Temperature Dependence of Sputtered Conductive Carbon Thin Films Bull. Korean Chem. Soc. 2011, Vol. 32, No.

Vol. 32, No. 3 939

DOI 10.5012/bkcs.2011.32.3.939

Temperature Dependence on Structural, Tribological, and Electrical Properties of

Sputtered Conductive Carbon Thin Films
Yong Seob Park,* Byungyou Hong,† Sang-Jin Cho,‡ and Jin-Hyo Boo‡,*

Department of Electrical and Electronic Engineering, Seonam University, Namwon 590-711, Korea
*
E-mail: [email protected]
†
School of information and communication Engineering, Sungkyunkwan University, Suwon 440-476, Korea
‡
Department of Chemistry, Sungkyunkwan University, Suwon 440-746, Korea. *E-mail: [email protected]
Received December 28, 2010, Accepted January 13, 2011

Conductive carbon films were prepared at room temperature by unbalanced magnetron sputtering (UBMS) on
silicon substrates using argon (Ar) gas, and the effects of post-annealing temperature on the structural,
tribological, and electrical properties of carbon films were investigated. Films were annealed at temperatures
ranging from 400 °C to 700 °C in increments of 100 °C using a rapid thermal annealing method by vacuum
furnace in vacuum ambient. The increase of annealing temperature contributed to the increase of the ordering
and formation of aromatic rings in the carbon film. Consequently, with increasing annealing temperature the
tribological properties of sputtered carbon films are deteriorated while the resistivity of carbon films
significantly decreased from 4.5 × 10−3 to 1.0 × 10−6 Ω-cm and carrier concentration as well as mobility
increased, respectively. This behavior can be explained by the increase of sp2 bonding fraction and ordering sp2
clusters in the carbon networks caused by increasing annealing temperature.
Key Words : Conductive carbon film, Rapid thermal annealing, Magnetron sputtering, Tribological property,
Carrier concentration and mobility

Introduction is desirable to fabricate the hydrogen-free and dense

conductive carbon films for the application to the electrodes
Amorphous carbon (a-C) and hydrogenated amorphous in the electronic devices such as organic thin film transistor
carbon compounds (a-C:H) have attracted attention due to (OTFT), dye-sensitized solar cell (DSSC), and field emission
their tribological and physical properties such as high display (FED). The synthesized carbon films were annealed
hardness, low-friction coefficient, good wear resistance, at 400, 500, 600, and 700 oC by a vacuum furnace in vacuum
chemical inertness, and optical transparency.1-4 These films ambient, and the effects of annealing temperature on struc-
are used in a wide range of applications such as magnetic tural, tribological, and electrical properties were investigated.
storage disks, cutting tools, and optical windows. Further-
more, carbon-based films show high thermal stability, which Experimental
makes it possible to use them as protective coating materials
in high temperature applications. However, these films have The carbon films were deposited on a 2 cm × 2 cm p-type
limited adhesion to substrates due to high intrinsic com- (100) silicon substrate using an unbalanced magnetron
pressive stress. It is not easy to deposit carbon-based films sputtering (UBMS). The graphite (99.99%) and high purity
with low compressive stress, high hardness, and high film argon (99.99%) were used as the sputtering target and the
thickness simultaneously; the usual deposition conditions for sputtering gas, respectively. Silicon substrates were cleaned
diamond-like carbon (DLC) films result in films with high using the usual RCA method and the background pressure of
intrinsic residual stress between the substrate and the film. the process chamber was evacuated below 3 × 10−4 Pa using
The presence of large residual stresses leads to film failure diffusion pumps. The target power density was 20 W/cm2,
and restricts the thickness of DLC films that will adhere to and the working pressure was 0.4 Pa. Under these condi-
substrates. Residual stress can be minimized by annealing at tions, 150 nm-thick carbon films were synthesized at room
a suitable temperature over a sufficiently long time.5-7 temperature with a −200 V DC bias voltage. The fabricated
In this study, an unbalanced magnetron sputtering (UBMS) films were annealed for 30 min (5 °C /min) at 400, 500, 600,
method was used to prepare carbon films with a graphite and 700 °C by using a vacuum furnace [Lenton 1200 Atmo-
target in Ar gas and room temperature conditions. The sphere Tube Furnace; LAH-12/300] in vacuum ambient.
UBMS can raise the plasma density of the substrate though Internal structure was characterized by Raman spectro-
the selective strengthening of the magnetic field of the target metry [Jasco, MRS-300] and X-ray photoelectron spectro-
ends, so that more of the secondary electrons can escape scopy [VG MICROTECH, ESCA-2000]. Surface morpho-
their confinement and effectively enhanced the sputtering logy and Root mean square (Rms) surface roughness were
rate and film density. Therefore, the use of UBMS technique observed using atomic force microscopy [Seiko, SPA-400].
940 Bull. Korean Chem. Soc. 2011, Vol. 32, No. 3 Yong Seob Park et al.

Hardness was measured using a commercial nano-inden- G peak decreased with increasing annealing temperature,
tation instrument [Nano-indenter XP] with a continuous corresponding to an increase in the sp2 bonding contents.
stiffness method (CSM) option. Friction coefficients were Also, ID/IG is increased with increasing annealing temper-
analyzed using a ball-on disk (BOD) tribometer in normal, ature. In Raman spectra, D peak height should increase due
dry ambient against a polished AISI 52100 steel ball with a to transformation of disordered rings to ordered six-fold
diameter of 4.72 mm and sliding speed of 60 rpm. Film rings and the G peak relates only to bond stretching of sp2
stress and the adhesion value were confirmed using a residual pairs, so it retains its intensity, and the ID/IG ratio increases
stress tester [J&L Tech. JLCST022] and a nanoscratch tester with increased ordering.8-10 Therefore, the increase of an-
[J&L Tech. JLST022]. The electrical properties of annealed nealing temperature contributed to the increase of the order-
carbon films are investigated by Hall measurement [ECOPIA, ing and formation of aromatic rings, indicating sp2 contents
HMS-3000]. and sp2 clusters in the carbon film. At the temperature of 700
o
C, however, the D peak intensity and ID/IG ratio increase
Results and Discussion sharply. These results are related to the graphitization of
carbon films in response to removal of the disordering and to
Raman spectra of the carbon films annealed with increas- breakdown of the domain in sp2 clusters.
ing annealing temperature are shown in Figure 1(a). The Figure 2(a) shows the C1s peak in XPS spectrum for the
G-peak position and the intensity ratio of the two peaks (ID/ as-deposited carbon film and Figure 2(b) exhibits the
IG), observed by deconvoluting Raman spectra into two variation in sp3/sp2 bonding ratio according to annealing
Gaussian curve fits in order to obtain quantitative infor- temperature. The C1s XPS spectra were deconvoluted into
mation on sp3 content, are shown in Figure 2(b). From the two components with binding energies of 284.4 eV (sp2
Raman spectrum for as-deposited carbon film, the spectra C=C) and 286.8 eV (sp3 C-C).10,11 The sp3/sp2 bonding ratio
show two broad peaks centered at 1548 cm−1 and 1376 cm−1, decreased with increasing annealing temperature. These
which are assigned to G- (graphite) and D- (disorder) modes, results show the increase of sp2 components with increasing
respectively. G peak position in annealed carbon films annealing temperature.10-12 Consequently, the increase of
moved to higher wavenumbers and the FWHM width in annealing temperature leads to greater ordering of the inner

Figure 1. (a) Raman spectra of carbon films prepared at various Figure 2. (a) The C1s peaks in XPS spectrum of as-deposited
annealing temperatures and (b) the variation in G-peak position and carbon films and (b) the variation in sp3/sp2 bonding ratio as a
ID/IG ratio as a function of annealing temperature. function of annealing temperature.
Temperature Dependence of Sputtered Conductive Carbon Thin Films Bull. Korean Chem. Soc. 2011, Vol. 32, No. 3 941

Figure 4. The variation in rms roughness and friction coefficient of

carbon films prepared at different annealing temperatures with
inserted AFM topography images of carbon films prepared at as-
deposited and 700 oC annealing temperature.

in the sp2 clusters and is associated with a reduction of stress

due to the decrease of defect density.14,15 Therefore, the
increasing annealing temperature improves the intrinsic
stress of the films, but leads to a decline in hardness and
adhesion.
Figure 4 shows the variation in surface roughness and
friction coefficient as a function of annealing temperature.
The surface of the sputtered carbon films is ultra smooth due
to the resputtering effect of energetic ions by negative DC
Figure 3. (a) Hardness and elastic modulus, and (b) residual stress
bias voltage, and this would be considered to be related to
and critical scratch load of carbon films as a function of annealing the increase of sp2 bonding contents at the film surface. As
temperature. shown in Figure 4, however, the increase of annealing
temperature led to rougher surfaces and increased friction
coefficients. The degradation in surface morphology and
structure of clusters in the carbon matrix. friction coefficient are associated with the clustering of sp2
In this study, the as-deposited carbon film prepared by carbon,16 as revealed by Raman and XPS investigations.
UBMS method exhibited high hardness of about 25 GPa, Also, the rough surface and high friction coefficient in high
resulting in a structure of cross-linked sp2 clusters caused by annealing temperature are associated with the ordering sp2
the bombardments of high energetic ions.4,13 This means clusters and the graphitization in carbon films.12 Conse-
that the hardness of carbon film is dependent on the quently, the annealing temperature can affect the surface and
degree of disorder cross-linked bonds in carbon network. As density in film with the change of the film structure.12,14
shown in Figure 3, however, the hardness and elastic Figure 5 shows the resistivity, carrier concentration, and
modulus of carbon films are decreased with increasing
annealing temperature, corresponding to an increase in the
sp2 contents with the formation of aromatic rings, as reveal-
ed by Raman and XPS investigations. Specially, at the
annealing temperature of 700 oC, the hardness of carbon film
is sharply decreased. These indicate that the increasing
annealing temperature is associated with an the ordering of
sp2 clusters in the film, and high temperature in 700 oC
finally led to the change to a graphite-like structure.12,14,15
Also, the adhesion behavior of carbon films decreased with
increasing annealing temperature, indicating an increase in
ordered sp2 clusters in the carbon networks and a decrease
in cross-linked bonds between the film and substrate.7,14
However, intrinsic stress gradually decreased with increas-
ing annealing temperature. Thus, the increase of annealing Figure 5. The variation of the resistivity, carrier concentration, and
temperature leads to structural relaxation related to ordering Hall mobility of carbon films as a function of annealing temperature.
942 Bull. Korean Chem. Soc. 2011, Vol. 32, No. 3 Yong Seob Park et al.

carrier mobility of carbon films as a function of annealing roughness. However, it is attributed to the improvement of
temperature. The as-deposited carbon film prepared at the the stress and conductivity in the film, reflecting that
low temperature showed the conductive properties such as annealing of conductive carbon film will largely influence
low resistivity about 4 × 10−3 Ω·cm, high carrier concen- for the improvement of conductivity.
tration about 1.2 × 1020 cm−3, and high mobility about 3.2
cm2/V·s. Also, it can be seen that the resistivity of carbon Acknowledgments. Support of this research by the
films significantly decreased from 4.5 × 10−3 to 1.0 × 10−6 National Research Foundation of Korea (Grant No:
Ω-cm and carrier concentration and mobility increased with 20100025481) is gratefully acknowledged.
increasing annealing temperature, respectively. This behavior
can be explained by the increase of sp2 bonding fraction and References
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