Chemical Physics Letters 380 (2003) 419423

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Is aluminum a suitable buer layer

for carbon nanotube growth?
T. de los Arcos *, Z.M. Wu, P. Oelhafen
Institute of Physics, University of Basel, Klingelbergstr. 82, CH-4056 Basel, Switzerland
Received 30 June 2003; in nal form 4 September 2003
Published online: 7 October 2003

Abstract
The possibility of using Al buer layers for the catalytic chemical vapor deposition growth of carbon nanotubes has
been investigated by in situ photoelectron spectroscopy. It was found that at the temperatures used for carbon nanotube
growth, typically well above the eutectic temperature of the AlSi system, the liquid AlSi alloy formed getters eciently the metallic catalyst away from the surface, thus precluding nanotube growth.
2003 Elsevier B.V. All rights reserved.

1. Introduction
The use of buer layers between catalyst and Si
substrate in growth of carbon nanotubes (CNTs)
by chemical vapor deposition (CVD) has the two
eects of both increasing the eciency of the
growth process by avoiding undesired chemical
interaction between catalyst and substrate [1], and
of altering the catalyst-support interaction, therefore modifying the characteristics and growth rate
of CNTs [25]. In particular, the use of pure metal
buer layers like Al has been reported to favor the
growth of single-walled carbon nanotubes in conditions that produced multi-walled tubes in the
absence of buer layer [2,3]. We found these results intriguing, since usually the temperatures

Corresponding author. Fax: +41-61-2673784.

E-mail address: t.arcos@unibas.ch (T. de los Arcos).

involved in the CVD growth of CNTs are well

above the eutectic temperature (577 C) of AlSi
over which a liquid AlSi phase forms [6]. Furthermore, this AlSi eutectic is a good sink for
metals. This has turned aluminum metallization at
the backside of Si wafers into an ecient technique
for the removal of metallic impurities from device
active regions, especially in photovoltaics (see [7]
and references therein).
In our previous work the comparative eciency
of buer layers of Al, Al2 O3 , TiN and TiO2 in the
CVD growth of CNTs was investigated [5]. Making use of an experimental setup for CNT growth
combined with in situ photoelectron spectroscopy
analysis, we found that CNTs did not grow
whenever pure Al layers were employed, in opposition to the results published by Delzeit et al. [2,3].
However, when we used the corresponding oxide
Al2 O3 as buer layer CNT growth was successful.
Furthermore, Al2 O3 layers did indeed promote

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doi:10.1016/j.cplett.2003.09.057

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T. de los Arcos et al. / Chemical Physics Letters 380 (2003) 419423

formation of thinner nanotubes as compared with

other buer layers like TiN or TiO2 [5]. Since in
the mentioned work of Delzeit et al. no actual in
situ analysis of the Al chemical state was performed, we venture the possibility that their original Al layers could have been oxidized at some
point during the experimental procedure.
In the present contribution we analyze the Al
case in detail and show that under controlled
vacuum conditions, which ensure the non-oxidation of the Al layer, the Fe catalyst is depleted
from the sample surface during the annealing step.
We will also show that the Fe remains trapped
under the wafer surface, in an intermediate layer
were Al and Si coexist. For comparison the catalyst-buer layer interaction of Fe deposited onto
Al2 O3 buer layers is also shown.

2. Experimental
The Si(1 0 0) wafers used were rinsed in an ultrasonic bath of acetone and ethanol for several
minutes before its introduction into the deposition
chamber, which was pumped down to a pressure
of 1  10 6 mbar. Clean Al was deposited directly
onto the as-introduced Si substrates (without removal of the approximately 2 nm thick Si native
oxide layer) by magnetron sputtering in an atmosphere of 10 3 mbar of pure Ar. For Al2 O3 deposition, O2 was added to the Ar ow with a
partial pressure of 10 4 mbar. Fe was deposited by
ion beam sputtering. The substrate holder can be
rotated inside the chamber to dierent positions,
so that deposition of the dierent elements can be
performed sequentially without breaking the vacuum. The sample holder can be heated to a temperature of 840 C, adequate for the production of
CNTs by CVD. The vacuum chamber is attached
to an ultra high vacuum system (pressure during
sample measurement between 10 9 and 10 8 mbar)
housing a photoelectron spectrometer (Leybold
EA10N, with MgKa excitation). As reference for
x-ray photoelectron spectroscopy measurements
(XPS), the Au 4f7=2 core level line (at 84.0 eV
binding energy) of a clean gold sample was used.
The samples under study can be transferred between deposition chamber and spectrometer for

XPS analysis after each experimental step without

breaking the vacuum. CNTs can be grown in this
experimental setup by introducing acetylene gas
(C2 H2 ) in the deposition chamber at controlled
ow and pressure (35 sccm and 0.1 mbar) after the
sample has reached the desired CVD temperature
[5]. Temperature stabilization is reached in 8 min
after initiating the annealing.

3. Results and discussion

In a previous study performed in our laboratory,
we have shown that Al buer layers of 20 nm
thickness between Fe and the Si substrate prevented CNT growth [5]. In order to study in more
detail the possible interaction of buer layer with
substrate and/or catalyst, a thinner Al layer of
10 nm thickness was deposited in this case, and
1 nm of pure Fe was deposited on top. The sample
was annealed in vacuum to a temperature of 840 C
and allowed to cool down to room temperature
before XPS. The heating of the sample was in this
case stopped after 8 min, at the point when acetylene gas would have been introduced into the
chamber to start the CVD process in a CNT growth
experiment. After each experimental step (Al deposition, Fe deposition and annealing) the sample
was transferred to the spectrometer for analysis.
In Fig. 1 we can follow the chemical evolution
of the sample from the behavior of the Si 2p, Al
2p, and Fe 2p peaks as measured by XPS. The rst
case (a) corresponds to the Si wafer measured asintroduced. Two components corresponding respectively to bulk Si (99.5 eV binding energy) and
SiO2 (103.4 eV) from the native oxide layer can be
clearly distinguished in the Si 2p peak. After deposition of 10 nm of Al (b) no traces of Si can be
seen, which is to be expected from the low AlSi
inter-diusion at room temperature [6,8], and the
fact that due to the limited escape length of photoelectrons the sampled depth is only of the order
of 2 nm [9]. The feature marked with an asterisk
(*) in the Si 2p spectrum does not correspond in
this case to SiO2 , but to the second order plasmon
originating from the Al 2p signal. From the Al 2p
peak we can see that the Al deposited is chemically
pure (Al 2p at 72.7 eV), with a small oxide con-

T. de los Arcos et al. / Chemical Physics Letters 380 (2003) 419423

421

Fig. 2. XPS spectra corresponding to the Al 2p and Fe 2p core

level lines in a Fe-substrate system where an Al2 O3 buer layer
has been used. As in Fig. 1, case (c) corresponds to Fe as deposited onto the Al2 O3 , and case (d) to the situation after annealing to 840 C in 8 min.

Fig. 1. XPS spectra corresponding to the Si 2p, Al 2p and Fe 2p

core level lines showing the changes experienced under annealing by the Fe-substrate system when an Al buer layer is
used. (a) Spectrum of the Si wafer as introduced. (b) Deposition
of a 10-nm thick Al layer. (c) Deposition of 1 nm of Fe. (d)
Sample after annealing in vacuum up to 840 C in 8 min. The
spectra have not been normalized and they show the original
intensity ratios. The feature marked with an asterisk in spectrum (b) in the Si 2p region corresponds to a plasmon of the Al
2p line, and is therefore not related to SiO2 .

tribution at 75.4 eV. The deposition of 1 nm Fe (c)

does not greatly change the chemical situation of
the sample, except for an increase in the oxide
component of the Al 2p peak. After annealing the
sample up to 840 C (d) the situation changes
drastically: iron is practically depleted from the
sample surface, which is now mostly composed of
oxidized aluminum. The appearance of a peak
corresponding to Si, shifted by 0.4 eV towards
lower binding energy with respect to the Si 2p bulk
position, shows that there has been inter-diusion
of Al and Si.
When the same experiment is performed using
oxidized Al as buer layer the behavior of Fe catalyst is markedly dierent. As we can see in Fig. 2,
Fe catalyst remains on the surface of the sample
but suers a transformation into Fe2 O3 . The Fe 2p
peak intensity is reduced to approximately 50% of

the initial Fe amount, which can be attributed to

redistribution of Fe on the surface, maybe together
with a certain loss of Fe by diusion. On the other
hand, the Al2 O3 layer undergoes no chemical
change during annealing of the system up to 840 C.
Exposure of this system to C2 H2 resulted in dense
and fast growth of carbon nanotubes (see [5] for
details). The inuence of the Fe chemical state on
CNT growth mode and CNT characteristics will be
presented in a forthcoming work.
In the case of Al buer layers, Fe depletion, together with the appearance of a Si signal after the
annealing, supports the idea that an AlSi alloy has
formed. This alloy is expected to be in the liquid
state, and therefore at a temperature of 840 C it
should have a composition consisting of 3040 at.%
Si in Al [6]. Since the solubility of metals in such an
alloy is reported to be very high, exceeding in some
cases 10 at.% [10], the original 10 nm thick Al layer
would be enough to getter the whole 1 nm Fe layer
from the surface. With the Fe trapped in the liquid
AlSi layer the surface of the sample consists
mostly of an AlSi mixture with practically no
Fe content. In contact with the relatively high
background pressure present in the chamber
(12  10 5 mbar), the hot surface oxidizes easily.
The reason that Al2 O3 is the only oxide detected is
due to the fact that Al2 O3 formation is thermodynamically more favorable than SiO2 or Fe2 O3 ,
therefore it can promptly reduce the other two
components [11].

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T. de los Arcos et al. / Chemical Physics Letters 380 (2003) 419423

In order to nd out about the in-depth distribution of the dierent elements, the sample surface
was etched with Ar ions at 2 kV, and XPS analysis
was performed after each sputtering step. In Fig. 3,
we can follow the evolution of the Si 2p, Al 2p,
and Fe 2p signals as a function of the total sputtering time. The lower row of spectra shown in
Fig. 3, marked in situ corresponds to the annealed case showed in Fig. 1d. The spectra marked
ex situ correspond to the same sample after
exposure to air, before the start of the etching
procedure. Apart from a lowering of the overall
intensities mostly due to coverage by carbonaceous species from air exposure, the only noticeable eect is the oxidation of part of the Fe. This
oxidized component, roughly 1% of the initially
deposited amount is the only fraction of the original Fe still present on the sample surface. As we

Fig. 4. Depth prole with integrated peak areas taken from

Fig. 3.

go deep into the sample, there is an increase on the

intensity of the Si 2p peak, and an overall decrease
of the Al 2p signal. In Fig. 4, where the integrated
peak areas of the dierent components are represented as a function of sputtering time, we can see
how the aluminum oxide contribution decreases
with time, showing that the Al2 O3 layer is located
at the sample surface. On the other hand, the
contribution corresponding to Al has a maximum
in intensity located under the sample surface, in
the same way as metallic Fe, showing that metallic
Al and Fe coexist in the same region.

4. Summary

Fig. 3. Depth prole of the Fe/Al/Si sample, after annealing. At

the left-hand side, the total sputtering time of the sample is indicated.

After a previously unsuccessful attempt to grow

carbon nanotubes by CVD on Si wafers covered
with pure Al buer layers [5], the chemical changes
undergone by the system during the annealing step
of the CVD process have been investigated by in
situ photoelectron spectroscopy. We could determine that during the annealing step, the Fe catalyst
is eciently gettered away from the surface and
trapped in a possibly liquid AlSi layer. The uncovered Al present on the sample surface oxidizes
forming a protective Al2 O3 layer in such a way that
practically no Fe is present on the sample surface

T. de los Arcos et al. / Chemical Physics Letters 380 (2003) 419423

when the CVD process starts, which explains why

CNTs did not grow onto these substrates. On the
contrary, when Al2 O3 is employed as buer layer
Fe transforms to Fe2 O3 during the annealing, and
remains on the sample surface, providing a situation where CNT growth is very ecient.

Acknowledgements
We thank the National Center of Competence
in research for Nanoscience (NCCR) and the
Swiss National Foundation for nancial support.
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