Excerpt from the Proceedings of the 2011 COMSOL Conference in Boston

Efffect of Gaas Flow R

Rate and Gas Com
mpositionn in Ar/C
CH4
Indductively Coupledd Plasmass
Lizhhu Tong1
1
Kessoku Engineeering System
m Co., Ltd.
1-9-55 Uchikandaa, Chiyoda-kuu, Tokyo 1011-0047, Japann, tong@kescco.co.jp

Absttract: The ddischarge prooperties in low [7] studied thhe low-temperature deposiition of
presssure inductiveely coupled Ar/CH4 plasm mas oordered carboon nanostructtures in induuctively
operaating at a rf frequency of 13.56 MHz and ccoupled Ar/CH H4/H2 plasmass by experimeents and
total gas pressure oof 20 mTorr aare studied in this a spatially aveeraged (globall) model, in w which a
workk. The calculaation of gas fllow is perform med loow-frequency (0.46 MHz) ICP I source waas used.
in cooupling with thhe plasma simmulation. The gas Inn their reporrt, the densiities of neutrral and
flow rate is variedd from 20 to 1000 sccm. T The ccharged speciees were presennted and the eeffect of
speciies taken into account incluude electrons, six AAr dilution annd input flux oof CH4 in a raange of
kindss of moleculees, eleven kinnds of ions, ffive fl
flow rate oof 3-8 sccm m was disscussed.
kindss of neutral radicals, andd five kinds of UUnfortunately, their study did not revveal the
excitted species. 59 chemicaal reactions are spatial profiless of neutral annd charged speecies as
consiidered. The deensity profiles of all the plassma wwell as the proofiles of electtron temperatuure and
speciies for the different gas fllow rates andd Ar ccollisional powwer loss in thhe discharges,, which
fractiions are oobtained andd the electtron aare essential properties in low-tempperature
tempperature and thhe total collissional power lloss pplasma discharrges.
are ppresented. In this wwork, the indductively couppled rf
(13.56 MHz) plasmas
p in Arr/CH4 are studdied by
Keywwords: ICP pplasma, Gas ccomposition, G
Gas uusing an axisyymmetrical tw wo-dimensionaal fluid
flow rate, Coupledd calculation. mmodel providded in the Plasma Moddule of
CCOMSOL Muultiphysics. Thhe plasma sim mulation
1. In
ntroduction iss coupled witth the solutionn of fluid dynnamics.
TThe dischargee properties iincluding the spatial
Plasma-induced chemical-vvapor deposittion
P pprofiles of alll the plasma species as w well as
(PCVVD) is the moost common method used for eelectron tempeerature and coollisional pow wer loss
the deposition off carbon film ms. One of the aare reported. T
The effect of ggas flow rate aand gas
essenntial parameteers to determ mine the PC CVD ccomposition inn Ar/CH4 on ddischarge properties is
grow
wth of carbon film is the feeed gases, suchh as ppresented.
CH4. Inductively coupled
c ma (ICP) reactors
plasm
which have high input efficieency and operate
under lower gas ppressure havee been develooped
for microelectronnics fabricattion. The IICP
plasm a pressures lower
mas are typicaally operated at
than 100 mTorr inn typical electrron density raange
of 11016-1018m-3. Such high-ddensity plasm mas
contaaining CH4 are a useful soources of active
speciies, such as doominant radicaals like CH3, C
CH2
and H for depositioon [1-6].
T
The investigattions of induuctively couppled
plasmma discharges in CH4 and its i mixtures hhave
been reported [1,,7]. Bera andd co-workers [1]
used a self-conssistent two-diimensional fl fluid
modeel to study inductively coupled raddio-
frequuency (13.56MMHz) plasma ddischarges in C CH4
and a surface chhemistry moddel was usedd to
Figure 1. M
Model geometryy used in this woork.
prediict the diamond-like-caarbon thin-ffilm
deposition/etch ratte. Denysenkoo and co-workkers
2. Numerical Model mixtures are varied from 0 to 100%. The species
taken into account include electrons, atoms (Ar),
The model geometry used in this work is molecules (H2, CH4, C2H2, C2H4, C2H6, C3H8),
shown in Fig. 1, which has been described in ions (Ar+, H2+, H+, CH+, CH2+, CH3+, CH4+, CH5+,
earlier publications [8,9]. The simulations are C2H2+, C2H4+, C2H5+, C2H6+), neutral radicals (H,
performed for the case of Ar/CH4 ICP plasma CH, CH2, CH3, CH5) as well as the excited
discharges operating at the rf frequency of 13.56 species (Ar*,CH4*(2vib.),H(2p,3p)).The reactions
MHz and total gas pressure of 20 mTorr with the of electron impact collision and those of ions and
gas flow rates of 20-1000 sccm. The gas neutral species are listed in Tables 1 and 2.
temperature is assumed to be 300 K and input In calculations, the gas flow velocities and
power is 300 W. The Ar fractions in the Ar/CH4 gas pressures obtained from the gas flow
calculation are inputted into the plasma
Table 1: The electron reactions included in the model. simulation as well as the gas densities and
dynamic viscosities obtained from the plasma
No. Reaction Ref. simulation are inputted back into the gas flow
calculation. The calculation of gas flow is
1 Ar Ar ∗ 10 performed by a laminar flow model provided in
∗
2 Ar Ar 10 COMSOL Multiphysics. In plasma simulations,
3 Ar Ar 2 10 the initial electron number density is assumed to
4 Ar ∗ Ar 2 10 be 1×1012 m-3 and initial electron energy is 4 eV.
5 CH CH∗ 2 . 11 The electron energy distribution function
6 CH CH 2 11 (EEDF) is assumed Druyvesteynian distribution
7 CH CH H 2 11 Table 2: The reactions of ions and neutral species
8 CH CH H 11 included in the model.
9 CH CH 2H 11
10 CH CH 3H 11 No. Reaction Ref.
11 CH CH 3H 11 34 CH CH CH CH 4
12 H H 2 12 35 CH CH C H H 4
13 H 2H 12 36 CH CH CH CH 4
14 H H 2 , 3 13 37 H CH CH H 4
15 H 2 ,3 H 13 38 C H CH C H CH H 4
16 H H 2 13 39 CH Ar CH H Ar 7
17 C H C H 2 14 40 H Ar ArH H 7
18 C H C H 2H 14 41 H Ar Ar H 7
19 C H C H 2 14 42 CH CH C H 3
20 C H C H H 14 43 CH HCH 3
21 C H C H 2 14 44 C H HCH CH 3
22 C H C H H 2 14 45 C H CH C H 3
23 C H C H H 14 46 CH HCH H 3
24 C H C H 2H 14 47 CH CH C H 3
25 C H C H 2 14 48 CH CH CH CH 3
26 C H C H H 2 14 49 CH CH C H H 3
27 CH CH H 14 50 CH CHC H H 3
28 CH CH 2H 14 51 CH CH C H H 3
29 CH CH 2 14 52 C H HC H H 3
30 CH CH H 14 53 CH CH C H H 3
31 CH CH 2 14 54 Ar ∗ Ar ∗ Ar Ar 10
32 CH CH 2 14 55 Ar ∗ ArAr Ar 10
33 ArH Ar H 15 56 Ar ∗ H Ar H H 15
 F
Figure 2. Dischharge structure iin a 95%Ar/5%C
[1,7]]. The initiaal ion number densities are
assiggned by sustaiining the electtroneutrality. T
The
seconndary electronn emission duee to ion impacct is
set too zero and ionns are considerred as completely
absorrbed/neutralized when theey arrive at the
electrrodes. The exxcited moleculles and atoms are
set to revert to thheir ground sstates when tthey
contaact with the walls.
3. Results
F
Figure 2 show
ws the calculattion results foor a
95%AAr/5%CH4 ICCP plasma at a gas flow of 500
CH4 ICP plasma at a gas flow oof 50 sccm.
sccm. The fastt flow velocitiies appear aroound the
innlet and outleet of gas flow with a maaximum
vvalue of 7.51 m s-1. The m maximum of eelectron
ddensities arrivves at 3.03×10017 m-3. The eelectron
teemperature apppears in the range
r of 3.17~ ~4.02eV.
TThe collisionaal power losss has a tendeency to
eextend towardds the inlet off gas flow frrom the
ccenter of plasma dischargee, demonstratiing that
thhere exist stroong collisions between the charged
c
pparticles and inflow
i gas. T
The maximum m of the
ddensities of A Ar+ ions arrivees at 2.63×10017 m-3,
wwhich is aboout 87% off that of eleectrons,
ggoverning the discharge struucture. It is fouund that
the densities of H atoms are high, the maximum 1E+19
of their profiles arriving at 3.6× 1018 m-3. The
electron densities and electron temperatures in a

Electron density (m-3)

1E+18
function of gas flow rate for the different Ar
fractions, at the maximum of their profiles, are
shown in Fig. 3. The electron densities increase 1E+17
and electron temperatures decrease with a rise in 0%Ar
gas flow rate for the different Ar fractions. The 1E+16 50%Ar
electron densities in a function of Ar fractions 95%Ar
are given in Fig. 4. It is known that the electron 100%Ar
densities rise with an increase in Ar fractions due 1E+15
0 200 400 600 800 1000
to the decrease of collisional power losses
Flow rate (sccm)
compared with molecular states. In the present
work, the effect of a small amount (5%mol) of 6
CH4 added to Ar is found to be so large that the
electron densities are greatly decreased. 5

Electron temperature (eV)

The densities of ions and neutral radicals, at
4
the maximum of their profiles, are given in Fig.5.
The effect of gas flow on Ar+ is little for the case 3
that the Ar fractions are less than 50% and
becomes important only when the Ar fractions 2 0%Ar
50%Ar
are increased close to pure Ar. The similar 1 95%Ar
effects are found for ions CH5+, C2H5+, and CH3+, 100%Ar
which present a largest increase at a small 0
amount (5%mol) of CH4 added to Ar. From 20 to 0 200 400 600 800 1000
Flow rate (sccm)
1000 sccm, the densities of CH3+ ions increase
one order and those of CH5+ and C2H5+ increase
over two orders. It is also found that at the pure Figure 3. Electron densities and electron temperatures
at the maximum of their profiles for the different Ar
CH4 discharges, CH5+ ions are the most
fractions at the gas flows of 20-1000 sccm.
important ions as consistent with the previous
study [3]. As the increase of Ar fractions, C2H5+
ions become the most important ions. The 1E+19
radicals CH3, CH2, and CH appear high densities
(5.5×1017~3.5×1018 m-3) in the plasmas even in 1E+18
Electron density (m-3)

the case of 5%CH4 added to Ar. In the present

work, the most major neutral radical is found to 1E+17
be H atom, which densities are over 3×1018 m-3. 20sccm
Barshilia and Vankar [5] have indicated that H 1E+16
100sccm
atoms are a major source to deposit/etch a 500sccm
diamond-like carbon thin film on a wafer [5]. 1000sccm
The present work provides an efficient method to 1E+15
estimate the distribution of H atoms, which 0 0.25 0.5 0.75 1
would be a key to the deposition of good quality Ar fractions
diamond thin films.
Figure 4. Electron densities at the maximum of their
profiles for the different flow rates at the Ar fractions
4. Conclusions from 0 to 1.

This paper presents the simulation results of Ar/CH4. The fully coupled calculation of plasma
low-pressure inductively coupled rf plasmas in discharge and fluid dynamics is realized by
COMSOL Multiphysics. It is found that the
 1E+20 1E+20 1E+20
Ar+ C2H5+ CH5+
1E+19 1E+19 1E+19

Density (m-3)
Density (m-3)
Density (m-3)

1E+18 1E+18 1E+18

1E+17 1E+17 1E+17

1E+16 1E+16 1E+16

50%Ar 0%Ar 0%Ar
1E+15 95%Ar 1E+15 50%Ar 1E+15 50%Ar
100%Ar 95%Ar 95%Ar
1E+14 1E+14 1E+14
0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000
Flow rate (sccm) Flow rate (sccm) Flow rate (sccm)

1E+20 1E+20 1E+20

CH4+ CH3+
1E+19 1E+19 1E+19
Density (m-3)

H atom
Density (m-3)

Density (m-3)
1E+18 1E+18 1E+18

1E+17 1E+17 1E+17

1E+16 1E+16 1E+16 0%Ar

0%Ar 0%Ar 50%Ar
1E+15 50%Ar 1E+15 50%Ar 1E+15 95%Ar
95%Ar 95%Ar
1E+14 1E+14 1E+14
0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000
Flow rate (sccm) Flow rate (sccm) Flow rate (sccm)

1E+20 1E+20 1E+20

CH radical CH2 radical
1E+19 1E+19 1E+19
Density (m-3)
Density (m-3)
Density (m-3)

1E+18 1E+18 1E+18

CH3 radical
1E+17 1E+17 1E+17

0%Ar 1E+16 0%Ar 1E+16 0%Ar

1E+16
50%Ar 50%Ar 50%Ar
1E+15 95%Ar 1E+15 95%Ar 1E+15 95%Ar

1E+14 1E+14 1E+14

0 200 400 600 800 1000 0 200 400 600 800 1000 0 200 400 600 800 1000
Flow rate (sccm) Flow rate (sccm) Flow rate (sccm)

Figure 5. Densities of ions (Ar+, C2H5+, CH5+,CH4+,CH3+) and neutral radicals (H,CH,CH2,CH3) at the
maximum of their profiles for the different Ar fractions at the gas flows of 20-1000 sccm.

electron densities increase and electron over two orders. It could be concluded that the
temperatures decrease with a rise in gas flow rate control of gas flow rate and gas composition
for the different Ar fractions. The radicals CH3, would be very beneficial in obtaining the
CH2, CH, and H appear the high densities over deposition of good quality thin films.
all the gas flow rates and different Ar fractions.
The gas flows present the largest influence on 5. References
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6. Acknowledgements
The author would like to thank Emeritus
Professor K. Nanbu of Tohoku University, Japan
for the helpful discussion regarding this research.