ARTICLE IN PRESS

Physica E 37 (2007) 21–25

www.elsevier.com/locate/physe

Effects of Ni catalyst–substrate interaction on carbon

nanotubes growth by CVD
G.P. Veronesea,, R. Rizzolib, R. Angeluccib, M. Cuffiania,
L. Malferraric, A. Montanaric, F. Odoricic
a
Dipartimento di Fisica, Università di Bologna, V.le B. Pichat 6/2, 40127 Bologna, Italy
b
Consiglio Nazionale Ricerche-IMM, Sezione di Bologna, V. Gobetti 101, 40129 Bologna, Italy
c
Istituto Nazionale di Fisica Nucleare, Sezione di Bologna, V.le B. Pichat 6/2, 40127 Bologna, Italy
Available online 16 October 2006

Abstract

An investigation of the effects of substrate type and various treatments on carbon nanotubes (CNT) growth, using an evaporated
Ni thin film as a catalyst, is presented. Barrier layers of SiO2, Si3N4, and TiN on Si were used as substrates. The catalyst-insulating
substrate systems have been processed in several gaseous atmospheres (Ar, NH3 and H2) and in the temperature range 700–900 1C, in
order to obtain the most appropriate morphology, size and density of catalyst particles as seeds for the subsequent CNT growth. On this
kind of substrates, the smallest nanoparticles were obtained on SiO2 layers, in H2 or NH3 atmosphere even at 700 1C. However, the best
vertically aligned and well-graphitized CNT resulted from the NH3 annealing process, followed by the CNT deposition at 900 1C in
C2H2 and H2.
On TiN conducting substrates, the best vertically aligned CNT were deposited using a shorter annealing step and a deposition process
at reduced pressure. The samples were characterized by means of scanning electron microscopy (SEM) and Raman spectroscopy
analysis.
r 2006 Elsevier B.V. All rights reserved.

PACS: 61.46.Df; 61.46.Fg; 81.15.Gh

Keywords: Carbon Nanotubes; Nickel nanoparticles; CVD

1. Introduction nanoparticle (NP) precursor. An additional layer is

Carbon nanotubes (CNT) have unique mechanical and
electrical properties [1] but, in order to fully exploit their
potential for nanoscale applications [2], the achievement of
a complete control of their characteristics in the course of
the synthesis process is mandatory. For applications in
nanoelectronics, appropriate, easy and cheap CNT synth-
esis processes, compatible with the IC microelectronic
technologies, must be developed. The catalyst-assisted
chemical vapour deposition (CVD) [3] technique seems to
be one of the best candidates for satisfying these require-
ments. In this paper, we focus our attention on Ni as a
catalyst, starting with a thin film on Si substrates as a
Corresponding author. Tel.: +39 051 6399120; fax: +39 051 6399216.
E-mail address: veronese@bo.infn.it (G.P. Veronese).
inserted between Ni and Si substrates as a diffusion barrier
to prevent silicides formation and metal diffusion through
silicon, which would substantially reduce the catalytic
activity of the metal for CNT synthesis [4]. We have been
developing this kind of process to study the relationships
between catalyst and substrate. This preliminary work is
aimed at the synthesis of vertically aligned CNT for
applications such as particle detectors and cold cathode
emitters for high density memory devices [5,6].
Many models have been proposed to describe the CNT
growth. The oldest vapour–liquid–solid (VLS) model [7] is
currently one of the most widely accepted for processes
above 600 1C, whereas different growth models are
accepted at lower temperatures [8]. All models agree in
predicting that CNT synthesis is strongly influenced by
catalyst features, especially in the early stages of growth,

1386-9477/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.physe.2006.09.002
 ARTICLE IN PRESS
22 G.P. Veronese et al. / Physica E 37 (2007) 21–25

being the CNT diameters correlated to the NP dimen-

sions [9].

2. Experimental

Either insulating or conductive layers (70 nm thick Si3N4

or SiO2 and 40 nm thick TiN, respectively) were deposited
on n+-type, 1 O cm, silicon substrates as barriers to the
diffusion of the catalyst. TiN films were deposited by RF
magnetron sputtering of Ti in N2/Ar reactive atmosphere,
holding the silicon substrate at 200 1C. Ni films, 2 nm thick,
were deposited by electron beam evaporation on the
insulating substrates, whereas on TiN the film thickness
was increased up to 30 nm. The catalyst film was then
fragmented into a randomly distributed NP population by
means of an annealing process. The samples were loaded at
room temperature in a quartz hot wall furnace. A three-
step reference process was then carried out at 750 Torr: (1)
a 100 min controlled warm up to the synthesis temperature
in the selected annealing gas, (2) a 20 min annealing and (3)
a 30 min deposition with a mixture of 5% C2H2 in a
reactive carrier gas (either H2 or NH3). Cooling was
performed in Ar flow. The effects of the annealing process,
step (2), on the Ni NP formation on Si3N4 and SiO2
substrates were studied by replacing the deposition, step
(3), with a ‘‘pseudo-deposition’’, during which no carbon
feedstock gas was injected in the furnace. Three different
gases (Ar, NH3 and H2) and three different annealing
temperatures (700, 800 and 900 1C) were investigated. The
synthesis of carbon nanotubes was studied at two different
temperatures (750 and 900 1C).
The samples were characterized by means of scanning
electron microscopy (FE-SEM LEO 1530) at low voltage
(5 kV) and micro-Raman spectroscopy (Renishaw 1000
spectrometer, with a HeNe laser source, at 633 nm,
maximum output power of 15 mW).

3. Results and discussion

Our investigation was first focussed on the effect of the
different substrates, annealing temperatures and gases on
Ni NP formation. Fig. 1 summarizes the results of the
reference process performed at 700 1C, using H2 as
annealing gas. On SiO2 (Fig. 1b) the NP are significantly
smaller than on Si3N4 (Fig. 1a), with an average dimension
of about 20 nm compared with 40 nm; in addition,
the width of the NP size distribution is narrower around
the average, as can be seen in Fig. 1c. As a consequence, the
NP density on SiO2 turns out to be an order of magnitude
larger than on Si3N4 (approximately 1011 NP/cm2 and
1010 NP/cm2, respectively).
The effect of temperature on the Ni NP formation in H2
annealing atmosphere was then studied in the range
700–900 1C. As shown in Fig. 2, with increasing the
temperature the NP minimum dimensions remain constant
on both substrates. On Si3N4 substrates, the width of the
Fig. 1. SEM plan views (same magnification) of Ni nanoparticles on
70 nm thick Si3N4 (a) and SiO2 (b) substrates, annealed at 700 1C in H2.
Size distributions of Ni nanoparticles on the two barrier layers (c).
NP size distribution (bars in Fig. 2) narrows around the
average at higher temperatures.
The effect of the annealing gas was investigated using
Ar, NH3 or H2 atmospheres. No clear dependence of NP
dimension upon the gaseous atmosphere can be seen; on
the other hand, there is an apparent change in the shape of
the NP. On SiO2, H2 annealing leads to the smallest NP
having the most regular morphology, Ar produces
elongated NP, while annealing in NH3 results in flatter
NP than in the case of H2. Therefore, as far as the
dimension of the catalyst NP is concerned, H2 seems to be
the most appropriate annealing gas for obtaining thin
CNT. However, the CNT carpet grown on those NP, at
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G.P. Veronese et al. / Physica E 37 (2007) 21–25
750 and 900 1C in H2 and C2H2, turns out to be highly non-
uniform on the sample area. On the other hand, when using
NH3 as annealing and carrier gas, vertically aligned and
homogeneous CNT carpets were deposited on the whole
sample area at both temperatures. Fig. 3 shows SEM
micrographs of CNT grown at 900 1C using NH3 as
annealing and carrier gas. On SiO2, the average dimension
of the Ni NP (Fig. 3a) is about 20 nm; the vertically aligned
CNT forming the 6 mm thick dense carpet, shown in
Fig. 3b, have diameters in the 20–25 nm range. On Si3N4,
Fig. 2. Average Ni nanoparticle dimension on SiO2 and Si3N4 as a
function of the H2 annealing temperature. Bars correspond to the width of
the size distributions.
Fig. 3. SEM micrographs of Ni NP treated in NH3 at 900 1C, on SiO2 (a) and on Si3N4 (c). CNT grown on these NP at 900 1C in NH3 and C2H2 on SiO2
(b) and Si3N4 (d).
23
the CNT carpet (Fig. 3d) is less dense and thick (about
3 mm, with some isolated CNT growing up to 7 mm). The
Ni NP on this substrate (Fig. 3c) have an average
dimension of about 100 nm, while the average diameter
of the corresponding CNT is about 60 nm. The SEM
investigation reveals Ni clusters inside the CNT hollows,
with typical dimensions smaller than the starting NP. In a
few samples, these clusters are located at the CNT tips.
Higher magnification images (Fig. 4) of the same sample
shown in Fig. 3d exhibit many elongated Ni clusters
(up to 300 nm long) distributed along the central CNT
hollows. A possible explanation of this result can be given
according to the VLS model [6]. The carbon feedstock gas
decomposes over the catalyst NP surface: carbon dissolves
inside the catalyst creating a liquid metal carbide com-
pound, which accumulates until a supersaturation is
reached. The excess carbon then precipitates in organized
structures, the CNT, whose graphene sheets tensile strength
can split part of the NP. The CNT internal diameter results
smaller than the starting NP diameter, because of the pear-
shape assumed by the liquid NP. The outer diameter also
depends upon the amorphous carbon which can deposit on
the CNT surface.
Further investigations concerning the H2 effects on the
synthesis of CNT were carried out by means of two mixed
processes at 900 1C: (1) ramp up and annealing in NH3 (NP
morphology as in Fig. 3a and 3c) and deposition in H2 and
C2H2; (2) ramp up and annealing in H2 and deposition in
NH3 and C2H2. In Fig. 5, the cross section SEM
micrograph of the sample grown using process (1) on
SiO2 shows a 4 mm thick carpet, made up of almost
vertically aligned multi-walls CNT, with diameter in the
range 25–35 nm. On the other hand, process (2) leads to
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24 G.P. Veronese et al. / Physica E 37 (2007) 21–25
Fig. 4. Back scattered electrons (a) and secondary electrons (b) SEM
micrographs of the sample synthesized at 900 1C on Si3N4 in NH3 and
C2H2 gas mixture. The Ni clusters appear brighter in the back scattered
electron image.
Fig. 5. Cross section SEM micrograph of CNT grown on SiO2 substrates
at 900 1C in H2 and C2H2, following Ni NP formation in NH3 (see
Fig. 3a).
highly non-uniform CNT deposition on the sample area.
Therefore, at 900 1C the Ni NP formed in H2 produces a
non-uniform CNT synthesis, both for H2+C2H2 and
NH3+C2H2 gas mixture.
Fig. 6 shows the Raman spectra of CNT deposited at
900 1C, using either a process with NH3 as annealing and
carrier gas (curve 2), or the mixed processes (curves 1 and 3)
described above. The ratios of the intensities of D and G
peaks, ID/IG, and the normalized intensities of the D and G
peak with respect to G0 (the second-order overtone of the D
peak) ID/IG0 , IG/IG0 , are also reported. The trend of these
ratios [10] indicates that the CNT quality dramatically
improves if Ni NP are formed in NH3, rather than in H2,
and the following deposition is carried out in H2 and C2H2.
However, the high D peak intensity and the presence of a
shoulder in the G peak (at about 1618 cm1) of spectrum of
curve 1 prove that the multi-walls CNT (see Fig. 5) are still
defective.
The results discussed above agree with data reported in
ref. [11], confirming that the NH3 treatment of the catalyst
Fig. 6. Raman spectra in the range 1000–3000 cm1 of CNT samples on
SiO2 substrates, synthesized at 900 1C using different gases for both the Ni
NP formation and the CNT synthesis.
Fig. 7. Raman spectra in the range 1000–3000 cm1 of CNT samples
synthesized on TiN substrate at 750 1C at 750 and 10 Torr. NH3 was used
as the annealing and carrier gas during the deposition step.
NP is important to keep the catalyst surface free of
amorphous carbon deposits during the first stages of CNT
synthesis, so that the site density of the NP effectively
active can be increased.
For applications such as cold cathode emitters, TiN/Ti
double layers can be used as CNT contacts on the Si
substrate. However, the structural and electrical properties
of the TiN films are strongly dependent on their deposition
conditions and the following treatments. Hence, the CNT
growth process has to be optimized for the specific TiN
layers. In our sputtering conditions, TiN conductive films
having an open microcrystalline structure were deposited.
Consequently, Ni diffusion through these layers was
supposed to be large. The catalyst film thickness was then
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G.P. Veronese et al. / Physica E 37 (2007) 21–25
increased up to 30 nm to balance the large diffusion of Ni
in these layers. In order to reduce Ni diffusion through the
TiN layers, the reference deposition process at 750 1C, with
NH3 as carrier and annealing gas, was modified: the
samples were introduced in the hot furnace, thus decreas-
ing the heating step duration, whereas the annealing and
deposition steps remained unchanged. SEM observations
showed highly defective carbon fibres, often covered by a
thick layer of amorphous carbon. In Fig. 7, the Raman
spectrum of that sample deposited at 750 Torr is compared
with the spectrum of a CNT film deposited at 10 Torr. As
can be deduced from Fig. 7, the sample quality dramati-
cally improves by performing the annealing and deposition
steps at a reduced pressure of 10 Torr. The D peak intensity
is still high (even if the peak width is smaller) and the ID/IG
value is greater than in the spectrum of the sample
deposited at 750 Torr. Both spectra exhibit an ID/IG value
of about 1.3, which has been previously reported in the
literature for films of CNT coated with amorphous carbon.
However, the ID/IG0 and IG/IG0 ratios, reported in Fig. 7,
largely decrease for the Raman spectrum of the sample
deposited at 10 Torr, thus indicating a lower number of
defects in the corresponding CNT or carbon fibres [10].
SEM investigations reveal a dense carpet of multi-walls
CNT, about 5 mm thick, with a few isolated nanotubes up
to 20 mm long. CNT have a broad diameter distribution
(20–100 nm) and often show Ni clusters distributed along
their length.
4. Conclusions
In order to achieve a good control over the CNT
synthesis process, we have investigated some of the
parameters influencing dimension and site density of a
catalytic nanoparticle distribution obtained by the frag-
mentation of a continuous nickel film by means of an
annealing process. The Ni film has been evaporated on
different barrier layers (either SiO2 or Si3N4) to avoid
catalyst diffusion in the Si substrate. The nature of this
barrier layer plays a major role in determining the
nanoparticles distribution: on SiO2 the nanoparticles are
about a factor of two smaller than on Si3N4, and the size
distribution turns out to be significantly narrower. Our
results indicate either H2 or NH3 as the most efficient
25
annealing gas for obtaining the smallest nanoparticles
dimension. However, the best results in the synthesis of
CNT are obtained using nanoparticles formed in NH3
rather than in H2, since a non-uniform CNT distribution
on the sample area is deposited in the latter case. After
NH3 annealing, the best vertically oriented CNT are
synthesized on SiO2 substrates at 900 1C using C2H2
and H2.
On TiN conductive substrates the deposition of verti-
cally aligned CNT carpets was achieved, using a shorter
annealing step and a reduced pressure process. The
fabrication of CNT structures on TiN patterned areas is
under way, in order to measure the field emission proper-
ties of our CNT.
Acknowledgement
This work was partially supported by the ‘‘NanoChanT’’
project of the Istituto Nazionale di Fisica Nucleare
(INFN). The authors thank Matteo Ferroni of the
University of Brescia and Franco Corticelli of the CNR-
IMM for assistance during SEM observations.
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