Optical and mass spectrometric

measurements of dissociation in low

frequency, high density, remote source O2/Ar
and NF3/Ar plasmas
Cite as: J. Vac. Sci. Technol. A 38, 023011 (2020); https://doi.org/10.1116/1.5126429
Submitted: 02 September 2019 . Accepted: 14 January 2020 . Published Online: 12 February 2020

Hanyang Li, Yingliang Zhou, and Vincent. M. Donnelly

J. Vac. Sci. Technol. A 38, 023011 (2020); https://doi.org/10.1116/1.5126429 38, 023011

© 2020 Author(s).
 ARTICLE avs.scitation.org/journal/jva

Optical and mass spectrometric measurements

of dissociation in low frequency, high density,
remote source O2/Ar and NF3/Ar plasmas
Cite as: J. Vac. Sci. Technol. A 38, 023011 (2020); doi: 10.1116/1.5126429
Submitted: 2 September 2019 · Accepted: 14 January 2020 · View Online Export Citation CrossMark
Published Online: 12 February 2020

Hanyang Li, Yingliang Zhou, and Vincent. M. Donnellya)

AFFILIATIONS
Department of Chemical and Biomolecular Engineering, University of Houston, Houston, Texas 77204

a)
Electronic mail: vmdonnel@central.uh.ed

ABSTRACT
Remote plasma sources are widely used in applications such as chamber cleaning and flowable chemical vapor deposition. In these
processes, it is desirable that the dissociation rate of feed gases be as high as possible and stable. Here, the authors present results on radical
densities and gas dissociation fractions for a 400 kHz toroidal transformer-coupled plasma source (MKS Instruments), operating at a power
density of 5–50 W/cm3 with feed gas mixtures of O2 or NF3 in Ar and pressures of 0.4 or 2.0 Torr. Radical densities and feed gas
dissociation percentages in the plasma were measured by optical emission spectroscopy combined with Ar actinometry. In the plasma, O2
was about 60% dissociated in dilute O2 mixtures (10%–20%). Dissociation decreased with the increasing addition of O2, dropping to 10%
dissociation for 90% O2 in the feed gas. NF3 was >95% dissociated for all NF3/Ar mixtures. Little or no dependence on the flow rate
was found. Plasma products flow into an anodized Al downstream chamber that is probed by vacuum ultraviolet (VUV) absorption
spectroscopy and line-of-sight molecular beam mass spectrometry. In the downstream chamber, O recombined on the walls to form O2
(detected by VUV O2 absorption). The measured downstream O/O2 ratio was a strongly increasing function of an increasing flow rate
reproduced by a downstream global model with O wall recombination probability of γO between 0.001 and 0.002. NF3 does not reform in
the downstream chamber, as verified by VUV absorption and mass spectrometry. No NF or NF2 was detected, and F mostly recombined to
form F2 at the back of the downstream chamber, along with N2. The F2, F, and N2 product absolute number densities were consistent with
the 3:1 F:N mass balance of the NF3 feed gas.

Published under license by AVS. https://doi.org/10.1116/1.5126429

I. INTRODUCTION
1,2
Modern plasma reactors used in etching, thin film chemical
vapor deposition (CVD),3–5 and chamber cleaning6–9 have many
configurations of electrodes and power delivery. When the substrate
is positioned in the plasma reactor, ion bombardment promotes
anisotropic etching, but ions as well as vacuum ultraviolet (VUV)
light can also damage materials. Remote plasma sources are some-
times used to etch or deposit materials as well as modify deposited
films. In this case, the substrate is not exposed to ion bombardment;
hence, etching is isotropic. Remote plasmas such as NF3-containing
plasmas are also used to clean chamber walls. In these and other
downstream applications, such as “flowable CVD” (FCVD),10,11 gas
is fed to the remote plasma source, generating radicals that flow
through a short tube to the process chamber, where they react with
the substrate or the interior surfaces of the downstream chamber.
The primary requirement for a remote plasma source is high effi-
ciency of radical production at high flow rates and stable number
densities of reactive species over time.
Initially, high power microwave plasmas were developed as
remote plasma sources.12 More recently, transformer coupled toroi-
dal plasma (TCTP) sources with relatively compact and simple
designs have provided an attractive alternative to microwave plasmas.
TCTP sources contain a donut-shaped toroidal chamber. RF power
is transferred to the plasma by a transformer circuit. The plasma
itself acts as the secondary closed loop of the transformer. Very high
power densities can be achieved in TCTPs (e.g., 5 W/cm3 for Ar and
15 W/cm3 for C2F613,14). Because processing rates scale with the flux
of radicals such as O, F, and H delivered by the remote plasma
source, it is important to measure and control the degree of dissocia-
tion of feed gases such as O2, NF3, NH3, and H2, as well as the rate
of atom recombination.

J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429 38, 023011-1
Published under license by AVS.

O2/Ar and NF3/Ar plasmas were chosen as prototype processes.
O2/Ar discharges have been extensively studied. Most of these inves-
tigations are of lower pressure, capacitively coupled,15,16 inductively
coupled,17–20 and electron cyclotron resonance sources,21 along with
modeling of these types of plasmas.22–26 Apparently, there are no
published studies on low frequency, high power density, inductive
toroidal oxygen plasmas. Similarly, most studies of NF3 plasmas,
with or without added Ar, are for lower pressure, capacitively
coupled,27,28 inductively coupled (nontoroidal),29 and hollow-
cathode discharge plasmas.30 Less work31,32 has been reported for
toroidal plasmas. Thus, the purpose of this study is to measure the
products in and downstream from a remote TCTP by optical emis-
sion spectroscopy (OES), combined with Ar actinometry, VUV
absorption, and mass spectrometry to gain insights into the dissocia-
tion processes in these sources.
II. EXPERIMENTAL METHODS
A. Experiment setup
The remote plasma source used in this study (MKS Corp.
ASTRON®ex AX7685) is shown schematically in Fig. 1. It consists
of a toroidal anodized aluminum chamber, inside of which a
plasma current loop is generated through inductive coupling from
an RF source (∼400 kHz). The remote plasma source was switched
FIG. 1. Side view of the schematic diagram of experimental apparatus. (The deuterium lamp and VUV spectrometer are perpendicular to the page.)
J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429
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ARTICLE avs.scitation.org/journal/jva
on by supplying a brief high voltage to a small electrode that capac-
itively couples to the gas through a thin sapphire window. The
plasma source was cooled with a closed loop of de-ionized water.
Emission along the lower half of the discharge loop was recorded
through a 1 in. diam. sapphire window.
As shown in Fig. 1, a water-cooled, anodized aluminum down-
stream chamber was connected to the plasma source by a 1.5 in. long
tube that is also made of anodized aluminum. This chamber was
connected to a 4 in. diam. stainless steel pipe that leads to a roots
blower pump (Leybold WS151), backed by a roughing pump (Leybold
D40BCS). The pressure could be controlled by a throttle valve between
the chamber and pumps. A capacitance manometer and a thermocou-
ple pressure gauge were connected to the chamber to measure the
pressure. Flows of O2, NF3, and Ar were fed to the plasma source by
mass flow controllers (MKS model 1259B or 1179A).
One of four spectrometers (Ocean Optics) was used to
perform OES along the axis of the lower half of the plasma loop.
These spectrometers covered wavelength ranges of 190–415 nm
(model Pro 2000), 400–615, 578–777, and 735–917 nm (models
HR 4000), with spectral resolutions (full width at half maximum)
of 0.14 nm. Light passing through the sapphire window was
directed, with the use of an optical fiber, to the spectrometer.
Optical emission spectra were recorded with a 10 ms integration
time, averaged over 20 exposures.
38, 023011-2

The downstream chamber contained opposing sapphire and
MgF2 windows to allow VUV absorption measurements to be
carried out along an axis perpendicular to the OES axis. The VUV
absorption axis is at a distance of 7.6 cm from the face of the output
flange of the plasma source. A deuterium lamp (Hamamatsu
L11798) was connected to one MgF2 window of the downstream
chamber. On the other side, a VUV monochromator (McPherson
model 234/302), equipped with a photomultiplier tube (Hamamatsu
model No. R6095), was connected to another MgF2 window. Both
the light source and the UV monochromator were pumped by an
ion pump (Varian 020-TT).
A molecular beam line-of-sight quadrupole mass spectrometer
(Extrel QMS flange mounted system) was installed at the back of the
downstream chamber. Downstream neutral species were sampled
along the OES axis through a 0.254 mm diam. anodized aluminum
aperture at the back of the chamber, 13.5 cm from the face of the
output flange of the plasma source, as shown in Fig. 1. Sampled
species passed through three differentially pumped chambers and
then were modulated by a tuning fork chopper (103 Hz) in the third
differentially pumped chamber, positioned near the middle of the
chamber, 8.9 cm from the entrance aperture of the mass spectrome-
ter. The apertures and chopper were all precisely aligned along the
OES axis. The chopped molecular beam passed through and mostly
exited the mass spectrometer ionizer without colliding with any
surface. A small fraction was ionized with an electron ionization
source and extracted by the mass spectrometer. With a flow of Ar in
the plasma chamber and the plasma off, the beam signal for Ar is
about four times larger than the Ar background signal.
The mass spectrometer signal was amplified and detected in
the analog mode by a lock-in amplifier (Stanford Research model
SR510). The component in phase with the chopper frequency pro-
vided the molecular beam signal. Alternatively, in some measure-
ments, a two channel gated photon counter (Stanford Research
model SR400) was used to monitor the separate chopper-open and
chopper-closed signals in the pulse-counting mode. In both modes,
the detection electronics were triggered by a signal in phase with
the chopper frequency. In pulse-counting mode, 1 ms wide gates
were set to detect the beam-plus-background signal and the back-
ground signal. Subtracting the two provided the molecular beam
signal. Both the lock-in and gated pulse detection methods pro-
vided nearly identical results.
The mass spectrometer was mounted horizontally, so that its
ionizer was on axis with the molecular beam. The ionizer region is
designed such that a collimated beam of neutrals will not collide
with the walls and will pass through the exit aperture. In addition,
this and the downstream region of the mass spectrometer are fairly
open, such that the probability for collision of neutral species with
the walls and the return of species to the ionizer is small. This was
borne out in measurements of F atoms. When F collides with the
walls, a likely outcome is the generation of HF from reactions with
water and hydrocarbons adsorbed on the walls. If this HF returns
to the ionizer region, then an HF+ peak would be detected as a
modulated signal. In fact, the modulated HF+ signal is very small as
shown below; therefore, it appears that the mass spectrometer
detects reactive radicals and stable neutrals with similar efficiency.
The power transfer efficiency from the power supply output
to the plasma is nearly 100% for such purely inductive plasmas.33
J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429
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ARTICLE avs.scitation.org/journal/jva
The 60 cycle current, I, flowing through the power cord to the
plasma source was measured by a clamp-on current meter (Fluke
373 True RMS clamp meter), and the power of the plasma source
was determined from the following equation:34
pffiffiffi
P¼ 3*V*I*cos θ, (1)
where V is the line voltage (208 V) and cos θ = 0.7. The manufac-
turer specifies that only 5%–20% of the power from the 208 V,
60 Hz, three-phase input is lost in conversion to 400 kHz power
delivered through the ferrites to the plasma.35 The powers stated
throughout are from Eq. (1) with no correction for this 5%–20% lost
power. The plasma source is designed to operate at a constant
current (∼33A) through the transformer. As the feed gas is changed,
the plasma impedance and power delivered to the plasma change.
Thus, it is not possible to operate at constant power. Fortunately,
the power does not change dramatically as a function of operating
conditions.
Feed gas compositions and flow rates were varied from low to
high or from high to low, with no significant hysteresis.
B. Number densities by actinometry
Optical emission actinometry can be used to estimate number
densities for a selected few species.36–39 For actinometry to be valid,
the emission must primarily result from electron impact on the
species, rather than dissociative excitation from a larger molecule. If
this criterion is met, then the number density of species X, relative
to the known number density of an added trace of rare gas A is
given by
nX IX γ A
¼ aX , (2)
nA IA γ X
where IX and IA are the measured emission intensities of X and A,
and γ X and γ A are relative sensitivities of the spectrometer at the
wavelengths where the species and actinometer emit. Quenching by
the gas and by electrons must be considered. The radiative lifetimes,
τ, of the emitting states of Ar, F, and O are 20, 26, and 36 ns, respec-
tively.40,41 The electronic quenching rate constants, kq, for excited
O by O2 and Ar are 9.4 and 0.14 × 10−10 cm3 s−1, respectively.42 For
the Ar 2p1 emitting level, kq = 0.29 × 10−10 cm3 s−1 for Ar and
7.6 × 10−10 cm3 s−1 for O2.43 The fluorescence quantum yield is
approximately 1/[1 + τkqng(300/Tg)1/2], where ng is the room temper-
ature gas density and Tg is the gas temperature (assumed to be
600 K). For the highest O2 partial pressures (2 Torr), quenching
becomes significant. The fluorescence quantum yields are approxi-
mately 0.41 for O emission and 0.61 for Ar emission. Therefore, the
O/Ar ratio at 2 Torr should be multiplied by 0.61/0.41 = 1.5. The
measurements were not corrected for this rather small effect. We
could find no data for F emission quenching F or Ar but is safe to
assume it is slow compared to quenching of Ar or O emission by
O2; hence, it can be ignored. Concerning electron quenching, we
could not find these rate constants, but if we assume a rate constant
typical for quenching of rare gas metastables by electrons
of 2 × 10−7 cm3 s−1, and further assume an electron density of
1 × 1013 cm−3, then the quantum yield for Ar will be
38, 023011-3

1/(1 + 20 × 10−9 s × 2 × 10−7 cm3 s−1 × 1 × 1013 cm−3) = 0.96. Therefore,
it is probably not important. Even if the rate constant or electron
density exceeds these values, the emission ratios will be less affected.
Ignoring quenching, the proportionality constant, aX , is given by
kA bA
aX ¼ : (3)
kX bX
Here, kA and kX are rate coefficients for electron impact excitation
from the ground states, and bA and bX are branching ratios at the
measured wavelength for the emitting states. Often the rate constants
are unknown, so calibrations are necessary to determine aX.
C. UV absorption
UV absorption also provides absolute or relative number
densities. The absorbance, A, at a wavelength, λ, is given by the
Beer–Lambert law, expressed here as
A ¼ αlc ¼ ln(I=I0 ),
where I and I0 are UV absorbed and incident intensities of the light
source, α is the absorption coefficient at λ, l is the path length, and
c is the concentration of the absorbing species. When measuring
the dissociation of the feed gas, such as O2 and NF3 in the present
study, the concentration with the plasma on is simply
Aon
con ¼ coff , (5)
Aoff
where the subscripts on and off refer to the plasma power being on
or off.
D. Mass spectroscopy
Following the procedure outlined previously,44 the absolute
number densities, nX,on, of stable species, X (i.e., O2, NF3, N2, and
Ar), in O2/Ar and NF3/Ar plasmas are given by
nX,on ¼ (SP,X
on =Soff )nX,off ,
P,X
P,X
where SP,X
on and Soff are the mass-to-charge (m/e) ratio intensities
of the singly charged parent ion of X with the plasma on and off,
and nX,off is the known number density with the plasma off (simply
determined from the known partial pressure in the feed gas and
the known temperature). For products, R, formed in the plasma, in
general, their number densities nR (here R = O, F, F2, and N) are
given by
nR ¼ (SP,R
on =Soff )(β
P,Ar P,Ar
=β P,R )[σ Ar (Ee )=σ R (Ee )]nAr,off :
The signals, SP,R
on ,
are those of the species, R, where the parent
ion m/e for Ar, O, F, F2, and N is P = 40, 16, 19, 38, and 14, respec-
tively. For O, F, and N, the signals are obtained by subtracting the
daughter peaks at m/e = 16 from O2, 19 from F2, and 14 from N2,
based on the measured (with the plasma off for O2 and N2) or
reported (for F2)45 cracking pattern and the intensity of the parent ion
measured with the plasma on. σAr(Ee) and σR(Ee) are electron-impact
J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429
Published under license by AVS.
ARTICLE avs.scitation.org/journal/jva
ionization cross sections for Ar and R at electron energy, Ee
(fixed at 70 eV in this study). σAr(Ee) = 2.65 × 10−16 cm2,46 and
σR(Ee) = 0.87 ± 0.17, 1.10, 1.55, and 1.363 × 10−16 cm2 for F,47 F2,48
N,49 and O,49 respectively. For N2 and O2, σ N2 (Ee ) = 2.55 × 10−16 cm2
(Ref. 50) and σ O2 (Ee ) = 2.44 × 10−16 cm2.50
To complete the conversion of mass spectrometer signals
of species to absolute number densities, the relative sensitivity of
the mass spectrometer as a function of m/e must be known.
At relatively high energy at which ions are accelerated to before
striking the input of the channeltron detector (5 keV), the relative
detection efficiency has little mass dependence. Thus, most of
the mass dependence is due to the transmission through the
quadrupole mass filter. The mass spectrometer was tuned for two
different m/e-dependent sensitivities, β P,R , relative to β P,Ar ¼ 1 for
Ar: one favoring low mass (β P,R ¼ 7:35, 6.13, 3.93, and 1.49 for N,
F, N2, and F2) and one for nearly mass-independent response
(β P,R ¼ 0:936, 1.04, and 1.02 for N, F, N2, and F2).
Uncertainties on number densities determined by mass spec-
(4) trometry are due mainly to the uncertainties in the reported ioniza-
tion cross sections. For F, this is ±20%. No uncertainties were
reported for the other cross sections, but they are likely accurate to
a similar degree. The cross section error also propagates into the
mass sensitive calibration of relative intensity. The error bars for
mass spectrometric measurements presented below are largely
based on these two sources of error.
III. RESULTS AND DISCUSSION
A. O2/Ar
O2/Ar plasmas produced the expected optical emissions from
O and Ar in the 700–900 nm regions. Emission from Ar at
750.4 nm (4p2[1/2]–4s2[1/2]0), originates from an upper level with
an energy of 13.48 eV. This emission line is the best for actinometry
because it is excited almost exclusively from electron impact excita-
tion on ground state Ar, and radiation-trapping-enhanced cascad-
ing transitions into the emitting state are relatively unimportant.
For O, 844.6 nm (3p3P–3s3S0) emission was used rather than
777 nm (3p5P–3s5S0), because dissociative excitation of O2 contrib-
(6) utes heavily to emission at 777 nm, and relatively less to 844.6 nm
emission.51 Figure 2 presents O-to-Ar number density ratios as a
function of O2 percentage in the O2/Ar plasma, using Eq. (2) with
aO = 0.0717 and γAr/γO = 2.552 for the spectrometer employed. As
expected, nO/nAr increases with increasing O2-to-Ar feed gas ratio.
From mass balance, the percent dissociation of O2 in the
plasma is simply
n0 fAr
% dissociation ¼ 50 , (8)
nAr fO2
(7)
with ffOAr being the flow rate ratio of oxygen and argon feed gases
2
and ignoring small transport differences between O, O2, and Ar.
The red solid line in Fig. 2 represents 100% dissociation.
Dissociation drops from 60% at 10% O2 to 10% above 80% O2 feed
gas. At % dissociations of ≥10% O emission from O2, dissociative
excitation will be negligible relative to electron impact on O,17 espe-
cially at higher pressures and resulting lower electron energy distri-
butions in the present study.
38, 023011-4

FIG. 2. Left y axis: O-to-Ar number density ratio vs O2% in the O2/Ar feed gas;
right y axis: power to the plasma reactor and ratio of Ar intensity to Ar number
density. Total pressure = 0.4 Torr and total flow rate = 400 SCCM. Black solid
square points: measured values; red line: theoretical number density ratio for
100% dissociation of O2; black open circle points: power to the plasma reactor;
blue triangle points: ratio of Ar intensity to Ar number density.
O2/Ar plasmas were also investigated at a total pressure of
2.0 Torr. OES actinometry measurements are shown in Fig. 3. The
results are similar to those at 0.4 Torr when the O2 feed gas
percentage is ≥30%. Below 20% O2, dissociation appears to
approach 100%.
FIG. 3. Left y axis: O-to-Ar Number density ratio vs O2% in the O2/Ar feed gas;
right y axis: power to the plasma reactor and ratio of Ar intensity to Ar number
density. Total pressure = 2.0 Torr and total flow rate = 400 SCCM. Black solid
square points: measured values; red line: theoretical number density ratio for
100% dissociation of O2; black open circle points: power to the plasma reactor;
blue triangle points: ratio of Ar intensity to Ar number density.
J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429
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ARTICLE avs.scitation.org/journal/jva
The percent dissociation of O2 in the plasma (see Fig. 1) was
measured by OES as a function of the total flow rate at a fixed total
pressure and 50% O2 in the feed gas (Fig. 4, black squares). Percent
dissociation is somewhat higher at high flow rates. This is partly
due to an increase in power from 5.7 kW at 300 SCCM to 6.8 kW at
4000 SCCM.
O2 number densities along the perpendicular center line in
the downstream chamber (see Fig. 1) were also determined as a
function of the total flow rate by VUV absorption (Fig. 4, red
circles) at 160.4 nm, using the plasma on and off values and
Eqs. (4) and (5). With the plasma off, the known number density
of O2, coff, was used to compute an absorption coefficient of
108 cm−1 atm−1, in good agreement with the reported value of
100 cm−1 atm−1.53 The O2% dissociation derived from con and coff
computed in the downstream chamber was found to be a strongly
increasing function of flow rate, unlike the OES measurements in
the plasma region. The falloff in O2 dissociation at low flow rates is
attributed to the longer residence time in the downstream chamber,
providing more opportunity for recombination on the walls. If we
take the total volume of the downstream chamber, including the
tubing leading to the plasma source and pumping port up to its
throttle valve (500 cm3), then at a flow rate of 2000 SCCM, corre-
sponding to a roughly twofold falloff in O number density com-
pared to the highest flow rate, the gas residence time, and therefore
the time it takes for half the O atoms to recombine is 0.04 s.
Finally, O2% dissociation at the back of the downstream
chamber (see Fig. 1), 12.7 cm from the output flange, was measured
with the mass spectrometer and was found to increase from ∼0%
to ∼1.0% with increasing flow rate (Fig. 4, blue triangles).
O number density at the back of the downstream chamber drops to
this low level due to wall recombination.
FIG. 4. O2% dissociation measured by OES in the plasma (black squares), by
VUV absorption along a center line in the downstream chamber (red circles),
and by mass spectrometry close to the rear of the downstream chamber (blue
triangles). O2:Ar = 1:1, pressure = 2.0 Torr.
38, 023011-5
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O could be lost by recombination on the walls to form O2 or O recombines on the walls to form O2 via
by the formation of O3. No absorption by O3 in the 240–280 nm
region was detected in the downstream chamber. The peak absorp- O þ W ! O–W (10)
tion coefficient53 of 130 cm−1 atm−1 would have led to an easily
detectable 17% absorption if the O3 mole fraction reached 3%. followed by
Instead, <1% absorption by O3 was found along the perpendicular
center line probed by VUV absorption in the downstream chamber. O þ O–W ! O2 þ –W, (11)
Also, no O3 was detected by mass spectrometry at the back of the
chamber; hence, all of the loss of O in the downstream chamber is where –W is a site where O can adsorb, and reaction (10) is fast
attributed to heterogeneous recombination to reform O2. compared to (11). Assuming negligible O formation in the down-
The results presented here indicate a somewhat higher percent stream chamber, at steady state
dissociation of O2 than in other studies.15–17,19,20,24 This is attribut-
able to the higher power density in the current study (∼20 W/cm3), dnO
¼ 0 ¼ fO =V  krec nO  k pump nO , (12)
compared with other investigations. In capacitively coupled dt
plasmas (CCPs) at lower power densities, Naz et al.15 found 10%
dissociation in a 5% Ar/O2 13.56 MHz plasma at 0.007 W/cm3, where nO is now the downstream O atom number density, fO is the
while Imran et al.16 reported 6% dissociation in a 2% Ar/O2 CCP flow rate (cm−3 s−1) of O into the downstream chamber, krec is the
with an estimated power density of ∼0.01–0.1 W/cm3. In recombination rate constant for O on the walls, and kpump is a rate
13.56 MHz inductively coupled plasmas (ICPs), Fuller et al.17 mea- constant for loss of O by pumping.
sured 2% dissociation of O2 with 5% trace rare gases (equimixture Approximating the downstream chamber as a cylinder of
of the five rare gases) in a flat coil ICP at a power density of radius, r (=2 cm), and length, l (=40 cm, including four perpendicu-
∼0.05 W/cm3. Lee et al.19 reported up to 7% dissociation of O2 lar cylindrical regions and tubing leading to the pump gate valve),
with varying Ar content in a 13.56 MHz ICP at 0.025 W/cm3. All defining a volume, V, and surface area, S, krec is obtained from Eqs.
of these studies used O atom OES combined with Ar actinometry, (13)–(16),56
where O emission is at 844 nm and Ar emission is at 750 nm.
Using mass spectroscopy, Wang et al.20 found a somewhat higher 1 1 1
8% dissociation with 80% Ar added to O2 in a 13.56 MHz ICP at ¼ þ , (13)
krec kD kW
0.35 W/cm3. Simulations by Takechi and Lieberman22 predicted an
enhancement in O-atom density with the addition of Ar due to dis-
DO,O2
sociative collisions with Ar metastables. Bogaerts24 computed ∼1% kD ¼ , (14)
O2 dissociation in the range between 0.05 and 5% O2 in a 6.4 Torr Λ20
Ar DC discharge, using a hybrid Monte Carlo-fluid model.
Hsu et al.26 predicted around 4% O2 dissociation at 10 mTorr γO
vO,O2 S
and 150 W ICP power in pure O2. kW ¼ , (15)
2(2  γ O ) V
O2 percent dissociation increases as a function of increasing %
Ar, despite a small drop in power absorbed by the plasma. As
where kD is the diffusion rate for transport of O to the walls, kW is
reported by others, such a trend is due to a Penning dissociation
the loss rate at the walls, and γO is the probability for recombina-
process, resulting from energy transfer from Ar metastables, Ar*,
tion of O at the walls. The binary diffusion coefficient for O and
(3P2 at 11.55 and 3P0 at 11.72 eV) to lower-lying dissociative states
O2, DO,O2 , was taken from the measurements of Morgan and Schiff
of O2,22–24
(0.32 cm2 s−1 at 300 K and 760 Torr).57 Λ0 is the characteristic
length given by
Ar* þO2 ! Ar þ 2O: (9)
1 π 2 2:4052
¼ þ : (16)
The rate constant for this process is 2.1 × 10−10 cm3 s−1,54 Λ20 l r
while that for electron impact dissociation is 2.9 × 10−10 cm3 s−1  12
at an electron temperature, Te = 2 eV, and 1.3 × 10−11 cm3 s−1 at ~vO,O2 is the mean thermal speed, 8kT
πm , for the gas impinging
Te = 1 eV.55 At high pressures in the present study, Te will be on the walls, for the reduced mass, MO MO2 =(MO þ MO2 ), at a
roughly 2 eV near peak positive and negative applied voltages.55 In temperature assumed to be the wall temperature (300 K).
addition, the low frequency of the applied power leads to modula- The input O flow rate is given by
tion of the electron energy and hence a lower average Te. Therefore,
for comparable number densities of electrons and Ar metastables, fO ¼ 2fO02  (% diss)=100, (17)
the rate of Penning dissociation will likely exceed that for electron
impact. Consequently, in mostly Ar plasmas at pressures near with fO02 being the feed gas O2 flow rate into the plasma source in
1 Torr, Penning dissociation is expected to dominate, while in O2 molecules/s (4.48 × 1017 × flow rate in SCCM) and % diss being the
plasmas with little added Ar, the ineffective electron impact measured percent dissociation of O2 in the plasma (taken here to
dissociation results in a low percent dissociation of O2. be the black solid squares in Fig. 4). The pumping rate constant is

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FIG. 6. Number density ratio, nF/nAr, intensity ratios, I(N)/I(Ar), I(N)/I(N2),

FIG. 5. Percent dissociation of O2 (left y axis) and O number density (right y I(Ar)/n(Ar), power and NF3% dissociation as a function of %NF3 in Ar carrier
axis) in the downstream chamber as a function of total flow rate for several gas. Total flow rate = 400 SCCM, pressure = 0.4 Torr.
values of γO in a 2.0 Torr, 50% O2/Ar plasma, compared with data (see Fig. 4)
derived from O2 VUV absorption.

For F number densities, this is roughly 20%, based on several

reported calibrations.27,49 This is indicated by the error bars in
simply the inverse of the gas residence time in the downstream
Fig. 6.
chamber, which is proportional to total flow rate at constant
The emission lines are for N 746.8 nm (3p4S0[3/2]
pressure,
→ 3s4P[5/2]) and N2 at 337.1 nm (C3Πu, v0 = 0–B3Πg, v00 = 0). As
    expected, nF/nAr and I(N)/I(Ar) increase with increasing % NF3.
total flow rate (SCCM) 760 T(K)
k pump ¼ : (18) Included in Figs. 6 and 7 are NF3 percent dissociations com-
60V P(Torr) 273 puted from measured nF/nAr,
The number densities computed from (12), plotted in Fig. 5
as a function of total flow rate, were then used to compute O n F NF
% dissociation ¼ 100* = , (19)
number densities and percent dissociation in the downstream nAr NAr
chamber, using several values of γO (red lines) for comparison with
the measurements along the center of the downstream chamber.
The γO value that best reproduces the downstream O number
density measurements is between 0.001 and 0.002 for the condi-
tioned, anodized aluminum chamber. These values are in good
agreement with the result reported by Greaves and Linnett
(1.8–3.4 × 10−3 at 50 mTorr),58 but around 20 times lower than the
result measured by Guha et al. (0.04 at 20 mTorr).59

B. NF3 dissociation
NF3 is widely used for chamber cleaning, mainly because of
its ease of dissociation.60–62 Emission spectra of NF3/Ar plasmas
revealed the expected features for F, Ar, N, and N2, and no
emission from NF or NF2. The emission lines of F 703.8 nm
(3p2P0–3s2P) and Ar 750.4 nm were chosen to determine F atom
number densities inside the plasma. Equation (2) with aF = 2.8452
and γAr =γF ¼ 0:6152 was used to estimate the density ratio nF/nAr.
Figures 6 and 7 present nF/nAr, along with the intensity ratios
I(N)/I(Ar) and I(N)/I(N2) as a function of % NF3 at 0.4 and
2.0 Torr total pressure. The error in emission intensities is very FIG. 7. Number density ratio, nF/nAr, intensity ratios, I(N)/I(Ar), I(N)/I(N2),
I(Ar)/n(Ar), power and NF3% dissociation as a function of %NF3 in Ar carrier
small. The main source of error in number densities obtained from gas. Total flow rate = 400 SCCM, pressure = 2.0 Torr.
actinometry lies in the accuracy of the actinometry method itself.

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where F-to-Ar number density ratios, NF/NAr, are for 100% dissoci-
ation of NF3 into F,

NF fNF
¼3 3, (20)
NAr fAr

f
with NFfAr being the feed gas flow rate ratio of NF3 to Ar. The NF3%
3

dissociations computed from Eqs. (19) and (20) and included as

blue triangles in Figs. 6 and 7 are close to 100%.
NF3 dissociation percentage was also measured in the down-
stream chamber by UV absorption. Figure 8 presents the absorption
spectrum recorded with the plasma on and off. With the plasma off,
NF3 absorbs between 150 and 200 nm.63 With the plasma on, this
NF3 absorption band decreases and no new bands were observed in
the 240–270 nm region, where NF2 or N2F4 absorb.64 From the
decrease in absorption with the plasma on, a 93% dissociation of
NF3 was obtained for 100% NF3 plasmas at a pressure of 2 Torr and
a total flow rate of 200 SCCM. Nearly the same % dissociation was
found at 400 and 500 SCCM. This high degree of dissociation is con-
FIG. 9. 95% NF3/5% Ar plasma at 600 SCCM flow rate mass spectra during
sistent with the OES measurement in Figs. 6 and 7. plasma on (red) and plasma off (black) at 2.0 Torr. Spectra recorded with the
Mass spectrometry was used to identify products of NF3 disso- nearly mass-independent quadrupole transmission tuning.
ciation and determine their number densities. The mass spectrum
of 100% NF3 with the plasma off (black spectrum in Fig. 9) con-
tains all expected ion peaks corresponding to cracking of NF3, were entirely attributable to cracking of N2 in the mass spectrome-
which contains no F2 and very little F signals. With the plasma on ter ionizer; hence, N atom concentrations are extremely low.
(red spectrum in Fig. 9), the F peak rises about tenfold, new peaks Therefore, within the detection limits, the only form of nitrogen is
appear corresponding to formation of F2 and N2, and all the NFx N2. In both sets of measurements, substantial F is detected, but
peaks correspondingly drop to very low levels, indicating a >95%
dissociation of NF3, in agreement with OES and VUV experiments.
Species number densities in 95% NF3/5% Ar plasmas are
shown in Fig. 10 as a function of total flow rate. Under no condi-
tions were any detectable NF or NF2 found. Signals at m/e = 14

FIG. 10. Number densities of species in NF3/Ar plasma (NF3:Ar = 95:5) at

FIG. 8. I/I0 vs wavelength with the NF3 plasma on and NF3 plasma off at
200 SCCM total flow rate (100% NF3, 2.0 Torr).
2.0 Torr as a function of total flow rate. Data recorded with the nearly
mass-independent quadrupole transmission tuning are indicated by solid points
and those with tuning that favored low masses are shown in open symbols. Also
shown are the F:N stoichiometry and % Ar determined from the mass spectrom-
eter measurements. Dashed lines indicate the values determined from the feed
gas. Error bars for F are based mainly on uncertainties in electron impact cross
sections and mass-dependent sensitivity calibrations. Relative error bars for
other species are equivalent but are not shown for clarity.

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fluorine is mainly present as F2. It should be noted that no
emission was detected by OES in the 530–660 nm region, which
has been correlated with the presence of F2 or F+2 .65,66 F2 formed in
the plasma by recombination of F on the walls will be largely disso-
ciated by collisions with electrons.
The strong increase in F number density with increasing flow
rate is expected for loss of F by surface recombination in the down-
stream chamber, forming F2. The agreement between the two sets
of measurements is reasonable, given the fact that recombination
rates can vary, depending on chamber conditions. The total F:N
ratio determined from the mass spectrometer measurements is
reasonably consistent with the 3:1 value of NF3. The % Ar deter-
mined from the average of the total nitrogen and total fluorine
values is also consistent with the input flow of 5%Ar.
As reported previously, the gas temperature can be measured
by adding a small amount of Ar (5%), and using two channel-gated
photon counter to measure the Ar background signal, sAr,bg,on and
sAr,bg,off , with plasma on and off, recorded during the chopper-
closed periods.44
The gas temperature is given by
   e þ NFx ! NFx1 þ F þ e,
sAr,bg,on sAr,off 2
Tg ¼ Tm * * ,
sAr,bg,off sAr,on
where sAr,on and sAr,off are the Ar beam signals (i.e.,
chopper-open – chopper-closed signals) for the NF3/Ar plasma-on
and off conditions, and Tm (=300 K) is the temperature of mass
spectrometer. Figure 11 shows that the gas temperature is around
450 K for a 95% NF3/5% Ar plasma and is nearly independent of
the total flow rate, at most increasing by ∼100 K from lowest to
highest flow rate.
FIG. 11. Gas temperature as a function of total flow rate in an NF3/5%Ar
plasma at 2.0 Torr.
J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429
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The high percentage of NF3 dissociation in low frequency,
high plasma density, high pressure toroidal plasmas is similar to
reported values in CCP and ICP reactors.27–31 Donnelly et al.27
found NF3 to be close to 100% dissociated in a low frequency
(100 kHz) CCP for 5% to 25% NF3 diluted with Ar, even at the low
power density of 0.065 W/cm3. In that study, F atom density was
also measured by actinometry, calibrated with a chemiluminescence
titration reaction with Cl2. They also found that NF3 plasmas were
much more highly dissociated than for CF4/O2 plasmas. Kimura
and Hanaki29 found similar results for 13.56 MHz ICPs. Greenberg
and Verdeyen30 reported a high NF3 dissociation (up to 80%) in
a hollow-cathode discharge using a mass spectrometer. Hargis
and Greenberg28 similarly found >90% dissociation of NF3 in a
13.56 MHz CCP. Gangoli et al.31 computed <95% dissociation of
the NF3 in a 400 kHz toroidal plasma, using a global model.
NF3 dissociates by attachment
e þ NFx ! NFx1 þ F (22)
as well as by electron impact dissociation
(23)
(21)
where x = 1–3. For NF3, dissociative attachment is very fast,67,68 rel-
ative to electron impact dissociation. The measured cross sections
for attachment68 peak at a very high value (2 × 10−16 cm2) near
3 eV and exceed those computed for electron impact dissociation69
until electron energy exceeds ∼10 eV. As mentioned above, the
average Te is expected to be <2 eV for this low frequency plasma
source at high pressures in this study. Consequently, dissociative
attachment of NF3 will dominate electron impact dissociation, with
a ratio of the rate constants for attachment, relative to electron
impact, computed from these cross sections, of 3000 at Te = 1 eV
and 40 at Te = 2 eV. The dissociative rate constant is very large
(8 × 10−9 cm3 s−1), nearly independent of Te between 0.5 and 3 eV.
Cross sections have recently been computed for the produc-
tion of F− and F from NF3, NF2, and NF by dissociative attachment
and electron impact dissociation.70,71 The dissociative attachment
cross section for NF3 agrees well with the experimental value68 at
the peak near 3 eV, but computed values fall about one order of
magnitude below the experimentally measured cross sections on
either side of the maximum. No measurements have been made for
NF2 or NF. Compared with NF3, the computed peak cross sections
for dissociative excitation of NF2 and NF are lower by factors of 20
and 104, while those for electron impact dissociation of NF2 and
NF exceed that for NF3 by approximately two- to fivefold.70 F−
formed in reaction (22) will be rapidly converted to F by mutual
neutralization collisions with positive ions, A+,
F þAþ ! F þ A: (24)
F is also expected to be formed by Penning dissociation by Ar*,
Ar* þNFx ! NFx1 þ F þ Ar: (25)
The rate constant for quenching of Ar* by NF3, presumably
leading to dissociation via reaction (25), is 1.4 × 10−10 cm3 s−1.71
38, 023011-9

F can also be produced by several secondary reactions of NFx
species. One exothermic reaction that also produces N2 is
NF þ NF ! N2 þ 2F: (26)
The rate constant for this process has been reported to be <5 × 10−12
at 300 K,72 3.5 × 10−12 at 420 K,73 and 4.0 × 10−11 cm3 s−1 at
2500 K.74 NF also reacts with NF2 to generate F,
NF þ NF2 ! N2 F2 þ F: (27)
The reported rate constant for this reaction is 2.0 × 10−12 cm3 s−1
at 298 K72 and 2.4 × 10−12 cm3 s−1 at 420 K.73 N2F2 would be expected
to undergo rapid dissociative attachment,
N2 F2 þ e ! N2 þ F- þ F: (28)
Reaction (28) is exothermic for zero energy electrons by 2.5 eV for
cis-N2F2 and 2.7 eV for trans-N2F2.75
N formed in the dissociation of NF in reactions (22), (23),
and (25) will react with NF2 and NF,
N þ NF2 ! N2 þ 2F, (29)
N þ NF ! N2 þ F: (30)
Since the rate constants for reactions (29) and (30) are very
large (5.71 × 10−11 and 2.5 × 10−10 cm3 s−1, respectively76,77), N will
be lost in reactions (29) and (30) much faster than it can diffuse to
the walls and form N2 or NFx products, until the NF2 and NF
number densities are well below 1014 cm−3.
Regardless of the NF3:Ar feed gas ratio, NF3 dissociation
occurs mainly by dissociative attachment, with electron impact and
Penning dissociation playing a minor role. For NF2, the sum of
reactions (22), (23), and (25) is large across the range of NF3:Ar
feed gas ratios. When NF3 is the dominant feed gas, reactions (23)
and (26)–(30) are the likely pathways for loss of NF, completing
dissociation of NF3 to ½ N2 + 3F. When Ar is the dominant feed
gas, NF decomposition via reaction (25) completes the formation
of F, while N2 will increasingly be formed at the walls in the limit
of zero NF3 feed gas,
N þ W ! N  W (31)
followed by
N þ N  W ! N2 þ W, (32)
where –W is a site where N can adsorb. F can also recombine at
the walls
F þ W ! F  W (33)
followed by
F þ F  W ! F2 þ W, (34)
J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429
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ARTICLE avs.scitation.org/journal/jva
but F2 will be rapidly dissociated by extremely fast attachment;78
thus, the steady-state number density of F will greatly exceed that
of F2 in the intense plasma region.
Unlike previous studies at lower plasma densities,27,28,30 emis-
sion from atomic nitrogen is relatively intense in the high density,
high pressure toroidal plasma. The N-to-N2(C3Πu) intensity ratio
decreases somewhat with increasing NF3 content (Figs. 6 and 7). In
addition to NF decomposition reactions (22), (23), and (25), N can
be produced by electron impact dissociation of N2,
e þ N2 ! e þ 2N (35)
by Penning dissociation
Ar* þN2 ! Ar þ 2N (36)
and by ion–electron recombination
e þ Nþ
2 ! 2N: (37)
IV. CONCLUSIONS
Dissociation percentages of O2 and NF3 were measured in a
low frequency (400 kHz), high density (5–50 W/cm3) remote induc-
tively coupled toroidal plasma source (MKS Instruments model
ASTRON®ex AX7685).
Various mixtures of O2 and NF3 feed gases with Ar were fed
to the plasma at 0.4 or 2.0 Torr. The radical densities and feed gas
dissociation percentages in the plasma were measured by OES,
combined with Ar actinometry. The dissociation of O2 drops from
60% to 10% with an increase in O2 percentage at 0.4 Torr and from
nearly 100% to 10% at 2.0 Torr. The increasing % dissociation with
increasing Ar content was attributed to Penning dissociation by Ar
metastables. For NF3/Ar plasmas, the dissociation is nearly 100%,
and the main products, determined by OES, were F, N, and N2.
Plasma effluents were flowed into a downstream chamber that
was probed by UV absorption and line-of-sight mass spectrometry.
UV absorption by O2 increases with decreasing flow rate. This
behavior can be reproduced with a downstream global model with
a probability of 0.001–0.002 for O recombination on the anodized
walls of the downstream chamber. Weak UV absorption by NF3
with the plasma on, relative to that with it off, indicated that refor-
mation of NF3 by heterogeneous processes did not occur in the
downstream chamber; the percent dissociation was the same high
value as in the plasma source.
Mass spectrometry was used to measure radicals at the back of
the downstream chamber. The O number density in this region was
much lower than near the center due to the strong gradient and low
density near the walls caused by recombination. For NF3/Ar
plasmas, mass spectrometry shows that the main species in the
downstream chamber are F2, N2, and F. The number density of F
radical increases with the rise of total flow rate because of less oppor-
tunity for recombination on the walls at high flow rates. The F2, F,
and N2 product absolute number densities confirmed the 3:1 F:N
mass balance of the NF3 feed gas. The gas temperature at the back
downstream chamber was also measured by mass spectrometry and
38, 023011-10
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32
was found to be 450 K for 95% NF3/Ar at a flow rate from 200 to B. Bai, “An experimental study and modeling of transformer-coupled toroidal
600 SCCM and 2.0 Torr. plasma processing of materials,” thesis (Massachusetts Institute of Technology,
2006).
33
V. A. Godyak, R. B. Piejak, and B. M. Alexandrovich, Plasma Sources Sci.
Technol. 11, 525 (2002).
ACKNOWLEDGMENTS 34
See: https://www.electricaltechnology.org/2014/09/comparison-between-star-and-
Support by MKS Instruments Inc. is gratefully acknowledged. delta-connections.html
35
The name of and reference to “MKS Instruments, Inc.” is used MKS Corp., Andover, MA, private communication (January 8, 2018).
36
with permission from MKS Instruments, Inc. R. A. Gottscho and V. M. Donnelly, J. Appl. Phys. 56, 245 (1984).
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E. Karakas, V. M. Donnelly, and D. J. Economou, Appl. Phys. Lett. 102,
034107 (2013).
38
J. Guha and V. M. Donnelly, J. Appl. Phys. 105, 113307 (2009).
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J. Vac. Sci. Technol. A 38(2) Mar/Apr 2020; doi: 10.1116/1.5126429 38, 023011-12
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