An investigation of Ar metastable state density in low pressure dual-frequency

capacitively coupled argon and argon-diluted plasmas

Wen-Yao Liu, Yong Xu, Yong-Xin Liu, Fei Peng, Qian Guo, Xiao-Song Li, Ai-Min Zhu, and You-Nian Wang

Citation: Journal of Applied Physics 117, 023306 (2015); doi: 10.1063/1.4905953

View online: http://dx.doi.org/10.1063/1.4905953
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/117/2?ver=pdfcov
Published by the AIP Publishing

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 JOURNAL OF APPLIED PHYSICS 117, 023306 (2015)

An investigation of Ar metastable state density in low pressure

dual-frequency capacitively coupled argon and argon-diluted plasmas
Wen-Yao Liu,1,2 Yong Xu,1,2,a) Yong-Xin Liu,1 Fei Peng,1,2 Qian Guo,1,2 Xiao-Song Li,1,2
Ai-Min Zhu,1,2 and You-Nian Wang1
1
Key Laboratory of Materials Modification by Laser, Ion, and Electron Beams (Ministry of Education), School
of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116024, China
2
Laboratory of Plasma Physical Chemistry, Dalian University of Technology, Dalian 116024, China
(Received 22 August 2014; accepted 4 January 2015; published online 14 January 2015)
An tunable diode laser absorption spectroscopy has been used to determine the Ar*(3P2) and
Ar*(3P0) metastable atoms densities in dual-frequency capacitively coupled plasmas. The effects of
different control parameters, such as high-frequency power, gas pressure and content of Ar, on the
densities of two metastable atoms and electron density were discussed in single-frequency and dual-
frequency Ar discharges, respectively. Particularly, the effects of the pressure on the axial profile of
the electron and Ar metastable state densities were also discussed. Furthermore, a simple rate model
was employed and its results were compared with experiments to analyze the main production and
loss processes of Ar metastable states. It is found that Ar metastable state is mainly produced by
electron impact excitation from the ground state, and decayed by diffusion and collision quenching
with electrons and neutral molecules. Besides, the addition of CF4 was found to significantly
increase the metastable destruction rate by the CF4 quenching, especially for large CF4 content and
high pressure, it becomes the dominant depopulation process. V C 2015 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4905953]

I. INTRODUCTION relatively low-cost way has been widely employed to diag-

Recently, dual-frequency (DF) capacitively coupled plas-
mas (CCP) have attracted increasing attention due to the abil-
ity of independent controlling both plasma density and ion
bombardment energy by the high-frequency (HF) and low-
frequency (LF) sources, separately.1–5 In practical process,
argon is always mixed with other gases, such as nitrogen,
hydrogen, fluorocarbon gases and their mixture, and then
used in numerous of microelectronics fabrication proc-
esses.6–11 The role of Ar metastable atoms is important in a
number of secondary processes (collisions) occurring in
argon-containing discharges due to the longer lifetime and
higher internal energy.12 And the cross sections for excitation
from metastable states are several orders of magnitude higher
than those from the ground state, and if the population of
metastable states is high enough, two-step excitation through
metastable states may be more important, especially in some
electronegative gases discharges, where the density of meta-
stable state atom is comparable to the electron density.13
In Ar discharge, the lowest energy metastable states are
denoted by 1s5 and 1s3 (with excitation energies of 11.55
and 11.72 eV, respectively) in Paschen notation.14 Owing to
the non-radiative nature, the direct optical emission spectros-
copy (OES) can hardly be employed to measure the metasta-
ble state atoms density. Thus, the optical absorption
spectroscopy is a more appropriate method, such as, self-
absorption method and laser absorption spectroscopy (LAS).
The self-absorption method is using the branching fraction
of different emission line intensity to determine the escape
factors and then calculate the densities. This simple and
a)
Electronic mail: yongxu@dlut.edu.cn
nose the Ar metastable states and resonance states den-
sities.15–19 While at present, an alternative method, the
tunable diode laser absorption spectroscopy (TDLAS), is
employed here, because of its advantage of more accurate
and higher sensitivity than the self-absorption method.
Besides, this high-power coherent source could greatly
improve the sensitivity and the signal-to-noise ratio, so that
it could be used to detect the low concentration species.
Furthermore, line width of the laser radiation is much
smaller than the width of the Doppler-broadened absorption
profile, so the gas temperature could be measured directly in
low-pressure plasmas.9,20–23
The determination of the magnitude and spatial distribu-
tions of argon metastable atoms densities is a necessary step
to investigate the production mechanisms of ions and radi-
cals in argon and argon-diluted plasmas.16,24–27 According to
the report of several authors, the addition of inert Ar gas
could significantly affect the plasma property, which is
mainly attributed to the important role of metastables and
especially their stepwise processes in discharge. Nakano
et al.10 investigated the effects of addition of Ar in C4F8-
based plasmas, and found that the Ar dilution results in a fact
that the electron energy distribution function (EEDF)
extends toward the higher energy region. Czerwiec et al.28
have reported that in the ICP discharge the nitrogen dissocia-
tion fraction can be enhanced by argon addition, and the
nitrogen dissociation reach its maximum when adding 10%
Ar to N2 gas. On the other hand, due to the collision quench-
ing loss process, even a few percent of neutral molecules can
significantly affect the Ar metastable state density. Hioki
et al.11 showed that if 5% CF4 is introduced into the pure

0021-8979/2015/117(2)/023306/9/$30.00 117, 023306-1 C 2015 AIP Publishing LLC

V

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 023306-2 Liu et al.
argon at higher pressure the radial and axial profiles of Ar
metastable density are changed dramatically. McMillin
et al.27 have also observed that the addition of only a few
percent of CF4 leads to the significant decrease of Ar meta-
stable density in CCP discharge. Therefore, the determina-
tion of metastable atom is important for improving the
understanding of the plasma kinetics in mixtures of argon
with other gases. However, there have been few works on
the effect of LF components on the Ar metastable and few
measurements on the spatial profile of Ar metastable density
for these low-pressure argon and argon-diluted DF-CCPs.
Furthermore, a comparative study between the experimental
measurements and rate model based on the production and
loss processes of Ar metastable is urgently required.
In this work, we report TDLAS measurements of argon
metastable (1s3 and 1s5) densities and gas temperatures in a
low-pressure DF-CCPs, and discuss the effects of different
control parameters on them. Moreover, a simple rate model
is employed to determine the dominant production and loss
processes. Section II is devoted to the experimental setup.
The effects of different control parameters are presented and
discussed in Sec. III. Finally, we conclude in Sec. IV.
II. EXPERIMENTAL SETUP
A schematic view of the experimental setup and diagnos-
tic tools are shown in Figure 1. The discharge chamber is the
same as that described in our earlier study.29 The reactor
FIG. 1. Schematic of the experimental setup together with the diagnostic systems.
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J. Appl. Phys. 117, 023306 (2015)
contains two parallel circular electrodes, the upper electrode
is driven by both the HF and LF sources (2/60 MHz,
Thamway, Japan) and the lower electrode is grounded to-
gether with the chamber wall. The diameters of the powered
and grounded electrodes are 210 mm and 150 mm, respec-
tively. And the electrode gap could be adjusted between
20 mm and 50 mm by changing the height of the lower elec-
trode. Two viewports are symmetrically fixed in the sidewall.
In order to avoid the CFx polymer depositing on the windows,
both of viewports are extended by two stainless steel tubes,
meanwhile two apertures are installed between the extension
tubes and the chamber. In this experiment, high-purity
(99.999%) Ar and CF4 gases were supplied into the discharge
zone through the showerhead-like structure in the upper elec-
trode and the total flow rates was kept at 20 sccm.
The density of metastable (3P2 and 3P0) argon atoms
was measured by using TDLAS technique. In order to
scan the absorption feature over the wavelength range
(772.3–772.5 nm), the tunable diode laser (LD-0773–0075-
DFB-1, Toptica) was tuned via a current controller unit
(LDC205, Thorlabs), and the current can be controlled by a
10 Hz triangle voltage signal provided by function genera-
tor. The temperature of the diode was kept at 31  C by a
temperature controller (Thorlabs, TED 200C). The modu-
lated light was diverted by a mirror and then was directed
to a beam splitter. The transmitted light was coupled into a
wavemeter (Burleigh WA-1000) for monitoring precise
wavelength. In order to avoid the light saturation, the
 023306-3 Liu et al.
reflected parallel light beam was filtered by a neutral den-
sity filter placed close to the entrance of the chamber. The
filtered light then passed through the mid-gap of discharge
region and was finally detected by a photodiode (PD). The
distance between the collimated laser light and the power
electrode could be adjusted by moving the beam splitter
and photo diode, which allows the axially resolved meas-
urements. In addition, the windows were little affected by
the polymer depositing during the axially resolved meas-
urements in CF4/Ar discharge, due to the short period of
time and the small proportion of CF4, and thus, the exten-
sion tubes and apertures were removed temporarily (the
region marked by blue dashed boxes), two quartz windows
(50 mm diameter) were fixed at the viewports symmetri-
cally, so that the laser light could be adjusted between the
electrodes. The signal from PD was simultaneously meas-
ured by a digital oscilloscope (LeCroy Waverunner). We
average 50 scanned signals to improve the ratio of signal to
noise.
The absorption profile is obtained via the four-step
procedure.
(1) Plasma on, light source on: Lp(k)
(2) Plasma off, light source on: L0(k)
(3) Plasma on, light source off: P(k)
(4) Plasma off, light source off: B(k)
From these measurements, according to the Beer-
Lambert law the absorbance can thus be defined as follows:30
  ! gon. Moreover, the lower increase rates of the argon metasta-
IT LP ðkÞ  PðkÞ
AðkÞ ¼ ln ðkÞ ¼ ln ¼ kðkÞL; (1)
I0 L0 ðkÞ  BðkÞ
where A(k) is the absorbance. IT(k) and I0(k) are the inten-
sities of the transmitted light at wavelength k with and with-
out absorbing species, respectively, k(k) is the absorption
coefficient, and L is the path length. The line-integrated
absolute metastable density can then be given by31,32
ð word, the metastable density increases slowly and tends to
8pgj c
Nm ¼ 4 AðkÞdk; (2)
k0 gi Aij L
where j and i refer to the lower and upper energy levels of
the transition at wavelength k0, respectively, gj and gi are the
statistical weights of these states, Aij is the Einstein coeffi-
cient, and c is the speed of light. These parameters available
from the NIST spectral database are listed in Table I.33
In our discharge operating at low pressure, the main line
broadening is the Doppler broadening. For Doppler broaden-
ing, the line shape exhibits a Gaussian shape, thus the gas
temperature could be deduced by using the Doppler width of
metastable atoms. The FWHM of Doppler broadening is
given by30
TABLE I. Parameters for calculating the metastable density.33
Transition k0 (nm) Ej (eV) Aij (s1) gj gi k40 gi Aij
1s5 ! 2p7 772.376 11.55 5.18  106 5 3
1s3 ! 2p2 772.421 11.72 1.17  107 1 3
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J. Appl. Phys. 117, 023306 (2015)
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi rffiffiffiffiffi
2k0 2 ln2RTg 7 Tg
DkD ¼ ¼ k0  7:16  10  ; (3)
c M M
where Tg is the gas temperature in kelvins, M is the atomic
mass of the individual absorbing atom, and R is the molar
gas constant.
In addition, in this discharge the electron density was
measured by a hairpin probe.34
III. RESULTS AND DISCUSSIONS
A. High frequency power effect
The effect of the HF power on the Ar* 1s5, 1s3 states,
and electron densities at different LF powers are shown in
Figures 2(a)–2(c), respectively. One sees that in single-
frequency (SF) plasma (i.e., the LF power is 0 W), initially,
the metastable argon atoms (1s5 and 1s3) densities increase
significantly with HF power, and then increase slowly when
the HF power is more than 60 W. Similar measurements
were done in DF plasmas for a fixed LF powers (i.e., 50 and
100 W), and we see that a more gentle increase in Ar* 1s5
and 1s3 state densities with HF power than the electron,
more specifically, as the HF power increases from 20 to
180 W, the electron density increases by a factor of about
8.5, while the Ar* 1s5 and 1s3 state densities increase by a
factor of 2.2. The similar trend for electron and argon meta-
stable indicates that electron impact ground state excitation
may be responsible for the production of the metastable ar-
ble than electron with HF power is attributed to their
stronger loss processes. For electron, diffusion together with
loss to the wall is the main loss source so that the electron
density rises almost linearly with the HF power, while for ar-
gon metastable, quenching collision with electron plays an
equally important role. In particular, as we can see from
Figures 2(a) and 2(b) that there are obvious inflexions in the
curves for Ar* 1s5 and 1s3 state at about 60 W, in other
be saturated at higher HF power. This suggests that at high
HF powers, the higher electron density enhances the loss of
metastable argon due to the quenching collision between
electron and metastable. Furthermore, we find that for each
HF power point, the metastable density is lower in presence
of the LF power, which is consistent with electron density.
This may be due to the argon metastable production process
by the electron impact excitation and will be discussed later
in more detail.
B. Pressure effect
Figures 3(a)–3(c) show the variation of argon 1s5, 1s3
states, and electron densities with the pressure in SF and DF
pure Ar plasmas, respectively. Taking SF case, for example,
we can see that both the 1s5 and 1s3 states densities increase
with the pressure, and when the pressure is above 60 mTorr,
8pgj c
(cm3) the metastable densities tend to be saturated, and show a
6.81  1021
slight decay above 110 mTorr. At low gas pressure (below
6.03  1020 60 mTorr), the increase in pressure raises the electron ioniza-
tion rate, and thus raises the electron density, which results
 023306-4 Liu et al. J. Appl. Phys. 117, 023306 (2015)

FIG. 2. The densities of metastable states 1s5 (a), 1s3 (b), and electron (c) as a function of the HF power at different LF powers in pure Ar discharges. The gas
pressure is constant at 50 mTorr and the electrode gap is 30 mm.

in an increase in argon metastable state atom densities.
Moreover, the increase of the pressure also leads to a lower
loss rate due to the diffusion.
The elevated pressure increases the electron-neutral col-
lision frequency and thus leads to the decrease in electron
temperature. Together with some other reasons, such as low
power deposition rate at high pressure and change of the
electron heating mechanisms, when the pressure is higher
than 60 mTorr, both the electron temperature and electron
density decrease with increasing pressure at higher pressure,
and these contribute to the decrease of Ar metastable produc-
tion rate. In addition to these, at higher pressure, the loss rate
of metastable state atom due to quenching collisions with the
ground state Ar atom is increased. So, when the pressure is
above 60 mTorr, the metastable state atom tends to be satu-
rated and even declines with pressure further to increase,
which is similar to that observed in previous studies for low-
pressure Ar ICP discharges.15
C. Axially resolved
Figures 4(a) and 4(b), respectively, show the axially
resolved density of the metastable argon (Ar*) in 1s5 and 1s3
states in SF and DF discharges at the HF power of 100 W
and pressure of 40 mTorr. One can see that the metastable
density is higher in SF discharge than that in DF discharge,
which is consistent with the results in Figures 2 and 3, and
this is mainly due to the higher electron density in SF dis-
charge. However, the variations of axial profiles of the meta-
stable states (1s5 and 1s3 states) with the pressure are similar
in both SF and DF discharge cases. At low pressure, i.e., 40
mTorr, the axial profiles of different species show asymmet-
rical parabolic distribution with the density peak at
z ¼ 7.5 mm. At 150 mTorr, the location for maximum meta-
stable density shifts to the powered electrode, i.e., at
z ¼ 5 mm as shown in Figures 4(c) and 4(d). The change
with pressure is in good agreement with previous
reports.35,36 The electron density, which was measured using
a hairpin probe along the reactor axis, shows the same trend,
i.e., at higher pressure, the peak of the electron density is
closer to the powered electrode. This is mainly due to the
asymmetric configuration of our discharge chamber, the
lower electrode and chamber walls were grounded, thus the
ground area is much larger than the powered electrode. This
leads to a high bias voltage at the powered electrode, which
enhances the electron heating and electron impact excitation
of Ar atom there. More importantly, this also could suggest
that the metastable states are largely formed by direct
electron-impact excitation.
The axial profiles of the metastable states 1s5 and 1s3
densities in Ar/CF4 mixed discharges at different pressures
are shown in Figures 5(a) and 5(b), respectively. Compared
to the results in Figure 4, we clearly see that the variation of
the axial profile of metastable state density with pressure
shows the same trend, and the addition of 10% CF4 results in
a significant decrease in the metastable density (the effect of
CF4 proportion on metastable state density will be discussed
later in more detail). As the pressure increases, the axial pro-
file of the metastable density shows a transition from sym-
metrical parabolic type to asymmetrical parabolic type with
the peak moving to the powered electrode, and especially, at
150 mTorr the metastable density shows a monotonous
decrease toward the ground electrode. Note that the monoto-
nous decreased density is different from the curve in pure ar-
gon discharge as shown in Figure 4. This may be due to the

FIG. 3. The densities of metastable states 1s5 (a), 1s3 (b), and electron (c) as a function of the pressure in SF (a) and DF (b) pure Ar discharges, respectively.
Note that the HF power is fixed at 100 W, and in DF discharge the LF power is fixed at 100 W. The electrode gap is 30 mm.

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 023306-5 Liu et al. J. Appl. Phys. 117, 023306 (2015)

FIG. 4. The axially profiles of the metastable states 1s5, 1s3, and the electron density at 40 mTorr (SF (a) and DF (b) discharges) and 150 mTorr (SF (c) and
DF (d) discharges), respectively. Note that the HF power is fixed at 100 W and in DF discharge the LF power is fixed at 100 W. The gap is fixed at 25 mm. The
values of 1s3 state density and electron density are increased in 10 and 20 times, respectively. The axial distance 0 mm corresponds to the powered electrode.
The red vertical dashed lines in these figures mark the maximum of the metastable density.

addition of 10% CF4, in which condition the sheath becomes
thin and thus the density peak is much closer to the powered
electrode. The move of density peak with the pressure can be
understood like this: at low pressure, the energy relaxation
length is much large than electrode spacing, and the axial
profile of electron density is dominated by diffusion rather
than axial power deposition profile, so it exhibits a symmet-
rical parabolic profile. When the pressure is higher, the
energy relaxation length becomes smaller than the electrode
gap and the power deposition is local rather than global. In
this situation, the axial density profile is determined by
power deposition and thus local ionization rate profile, which
is closer to the powered electrode at high pressure.

D. Proportion of CF4 effect

FIG. 5. The axially resolved profiles of the metastable states 1s5 (a) and 1s3
density (b) at different pressures. Note that the concentration of CF4 is fixed
at 10% in the Ar/CF4 discharge, and both of the HF and LF power are fixed
at 100 W and the gap is fixed at 25 mm.
Figures 6(a) and 6(b) show the variation of metastable
atoms densities with CF4 content at different pressures of 10
mTorr, 50 mTorr, and 100 mTorr. It shows that a small
amount addition of the CF4 leads to a significant decrease in
the metastable atom density for both 1s5 and 1s3 states. At
10 mTorr, the density of 1s5 state atom decreases by a factor
of 4–5 when the proportion of CF4 increases from 0% to
35%, while more than an order of magnitude drop is
observed for 100 mTorr pressure. That is, to say, the density
of Ar 1s5 and 1s3 states in higher pressures (100 mTorr) case
decrease more dramatically with the proportion of CF4 than
that in lower pressures (10 mTorr). For pure argon discharge,
the dominant loss processes for Ar metastable atom are
electron-induced quenching and diffusion. While as the
increased of CF4 proportion the electron density drops rap-
idly and thus leads to the decrease in electron-induced
quenching. The dramatic decrease in the two metastable
states densities was attributed to the quenching process
induced by the CF4 molecule.37 Especially, in higher pres-
sure (100 mTorr) CF4/Ar discharge the collision quenching

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 023306-6 Liu et al.
FIG. 6. The metastable states density in argon 1s5 (a) and 1s3 (b) states as a
function of CF4 content for different pressure of 10, 50, and 100 mTorr. In
SF discharge, the HF power is fixed at 100 W, and in DF discharge both the
HF and LF power are fixed at 100 W. The electrode gap is 30 mm. Note that
the solid lines indicate the measurements in SF discharge, and the dashed
lines indicate that in DF discharge.
with CF4 dominates the metastable destruction processes,
and the loss rate is almost linearly with the CF4 density
increasing. Thus, in lower pressure discharge this loss rate is
less than that in higher pressure at the same CF4 content. The
production and loss mechanisms of the Ar metastable state
will be presented later in more detail.
E. Simple rate model
In order to explain the experimentally observed Ar met-
astable state density, a simple rate model, including different
production and loss processes, was employed. In this work,
the measured Ar*1s5 density was about an order of magni-
tude greater than the 1s3. To simplify the analysis, we only
investigate the Ar*1s5 state.
In the literature the production of the Ar metastable
atoms are mainly due to three processes: (1) Electron impact
process, such as electron impact ground state excitation (Ar
(g) þ e ! Ar* þ e), direct conversion of the resonant to the
metastable state by electron collisions (Ar (r) þ e ! Ar* þ e,
3  107 cm3 s1).27,35,38 (2) Ion impact process, such as Arþ
ion and Ar atom impact excitation to the metastable state
(Ar þ Arþ ! Ar* þ Arþ Ion-impact excitation) and radiative
recombination (Arþ þ e ! Ar* þ hv, krec ¼ 1  1011 cm3
s1).39 (3) The radiative transition from higher excited states
(most are 2p states) to the metastable states (Ar (2p) !
Ar* þ hv, krad ¼ 3  107 s1).40 Figures 2(a) and 2(c) show
the Ar metastable atoms and the electron densities in SF
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J. Appl. Phys. 117, 023306 (2015)
discharge is generally higher than these in the DF case at vari-
ous HF powers. Furthermore, Figure 4 shows that the axially
resolved density of the metastable argon (Ar*), for example,
at 150 mTorr, highly resembles axial profile of electron den-
sity. These results indicate the metastables are largely formed
by direct electron-impact excitation rather than the ion-impact
excitation. The contribution of the reaction of Ar (r) þ e !
Ar* þ e also could be ignored compared with the direct elec-
tron impact excitation with the feedstock gas, due to the lower
densities of resonant states.16 Similarly, the densities of 2p
states are lower than resonant states Ar atoms due to the
higher energy, thus this process is also negligible. We
deduced that under this conditions, and in Ar/CF4 discharges
the Ar metastable atoms are primarily produced by direct
electron-impact ground state Ar atom excitation, which is also
in agreement with McMillin’s result under the similar condi-
tions.27 And the balance equation for the metastable atoms is
given as6,26,38
X
nArðgÞ ne kge ¼ kmj nArðmÞ ne þ kqCF4 nArðmÞ nCF4
j
þ kqAr nArðmÞ nAr þ kdif nArðmÞ ; (4)
where nAr(g) is the density of background argon, ne is the
electron density, nAr(m) is the density of metastable state
atom, and nCF4 is the density of CF4 molecule. kge is the rate
coefficients for metastable excitation from the ground state
argon, kqCF4 and kqAr are the rate coefficient of quenching
induced by the ground state CF4 and Ar, respectively. kmj is
the total rate coefficients of electron impact loss processes
for the metastable state, including the conversion from the
metastable state to a 4p and nearby resonant levels (kexc),
ionization (kion), superelastic collisions (ksup) and conversion
from metastable to resonant state (kres), respectively. The dif-
fusion losses of the metastable atoms to the wall are esti-
mated by an effective loss rate coefficient given by1
" #1
K20 2ð2  cÞ V
kdif ¼ þ ; (5)
D ct S
here K  L/p is the characteristic diffusion length, where L
is the interelectrode spacing, c is the sticking coefficient on
the wall, for the Ar metastable states atom the sticking
coefficient equal to 1.41 The S and V, respectively, represent
the surface area of the electrode and volume of the plasma,
t ¼ ð8KB Tg =pMR Þ1=2 is the neutral mean velocity. D is the
diffusion coefficient of the metastable state atom given by42
KB Tg k
D¼ ; (6)
t MR
where KB is the Boltzmann coefficient, Tg is the gas tempera-
ture, k is the neutral–neutral species mean free path calcu-
lated from the neutral–neutral collision cross section data,
and MR is the reduced mass.
In pure Ar discharge, the main production mechanism of
Ar metastable states is the direct electron impact excitation,
while the dominate loss process is diffusion and electron
impact loss processes, i.e., the metastable atom is excited into
 023306-7 Liu et al.
TABLE II. Rate coefficients used in the simplified model.
Reaction
Ar (g) þ e ! Ar(1s5) þ e
Ar* þ e ! Ar (2pn) þ e
Ar* þ e ! Ar (r) þ e
Ar* þ e !Arþ þ e
Ar* þ CF4 ! Ar (g) þ CF3 þ F
2p-levels, converted into resonant states and ionized. Other
electron impact loss mechanism for the metastable state could
be ignored due to the lower rate coefficients.27,40,43 Moreover,
two- and three-body quenching with background Ar atoms
are also not important in this low pressure discharge.39 Thus,
in pure Ar discharge, this equation can be rewritten as
nArðgÞ ne kge
nArðmÞ ¼ : (7)
kdif þ ðkexc þ kres þ kion Þne
In this equation, the rate coefficients are summarized in
Table II. Note that the electron density were measured by a
hairpin probe and taken as the input variable. The densities
of ground state argon atom can be calculated by the ideal gas
law when the gas temperatures are deduced by the Doppler
width of the metastable atoms absorption line. In this dis-
charge, the gas temperatures increase with HF power, LF
power and pressure. When the gas pressure is 100 mTorr and
the HF power is 20–180 W, gas temperatures are calculated
to be about 400–440 K in SF discharge, and when the LF is
applied the temperatures increase about 5 K.45,46 So it is pos-
sible to make a quantitative estimation of the argon 1s5 meta-
stable state density.
Figure 7 shows comparison of 1s5 metastable state den-
sity obtained by experiment and calculation using Eq. (7).
Herein, kge, kexc, and kion are the exponential function of
electron temperature Te, as shown in Table II. To simplify
the calculation process, we assume a constant electron tem-
perature Te at different HF powers when the pressure is fixed.
The assumption is rational, as the electron temperature has a
FIG. 7. Measured and calculated 1s5 metastable density from the simplified
model as a function of HF power in DF discharges with pure Ar at 20
mTorr, 50 mTorr, and 100 mTorr. Both of the HF and LF powers are fixed
at 100 W. The electrode gap is 30 mm.
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Rate coefficient (cm3 s1) Ref.
9
kge ¼ 2.7  10 exp(11.9/Te) 40
kexc ¼ 1.26  106 exp(2/Te) 40
kres ¼ 3  107 Te0.5 40
kion ¼ 1  107 exp(4.2/Te) 43
kq CF4 ¼ 4  1011 44
weak dependence on the HF power. The electron tempera-
tures are measured by a floating double probe, and the meas-
ured results are 4.8 eV, 3.7 eV, and 3.2 eV at 20 mTorr, 50
mTorr, and 100 mTorr, respectively. One can see from
Figure 7 that the optimal agreement between experiment and
calculation is obtained at 100 mTorr. In particular, we can
notice that with the decrease of the pressure, the deviation of
calculated results from experiment gradually get large. This
is attributed to the fact that in low pressure CCPs, the EEDF
typically exhibits a bi-Maxwellian distribution, in which the
electrons can be divided into two groups, i.e., high-
temperature high-energy electron group and low-temperature
low-energy electron group, and thus the rate coefficient
should be calculated by integrating over the EEDF rather
than an simple exponential function of electron temperature
Te.47 However, as pressure increases (100 mTorr and above),
the EEDF tends to be Maxwellian-like distribution, and reac-
tion rate coefficients could be directly obtained by a simple
exponential function. So, at 100 mTorr, the calculated results
show a good agreement with experiment.
We have seen from Figure 6(a) that the addition of 5%
CF4 in background argon at pressure of 100 mTorr results in
a decrease of Ar metastable state density by 60%. The rea-
son is twofold: (1) a reduction in electron density due to the
presence of negative ions; (2) the decay of argon metastables
by quenching collision with CF4 molecule. Both of these fac-
tors give rise to a decrease in production rate and an increase
in destruction rate for Ar metastables. Thus, in this Ar/CF4
discharges, CF4 quenching process can dominate the meta-
stable destruction mechanism.27 And after considering the
quenching collision with CF4, the Eq. (7) can be rewritten as
nArðgÞ ne kge
nArðmÞ ¼ : (8)
kdif þ ðkexc þ kres þ kion Þne þ kqCF4 nCF4
Figure 8 shows the calculated 1s5 metastable density as a
function of proportion of CF4 at 100 mTorr. In this discharge,
since the threshold energy for the dissociative ionization of
CF4 molecules is almost same as the ionization potential for
Ar atoms, the electron temperature is weakly influenced by the
CF4 dilution.10 Note that, in Ar/CF4 mixed discharge, it is diffi-
cult to measure the electron temperature accurately using a
double probe due to contamination. So, we assume that the
electron temperatures were almost unchanged at different pro-
portions of the CF4. As reported by Nakano et al.,10 since the
threshold energy for the dissociative ionization of CF4
molecule(16.2 eV) is almost same as the ionization potential
for Ar atom(15.8 eV), the electron temperature is weakly
 023306-8 Liu et al.
influenced by the CF4 dilution. So the electron temperature
(i.e., 3.2 eV) that has been measured in pure Ar discharge
under the same discharge conditions is roughly taken as the
input parameter of Eq. (8). When we adopt kq CF4 ¼ 4  1011
cm3 s1 as the rate coefficient of metastable atom quenched by
CF4 molecule with the reaction Ar* þ CF4 !
Ar þ CF3 þ F.43,44 We find that the calculated densities of met-
astable argon are overestimated.44 We suspect that in addition
to the dissociation reaction Ar* þ CF4 ! Ar þ CF3 þ F, there
may exist other quenching reactions, such as, the reaction of
radicals and metastable atom.48 In this discharge, when the gas
pressure is 100 mTorr and CF4 content is 10% in mixed gas,
the density of CF2 is measured to be about 1012 cm3 by the
broadband ultraviolet absorption spectroscopy. The density of
CF3 is almost one order of magnitude higher than that of CF2
as reported by Rakhimova et al.49 under the same conditions.
In general, the large quenching rate constants are always found
when the metastable energy is very close to or above the
energy thresholds.50 Although the rate coefficient of metasta-
ble atom quenched by CF3 radical is not known, but it is
expected to be higher than that of CF4 molecule, since the
energy thresholds of CF3 dissociation is lower than CF4.
Furthermore, as reported by Velazco et al.51 the rate coefficient
of metastable atom (1s5) quenched by F2 molecule is
75  1011 cm3 s1, which is about 20 times higher than that
of CF4 molecule. The molecular F2 is formed by wall cata-
lyzed recombination of F atoms, and the reaction CF þ F2 !
CF2 þ F is the dominant loss mechanism of CF in the gas
phase.52 In this case, the contribution of F2 may not be negligi-
ble when the density of F2 is of the same order of magnitude
as that of CF2. So that we speculate that in this discharge some
higher density and higher quenching coefficient radicals, such
as CF3, F2, also contribute to the quenching of metastable
states. And the neglect of the quenching reactions of metasta-
ble states with other radicals may lead to the deviation of the
calculated and experimental values in Figure 8.
Figure 9 shows calculated loss rates for Ar metastables
due to diffusion, electron collisions, and CF4 quenching as a
function of the proportion of CF4 in Ar/CF4 discharges for
20 mTorr and 100 mTorr. From this figure, we can conclude
FIG. 8. Measured and calculated 1s5 metastable density as a function of pro-
portion of CF4 in DF discharges at 100 mTorr. Both the HF and LF powers
are fixed at 100 W. The electrode gap is 30 mm. Note that the short dashed-
dotted line indicates the calculated 1s5 metastable densities when the rate
coefficient of metastable atom quenched by CF4 molecule is 4.0  1011.
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FIG. 9. Calculated loss rates for Ar metastables by diffusion, electron
quenching and CF4 quenching in an Ar/CF4 discharges at 20 mTorr (solid
line) and 100 mTorr (dashed line). Both the HF and LF powers are 100 W
and the electrode gap is 30 mm.
that in 20 mTorr pure Ar discharge, the fraction of Ar meta-
stables lost by the electron quenching is close to diffusion
loss. While at 100 mTorr the role of diffusion is decreased
rapidly, and the electron quenching loss is the primary pro-
cess for the metastable state loss. However, in the Ar/CF4
discharges, only a small amount addition of CF4, CF4
quenching loss can dominate the metastable destruction pro-
cess. At 20 mTorr, when the CF4 concentration is more than
10%, the relative loss fraction of metastable by CF4 quench-
ing is nearly half of the total loss rate. At higher pressure
(i.e., 100 mTorr), other loss processes could be negligible
compared with the CF4 quenching loss. Thus, in the Ar/CF4
discharges, for large CF4 content and high pressure, CF4
quenching loss becomes the dominant depopulation process.
IV. CONCLUSION
In this work, we measured the Ar*(3P2) and Ar*(3P0)
metastable atoms densities in dual-frequency capacitively
coupled discharges in Ar and Ar/CF4 mixtures using the tun-
able diode laser absorption spectroscopy. The effects of dif-
ferent control parameters, such as HF power, LF power, gas
pressure, and content of CF4, on the densities of metastable
atoms and electron density are discussed, respectively.
Especially, the axial profiles of the two metastable atoms
densities at different pressures are discussed. In addition, a
simple rate model is employed to analyze the dominant pro-
duction and loss processes. It is found that metastable is
mainly produced by electron impact excitation from the
ground state, and decayed by diffusion and collision quench-
ing with electrons and neutral molecules. In pure Ar dis-
charge, at low pressure (20 mTorr) the mainly loss processes
for Ar metastable states are electron quenching and diffu-
sion; while only the electron quenching process will domi-
nate the metastable loss for the pressure at 100 mTorr. In the
Ar/CF4 discharges, CF4 quenching loss plays an important
role in the metastable destruction rate. At 20 mTorr, the rela-
tive loss fraction of metastable by CF4 quenching is nearly
half when CF4 concentrations is above 10%; especially at
higher pressure (i.e., 100 mTorr), other loss mechanisms
may be negligible compared with the CF4 quenching loss.
 023306-9 Liu et al. J. Appl. Phys. 117, 023306 (2015)

21
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