Control of Cobalt Catalyst Thin Film Thickness by Varying Spin Speed in Spin Coating towards Carbon Nanotube Growth.

Applied Mechanics and Materials Vol. 761 (2015) pp 421-425
© (2015) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMM.761.421

Submitted: 12.11.2014
Accepted: 12.11.2014

Control of Cobalt Catalyst Thin Film Thickness by Varying Spin Speed
in Spin Coating towards Carbon Nanotube Growth
Nor Najihah Zulkaplia, Mohd Edeerozey Abd Manaf,
Hairul Effendy Ab Maulod, Nor Syafira Abdul Manaf,
Raja Noor Amalina Raja Seman, Mohd Shahril Amin Bistamam,
ElyasTalib and Mohd Asyadi Azamb
1

Carbon Research Technology Group, Faculty of Manufacturing Engineering, UniversitiTeknikal
Malaysia Melaka (UTeM),Hang Tuah Jaya, 76100 Durian Tunggal, Melaka, Malaysia
a

m051320004@student.utem.edu.my, basyadi@utem.edu.my


Keywords : Cobalt catalyst, Thin films, Spin coating, Catalytic chemical vapor deposition

Abstract. Cobalt (Co) catalyst thin film is an active metal catalyst that can be very helpful to grow
carbon nanotubes (CNTs). The catalyst thin films were prepared on silicon wafers by spin coating
the solution of cobalt acetate tetrahydrate and ethanol. The effects of different spin speed parameter
during the spin coating process were investigated. The findings showed that the optimum thickness
of the Co catalyst thin films, i.e., 12.1 nm, was obtained at the highest spin speed of 8000 rpm. The
uniformity of the thin films was also found to increase with increasing spin speed. The study also
demonstrated that single-walled carbon nanotubes could be grown from Co catalyst particles after
the catalytic chemical vapor deposition of ethanol. The particle and thickness analysis, as performed
by means of FESEM while the existence of CNTs, was performed by Raman spectroscopy.
Introduction
The synthesis of carbon nanotubes (CNTs), especially single-walled carbon nanotubes
(SWCNTs), by the catalytic chemical vapor deposition (CCVD) method has been widely studied
due to their extraordinary electrical, mechanical, and thermal properties, accompanied with cost
effective and good quality of CNTs produced [1]. The transition metals such as Fe, Ni and Co have
been extensively employed as the metal catalyst in the synthesis of SWCNTs by this method
[2,3].These metals have high solubility of carbon at high temperature and high diffusion rate –
features which are very helpful during the CNT growth process. The catalyst particles formed on
the substrates provide active sites for the nucleation of CNTs, and the size of catalyst particles

vigorously corresponds to the diameter of CNTs produced [4].In order to attain a smaller diameter
of CNTs, the size of particles can be controlled by controlling the thickness of catalyst thin films on
the substrates. SWCNTs can be grown from the catalyst particles that have diameters in range of 34 nm [5].
Other than arc-discharged and laser ablation, physical vapor deposition (PVD) is one of the
attractive techniques to deposit catalyst thin films onto selected substrates. Smaller and more
uniformed thickness of catalyst thin films can be easily attained by the PVD technique. Several
studies have been reported regarding the formation of catalyst thin films thickness less than 1.0
nm[6,7]. However, the employment of PVD leads to the cost ineffectiveness in the electronic
devices manufacturing due to the need of high power of electrical supply in order to provide a
vacuum condition in the system. Thus, other deposition techniques, spin coating [8-10], dip-coating
[11,12], spray coating [13] and patterning [14], which are based on the solution-based catalytic
precursors have been progressively prominent to gain uniformed thin films. Out of these techniques,
spin coating is extensively investigated due to the easy and simple technique to form uniformed
catalyst thin films that will contribute to the direct growth of CNTs onto the substrates. It also
allows obtaining smaller thickness of thin films. With those merits, it has high potential to produce
CNTs for the use in the development of high performance electrochemical capacitor [15].

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Recent Technologies in Design, Management and Manufacturing

In this paper, the effect of spin speed on thickness of Co catalyst thin films produced by spin
coating technique is investigated. The main aim for this research is to achieve smaller thickness of
thin film which will be used to grow CNTs on the silicon substrates. The thickness of Co catalyst
thin films over various spin speed of spin coating is studied. The ability of the produced Co catalyst
particles to grow CNTs on the substrates is also discussed.
Experimental
Co catalyst thin films were prepared by diluting Co acetate tetrahydrate,
Co(CH3COOCH)2.4H2O, in absolute ethanol to produce a solution with a concentration of 16.8
mmol/L. The solution was continuously stirred for 12 hours and left for 36 hours aging. The silicon
wafer of 101.6mm diameter, with one sided polished and 1000 Å thermal oxide layer, was used as
substrate. The substrate was cut into squares of 15x15 mm2. Next, the wafers were rinsed with
acetone and stirred with ethanol for 10 min for cleaning purpose. Then, the cleaned wafers were
dried with nitrogen gas.
Co acetate tetrahydrate/absolute ethanol solution was spin-coated on the cleaned silicon wafer at
spin speed of 6500, 7000, 7500, 8000 rpm for 60 s. The coated wafers were quickly pre-heated at
250°C for 5 min to vaporise the solvent, leaving Co catalyst thin films on the wafers. Then the preheated wafers were placed in a vacuumed furnace for heat treatment process of 450°C, 500°C,

550°C and 600°C for 10 min to obtain Co catalyst nanoparticles.
The smallest and most uniform thickness of Co catalyst thin film was then employed to study the
ability of that catalyst thin film to grow carbon nanotubes by CCVD at 725°C for the growth
duration of 15 min. The CCVD system was allowed to cool to room temperature under the argon
flow after the reaction. A field emission scanning electron microscope (FESEM, Hitachi SU8100,
HTI lab, Selangor) was used to analyze the obtained samples at 5.0kV. Raman analysis was
performed by RenishawInViaRaman Microscope (Wotton-under-Edge, UK) with laser excitation of
632.8 nm wavelength HeNe laser.
Results and discussion
In order to investigate the dependence of thickness of Co catalyst thin films on spin speed of spin
coating, four different spin speeds parameter were used for the coating of Co catalyst solution on
the substrates. The resulted films were characterized by FESEM as shown in Fig. 1(a) to (d). A
variation in the thin film thickness obtained showed that the deposited thin films were in continuous
pattern. As the spin speed was increased from 6500 to 8000 rpm, the thin film thicknesses were
decreased from 25.5 nm to 12.1 nm (Fig. 2(a)-(e)).These results indicate that increasing the spin
speed rotation effectively decreases the thickness of thin film deposited on the silicon substrate. The
thinning process is due to the developed centrifugal force that causes shear thinning of the precursor
solution to form a film layer on top of the substrate. The thickness of thin film plays an important
role because it determines the depth of the stacked particle on top of each other which affects the
surface roughness and the uniformity of the particle distribution all over the surface of the substrate.

If the thickness of the thin film is increased, there will be more stacking of particles, which causes
non uniformed particle distribution on the substrate.
(a)

(b)

Applied Mechanics and Materials Vol. 761

(c)

423

(d)

(a)

n=30

Thickness (nm)


(d)

Average thickness
(nm)

Number of counts

Thickness (nm)
n=30

(b)

Number of counts

n=30

Number of counts

Number of counts


Fig. 1 FESEM micrographs of Co catalyst thin films at the spin speed of (a) 6500 rpm, ( b)
7000 rpm, (c) 7500 rpm, (d) 8000 rpm. The samples are cross-sectional, tilted to 45° and in
different scales.
n=30

(c)

Thickness (nm)
(e)

30
20
10
0
6500

7000

7500


8000

Spin speed (rpm)

Thickness (nm)
Fig. 2 The histograms of Co catalyst thin films thickness with the spin speed of (a) 6500 rpm,
(b) 7000 rpm, (c) 7500 rpm, (d) 8000 rpm and (e) graph of average thickness of Co catalyst thin
films at four different spin speeds.
The catalyst thin film with the smallest thickness which was obtained at 8000 rpm of spin speed
was selected for the CCVD process to grow CNTs in order to prove that the deposited Co catalyst
can be used for the CNT growth. The result of Raman spectroscopy analysis as shown in Fig. 3
shows that single-walled CNTs are successfully grown on the substrate. Using the results of Raman
analysis, the structural properties of as-grown CNTs were also studied. The Raman spectrum of the
sample exhibits peaks of the radial breathing mode (RBM) from 100 to 350 cm-1, which reveal the
presence of SWCNTs, a D-band at approximately 1326 cm-1, and a G-band at approximately
1587cm-1 (Fig. 3). The quality of the CNTs can be assessed by calculating the intensity ratio of the
G band to D band (IG/ID). The (IG/ID) ratio of this sample was 1.71, indicating that the as-grown
CNTs have small portion of structural defects.

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Recent Technologies in Design, Management and Manufacturing

7000
6000
5000
Counts

4000

SWCNTs

3000

D-band
(1326 cm-1)

G-band
(1587 cm-1)


2000
1000
0
-1000

0

500

1000

1500

2000

2500

3000

Raman shift / cm-1


Fig. 3 Raman spectrum of the as-grown CNTs on the Co catalyst thin film obtained by spin
coating at 8000rpm.
Conclusion
The Co catalyst thin film produced from the spin coated of 16.8 mmol/L solution of cobalt
acetate tetrahydrate and ethanol at 8000 rpm for 60 s was found to have the smallest thickness of
thin film with uniformed thickness. As mentioned earlier, the size of catalyst particles can be
controlled by controlling the thickness of catalyst thin films. In order to obtain a smaller size of
catalyst particles, the favored thickness of thin films is as small as possible. This condition leads to
the growth of SWCNTs since SWCNTs can be grown from the catalyst particles that have
diameters in the range of 3-4 nm. The potential of SWCNTs to grow on this catalyst thin film by
ethanol CCVD was proven by the Raman spectrum of the sample that exhibited peaks of the RBM
from 100 to 350cm-1, which reveal the presence of SWCNTs.
Acknowledgements
Special thanks to Carbon Research Technology (CRT), UTeM group for continuous mutual
support and knowledge proof-read. The authors are also grateful for the financial support by the
Ministry of Higher Education (MOE), Malaysia under the Exploratory Research Grant Scheme
(ERGS) with research grant numbered E00032.
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