OES in Ar and N - Determination of Electron T and Density by Line-Ratio Method

Optical emission spectroscopy in low-temperature plasmas containing argon and nitrogen:
determination of the electron temperature and density by the line-ratio method

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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 43 (2010) 403001 (24pp) doi:10.1088/0022-3727/43/40/403001
TOPICAL REVIEW
Optical emission spectroscopy in
low-temperature plasmas containing
argon and nitrogen: determination of the
electron temperature and density by the
line-ratio method
Xi-Ming Zhu and Yi-Kang Pu
Department of Engineering Physics, Tsinghua University, Beijing 100084, Peoples Republic of China
E-mail: puyikang@tsinghua.edu.cn
Received 28 June 2010, in nal form 3 August 2010
Published 21 September 2010
Online at stacks.iop.org/JPhysD/43/403001
Abstract
This article reviews a variety of methods to obtain the electron temperature and density by the
emission line ratios for low-temperature plasmas containing argon or nitrogen gas. Based on
the collisionalradiative model of excited particles, the underlying principle of each of these
methods is described, along with the criterion on how to select an appropriate line-ratio
method according to the discharge conditions. Limitations on the application of each line-ratio
technique are also discussed.
(Some gures in this article are in colour only in the electronic version)
List of abbreviations
APPJ atmospheric-pressure plasma jet
ASDF atomic state distribution function
CCD charge-coupled device
CCP capacitively coupled plasma
CRM collisionalradiative model
DBD dielectric barrier discharge
DCGD direct current glow discharge
ECR electron cyclotron resonance (plasma)
EEDF electron energy distribution function
EEPF electron energy probability function
gs ground state
ICCD intensied charge-coupled device
ICP inductively coupled plasma
IR infrared radiation
MD microwave discharge
NLD neutral loop discharge
OES optical emission spectroscopy
PMT photomultiplier tube
SR synchrotron radiation
SRR split-ring resonator (plasma)
SWD surface wave sustained discharge
TRG-OES trace rare gases optical emission
spectroscopy
TRL tungsten ribbon lamp
UV ultraviolet (radiation)
VDF vibrational distribution function
VUV vacuum ultraviolet (radiation)
List of symbols
A Einstein A coefcient
B Einstein B coefcient
d plasma dimension
D diffusion coefcient
e electron
E
a
activation energy
0022-3727/10/403001+24$30.00 1 2010 IOP Publishing Ltd Printed in the UK & the USA
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review
E
e
electron kinetic energy
E
th
excitation threshold energy
E energy difference between two excited levels
E/N reduced electric eld
g
e
electron energy distribution function (EEDF)
g
p
electron energy probability function (EEPF)
h photon
I emission intensity
J total angle momentum quantum number
K volume-averaged diffusion-controlled reaction
coefcient
m
e
electron mass
n species density
n
e
electron density
n
eC
characteristic electron density
n
g
gas density
p pressure
Q rate coefcient of collisional process in the gas phase
Q
exc
rate coefcient of electron-impact excitation
Q
trans
rate coefcient of electron-impact
population transfer
T
e
electron temperature
T
high
e
electron temperature corresponding to the
high-energy electrons
T
low
e
electron temperature corresponding to the
low-energy electrons
T
g
gas temperature
escape factor
exc
excitation cross section
1. Introduction
Optical emission spectroscopy (OES) is one of the most
widely used diagnostic methods for low-temperature plasmas
(Behringer 1991, Malyshev and Donnelly 1997, Boffard
et al 2004, Fantz 2006). It requires only a simple
and inexpensive experimental setup: a diagnostic viewport
and a relative intensity-calibrated spectroscopic system,
covering a wavelength range of UVvisiblenear-IR region
(2001100 nm). From the emission spectra of atomic
or molecular species, being excited by the electron-impact
processes inplasmas, one mayextract the electrontemperature,
T
e
(assuming a Maxwellian electron energy distribution
function, EEDF), and the electron density, n
e
(Behringer and
Fantz 1994, Bibinov et al 1998, 2005, 2008, Kano et al
2000, 2001, Pu et al 2000, 2006, Donnelly and Schabel 2002,
Donnelly 2004, Zhu and Pu 2005, 2008, Zhu et al 2006,
Iordanova and Koleva 2007).
In order to use the OES method to determine the T
e
and n
e
, one usually applies the so-called line-ratio technique.
First, for a given pair of excited levels, which emit light, one
builds up a population model by considering their dominant
production and depopulation processes. Then, from this
model, which consists of a set of rate balance equations of these
two excited levels and other relevant species, one can solve for
the density ratio of these two levels. This ratio is a function of
plasma parameters (T
e
, n
e
, etc) as well as operating parameters
(pressure, plasma dimension, etc). By tting the calculated
density ratio with the measured emission intensity ratio, one
can obtain the plasma parameters with the known operating
parameters. These line-ratio techniques are used for a variety
of low-temperature plasmas at low to atmospheric pressures
(Kano et al 2000, Crintea et al 2009, Zhu et al 2009b).
At very low pressures (<1 Pa) and low ionization
ratios (<10
5
), the excited species are mainly produced by
the electron-impact excitation from the ground state (see
equation (1) in section 2.1.1) and are depopulated by the
spontaneous radiation (equation (2)). Therefore one can write
a set of rate equations for excited species containing only these
two processes. This is called the corona model. With such a
model, by selecting two excited levels with different excitation
threshold energies (E
th
), the obtained line ratio is a function
of T
e
, independent of n
e
and other plasma parameters. This
relationship allows one to obtain T
e
at pressures 0.011 Pa
in electron cyclotron resonance (ECR) plasmas (Pu et al
2000, Crolly and Oechsner 2001). By selecting the particular
levels insensitive to the excitation from the metastables, this
simple method may still be extended to higher pressures,
say, 110 Pa, for microwave discharges (Behringer 1991),
dc glow discharges (Behringer and Fantz 1994), inductive
discharges (Ma and Pu 2003, Pu et al 2006, Britun et al 2007,
Kang et al 2008) and helicon discharges (Foissac et al 2009).
A comprehensive review of the line-ratio technique with the
corona model, as well as the excitation cross sections involved,
is given by Boffard et al (2004).
Based on this simple method, a diagnostic technique
named trace rare gases optical emission spectroscopy (TRG-
OES) is developed (Malyshev and Donnelly 1997, Donnelly
2004). In particular, traces of Ne, Ar, Kr and Xe with known
concentrations are added to the reactive gases. The electron
temperature is obtained from the emission line ratios of the
Paschen 2p levels of these rare gas atoms. The TRG-OES
method has been widely used in a variety of low-pressure
discharges, including the chlorine plasmas (Malyshev and
Donnelly 1999, Donnelly and Schabel 2002), uorocarbon
plasmas (Schabel et al 2002, Chen et al 2009a, Zhu et al 2009a)
and oxygen plasmas (Fuller et al 2000, Stafford et al 2009).
Zhu and Pu (2007a, 2007b) and Zhu et al (2007) develop
a n
e
measurement technique of using the line ratios of certain
argon 3p, 4p and 5p levels for low-pressure plasmas. Since the
lifetimes of these levels are signicantly longer than those of
2p levels, the electron-impact population transfer processes,
being dependent on n
e
(see equation (8) in section 2.1.2),
can be as important as the radiation processes even at low
pressures (110 Pa). As a result, the line ratios of these levels
are functions of n
e
(Boffard et al 2004), nearly independent of
T
e
(for reasons explainedinsection2.1.2). The obtainedresults
of n
e
from this method are in good agreement with those from
the Langmuir probe in inductive Ar/O
2
plasmas (Zhu and Pu
2008), as well as those from the method of deriving n
e
from
the ion energy distribution function in a capacitively coupled
plasma (CCP) (Chen et al 2009b).
At higher pressures (>10 Pa) or with a relatively high
ionization ratio (>10
5
), the line ratios of all the argon-excited
states are functions of both T
e
and n
e
due to the excitation
processes out of the metastable or excited states, as indicated
2
in the collisionalradiative models (CRM) for argon plasmas
(Vl cek 1989, Bogaerts et al 1998, Bultel et al 2002). Using
such a model for 1s and 2p levels, Iordanova and Koleva (2007)
propose a line-ratio method to simultaneously determine T
e
and n
e
in low-pressure inductively coupled plasmas (ICP). It
is also used to obtain T
e
and n
e
in a neutral loop discharge
(NLD), with the results in good agreement with those from
the laser Thomson scattering method (Crintea et al 2009).
Using a similar line-ratio method, Palmero et al (2007) obtain
T
e
and n
e
in a magnetron sputtering plasma. Based on the
CRM by Vl cek (1989), Kano et al (2000, 2001) determine
the values of T
e
and n
e
with the line ratios of several argon
2p, 3s and 5d levels (in Paschens notation) in a dc glow
discharge (DCGD) at medium pressures (10
2
10
4
Pa) and in
a low-pressure plasma jet (10 Pa). Vries et al (2006) present
another method: tting the calculated atomic state distribution
function (ASDF) with the measured one. They use this method
to obtain the values of T
e
and n
e
in a surface wave sustained
discharge (SWD) at mediumpressure (10
3
Pa). For the SWD
at atmospheric pressure, Yanguas-Gil et al (2006) develop
a theoretical approach to determine T
e
from the excitation
temperature of argon excited levels. Asimilar method, with the
line ratios of argon 2p and 3p levels, is proposed by Akatsuka
(2009) and is applied in the investigation of a microwave-
excited microplasma (Zhu et al 2008). More recently, Zhu
and Pu (2010) nd that the atomatom collision processes
may lead to a non-Boltzmann ASDF of the 2p multiplet at
atmospheric pressure. By adding this effect into the CRM, a n
e
measurement technique is proposed for non-equilibriumargon
discharges. It is usedinthe investigationof pulsedrf discharges
and microwave microplasmas at atmospheric pressure, with
the results in agreement with those from the Stark broadening
method (Zhu et al 2009b, Tian et al 2010).
Thanks to the development of nitrogen CRMs, which
are also called nitrogen kinetic models (Loureiro and Ferreira
1986, Guerra et al 2004, Shakhatov and Lebedev 2008), the
line-ratio methods to determine T
e
and n
e
can be applied for
the nitrogen plasmas under the conditions when the corona
model is invalid. Such a method is proposed by Zhu and Pu
(2005, 2008) and Zhu et al (2006) for low-pressure nitrogen
plasmas (110 Pa). They use a CRMcontaining the collisional
processes between the metastable molecules N
2
(A
3
+
u
) and
the vibrationally excited ground-state molecules. Based on
this model, T
e
is obtained by the line ratio of electronic
states N
2
(C
3
u
) and N
2
(B
3
g
) and n
e
is obtained by that of
vibrationally excited levels N
2
(C
3
u
, v = 0) and N
2
(C
3
u
,
v = 1). With a similar nitrogen CRM, Bibinov et al (1998)
establish a line-ratio method to obtain the electron temperature
in a nitrogen DCGD. It is also used in the investigation of ECR
and ICP discharges (Bibinov et al 2005, 2008). As for the
nitrogen plasmas at medium to high pressures (10
2
10
5
Pa),
more collisional processes, such as the collisional quenching
of excited molecules and the collisional processes involving
nitrogen atoms and molecular ions, need to be included in
the CRMs (Kim et al 2006, Lebedev and Shakhatov 2006).
From such models, one can calculate the population ratios
of N
2
(C
3
u
), N
2
(B
3
g
) and N
+
2
(B
2
+
u
) and the vibrational
distribution functions (VDFs) of these states. By tting these
ratios with the measured ones, one can obtain the values of T
e
and n
e
and the reduced electric eld, E/N, in the stationary
or pulsed dc discharges, microwave discharges and dielectric
barrier discharges in nitrogen (Kim et al 2006, Lebedev and
Shakhatov 2006, Cicala et al 2009, Isola et al 2010). The line
ratio of N
2
(C
3
u
) and N
+
2
(B
2
+
u
) is also used to measure
the values of T
e
or E/N in dielectric barrier discharges in air
at atmospheric pressure (Kozlov et al 2001, Paris et al 2005,
Wu et al 2008).
In the following sections, we intend to provide a detailed
discussion on the line-ratio techniques for low-temperature
plasmas containing argon and nitrogen. This includes their
fundamental principles, applications and limitations. Section 2
illustrates three kinds of line-ratio techniques, which are used
under different discharge conditions. The rst method rises
fromthe method with the corona model, applicable for plasmas
containing argon and nitrogen at low pressures and with a
low ionization ratio. At medium to high pressures or with
a relatively high ionization ratio, the second method uses an
argon CRM for argon containing plasmas, which includes
the excitation processes from metastable or excited states, as
well as the atomatom collision processes. The third method
uses a nitrogen CRM for nitrogen-containing plasmas, and
it can be used when the corona model is invalid for excited
nitrogen molecules. Section 3 further discusses the inuence
of discharge conditions on the selection of a line-ratio method,
as well as their inuence on the collisional processes in the rate
balance. In particular, for gas-mixture discharges, the effect of
other species on the kinetics of argon or nitrogen is discussed.
Section 4 discusses some of the practical limitations of the
line-ratio methods, due to optical absorption and reection as
well as the sensitivity and resolution of the spectrometers.
2. Line-ratio methods
In this section, we will describe three kinds of line-ratio
methods used to determine the values of T
e
and n
e
for
plasmas containing argon or nitrogen. Each of these line-
ratio methods needs a population model. This model contains
a set of rate balance equations for excited species and
other relevant species, in which the sum of the rates of the
productionprocesses equals that of the depopulationprocesses,
under steady-state conditions. In general, the production
processes of excited species include the electron-impact
excitations from the ground state and from the metastable
states, the radiation decay from the higher excited states, etc.
The depopulation processes include the spontaneous radiation,
the collisional quenching with electrons and with heavy
species, etc. Although the general rate balance containing all
the possible processes is a very complicated one, under certain
discharge conditions and for certain excited states, only very
few dominant processes need to be included in a particular
model. This is the major difference between these models
discussed in this work, i.e. different choices of levels (emission
lines) and the associated processes. For discharges containing
argon and nitrogen, the levels of interest for all these models
are shown in gure 1. In the following, we rst describe the
population model for some given excited levels under a given
3
Figure 1. A collection of the partial energy diagrams of the relevant
species used in the line-ratio methods.
discharge condition and how to obtain the line ratios using the
model, and then describe how to determine T
e
and n
e
from the
measured spectral data.
2.1. Corona model method
The corona model comes from the modelling of excited
species in the solar corona, where the electron density is
very low (10
6
cm
3
) and the electron temperature is high
(100 eV) (Fantz 2006). In this case, only two processes
are important: the electron-impact excitation process from
the ground-state species and the spontaneous radiations from
the excited species. This model is valid for excited atoms,
molecules and ions in low-temperature plasmas with very low
pressures (<1 Pa) and low ionization ratios (<10
5
). This is
because, under these conditions, other collisional processes
are not important and the density of metastables is too low to
make a signicant contribution to the excitation of the excited
species (Pu et al 2000, Crolly and Oechsner 2001, Boffard et al
2004, Donnelly 2004).
2.1.1. T
e
determination. We take the low-pressure Ar/Xe
discharges as an example. Usually, strong emission lines
from the Paschen 2p levels of argon and xenon atoms can be
observed, such as the ones with wavelengths of 750.4 nm (Ar,
2p
1
1s
2
) and828.0 nm(Xe, 2p
5
1s
4
) (see gure 1). Note
that the 2p levels with zero total angle momentum quantum
number (J = 0) of rare gases (in Paschens notation, 2p
1
and 2p
3
for Ne, 2p
1
and 2p
5
for Ar, Kr and Xe) are the most
suitable for the line-ratio methods with a corona model, since
these levels have relatively large excitation cross sections from
the ground state and very small excitation cross sections from
the metastables (Boffard et al 2004). In a corona model for
these levels, we have the electron-impact excitation from the
ground-state atom,
Ar(gs) + e Ar(2p
1
) + e,
Xe(gs) + e Xe(2p
5
) + e,
(1)
and the spontaneous radiation,
Ar(2p
1
) Ar(1s) + h,
Xe(2p
5
) Xe(1s) + h.
(2)
The symbol gs denotes the ground state, 1s denotes the Paschen
1s levels, e is for an electron and h is for a photon.
The rate balance equations of Ar(2p
1
) and Xe(2p
5
) are
n
e
n
Ar
Q
Ar(2p
1
)
exc
= A
Ar(2p
1
)
n
Ar(2p
1
)
,
n
e
n
Xe
Q
Xe(2p
5
)
exc
= A
Xe(2p
5
)
n
Xe(2p
5
)
,
(3)
where n
e
is the electron density, n
Ar
and n
Xe
are the densities
of ground-state argon and xenon atoms and A is the Einstein
A coefcient. Q
exc
is the excitation rate coefcient from the
ground state,
Q
exc
=
_

E
th
exc
_
2E
e
m
e
g
e
(E
e
) dE
e
,
=
_

E
th
exc
_
2
m
e
E
e
g
p
(E
e
) dE
e
,
(4)
where E
e
is the electron kinetic energy, E
th
is the excitation
threshold energy,
exc
is the excitation cross section, m
e
is
the electron mass, g
e
is the EEDF, g
p
is the electron energy
probability function (EEPF) and is related to the EEDF g
e
by g
e
(E
e
) = E
1/2
e
g
p
(E
e
). When g
p
is plotted in a log scale
versus E
e
, a linear function indicates a Maxwellian distribution
(Donnelly 2004, Pu et al 2006). Note that the electron-impact
excitations from the ground state can also produce excited
atoms in higher levels, such as Ar(2s), Ar(3s), Ar(4d) and
Ar(5d). The radiation decay of these atoms also contributes to
the production of atoms in 2p levels. This so-called cascade
process shouldbe includedonthe left-handside of equation(3).
As a result, one should use the apparent excitation cross section
in calculating Q
exc
from equation (4), which is the sum of the
excitation cross section from the ground state and the cascade
cross sections from the higher excited levels (see Boffard et al
(2007); we will further discuss the apparent excitation cross
section in section 4.1).
The emission intensity, I, from an excited state x is given
by (in this work it refers to the number of photons emitted per
unit volume per unit time from this state)
I
x
= A
x
n
x
, (5)
if the self-absorption process (or the radiation trapping, see
Griem (1997)) can be ignored. In fact, this assumption is valid
under the discharge conditions considered in this subsection.
Here n
x
refers to the population density of species in this state
and A
x
is its Einstein A coefcient.
4
Figure 2. Ratios of the excitation rate coefcients from the ground
state as functions of electron temperature: Ar(2p
1
)/Xe(2p
5
),
Ar(3p
1
)/Ar(2p
1
), N
2
(C
3
u
)/N
2
(B
3
g
) and N
+
2
(B
2
+
u
,
v = 0)/N
2
(C
3
u
, v = 0). A Maxwellian EEDF is assumed. The
cross sections are from Itikawa et al (1986), Majeed and Strickland
(1997), Chilton et al (1998), Fons and Lin (1998) and
Weber et al (2003).
From equations (3) and (5), the emission line ratio is
I
Ar(2p
1
)
I
Xe(2p
5
)
=
A
Ar(2p
1
)
n
Ar(2p
1
)
A
Xe(2p
5
)
n
Xe(2p
5
)
=
n
e
n
Ar
Q
Ar(2p
1
)
exc
n
e
n
Xe
Q
Xe(2p
5
)
exc
= C
Q
Ar(2p
1
)
exc
Q
Xe(2p
5
)
exc
,
C
n
Ar
n
Xe
. (6)
The constant C is the density ratio of the ground-state atoms
and can be obtained from the partial pressures of argon and
xenon assuming they have equal gas temperatures. For a
Maxwellian EEDF, using the experimental cross sections and
equation (4), the excitation rate coefcient ratio is a function of
T
e
(see gure 2). Therefore, once two levels are selected, one
may obtain T
e
from the measured line ratio using equation (6),
taking into account the response function of the spectrometer.
Some of the excitation rate coefcients, such as those
from the ground state to the Paschen np (n = 25) levels of
argon and xenon and those to the nitrogen states N
2
(B
3
g
),
N
2
(C
3
u
) and N
+
2
(B
2
+
u
), can be approximated by an
Arrhenius form (Zhu et al 2009a) within the range of electron
temperatures of interest and we have
Q
Ar(2p
1
)
exc
Q
Xe(2p
5
)
exc
Q
Ar(2p
1
)
0
exp
_
E
Ar(2p
1
)
a
T
e
_
Q
Xe(2p
5
)
0
exp
_
E
Xe(2p
5
)
a
T
e
_
exp
_
E
Ar(2p
1
)
a
E
Xe(2p
5
)
a
T
e
_
exp
_
E
T
e
_
, (7)
where Q
0
is a constant (pre-exponential factor), E
a
is the
activation energy, roughly equal to the threshold energy of
Figure 3. The values of electron temperature in a Ne/Ar/Xe ICP
determined by the line ratio of 750.4 nm (Ar, 2p
1
1s
2
) and
828.0 nm (Xe, 2p
5
1s
4
) with the corona model and those
determined by the Langmuir probe. The dimensionless parameter x
c
is a function of the partial pressures of argon, xenon and neon. The
driving frequency is 13.56 MHz. The discharge power is 100 W
(Zhu et al 2009a).
an excited level, and E is the energy difference between the
two excited levels.
Equation (7) indicates that, in order to get a functional
form that is sensitive to T
e
, it is desirable to select two
excited states with E comparable to T
e
. If E is much
smaller than T
e
, the rate coefcient ratio is nearly independent
of T
e
(Ar(3p
1
)/Ar(2p
1
), gure 2). Although a large E
can lead to the line ratio, a very sensitive function of T
e
(N
+
2
(B
2
+
u
,v = 0)/N
2
(C
3
u
, v = 0), gure 2), one of the
emission lines may be too weak to have a good signal-to-
noise ratio, when T
e
in the discharge is low. For example,
at T
e
1.5 eV, the emission lines from N
+
2
(B
2
+
u
) are very
weak, owing to the very lownumber of electrons with energies
higher than the threshold energy, 19 eV, for the excited
ionization process from N
2
(X
1
+
g
) to N
+
2
(B
2
+
u
) (Zhu and
Pu 2008). Note that equation (7) is for illustrative purpose
only and the most accurate way to obtain the ratio of the rate
coefcients is usingthe experimental cross sectiondata directly
and equation (4). For some other levels, their cross sections
may behave differently with the electron energy fromthe levels
discussed here and equation (7) may not be appropriate to
represent the dependence of rate coefcients on the electron
temperature over the range of interest. In this case, when
employing equation (6) to obtain the electron temperature, it
is still helpful to select two levels with very different threshold
energies.
Figure 3 shows the results of determining T
e
by the line
ratio of Ar(2p
1
) and Xe(2p
5
) in a Ne/Ar/Xe ICP (Zhu et al
2009a). This line-ratio method can be used to obtain T
e
s in the
range of 14 eV, being comparable to the energy difference
between Ar(2p
1
) and Xe(2p
5
) (see gure 1). At a constant
power of 100 W, T
e
is changed by varying the partial pressures
of gases: p
Ne
110 Pa, p
Ar
p
Ne
/5, p
Xe
p
Ne
/20 in
the Ne/Ar/Xe mixture and p
Ar
18 Pa, p
Xe
p
Ar
/4 in
the Ar/Xe mixture. A dimensionless parameter x
c
is used in
5
Table 1. Some works using the line-ratio method to determine T
e
with the corona model. The method to obtain T
high
e
in the TRG-OES
technique is included.
Excited states selected Plasmas Feed gases Trace gases
Behringer (1991) He(3d
1
D)/Ar(2p) ECR N
2
or CH
4
Ar and He
or N
+
2
(B
2
+
u
)/N
2
(C
3
u
)
Behringer and Fantz (1994) He(3d
1
D)/Ar(2p)/N
2
(C
3
u
) DCGD He Ar and N
2
Pu et al (2000) N
+
2
(B
2
+
u
)/N
2
(B
3
g
) ECR N
2
Crolly and Oechsner (2001) Ar
+
(4p
2
S, 4p
2
P)/Ar(3p) ECR Ar or N
2
or N
+
2
(B
2
+
u
)/N
2
(C
3
u
)
Donnelly (2004) Ar(2p
1
, 2p
5
)/Kr(2p
1
, 2p
5
)/Xe(2p
1
, 2p
3
, 2p
5
) ICP Cl
2
, O
2
Ar, Kr and Xe
or Ar/C
2
F
6
/C
4
F
8
Boffard et al (2004) Ar(3p
1
)/Ne(2p
1
) ICP Ar/Ne
Britun et al (2007) N
+
2
(B
2
+
u
)/N
2
(C
3
u
) ICP N
2
or Ar/N
2
Chen et al (2009a) Ar(2p
1
, 2p
5
)/Kr(2p
1
, 2p
5
, 2p
7
)/Xe(2p
3
, 2p
5
) CCP CF
4
/O
2
Ar, Kr and Xe
Stafford et al (2009) Ar(2p
1
, 2p
5
)/Kr(2p
1
, 2p
5
) SWD O
2
Ar, Kr and Xe
/Xe(2p
1
, 2p
3
,2p
5
)
Zhu et al (2009a) Ar(2p
1
, 2p
5
)/Xe(2p
5
) ICP, CCP Ar/Xe/CF
4
Foissac et al (2009) Ar(3s)/Ar(2p) Helicon Ar
gure 3, which is a function of the partial pressures of argon,
xenon and neon. The results are in good agreement with those
from the Langmuir probe (Zhu et al 2009a).
The above method can also be used for discharges
containing excited N
2
, N
+
2
, Ar
+
, He, Ne and Kr species, as
listed in table 1.
2.1.2. n
e
determination with extended corona model. As for
higher excited levels, such as Ar(3p
1
) and Ar(5p
5
), they have
very small excitation cross sections fromthe metastables, since
J = 0 (as mentioned in section 2.1.1). As a result, their major
production source is still the ground-state excitation. However,
in the destruction channel, the electron-impact population
transfer processes,
Ar(3p
1
) + e Ar(2s, 3s, 3d, 4d) + e,
Ar(5p
5
) + e Ar(4s, 5s, 5d, 6d) + e,
(8)
should be added in the corona model, due to the relatively
small Einstein coefcients of these levels. Therefore, the rate
balance equation becomes
n
e
n
Ar
Q
Ar(3p
1
)
exc
=A
Ar(3p
1
)
n
Ar(3p
1
)
+ n
e
n
Ar(3p
1
)
Q
Ar(3p
1
)
trans
,
n
e
n
Ar
Q
Ar(5p
5
)
exc
=A
Ar(5p
5
)
n
Ar(5p
5
)
+ n
e
n
Ar(5p
5
)
Q
Ar(5p
5
)
trans
,
(9)
where Q
trans
is an effective rate coefcient of the electron-
impact population transfer process. Note that, on the left-hand
side of the equation, only high-energy electrons contribute
to the excitation; however, due to the very small excitation
thresholdenergyof the populationtransfer process, low-energy
electrons make the maximum contribution to Q
trans
, and thus
Q
trans
is only weakly dependent on T
e
. Therefore, a parameter,
n
eC
, named the characteristic electron density, can be dened
as (Zhu and Pu 2007a, 2007b)
n
eC

A
Q
trans
. (10)
In many low-pressure ICP and CCP discharges with argon
partial pressures 110 Pa, the n
eC
of certain excited levels
can be considered as constants. In fact, the values of n
eC
can be obtained experimentally using a Langmuir probe and a
spectrometer: 310
11
cm
3
for argon 3p levels, 10
11
cm
3
for argon 4p levels and 210
10
cm
3
for argon 5p levels (Zhu
and Pu 2008, Zhu et al 2009a). Therefore, the rate equations
of Ar(3p
1
) and Ar(5p
5
) can be rewritten as
n
e
n
Ar
Q
Ar(3p
1
)
exc
= A
Ar(3p
1
)
n
Ar(3p
1
)
_
1 +
n
e
n
eC,3p
1
_
,
n
e
n
Ar
Q
Ar(5p
5
)
exc
= A
Ar(5p
5
)
n
Ar(5p
5
)
_
1 +
n
e
n
eC,5p
5
_
.
(11)
The line-ratio equation for Ar(3p
1
) and Ar(5p
5
) is
I
Ar(3p
1
)
I
Ar(5p
5
)
=
A
Ar(3p
1
)
n
Ar(3p
1
)
A
Ar(5p
5
)
n
Ar(5p
5
)
=
n
e
n
Ar
Q
Ar(3p
1
)
exc
(1 + n
e
/n
eC,5p
5
)
n
e
n
Ar
Q
Ar(5p
5
)
exc
(1 + n
e
/n
eC,3p
1
)
, (12)
that is,
I
Ar(3p
1
)
I
Ar(5p
5
)
= C
(1 + n
e
/n
eC,5p
5
)
(1 + n
e
/n
eC,3p
1
),
C
Q
Ar(3p
1
)
exc
Q
Ar(5p
5
)
exc
.
(13)
When T
e
1 eV, the excitation rate coefcient ratio, C,
of Ar(3p
1
) and Ar(5p
5
) is nearly independent of T
e
, from
the calculations based on the cross section measurements
(Weber et al 2003, Boffard et al 2004). This is because their
cross sections have very close values of the threshold energy.
Therefore, the line-ratio equation (13) is basically independent
of T
e
and can be used to determine n
e
.
In order to use equation (13) to determine n
e
effectively,
at least one of the n
eC
values should be comparable to the n
e
value in plasmas. If n
e
n
eC,5p
5
< n
eC,3p
1
, the line ratio
is nearly independent of n
e
(the left region in gure 4). This
is because the spontaneous radiation is a much faster process
than the electron-impact population transfer. Otherwise, if
6
Figure 4. The line ratio of Ar(3p
1
) and Ar(5p
5
) versus electron
density, calculated using equation (13). The excitation coefcient
ratio is calculated from the cross sections given by Boffard et al
(2007). The n
eC
values are from Zhu et al (2009a).
Figure 5. The electron densities in an Ar/O
2
ICP determined by the
line ratio of 425.9 nm (Ar, 3p
1
1s
2
) and 357.2 nm (Ar, 5p
5
1s
2
)
with the extended corona model (with the electron-impact
population transfer process added) and the results by the Langmuir
probe (Zhu and Pu 2008).
n
eC,5p
5
< n
eC,3p
1
n
e
, the line ratio is insensitive to n
e
as well
(the right region in gure 4), since only the electron-impact
population transfer is important for both species. Therefore,
to make the line ratio a sensitive function of n
e
, both processes
should play comparable roles in the depopulation of Ar(3p
1
)
or Ar(5p
5
).
Figure 5 shows the results of determining n
e
by the line
ratio of Ar(3p
1
) and Ar(5p
5
) in an Ar/O
2
ICP (Zhu and Pu
2008). In this plasma, n
e
is increased by the power at constant
pressures of argon and oxygen. This line-ratio technique is
valid when n
e
is in the range 10
9
10
12
cm
3
(in the middle
region in gure 4). The results are also in good agreement
with those from the Langmuir probe.
The other line ratios of argon 3p, 4p or 5p levels (with
J = 0) can be used instead of the line ratio 3p
1
/5p
5
in the
n
e
measurement. However, their excitation rate coefcient
ratio may have a stronger dependence on T
e
(Zhu et al
2009a), and thus the T
e
in plasmas should be measured before
determining n
e
.
T
e
and n
e
can be simultaneously obtained using the
above line ratios. Such an example is given in gure 6
for an Ar/Xe/CF
4
CCP (Zhu et al 2009a). The T
e
and
n
e
variation versus driving frequency in the electronegative
discharges containing CF
4
is different from that in the
electropositive discharges, because the energy balance
between the electron heating and the energy loss mechanisms
is affected signicantly by the inelastic collisions with CF
4
(Zhu et al 2007).
As for the electron-impact excitation processes from the
ground state, only the electrons with energies higher than the
excitation threshold energy (E
th
) contribute to the calculation
of the excitation rate coefcient, as seen in equation (4).
Therefore, when a line-ratio method with the corona model,
such as that of using Ar(2p
1
)/Xe(2p
5
), is applied to determine
T
e
in a plasma with a non-Maxwellian EEDF, one obtains an
electron temperature corresponding solely to the high-energy
tail of an EEDF, T
high
e
(Donnelly 2004, Pu et al 2006). This
T
high
e
represents the local slope of the higher energy tail of
an EEPF when it is plotted in a log scale versus the electron
energy (as discussed after equation (4)).
The low-energy electrons play a dominant role in the
electron-impact population transfer process between excited
species (equation (8)). The rate coefcient of this process,
Q
trans
, may be dependent on the electron temperature
corresponding to the low-energy electrons, T
low
e
. However,
this effect is very weak. As a result, the parameter n
eC
,
calculated fromQ
trans
(equation (10)), is nearly independent of
T
low
e
, which is experimentally conrmed in low-pressure ICP
and CCP discharges (110 Pa) (Zhu and Pu 2007a, 2007b,
Zhu et al 2007). For this reason, T
low
e
cannot be effectively
obtained from the corona model in a non-Maxwellian EEDF
case, which is a fundamental limitation of the line-ratio method
described in this subsection.
2.2. Argon CRM method
In low-temperature argon plasmas at pressures >10 Pa or with
ionization ratio 10
4
10
3
, the corona model is invalid for
most of the excited species, since the excitation process out
of metastable atoms is an important production mechanism
for them (Bogaerts et al 1998, Iordanova and Koleva 2007).
In addition, several other processes, including the collisions
between two argon atoms and the recombination of electrons
and ions, can be of importance at medium to high pressures
(10
3
10
5
Pa) (Rolin et al 2007, Dyatko et al 2008). In these
cases, one should apply an argon CRM (Vl cek 1989, Benoy
et al 1991) instead of the corona model to calculate the line
ratios.
In argon CRMs, the rate balance equations for the steady-
state densities of species, including the excited atoms, the
ground-state atoms, the atomic ions, the molecular ions as well
7
Figure 6. T
e
and n
e
versus the driving frequency at a constant power 50 W in a capacitive discharge, obtained from the line-ratio techniques
using Ar(2p
1
)/Xe(2p
5
) and Ar(3p
1
)/Ar(5p
5
), respectively (Zhu et al 2009a).
as the molecular excimers, are
n
e
y=x
n
y
Q
yx
eAr
+ n
Ar
y=x
n
y
Q
yx
ArAr
+
y=x
yx
A
yx
n
y
+
y=x
z=x
n
y
n
z
Q
y,zx
ArAr
+ n
2
e
n
Ar
+
Q
e,e,Ar
+
x
3-body
+n
e
n
Ar
n
Ar
+
Q
e,Ar,Ar
+
x
3-body
= n
e
n
x
y=x
Q
xy
eAr
+ n
Ar
n
x
y=x
Q
xy
ArAr
+
y=x
xy
A
xy
n
x
+ 2n
2
x
Q
x,x
ArAr
+n
x
y=x
n
y
Q
x,y
ArAr
+ n
2
Ar
n
x
Q
Ar,Ar,x
3-body
+ K
x
wall
n
x
. (14)
x refers to a species in a certain state while y and z refer
to other states or other species. n
x
, n
y
and n
z
refer to their
densities, respectively, Q is the reaction rate coefcient of
collisional process in the gas phase, K is the volume-averaged
diffusion-controlled reaction coefcient (see Donnelly 2004),
A is the Einstein A coefcient and is the escape factor
due to the self-absorption process. The superscripts denote
the species involved in each process. The subscripts give the
reaction types: eAr, the collision processes between electrons
and argon species, ArAr, the collision reactions between two
argon species, 3-body, the three-body collisions, wall, the
quenching processes at the chamber wall. Fromequation (14),
one can calculate the population density ratios of the excited
species.
Table 2 lists several of these kinds of line-ratio methods
used in the literature. It can be seen that all of these
works consider the following processes: the electron-impact
excitation processes from the ground state and metastable
levels, the spontaneous radiation and radiation trapping, as
well as the quenching processes of metastables at the chamber
wall. At medium and high pressures, one should pay attention
to the fact that the electron-impact excitation processes out of
the excited levels, the atomatomcollisions and the three-body
collisions play important roles. References for the collision
cross sections are listed in table 3.
In the following, we show in detail an example of using
the line-ratio method with the argon CRM to determine T
e
and
n
e
with the emission lines from the argon 2p levels, which
are usually the strongest emission lines from low-temperature
argon plasmas, as shown in gures 7(a), (c) and (e) for three
types of argon plasmas (Zhu and Pu 2007a, 2009, Zhu et al
2007, 2008). The operating parameters of these experiments
are given in table 4.
Since the pressure or the ionization ratio is higher than
the cases discussed in section 2.1, the population densities of
Ar(1s
2
) and Xe(1s
4
) are no longer low. The self-absorption
processes canbe signicant. Inthis case, the emissionintensity
is related to the population density of the excited species by
(Griem 1997)
I
xy
=
xy
(n
y
; d, B
xy
,
xy
) A
xy
n
x
. (15)
Here x and y refer to the upper and lower levels of an optical
transition, respectively. The escape factor, , is a function of
the population density of the lower level (n
y
), as well as the
plasma dimension (d), the Einstein B coefcient for absorption
(B) and the spectral line width (), which is caused mainly by
the Doppler broadening, as well as the collisional broadening
when the gas pressure is high (>10
4
Pa) (Wang et al 2005).
With d, B and known, the new line ratio is
I
Ar(2p
i
1s
k
)
I
Ar(2p
j
1s
l
)
=

2p
i
1s
k
(n
1s
k
) A
2p
i
1s
k
n
2p
i
2p
j
1s
l
(n
1s
l
) A
2p
j
1s
l
n
2p
j
,
1 i, j 10, 2 k, l 5. (16)
Here i, j andk, l refer todifferent 2pand1s levels, respectively.
As seen in equation (16), in order to relate the emission line
ratios to the population ratios of 2p levels, one needs to obtain
8
Table 2. The excited levels and processes in some argon CRMs and the selected line ratios used to obtain T
e
and n
e
. Note that the work by
Donnelly is included for the method to obtain T
low
e
in the TRG-OES technique. hl refers to the high-lying levels such as the 2s, 3d and 3p;
eAr means the collision processes between electrons and argon species; ArAr refers to those between argon species;. rad, wall and 3-body
are for the radiation processes, the quenching processes at chamber wall and the three-body collision processes, respectively. These
processes are described in more detail in table 3.
Modelling Experiments and results
Levels Processes Plasmas Line ratios Parameters
Donnelly (2004) 1s, 2p eAr, rad, wall ICP, CCP 2p T
low
e
(0.110 Pa)
Iordanova and Koleva (2007) 1s, 2p eAr, rad, wall ICP 2p T
e
, n
e
ArAr (1100 Pa)
Kano et al (2000) 1s, 2p, hl eAr, rad, wall DCGD 2p, 3s, 5d T
e
, n
e
ArAr, 3-body (10
2
10
4
Pa)
Vries et al (2006) 1s, 2p, hl eAr, rad, wall SWD 2p, 3s, 4s, T
e
, n
e
ArAr, 3-body (10
3
Pa) 5d, 6d, 7d
Akatsuka (2009) 1s, 2p, hl eAr, rad, wall APPJ
a
2p, 3p T
e
ArAr, 3-body (10
5
Pa)
Zhu et al (2009b) 1s, 2p, hl eAr, rad, wall SRR, DBD
b
2p n
e
ArAr, 3-body (10
5
Pa)
a
APPJ refers to atmospheric-pressure plasma jet.
b
SRR is for split-ring resonator, which is a microwave-excited microplasma. DBD is for dielectric barrier
discharge.
Table 3. Major processes considered in the argon CRMs. The subscripts i and j refer to different levels in the 1s or 2p multiplet. The
parameters involved in calculating the rates of processes are T
high
e
, the electron temperature corresponding to the high-energy electrons,
T
low
e
, that corresponding to the low-energy electrons, n
e
, the electron density, T
g
, the gas temperature, n
g
, the gas density and d, the plasma
dimension.
Processes Parameters References
eAr e + Ar e + Ar(1s, 2p, hl) T
high
e
, n
e
, n
g
Chilton et al (1998), Chilton and Lin (1999),
Stewart et al (2002),
Weber et al (2003),
Khakoo et al (2004)
e + Ar(1s) e + Ar(2p, 3p) T
low
e
, n
e
Boffard et al (1999),
Jung et al (2007)
e + Ar(1s
i
) e + Ar(1s
j
) T
low
e
, n
e
Bartschat and Zeman (1999),
e + Ar(2p
i
) e + Ar(2p
j
, 2s, 3d) Pokrzywka (2002)
e + Ar(1s, 2p, hl) e + e + Ar
+
T
low
e
, n
e
Deutsch et al (2004)
e + Ar
2
e + Ar + Ar(1s) T
low
e
, n
e
Neeser et al (1997)
e + Ar
+
2
Ar + Ar(hl) T
low
e
, n
e
, T
g
Bultel et al (2002)
rad Ar(1s
4
, 1s
2
) Ar + h NIST (2010)
Ar(2p, 3p) Ar(1s) + h
Ar(2s, 3d) Ar(2p) + h
ArAr Ar + Ar(2p
i
) Ar + Ar(1s, 2p
j
) n
g
, T
g
Chang and Sester (1978),
Ar + Ar(3p) Ar + Ar(2s, 2p, 3d) Inoue et al (1982),
Sadeghi et al (2001)
Ar(1s) + Ar(1s) e + Ar
+
2
T
g
Bultel et al (2002)
3-body e + e + Ar
+
e + Ar(hl) n
e
, T
low
e
, n
g
, T
g
Dyatko et al (2008)
e + Ar + Ar
+
Ar + Ar(hl)
Ar(1s) + Ar + Ar Ar
2
+ Ar n
g
, T
g
Rolin et al (2007)
Ar
+
+ Ar + Ar Ar
+
2
+ Ar
wall Ar(1s
5
, 1s
3
)
wall
Ar n
g
, T
g
, d Bogaerts et al (1998)
the densities of 1s levels, using the line ratios with the same
upper state, such as
I
Ar(2p
i
1s
k
)
I
Ar(2p
i
1s
l
)
=

2p
i
1s
k
(n
1s
k
) A
2p
i
1s
k
2p
i
1s
l
(n
1s
l
) A
2p
i
1s
l
. (17)
Note that we have tens of equations like (17) for the 2p1s
transitions and thus the densities of four 1s levels can be
easily obtained. This method is called the branching fraction
method, which is described in detail by Boffard et al (2009)
and Schulze et al (2008).
Using equations (16) and (17), we obtain the population
distributions of 2p levels from the spectral data of three types
of plasmas, as shown in gures 7(b), (d) and (f ).
The next step is to calculate the population ratio as
a function of T
e
and n
e
from the rate balance equations,
which contain the dominant production and depopulation
9
Figure 7. Experimental emission spectra of argon plasmas: (a) ICP at 1 Pa, (c) CCP at 120 Pa and (e) SRR at 10
5
Pa. SRR means split-ring
resonator, which is a microwave-excited microplasma. The corresponding population distributions of argon 2p levels are shown in (b), (d)
and (f ). n
2p
and g
2p
are the population density and the degeneracy degree of 2p levels, respectively. The values of n
2p
/g
2p
are normalized
to 100.
Table 4. Operating parameters and plasma parameters for several
types of argon plasmas.
ICP CCP SRR
Driving frequency 13.56 MHz 27.12 MHz 0.9 GHz
Discharge pressure 115 Pa 4120 Pa 10
3
10
5
Pa
Absorbed power 75 W 50 W 1 W
Plasmas dimension 15 cm 4 cm 0.11 mm
Gas temperature 400 K 400 K 500 K
processes. At low pressures (110 Pa), atoms in the 2p
levels are produced mainly by the electron-impact excitations
from the ground state as well as from the metastables
(1s
3
and 1s
5
). The dominant depopulation process is the
spontaneous radiation. At medium pressures (10
2
10
3
Pa),
the densities of the resonance levels (1s
2
and 1s
4
) become
of the same order as those of the metastables, due to the
strong radiation trapping by the ground state. As a result,
the excitations from these resonance levels to the 2p levels
also play important roles. At high pressures (10
4
10
5
Pa),
the atomatom collisional processes and the three-body
collisions are important, owing to the high gas densities
(Zhu and Pu 2010).
Figures 8, 9 and 10 show the contour graphs of the
population ratios versus T
e
and n
e
at 1 Pa, 120 Pa and 10
5
Pa,
respectively. In each contour graph, we show two population
ratiosone is more sensitive to the variation of T
e
and the
other is more sensitive to n
e
. Different population ratios are
selected at different pressures, owing to the different kinetic
mechanisms under these discharge conditions. Inthe following
part of this section, we discuss the effects of T
e
and n
e
on the
excited level population ratios in detail, assuming a constant
gas temperature and the plasma dimension (listed in table 4).
The effects of variation in these parameters, even though may
not be as signicant as T
e
and n
e
, are still very important under
certain conditions (section 3.2).
In gure 8, where the pressure is 1 Pa, we nd that T
e
is very sensitive to the population ratio 2p
9
/2p
10
. Both these
levels have large excitation cross sections from the metastable
level 1s
5
(Boffard et al 1999), and thus, under the discharge
conditions shown in this gure, the dominant production
sources of 2p
9
and 2p
10
are the excitations from 1s
5
. The ratio
of the rate of these excitation processes is nearly a constant,
due to their similar excitation threshold energies from 1s
5
.
The signicant increase in the ratio 2p
9
/2p
10
with T
e
is caused
by the depopulation mechanismsthe spontaneous radiations
and the self-absorption processes. Not that the selection rule
of the optically allowed transition from a 2p level to a 1s level
is J = 0, 1 except J = 0 J = 0. Thus 2p
9
(J = 3)
can only decay to 1s
5
(J = 2) but 2p
10
(J = 1) can decay
to 1s
5
(J = 2), 1s
4
(J = 1), 1s
3
(J = 0) and 1s
2
(J = 1).
When T
e
increases, the density of 1s
5
increases due to the
ground-state excitation due to the high-energy electrons. As a
result, the self-absorption by 1s
5
is largely enhanced and the
effective decay rate from 2p
9
to 1s
5
is largely reduced. On
the other hand, the decay of 2p
10
by spontaneous radiation is
not much affected by this process, since it can also decay to
the resonance levels (1s
2
and 1s
4
), whose densities are much
10
Figure 8. Contour graph of population ratios of argon 2p levels at
1 Pa: 2p
3
/2p
1
and 2p
9
/2p
10
, calculated from a CRM (Zhu and Pu
2010). The gas temperature T
g
is assumed to be 400 K, and the
plasma dimension d is assumed to be 15 cm.
120 Pa: 2p
1
/2p
5
and 2p
3
/2p
10
. T
g
= 400 K and d = 4 cm are
assumed.
lower than the metastables at this pressure. Therefore it is the
change in loss rate which makes the population ratio 2p
9
/2p
10
increase with T
e
.
Figure 8 also shows that the population ratio 2p
3
/2p
1
has a strong n
e
dependence. As mentioned before, the level
2p
1
(J = 0) has a relatively large excitation cross section
from the ground state and its excitation cross section from the
resonance level 1s
2
is quite small. However, the opposite is
true for 2p
3
, whose ground-state excitation cross section is
small and its excitation cross section from 1s
2
is quite large
(Zhu and Pu 2010). Under the discharge conditions shown
in gure 8, the density of 1s
2
signicantly increases with n
e
,
due to the electron-impact population transfer processes from
the metastables. As a result, the population ratio 2p
3
/2p
1
also
increases with n
e
.
In gure 9, where the pressure is 120 Pa, the population
ratio 2p
1
/2p
5
shows its variation with T
e
. With J = 0, these
10
5
Pa: 2p
1
/2p
5
and 2p
9
/2p
6
. T
g
= 500 K and d = 100 m are
assumed.
two levels have relatively large ground-state excitation cross
sections, as discussed above. Thus, even at lowT
e
s (12 eV),
as found in many medium-pressure plasmas (10
2
10
3
Pa)
(Kanoet al 2000, Vries et al 2006, Iordanova andKoleva 2007),
the ground-state excitation due to the high-energy electrons
is still important for these two levels. The excitations from
the 1s levels are also important. Since 2p
1
has a larger rate
coefcient than 2p
5
for the ground-state excitation but 2p
5
has
larger excitation rate coefcients from the 1s levels, the ratio
2p
1
/2p
5
increases with T
e
, as seen in gure 9.
However, for the other 2p levels with J = 0, only the
excitations from the 1s levels are important. Their population
ratios (such as 2p
3
/2p
10
) are nearly independent of T
e
, due to
the close excitation threshold energies fromthe 1s levels. But it
can have a strong dependence on n
e
, as shown in gure 9. The
n
e
dependence comes from two different production sources
of 2p
3
and 2p
10
, even though both are excited mainly from the
1s levels: 2p
3
from the resonance level 1s
2
and 2p
10
from the
metastable level 1s
5
. Due to the electron-impact population
transfer from 1s
5
to 1s
2
, the density ratio 1s
2
/1s
5
increases
with n
e
. As a result, the population ratio 2p
3
/2p
10
increases
with n
e
.
In gure 10, at atmospheric pressure, the population
ratio 2p
1
/2p
5
also varies with T
e
for the same reasons as in
gure 9. On the other hand, the population ratio 2p
9
/2p
6
is selected to show its variation with n
e
. This is because
their depopulation processes have different dependence on
n
e
. At atmospheric pressure (gas temperature 500 K, plasma
dimension 100 m), the 2p
6
level is depopulated mainly by
the collisional quenching with the electrons, while 2p
9
has
an additional important destruction channelthe collisional
quenching with the ground-state atoms. Therefore, for the
2p
9
level, its rate of decrease with n
e
is slower than that for
2p
6
level. This causes the population ratio 2p
9
/2p
6
to increase
with n
e
.
At atmospheric pressure, the gas temperature, T
g
, can
affect the rate of the atomatomcollisional quenching process,
11
Figure 11. T
e
and n
e
versus neutral gas pressure, determined by tting the calculated population ratios of argon 2p levels with those
obtained from the experimental line ratios: (a) n
e
for an argon ICP at pressures 115 Pa, (b) n
e
for an argon CCP at pressures 4120 Pa,
(c) n
e
for an argon SRR at pressures 10
3
10
5
Pa, (d) T
e
for ICP, (e) T
e
for CCP and (f ) T
e
for SRR. The probe, IEDF and broadening
refer to the Langmuir probe method (Zhu and Pu 2008), the method of deriving n
e
from the measured ion energy distribution function (Chen
et al 2009b) and the Stark broadening method (Zhu et al 2008).
due to its effect on the gas density, n
g
(T
1
g
), and that
on the collisional quenching rate coefcient (T
1/2
g
, Rolin
et al (2007) and Zhu and Pu (2010)). When T
g
increases,
the reduction in the rate of atomatom collision process
(n
2
g
T
1/2
g
T
3/2
g
) is faster than that of the electronatom
process (n
g
T
1
g
). As a consequence, the population ratio
2p
9
/2p
6
increases with T
g
. For example, the ratio of 2p
9
/2p
6
at
a gas temperature of 1000 K is larger than that at 500 K (used
in gure 10) by 5%. This will cause the variation in the value
of n
e
, obtained from the line-ratio method, as much as 40%.
In this case, while using the line-ratio method, one needs to
estimate the gas temperature by the OES method (Wang et al
2005, Zhu et al 2008).
As seen in gures 8, 9 and 10, the values of T
e
and n
e
can be simultaneously obtained from the intersection of two
contour lines. However, the most accurate values of T
e
and n
e
can be obtained by tting the experimental with the calculated
population distributions for all the 2p levels at the same time.
Figure 11 shows the results of this method for several argon
plasmas. Theyagree well withthe data froma Langmuir probe,
n
e
s derived from the ion energy distribution function (Chen
et al 2009b) or by the Stark broadening method. The line-
ratio method has the prominent advantage of being a universal
method for many different types of plasmas when a suitable
CRM is used.
A Maxwellian EEDF is often assumed in the CRMs
to calculate line ratios. For the low-pressure plasmas, this
assumption is often proved to be valid from the Langmuir
probe data (Zhu and Pu 2007a, 2007b) or the laser Thomson
scattering data (Crintea et al 2009). Otherwise, the TRG-
OES method to determine T
high
e
and T
low
e
separately is
recommended, which uses different line ratios either sensitive
to the high-energy EEDF tail or the low-energy EEDF
bulk (Donnelly (2004), Chen et al (2009a) and Stafford
et al (2009), see tables 1 and 2). At medium to high
pressures (10
2
10
5
Pa), however, all the line ratios of 2p
levels may be affected mainly by the EEDF bulk. This
is because the excitation processes from 1s levels dominate
the excitation processes from the ground state. In this
case, one has to assume a Maxwellian EEDF for the low-
energy electrons, while using the CRMs to calculate the
line ratios of these 2p levels. It may be a reasonable
assumption for many low-temperature plasmas, since the
non-Maxwellian EEDF is usually caused by the inelastic
collisions of the high-energy electrons with the ground-state
species or by the non-local heating of these energetic electrons
(Godyak 2006).
2.3. Nitrogen CRM method
For nitrogen plasmas at pressure 1010
5
Pa, the corona
model is invalid, due to the collision processes between
metastable molecules, excited molecules and vibrationally
excitedground-state molecules, as well as the electroncollision
processes with these molecules (Piper 1988a, 1988b, 1989,
Adamovich et al 1998, Mihajlov et al 1999, Ahn et al 2004,
Dilecce et al 2006, 2007, 2010). In this case, in order to apply
the line-ratio methods to determine T
e
or n
e
, one should use
12
Table 5. The excited states and processes considered in several nitrogen CRMs used for the line-ratio techniques. eN
2
or eN
+
2
represents
the collision processes between electrons and nitrogen molecules or molecular ions; N
2
N
2
and N
2
O
2
are for the moleculemolecule
collisions; rad and wall are for the radiation processes and the collision processes at the chamber wall, respectively. These processes are
described in more detail in table 6.
Modelling Experiments and results
States Processes Plasmas Parameters
Bibinov et al (1998) N
2
(X), N
2
(C), eN
2
, rad, wall, N
2
(X)N
2
(X) DCGD T
e
N
+
2
(B) (N
2
, 1030 Pa)
Kozlov et al (2001) N
2
(X), N
2
(C), eN
2
, rad, N
2
(C)N
2
/O
2
, DBD E/N
N
+
2
(B) N
+
2
(B)N
2
/O
2
(air, 10
5
Pa)
Lebedev and Shakhatov (2006) N
2
(X), N
2
(A), eN
2
, rad, wall, N
2
(X)N
2
(X), DCGD, MD
b
E/N, n
e
N
2
(B), N
2
(C)
a
N
2
(A)N
2
(A), N
2
(A/B/C)N
2
(X) (N
2
, 10
2
10
3
Pa)
Zhu and Pu (2008) N
2
(X), N
2
(A), eN
2
, rad, wall, N
2
(X)N
2
(X), ICP T
e
, n
e
N
2
(B), N
2
(C) N
2
(A)N
2
(A), N
2
(A/B)N
2
(X) (N
2
, 0.110 Pa)
Isola et al (2010) N
2
(X), N
2
(C), eN
2
, eN
+
2
, rad pulsed DCGD T
e
, n
e
N
+
2
(B) (N
2
, 300 Pa)
a
The model also includes some other species, such as N
2
(a
1
u
), N
2
(a
1
g
), N(
4
S), N(
2
D), N(
2
P), as well as the relevant
kinetic processes.
b
MD refers to microwave discharge.
Figure 12. Experimental emission spectra of a nitrogen CCP (pressure 10 Pa, driving frequency 13.56 MHz, power 80 W, Chen et al
(2009b)): (a) part of the second positive system, SPS (N
2
, C
3
u
B
3
g
); (c) part of the rst positive system, FPS
(N
2
, B
3
g
A
3
+
u
). Partial energy diagrams of states N
2
(A
3
+
u
), N
2
(B
3
g
) and N
2
(C
3
u
) are given in (b) and (d).
more detailedCRMs (Bibinovet al 1998), whichare alsocalled
nitrogen kinetic models (Guerra and Loureiro 1997, Guerra
et al 2001, 2004, S a et al 2004).
Table 5 lists several works of using nitrogen CRMs to
determine T
e
and n
e
in nitrogen-containing plasmas (line-ratio
methods for gas-mixture discharges are further discussed in
section 3.3). Although the works in table 5 are different in
details, we may use that by Zhu and Pu (2008) as an example
to outline their general principle.
Usually, the strongest emission bands in low-temperature
nitrogen plasmas with a relatively low ionization ratio
10
6
10
4
are the second positive system (N
2
, C
3
u

B
3
g
) and the rst positive system (N
2
, B
3
g
A
3
+
u
), as
shown in gure 12. For low-pressure ICP and CCP discharges
(<10
3
Pa), the important production processes for the
excited molecules N
2
(C
3
u
) and N
2
(B
3
g
) are the electron-
impact excitation from the vibrationally excited ground-
state molecules N
2
(X
1
+
g
,v) and the reactions between
13
N
2
(X
1
+
g
,v) and N
2
(A
3
+
u
) (see table 6). As a result, to
calculate the line ratios of those two emission band systems,
we should solve the rate balance equations of N
2
(X
1
+
g
,v),
N
2
(A
3
+
u
), N
2
(B
3
g
) and N
2
(C
3
u
):
n
e
=v
n
X,v
Q
v
v
eN
2
+ n
X,v1
w
n
X,v
+1
Q
v1,v
+1v,v
N
2
(X)N
2
(X)
+n
X,v+1
n
X,v
Q
v+1,v
v,v
+1
N
2
(X)N
2
(X)
+ K
v+1v
wall
n
X,v+1
= n
e
n
X,v
=v
Q
vv
eN
2
+ n
X,v
n
X,v
+1
Q
v,v
+1v+1,v
N
2
(X)N
2
(X)
+n
X,v
n
X,v
Q
v,v
v1,v
+1
N
2
(X)N
2
(X)
+ K
vv1
wall
n
X,v
, (18)
n
e
v
n
X,v
Q
X,vA
eN
2
+ n
B
_
v
n
X,v
_
Q
BA
N
2
(B)N
2
(X)
+A
B
n
B
= n
e
n
A
Q
AX
eN
2
+n
A
_
_

5v14
n
X,v
_
_
Q
AB
N
2
(A)N
2
(X)
+2n
2
A
_
Q
A,AB
N
2
(A)N
2
(A)
+ Q
A,AC
N
2
(A)N
2
(A)
_
+ K
A
wall
n
A
, (19)
n
e
v
n
X,v
Q
X,vB
eN
2
+ n
A
_
_

5v14
n
X,v
_
_
Q
AB
N
2
(A)N
2
(X)
+n
2
A
Q
A,AB
N
2
(A)N
2
(A)
+
A
C,v
n
C,v
+
_
v
n
X,v
_
n
C,v
Q
C,v
B
N
2
(C)N
2
(X)
= n
e
n
B
Q
BX
eN
2
+n
B
_
v
n
X,v
_
Q
BA
N
2
(B)N
2
(X)
+ A
B
n
B
, (20)
n
e
v
n
X,v
Q
X,vC,v
eN
2
+ n
2
A
Q
A,AC,v
N
2
(A)N
2
(A)
+
_
v
n
X,v
_

v
>v
n
C,v
Q
C,v
C,v
N
2
(C)N
2
(X)
=n
e
n
C,v
Q
C,v
X
eN
2
+
_
v
n
X,v
_
n
C,v
<v
Q
C,v
C,v
N
2
(C)N
2
(X)
+
_
v
n
X,v
_
n
C,v
Q
C,v
B
N
2
(C)N
2
(X)
+ A
C,v
n
C,v
. (21)
Here v and v
refer to the vibrational levels in the ground state,

v
and v
refer to the vibrational levels of state N

2
(C
3
u
).
n
X
, n
A
, n
B
and n
C
are the densities of states N
2
(X
1
+
g
),
N
2
(A
3
+
u
), N
2
(B
3
g
) and N
2
(C
3
u
), respectively. Just as
dened in section 2.2, Q is the rate coefcient for gas-phase
collisions, K is the diffusion-controlled reaction coefcient
and A is the Einstein A coefcient. The superscripts and
subscripts denote the species involved in each process, as listed
in table 6. The self-absorption processes are not considered
for the optical transitions from N
2
(B
3
g
) to the metastable
state N
2
(A
3
+
u
), due to the small Einstein B coefcients for
absorption (equation (15)). For the nitrogen ICP discharges
investigated here (Zhu and Pu 2005), the vibrationtranslation
relaxationprocesses bynitrogenmolecules are not as important
as the vibrationvibration transfer processes and can be
ignored (Zhu et al 2006). The nitrogen atoms and their relevant
processes, including the energy transfer with N
2
(A
3
+
u
) and
the vibrationtranslation relaxation with N
2
(X
1
+
g
,v > 0),
are not included in the model, due to the low dissociation ratio
of nitrogen molecules in this ICP discharge (<0.1%). In the
case of a relatively high dissociation ratio, 110%, these
processes and the kinetic modelling of nitrogen atoms should
be included, such as that for a nitrogen ECR plasma (Bibinov
et al 2005).
By solving the rate balance equations (18)(21), the
population ratios N
2
(C
3
u
)/N
2
(B
3
g
) and N
2
(C
3
u
,v =
1)/N
2
(C
3
u
, v = 0) can be calculated, as plotted in gure 13
(at 1 Pa) and gure 14 (at 10 Pa). In the calculation, one also
needs the plasma dimension and the gas temperature, due to
the presence of diffusion-controlled deactivation at the wall
and collisions between heavy species (Zhu and Pu 2008).
According to the nitrogen CRM above, the electron-
impact excitationprocesses fromthe groundstate are important
for both N
2
(C
3
u
) and N
2
(B
3
g
). In addition, these two
states have an energy difference, E, 3.7 eV (gure 12).
Therefore, the population ratio of N
2
(C
3
u
)/N
2
(B
3
g
) is
sensitive to the variation of T
e
in the range 14 eV, as
seen in gures 13 and 14. The E between vibrational
levels N
2
(C
3
u
,v = 1) and N
2
(C
3
u
, v = 0) is much
smaller than the T
e
values. Thus their population ratio is
insensitive to the variation of T
e
. The low-lying vibrational
levels, N
2
(X
1
+
g
,v = 18), are produced mainly by the
electron-impact vibrational excitation from N
2
(X
1
+
g
,v = 0)
and depopulated by both electron collisions and vibration
vibration transfer processes (note that the vibrationvibration
transfer is dominant in both the production and depopulation
of intermediate vibrational levels with v 1040, Guerra
et al (2004)). Owing to the electron-impact excitation, the
concentration of molecules N
2
(X
1
+
g
, v = 18) signicantly
increases with n
e
, which, according to the FranckCondon
principle, can lead to the increase in ratio N
2
(C
3
u
,v =
1)/N
2
(C
3
u
, v = 0) versus n
e
, as shown in gures 13 and
14. Unlike the vibrational levels of the ground state, these
levels do emit light.
For the rst positive system (N
2
, B
3
g
A
3
+
u
), the
self-absorption processes can be ignored due to the small
Einstein B coefcients. For the second positive system (N
2
,
C
3
u
B
3
g
), they are ignored since the lower state
N
2
(B
3
g
) is an excited state and has a very low density.
Therefore, the measured emission line ratios are related to the
excited state population ratios by
I
N
2
(C)
I
N
2
(B)
=
A
C
n
C
A
B
n
B
, (22)
I
N
2
(C,v=1)
I
N
2
(C,v=0)
=
A
C,v=1
n
C,v=1
A
C,v=0
n
C,v=0
. (23)
14
Table 6. Major processes in the nitrogen CRMs used for the emission line-ratio methods. Here v and v
refer to different vibrational levels

in an electronic state. The parameters involved in calculating the rates of processes are T
high
e
and T
low
e
, the electron temperatures
corresponding to the high-energy and low-energy electrons, respectively, n
e
, the electron density, T
g
and n
g
, the gas temperature and density
and d, the plasma dimension.
Processes Parameters References
eN
2
e + N
2
(X) e + N
2
(A/B/C/a
/a) T
high
e
, n
e
, n
g
Itikawa et al (1986), Itikawa (2006),
e + N
2
(X) e + e + N
+
2
(X/B) Majeed and Strickland (1997)
a
e + N
2
(X, v) e + N
2
(X, v
) T
low
e
, n
e
Mihajlov et al (1999)
eN
+
2
e + N
+
2
(X) e + N
+
2
(B) T
low
e
, n
e
Tabata et al (2006)
N
2
(X)N
2
(X) N
2
(X, v) + N
2
(X, v
) T
g
Adamovich et al (1998),
N
2
(X, v + 1) + N
2
(X, v
1) Ahn et al (2004)
N
2
(A)N
2
(A) N
2
(A) + N
2
(A) N
2
(B) + N
2
(X) T
g
Piper (1988a, 1988b)
N
2
(A) + N
2
(A) N
2
(C) + N
2
(X)
N
2
(A)N
2
(X) N
2
(A) + N
2
(X, 5 v 14) T
g
Piper (1989)
N
2
(B) + N
2
(X)
N
2
(B)N
2
(X) N
2
(B) + N
2
(X) N
2
(A) + N
2
(X) n
g
, T
g
Guerra et al (2004)
N
2
(C)N
2
/O
2
N
2
(C, v) + M N
2
(C, v
)/N
2
(B) + M n
g
, T
g
Dilecce et al (2006, 2007),
v
< v, M = N
2
/O
2
Lebedev and Shakhatov (2006)
N
+
2
(B)N
2
/O
2
N
+
2
(B) + M N
+
2
(X) + M n
g
, T
g
Dilecce et al (2010)
M = N
2
/O
2
rad N
2
(B) N
2
(A) + h Gilmore et al (1992)
N
2
(C) N
2
(B) + h
N
+
2
(B) N
+
2
(X) + h
wall N
2
(X, v)
wall
N
2
(X, v 1) n
g
, T
g
, d Black et al (1974)
N
2
(A)
wall
N
2
(X) n
g
, T
g
, d Augustyniak and Borysow (1994)
a
The state-to-state excitation cross sections can be calculated according to the FranckCondon principle, with the
FranckCondon factors from Lofthus and Krupenie (1977).
Figure 13. Contour graph of population ratios of nitrogen
molecules at 1 Pa: N
2
(C
3
u
)/N
2
(B
3
g
) (100) and N
2
(C
3
u
,
v = 1)/N
2
(C
3
u
, v = 0), calculated using a nitrogen CRM (Zhu
and Pu 2008). T
g
= 400 K and d = 15 cm are assumed.
I
N
2
(C,v=0)
and I
N
2
(C,v=1)
are the emission intensities from
vibrational levels 0 and 1 of state N
2
(C
3
u
), similar to I
Ar(2p
1
)
and I
Xe(2p
5
)
used in equation (6). I
N
2
(B)
and I
N
2
(C)
are the
sum of emission intensities from all the vibrational levels of
states N
2
(B
3
g
) and N
2
(C
3
u
), respectively. A and n are
the Einstein A coefcients and the species densities, as used
in equations (19)(21).
Using the line-ratio equations (22) and (23) and the
calculated contour graphs as in gures 13 and 14, the values of
T
e
and n
e
in nitrogen plasmas are obtained. Figure 15 shows
Figure 14. Contour graph of population ratios of nitrogen
molecules at 10 Pa: N
2
(C
3
u
)/N
2
(B
3
g
) (100) and N
2
(C
3
u
,
v = 1)/N
2
(C
3
u
, v = 0) T
g
= 400 K and d = 15 cm are assumed.
the results of this method in a nitrogen ICP discharge (Zhu and
Pu 2005, 2008, Zhu et al 2006). In gure 15(a), T
e
is tuned
by varying the pressure at a constant power. n
e
increases with
power at a constant pressure in gure 15(b). In both cases,
the results of line-ratio method with nitrogen CRM agree well
with those obtained by the Langmuir probe.
As for nitrogen plasmas with non-Maxwellian EEDFs,
Bibinov et al (1998, 2005, 2008) develop a method to
determine both T
high
e
(for electrons with energies >11 eV) and
T
low
e
(for electrons in the energy range 1.54.5 eV). T
high
e
is
obtained using the line ratio of two excited states N
2
(C
3
u
)
15
Figure 15. T
e
and n
e
obtained by tting the measured with the calculated population ratios N
2
(C
3
u
)/N
2
(B
3
g
) and N
2
(C
3
u
,
v = 1)/N
2
(C
3
u
, v = 0): (a) T
e
for a nitrogen ICP versus pressure at constant power 600 W, (b) n
e
versus power at constant pressure 2 Pa.
The probe refers to the Langmuir probe method (Zhu and Pu 2005, 2008, Zhu et al 2006).
and N
+
2
(B
2
+
u
). These excited species are produced mainly
by the excitation processes due to high-energy electrons. T
low
e
is determined by the line ratio N
2
(C
3
u
,v = 4)/N
2
(C
3
u
,
v = 0). At low pressures (0.1100 Pa), this line ratio
depends on the population ratio of N
2
(X
1
+
g
,v = 4-7)
and N
2
(X
1
+
g
,v = 01), according to the FranckCondon
principle (Levaton et al 2004). This population ratio is
signicantly affected by the vibrational excitation processes
due to low-energy electrons. In addition, E between
N
2
(X
1
+
g
,v = 47) and N
2
(X
1
+
g
,v = 01) is as large as
1.5 eV. Therefore, this ratio can be sensitive to the variation
of T
low
e
.
3. Conditions of using line-ratio methods
The conditions of using each line-ratio method have been
briey discussed in section 2the corona model can be
used for plasmas with low pressure and low ionization ratio;
otherwise, the argon or nitrogen CRMs should be applied. In
this section, we further discuss this point.
3.1. Pressure and ionization ratio
To distinguish the conditions for different line-ratio methods,
we propose some application regions, whose scopes are
functions of pressure and ionization ratio (see gures 16
and 17). These regions have different major collisional
radiative processes and thus different line-ratio methods should
be chosen for each of them. The scopes of application regions
are determinedusingthe argonandnitrogenCRMs insection2,
together with the experimental results in the reference works
in tables 1, 2 and 5, and gures 16 and 17.
In gure 16, there are four application regions for low-
temperature argon plasmas in the pressure range 0.110
5
Pa
Figure 16. A diagram for the line-ratio methods used in
low-temperature argon plasmas with different regions: C for the
corona model region, L for the low-pressure region, H for the
high-pressure region and B for the Boltzmann-plot method region.
A gas temperature of 400 K and a dependence of plasma dimension
on the pressure, d = 10 p
3/5
(d in cm, p in Pa), are assumed
(Zhu and Pu 2009).
and in the ionization ratio range 10
6
10
3
. In the C-region,
the corona model is valid and the line-ratio method described
in section 2.1.1 can be applied to measure the electron
temperature (Crolly and Oechsner 2001). In the L-region
(low-pressure region), due to the excitation processes from
metastable levels, one needs to use an argon CRMto determine
both T
e
and n
e
(Iordanova and Koleva 2007, Crintea et al 2009).
In the H-region (high-pressure region), the excitations out of
excited levels, the atomatom collisions and the three-body
collisions should be added in the CRM(Kano et al 2000, Vries
et al 2006). This difference in major processes between the
L-region and H-region will affect the selection of line ratios,
16
Figure 17. A diagram for the line-ratio methods used in
low-temperature nitrogen plasmas with different regions: C for the
corona model region, L for the low-pressure region and H for the
high-pressure region. A gas temperature of 400 K and a dependence
of plasma dimension on the pressure, d = 10 p
3/5
(d in cm, p
in Pa), are assumed (Zhu and Pu 2009).
as shown in gures 810. At high to atmospheric pressure and
with relatively high ionization ratio (B-region), the electron
atom collision processes are dominant in both production and
depopulation of the excited atoms, which, as a result, may
have a Boltzmann (or Boltzmann-like) population distribution.
The Boltzmann-plot methodderiving T
e
from the excitation
temperature of excited atomscan be used in this region
(Garca et al 2000). However, a non-Boltzmann ASDF
is caused due to the atomatom collisions in atmospheric-
pressure plasmas witha lowionizationratio(ZhuandPu2009).
The Boltzmann-plot method is invalid in this case and a CRM
is needed in the determination of T
e
and n
e
, accounting for the
non-Boltzmann ASDF (Zhu et al 2009b).
Note that the selection of line-ratio methods is not only
affected by the operating conditions but also depends on the
characteristics of excited levels. Even in the low-pressure
region in gure 16, the corona model can be valid if special
excited levels are chosen, such as Ar(3p
1
) and Ar(5p
5
), as
described in section 2.1.2. This is because the electron-
impact excitation processes from metastable levels to 3p
1
and
5p
5
are very weak (Boffard et al 2004). Therefore, their
dominant production process is the excitation from the ground
state. As for the depopulation mechanism, the electron-impact
population transfer process should be added in the corona
model. With this extended corona model, n
e
can be determined
by the line ratio Ar(3p
1
)/Ar(5p
5
) (Zhu and Pu 2007a).
The region diagram for nitrogen plasmas is shown in
gure 17. The corona model can be used in the C-region
(Pu et al 2000, Britun et al 2007). There are two kinds
of nitrogen CRMs, proposed for the L-region and H-region,
respectively (Guerra et al 2004, Zhu and Pu 2005). In addition
to the species and processes in the corona model, the former
CRM also includes the metastable species N
2
(A
3
+
u
) and
N
2
(X
1
+
g
,v > 0) and the collisional processes between these
molecules (Bibinov et al 1998, Zhu and Pu 2008). In addition,
the latter CRMincludes N
2
(a
1
u
), N
2
(a
1
g
), N(
4
S), N(
2
D)
and N(
2
P), owing to their collisional processes with N
2
(A
3
+
u
)
and N
2
(X
1
+
g
,v > 0), which can be important at medium
pressures (10
3
Pa) (Lebedev and Shakhatov 2006).
With the pressure and ionization ratio roughly known, one
can choose a suitable line-ratio method according to the region
diagrams (gures 16 and 17).
3.2. EEDF, plasma dimension and gas temperature
Even though the pressure and ionization ratio are the most
important parameters in determining the dominant processes
for a given pair of levels (thus affecting the results of the line
ratios obtained from the models), under certain conditions,
the variation in the EEDF, the plasma dimension and the gas
temperature may also change the identication of dominant
processes in a very signicant way (Zhu and Pu 2010). This
is particularly true around the borderline between two regions
in gures 16 and 17, which are plotted with a constant gas
temperature of 400 K, with the assumption of a Maxwellian
EEDF and an assumed dependence of plasma dimension on
the pressure, d = 10 p
3/5
(d in cm, p in Pa, Zhu and
Pu (2009)).
In a plasma with a non-Maxwellian EEDF, the ground-
state excitation is sensitive to the variation of EEDF tail (T
high
e
)
while the metastable-level excitation is sensitive to the EEDF
bulk (T
low
e
). Therefore, in gures 16 and 17, if T
high
e
> T
low
e
,
the C-region is expanded somewhat to the right, while in the
opposite case, the L-region is expanded to the left where the
pressures and ionization ratios are lower.
Boththe plasma dimension, d, andthe gas temperature, T
g
,
can affect the diffusion-controlled quenching and the radiation
trapping. At a constant pressure, the diffusion-controlled
quenching is increased by decreasing d or by increasing T
g
,
and as a result, the metastable density becomes lower and the
C-region is expanded to the right (Zhu and Pu 2010). The
radiation trapping process, being important to the relationship
of the line ratios with T
e
at low pressures (see the above
discussion about gure 8), is enhanced by increasing d or by
decreasing T
g
, since T
g
can affect the broadening width of
emission lines.
At atmospheric pressure, the atomatom collision
becomes a very important process (see the above discussion
on gure 10), whose rate increases with T
g
(Zhu and Pu 2010).
Therefore, in gure 16, the high-pressure nonequilibrium
regionthe H-regionis expanded to higher ionization ratio
regions with an increase in T
g
.
3.3. Gas-mixture discharges
Although the region diagramsgures 16 and 17are plotted
for pure argon and pure nitrogen discharges, respectively,
they may also be used to select line-ratio methods for gas-
mixture discharges containing argon or nitrogen, after the
energy transfer processes for excited species, such as
Ar(1s, 2p, 3p, 5p) + O
2
Ar(
1
S) + O + O, (24)
Ar(1s, 2p, 3p, 5p) + CF
4
/CH
4
/C
2
H
2
/SF
6
Ar(
1
S) + product, (25)
N
2
(A) + O
2
N
2
(X) + O + O, (26)
17
are considered (Velazco et al 1978, Guerra et al 2001, Sadeghi
et al 2001). These are the depopulation processes for the
relevant excited species or metastable species, which play
important roles in the rate balance equations. For excited
species with large Einstein coefcients, such as Ar(2p), these
kinds of processes should be included in the CRM at high
pressures (>10
3
10
4
Pa). For those with small Einstein
coefcients, such as Ar(5p), it should be added in the model
starting at an even lower pressure (100 Pa). For the
metastable species, these processes can be important at low
pressures (1 Pa), since their magnitude will be comparable
to that of diffusion-controlled deactivation at the chamber
wall. When the densities of the metastable species are largely
reduced by processes (24)(26), the excitation processes from
the metastables may be much weaker than those from the
ground state, and, as a result, one may use the corona model
instead of a CRM.
On the other hand, some reactions can produce excited
species used in a line-ratio method. Such an example is the
Penning ionization (Petrov et al 2000),
He(2
1
S, 2
3
S) + N
2
(X) He(1
1
S) + N
+
2
(B) + e. (27)
When this kind of process is present, one should make a careful
examinationwhether it becomes the major production
process for excited species instead of the electron-impact
excitation process. For example, in helium plasmas with
nitrogen impurity, the emission intensity of N
+
2
(B
2
+
u
) has
sensitive functions on the densities of the metastable atoms,
He(2
1
S) and He(2
3
S) (DeJoseph et al 2007). In this case,
the Penning ionization process, as well as the other relevant
processes of He(2
1
S) and He(2
3
S), should be included in the
population model of nitrogen species to calculate the emission
line ratios.
4. Limitations
In this section, we discuss the limitations in the application of
line-ratio methods. One of them is about the measurement
range of T
e
and n
e
(see gures 2 and 4). As mentioned
before, one should select excited species with suitable energy
difference (E, equation (7)) and characteristic electron
density (n
eC
, equation (10)) according to the T
e
and n
e
values
in the plasmas to be investigated (therefore, one needs a rough
estimation of these to be measured parameters at rst). For
similar reasons, a careful selection of the correct CRMs is
needed, according to the discharge conditions, in order to
obtain the optimal sensitivity of the line ratio to T
e
and n
e
(see gures 810 and tables 2 and 5). In addition, there are
some practical considerations for the application of line-ratio
methods, as discussed in the following.
4.1. Optical absorption and reection
Usually, there are two kinds of optical absorption processes
(also called self-absorption process or radiation trapping) in
low-temperature plasmas.
One is the absorption process by species in the metastable
or excited states. For example, the photons emitted in the
Figure 18. A schematic energy diagram for some argon atomic
levels, with the resonance radiation and the cascade process shown.
optical transition of Ar(2p
2
) Ar(1s
5
) are re-absorbed by the
Ar(1s
5
) atoms in plasmas (gure 18). Due to this absorption
process, as mentioned earlier, the densities of lower levels can
be determined using the branching fraction method (Boffard
et al 2009), which are used to calculate the population ratios of
the upper levels from the measured emission line ratios using
equation (16).
The other absorption process is the resonance radiation
trapping by the ground state. For example, the VUV photons
emitted in the resonance transition of Ar(3s
2
) Ar(
1
S)
are re-absorbed by the ground-state atoms Ar(
1
S) (gure 18).
Obviously, the effective decay rate by resonance radiation, for
example, Ar(3s
2
) Ar(
1
S), can be signicantly reduced
by increasing the pressure (thus Ar(
1
S) density). As a
result, the cascade processes out of resonance levels, for
example, Ar(3s
2
) Ar(2p
2
), are enhanced. As mentioned
in section 2.1.1, the apparent excitation cross sections, being
used in the corona model (equation (4)), are the sum of
direct excitation cross sections and cascade cross sections.
Therefore, the apparent cross sections vary with the gas
pressure due to the pressure-dependent cascade cross sections.
The escape factor of resonance radiation trapping is a function
of n
g
T
1/2
g
l
eff
at lowpressures <100 Pa (l
eff
is an effective
path length, of the order of the plasma dimension). Thus,
with n
g
, T
g
and l
eff
known, the apparent cross sections in
a plasma can be calculated, based upon the excitation cross
sections measured at a variety of gas pressures (Boffard et al
2004, 2007). The calculation procedure is described in detail
by Schabel et al (2002). For plasmas at higher pressures
(>100 Pa), the CRMs are used instead of the corona model.
The CRMs use the direct excitation cross sections of electron-
impact processes, which do not suffer from the radiation
trapping effect.
Emission lines from plasmas can be reected on the
discharge chamber walls, which, sometimes, contribute to
18
Table 7. Spectroscopic systems used to record the emission lines in references. CCD refers to charge-coupled device, ICCD refers to
intensied CCD and PMT refers to photomultiplier tube. TRL means tungsten ribbon lamp, SR means synchrotron radiation and D
2
lamp is
deuterium lamp.
Lines Spectrometer Wavelength (nm) Resolution () Detector Calibration References
Ar, TRIAX550, 330500 0.5 PMT TRL Zhu and Pu (2007a)
5p 1s Jobin Yvon
Ar, SPEX 1870c 335925 1 ICCD TRL Boffard et al (2004)
3p 1s
Ar, HR4000, 735915 2 CCD TRL Chen et al (2009a)
2p 1s Ocean Optics
Xe, Avaspec2048, 6001100 4 CCD TRL Zhu et al (2009a)
2p 1s Avantes Inc.
N
+
2
, AS50, 110400 3 PMT D
2
lamp, Bibinov et al (2008)
B
2
+
u
X
2
+
g
Jobin Yvon TRL
N
2
, SQ2000, 200530 6 CCD SR, Zhu et al (2006)
C
3
u
B
3
g
Ocean Optics TRL
N
2
, Avaspec2048, 2001100 8 CCD TRL Cicala et al (2009)
B
3
g
A
3
+
u
Avantes Inc.
the emission intensities recorded by a spectroscopic system.
The reectivity of some stainless steel chamber walls may
be wavelength dependent. The observed emission line ratios
are thus affected. This reection effect can be enhanced due
to the lms deposited by CH
4
/N
2
plasmas (Pu et al 2005a),
owing to the interference between the light reected from the
lm surface and that which re-emerged from the surface after
being reected by the stainless steel chamber wall. Pu et al
(2005b) nd that this effect can cause errors 20% in the T
e
measurement by the line ratio of lines 391.4 nm and 762.6 nm
(see gure 12). They use a practical method to eliminate the
optical reection effect. It is to arrange a black-surface plate
with a very small reection coefcient facing the diagnostic
viewport.
4.2. Spectroscopic system
Table 7 lists several typical spectroscopic systems used for the
line-ratio methods. The line-ratio methods only need a low
or moderate spectral resolution (usually, several angstroms)
to distinguish between the emission lines or bands. The
requirement of detector sensitivity is not high unless some very
weak lines are needed to be recorded, such as those out of argon
4p and 5p levels (see gure 19), for which a photomultiplier
tube (PMT) or an intensied charge-coupled device (ICCD)
should be used.
The wavelength and intensity calibration of a spectro-
scopic system is necessary for the application of line-ratio
methods. Wavelength calibration can be done using atomic
emission lines, from a low-pressure mercury lamp or a plasma
(Fantz 2006). Tungsten ribbon lamps with temperatures
20003000 K are suitable for intensity calibration in the
wavelength range 3001100 nm (Bibinov et al 1997). At
shorter wavelengths, one can use synchrotron radiation (SR)
or secondary standard light sources, such as a deuterium lamp.
In some special cases, two emission lines with similar wave-
lengths are used. For example, Britun et al (2007) use the
391.4 nm and 394.3 nm bands from N
+
2
(B
2
+
u
,v = 0) and
N
2
(C
3
u
,v = 2). Crolly and Oechsner (2001) use the 454.5
and 451.1 nm lines from Ar
+
(4p
2
P
3/2
) and Ar(3p
5
). In this
Figure 19. Experimental emission spectra containing the weak
emission lines out of argon 4p and 5p levels (CCP,
Ar/O
2
= 0.5/2 Pa, driving frequency 27.12 MHz, power 200W,
Chen et al (2009b)). The spectral resolution of the spectroscopic
system used is 0.5 . The detector is a PMT in photon counting
mode (cooled to 5
C).
case, the requirement of intensity calibration may be reduced,
assuming the response function of the spectroscopic system
varies smoothly at these wavelengths.
4.3. Temporal and spatial resolution
Temporally and spatially resolved diagnostics of low-
temperature plasmas can be accomplished using the line-ratio
methods, if one uses timespace dependent CRMs. In these
models, the rate balance equation of an excited state, x, is
written as
n
x
( r, t )
t
+
r
(D
x

r
n
x
( r, t ))
=
i
R
i
[n
e
( r, t ), T
e
( r, t ), n
x
( r, t ), n
y,y=x
( r, t ),
T
g
( r, t )]. (28)
19
Figure 20. The lifetime of excited species (curves) and the temporal
resolution achieved in the references (squares). The gas temperature
is assumed to be 400 K.
Here y refers to the other excited species except x, as well as
the ground-state species, n is the species density, r and t refer
to the position and the time, D is the diffusion coefcient,
R is the rate of the collisionalradiative processes, which is
a function of plasma parameters (n
e
, T
e
, n
x
, n
y
, T
g
). Using
these kinds of rate balance equations, one can obtain the
timespace dependent plasma parameters from the population
density ratios of excited species (from the measured emission
line ratios) (Kozlov et al 2001, Schulze et al 2010). In the
following, we use some examples to illustrate the temporal
and spatial resolution achieved by these kinds of line-ratio
methods, which not only depend on the instrument used in
the experiment, but also depend on the collisional processes.
Hu and Pu (2009) investigate the emission spectra from
neon atoms in an afterglow plasma. A PMT is used as
the detector of the spectroscopic system, whose temporal
resolution is 30 ns. Schulze et al (2010) investigate a low-
pressure Ar/Ne plasma by the phase resolved OES method.
The spectroscopic system containing a fast-gateable ICCD
camera has a temporal resolution of 5 ns. Higher temporal
resolution, 0.10.2 ns, is achieved by means of the cross-
correlation spectroscopy technique (Kozlov et al 2001), in
the investigation of dielectric barrier discharges in air at
atmospheric pressure. Figure 20 shows the temporal resolution
values above, together with the lifetimes of excited species
relevant in the line-ratio methods. The lifetimes are calculated
by considering the spontaneous radiation processes as well as
the collisional quenching processes. The temporal resolution
of the spectroscopic system used by Schulze et al (2010)
(5 ns) is shorter than the species lifetimes at low pressures.
In this case, note that the actual temporal resolution achieved
in the determination of plasma parameters (T
e
, n
e
, E/N) by
an OES method cannot be better than the lifetime of excited
species observed (>10 ns).
As for the spatially resolved measurement, the OES
method suffers from a fundamental challenge: the signal is
either a volume-averaged one or a line-averaged one if one
uses a ne collimator. Bymovinga light collectingoptical bre
step by step, Chen et al (2007) do a spatially resolved OES
investigation of low-pressure Ar/N
2
plasmas, with a spatial
Figure 21. The energy-loss mean free path of species (curves) and
the spatial resolution achieved in the references (squares). The gas
temperature is assumed to be 400 K. The ionization ratio of argon
plasma and nitrogen plasma is assumed to be 10
4
.
resolution of 3 mm. Two-dimensional spatially resolved
OES measurement can be accomplished using spectroscopic
systems containing ICCD cameras, with a spatial resolution
of 0.11 mm (Kozlov et al 2001, Schulze et al 2010).
When a microscope mirror system is used together with the
spectroscopic system, the spatial resolution can be as high
as 10 m (Tian et al 2010). Figure 21 compares these
spatial resolution values with the energy-loss mean free path of
some species inlow-temperature plasmas, whichare calculated
using the argon and nitrogen CRMs assuming ionization ratio
10
4
and T
g
400 K. The energy-loss mean free path of excited
species is the fundamental spatial resolution limit of the OES
methods, which can be as large as 110 m, as seen in
gure 21.
Sometimes, the spatial distribution of the metastable
species, such as the vibrationally excited ground-state nitrogen
molecules, N
2
(X
1
+
g
, v > 0), also affects the spatial
resolution in determining T
e
and n
e
. This is because their
vibrational distribution can be very much spatially uniform,
due to their extremely long energy-loss mean free paths (see
gure 21). Such an example is the line-ratio method of using
N
2
(C
3
u
,v = 1)/N
2
(C
3
u
, v = 0). Molecules in these two
levels come mainly from the ground-state excitations, which
can be enhanced due to the increase in T
e
and n
e
. Thus the
emission intensities from these levels vary strongly with T
e
and n
e
. However, these two levels have very similar excitation
threshold energies; as a result, the ratio of their excitation
rates is nearly a constant and can be represented by the
FranckCondon factors. On the other hand, according to the
FranckCondon principle, the population ratio N
2
(C
3
u
, v =
1)/N
2
(C
3
u
,v = 0) varies only with the VDF of the ground-
state molecules, which can be very uniform in space due to
their long energy-loss mean free paths, despite the possibility
of a very non-uniform distribution of T
e
and n
e
. Therefore,
using the nitrogen CRMs for vibrationally excited ground-state
molecules, one can only obtain the volume-averaged T
e
and
n
e
. For this reason, this line-ratio method is not suitable for
spatially resolved optical diagnostics (Zhu et al 2006).
20
5. Conclusions
The line-ratio method which focuses on the excited argon
and nitrogen species can be used to determine the electron
temperature and density in a variety of low-temperature
plasmas containing argon and nitrogen. It is a non-intrusive
and in situ diagnostic method and has the prominent advantage
of being a universal method for many different types of low-
temperature plasmas at low to atmospheric pressures. With a
suitable experimental setup, it can also be used for temporally
and spatially resolved optical diagnostics.
The line-ratio method requires a relative intensity-
calibrated spectroscopic system and, more crucially, a suitable
population modelthe corona model or the CRMfor excited
species in the plasmas to be investigated. The emphasis of
these models is the identication of major production and
depopulation processes under different discharge conditions
and for different kinds of excited species. The quality of the
modelling results, which determines the accuracy of diagnostic
results by the line-ratio method, depends on the existence
and quality of cross section and rate coefcient data for the
collisionalradiative processes. Owing to the tremendous
progress in this eld (Itikawa 2006, Boffard et al 2007,
Gargioni and Grosswendt 2008), the line-ratio method will
be further developed in the future.
Acknowledgments
The authors are grateful to Professor V M Donnelly, Professor
M A Lieberman, Dr V A Godyak, Professor U Czarnetzki,
Professor R Boswell, Professor C C Lin, Dr T K Chu and
Dr J B Boffard for enlightening discussions. They thank
Drs A A Mihajlov, I V Adamovich, V Guerra and H Akatsuka
for providing rate coefcient data and helpful discussions.
They also thank Wen-Cong Chen, Da-Wei Hu, Jiang Li and
Yu-Dong Pu for their help with the experiment. The work is
supported in part by the National Natural Science Foundation
of China under Grant Nos 10775087 and 10935006.
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OES in Ar and N - Determination of Electron T and Density by Line-Ratio Method

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Optical emission spectroscopy in low-temperature plasmas containing argon and nitrogen:

determination of the electron temperature and density by the line-ratio method

refer to the vibrational levels in the ground state,

refer to the vibrational levels of state N

refer to different vibrational levels

) states J. Chem. Phys. 76 97783

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