Journal of Crystal Growth 334 (2011) 177180

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Nucleation of GaN nanowires grown by plasma-assisted molecular beam

epitaxy: The effect of temperature
Rafael Mata a,b, Karine Hestroffer b, Jorge Budagosky a, Ana Cros a, Catherine Bougerol b,
Hubert Renevier c, Bruno Daudin b,n
a

Materials Science Institute, University of Valencia, P.O. Box 22085, E46071 Valencia, Spain
CEA-CNRS group ) Nanophysique et Semiconducteurs* , Institut Neel/CNRS-Univ., J. Fourier and CEA Grenoble, INAC, SP2M, 17 rue des Martyrs, 38 054 Grenoble, France
c
Laboratoire des Materiaux et du Genie Physique, Grenoble INP-MINATEC, 3 parvis L. Neel, 38016 Grenoble, France
b

a r t i c l e i n f o

abstract

Article history:
Received 18 May 2011
Received in revised form
10 August 2011
Accepted 13 August 2011
Communicated by K. Deppert
Available online 22 August 2011

The growth of GaN nanowires by means of plasma assisted molecular beam epitaxy directly on Si(1 1 1)
has been investigated as a function of temperature. Statistical analysis of scanning electron microscopy
pictures taken for different growth temperatures has revealed that density, diameter, length and length
dispersion of nanowires were strongly dependent on temperature. Length dispersion, in particular, was
found to be signicant at high temperature. These features have been assigned to the different duration
of the nucleation process with temperature, namely to the dependence with temperature of the time
necessary for the size increase of the three-dimensional precursors up to a critical value.
& 2011 Elsevier B.V. All rights reserved.

Keywords:
A1. Nanostructures
A1. Nucleation
A3. Molecular beam epitaxy
B2. Semiconducting IIIV materials

1. Introduction
The current interest in III-nitride nanowires (NWs) relies to a
large extent on their excellent structural and optical properties,
making them an alternative to their dislocation-plagued twodimensional counterparts. Among the various growth techniques
used upto date to grow such wires, plasma-assisted molecular
beam epitaxy (PA-MBE) is particularly attractive as it does not
require the use of catalysts, which are a potential source of
impurity contamination [1]. As a further advantage with respect
to 2D material, NWs can be grown on (1 1 1) Si. GaN NWs grown
using PA-MBE are usually found to be vertically aligned, especially when using a thin AlN buffer layer deposited on (1 1 1) Si, a
favorable situation for the growth of axial heterostructures [2]. As
a matter of fact, the demonstration that GaN/InGaN or GaN/AlGaN
NWs heterostructures could be used to achieve light emitting
diodes (LEDs) in the visible [35] and UV [6] range has been made
recently. Nevertheless, compared to the standard 2D LEDs, additional difculties specic to NW arrays are faced: for instance,
processing of NW LED structures requires a planarization step, in
order to optimize the upper electrode. This step is expected to be
greatly eased if the height distribution of NWs is narrow enough,

Corresponding author. Tel.: 33 438 783 750; fax: 33 438 785 197.
E-mail address: bruno.daudin@cea.fr (B. Daudin).

0022-0248/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2011.08.015

which raises the issue of precisely controlling the growth process.

However, despite the practical importance of such an issue, it
appears that growth studies dealing with the nucleation and
height control of NWs are relatively scarce in literature [715].
It has to be emphasized that the role of the AlN buffer layer
optionally deposited on Si(1 1 1) before growth of GaN NWs to
ensure a better verticality [2] cannot be neglected. As a matter of
fact, it has been found that the nal density of GaN NWs could be
correlated to the grain size of the AlN buffer layer [11]. Then, with
the prospect of dealing with intrinsic nucleation mechanisms
uninuenced by the presence of a buffer layer, we address in this
article the issue of nucleation processes of GaN NWs grown
directly on Si(1 1 1) as a function of temperature. Based on the
statistical processing of scanning electron microscopy (SEM)
pictures, it will be shown that the density of NWs as well as
their diameter and length variability strongly depends on growth
temperature, suggesting that they are governed by a kineticallydriven process. By contrast, the size of 3D precursors is temperature-independent, suggesting that it is not governed by kinetics
but rather related to the relaxation of their elastic energy.

2. Experiment and results

The samples studied have been grown by plasma-assisted molecular beam epitaxy (PA-MBE) on 2-in Si(1 1 1) wafers. Prior to growth

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R. Mata et al. / Journal of Crystal Growth 334 (2011) 177180

the substrates were cleaned with a hydrouoric acid solution and

thermally outgassed for 15 min at 300 1C until the 7  7 reconstruction of the Si(1 1 1) surface was observed. Growth of GaN NWs was
performed in N-rich condition with a Ga/N ratio of 1/3.
In order to ensure NW growth reproducibility, reection high
energy electron diffraction (RHEED) was used to determine the Si
surface temperature by measuring the Ga desorption transient
from the 7  7 Si(1 1 1) reconstructed surface, following its
exposure to a Ga ux. Such an exposure results in the formation
of a self-regulated Ga amount on the Si surface, independent of
ux/exposure time uctuations in the 740860 1C growth temperature range [16]. Then measuring the Ga desorption transient
leads to the determination of a reproducible relationship between
the Ga desorption time and the temperature indicated by the
thermocouple in mechanical contact with the rear face of the Si
wafer. As the thermocouple measurement is biased by direct
thermal radiation from the heater lament, a correction was
further applied by observing the appearance/disappearance of
the 7  7 reconstruction, which was set at 860 1C [17]. Finally, this
two-steps procedure provided a relationship between the Ga
desorption transient and the surface temperature (see inset of
Fig. 1). In a next stage, the dependence of the NW density as a
function of the transient desorption time was studied, eventually

Temperature (C)

Nanowires density (108/cm2)

1000
800
600

870
840
810
780
750

400

10
1
Ga desorption time (s)

200
0
780

790

800
810
Temperature (C)

820

830

Fig. 1. GaN nanowire density as a function of the corrected temperature. Inset:

substrate temperature (as read by the thermocouple in contact to the rear face of
the (1 1 1) Si wafer) as a function of Ga desorption time from the Si surface.

leading to the densitytemperature relationship as shown in

Fig. 1 where each experimental point corresponds to a single
sample. For each single sample, the NW density was measured in
the center of the wafer. The GaN deposition time was 90 min. In
agreement with the results recently obtained using a pyrometer
to measure the temperature [14], Fig. 1 reveals that GaN NWs
density is drastically decreasing between 780 and 805 1C and falls
down to zero above 805 1C, consistent with the rapid increase of
the decomposition of GaN in MBE environment above 800 1C,
which has been observed by Grandjean and coworkers [18].
In a next stage of the experiments reported in the present
work and with the purpose of investigating NW nucleation and
morphology as a function of temperature on a single sample,
advantage was taken of the marked temperature gradient from
the center of the 2 in silicon wafer towards the edge, depending
on the mechanical design of the substrate holder. For this
purpose, two types of samples were grown: sample #1 consists
of GaN NWs, which were grown during 3 h in order to study the
evolution of their dispersion length as a function of density/
temperature. Sample #2 was grown under the same conditions
but the growth time was limited to 20 min in order to analyze the
rst stages of the nucleation process as a function of temperature.
The morphological characteristics of samples #1 and #2 were
analyzed by means of top-view and cross section Scanning
Electron Micrographs (SEM) (ZEISS Ultra 55 microscope) taken
at regular intervals along the wafer radius. Fig. 2(ac) shows
representative SEM images of sample #1 taken at three different
positions of the wafer. Consistent with data of Fig. 1, a decrease of
NWs density is observed as growth temperature increases. Moreover, changes in diameter and length are observed, both of them
decreasing for the higher temperatures. Fig. 2(df) shows similar
SEM micrographs from sample #2. Due to the short growth time
of sample #2 the onset of NW formation has only taken place in
low temperature regions (Fig. 2(d), close to the wafer edge).
Regions closer to the wafer center, at higher temperatures,
present the formation of small islands, namely the 3D precursors,
which are formed in a nucleation stage prior to the steady state
growth of NWs [11,12]. A clear decrease in density for higher
substrate temperature is observed.
Based on a detailed statistical analysis of the SEM pictures,
diameter, length and length dispersion of NWs were determined
as a function of temperature. In practice, images with less than 20
wires have been excluded from the analysis. Results are plotted in
Fig. 3, which show the length and the length dispersion of the
NWs as a function of temperature. NW length remains almost
constant in most of the temperature range studied, with a rapid

Fig. 2. SEM micrographs of sample #1 taken in cross section (top) and top view (middle) from the sample edge (a, lower temperature), and two regions closer to the wafer
center (b, c, higher temperature). Bottom: similar top view SEM micrographs of sample #2 taken from the sample edge (d, lower temperature), and two regions closer to
the wafer center (e, f, higher temperature).

R. Mata et al. / Journal of Crystal Growth 334 (2011) 177180

350

Mean length (nm)

300
250

100

200
150

50

Length dispersion (nm)

150

100
50
775

780

785
790
795
Temperature (C)

800

0
805

Fig. 3. Variation of the mean length (dots) and of the length dispersion (triangles)
of GaN NWs as a function of temperature. Lines are guides to the eyes.

28

#1

Mean diameter (nm)

#2
24
20
16
12
8
770

780

790
Temperature (C)

800

810

Fig. 4. Variation of the mean diameter of the NWs (dots) and precursor islands
(triangles) as a function of temperature. Lines are guides to the eyes.

decrease for temperatures larger than 790 1C, associated to the

rapid increase in GaN decomposition rate in this temperature
range [18]. Length dispersion increases with temperature, with a
marked increase in the high temperature range.
Similar statistical analysis for the diameter of samples #1 and
#2 is shown in Fig. 4. The NWs diameter dependence with
temperature is almost linear, with a marked decrease as the
temperature is raised, reaching a value of E12 nm at the higher
temperatures. Interestingly, it is found that the diameter of 3D
precursor islands is almost constant (about 12 nm) and independent of temperature, increasing only slightly for the lowest
temperatures, where NWs have already formed, which is assigned
to the reduced nucleation delay in the low temperature range.
This suggests that precursors have to reach a critical size before
turning into NWs, consistent with data reported by Consonni and
coworkers [19]. It also indicates that this critical size is not
governed by nucleation kinetics. Indeed, it has been previously
demonstrated that NW 3D precursors grown on Si(1 1 1) covered
by a thin AlN buffer layer are plastically relaxed, consistent with
the observation of mist dislocations at the interface between the
3D precursor and the thin AlN buffer layer [11,12]. As shown by
Furtmayr and coworkers, when no AlN buffer layer is used, the
absence of wetting layer rather evidences that nucleation of GaN
islands is of VolmerWeber type [20]. Actually, the data of Landre
and coworkers [11] as well as those presented here furthermore

179

suggest that with or without AlN buffer layer the 3D precursor

size is governed by the elastic strain relaxation mechanism and
not by kinetic considerations.
More precisely, a detailed analysis of the NW nucleation
process by X-ray diffraction performed in situ on NWs grown in
an MBE machine connected to a synchrotron beam line at the
European synchrotron research facility in Grenoble (France) is
reported in Ref. [11]. The presence of three regimes has been
established, namely a rst stage corresponding to the nucleation
of a wetting layer on the thin AlN buffer layer followed by a
second stage associated with the size increase of 3D NW precursors, and nally a third stage corresponding to the steady state
NW growth. Depending on Ga ux and substrate temperature, it
was established that the duration of the second stage corresponding to precursor size increase ranged from a few seconds to
almost one hour. During this stage, the amount of GaN deposited
was found to vary as At2 d, t being the growth time. The
exponent, 2 d, of this supralinear regime was found to be in
the range of 1.92.3, depending on Ga ux. According to the
model developed by Osipov [21], this implies that the twodimensional size increase of NW precursors in the stage immediately following the deposition of the wetting layer is not
isotropic but characterized by a rapid increase of the island
diameter/perimeter till reaching a critical size associated with
mist dislocation formation at the AlN/GaN interface [11,12].
These results lead to the conclusion that the 3D precursor
nucleation process, which depends on the areal density of Ga
adatoms, will be controlled by both temperature and Ga ux. As
the critical size of precursors giving rise to NW growth is only
governed by an elastic energy relaxation process, this implies that
the time spreading of the onset of steady-state NW growth will
reect the duration of the 3D precursor nucleation process till
reaching their critical size. Consequently, a length dispersion of
the NWs will be observed, as it is actually, associated to the
duration of the 3D precursor nucleation process, which indeed
increases with temperature.
This qualitatively supports the hypothesis that at low temperature all 3D precursor islands are almost simultaneously formed and
will reach the critical size for plastic relaxation at the same time,
giving place to the continuous growth of NWs with the same
length. On the contrary, at high temperature, the decrease in
nucleation probability and the drastic increase in GaN dissociation
rate both lead to a marked increase of the time elapsed between
the formation of the rst precursor having reached its critical size
and the formation of the last one. Then, the onset of steady state
growth of NWs is signicantly scattered, reecting the time
duration of the precursor nucleation process and leading to the
growth of wires with different lengths, presenting a much larger
dispersion than those grown at lower temperature.
Interestingly, it is worth noting that at low temperature,
although it can be safely assumed that all 3D precursor islands
are almost simultaneously formed, a NW length dispersion of about
12 nm is still observed (see Fig. 2a). This residual size dispersion is
assigned to uctuations inherent to the growth process itself. As a
matter of fact, it is well known that GaN NWs is governed to a large
extent by Ga diffusion in the basal plane and along the NWs side
walls [16]. Then, random nucleation of NWs combined to shadow
effects may lead to uctuations in the amount of Ga atoms reaching
the top of individual NWs, resulting in a residual size dispersion of
about 5% in the present growth conditions.

3. Conclusion
In summary, it appears on one hand that GaN NWs growth
proceeds through the formation of 3D precursor islands, for which

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R. Mata et al. / Journal of Crystal Growth 334 (2011) 177180

critical size before turning into NWs is independent of the growth

temperature. However, on the other hand, both nucleation probability and size increase of these 3D precursor islands, which are
kinetically driven processes, depend on growth temperature
through the temperature dependence of Ga adatom density/
diffusion and of GaN dissociation rate. Then, as a consequence
of the statistical nature of the nucleation process and of its
marked temperature dependence, it is expected that the nucleation of 3D GaN precursors of NWs till reaching their critical size is
actually occurring during a time span, the duration of which
increases with growth temperature. This leads to a marked
temperature dependence of the length dispersion of GaN NWs
grown catalyst-free by MBE on Si(1 1 1). For practical applications
requiring NWs with reduced length dispersion, the present study
suggests to disconnect the nucleation stage, which should be
performed at low/moderate temperature, from the steady-state
growth stage, which could be performed at higher temperature in
order to optimize structural/optical properties.

Acknowledgments
This work has been supported by the funding awarded by the
Ministry of Science and Innovation of Spain, FEDER (MAT2009010350). Support of French national research agency (ANR)
program BONAFO is acknowledged. We are grateful to Y. Cure
for technical assistance during experiments.
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