CARBON 5 0 ( 2 0 1 2 ) 1 2 3 5 –1 2 4 2

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Low temperature growth mechanisms of vertically aligned

carbon nanofibers and nanotubes by radio frequency-plasma
enhanced chemical vapor deposition

Huiyao Wang *, John J. Moore

Department of Metallurgical & Material Engineering, Colorado School of Mines, 1500 Illinois Street, Golden, 80401 CO, USA

A R T I C L E I N F O A B S T R A C T

Article history:
Received 29 July 2011
Accepted 25 October 2011
Available online 29 October 2011
Using radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD), carbon
nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at low temperature. Base
growth vertical turbostratic CNFs were grown using a sputtered 8 nm Ni thin film catalyst
on Si substrates at 140 °C. Tip growth vertical platelet nanofibers were grown using a Ni
nanocatalyst in 8 nm Ni films on TiN/Si at 180 °C. Using a Ni catalyst on glass substrate
at 180 °C a transformation of the structure from CNFs to CNTs was observed. By adding
hydrogen, tip growth vertical multi-walled carbon nanotubes were produced at 180 °C
using FeNi nanocatalyst in 8 nm FeNi films on glass substrates. Compared to the most
widely used thermal CVD method, in which the synthesis temperature was 400–850 °C,
RF-PECVD had a huge advantage in low temperature growth and control of other deposition
parameters. Despite significant progress in CNT synthesis by PECVD, the low temperature
growth mechanisms are not clearly understood. Here, low temperature growth mecha-
nisms of CNFs and CNTs in RF-PECVD are discussed based on plasma physics and chemis-
try, catalyst, substrate characteristics, temperature, and type of gas.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction vapor deposition (T-CVD) by decomposition of a carbon source

Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) were
molecular-scale 1D wires with excellent mechanical and
electronic properties. Recent experimental studies showed
that CNTs were one of the stiffest materials [1,2] and buckle
elastically under large bending or compressive strains [2,3]
compared to other nanoscale materials. Research [4–7] also
indicated ballistic transport through metallic CNTs. Because
of these unique characteristics of CNTs and CNFs, a number
of potential applications had been studied, such as hard
composite tribological coating [8], gas storage media [9–11],
gas sensors [12], electrode materials [13], flat panel displays
[14,15], adsorbents [16,17], and quantum devices [18,19].
CNTs and CNFs have been mainly synthesized using laser
vaporization [20], arc discharge [21], and thermal chemical
on selective catalysts (Fe, Co, Ni, or their alloys) [22–24]. The
laser and arc methods involve a local temperature well over
1000 °C. Although the T-CVD operates at relatively lower
temperature compared to other methods, the synthesis
temperature above 400 °C still limits its application because
the decomposition temperature of most hydrocarbons used
for CNTs growth well exceeds 400 °C [25,26]. For instance,
glass, polymer and different metal substrates have been used
for field emission display and electrode device applications. A
low temperature process is required for the growth of CNTs
or CNFs to maintain thermal stability of these substrate
materials.
Plasma enhanced chemical vapor deposition (PECVD) is
an efficient alternative low temperature production method
because it provides an improved control of the synthesis

* Corresponding author.
E-mail address: huwang@mines.edu (H. Wang).
0008-6223/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2011.10.041
1236 CARBON 5 0 ( 2 0 1 2 ) 1 2 3 5 –1 2 4 2
parameters such as plasma power, low reaction tempera-
ture, gas species, and carbon source. Although it was re-
ported that PECVD might generate undesirable defects in
the CNT structure due to etching by ionized species [27,28],
single-walled carbon nanotubes were able to be produced
using remote-PECVD [29]. Theoretically, growth of high qual-
ity multiwalled carbon nanotubes (MWCNTs) may not be
problematic for PECVD. In PECVD, the plasma could decom-
pose a carbon source, and ionize hydrocarbon and hydrogen
to produce reactive radicals (such as H+ ions, C, CH, CH2, and
CH3) at relatively low temperatures. Meanwhile hydrogen
ions could reduce the metal oxides on the surface of metal
catalysts and hence increase their activity and wetting abil-
ity [30]. Compared to direct current-PECVD (DC-PECVD),
radio frequency-PECVD (RF-PECVD) can generate a much
higher concentration of reactive radicals under the same
deposition conditions [30]. Therefore, the RF-PECVD should
be more suitable for low temperature growth of CNTs and
CNFs than DC-PECVD.
In this study, using sputtered Ni or FeNi catalytic thin films
and methane as a carbon source, vertically aligned CNFs (e.g.,
platelet graphite nanofibers (PGNFs), and turbostratic CNFs),
and MWCNTs were grown by RF-PECVD at temperatures of
140 °C and 180 °C. The low temperature growth mechanisms
of the CNFs and CNTs were systematically studied based on
the deposition parameters such as catalysts structure, flow
rate and composition of gases, substrate temperature, plasma
power, and different types of substrates. This study fills the
gap in understanding the low temperature growth mechanism
of vertically aligned CNFs and CNTs by RF-PECVD method.
2. Experimental details
CNFs and CNTs were synthesized using an industry-standard
single chamber RF-PECVD system (MVsystems, Inc., Golden,
CO, USA). The experimental detail can be found in our previ-
ous work [30]. Low plasma powers (30 and 80 W) were used for
deposition to maintain the plasma temperature low. The sub-
strate temperature was measured by mounting a thermocou-
ple on substrates. No increase in substrate temperature due
to the plasma was measured after the substrate temperature
Table 1 – Growth conditions for the CNTs and CNFs.
Substrate Si(1 0 0) TiN/Si(1 0 0) or glass
Catalyst 8 nm Ni layer 8 nm Ni layer
Catalyst No crystallization Nanoparticles layer
morphology
Gases for growth Ar (100 sccm) + CH4 Ar (100 sccm) + CH4
(10 sccm) (10 sccm)
Substrate 140 180
temperature (°C)
Type of growth Base growth Tip growth
CNF or CNT Turbostratic CNFs PGNFs
Plasma power 30 30
(Watts)
Length of 0.6 lm 0.7 lm
CNT(CNF)
reached 180 °C (or 140 °C). The parallel plate PECVD system
was powered by a Coaxial Power Systems 600 W RF source
(13.56 MHz). The catalysts used for producing the CNFs were
8 nm Ni thin films deposited on a c-Si(1 0 0) wafer using the
sputtering method. Besides the c-Si(1 0 0) substrates, a TiN
intermediate layer was deposited on a c-Si(1 0 0) wafer to con-
trol the reaction between Ni catalytic films and Si substrate.
The experimental conditions are summarized in Table 1.
2.1. Preparation of CNFs
An 8 nm thin Ni layer was first deposited on a Si or TiN/Si sub-
strate using a magnetron sputtering method at room temper-
ature. Then the Ni-coated wafer was loaded into the PECVD
chamber. After the chamber was pumped down to a base
pressure of 1 Pa, the sample was heated to 140 °C or 180 °C
at an Ar flow rate of 100 standard cubic centimeters per min-
ute (sccm). After the working temperature stabilized, a
10 sccm CH4 gas was introduced into the chamber and plas-
ma was ignited at 30 W. The CNFs were synthesized at a work-
ing pressure of 128 Pa for 120 min.
2.2. Preparation of CNTs
Eight nanometer FeNi alloy thin films for CNTs growth were
formed on glass substrates by the magnetron sputtering of a
FeNi alloy target. The FeNi-coated glass in the PECVD cham-
ber was heated in Ar up to 180 °C. Once the working temper-
ature stabilized, a 10 sccm CH4 and a 100 sccm of
90%Ar + 10%H2 gases were introduced into the chamber to re-
place the existing Ar. After the working pressure stabilized at
128 Pa, plasma was ignited at 30 W. CNTs were synthesized
for 120 min. Four nanometers of FeNi alloy thin films were
also used to grow CNTs at 30 and 80 W using same deposition
conditions (except power).
The structure and morphology of the CNFs and CNTs were
studied using a field emission scanning electron microscope
(FESEM, JEOL-7000) and a transmission electron microscope
(TEM, JEM2000EX). The CNFs and CNTs were scraped off the
substrates and placed onto holey carbon Cu grids for TEM
analysis.
Glass Glass
8 nm FeNi layer 4 nm FeNi layer
Nanoparticles layer Nanoparticles layer
(90%Ar + 10%H2) (96%Ar + 4%H2)
(100 sccm) + CH4 (100 sccm)+CH4
(10 sccm) (10 sccm)
180 180
Tip growth Tip growth
CNTs CNTs
30 30 or 80
1.7 lm 1.7 or 5.2 lm
 CARBON 5 0 ( 20 1 2 ) 1 2 3 5–12 4 2 1237

3. Results and discussion morphology of an 8 nm Ni catalyst layer deposited by sputter-

3.1. Growth of CNFs at low temperature
In previous studies, CNFs were produced by T-CVD at tempera-
tures of 500–600 °C [31], where it was noted that the dissocia-
tion rate of the carbon source depended upon the surface
structure of the catalyst. The diameter of the CNFs and CNTs
can be controlled by changing the particle size of catalysts
[23]. Depending upon the stacked orientation of the graphene
layers to the fiber axis, CNFs are commonly classified into
two types: (1) platelet graphite nanofibers (PGNFs) of which
the graphene layers are perpendicular to the fiber axis; and (2)
herring-bone CNFs of which the graphene layers are inclined
at an angle to the fiber axis [23]. In single or multi-walled carbon
nanotubes, the graphene layers are parallel to the tube axis.
In this study, the growth of CNFs films on Ni catalytic films
was investigated at different temperature. The structure and
ing was shown in Fig. 1(a). The surface morphology of the Ni
catalytic layer deposited on a single crystal Si(1 0 0) wafer was
flat without significant crystallization, which was attributed
to the smooth Si surface and low sputtering energy. Fig. 1(b)
shows the SEM image of the CNFs grown on an 8 nm Ni layer
on a Si wafer at 140 °C (top view). CNFs with those pores and
open edges were created by the stacking of disordered gra-
phitic layers during the growth of CNFs. The CNFs without
catalyst particles on their tops were oriented vertically from
the substrate, and their length was 600 nm. These were tur-
bostratic CNFs with rough and porous surface [32].
The chemical reactions between the catalyst and Si sub-
strate can cause poisoning of catalyst and reduce the catalyst
activity during CNTs and CNFs growth. Using the TiN/Si or
glass substrate is anticipated to avoid reactions between the
catalyst and the substrate and poisoning of catalyst. After
sputtering deposition of a 40 nm TiN intermediate layer on

Fig. 1 – SEM images of (a) 8 nm Ni layer on Si, (b) CNFs grown on 8 nm Ni layer on Si at 140 °C.

Fig. 2 – SEM images of (a) 8 nm Ni layer on TiN/Si; (b) CNFs grown on TiN/Si at 180 °C; (c) TEM image of the CNFs dispersed on a
carbon microgrid; (d) HR-TEM of a CNF grown on Ni/TiN/glass substrate.
1238 CARBON 5 0 ( 2 0 1 2 ) 1 2 3 5 –1 2 4 2
Si, an 8 nm Ni catalytic layer containing a large amount of
small nanoparticles was deposited on the TiN layer on top
of the Si substrate (Fig. 2(a)). The diameter (150 nm) of the
CNFs grown on the Ni/Si film was much larger than that of
those grown on the Ni/TiN/Si film (35 nm) as shown in
Fig. 2(b). Furthermore, the CNFs grown on the Ni/TiN/Si film
appeared denser than those grown on the Ni/Si film. The Ni
layer on TiN/Si consisted of numerous nano-Ni particles in
Fig. 2(a), but the Ni catalyst on Si was almost non-crystalline
as shown in Fig. 1(a). This kind of Ni catalysts produced a
large amount of CNFs with rough edges, pores, and defects,
but no metal catalyst was observed on the top of the CNFs.
In contrast to the CNFs grown on Ni/Si films, all the CNFs
on Ni/TiN/Si exhibited smooth edges with metal catalyst par-
ticles on their tops.
Two growth modes, base growth and tip growth, had been
previously identified as the catalytic growth of carbon fila-
ments in T-CVD [33,34]. The growth of CNFs on Si was ob-
served to be of base growth type as shown in Fig. 2(a).
Fig. 2(b) illustrates that catalyst metal particles were located
at the tips of CNFs on TiN/Si, indicating tip growth. The inter-
nal structure and crystallinity of the CNFs on Ni/TiN/Si at
180 °C were further studied using TEM analysis. Fig. 2(c)
shows the TEM image of the CNFs grown on Ni/TiN/Si. Some
catalyst particles with smooth edges were observed at the tip
of CNFs. Fig. 2(d) shows that the PGNF exhibits a good
arrangement of the graphene layers, a high graphitization de-
gree, a large number of open edges, and an ellipsoidal cross-
section with a solid center. The graphene layers were stacked
perpendicular to the nanofiber axis. Although CNFs were
grown at low temperature (180 °C), clear lattice fringes of
graphite sheets are observed in Fig. 2(d).
There is a subtle interaction between the degree of graph-
ene ordering in the CNFs and the wetting ability of the metal
catalyst particles in T-CVD [35]. The geometry of metal parti-
cles governs the strength of the interaction between the me-
tal catalyst atoms and the graphite species. Metal catalysts
should have shown good wetting characteristics (spreading
action) with respect to the highly graphitic carbon nanostruc-
tures, whereas metal catalysts which exhibit a weaker inter-
action with graphite produced nanofiber structures with
many defects [36].
Under same preparing condition, CNFs can be obtained at
low temperature while CNTs can be obtained at high temper-
ature. Huang et al. [32] used thermal decomposition of a mix-
ture of poly(ethylene glycol) and NiCl2 to synthesize CNFs and
CNTs by T-CVD method at high temperature. At 600 °C, the
irregularly shaped Ni nanocatalysts with rough surface re-
sulted in the formation of turbostratic CNFs with many de-
fects (pores and open edges). Cubic-like nanocatalysts
formed at 750 °C produced PGNFs. The thermal equilibrium
at 850 °C introduced crystallized Ni nanoparticles, therefore
the T-CVD process formed smooth-edged, truncated, cone-
like Ni nanoparticles at 850 °C that resulted in the growth of
MWCNTs, with graphene layers parallel to the long-axis of
the CNTs.
In PECVD, there are different growth mechanisms for low
substrate temperatures. When the substrate temperature
was very low (e.g., 140 °C), insufficient thermal energy could
not transform the non-crystallized (amorphous) catalyst into
nano-crystalline, so CNFs with rough edges and pores could
be grown (the same structure of CNFs was observed grown
by T-CVD but at higher temperature 600 °C), and catalytic
particles were remained at the bottom of the CNFs and on
the substrate as shown in Fig. 2(a). Ni atoms with high energy
could react with the Si substrate during sputtering to form
Ni–Si bonds, so the adhesion of the Ni catalyst to the Si sub-
strate increased, meanwhile insufficient thermal energy
could not make catalyst wet. Therefore the particle anchored
to the substrate while carbon precipitated from the top sur-
face of particle and formed CNFs, i.e., base growth at 140 °C.
When the substrate temperature increased to 180 °C, the
nano-Ni catalyst particles on TiN/Si exhibited better wetting
ability due to increased temperature. No strong chemical
bonds between Ni catalyst and TiN layer and the wetted
nano-catalyst particles at a higher temperature (180 °C) re-
sulted in weak adhesion between Ni catalyst and TiN/Si.
Therefore CNFs lifted the catalyst particle as the CNFs grew
and carbon precipitation occurred at the bottom surface of
the Ni particle. In this case, the tips of the CNFs were deco-
rated with the catalyst particle in Fig. 2(b), confirming tip
growth. CNFs with a smooth edge were produced due to the
wet catalysts and the TiN substrates, and the higher tempera-
tures. The effect of 180 °C of substrate temperature in PECVD
appears comparable to that of 750 °C in CVD. The micrographs
revealed that the morphological characteristics and the de-
gree of crystallinity of the CNFs could be controlled by the
reaction temperature, catalyst, substrate, and their structure.
3.2. Growth of CNTs at low temperature
CNTs have been grown on Ni, Fe, and Co metal catalysts at
high temperatures (400–850 °C) by T-CVD method [26,37]. In
contrast, aligned and uniform CNFs were grown using PECVD
method at temperature as low as 120 °C [38]. In our experi-
ment, Ni catalysts on glass substrate were used to grow CNTs
at 180 °C, a transformation of the structure from CNFs–CNTs
was observed. The SEM image (top view) of the CNFs grown
on an 8 nm Ni layer on glass is shown in Fig. 3(a). Fig. 3(b)
shows the TEM image of the CNFs dispersed on TEM grid,
and the catalyst particles with smooth edges were decorated
on the tip of CNFs. Some CNFs exhibited a transformation of
the structure from CNFs to CNTs with a tiny tube in center,
and some are solid in center. Fig. 3(c) shows that a PGNF with
a good arrangement of the graphene layers. An example of a
CNF that looks like a CNT with empty parts and solid parts in
center is shown in Fig. 3(d). This is because the activity of pure
Ni at low temperature was low due to its high melting point,
so only CNFs could be grown at 180 °C using pure Ni catalyst.
Previous study demonstrated that CNTs could be obtained
by increasing substrate temperature using Ni catalyst [32]. But
how can we grow CNTs at low temperature (e.g., 180 °C)?
According to the FeNi binary phase diagram [39], FeNi alloy
with a Fe atomic fraction of 50% has a low melting point,
which could theoretically provide a good environment for
low temperature CNT growth and enhance the carbon diffu-
sion. Carbon could diffuse faster at the surface or in the bulk
of the bi-metal alloy catalysts. The low eutectic point of FeNi
was more suitable for the growth of CNTs at low tempera-
tures than Ni catalysts. Therefore, 1:1 atom ratio of Fe to Ni
 CARBON 5 0 ( 20 1 2 ) 1 2 3 5–12 4 2 1239

Fig. 3 – (a) SEM image of CNFs grown on TiN/Si at 180 °C; (b) TEM image of the CNFs dispersed on a carbon microgrid; (c) TEM
of a CNF grown on Ni/TiN/glass substrate, (d) TEM of a CNF grown on Ni/TiN/glass substrate.

as catalyst compositions was used in this study to investigate
the CNTs growth at a relative low temperature. Shen et al. [40]
also found that Fe–M (M = Pd, Mo, Ni) bimetallic catalysts low-
ered the decomposition temperature of methane and
achieved a high conversion rate of methane into pure hydro-
gen and MWCNTs production. In addition, enough hydrogen
ions present in PECVD could increase the activity of the metal
catalyst through reduction and increase the wetting ability of
the catalyst along with facilitating the etching of amorphous
carbons. Because methane alone could not provide enough H
ions by plasma decomposition, a 10 sccm hydrogen gas was
introduced into the chamber during the CNTs growth.
Fig. 4 shows the (a) SEM image of 8 nm FeNi layer on glass;
SEM images of the CNTs grown on an 8 nm FeNi layer on glass
(b) top view and (c) cross-section. Different from the former
two catalysts, an 8 nm catalytic FeNi layer deposited on a
glass substrate displayed a rough surface and bigger nanopar-
ticles due to a rough glass substrate (Fig. 4(a)). It appears that
substrate roughness played an important role in forming the
particle structure of the catalysts. The vertical CNTs with a
height of 1.7 lm were grown at 180 °C. Due to their high
density, CNTs deposited on FeNi/glass looked like ‘‘grass’’
and were almost vertically aligned.
Fig. 4(d), (e) and (f) shows the TEM images of CNTs, an
individual CNT, and CNT tip, respectively. The CNTs synthe-
sized at 180 °C were almost straight, with a smooth surface
and a uniform diameter (10–30 nm). Fig. 4(e) and (f) shows
the high resolution TEM images of the CNTs obtained from
the FeNi catalyst, in which the CNT diameter is 10 nm. The
graphene layers of CNT are parallel to the CNT axis, a straight

Fig. 4 – (a) SEM image of 8 nm FeNi layer on glass; SEM images of CNTs grown on 8 nm FeNi/glass at 180 °C (b) top view; (c)
cross-section; (d) TEM image of the CNTs dispersed on a TEM grid; (e) HR-TEM of a CNT grown on FeNi/glass substrate; (f) HR-
TEM of a top of the CNT grown on FeNi/glass substrate.
1240 CARBON 5 0 ( 2 0 1 2 ) 1 2 3 5 –1 2 4 2
multi-welled nanotube with hollow inside reveals the well-
ordered lattice fringes of the nanotubes as shown in Fig. 4(e).
The outer and the inner diameters of the MWCNT are
14 nm and 5 nm, respectively. Fig. 4(e) depicts the CNT wall
thickness as 4.35 nm, corresponding to 13 graphitic layers. In
Fig. 4(f), the presence of nano-catalysts embedded in the tip
of CNT indicates that these CNTs grew from the tip. The grain
size of the nano-catalysts with smooth edges is 8 nm.
The vapor–liquid–solid mechanism (VLS) can be used to ex-
plain the formation of CNTs. The catalytic particle surface ad-
sorbs hydrocarbons such as methane and releases carbon
upon decomposition at high temperature, which dissolves
and diffuses into the catalytic metal droplet or particle. When
a supersaturated state is reached, carbon precipitates in a crys-
talline tubular formed at high temperatures. The melt solidifies
when the temperature drops below the eutectic temperature of
the system. Because much more carbon can be dissolved in a
melt than in a solid [41], process temperature must be high en-
ough (400–850 °C) so that methane is thermally decomposed in
T-CVD. Without thermal decomposition, plasma in PECVD
decomposes methane into C and H ions and other reactive rad-
icals directly at very low temperature, meanwhile the produced
H ions enhance the activity and wetting ability of catalysts
through its reduction reaction. Because methane is easier to
be decomposed to C ions by plasma at very low temperature,
and the concentration of C ions is high even though the growth
temperature is low, CNTs or CNFs growth temperature in PEC-
VD could, therefore, reduce significantly.
The main effect of plasma power can be explained by the
impact on methane decomposition. Using different plasma
powers, CNTs were grown by 4 nm FeNi layer on glass at the
same deposition conditions. The cross-sections of the CNTs
images at different powers are shown in Fig. 5(a) and (b). At
180 °C, the top growth vertical CNTs achieved a height of
1.7 lm and 5.2 lm at 30 and 80 W, respectively. Methane
can be decomposed by plasma [42]:
CH4 ! C þ 2H2 ;
e þ CH4 ! CHþ
3 þ H þ e þ e;
e þ CHþ
3 ! CH2 þ H;
Increasing plasma power can increase the growth rate of
CNT due to the increase of the concentration of C and H ions
by strong plasma decomposition of CH4 at higher power. High
Fig. 5 – SEM cross-section images of CNTs grown on 4 nm FeNi/glass at (a) 30 W and (b) 80 W.
plasma power also can produce straight vertically aligned
CNTs. The high voltage may enhance the vertical alignment
when high power is applied.
Fe is the most common catalyst for CNFs and CNTs
growth. In order to compare with FeNi catalyst, 4 nm Fe cata-
lyst layer was deposited on a glass substrate by sputtering.
Using a 30 W plasma power and the same deposition condi-
tion for the CNTs grown on 4 nm FeNi/glass, CNTs were ob-
tained on 4 nm Fe/glass by PECVD, as shown in Fig. 6. The
TEM image in Fig. 6(b) proves that they are CNTs not CNFs
due to their empty center. The CNTs are top growth and their
diameters are 8 nm. Adding H2 can also help Fe catalyst to
produce CNTs at low substrate temperature (180 °C). At the
same deposition condition and time, the length of CNTs
grown by Fe catalyst layer is 0.8 lm, and shorter than the
CNT (1.7 lm) grown by FeNi. This infers that the activity of
pure Fe catalyst is lower than the activity of FeNi catalyst.
In PECVD, carbon atoms or ions for CNT growth do not come
from the thermal decomposition of methane like T-CVD,
which needs high temperature, but come from methane
decomposed by plasma at low temperature. Hofmann et al.
[38] also proposed that the lower activation energy for PECVD
growth occurred because the process changed to carbon
diffusion over the metal catalyst surface. Furthermore, surface
diffusion of carbon on metal catalyst is known to have lower
activation energy than bulk diffusion. Therefore, the concen-
tration of C ions on the surface of catalyst is high even though
the growth temperature is low and the metal catalyst does not
melt. Carbon diffusion occurs over the metal catalyst surface
not into the metal catalyst at low growth temperature in
PECVD. If the particles are considered to be spherical or
‘‘pear-like’’ shaped, the deposition of carbon atoms takes place
on one half of the surface (on the lower curvature face of the
‘‘pear-like’’ shape). The carbon diffuses along the surface of
the particles and precipitates on the opposite half, around
and below the bisecting diameter [40]. If the catalytic particle
is big enough or there is not enough energy in the system
(low temperature) CNFs growth takes place. At 140 °C the metal
catalysts did not melt and recrystallize, therefore there were
no changes of their structure and shape. The non-crystallized
catalyst produced turbostratic CNFs, as shown in Fig. 7(a).
When the CNFs grew on Si at 140 °C, the strong catalyst adhe-
sion due to the formation of bonding between Si and sputtered
Ni atoms with high energy was maintained because the
catalyst was not wetted. CNFs or CNTs continued growing with
 CARBON 5 0 ( 20 1 2 ) 1 2 3 5–12 4 2
Fig. 6 – (a) SEM top view image of CNTs grown on 4 nm Fe/glass at 180 °C, one scratch on the right side; (b) TEM image of the
CNTs dispersed on a TEM grid.
Fig. 7 – Schematics of growth mechanism of CNFs and CNTs:
(a) Base growth turbostratic CNFs from amorphous Ni
catalytic particles. (b) Tip growth PGNFs from nano-Ni
particles. (c) Tip growth CNTs from nano-FeNi particles.
the particle anchored to the substrate and carbon precipitated
from the top surface of the particle, indicating base growth.
When CNFs and CNTs grew on TiN or glass at 180 °C, the Ni
or FeNi metal catalysts for CNFs and CNTs growths could not
form bonds with the high melting point TiN or glass. Also the
higher temperature facilitated wetting of the metal catalysts.
Therefore, the particle attachment to the TiN and glass was
weak. The CNFs or CNTs lifted the particle and they grew from
the tip, as shown in Fig. 7(b). In this case, the top end of the
CNFs or CNTs was decorated with the catalyst particle, indi-
cating tip growth. However, for CNTs, carbon does not precip-
itate from the apex of the hemisphere, which accounts for the
hollow core that is characteristic of these CNTs in Fig. 7(c).
CNTs growth not CNFs at low temperature were led by enough
hydrogen reduction effect and the higher activity of crystal-
lized FeNi with lower eutectic temperature. As discussed
above, two different modes – base and tip growth, are possible
for CNT growth using T-CVD [29,30]. In PECVD they also exhib-
ited similar growth mechanisms at low temperature. The
adhesion between catalyst and different substrate determined
growth types (tip or base growth). By choosing different
growth conditions and catalysts, CNTs and CNFs with differ-
ent structures can be obtained at low temperatures.
The effects of Si substrate on growth mechanism can be
summarized as: (1) Ni and Fe can react with the Si substrate
to form silicide; (2) silicide increases the adhesion of the cat-
alyst on Si substrate; (3) the adhesion and low temperature
(not wet enough) can cause CNFs continue to grow with the
particle anchored to the substrate at 140 °C (base growth).
1241
The effects of TiN intermediate layer or glass substrate in-
clude: (1) minimize the reaction with catalyst; (2) no strong
chemical bonds between metal catalyst and TiN layer or glass.
Catalyst particles began to wet at the higher temperature
(180 °C), resulting in weak adhesion, so CNF or CNT lifted
the particle as it grew (tip growth).
4. Conclusions
In summary, (1) low activity, and wetting ability of metal cat-
alyst with high melting temperature led to growth of CNFs
(non-crystallization (amorphous) or nano-Ni, 140 °C and
180 °C, CH4, and Ar); (2) enough hydrogen ions present in PEC-
VD could increase activity and wetting ability of metal cata-
lyst and facilitate the etching of amorphous carbon; high
activity and wetting ability of low eutectic metal catalyst led
to the low temperature growth of CNTs [nano-FeNi, 180 °C,
10 sccm of CH4 and 100 sccm of (10% H2 and 90% Ar)]; (3)
the tip and base growth mechanism of CNTs and CNFs in PEC-
VD at low temperature were similar to that in regular CVD,
and the adhesion between catalyst and different substrate
determined growth types (tip or base growth); (4) the plasma
in PECVD decomposed methane into C and H ions and other
reactive radicals directly at low temperature, meanwhile the
H ions produced increased the activity and wetting ability of
catalysts through its reducing effect. Therefore growth tem-
peratures of CNTs or CNFs were decreased significantly.
R E F E R E N C E S
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