si on Si(1 1 1) at: (a)
Tc /325 8C, (b) Tc /460 8C, (c) Tc /590 8C and (d) on 1 ML Sb/
Si(1 1 1) at Tc /590 8C.
ening at low temperature (Tc /325 8C) revealed by
almost no oscillations (trace not presented here). We
deduce that Si adatoms have a lower diffusion length on
Sb/Si than on Si. (2) Layer by layer 2D nucleation at
high temperature (Tc /590 8C) revealed by RHEED
oscillations with low damping (Fig. 1d). At this tem-
perature, the growth of Si/Si(1 1 1) changes from step
flow without Sb to 2D nucleation with Sb.
We interpret the effect of Sb on the growth mode
changes by a decrease of the diffusion length of Si
adatoms in presence of Sb. We suggest that the exchange
of Si adatoms with the subsurface atoms could be a
relevant mechanism responsible of the reduced diffusion
length in the presence of Sb. The high rate of exchange
(which is also responsible for the large Sb dynamic
segregation) is explained by an activation barrier of
exchange between Si adatoms and Sb adatoms of the
same order than the diffusion barrier [14,21,22].
One can note that this mechanism does not require
the coefficient of diffusion of Si adatoms to decrease on
Sb/Si(1 1 1), but states that the time during which
adatoms can diffuse is shorter (leading to a lower
diffusion length) owing to the high exchange rate
between Si adatoms and Sb atoms.
Regarding the growth of Ge on Si, at Tc /350 8C,
because of the larger surface diffusion of Ge adatoms
than of Si adatoms, kinetic roughness is not observed
and the growth proceeds by nucleation of islands: it
starts by the nucleation of 2D islands during the growth
of the wetting layer and then nucleation of 3D islands
for the rest of the deposition. The thickness of the
wetting layer can be approximately estimated by count-
ing the number of oscillations. In the growth conditions
used here, this number varies from 3 for the growth of
Ge/Si to 6 for the growth of Ge/Sb/Si (Fig. 2a and c).
This proves that the thickness of the wetting layer is
increased by a factor of 2 in the presence of Sb. The
onset of 3D diffraction spots representative of 3D
islands on the RHEED pattern confirm the 2D
/3D
growth mode transition after 3 and 6 ML for the growth
of Ge/Si and Ge/Sb/Si, respectively. As an example, we
show the very different RHEED patterns recorded after
Fig. 2. RHEED oscillations during the growth of Ge on Si(1 1 1) at:
(a) Tc /350 8C, (b) Tc /550 8C and on 1 ML Sb/Si(1 1 1) at: (c) Tc /
350 8C and (d) Tc /550 8C.
 A. Portavoce et al. / Materials and Engineering B101 (2003) 181
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Fig. 3. RHEED patterns after the growth of 7 ML Ge deposited on Si(1 1 1) at: (a) 350 8C, (b) 550 8C and on 1 ML Sb/Si(1 1 1) at: (c) 350 8C and
(d) 550 8C.
7 ML of Ge without (Fig. 3a) and with Sb (Fig. 3c)
predeposited on Si. We see that while 3D diffraction
spots are clearly visible in the first case (we can also
notice the absence of the 5/5 reconstruction spots),
streaks representative of 2D layer are still present in the
second case (reconstruction is 1/1 for 1 ML Sb/Si).
Moreover, the AFM image of 7 ML of Ge deposited on
Si (Fig. 4a) exhibits small Ge islands and a root mean
square surface roughness RMS /18.3 Å. For the
deposition of the same amount of Ge on Sb/Si, the
surface is very flat (RMS /2.4 Å) and exhibits a regular
train of biatomic steps (typical height /6 Å) separated
by large terraces (mean width /300 nm). All these
results show that the 2D
/3D growth transition is
delayed by Sb predeposition.
At higher temperature (550 8C), we observe no
RHEED oscillations during the growth of Ge/Si and
about four oscillations during the growth on Sb/Si.
Analyzing these results with the same arguments than
previously, we deduce that the Ge wetting layer grows
by step flow without Sb and by 2D nucleation with Sb.
However, the small number of oscillations suggests that
the nucleation/step flow transition occurs after the
growth of /4 ML Ge. For larger deposited thickness,
when elastic energy becomes high, the well-known
Stranski
/Krastanov growth takes place and 3D islands
nucleate. But a remarkable point is that we find a huge
increase of the islands density for the growth of 7 ML
Ge on Sb/Si (Fig. 4d) as compared with the growth on Si
(Fig. 4b). As can be seen on the AFM images, this is
accompanied by the decrease of the lateral size of the
islands. In the case of Ge/Si, as commonly reported in
the literature, AFM image (Fig. 4b) reveals flat huge
islands with h /10 nm, L /1.5 mm and a surface
density (d /2.15 /107 cm 2). RMS /8.5 Å was also
measured onto and between the islands. The islands are
expected to be relaxed (by misfit dislocations) owing to
their large lateral size [23] and because of the presence of
small pits attributed to dislocations on their surface. The
183
RHEED pattern does not evidence 3D diffraction spots
because of the large lateral size ]/1 mm and flat surface
of islands (Fig. 3b). In the case of Ge/Sb/Si, 3D
diffraction spots prove the presence of smaller islands
(Fig. 3d). This is confirmed by AFM image which shows
small islands with 6B/h B/13 nm, L /80 nm and d /
8.68 /109 cm2 (Fig. 4d). The RMS measured was /
27.2 Å. The lateral size of islands is reduced by a factor
of /20 and the islands surface density is increased by a
factor of /400 as compared with Ge islands grown on
Si.
To sum up the experimental results, we have found
that Sb has the same surfactant effect for the growth of
Ge/Si on (1 1 1) and (0 0 1) orientations. Two main roles
have been clearly identified: an increase of the thickness
of the 2D wetting layer and a decrease of the islands size
(accompanied by an increase of their density). We
attribute these two effects to (i) a thermodynamic role
[2,15,24], since surface energy of the substrate is
decreased by the predeposition of 1 ML Sb and (ii) a
kinetic role, since the diffusion length of adatoms is
decreased because of the high exchange rate with
subsurface atoms (related to a low barrier of exchange).
This phenomenon also explains the important surface
segregation of Sb during growth.
In order to roughly estimate these two roles, we first
compare the total energies of the structures consisting of
Ge/Si and of Ge/Sb/Si. This basic calculation is based on
an energetic balance between surface energy and elastic
strain energy. It deliberately neglects surface effects
(stress, reconstruction) and atomistic mechanisms (steps
energy formation, etc.). Considering a Ge layer epitaxi-
ally grown on Si and capped by a fraction of ML of Sb,
with h being the thickness of the Ge layer and u ( 5/1)
the coverage of Sb, we define a critical thickness hc at
which the gain of elastic energy cannot be any more
compensated by the decrease of surface energy. If we
simply assume that at h /hc, the elastic energy stored in
the film can be relieved either by 3D islands or by
184 A. Portavoce et al. / Materials and Engineering B101 (2003) 181
/185
Fig. 4. AFM images of 7 ML Ge deposited on Si(1 1 1) at: (a) 350 8C (2/2 mm2), (b) 550 8C (5/5 mm2) and on 1 ML Sb/Si(1 1 1) at: (c) 350 8C
(2/2 mm2) and (d) 550 8C (4/4 mm2).
dislocations and that the critical energy (Ec) of the
system before the relaxation of strain is constant, we can
write
DEc Dg(u)DEel (hc )0:
With Dg (u ) the gain of surface energy and DEel(hc) the
excess elastic energy for different Sb surface coverages.
For the initial state, we use the experimental values of
hc /3 ML for u /0 on (1 1 1). Surface energy is simply
calculated using a Vegart law (Eq. (2)), where gSb and
gGe are the surface energies of Sb and Ge, respectively.
Elastic energy is calculated using the elasticity theory
(Eq. (3)) where m is the shear modulus, n the Poisson
ratio of Ge, o the strain (lattice parameter perpendicular
to the substrate surface) and V /hS the volume of the
Ge layer. We have calculated hc versus u . The values of
hc for typical Sb coverages on the two orientations are
summarized in Table 1:
g(u)ugSb (1u)gGe ;
1n
Eel (h)2m o2 V :
1n
We see that the predeposition of 1 ML Sb induces an
increase of the critical thickness Dh /5 ML on Si(1 1 1)
that is in a first approximation in good agreement with
the experimental results (Dh /3 ML experimentally
found) (for experimental results on (1 0 0), see [19]).
Moreover, the calculations show that at higher tem-
perature, the formation of islands would be completely
inhibited in the presence of 1 ML Sb, since hc is larger
than the experimental deposited thickness measured.
Replacing the experimental values of hc on Si(1 0 0)
Table 1
Typical values of hc for different coverages of Sb
hc/u (Sb) 1 ML 0.5 ML 0 ML
hc/Si(1 1 1) 8 ML (25.4 Å) 5.5 ML (17.4 Å) 3 ML (9.4 Å)
hc/Si(1 0 0) 24 ML (33 Å) 16.5 ML (22.3 Å) 9 ML (12 Å)
found in [19] (at 550 8C, with predeposition of 1 ML
Sb) in Eq. (3) gives a theoretical coverage of u /0.3
ML. We then conclude that the islands nucleation at
550 8C can only be explained by a partial desorption of
(1)
Sb.
4. Conclusion
In this paper, we have shown that Sb has mainly two
effects on the growth of Ge/Si(1 1 1) and (1 0 0): first it
increases the thickness of the wetting layer and second it
promotes the nucleation of ultra-small dense islands.
These effects are explained by the conjugated roles of
thermodynamics (reduction of the surface energy) and
of kinetics (decrease of the surface diffusion length).
Considering the thermodynamic aspect, we simply
calculate the critical thickness of 2D
/3D transition
(hc) for different Sb coverages. Comparison with experi-
(2) mental results proves that the formation of islands at
550 8C can only be attributed to the Sb partial
(3) desorption during growth.
Acknowledgements
The authors wish to thank the EC projects SiGeNet
(No. IHP-RTN-99-1) and FORUM FIB (No. IST-2000-
29573) for financial support.
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