Journal of Alloys and Compounds 650 (2015) 86e91

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Patterned growth of vertically aligned carbon nanotube arrays using

colloidal lithography and plasma enhanced chemical vapor deposition
Yuhong Man*, Zhiqian Chen, Yongping Zhang, Peitao Guo
Faculty of Materials and Energy, Southwest University, Chongqing 400715, China

a r t i c l e i n f o a b s t r a c t

Article history: Patterned carbon nanotube structures were synthesized on silicon substrates by plasma enhanced
Received 7 March 2015 chemical vapor deposition and solution dipping deposition assisted by monolayer colloidal crystals for
Received in revised form the first time. Through the regulation of the concentration of the precursor solution and plasma treat-
29 July 2015
ment conditions, we have grown carbon nanotube bundles into periodic structures with different growth
Accepted 30 July 2015
site and density. The proposed method greatly reduces the fabrication cost and can tune the periodic
Available online 3 August 2015
structure of carbon nanotubes quite flexibly. Furthermore, the synthesis strategy can also be applied to
synthesize CNT/Fe3C nanocomposites with excellent magnetic property, indicating a potential applica-
Keywords:
Carbon nanotubes
tion in magnetic devices.
Plasma enhanced chemical vapor deposition © 2015 Elsevier B.V. All rights reserved.
Colloidal lithography
Monolayer colloidal crystals
Patterns

1. Introduction Colloidal lithography based on monolayer colloidal crystals

Recently, plasma enhanced chemical vapor deposition (PECVD)
has been recognized as one of the viable fabrication techniques of
carbon nanotubes (CNTs) for its ability to grow individual, free-
standing, vertical CNTs at lower growth temperatures relative to
thermal CVD [1]. However, CNTs are generally randomly deposited
on plain substrates with no control or limited control on the growth
site by plasma pretreatment during PECVD [2]. Two-dimensionally
(2D) patterned carbon nanotube structures have attracted intensive
interest because they exhibit unique pattern-dependent properties
and show promising applications in optics [3], electronics [4] and
field emission devices [5]. The most direct method to achieve
patterned carbon nanotube structures is to utilize patterned cata-
lyst seed layers which directly determine where the nanotubes can
grow. Up to now, significant research effort has been dedicated to
patterning the catalyst layers into ordered geometries by various
methods, such as photolithography [6], e-beam lithography [7],
shadow mask lithography [8] and microcontact printing [9] to grow
ordered carbon nanostructures. However, these methods usually
suffer from high cost and low throughput.
* Corresponding author.
E-mail address: manyh05@swu.edu.cn (Y. Man).
(MCCs) has been proven to be a facile, inexpensive, efficient and
flexible technique for large-scale fabrication of 2D patterned
nanostructures [10,11]. The nanoparticle patterns templated with
MCCs are applied as patterned catalysts for growing periodic car-
bon nanotube arrays by PECVD [12e17]. However, the nano-
particles such as Fe, Co or Ni were deposited on the substrate by
physical vapor deposition such as electron beam evaporation or DC
sputtering which requires expensive equipment, thus greatly in-
creases the fabrication complexity and cost. Solution dipping
deposition assisted by MCC templates is quite simple and can
obtain diverse ordered porous structured films, including Ag, Fe2O3,
NiO etc [18e20]. Nevertheless, growing patterned carbon nanotube
structures by the simple solution dipping deposition has rarely
reported.
Herein, we attempt to employ solution dipping deposition
instead of physical vapor deposition for fabricating patterned
catalyst layers for the patterned growth of CNTs. The influence of
the concentration of the precursor solution and plasma treatment
conditions on the patterned growth of CNTs has been discussed.
Moreover, carbon nanotube arrays terminated with Fe3C
nanomagnets have been synthesized. The proposed synthesis route
could facilitate the direct fabrication of more cost-effective and site-
selective periodic CNT structures compatible with novel nano-
electronic devices, field emission devices and magnetic devices.

http://dx.doi.org/10.1016/j.jallcom.2015.07.286
0925-8388/© 2015 Elsevier B.V. All rights reserved.
 Y. Man et al. / Journal of Alloys and Compounds 650 (2015) 86e91
Fig. 1. XRD pattern of the Fe2O3 polycrystalline film on silicon substrates.
2. Experimental details
2.1. Material synthesis
2.1.1. Self-assembly of monolayer colloidal crystal templates
Polystyrene (PS) nanosphere suspensions (2.5 wt %) were
bought from Alfa Aesar Corporation, and glass substrates were
washed in ethanol and distilled water in an ultrasonic bath, and
then sequentially cleaned according to the method proposed by
Haynes et al. [21]. Centimeter square sized hexagonal-close-packed
(hcp) MCCs were spincoated on cleaned glass substrates in a
custom-built spin-coater.
2.1.2. Preparation of catalyst films
The MCC template was transferred onto silicon substrates by
lifting off in Fe (NO3)3 aqueous solutions according to the method
given by Sun et al. [18]. The samples were then dried at 383 K for
10 min by placing horizontally in an oven. Ordered catalyst films
were obtained by subsequent heat treatment at 673 K for 8 h to
burn off the latex nanospheres and to decompose Fe (NO3)3 entirely
into Fe2O3. The calcined samples were ultrasonically washed for
20 min before sample characterization and growth of carbon
nanotubes.
2.1.3. Preparation of carbon nanotubes
Carbon nanotubes were synthesized with the growth temper-
ature of 500
C, a rf power of 50 W and a 5:2 flow of argon and
Fig. 2. SEM images of Fe2O3 porous films with a periodic spacing of 1000 nm. (A) vertical top view; (B)side view.
87
ethylene gases in a homemade rf- PECVD reactor which is described
in detail elsewhere [22]. The growth time was varied from 5 min to
45 min in order to clarify the patterned growth mechanism by
colloidal lithography and PECVD.
2.2. Material characterizations
The morphology and microstructure of catalyst films and CNTs
were performed by a field emission scanning electron microscope
(SEM, JEOL JSM-7001F) operated at an accelerating voltage of 15 kV.
The composition of the products were identified by X-ray diffrac-
tion analyzer (XRD, Rigaku D/max- 2500) using Cu Ka radiation
(l ¼ 1.5418 Å). A JEOL-2011F high-resolution transmission electron
microscopy (HRTEM) operated at 200 Kev was used to determine
the crystal structure of CNTs and Fe3C nanoparticles. The magnetic
properties of the products were evaluated using a vibrating sample
magnetometer (Lakeshore 7307) at room temperature.
3. Results and discussions
2D ordered Fe2O3 porous films were synthesized on silicon
substrates through solution dipping deposition assisted by MCC
templates. XRD confirmed that the porous films consist of crystal a-
Fe2O3, as shown in Fig. 1. Fig. 2 shows the SEM images of Fe2O3
porous films obtained by using MCC templates made of 1000 nm
colloidal spheres and 0.1 M Fe (NO3)3 aqueous solutions as the
precursor. The vertical top view of the Fe2O3 porous films show
highly ordered hexagonal close packed structure with a long-range
periodicity, as shown in Fig. 2A. The resulting thin films exhibit a
periodic spacing (i.e. the distance between the centers of two
neighboring pores) of 1000 nm, which corresponds well to the
diameter of the colloidal spheres. Interestingly, each unit takes on a
bowl-like structure in the array film, and the thickness of the bot-
tom of the bowl is relatively thin compared to the wall of the bowl,
as shown in Fig. 2B. The thickness of Fe2O3 film is between 30 nm
and 430 nm. The self-assembled ordered Fe2O3 array film was
directly applied as the catalyst layer for the growth of CNTs by
PECVD.
3.1. Effect of plasma treatment conditions on the patterned growth
of CNTs
During the PECVD process, the catalyst film was constantly
bombarded and etched by plasmas. Therefore, we investigated the
morphological and structural evolution of products to clarify the
role of plasmas. The morphology of CNTs grown at different time
was shown in Fig. 3. Fig. 3A and B displays that CNTs preferred to
grow at the center of each bowl-like structure unit. When the
88 Y. Man et al. / Journal of Alloys and Compounds 650 (2015) 86e91

Fig. 3. (A), (C), (E) and (G) are SEM images with low resolution of CNTs grown at 5 min, 15 min, 30 min and 45 min, respectively; (B), (D), (F) and (H) are the corresponding SEM
images with high resolution.
 Y. Man et al. / Journal of Alloys and Compounds 650 (2015) 86e91
Fig. 4. XRD patterns of the CNTs on silicon substrates grown at different time in the
PECVD reactor at: (a) 5 min, (b) 15 min, (c) 30 min and (d) 45 min.
carbon source was pumped in for 15 min, well aligned periodic CNT
arrays were obtained, and the CNT bundles were arranged into a
unique hexagonal lattice structure, as shown in Fig. 3C and D.
Fig. 3E and F exhibits that CNTs were entwined without any order at
the growth time of 30 min. As the growth time prolonging to
45 min, uniform vertically aligned CNT array film was deposited on
silicon substrates, as shown in Fig. 3G and H. From Fig. 3, one can
clearly see that with the increase of the growth time, the length of
carbon nanotubes had slight change while the growth site
extended from the center of bowl-like structure units to the entire
substrate. Meanwhile, the ordered Fe2O3 array film was gradually
etched away because of plasmas.
The possible patterned growth mechanism of CNTs by colloidal
lithography and PECVD is discussed as follows. The self-assembled
ordered Fe2O3 catalyst film consists of bowl-like structure units.
During the PECVD process, the catalyst film was constantly bom-
barded and etched by plasmas leading to the decrease in the size of
catalyst nanoparticles. There is a consensus in the literature that
larger particles always appear to be onionated and so are inactive
for catalysis of CNTs [23]. When the 1 mm PS monolayer was used as
the template, the catalytically active particles expanded from the
center of each bowl-like structure unit to the entire substrate,
Fig. 5. HRTEM image of the Fe3C nanoparticles encapsulated by CNTs.
89
Fig. 6. The VSM measurement curves for CNTs encapsulated Fe3C nanoparticles.
therefore, the growth site of CNTs gradually extended to all over the
substrate with increasing the growth time.
In addition to the change of the microstructure, the composition
and crystal structure of the products has also changed under the
action of plasmas. Fig. 4 shows the XRD patterns of the as-prepared
samples grown at different time. The original catalyst film was
crystal a- Fe2O3. When the carbon source was pumped in within
15 min, the products revealed weak diffraction peaks of Fe2O3,
indicating that great amount of catalyst particles have been etched
away by plasmas, as shown in Fig. 4a and b. While increasing the
growth time to 30 min, the catalyst film exhibited intense signals at
2q ¼ 44.7
, which can be assigned to Fe (JCPDS No. 3-1050), as
shown in Fig. 4c. As the growth time increasing to 45 min, there
only remain the diffraction peaks at around 2q ¼ 37.7, 39.8, 40.6,
42.9, 43.7, 44.5, 45.1, 46.0, 48.6 and 49.1
, correspond to (210),
(002), (201), (211), (102), (220), (031), (112), (131) and (221) planes
of Fe3C nanoparticles (JCPDS No. 89e2867), respectively, as Fig. 4d
displays. Thus it can be seen that the catalyst nanoparticles were
gradually reduced to Fe by plasmas, and then the dissoluted carbon
atoms combined with Fe to form a certain amount of Fe3C [24,25].
TEM images have also been used to further analyze the features
of the obtained nanocomposite. Fig. 5A shows well-crystallized
structures with lattice fringes of about 0.34 and 0.21 nm, corre-
sponding to an interplanar spacing of graphite (002) and Fe3C (211)
90 Y. Man et al. / Journal of Alloys and Compounds 650 (2015) 86e91
crystal plane, respectively. This agreed with the XRD results. The
well-aligned CNTs were quasi-continuously filled with Fe3C nano-
particles, as shown in Fig. 5B. And the Fe3C nanoparticles were in
the range of 5e20 nm in size. The magnetic properties of the CNT/
Fe3C nanocomposites were measured at room temperature by
vibrating sample magnetometer (VSM) and its hysteresis loops are
shown in Fig. 6. As can be seen that the MH curves taken with the
external field both parallel and perpendicular to the nanotube's
axis are strongly sheared, suggesting the presence of a strong
magnetostatic interaction in this system. A value of 292 Oe for Hc
was obtained when the external field is applied perpendicular to
the nanotube's axis. The coercivity shifts to 250 Oe when the field
paralleling to the nanotube's axis. The experimentally found mag-
netic anisotropy of the aligned Fe3C-filled CNTs may be attributed
to the following two factors. Firstly, the quantity of iron carbides
along the tube direction is less compared to the surface direction.
Therefor, the nanocomposite shows weaker magnetic property
when the external field along tube direction. Generally, this factor
was neglected when analyzing the magnetic anisotropy of Fe or
Fe3C filled CNTs [26,27]. Secondly, large shape anisotropy [28] and
magnetocrystalline anisotropy contribution [29] should be
responsible for the magnetic anisotropy of the CNT/Fe3C nano-
composites. Which mechanism plays a key role need to be further
studied. Nevertheless, iron carbides exhibit excellent properties
compared with iron or iron oxide nanoparticles [30e32] due to
carbon atoms occupying the interstices between close-packed iron
atoms [33]. Therefore, the proposed synthesis route could facilitate
the direct fabrication of CNT/Fe3C nanocomposites for applications
in catalysis, electrochemistry and solar cells.
Fig. 7. SEM images of Fe2O3 porous films and CNTs with different concentrations of precursor solution: (A) and (C) 0.05 M; (B) and (D) 0.005 M. The inset is the side view of Fe2O3
porous film.
3.2. Effect of the concentration of the precursor solution on the
patterned growth of CNTs
We also investigated the effect of the concentration of the
precursor solution on the morphology of CNTs. Fig. 7A and B shows
the morphology of Fe2O3 porous films obtained through a 0.05 M
and 0.005 M Fe (NO3)3 aqueous solution as the precursor, respec-
tively. Combined with Fig. 2, it can be seen that with the concen-
tration of the precursor decreasing, the thickness of the Fe2O3
porous film gradually decreased. If the solution concentration is
reduced to a very level (0.005 M), Fe2O3 nanoparticles are mainly
present at the interstitial position of the closely packed 3-spheres
[18]. Fig. 7C and D shows the morphology of CNTs grown at 15 min
in the PECVD reactor. When the solution concentration is reduced
to 0.05 M, carbon nanotubes were preferentially formed at the
center of each bowl-like structure unit, which is consistent with
Fig. 3D because the morphology of Fe2O3 porous film had no big
change. When the solution concentration is reduced to 0.005 M,
CNTs preferred to grow at the interstitial position of nanospheres,
and thus CNT bundles were arranged into a unique periodic
structure, as shown in Fig. 7D. Therefor, the growth site of CNTs can
be flexibly adjusted by the concentration of the precursor solution.
4. Conclusions
In summary, we have synthesized patterned carbon nanotube
arrays by colloidal lithography and PECVD on silicon substrates.
Catalyst seed layers were one-step self-assembled on silicon sub-
strates by solution dipping deposition assisted by MCCs,
 Y. Man et al. / Journal of Alloys and Compounds 650 (2015) 86e91
eliminating the need for expensive lithography and physical vapor
deposition. The growth site and density of CNTs were determined
by the concentration of the precursor solution and plasma treat-
ment conditions. We also discussed the formation mechanism of
patterned carbon nanotube structures. This work further demon-
strated that colloidal lithography is a simple, feasible and efficient
method to prepare patterned nanostructures. The proposed strat-
egy can also be applied to synthesize CNT/Fe3C nanocomposites
and other CNT supported nanoparticle composites, which will have
more potential applications.
Acknowledgments
This work was financially supported by National Natural Science
Foundation of China (No. 51302227) and Fundamental Research
Funds for the Central Universities (No. XDJK2015B017).
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