Investigation of C60 films for surface finishing applications

Ahalapitiya H. Jayatissaa*, Arunan Nadarajahb and Achyut K. Duttac

a
Department of Mechanical, Industrial, and Manufacturing Engineering,
b
Department of Chemical and Environmental Engineering
The University of Toledo, Toledo, OH 43606, USA.
c
Banpil Photonics Inc., Suite 400, 2953 Bunker Hill Lane, Santa Clara, CA 95054, USA.
*E-mail: ajayati@utnet.utoledo.edu.

ABSTRACT

The thin films of C60 fullerenes were investigated as a coating material in surface finishing applications. The films were
coated by vacuum evaporation on glass and silicon substrates. These films were annealed in oxygen ambient and
exposed to a oxygen plasma. The C60 films coated substrates were also kept immersed in water and NaOH for a long
time and tested for mechanical and optical properties. It was found that the optical properties and bulk properties were
stable or modified favorably for surface finishing applications during these treatments. Though low temperature heating
resulted in densification of C60 films, higher temperature above 300 oC resulted in graphitization in oxygen ambient.
These findings indicated that the thin films of C60 can be used as a corrosion resistive coating and UV cutting surface
material below 300 oC.

Keywords: C60 Fullerenes, thin films, oxygen plasma, optical transparency, X-ray diffraction, atomic force microscopy

1. INTRODUCTION

The C60 fullerenes attracted global interest as a nanostructured material. Thin films of C60 have been fabricated by
vacuum evaporation and other mass transport methods such as molecular beam evaporation (MBE), laser ablation and
spray coating. Intensive research has been carried out to fabricate organic electronic devices such as thin film transistors
(TFTs) for liquid crystal display device applications [1-5]. Though C60 films exhibit extremely high carrier mobility
compared with other organic materials tested for the same applications, the stability of electronic properties of C60 thin
films in oxygen atmosphere is extremely poor. This phenomenon hindered the possibility of using C60 in electronic
devices like in TFTs. Numerous fundamental studies can be seen in the literature regarding application of C60 for
synthesis of hard materials, drug delivery and storage, and photovoltaic applications [1-8].

Besides significant academic interest, the application of C60 in a significant commercial product is unknown. Such
structural material has been used to fabricate composites. For example, carbon nanotubes are under investigation for
unlimited applications because of their excellence electronic properties, mechanical strength as well as modification
capability in doping and addition of molecules. When the properties of C60 are compared with carbon nanotubes, no such
special property can be achieved using C60.

In this paper, we have investigated the thin films of C60 as a surface finishing material. In order to satisfy the surface
finishing coating applications, the material must be very stable under atmospheric conditions having mechanically
robust, chemically stable, and attractive finishing. In addition, desired properties such as optical properties, corrosion
resistivity, and chemical stability are very important depending on the coating application. Carbon materials are well
known for low friction and hard coating applications. For instance, diamond-like carbon (DLC) has been investigated for
many surface finishing uses such as tribology, ultra-low friction, and passivation coating material [6-10]. In this study,
we have investigated the variation of properties of C60 thin films by exposing them to different treatments such as
extremely high alkaline aqueous medium, oxygen rf-plasma, and heating in ambient conditions. The properties of
exposed C60 films for different conditions were compared with those of as-deposited C60 films. The thin films of C60 can
be coated using evaporation method on very large area substrates. Vacuum evaporation is known as a low cost technique
for large-area surface finishing applications. Also, the amount of C60 needed to coat large-area is very small and

Nanofabrication: Technologies, Devices, and Applications II

edited by Warren Y.-C. Lai, Leonidas E. Ocola, Stanley Pau
Proc. of SPIE Vol. 6002, 60021A, (2005) · 0277-786X/05/$15 · doi: 10.1117/12.631051

Proc. of SPIE Vol. 6002 60021A-1

therefore, the application of C60 for coating can be acceptable in economical viewpoint. Moreover, one of the draw backs
of C60 is that the interaction of C60 with oxygen which results in the creation of trapping centers. These trapping centers
reduce the flow of free carries through C60 films. We believe that the latter reason can be an added advantage in surface
finishing coating application because the coating of electrically inactive layers on surfaces may prevent oxidation and
reactivity in hazardous chemical environments.

2. EXPERIMENTAL PROCEDURE

High purity C60 fullerene powder (99.9+ %, Alfa Aesar) was evaporated using a tantalum boat filament in a high vacuum
chamber (pressure <10-6 Torr). During the deposition process, the filament temperature did not exceed 420 oC. C60
powder remaining in the filament after a deposition run was found to have C60 structure similar to as-received powder
indicating that the C60 powder did not decompose during heating process. The distance between the substrate and the
filament was around 12 cm. This long distance between substrate and filament produced quite uniform films. The films
were deposited on the surfaces of clean non alkaline glass substrate, Si wafers, transparent conductive substrate
(Indium–Tin-Oxide [ITO] coated glass) and stainless steel (SST) foil surfaces.

The C60 films deposited on glass and Si substrates were exposed to the oxygen plasma. The plasma was produced using
13.56 rf plasma system under 20 mTorr pressure and room temperature for 120s. The films were also annealed at 100
o
C, 200 oC, 300 oC and 400 oC temperatures in air for 3 hours. Some of the as-deposited films were kept immersed in
30% NaOH (aq.) solution for 14 days. The structure, degree of crystallinity and surface properties of C60 films were
investigated using Raman spectroscopy (Excitation 633nm), X-ray diffraction (XRD, Cu, Kα radiation, 100 mA, 40 kV)
and atomic force microscopy (AFM) measurements. The optical transmittance in UV/visible range was measured with a
double beam spectrophotometer (Shimadzu). Scratch testing was carried out to determine the adhesion and mechanical
properties of C60 coated on the optical fiber surfaces. The adhesion was measured using an elcometer (pull off testers).

3. RESULTS AND DISCUSSION

3.1 As-deposited films

The structure of deposited films was investigated using the XRD and Raman spectroscopy. Fig. 1 shows the XRD
spectra of as-deposited C60 film on a glass substrate. All the peaks in this spectrum are corresponding to the
polycrystalline C60 films. This result indicated that the deposition of C60 by vacuum evaporation formed crystalline C60
on a cold substrate. Raman spectra of C60 has a peak at 1469 cm-1 due to the Ag(2) band [11]. The Raman spectrum of as-
deposited film has a peak centered at 1467 cm-1 corresponding to the Ag(2) band. Other workers have also reported the
strong feature corresponding to Ag(2) band at 1467 cm-1.
Intensity (a.u.)

0
5 15 25 35 45 55 65 75
2Q (deg.)
2θ (deg.)
Fig. 1. XRD pattern of as-deposited C60 films (Cu Kα, 100 mA, 40 kV).

Proc. of SPIE Vol. 6002 60021A-2

3.2. Testing of mechanical properties

The C60 films coated glass substrate was tested with adhesion tester. The epoxy layer was employed to remove the film
using an elcometer (adhesion testing equipment). We could remove the film very well from the glass substrate as shown
in Fig.2. The force indicated in the adhesion tester was 15 Mpa/3 cm2. These results show that the adhesion properties
between glass and the C60 films were quite strong. Furthermore, we have compared the adhesion testing results of ITO
(indium tin oxide) films coated by rf magnetron sputtering method. The adhesion between glass and sputter deposited
ITO layer was 18 Mpa/3 cm2.

(a) (b) (c)

Fig. 2. (a) Preparation of sample for adhesion testing, (b) substrate after removal of C60 film and (c) removed film stacked on to the
epoxy layer.

3.3 Films treatment with NaOH

The films coated on glass and SST were kept immersed in aqueous 30% NaOH for 14 days. After 14 days, these films
were rinsed with deionized water and tested for mechanical (adhesion) and optical properties. It was observed that the
adhesion and optical properties if C60 films were unchanged by exposure to the alkaline solution. The optical
transmittance spectra indicated that the immersing did not damage any surface or create defects in the films. The
adhesion test indicated that we were obtaining the same strength of adhesion between the C60 film and substrate.
Stability of C60 for alkaline solution is a very important property for coating applications.

3.4 Plasma treated surfaces

The C60 films coated surfaces were exposed to oxygen plasma made in a radio frequency (13.56 MHz) parallel bed
reactor at room temperature. The films were studied after and before plasma treatment using optical transmittance
measurements in UV/visible range. The optical transmittance spectra are shown in Fig. 2 for the films with and without
exposing to the plasma treatment. It can be seen that the oxygen plasma treatment results in slight modification of optical
transmittance through the film. After plasma treatment, the optical transmittance has been slightly increased in visible
light region and the absorption gap is slightly shifted to a higher wavelength. These two phenomena can be attributed to
the slight change of film thickness due to etching of C60 surface by plasma oxygen. When the film thickness is reduced,
the transmittance is increased and the optical absorption gap can be slightly shifted. The transmittance of plasma treated
film has slightly increased in the UV region close to 230 nm. The reason for such phenomena is unknown at present.

The surface morphology of C60 films were investigated with atomic force microscopy (AFM) before and after the plasma
treatment. The AFM images are shown in Fig. 5. The AFM images indicated that the plasma treated film has a lower
roughness than as-deposited film. It is known that oxygen can penetrate into the C60 lattice and act as charge trapping
centers even in oxygen atmosphere [13]. When the films were treated with oxygen plasma, the saturation of cavities with
oxygen is possible. These facts lead the high resistivity of films.

It is known that the outer layer of diamond is graphitic carbon layer due to the atmospheric oxidation for a long time.
Moreover, oxygen plasma convert diamond surface into graphite and therefore, the conductivity of surface layers has
been increased. However, the dependence of C60 surface in oxygen plasma is very different from DLC and Diamond

Proc. of SPIE Vol. 6002 60021A-3

films. In the presence of oxygen, the C60 surface becomes more stable and acquires insulating properties. This interesting
property can be applied in the places where high insulation is required.

It was observed that the C60 films have extremely high resistivity after plasma treatment. High resistivity results in
storage of statistical charges in these films and we could not take better quality AFM images. On the other hand, our
AFM measurements were able to get high quality images of many samples which have relatively high conductivity
[compare Fig.5(a) and (b)].

100
90
80
70
60
As-deposited
T%

50
O2 plasma treated
40
30
20
10
0
200 300 400 500 600 700 800 900
Wavelength (nm)
Fig. 3. optical transmittance spectra of as-deposited and oxygen plasma treated C60 film coated on glass substrate.
(measurements were carried out using a double beam spectrophotometer using a bare glass substrate as the
reference.

25000
7000

6500

20000 6000

5500

5000

14 0 0 14 2 0 14 4 0 14 6 0 14 8 0 15 0 0
Intensity (a.u.)

15000
W a v e N umbe r ( c m- 1 )

10000

5000

0
50 250 450 650 850 1050 1250 1450 1650 1850
Wavenumber (cm-1)

Fig.4. Raman spectra of thin C60 film after and before placing in Oxygen plasma. The both spectra are identical indicating that the
structure of bulk region of C60 film was unchanged. The insert is the Raman peak corresponding to C60 structure. (The film
was coated on Si substrate and Raman spectra has Si-peak at 520 cm-1 and 940 cm-1.

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 Z-rangE 31 9Onm

Li

-492 0493 493 4493

1<-range. 986nm 4<-range. 989nm

(a) (b)
Fig.5. AFM images of as-deposited (a) and oxygen plasma treated (b) C60 films.

3.5 Heat treated surfaces

We have investigated thermal annealing effect of the structure of C60 films using Raman spectroscopy. The Raman peak
of C60 has been shifted to 1469 cm-1 for all annealed films in contrast to the Raman band of as-deposited film (1467 cm-
1
) (See Fig.6). The red shift of Raman band can be attributed to the residual stress developed during the formation of the
films. The Raman spectra of these films indicated that the Ag(2) peak position did not change by annealing above 100 oC.
However, the FWHM of Raman bands are increased with the increase of annealing temperature above 100 oC. Further
annealing results in the development of larger grains and therefore, the development of grain boundaries. Moreover, the
full width at half maximum (FWHM) of 100 oC annealed film is the smallest among Raman bands (See Fig.6). These
results indicate that the microstructure of C60 films can be modified by heat treatment at low temperature. The C60 films
annealed at 400 oC and high temperature exhibited D and G band of corresponding to the microcrystalline graphite.
Furthermore, the mechanical property of high temperature annealed films was degraded. It was also found that the film
surfaces were uniform for high temperature annealed films but the film thickness was reduced gradually with increase of
annealing time or temperature. This latter phenomenon is attributed to the sublimation of the film and removal from the
substrate surface.
Relativeintensaity(a.u.)

as-depo

100 C

200 C

300 C

1450 1455 1460 1465 1470 1475 1480

Raman Shift (cm-1)

Fig. 6. Change in Raman intensity of C60 films with annealing temperature (Excitation λ = 630 nm. Annealing
temperature is given at the curves).

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Figure 7 compares the surface morphology of as-deposited film with films annealed at 100, 200 and 300 oC. A clear
difference can be seen between as-deposited and annealed samples. The film annealed at 100 oC shows close packed
small grains with a uniform distribution. The films annealed at 200 oC and 300 oC have slightly larger grains than 100 oC
annealed films. Furthermore, the grain boundaries clearly appeared after annealing at a higher temperature than 100 oC.
The surface roughness is reduced with the increase of temperature as expected.

(a) (b)

(c) (d)

Fig. 7. AFM images of as-deposited C60 films on glass substrate. annealed at different temperatures: (a) as-deposited; (b)
film annealed at 100 oC; (c) film annealed at 200 oC; and (d) film annealed at 300 oC.

4. CONCLUSIONS

Coating of C60 fullerenes films as a surface finishing material was investigated. The evaporation based coating which is
economical and simple for large-area and frequent application was employed in this project. As a coating material,
several important factors such as exposure to hazardous environments, thermal effect, adhesion and attractive finishing
were investigated. It was found that the C60 films coated by thermal evaporation have important properties: (i) exposure
to hazardous and reactive atmosphere, such as oxygen plasma and NaOH solution, did not change the bulk properties of
C60 films significantly, (ii) the film adhesion on non-reactive surfaces was in an acceptable range, and (iii) thermal
stability of films were excellent up to 300 oC. Furthermore the optical absorbance edge of C60 films is near 350 nm.
Based on our experimental results, we conclude that the C60 films can be potential coating material for industrial
applications requiring corrosive resistivity and good stability at elevated temperatures.

ACKNOWLEDGEMENTS

This project was partially supported by a grant provided by National Science Foundation (ECS-0403930).

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