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Nuclear Instruments and Methods in Physics Research B 197 (2002) 107113

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The irradiation studies on diamond-like carbon lms q


Guiang Liu
a
b

a,*
,

Tianmin Wang b, Erqing Xie

College of Science, Zhanjiang Ocean University, Zhanjiang 524088, China


Beijing University of Aeronautics and Astronautics, Beijing 100083, China
c
Department of Physics, Lanzhou University, LanZhou 730000, China
Received 14 March 2002; received in revised form 29 July 2002

Abstract
Diamond-like carbon (DLC) lms have been deposited on glass substrates using radio-frequency (r.f.) plasma deposition method. c-ray, ultraviolet (UV) ray and neutron beam were used to irradiate the DLC lms. Raman spectroscopy and infrared (IR) spectroscopy were used to characterize the changing characteristics of SP3 CH bond and
hydrogen content in the lms due to the irradiations. It showed that, the damage degrees of the c-ray, UV ray and
neutron beam on the SP3 CH bonds are dierent. Among them, the damage of c-ray on the SP3 CH bond is the
weakest. When the irradiation dose of c-ray reaches 10  104 Gy, the SP3 CH bond reduces about 50% in number.
The square resistance of the lms is reduced due to the irradiation of UV ray and this is caused by severe oxidation of
the lms. Compared with that of the as-deposited one, the IR transmittance of the lms irradiated by both c-ray and
neutron beam is increased to some extent. By using the results on optical gap of the lms and the fully constrained
network theory, the hydrogen content in the as-deposited lms is estimated to be 1025 at.%.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Diamond-like carbon lms; c-ray irradiation; Neutron irradiation; Ultraviolet ray irradiation; Raman spectroscopy; SP3 C
H bond; Infrared transmittance

1. Introduction
Much work has been done on the synthesis of
diamond thin lms during the last 20 years and great
progress has been made. However, the preparation
and processing conditions of the lms are hard to
master and are still far from wide applications in
industry. The properties of diamond-like carbon
q
This research was supported by the aeronautics science
foundation of China (no: 98G51124).
*
Corresponding author. Tel.: +86-759-238-2059; fax: +86757-6581272.
E-mail address: liuga@pub.zhanjiang.gd.cn (G. Liu).

(DLC) lms are not so good as those of diamond


lms in certain aspects, but it is much easier to
prepare DLC lms compared with that of diamond
lms. More than ten preparation methods have
been proposed up to now. We believe that DLC
lm is a promising high-tech product in the future.
It is well known that DLC lms have many excellent properties [1]. This makes it promising in
application areas such as on the parts being used in
space and in nuclear reactors. Under such conditions, the lms will be irradiated by various particles, such as ions, neutrons, and photons. Thus the
changing behavior of both property and structure
of the lms is of great importance for practical use

0168-583X/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 8 - 5 8 3 X ( 0 2 ) 0 1 3 8 0 - 0

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G. Liu et al. / Nucl. Instr. and Meth. in Phys. Res. B 197 (2002) 107113

of the lms in these conditions. So far, some work


has been done on the irradiation eect of ions on
DLC lms and dierent ions, such as C , Ar , Xe ,
H , He , F , Au , Ni , Si , N , B , were used
to irradiate the lms. The irradiation dose ranges
within 1  1012 1018 ions/cm2 and the ion energy
ranges from 50 keV to 100 MeV [2]. However, to
our best knowledge, few work has been done on the
irradiation eects of neutrons and photons on
DLC lms. We report in this article our new results
on the irradiation eects of ions, neutrons and, in
particular, photons on the DLC lms.
2. Experimental details
DLC lms used in the research were deposited
by r.f. glow discharge plasma chemical vapor deposition techniques onto glass substrates. The
working gas was pure CH4 and the deposition
chamber was made of quartz. Two parallel r.f.
electrodes were made of stainless steel and their
distance was 23 cm. During the deposition, the
substrates were placed onto the cathodes and their
temperature was kept at 160 C by four parallel
baking lamps. The lm thickness is about 0.91
lm. After deposition, the samples were cut into
small pieces of the size 15  15 mm2 and were irradiated by c-ray, neutron beam or ultraviolet
(UV) ray respectively under dierent energies and
dose ranges. The c-ray was generated by 60 Co and
the average photon energy is 1.25 MeV. The c-ray
irradiation was performed in the air at room
temperature (20 C). The irradiation doses are
shown in Table 1. The neutron energy was 14 MeV
and the neutron irradiation was performed at
room temperature in the air. The irradiation doses
are shown in Table 2. The UV ray was provided by
an UV lamp, and working at 15 W. During the
irradiation of UV ray, the sample-lamp distance
was 10 cm. The power density at the sample surface was 70 mw/cm2 . The UV ray irradiation was
also performed at room temperature in the air.
Table 1
The irradiation dose of c-ray
Sample number
Irradition dose
(104 Gy)

10
0

11
2

12
4

13
6

14
8

15
10

Table 2
The irradiation dose of neutron beams
Sample number
Irradiation dose
(1012 n/cm2 )

20
0

21
1.4

22
2.3

23
7.2

Table 3
The irradiation conditions for UV ray
Sample number
Irradiation time of
UV ray (min)

30
0

31
10

32
60

33
150

34
270

The irradiation time for dierent samples is shown


in Table 3.
The excitation wavelength of Raman spectroscopy in this research was 1064 nm (which corresponds to photon energy of 1.17 eV). This
wavelength is much longer than the 500700 nm
that is commonly used. The infrared (IR) spectroscopy is the IFS120HR Fourier spectrometer.
Its best resolution is 0.008 cm1 .
According to literatures [35], the number of
SP3 CH bond and hydrogen content in DLC lms
play a very important role in determining the
structure and property of DLC lms, especially in
determining the optical properties of the lms.
Thus it is of great importance in practice to study
the relative changes of SP3 CH bond and hydrogen content due to the irradiations. It is hard to
measure directly the hydrogen content and
its changing feature in thin lms because of the
small atomic number of hydrogen. Up to now, IR
spectroscopy and nuclear reaction technique have
been used to estimate the hydrogen content in
DLC lms. In the present research, Raman spectroscopy, UVVISNIR spectroscopy have been
used to determine the SP3 CH bond and hydrogen
content indirectly. The property changes of DLC
lms due to the irradiations are also reported here.
3. Results and discussions
3.1. c-ray irradiation of DLC lms
3.1.1. Relationship between hydrogen content and cray irradiation dose
Due to the c ray irradiation, the DLC lms
changed from light brown to dark brown in color.

G. Liu et al. / Nucl. Instr. and Meth. in Phys. Res. B 197 (2002) 107113

This evident color change implies that the structure and optical property of the lms have been
changed by the irradiation.
Raman spectroscopy has been used for characterizing the DLC lms. Two strong CH peaks
around wave numbers of 2934 and 2871 cm1 are
observed, as shown in Fig. 1. Both peaks can be
attributed to SP3 CH2 asymmetric [6] and SP3 CH3
symmetric stretching vibrational mode [7], respectively. With the increase of irradiation dose,
the intensities of the two peaks reduce, indicating
the stretching vibrations of both bonds become
weak due to the irradiation. Based on the theory
that the Raman peaks should be symmetrical in
shape [8], we noticed that some peaks are overlapped in the spectra. Detailed observation showed
that, another two peaks, centered at about 2855
and 2960 cm1 also appear in the spectra in spite
of their weak intensities. According to the references [9,10], the appearance of the two peaks at
2855 and 2960 cm1 is reasonable and they are
attributed to SP3 CH2 symmetric stretching vibrational mode and SP3 CH3 asymmetric stretching
vibrational mode, respectively. Because all these
four peaks are related to SP3 stretching vibrational
mode, so the relative areas of the peaks can be
considered as identication of stretching vibra-

109

Fig. 2. The area ratio of dierent irradiation dose sample in


SP3 CH spectrum band.

tional intensity of SP3 CH or of the density of SP3


bond [11]. If the peak area of the as-deposited
sample (10# ) is considered as 1, then the relative
ratio of peak area of the irradiated samples can be
calculated, as shown in Fig. 2. It can be seen from
Fig. 2 that the number of SP3 CH bond reduces
due to the irradiation. At the lower dose, the reduction speed is much faster. When the irradiation
dose reaches 10  104 Gy, only half of the original
SP3 CH bonds are left. This indicates that the irradiation of c-ray on DLC lms will damage the
SP3 CH bond in the lms.
Because the peak area of CH bond is proportional to the hydrogen content in the lms
[7,12], so we can conclude from Fig. 2 that the
hydrogen content in DLC lms was reduced because of the c-ray irradiation.
According to the UVVIS spectroscopy (both
transmission and reection spectra), the relation
between optical gap and irradiation dose has been
obtained by using Tauces method [13]. The results
are shown in Table 4.
It can be seen that, with the increase of irradiation dose, the optical gap has a tendency to increase. This is because of the decreases in number
and size of SP2 cluster in DLC lms due to the
irradiation [14]. It is known that the optical gap is
closely related to the hydrogen content in DLC
lms [14]. When the optical band gap is 0.51.5 eV,
Table 4
Relation between optical gap and irradiation dose

Fig. 1. Raman spectrum irradiated by dierent irradiation dose


of c-rays.

Sample number
Optical gap eV

10
11
12
13
14
15
0.90 1.01 1.01 1.02 1.06 1.06

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G. Liu et al. / Nucl. Instr. and Meth. in Phys. Res. B 197 (2002) 107113

the corresponding hydrogen content is about 10


35 at.%. Our results on optical gap in Table 4 is
around 1 eV, indicating that the hydrogen content
is in the range of 1035 at.%.
For amorphous DLC lms, it can be analyzed
by fully constrained network (FCN) theory [15].
According to this theory, the relation among optical gap Eg , hydrogen content X1 and number of
SP2 CH bond X2 in the lms can be expressed as
[16]
Eg 0:95 2:2X1  0:55X2 :

It has been shown that this formula is in agreement


well with many experimental results [16].
As can be seen from Table 4, in our experiment,
Eg  1 eV. So, from formula 1, we can get
X1 1
 ;
X2 4
i.e., X2 4X1 6 1, X1 6 25%. Considering the
above estimations on hydrogen content, we think
the convincible data for hydrogen content is about
1025 at.%. We can also get from formula 1 that
X1

Eg 0:55X2  0:95
:
2:2

Since the number and size of SP2 clusters in


DLC lms decrease due to the high energy c-ray
irradiation, so, X2 will reduce with irradiation.
Table 4 shows that the Eg also reduces a little bit
due to the irradiation. Thus we can know from
formula 2 that the hydrogen content X1 in the lms
will decrease with irradiation dose.
3.1.2. IR transmittance of DLC lms
The best resolution of the IFS120HR Fourier
IR spectrosmeter we used is 0.008 cm1 . The
pressure inside the optical chamber is 0.02 Torr.
The IR transmittance spectrum at dierent irradiation dose is shown in Fig. 3. It can be seen that,
compared with the as-deposited sample (10# in
Figure), the IR transmittance of the DLC lms
over the wave number range of 37504650 cm1
increases because of the c-ray irradiation. This is
because the c-ray irradiation tends to increase the
bond number of SP3 CC, thus causing more evident diamond-like feature [17]. However, it is interesting to note from Fig. 3 that, with the further

Fig. 3. The IR transmittance spectrum of dierent irradiation


dose.

increase of the irradiation dose (11# ! 13# ! 15# ),


the IR transmittance has a tendency to drop. According to the literatures [5,18], the optical properties of DLC lms are closely related to hydrogen
content in the lms. Generally speaking, more hydrogen content causes better (higher) IR transmittance. This implies that, the c-ray irradiation
caused the reduction of hydrogen content in our
lms.
A possible mechanism for this is: the irradiation
of c-ray with an average energy of 1.25 MeV
produces high energetic positron-electron pairs
directly or high energy recoil electrons through
Kanpton scattering. The electrons can then break
the CH bond or even the C@H bond in the DLC
lms, causing the rearrangement of lm atoms.
Stronger CC bonds are formed in this way and
the free hydrogen atoms will then be released from
the lms by forming hydrogen molecules.
3.2. Neutron irradiation of DLC lms
3.2.1. Relation between the lms thickness or
refractive index and neutron irradiation
The thickness and refractive index were measured by the TP-77 ellipse polarizing instrument.
The change of the thickness by neutron irradiation
are shown in Table 5. It can be seen from Table 5
that neutron irradiation led to the thicknesss increase of the lms, and the changing extent was
between 4% and 17%. The reasons may be that
graphite carbon was produced by neutron irradiation.

G. Liu et al. / Nucl. Instr. and Meth. in Phys. Res. B 197 (2002) 107113
Table 5
Relation between the lms thickness or refractive index and
neutron irradiation dose
Sample number
Refractive index (n)
)
Thickness d
200 (A

20
2.15
9300

21
2.20
10500

22
2.25
9600

23
2.30
10920

The increase of refractive index in Table 5 also


give evidence for the structural change. In general,
the more the hydrogens content, the less the refractive index. The fact that the lms refractive
index became large shown that the hydrogens
content became small. Therefore, hydrogens were
releasing from the lms. From the above analysis,
we can see indirectly that, the CH bonds were
broke by neutron irradiation.
3.2.2. Relation between content of SP3 CH bond
and neutron irradiation dose
Raman spectra of neutron beam irradiated
samples are shown in Fig. 4. According to the
literature [17], the peaks centered at 2855, 2871,
2934 and 2960 cm1 are all correlated to SP3 CH

Fig. 4. Raman spectrum irradiated by dierent irradiation dose


of neutron.

111

bond. It can be seen from Fig. 4 that the neutron


irradiation has very strong inuence on the SP3 C
H peaks and this eect is much larger than that of
c-ray irradiation. Under the irradiation dose range
of our experiment, the damage eect of the irradiation has no evident relation with irradiation
dose. Even at very low dose (1:4  1012 n/cm2 ), the
SP3 CH peaks have almost disappeared, indicating that the SP3 CH bond is very sensitive to the
high energetic neutron irradiation.
3.2.3. Relation between IR transmittance characteristics and neutron irradiation dose
The IR transmittances of samples before and
after the neutron irradiation are shown in Fig. 5. It
can be seen that, within the IR wave number range
of 37505000 cm1 , the IR transmittance of the
DLC lms increases about 10% due to the irradiation. And this increase has no evident relation
with the irradiation dose. This indicates that, under our irradiation dose, the neutron irradiation
can increase the IR transmittance of the DLC
lms. As stated above, the neutron irradiation will
lead to the breaking of SP3 CH bond and thus the
release of hydrogen molecules from the lms. It

Fig. 5. IR transmittance irradiated by dierent irradiation dose


of neutron.

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G. Liu et al. / Nucl. Instr. and Meth. in Phys. Res. B 197 (2002) 107113

has been known that the optical properties of DLC


lms are determined by hydrogen content and
carbon cluster size in the lms [13]. And the reduction of hydrogen content will lead to drop of
the IR transmittance. In our experiment, the increase of the IR transmittance with neutron irradiation may be caused by formation of certain new
structure such as straight line carbon. This is in
contrast with the previous report that the IR
transmittance of DLC lms will decrease due to
the MeV proton irradiation [19,20].
3.3. UV ray irradiation of DLC lms
3.3.1. Relation between content of SP3 CH bond
and UV ray irradiation time
The Raman spectra of DLC lms before and
after the UV ray irradiation are shown in Fig. 6. It
is clear that the SP3 CH peak centered at 2934
cm1 has been strongly inuenced by the UV ray
irradiation. The peak has almost disappeared even
after irradiation for 10 min. This is much similar
with that of neutron irradiation. When the irradiation time is up to 150 min, there is still no evident change for the peak shape compared with
that of 10-min irradiation.

It can also be seen from Fig. 6 that the CH


scattering peak centered at about 2934 cm1 decreases substantially due to the UV ray irradiation.
It is known that the light wavelengths emitted
by low pressure Hg lamp are mainly 1849 and 2537
 which correspond to photon energies of 6.72 and
A
4.90 eV respectively. During the irradiation, the O2
in the air may decompose, forming O3 and atomic
oxygen (O ). The O3 and atomic oxygen may then
combine with carbon atoms in the lms, forming
CO and CO2 , and promote the release of gases
such as CH4 and H2 from the lms [21]. This will
consequently lead to the reduction of hydrogen
content in the lms. In another aspect, the bond
energy of CH bond is 3.5 eV [22]. This is smaller
than the UV photon energies (6.72 and 4.90 eV)
used. So it is possible that the CH bond will be
broken by the direct UV photon irradiation. This
has been conrmed by previous report [23].
3.3.2. Film resistance changes due to UV photon
irradiation
The square resistance of DLC lms was measured before and after UV photon irradiation.
During the measurement, the distance between the
electrodes was 1 mm, the length of conducting
paste was 10 mm, and the applied voltage between
the electrodes was 10 V. The results are summarized in Table 6.
It can be seen from Table 6 that, for sample 30# ,
the UV photon irradiation can be divided as two
stages. When the irradiation time is shorter than
10 min, the square resistance increases up to
6:0  1012 X. However, when the irradiation time
is larger than 60 min, the square resistance reduces. For the rst stage, we consider that the UV
photon irradiation promoted the mobility of free
hydrogen atoms in the lms. The hydrogen atoms
then passivate the broken bonds and increased the
SP3 CH bonds, leading to the resistance increase.

Table 6
Change of square resistancedue to UV photon irradiation

Fig. 6. Raman spectrum irradiated by dierent UV irradiation


time.

Sample number
Square resistance q
(1012 X)

30
4.5

31
6.0

32
4.6

33
3.6

34
2.5

G. Liu et al. / Nucl. Instr. and Meth. in Phys. Res. B 197 (2002) 107113

For the second stage, the resistance drop was


caused by the oxidation of lms, the subsequent
breaking of CH bonds and weakness of CC
bonds. According to [23] and our speculations, H2 ,
CO2 and CH4 may be released from the lms.
4. Conclusions
In summary, the following conclusions were
obtained from the present study.
1. By using Raman spectroscopy techniques, the
changing behaviors of SP3 CH bond in DLC
lms with c-ray, neutron beam and UV photon
irradiations were obtained. This expanded the
application area of Raman spectroscopy.
2. The damage degree of c-ray, neutron beam and
UV photon on SP3 CH bond are dierent.
Among them, the damage degree of c-ray is the
weakest. When the irradiation dose of c-ray
reached 10  104 Gy, the number of SP3 CH
bond in the lms was reduced for about 50%.
Meanwhile, the hydrogen atoms released from
the lms by forming hydrogen molecules.
3. By using Tauce method, the relation between
optical gap and c-ray irradiation dose has been
obtained and thus the hydrogen content in
DLC lms was estimated to be 1035 at.%. Further calculations by FCN theory showed that
the hydrogen content in the as-deposited lms
should be within 1025 at.%, and it reduces
with the increase of irradiation dose.
4. The IR transmittance of DLC lms was increased about 10% because of the neutron beam
irradiation. This increase is believed to be related to the formation of some new structures,
such as the straight line carbon in the lms.
5. The irradiation of UV photon caused severe oxidation of DLC lms, the breaking of CH
bond and weakness of CC bond. Consequently, the H2 , CO2 and CH4 releases from

113

the lms, causing the reduction of lm resistance with the increase of irradiation time.

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