Surface & Coatings Technology 380 (2019) 125062

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Preparation of DLC films on inner surfaces of metal tubes by nanopulse T

plasma CVD
Yoshinao Iwamotoa,∗, Keitaro Takenamia,1, Ryota Takamuraa,2, Masaki Inouea,3, Yuki Hirarab,∗∗,
Hiroki Akasakaa, Naoto Ohtakeb,∗∗∗
a
Department of Mechanical Engineering, Tokyo Institute of Technology, O-okayama 2-12-1, Meguro-ku, Tokyo, 152-8552, Japan
b
Institute of Innovative Research, Tokyo Institute of Technology, Nagatuta-cho 4259, Midori-ku, Yokohama 226-8503, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: A method of depositing diamond-like carbon (DLC) films on the inner surface of a circular tube by combining a
DLC nanopulse power source with chemical vapor deposition (CVD) was developed. Because a nanopulse power
CVD source can supply a high-voltage pulse with a narrow width, it is possible to generate a stable glow plasma even
Nanopulse inside a narrow tube under a relatively high source gas pressure. As a result, DLC films were successfully formed
Inner wall deposition
on the inner surfaces of carbon steel pipes with an inner diameter of 40 mm and a length of 300 mm by using CH4
Optical emission spectroscopy
or C2H2 as a source gas. When CH4 was used, DLC films with a hardness of more than 9.3 GPa, a deposition rate
of 0.7 μm/h, and a source gas yield of 42.3% were obtained. In contrast, when C2H2 was used, DLC films with a
hardness of about 5 GPa, a much higher deposition rate of 14.5 μm/h, and a source gas yield of 42.1% were
obtained. Wavelength- and time-resolved optical emission spectral measurements were conducted for the plasma
generated inside the tubes under the nanopulse power source with various nanopulse repetition frequencies,
which indicated the nanopulse-repetition-frequency-dependent behavior of the generated plasma.

1. Introduction
Diamond-like-carbon (DLC) films, which have excellent tribological
properties, are widely applied as wear-resistant films for sliding ma-
chine parts. If DLC films can be formed on the inner surfaces of tubes
used for various parts such as suspension, air, and oil hydraulic cylin-
ders, excellent performance of these parts can be expected, including a
long life time and a low friction coefficient, enabling reduced energy
loss. However, a technique of depositing DLC films on the inner surface
of a tube with a millimeter-scale diameter has not yet been established
because it is extremely difficult to generate plasma stably inside narrow
tubes.
Thus far, various methods including the plasma source ion im-
plantation (PSII) [1–3], microwave sheath-voltage combination plasma
(MVP) [4,5], pulse plasma CVD [6–8], plasma-enhanced chemical
vapor deposition (PECVD) [9], hollow cathode plasma immersion ion
processing (HCPIIP) [10–12], and plasma immersion ion implantation
and deposition (PIII&D) [13] methods have been investigated. Each
method has advantageous features but industrial applicability and
scalability may become crucial factors for selecting one method over
another. For example, PSII, PIII&D, pulse plasma CVD, PECVD, and
MVP are performed in a low-pressure vacuum chamber, and the size of
the tube on which the film is formed is limited by the size of the vacuum
chamber, and hence expensive and large-scale equipment may be re-
quired. The HCPIIP method achieved deposition on a tube with an as-
pect ratio of 24 [10], but it may be difficult to use this method to
synthesize DLC films for longer tubes with a smaller diameter.
In all of these methods, the issue of the plasma generation limit has
to be resolved for tubes with a smaller diameter and a higher aspect
ratio. That is, in the case of a DLC coating on the internal surfaces of
tubes, a low-density plasma cannot stably exist inside a narrow tube,
because the width of the ion sheath formed along the internal surface of
the tube is more than half of the inner radius of the tube under con-
ventional low-pressure processing conditions.

∗
Corresponding author.
∗∗
Corresponding author.
∗∗∗
Corresponding author.
E-mail addresses: iwamoto.y.ag@m.titech.ac.jp (Y. Iwamoto), hirata.y.ac@m.titech.ac.jp (Y. Hirara), ohtake.n.aa@m.titech.ac.jp (N. Ohtake).
1
Presently at Electric Power Development Co., Ltd.
2
Presently at SWCC Showa Cable Systems Co., Ltd.
3
Presently at Lasertec Corporation.

https://doi.org/10.1016/j.surfcoat.2019.125062
Received 2 September 2019; Received in revised form 8 October 2019; Accepted 10 October 2019
Available online 16 October 2019
0257-8972/ © 2019 Elsevier B.V. All rights reserved.
Y. Iwamoto, et al. Surface & Coatings Technology 380 (2019) 125062

On the other hand, when using a process with a higher source gas
pressure of more than 100 Pa, it becomes possible to generate plasma
even in very narrow tubes because the sheath thickness decreases with
increasing source gas pressure. Moreover, since ordinary CVD film de-
position is performed under a low pressure of Pa order or less, the
density of active species is low, and hence the film deposition rate is
much lower than 1 μm/h, which is also a problem from the viewpoint of
productivity in industrial use. However, a significant improvement in
deposition rate can be expected in a high-gas-pressure process, and
furthermore, the vacuum apparatus can be considerably simplified in
the case of a higher gas pressure, and hence, the cost of the processing
apparatus can be reduced.
In a high-gas-pressure process, however, the transition from a glow
discharge to an arc discharge should be prevented. Fortunately, if the
discharge is stopped within a sufficiently short period when it starts, a
glow-like low-temperature plasma can exist even under a high gas
pressure without a glow-to-arc transition [14].
Fig. 2. Output voltage and current waveform of nanopulse power source during
In this paper, we propose a promising CVD-based DLC film de-
film deposition (sample E3).
position method for the internal surface of a tube that adopts a nano-
pulse power source that can supply high-voltage pulses with rapid rise
and fall characteristics of nanosecond order [15,16]. We describe the about 1 µs FWHM) and a high repetition frequency of more than 10
DLC deposition apparatus and several evaluation results for films kHz. The outer diameter of the inner electrode made of the titanium rod
formed on the inner surfaces of STKM11A carbon steel tubes with an was determined to be 30 mm considering that it is appropriate to set the
inner diameter of 40 mm and a length of 300 mm, under a stable glow nanopulse voltage to around 1 kV or less. We used a DC power source
plasma with a relatively high pressure of 100–500 Pa using CH4 or C2H2 (PAN 160–3.5, Kikusui Denshi Kogyo Co., Ltd.) for the nanopulse power
as the source gas. We also report the wavelength- and time-resolved source.
optical emission spectroscopic analysis of the plasma discharge excited The flanges at both ends were made of polycarbonate and func-
by the nanopulse power source. We show that a very high source gas tioned as an electric insulator. The gas used for CVD was introduced
yield was obtained in the experiments. from the center axis of the flange at the left end. The flow of each source
gas was controlled by a mass flow controller attached to the left flange.
A Pirani gauge was connected to the left flange to measure the gas
2. Film deposition apparatus and evaluation equipment pressure inside the circular tube. The inside of the circular tube was
evacuated by a rotary pump through the exhaust valve at the right
Fig. 1 shows a schematic view of the CVD apparatus used to form flange. Only a rotary pump was used in the apparatus owing to the
DLC films on the inner surface of a metal circular tube. A feature of the relatively high gas pressure during the process. Hereinafter, the left side
apparatus is that it uses the circular tube itself as a CVD vacuum of the tube is called the upstream and the right side is called the
chamber. The circular tubes used in the experiments had an inner downstream, because gases were supplied at the left flange and traveled
diameter of 40 mm, a wall thickness of 25 μm, and a length of 300 mm. to the right (downstream).
A titanium rod with an outer diameter of 30 mm, which functioned as For the characterization of the film deposited on the inner surface of
an anode, passed through the center of the left and right flanges and the tube, Raman scattering spectroscopy using a laser Raman spectro-
was positioned along the center axis of the tube. The positive electrode scope (NRS-4100, JASCO Corporation), in which the laser wavelength
of the nanopulse power source was connected to the circular titanium was 532 nm, a laser microscope for evaluating the appearance of the
rod and the negative electrode was connected to the outer surface of the films (LEXT OLS4100, Olympus Corp.) and a nanoindentation hardness
tube. An example of a voltage and current pulse waveforms of the na- tester (HM500, Fisher Instruments), in which a square Vickers indent
nopulse power source during the deposition process are shown in Fig. 2. was used and the maximum test load was set to 0.3 mN, were used.
It could output a high voltage with a narrow pulse width (less than

Fig. 1. Schematic of the CVD apparatus.

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Y. Iwamoto, et al. Surface & Coatings Technology 380 (2019) 125062

These measurements were performed by cutting the circular tube axi-

ally in half after film deposition. However, since the inside of the cir-
cular tube had a curved surface, the nanoindentation test could not be
performed directly, so rectangular silicon substrates with dimensions of
5 mm X 15–20 mm were installed inside the tube in the upstream and
downstream. In the film thickness measurement with a laser micro-
scope, a masking method was applied to measure the height difference
between the undeposited and deposited portions of the film. For the
optical emission spectroscopic analysis of the plasma generated inside
the tube, a multichannel spectrometer (PMA-12 series C10029,
Hamamatsu Photonics) was used.

3. Results and discussion

3.1. Deposition conditions

The deposition of the DLC film on the internal surface of the tube
was conducted extensively using CH4 or C2H2 as the source gas and a
nanopulse power source to discharge the source gas. The voltage and
repetition frequency of the nanopulse power source, and the flow rate Fig. 3. Raman spectra of samples B1 to B4 deposited using CH4 under fixed
and mixing ratio of the source gas and Ar gas used for dilution were primary voltage to nanopulse power source and different Ar/CH4 gas flow ratios
varied to determine the optimum film deposition conditions. The gas (B1: Ar/CH4: 1.1, gas pressure: 200 Pa, B2: Ar/CH4: 0.37, 250 Pa, B3: Ar/CH4:
pressure was set at 145–520 Pa. The power of the nanopulse power 0.12, 400 Pa, B4: Ar/CH4: 0. 440 Pa).
source was controlled by varying the input DC voltage between 50 and
95 V, which provided an input power of about 30–110 W to the nano- the subsequent experiments.
pulse power source. Before the deposition of the film, the inner surface
of the tube was cleaned by Ar sputtering, and then an a-C:Si:H inter-
mediate layer was formed by providing tetramethylsilane (Si(CH3)4) to 3.1.2. Effects of primary voltage to nanopulse power source on film
improve the adhesion of the DLC film to the inner surface of the tube. properties with gas pressure fixed
The deposition conditions of the samples are tabulated in Table 1, in Next, to evaluate the effects of the primary voltage to the nanopulse
which the samples are denoted A to E4, where the primary voltage to power source on the properties of the film, samples A, B1, C1, D1, and
the nanopulse power source, the CH4 and Ar gas pressure, and the Ar/ E2 were compared, where the gas pressure and the Ar/CH4 flow ratio
CH4 flow ratio are given. were fixed at 200 Pa and 1.1, respectively, but the primary voltage to
the nanopulse power source was varied (A: 50 V, B1: 60 V, C1: 75 V, D1:
85 V, E2: 95 V). The Raman spectra are shown in Fig. 4 and show that
3.1.1. Effect of Ar gas on film deposition
DLC films were formed for all the samples. The blackest film was
To investigate the effects of the Ar gas flow and the ratio of Ar to
sample E2, for which the largest nanopulse power was supplied. The
CH4 on the film properties, samples B1 to B4 were compared, where the
slope of the baseline in the Raman spectra between wavenumbers of
input voltage to the nanopulse power source was fixed at 60 V, the total
1700 and 2200 cm−1 tended to decrease with increasing input power to
flow of CH4 and Ar gases was varied from 200 to 440 Pa, and the Ar/
the nanopulse power source. The same tendencies were also observed
CH4 flow ratio was varied between 0 and 1.1. From a visual observation
for samples C2, D2, and E3 in the experiments using a higher gas
of the films of samples B1 to B4, the blackest film was sample B1, in
pressure of 380 Pa.
which the Ar/CH4 flow ratio was the highest among the four samples.
The large slope of the baseline of the Raman spectra is thought to be
Fig. 3 shows the Raman spectra of samples B1 to B4. A broad peak
due to the photoluminescence resulting from the high hydrogen content
corresponding to the amorphous carbon film with the G band near
in the film such as in the C–H bonds [17–20], because the samples with
1550 cm−1 and the D band near 1350 cm−1 was observed in samples
a larger baseline slope were deposited under higher gas pressures.
B1 to B3, but no such peak was observed in sample B4. This result
shows the effectiveness of Ar, by which the Penning effect activated the
decomposition of CH4. Furthermore, with decreasing Ar/CH4 flow 3.1.3. Effects of gas pressure on the properties of films with primary voltage
ratio, it was observed that the baseline slope tends to increase, possibly fixed
owing to an increase in hydrogen content in the DLC film [17–20]. In Furthermore, to evaluate the effects of the source gas pressure on
consideration of such results, the Ar/CH4 flow ratio was fixed at 1.1 for the properties of the films, samples C1, C2, and C3 were compared, for

Table 1
Deposition conditions of DLC film on the inner surface of the SUS304 circular tube with inner diameter of 40 mm and length of 300 mm using CH4 as the source gas.
Sample A B1 B2 B3 B4 C1 C2 C3 D1 D2 E1 E2 E3 E4

Primary voltage [V] 50 60 75 85 95

Primary current [A] 0.37 0.51 0.50 0.51 0.50 0.77 0.82 0.83 0.98 1.02 1.09 1.13 1.22 1.03
Input power [W] 18.5 30.6 30.0 30.6 30.0 57.8 61.5 62.3 83.3 86.7 103.6 107.4 115.9 97.9
Repetition freq [kHz] 10
Peak voltage [kVp] 1.3 1.3 2.0 1.6 3.4 1.0 1.0 1.1 1.0 1.0 1.0 1.0 1.0 1.1
Peak current [Ap] – – – – – 13.0 13.6 13.5 15.1 16.3 17.3 17.5 18.5 16.4
Current pulse width – – – – – – – – 0.52 – 0.49 0.61 0.87 –
FWHM [μs]
Ar/CH4:flow ratio 1.1 1.1 0.37 0.12 0 1.1
Gas pressure [Pa] 200 200 250 440 400 200 380 520 200 380 170 200 380 145
Deposition time [min] 60 75

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Y. Iwamoto, et al.
Fig. 4. Raman spectra of samples A to E2 deposited using CH4 under fixed gas
pressure (200 Pa) and Ar/CH4 flow ratio (1.1), and variable primary voltage to
nanopulse power source (A: 50 V, B1: 60 V, C1: 75 V, D1: 85 V, E2: 95 V).
Fig. 5. Raman spectra of samples C1 to C3 deposited using CH4 under fixed
primary voltage (75 V) to nanopulse pulse power source and Ar/CH4 gas flow
ratio (1.1), and variable gas pressure (C1: 200 Pa, C2: 380 Pa, C3: 520 Pa).
which the primary voltage and Ar/CH4 flow ratio were fixed at 75 V
and 1.1, respectively, but the source gas pressure was varied (C1:
200 Pa, C2: 380 Pa, C3: 520 Pa). The Raman spectra are shown in Fig. 5.
In each sample, G band and D band peaks corresponding to the amor-
phous carbon film were observed, thus confirming that DLC films were
formed.
In the Raman spectra, a large baseline slope for samples C2 and C3
compared with that for sample C1 was observed. As shown in Fig. 5, the
baseline slope increases in the order of C1 < C2 < C3, which is the
order of the pressures of the source gas. These baseline slopes correlate
with the hydrogen content in the deposited films as described in the
previous section.
3.1.4. Film hardness and deposition rate
The experimental results of the film deposition are shown in
Table 2, in which deposition rates, film hardnesses and source gas
yields are tabulated. Fig. 6 shows the relationship between the de-
position rate and the input power to the nanopulse power source for the
films obtained in the experiments. As can be clearly observed from
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Surface & Coatings Technology 380 (2019) 125062
Fig. 6, the deposition rate increased uniformly with the input power
and source gas pressure. The figure also shows that the deposition rate
downstream is larger than that upstream, but this is due to the fact that
the source gas is subjected to a larger amount of decomposition
downstream owing to high repetition-rate pulses [14].
Fig. 7 shows the film hardness and deposition rate plotted against
the source gas pressure for samples E1 to E4. Blue marks indicate the
hardness and red marks indicate the deposition rate, where triangles
represent upstream and squares represent downstream. The graph
shows that the hardness tended to be higher at low gas pressures and
lower at high gas pressures, and the deposition rate tended to increase
in proportion to the source gas pressure. That is, the hardness and de-
position rate were in a trade-off relationship as a function of the source
gas pressure.
As observed in Fig. 7, the maximum film hardness was obtained for
sample E4, for which the main deposition conditions were an input
voltage of 95 V, an input power of 97.9 W, CH4 and Ar as gas sources,
and a gas pressure of 145 Pa, and the film hardness was determined to
be 10.4 GPa upstream and 9.3 GPa downstream. On the other hand, the
deposition rate was only around 0.5 μm/h for this sample.
The relationship between the baseline slope of the Raman spectra
and the source gas pressure is shown in Fig. 8, and ID/IG for the Raman
spectra as a function of the source gas pressure is shown in Fig. 9. As
can be understood from both graphs, the baseline slope increased and
ID/IG decreased as the source gas pressure increased. These findings
indicate that the amount of hydrogen in the film increased with the
source gas pressure, thereby increasing the polymer-like character [18].
The reason why the film became softer with increasing source gas
pressure can be explained as follows. With increasing source gas pres-
sure, the mean free path of ions or radicals became shorter, for instance,
it was about 20 μm assuming a gas temperature of 300 K and a gas
pressure of 380 Pa. Hence, the number of collisions among particles
increased before they impinged on the inner wall of the tube, and thus
the energy of ions or radicals decreased when they reached the wall
surface. As a consequence, the gas was decomposed before reaching the
inner wall of the tube, thus, the chain hydrocarbon structure became
more prevalent in the film, resulting in a more polymer-like carbon film
[18].
On the other hand, the film deposition rate increased with the
source gas pressure. It is considered that this is due to the increased
number of active species contributing to film formation with increasing
source gas pressure [14].
Regarding the source gases, C2H2 has two carbon atoms per mole-
cule, whereas CH4 has only one carbon atom, and hence under the same
gas pressure, there are twice as many carbon atoms in the case of C2H2.
Thus, a higher deposition rate can be expected. Indeed in the experi-
ments using C2H2, in which the source gas pressure was set to 400 Pa,
an extremely high film deposition rate of 14.5 μm/h and a relatively
low film hardness of 5 GPa were obtained under almost the same na-
nopulse power source conditions, for example, a primary voltage of
95 V and an input power to the nanopulse power source of around
110 W. This result can be compared with sample E3, in which CH4 was
used, where the deposition rate was around 2.0 μm/h as shown in
Table 2.
3.2. Source gas yield
The carbon and hydrogen of the DLC film originated from the hy-
drocarbon gas used for film formation, thus, the source gas yield can be
calculated by dividing the weight of the film by the total weight of
flowed gas.
The approximate weight of the formed film was obtained by mul-
tiplying the thickness of the film, the total surface area of the inner wall
of the tube, and the density of the DLC film. The density of the film was
assumed to be 1.7 g/cm3, the value for an ordinary DLC film. The film
thickness was measured at points 50 mm from upstream and
Y. Iwamoto, et al. Surface & Coatings Technology 380 (2019) 125062

Table 2
DLC film deposition rate, hardness, and source gas yield values of samples C1 to E3 using CH4 as source gas.
Sample C1 C2 C3 D1 D2 E1 E2 E3 E4

Deposition rate [μm/h] Upstream 0.6 1.1 1 1 1.4 1.1 1.2 1.9 1
Downstream 0.8 1.2 1.4 1.1 1,8 0.8 1.3 2.1 0.7
Film hardness [GPa] Upstream – – – – – – – – 10.6
Downstream 8.4 – – – – 9.5 8.4 5.4 9.3
Source gas yield [%] 22.8 12.5 6.5 34.2 17.4 46.5 40.7 21.7 42.3

Fig. 8. Relationship between Raman baseline slope and source gas pressure.
The line is fit to the data.

Fig. 6. Relationship between deposition rate and input power to nanopulse

power source. △ denotes upstream and □ denotes downstream.

12 3.0

10 2.5
Film deposition rate [μm/h]
Film hardness [GPa]

8 2.0

6 1.5

4 1.0
Triangle: upstream
Square: downstream
2 0.5

0 0.0
0 100 200 300 400 500
Pressure [Pa] Fig. 9. Relationship between Raman ID/IG and source gas pressure. The line is
Fig. 7. Film hardness and deposition rate plotted against source gas pressure. fit to the data.
The lines are fit to the data. △ denotes upstream and □ denotes downstream.
excited plasma spectroscopic measurements in the wavelength- and
downstream ends of the tube and was assumed to change linearly be- time-resolved mode, and obtained the nanopulse-repetition-frequency-
tween these points. The source gas density was assumed to be 656 g/m3 dependent behavior of the plasma excited by the nanopulse power
for CH4 and 1100 g/m3 for C2H2. source.
The source gas yields calculated for the samples using CH4 as the gas The basic configuration used for plasma generation was almost
source varied from 6.5 to 46.5%, compared with 42.1–64.1% when equivalent to the system shown in Fig. 1, but for convenience of mea-
C2H2 was used as the gas source. Thus, the source gas yield is very high surement, a circular tube made of SUS304 with an inner diameter of
in nanopulse CVD. 14 mm and a length of 300 mm was used for the nanopulse CVD ap-
paratus, and a titanium rod with an outer diameter of 6 mm was used as
3.3. Spectroscopic analysis of plasma inside the tube the internal electrode. CH4 gas was used as the source gas and He gas
was used as the dilution gas instead of Ar. The plasma discharged inside
Conventionally, most plasma spectroscopic measurements have the tube was spectroscopically measured from the outside of the tube
been performed on a continuous plasma, but we performed nanopulse- through the quartz glass bonded to a recessed area of the tube surface

5
Y. Iwamoto, et al.
Fig. 10. Synchronization of nanopulse voltage waveform with digital delay
generator.
formed by a milling machine. An optical fiber probe was fixed to the
quartz glass window and the optical signal was led to the spectrometer.
The time resolution of the spectrometer was 10 nm. The pulse of the
nanopulse power source was triggered by a trigger pulse from a digital
delay generator (DG535, Standard Research), and the timing of the
pulse generation and the spectrometer was synchronized. Fig. 10 shows
the nanopulse voltage waveform and its time relationship with the
trigger obtained from the preliminary experiment for adjusting delay
time of the trigger pulse. The nanopulse voltage waveform has a total
duration of about 1 μs and comprises a sharp high voltage for about
100 ns, followed by a pulse voltage that gradually decays.
In the experiment, the primary voltage of the nanopulse power
source was set at 65 V, and thus the nanopulse peak voltage was about
2.2 kV. The CH4 gas flow was controlled at 40 cm3/min, the He gas flow
was controlled at 15 cm3/min, and the pressure of the gases was set to
500 Pa. The Raman spectroscopic analysis of the film deposited on the
inner surface of the tube, for which the pulse repetition frequency was
12 kHz, revealed the formation of an amorphous carbon film exhibiting
the G band and D band peaks, but no amorphous film was formed at the
pulse repetition frequency of 4 kHz.
Fig. 11 shows the results of wavelength- and time-resolved spec-
troscopic measurements under pulse repetition frequencies of (a) 12
and (b) 4 kHz. As indicated in this figure, various types of optical
spectra were observed, and the optical emission for one nanopulse
voltage had a duration of about 900 ns, which roughly corresponded to
that of the nanopulse voltage shown in Fig. 10, Furthermore, high-in-
tensity optical emission was generated, corresponding to the above
narrow high-voltage duration of about 100 ns. Clear differences in
optical emission were observed for the pulse repetition frequencies of
12 and 4 kHz.
To estimate the plasma conditions, we focused on the Hα (656 nm)
and Hβ (486 nm) peaks of the emission spectra of the hydrogen atom,
and the time-resolved emission intensities of Hα and Hβ, which were
accumulated from 0 to 900 ns, are shown in Fig. 12 for pulse repetition
frequencies of (a) 12 and (b) 4 kHz. As is known, the Hβ transition of
hydrogen requires more energy than the Hα transition, and hence a
higher optical emission intensity ratio of Hβ to Hα for a single nanopulse
discharge was observed. The electron temperature was estimated to be
about 1.1 eV at 12 kHz and about 0.98 eV at 4 kHz by the two-spectral-
line-ratio method [21–23] using Hβ and Hα. It was assumed that the
electron temperature in the case of 12 kHz being higher than that in the
case of 4 kHz promoted the generation of more active species and thus
the synthesis of the film under the nanopulse power source [14]. These
estimated values are generaly in good agreement with the results of
experiments conducted with the apparatus shown in Fig. 1 using C2H2
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Surface & Coatings Technology 380 (2019) 125062
Fig. 11. Wavelength- and time-resolved optical emission excited by nanopulse
power source for CH4 and He gases in a circular tube (14 mm inner diameter
and 300 mm length) at pulse repetition frequencies of (a) 12 and (b) 4 kHz.
as the source gas instead of CH4, in which 10 and 5 kHz nanopulse
power sources were applied. The other experimental conditions were
the same for both 10 and 5 kHz cases: the primary voltage to the na-
nopulse power source was 95 V and the source gas pressure was 170 Pa.
The deposition rates measured upstream were 6.1 μm/h for the 10 kHz
case and 3.9 μm/h for the 5 kHz case. This means that the deposition
rate is higher at the 10 kHz than at the 5 kHz, possibly owing to the
higher electron temperature in the case of the 10 kHz than that of
5 kHz.
4. Conclusion
We have described a novel nanopulse plasma CVD method that can
deposit DLC films on the inner surface of a circular tube under a rela-
tively high gas pressure of 100 Pa order with high deposition rates and
source gas yields. The CVD apparatus, using the tube itself as the
chamber, was realized successfully. To prevent the transition from a
glow discharge to an arc discharge under a high source gas pressure, a
novel nanopulse CVD method using a nanopulse power source with
rapid rise and fall characteristics and a narrow pulse width was applied.
We performed comprehensive experiments to determine the optimum
conditions for film deposition on the internal surface of the tube, under
which DLC films were successfully deposited.
Also, by using a high-pressure source gas with a pressure of 100 Pa
order, the film deposition rate was significantly improved compared
with that for ordinary CVD, which uses a pressure of Pa order or less. In
the experiments, the deposition rate was 0.7 μm/h, the film hardness
was more than 9 GPa, and the source gas yield was 42.3% when CH4
was used as the source gas, compared with a deposition rate of about
14.5 μm/h, a film hardness of 5 GPa, and a source gas yield of 42.1%
when C2H2 was used. The reasonably high source gas yield was realized
as a result of the nanopulse excitation and the high repetition frequency
Y. Iwamoto, et al.
(a)
(b)
Fig. 12. Optical emission spectra measured in wavelength range of 450–700 nm
and cumulated from 0 to 900 ns at pulse repetition frequencies of nanopulse
power source of (a) 12 and (b) 4 kHz.
of the nanopulse.
The optical emission spectroscopic measurement of the nanopulse
plasma generated inside the tube was successfully performed by wa-
velength- and time-resolved spectroscopy with nanopulse repetition
frequencies of 12 and 4 kHz. The calculation of the emission intensity
ratio of Hα to Hβ in the emission spectra of hydrogen atom was per-
formed. It was shown that at a repetition frequency of 12 kHz, an
electron temperature higher than that at 4 kHz was reached, enabling
the generation of more active species and thus a higher deposition rate,
in agreement with the experimental results.
Acknowledgments
This work was supported by JSPS KAKENHI Grant Number
Surface & Coatings Technology 380 (2019) 125062
JP16H02406.
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