ARTICLE IN PRESS

Vacuum 81 (2006) 22–24

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The influence of Ni catalyst on the growth of carbon

nanotubes on Si substrates
T. Daniša, M. Kadlečı́kováa, A. Vojačkováa, J. Brezaa,, M. Michalkab, D. Búca,
R. Redhammera, M. Vojsa
a
Faculty of Electrical Engineering and Information Technology, Department of Microelectronics, Slovak University of Technology,
Ilkovičova 3, 81219 Bratislava, Slovakia
b
International Laser Centre, Ilkovičova 3, 812 19 Bratislava, Slovakia
Received 28 July 2005; received in revised form 14 February 2006; accepted 14 February 2006

Abstract

This article treats the influence of the treatment of a Ni catalyst upon the growth of carbon nanotubes in alcohol catalytic chemical
vapour deposition (AC CVD) equipment. Prior to the growth of diamond, a thin film of Ni was deposited on a silicon substrate by
magnetron sputtering. We observed that a combination of annealing of the Ni catalyst in vacuum and NH3 had a positive effect upon the
growth of carbon nanotubes (CNTs). The prepared CNTs were analysed by scanning electron microscopy and Raman spectroscopy.
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Keywords: CVD; Catalyst; Carbon nanotubes; Raman spectroscopy

1. Introduction clusters. The thickness and morphology of the film affect

Arc discharge, laser ablation and chemical vapour
deposition (CVD) are the most often used methods for
preparation of carbon nanotubes (CNTs). Compared to
arc discharge and laser ablation, CVD allows large
amounts of high purity and aligned nanotubes to be
obtained. The basic mechanism of the growth of CNTs
involves dissociation of hydrocarbon molecules over metal
clusters heated to high temperatures (700–900 1C). The
metal clusters acting as a catalyst can be created by
different techniques, for instance by vapour or sputter
deposition of a thin metallic layer on the substrate, by
impregnation of porous materials by metals, by deposition
of solutions or suspensions of substances containing
catalyzing metals or by admission of organometallic
substances into the reaction chamber [1–4]. The simplest
way is evaporation or sputter-deposition of a thin metallic
film. The deposited metal film is usually treated by wet
etching in HF solution and/or annealing in an NH3
atmosphere to obtain stable and active nanosized catalyst
Corresponding author. Tel.: +421 2 60291328; fax: +421 2 65423480.
E-mail address: Juraj.Breza@stuba.sk (J. Breza).
the properties of CNTs strongly. Choi et al. [5] and Jang
et al. [6] have shown that NH3 treatment is a crucial step
towards obtaining a high density of nucleation sites for
CNT growth. Jang et al. [6] have described the role of NH3
as an inhibitor of amorphous carbon generation in the
initial stage of CNT synthesis. In our study we report on
the growth of carbon nanotubes using combined annealing
of Ni thin films in vacuum and in NH3 atmosphere.
2. Experiment
The nickel thin film used as a catalyst for the growth of
nanotubes was prepared on a Si substrate by reactive
unbalanced magnetron sputtering. Before deposition, the
vacuum system was pumped down to a base pressure of
10
5 Pa with a conventional oil diffusion pump and a two-
stage rotary pump. A liquid nitrogen trap was used to
reduce backstreaming of vapours. The film was sputtered
in the constant voltage mode at a frequency of 50 kHz and
a power of 150 W. Sputter-deposition was carried out in
Ar at a pressure of 0.2 Pa using a planar round Ni target
of 99.99% purity and 50 mm diameter in in-axis

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doi:10.1016/j.vacuum.2006.02.004
 ARTICLE IN PRESS
T. Daniš et al. / Vacuum 81 (2006) 22–24 23

Table 1 8000
Nickel pre-treatment procedure and conditions D
Si
G
Surface treatment Annealing in vacuum Pre-treatment in NH3
at 400 1C at 700 1C 6000 sample D G'

Intensity (arb. units)

t (min) t (min)

Sample A — — sample C
Sample B — 20 4000
Sample C — 30
Sample D 60 30 sample B
2000

sample A
target-substrate geometry. The target-to-substrate spacing
0
was 60 mm. The films were deposited in the constant 1000 1500 2000 2500 3000
voltage mode at a frequency of 50 kHz and a power of Raman shift (cm-1)
100 W. The deposition rate, as calculated from the final
coating thickness and corresponding deposition time using Fig. 1. Raman spectra of samples: (A) sample grown in C2H5OH on Ni
without pre-treatment, (B) sample pre-treated in NH3 at 700 1C for 20 min,
a prolonged deposition process (some minutes), ranged
(C) sample pre- in NH3 at 700 1C for 30 min, and (D) sample annealed in
from 0.4 to 1 nm/s. The thickness of a thin discontinuous vacuum at 400 1C for 60 min and subsequently pre-treated in NH3 at
Ni layer that was suitable for deposition of nanotubes was 700 1C for 30 min.
between 5 and 10 nm.
Alcohol (C2H5OH) vapour was used as a source of
carbon species for CNT growth. The biggest advantage of
alcohol catalytic chemical vapour deposition (AC CVD)
for the growth of CNTs is its simplicity [7,8]. The
apparatus for AC CVD used for the pre-treatment of the
Ni catalyst and the growth of CNTs consists of a stainless
steel vacuum chamber, an evaporator and halogen bulbs.
Halogen bulbs allow the required temperature to be varied
very quickly. Both substrate pre-treatment and the growth
of CNTs were conducted in the same cycle. Table 1
describes the procedure and conditions of the pre-
treatment for all samples.
Raman measurements were performed in a conventional
micro-Raman spectrometer using an ISA Labram appara-
tus (Jobin Yvon/Spex/Dilor, Horiba Group) equipped with
a 632.8 nm He–Ne laser in the backscattering geometry.
The morphology of CNTs was investigated in a scanning
electron microscope LEO 1550 with a Gemini column for Fig. 2. SEM image of carbon nanotubes grown after pre-treatment in
high resolution imaging even at low operating voltages. NH3 for 20 min (sample B).

3. Results and discussion

The objective of our experiment was to set the time of
annealing and the effect of NH3 required to obtain high-
density catalytic clusters of Ni. The CNT growth condi-
tions, such as time, pressure and temperature, were the
same for all samples: time t ¼ 30 min, pressure
p ¼ 5800 Pa, and growth temperature T ¼ 700 1C. The
surface of sample A, without any pre-treatment of the Ni
catalyst, consisted of catalyst clusters and a web of very
thin CNTs. To verify the presence of multi-walled or
single-walled nanotubes, analysis by a transmission elec-
tron microscope (TEM) would be needed. However, the
measured Raman spectrum (Fig. 1) of sample A is very
similar to the published spectra of isolated single walled
CNTs [9].
Figs. 2 and 3 show the surfaces of samples pre-treated in
NH3 for different times. It is clearly seen that an increase in
the NH3 pre-treatment time led to a high density of
nucleation sites. We can also see a change in the dispersion
of catalyst clusters. The clusters became smaller and
denser. In Fig. 4 (sample D) one can recognize the
significant influence of annealing in vacuum. In compar-
ison with the surface morphology of sample C, a
considerable difference is seen. Both samples were annealed
in NH3 for 30 min and, in addition, sample D was annealed
in vacuum before the NH3 treatment. After such a pre-
treatment, CNTs with high density but also with many
defects were grown. For this sample, a narrow Raman
band at approx. 1350 cm
1, marked as D (‘‘disordered’’)
dominates. The measured Raman spectra of all samples
 ARTICLE IN PRESS
24 T. Daniš et al. / Vacuum 81 (2006) 22–24
Fig. 3. SEM image of carbon nanotubes grown after pre-treatment in
NH3 for 30 min (sample C).
Fig. 4. SEM image of carbon nanotubes grown on a substrate annealed
in vacuum for 60 min followed by pre-treatment in NH3 for 30 min
(sample D).
(Fig. 1) contain typical CNT lines, marked G, D and G0 .
The D-line is attributed to defects in the graphite structure.
On the other hand, the G-line (1550–1605 cm
1) is related
to the graphite basis of the material and, typically for single
walled CNTs, it consists of two dominant features. The
maximum, at approx. 2700 cm
1 (G0 ), denotes a higher
harmonic G-line. In addition, second-order mode Si lines
can be seen.
We explain the mechanism of increased catalytic efficacy
due to annealing of Ni in vacuum combined with NH3
etching as follows. On annealing in vacuum, the sputter
deposited thin film of Ni segregates into ball-shaped
clusters. After exposure to the residual atmosphere
(approx. 80 Pa), Ni is oxidized and reacts also with the
silicon substrate (creating silicides). The resulting struc-
tures increase the adherence and stability of the catalyst at
higher temperatures (the created Ni oxide particles prevent
the catalyst clusters from agglomerating during the high
growth temperature). On the other hand, the metal oxide is
not suitable for the growth of CNTs. Annealing in NH3
removes the oxide and etches Ni. The clusters of Ni created
in this way are then catalytically more efficient than the
thin Ni layer without any pre-treatment.
4. Conclusion
We have found a positive influence of annealing on the
growth of CNTs. By combination of annealing at low
temperature in vacuum and in NH3, the morphology and
dispersion of Ni catalyst clusters on the substrate can be
changed. This is an important step in obtaining a uniform
distribution of nucleation sites for nanotubes. We also
observed an increase in Ni catalyst cluster density and a
decrease in the size of clusters which depended on the time
of annealing. The optimum time for the anneal pre-
treatment was about 90 min. Annealing of the Ni catalyst
(in the form of a thin film) in vacuum combined with
subsequent etching and activation in NH3 led to a high
catalyst activity for CNT growth. The results indicate that
the AC CVD method for deposition of CNTs can be
optimized by suitable pre-deposition annealing procedures.
Acknowledgements
The authors would like to thank J. Král for technical
support. This work has been supported by Grants VTP
1002/2003, VEGA 1/0275/03, 1/2040/05, 1/2061/05 and
APVT-20-013902 of the Ministry of Education of the
Slovak Republic.
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