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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

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2010 J. Phys. D: Appl. Phys. 43 403001

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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, People’s Republic of China
E-mail: puyikang@tsinghua.edu.cn

Received 28 June 2010, in final 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 collisional–radiative 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 figures in this article are in colour only in the electronic version)

List of abbreviations PMT photomultiplier tube

SR synchrotron radiation
APPJ atmospheric-pressure plasma jet SRR split-ring resonator (plasma)
ASDF atomic state distribution function SWD surface wave sustained discharge
CCD charge-coupled device TRG-OES trace rare gases optical emission
CCP capacitively coupled plasma spectroscopy
CRM collisional–radiative model TRL tungsten ribbon lamp
DBD dielectric barrier discharge UV ultraviolet (radiation)
DCGD direct current glow discharge VDF vibrational distribution function
ECR electron cyclotron resonance (plasma) VUV vacuum ultraviolet (radiation)
EEDF electron energy distribution function
EEPF electron energy probability function List of symbols
gs ground state
ICCD intensified charge-coupled device A Einstein A coefficient
ICP inductively coupled plasma B Einstein B coefficient
IR infrared radiation d plasma dimension
MD microwave discharge D diffusion coefficient
NLD neutral loop discharge e electron
OES optical emission spectroscopy Ea 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

Ee electron kinetic energy density ratio with the measured emission intensity ratio, one
Eth excitation threshold energy can obtain the plasma parameters with the known operating

E energy difference between two excited levels parameters. These line-ratio techniques are used for a variety
E/N reduced electric field of low-temperature plasmas at low to atmospheric pressures
ge electron energy distribution function (EEDF) (Kano et al 2000, Crintea et al 2009, Zhu et al 2009b).
gp electron energy probability function (EEPF) At very low pressures (<1 Pa) and low ionization
hν photon ratios (<10−5 ), the excited species are mainly produced by
I emission intensity the electron-impact excitation from the ground state (see
J total angle momentum quantum number equation (1) in section 2.1.1) and are depopulated by the
K volume-averaged diffusion-controlled reaction spontaneous radiation (equation (2)). Therefore one can write
coefficient a set of rate equations for excited species containing only these
me electron mass two processes. This is called the corona model. With such a
n species density model, by selecting two excited levels with different excitation
ne electron density threshold energies (Eth ), the obtained line ratio is a function
neC characteristic electron density of Te , independent of ne and other plasma parameters. This
ng gas density relationship allows one to obtain Te at pressures ∼0.01–1 Pa
p pressure in electron cyclotron resonance (ECR) plasmas (Pu et al
Q rate coefficient of collisional process in the gas phase 2000, Crolly and Oechsner 2001). By selecting the particular
Qexc rate coefficient of electron-impact excitation levels insensitive to the excitation from the metastables, this
Qtrans rate coefficient of electron-impact simple method may still be extended to higher pressures,
population transfer say, ∼1–10 Pa, for microwave discharges (Behringer 1991),
Te electron temperature dc glow discharges (Behringer and Fantz 1994), inductive
high discharges (Ma and Pu 2003, Pu et al 2006, Britun et al 2007,
Te electron temperature corresponding to the
high-energy electrons Kang et al 2008) and helicon discharges (Foissac et al 2009).
Telow electron temperature corresponding to the A comprehensive review of the line-ratio technique with the
low-energy electrons corona model, as well as the excitation cross sections involved,
Tg gas temperature is given by Boffard et al (2004).
 escape factor Based on this simple method, a diagnostic technique
σexc excitation cross section 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
1. Introduction
concentrations are added to the reactive gases. The electron
Optical emission spectroscopy (OES) is one of the most temperature is obtained from the emission line ratios of the
widely used diagnostic methods for low-temperature plasmas Paschen 2p levels of these rare gas atoms. The TRG-OES
(Behringer 1991, Malyshev and Donnelly 1997, Boffard method has been widely used in a variety of low-pressure
et al 2004, Fantz 2006). It requires only a simple discharges, including the chlorine plasmas (Malyshev and
and inexpensive experimental setup: a diagnostic viewport Donnelly 1999, Donnelly and Schabel 2002), fluorocarbon
and a relative intensity-calibrated spectroscopic system, plasmas (Schabel et al 2002, Chen et al 2009a, Zhu et al 2009a)
covering a wavelength range of UV–visible–near-IR region and oxygen plasmas (Fuller et al 2000, Stafford et al 2009).
(∼200–1100 nm). From the emission spectra of atomic Zhu and Pu (2007a, 2007b) and Zhu et al (2007) develop
or molecular species, being excited by the electron-impact a ne measurement technique of using the line ratios of certain
processes in plasmas, one may extract the electron temperature, argon 3p, 4p and 5p levels for low-pressure plasmas. Since the
Te (assuming a Maxwellian electron energy distribution lifetimes of these levels are significantly longer than those of
function, EEDF), and the electron density, ne (Behringer and 2p levels, the electron-impact population transfer processes,
Fantz 1994, Bibinov et al 1998, 2005, 2008, Kano et al being dependent on ne (see equation (8) in section 2.1.2),
2000, 2001, Pu et al 2000, 2006, Donnelly and Schabel 2002, can be as important as the radiation processes even at low
Donnelly 2004, Zhu and Pu 2005, 2008, Zhu et al 2006, pressures (1–10 Pa). As a result, the line ratios of these levels
Iordanova and Koleva 2007). are functions of ne (Boffard et al 2004), nearly independent of
In order to use the OES method to determine the Te Te (for reasons explained in section 2.1.2). The obtained results
and ne , one usually applies the so-called line-ratio technique. of ne from this method are in good agreement with those from
First, for a given pair of excited levels, which emit light, one the Langmuir probe in inductive Ar/O2 plasmas (Zhu and Pu
builds up a population model by considering their dominant 2008), as well as those from the method of deriving ne from
production and depopulation processes. Then, from this the ion energy distribution function in a capacitively coupled
model, which consists of a set of rate balance equations of these plasma (CCP) (Chen et al 2009b).
two excited levels and other relevant species, one can solve for At higher pressures (>10 Pa) or with a relatively high
the density ratio of these two levels. This ratio is a function of ionization ratio (>10−5 ), the line ratios of all the argon-excited
plasma parameters (Te , ne , etc) as well as operating parameters states are functions of both Te and ne due to the excitation
(pressure, plasma dimension, etc). By fitting the calculated processes out of the metastable or excited states, as indicated

2
J. Phys. D: Appl. Phys. 43 (2010) 403001
in the collisional–radiative models (CRM) for argon plasmas
(Vlček 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 Te
and ne in low-pressure inductively coupled plasmas (ICP). It
is also used to obtain Te and ne 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
Te and ne in a magnetron sputtering plasma. Based on the
CRM by Vlček (1989), Kano et al (2000, 2001) determine
the values of Te and ne with the line ratios of several argon
2p, 3s and 5d levels (in Paschen’s notation) in a dc glow
discharge (DCGD) at medium pressures (∼102 –104 Pa) and in
a low-pressure plasma jet (∼10 Pa). Vries et al (2006) present
another method: fitting the calculated atomic state distribution
function (ASDF) with the measured one. They use this method
to obtain the values of Te and ne in a surface wave sustained
discharge (SWD) at medium pressure (∼103 Pa). For the SWD
at atmospheric pressure, Yanguas-Gil et al (2006) develop
a theoretical approach to determine Te from the excitation
temperature of argon excited levels. A similar 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) find that the atom–atom collision processes
may lead to a non-Boltzmann ASDF of the 2p multiplet at
atmospheric pressure. By adding this effect into the CRM, a ne
measurement technique is proposed for non-equilibrium argon
discharges. It is used in the investigation of pulsed rf 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 Te and ne 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 (1–10 Pa). They use a CRM containing the collisional
processes between the metastable molecules N2 (A 3 u+ ) and
the vibrationally excited ground-state molecules. Based on
this model, Te is obtained by the line ratio of electronic
states N2 (C 3 u ) and N2 (B 3 g ) and ne is obtained by that of
vibrationally excited levels N2 (C 3 u , v = 0) and N2 (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 (102 –105 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 N2 (C 3 u ), N2 (B 3 g ) and N2+ (B 2 u+ ) and the vibrational
distribution functions (VDFs) of these states. By fitting these
3
Topical Review
ratios with the measured ones, one can obtain the values of Te
and ne and the reduced electric field, 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 N2 (C 3 u ) and N2+ (B 2 u+ ) is also used to measure
the values of Te 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 first method rises
from the 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 atom–atom 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 influence
of discharge conditions on the selection of a line-ratio method,
as well as their influence 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 reflection 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 Te and ne 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
production processes equals that of the depopulation processes,
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 figure 1. In the following, we first describe the
population model for some given excited levels under a given
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

ground-state atom,

Ar(gs) + e → Ar(2p1 ) + e,
(1)
Xe(gs) + e → Xe(2p5 ) + e,

and the spontaneous radiation,

Ar(2p1 ) → Ar(1s) + hν,

(2)
Xe(2p5 ) → Xe(1s) + hν.

The symbol gs denotes the ground state, 1s denotes the Paschen

1s levels, e is for an electron and hν is for a photon.
The rate balance equations of Ar(2p1 ) and Xe(2p5 ) are

ne · nAr · QAr(2p
exc
1)
= AAr(2p1 ) · nAr(2p1 ) ,
(3)
ne · nXe · QXe(2p
exc
5)
= AXe(2p5 ) · nXe(2p5 ) ,

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 Te and ne 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 (∼106 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 significant 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. Te 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,
2p1 → 1s2 ) and 828.0 nm (Xe, 2p5 → 1s4 ) (see figure 1). Note
that the 2p levels with zero total angle momentum quantum
number (J = 0) of rare gases (in Paschen’s notation, 2p1
and 2p3 for Ne, 2p1 and 2p5 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
where ne is the electron density, nAr and nXe are the densities
of ground-state argon and xenon atoms and A is the Einstein
A coefficient. Qexc is the excitation rate coefficient from the
ground state,

∞ 
2Ee
Qexc = σexc · · ge (Ee ) dEe ,
Eth me
(4)

∞ 
2
= σexc · · Ee · gp (Ee ) dEe ,
Eth me
where Ee is the electron kinetic energy, Eth is the excitation
threshold energy, σexc is the excitation cross section, me is
the electron mass, ge is the EEDF, gp is the electron energy
probability function (EEPF) and is related to the EEDF ge
1/2
by ge (Ee ) = Ee gp (Ee ). When gp is plotted in a log scale
versus Ee , 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 should be included on the left-hand side of equation (3).
As a result, one should use the apparent excitation cross section
in calculating Qexc 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)
Ix = Ax · nx , (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 nx refers to the population density of species in this state
and Ax is its Einstein A coefficient.

4
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Figure 2. Ratios of the excitation rate coefficients from the ground
state as functions of electron temperature: Ar(2p1 )/Xe(2p5 ),
Ar(3p1 )/Ar(2p1 ), N2 (C 3 u )/N2 (B 3 g ) and N2+ (B 2 u+ ,
v = 0)/N2 (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).
Figure 3. The values of electron temperature in a Ne/Ar/Xe ICP
determined by the line ratio of 750.4 nm (Ar, 2p1 → 1s2 ) and
828.0 nm (Xe, 2p5 → 1s4 ) with the corona model and those
determined by the Langmuir probe. The dimensionless parameter xc
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).

From equations (3) and (5), the emission line ratio is an excited level, and
E is the energy difference between the
two excited levels.
Ar(2p )
IAr(2p1 ) AAr(2p1 ) · nAr(2p1 ) ne · nAr · Qexc 1 Equation (7) indicates that, in order to get a functional
= =
IXe(2p5 ) AXe(2p5 ) · nXe(2p5 ) Xe(2p )
ne · nXe · Qexc 5 form that is sensitive to Te , it is desirable to select two
Ar(2p1 )
excited states with
E comparable to Te . If
E is much
Qexc smaller than Te , the rate coefficient ratio is nearly independent
=C· Xe(2p5 )
,
Qexc of Te (Ar(3p1 )/Ar(2p1 ), figure 2). Although a large
E
nAr can lead to the line ratio, a very sensitive function of Te
C≡ . (6) (N2+ (B 2 u+ ,v = 0)/N2 (C 3 u , v = 0), figure 2), one of the
nXe
emission lines may be too weak to have a good signal-to-
The constant C is the density ratio of the ground-state atoms noise ratio, when Te in the discharge is low. For example,
and can be obtained from the partial pressures of argon and at Te ∼ 1.5 eV, the emission lines from N2+ (B 2 u+ ) are very
xenon assuming they have equal gas temperatures. For a weak, owing to the very low number of electrons with energies
Maxwellian EEDF, using the experimental cross sections and higher than the threshold energy, ∼19 eV, for the excited
equation (4), the excitation rate coefficient ratio is a function of ionization process from N2 (X 1 g+ ) to N2+ (B 2 u+ ) (Zhu and
Te (see figure 2). Therefore, once two levels are selected, one Pu 2008). Note that equation (7) is for illustrative purpose
may obtain Te from the measured line ratio using equation (6), only and the most accurate way to obtain the ratio of the rate
taking into account the response function of the spectrometer. coefficients is using the experimental cross section data directly
Some of the excitation rate coefficients, such as those and equation (4). For some other levels, their cross sections
from the ground state to the Paschen np (n = 2–5) levels of may behave differently with the electron energy from the levels
argon and xenon and those to the nitrogen states N2 (B 3 g ), discussed here and equation (7) may not be appropriate to
N2 (C 3 u ) and N2+ (B 2 u+ ), can be approximated by an represent the dependence of rate coefficients on the electron
Arrhenius form (Zhu et al 2009a) within the range of electron temperature over the range of interest. In this case, when
temperatures of interest and we have employing equation (6) to obtain the electron temperature, it
 
Ar(2p )
Ea 1 is still helpful to select two levels with very different threshold
Ar(2p1 )
Ar(2p )
Q0 · exp − energies.
Qexc 1 Te
∼   Figure 3 shows the results of determining Te by the line
Xe(2p ) Xe(2p5 )
Qexc 5 Xe(2p5 ) Ea ratio of Ar(2p1 ) and Xe(2p5 ) in a Ne/Ar/Xe ICP (Zhu et al
Q0 · exp − 2009a). This line-ratio method can be used to obtain Te s in the
Te
range of 1–4 eV, being comparable to the energy difference
 Ar(2p ) Xe(2p5 )
  
Ea 1 − E a
E between Ar(2p1 ) and Xe(2p5 ) (see figure 1). At a constant
∼ exp − ∼ exp − , (7) power of 100 W, Te is changed by varying the partial pressures
Te Te
of gases: pNe ∼ 1–10 Pa, pAr
pNe /5, pXe
pNe /20 in
where Q0 is a constant (pre-exponential factor), Ea is the the Ne/Ar/Xe mixture and pAr ∼ 1–8 Pa, pXe
pAr /4 in
activation energy, roughly equal to the threshold energy of the Ar/Xe mixture. A dimensionless parameter xc is used in

5
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review
high
Table 1. Some works using the line-ratio method to determine Te with the corona model. The method to obtain Te in the TRG-OES
technique is included.
Excited states selected Plasmas Feed gases Trace gases
1
Behringer (1991) He(3d D)/Ar(2p) ECR N2 or CH4 Ar and He
or N2+ (B 2 u+ )/N2 (C 3 u )
Behringer and Fantz (1994) He(3d1 D)/Ar(2p)/N2 (C 3 u ) DCGD He Ar and N2
Pu et al (2000) N2+ (B 2 u+ )/N2 (B 3 g ) ECR N2
Crolly and Oechsner (2001) Ar+ (4p2 S, 4p2 P)/Ar(3p) ECR Ar or N2
or N2+ (B 2 u+ )/N2 (C 3 u )
Donnelly (2004) Ar(2p1 , 2p5 )/Kr(2p1 , 2p5 )/Xe(2p1 , 2p3 , 2p5 ) ICP Cl2 , O2 Ar, Kr and Xe
or Ar/C2 F6 /C4 F8
Boffard et al (2004) Ar(3p1 )/Ne(2p1 ) ICP Ar/Ne
Britun et al (2007) N2+ (B 2 u+ )/N2 (C 3 u ) ICP N2 or Ar/N2
Chen et al (2009a) Ar(2p1 , 2p5 )/Kr(2p1 , 2p5 , 2p7 )/Xe(2p3 , 2p5 ) CCP CF4 /O2 Ar, Kr and Xe
Stafford et al (2009) Ar(2p1 , 2p5 )/Kr(2p1 , 2p5 ) SWD O2 Ar, Kr and Xe
/Xe(2p1 , 2p3 ,2p5 )
Zhu et al (2009a) Ar(2p1 , 2p5 )/Xe(2p5 ) ICP, CCP Ar/Xe/CF4
Foissac et al (2009) Ar(3s)/Ar(2p) Helicon Ar

figure 3, which is a function of the partial pressures of argon, can be considered as constants. In fact, the values of neC
xenon and neon. The results are in good agreement with those can be obtained experimentally using a Langmuir probe and a
from the Langmuir probe (Zhu et al 2009a). spectrometer: ∼3×1011 cm−3 for argon 3p levels, ∼1011 cm−3
The above method can also be used for discharges for argon 4p levels and ∼2×1010 cm−3 for argon 5p levels (Zhu
containing excited N2 , N2+ , Ar + , He, Ne and Kr species, as and Pu 2008, Zhu et al 2009a). Therefore, the rate equations
listed in table 1. of Ar(3p1 ) and Ar(5p5 ) can be rewritten as
 
Ar(3p ) ne
2.1.2. ne determination with extended corona model. As for ne · nAr · Qexc 1 = AAr(3p1 ) · nAr(3p1 ) · 1 + ,
neC,3p1
higher excited levels, such as Ar(3p1 ) and Ar(5p5 ), they have  
very small excitation cross sections from the metastables, since Ar(5p ) ne
ne · nAr · Qexc 5 = AAr(5p5 ) · nAr(5p5 ) · 1 + .
J = 0 (as mentioned in section 2.1.1). As a result, their major neC,5p5
production source is still the ground-state excitation. However, (11)
in the destruction channel, the electron-impact population
transfer processes, The line-ratio equation for Ar(3p1 ) and Ar(5p5 ) is
IAr(3p1 ) AAr(3p1 ) · nAr(3p1 )
Ar(3p1 ) + e ↔ Ar(2s, 3s, 3d, 4d) + e, =
(8) IAr(5p5 ) AAr(5p5 ) · nAr(5p5 )
Ar(5p5 ) + e ↔ Ar(4s, 5s, 5d, 6d) + e, Ar(3p1 )
ne · nAr · Qexc · (1 + ne /neC,5p5 )
should be added in the corona model, due to the relatively = Ar(5p )
, (12)
ne · nAr · Qexc 5 · (1 + ne /neC,3p1 )
small Einstein coefficients of these levels. Therefore, the rate
balance equation becomes that is,
IAr(3p1 ) (1 + ne /neC,5p5 )
ne · nAr ·
Ar(3p )
Qexc 1 =AAr(3p1 ) · nAr(3p1 ) + ne · nAr(3p1 ) ·
Ar(3p )
Qtrans 1 , =C·
IAr(5p5 ) (1 + ne /neC,3p1 ),
Ar(5p5 ) Ar(5p )
ne · nAr · Qexc =AAr(5p5 ) · nAr(5p5 ) + ne · nAr(5p5 ) · Qtrans 5 , Ar(3p1 )
(13)
Qexc
(9) C≡ Ar(5p5 )
.
Qexc
where Qtrans is an effective rate coefficient of the electron-
impact population transfer process. Note that, on the left-hand When Te  1 eV, the excitation rate coefficient ratio, C,
side of the equation, only high-energy electrons contribute of Ar(3p1 ) and Ar(5p5 ) is nearly independent of Te , from
to the excitation; however, due to the very small excitation the calculations based on the cross section measurements
threshold energy of the population transfer process, low-energy (Weber et al 2003, Boffard et al 2004). This is because their
electrons make the maximum contribution to Qtrans , and thus cross sections have very close values of the threshold energy.
Qtrans is only weakly dependent on Te . Therefore, a parameter, Therefore, the line-ratio equation (13) is basically independent
neC , named the characteristic electron density, can be defined of Te and can be used to determine ne .
as (Zhu and Pu 2007a, 2007b) In order to use equation (13) to determine ne effectively,
A at least one of the neC values should be comparable to the ne
neC ≡ . (10) value in plasmas. If ne  neC,5p5 < neC,3p1 , the line ratio
Qtrans
is nearly independent of ne (the left region in figure 4). This
In many low-pressure ICP and CCP discharges with argon is because the spontaneous radiation is a much faster process
partial pressures ∼1–10 Pa, the neC of certain excited levels than the electron-impact population transfer. Otherwise, if

6
J. Phys. D: Appl. Phys. 43 (2010) 403001
Figure 4. The line ratio of Ar(3p1 ) and Ar(5p5 ) versus electron
density, calculated using equation (13). The excitation coefficient
ratio is calculated from the cross sections given by Boffard et al
(2007). The neC values are from Zhu et al (2009a).
Figure 5. The electron densities in an Ar/O2 ICP determined by the
line ratio of 425.9 nm (Ar, 3p1 →1s2 ) and 357.2 nm (Ar, 5p5 →1s2 )
with the extended corona model (with the electron-impact
population transfer process added) and the results by the Langmuir
probe (Zhu and Pu 2008).
neC,5p5 < neC,3p1  ne , the line ratio is insensitive to ne as well
(the right region in figure 4), since only the electron-impact
population transfer is important for both species. Therefore,
to make the line ratio a sensitive function of ne , both processes
should play comparable roles in the depopulation of Ar(3p1 )
or Ar(5p5 ).
Figure 5 shows the results of determining ne by the line
ratio of Ar(3p1 ) and Ar(5p5 ) in an Ar/O2 ICP (Zhu and Pu
2008). In this plasma, ne is increased by the power at constant
pressures of argon and oxygen. This line-ratio technique is
valid when ne is in the range 109 –1012 cm−3 (in the middle
region in figure 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 3p1 /5p5 in the
7
Topical Review
ne measurement. However, their excitation rate coefficient
ratio may have a stronger dependence on Te (Zhu et al
2009a), and thus the Te in plasmas should be measured before
determining ne .
Te and ne can be simultaneously obtained using the
above line ratios. Such an example is given in figure 6
for an Ar/Xe/CF4 CCP (Zhu et al 2009a). The Te and
ne variation versus driving frequency in the electronegative
discharges containing CF4 is different from that in the
electropositive discharges, because the energy balance
between the electron heating and the energy loss mechanisms
is affected significantly by the inelastic collisions with CF4
(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 (Eth ) contribute to the calculation
of the excitation rate coefficient, as seen in equation (4).
Therefore, when a line-ratio method with the corona model,
such as that of using Ar(2p1 )/Xe(2p5 ), is applied to determine
‘Te ’ in a plasma with a non-Maxwellian EEDF, one obtains an
‘electron temperature’ corresponding solely to the high-energy
high
tail of an EEDF, Te (Donnelly 2004, Pu et al 2006). This
high
Te 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 coefficient of this process,
Qtrans , may be dependent on the ‘electron temperature’
corresponding to the low-energy electrons, Telow . However,
this effect is very weak. As a result, the parameter neC ,
calculated from Qtrans (equation (10)), is nearly independent of
Telow , which is experimentally confirmed in low-pressure ICP
and CCP discharges (∼1–10 Pa) (Zhu and Pu 2007a, 2007b,
Zhu et al 2007). For this reason, Telow 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
(103 –105 Pa) (Rolin et al 2007, Dyatko et al 2008). In these
cases, one should apply an argon CRM (Vlček 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
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Figure 6. Te and ne versus the driving frequency at a constant power 50 W in a capacitive discharge, obtained from the line-ratio techniques
using Ar(2p1 )/Xe(2p5 ) and Ar(3p1 )/Ar(5p5 ), respectively (Zhu et al 2009a).

as the molecular excimers, are to the fact that the electron-impact excitation processes out of
  
ne
y→x
ny Qe–Ar + nAr
y→x
ny QAr–Ar + y→x Ay→x ny the excited levels, the atom–atom collisions and the three-body
y=x y=x y=x
collisions play important roles. References for the collision
 y,z→x +
→x
cross sections are listed in table 3.
+ ny nz QAr−Ar + n2e nAr+ Qe,e,Ar
3-body In the following, we show in detail an example of using
y=x z=x the line-ratio method with the argon CRM to determine Te and
→x + ne with the emission lines from the argon 2p levels, which
+ ne nAr nAr+ Qe,Ar,Ar
3-body are usually the strongest emission lines from low-temperature
 x→y  x→y
= ne nx Qe–Ar + nAr nx QAr–Ar argon plasmas, as shown in figures 7(a), (c) and (e) for three
y=x y=x types of argon plasmas (Zhu and Pu 2007a, 2009, Zhu et al
 2007, 2008). The operating parameters of these experiments
+ x→y Ax→y nx + 2n2x Qx,x
Ar –Ar are given in table 4.
y=x Since the pressure or the ionization ratio is higher than
 x,y the cases discussed in section 2.1, the population densities of
+ nx ny QAr–Ar + n2Ar nx QAr,Ar,x x
3-body + Kwall nx . (14)
Ar(1s2 ) and Xe(1s4 ) are no longer low. The self-absorption
y=x
processes can be significant. In this case, the emission intensity
x refers to a species in a certain state while y and z refer is related to the population density of the excited species by
to other states or other species. nx , ny and nz refer to their (Griem 1997)
densities, respectively, Q is the reaction rate coefficient of
collisional process in the gas phase, K is the volume-averaged Ix→y = x→y (ny ; d, Bx→y ,
νx→y ) · Ax→y · nx . (15)
diffusion-controlled reaction coefficient (see Donnelly 2004),
A is the Einstein A coefficient and  is the escape factor Here x and y refer to the upper and lower levels of an optical
due to the self-absorption process. The superscripts denote transition, respectively. The escape factor, , is a function of
the species involved in each process. The subscripts give the the population density of the lower level (ny ), as well as the
reaction types: e–Ar, the collision processes between electrons plasma dimension (d), the Einstein B coefficient for absorption
and argon species, Ar–Ar, the collision reactions between two (B) and the spectral line width (
ν), which is caused mainly by
argon species, 3-body, the three-body collisions, wall, the the Doppler broadening, as well as the collisional broadening
quenching processes at the chamber wall. From equation (14), when the gas pressure is high (>104 Pa) (Wang et al 2005).
one can calculate the population density ratios of the excited With d, B and
ν known, the new line ratio is
species.
Table 2 lists several of these kinds of line-ratio methods IAr(2pi →1sk ) 2pi →1sk (n1sk ) · A2pi →1sk · n2pi
= ,
used in the literature. It can be seen that all of these IAr(2pj →1sl ) 2pj →1sl (n1sl ) · A2pj →1sl · n2pj
works consider the following processes: the electron-impact 1
i, j
10, 2
k, l
5. (16)
excitation processes from the ground state and metastable
levels, the spontaneous radiation and radiation trapping, as Here i, j and k, l refer to different 2p and 1s levels, respectively.
well as the quenching processes of metastables at the chamber As seen in equation (16), in order to relate the emission line
wall. At medium and high pressures, one should pay attention ratios to the population ratios of 2p levels, one needs to obtain

8
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Table 2. The excited levels and processes in some argon CRMs and the selected line ratios used to obtain Te and ne . Note that the work by
Donnelly is included for the method to obtain Telow in the TRG-OES technique. hl refers to the high-lying levels such as the 2s, 3d and 3p;
e–Ar means the collision processes between electrons and argon species; Ar–Ar 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 e–Ar, rad, wall ICP, CCP 2p Telow
(∼0.1–10 Pa)
Iordanova and Koleva (2007) 1s, 2p e–Ar, rad, wall ICP 2p Te , ne
Ar–Ar (∼1–100 Pa)
Kano et al (2000) 1s, 2p, hl e–Ar, rad, wall DCGD 2p, 3s, 5d Te , ne
Ar–Ar, 3-body (∼102 –104 Pa)
Vries et al (2006) 1s, 2p, hl e–Ar, rad, wall SWD 2p, 3s, 4s, Te , ne
Ar–Ar, 3-body (∼103 Pa) 5d, 6d, 7d
Akatsuka (2009) 1s, 2p, hl e–Ar, rad, wall APPJa 2p, 3p Te
Ar–Ar, 3-body (∼105 Pa)
Zhu et al (2009b) 1s, 2p, hl e–Ar, rad, wall SRR, DBDb 2p ne
Ar–Ar, 3-body (∼105 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
high
parameters involved in calculating the rates of processes are Te , the electron temperature corresponding to the high-energy electrons,
low
Te , that corresponding to the low-energy electrons, ne , the electron density, Tg , the gas temperature, ng , the gas density and d, the plasma
dimension.
Processes Parameters References
high
e–Ar e + Ar ↔ e + Ar(1s, 2p, hl) Te , ne , ng 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) Telow , ne Boffard et al (1999),
Jung et al (2007)
e + Ar(1si ) ↔ e + Ar(1sj ) Telow , ne Bartschat and Zeman (1999),
e + Ar(2pi ) ↔ e + Ar(2pj , 2s, 3d) Pokrzywka (2002)
e + Ar(1s, 2p, hl) → e + e + Ar + Telow , ne Deutsch et al (2004)
e + Ar ∗2 → e + Ar + Ar(1s) Telow , ne Neeser et al (1997)
e + Ar +2 → Ar + Ar(hl) Telow , ne , Tg Bultel et al (2002)
rad Ar(1s4 , 1s2 ) → Ar + hν NIST (2010)
Ar(2p, 3p) → Ar(1s) + hν
Ar(2s, 3d) → Ar(2p) + hν
Ar–Ar Ar + Ar(2pi ) → Ar + Ar(1s, 2pj ) ng , Tg 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 Tg Bultel et al (2002)
3-body e + e + Ar + → e + Ar(hl) ne , Telow , ng , Tg Dyatko et al (2008)
e + Ar + Ar + → Ar + Ar(hl)
Ar(1s) + Ar + Ar → Ar ∗2 + Ar ng , Tg Rolin et al (2007)
Ar + + Ar + Ar → Ar +2 + Ar
wall
wall Ar(1s5 , 1s3 ) −→ Ar ng , Tg , d Bogaerts et al (1998)

the densities of 1s levels, using the line ratios with the same method, which is described in detail by Boffard et al (2009)
upper state, such as and Schulze et al (2008).
IAr(2pi →1sk ) 2pi →1sk (n1sk ) · A2pi →1sk Using equations (16) and (17), we obtain the population
= . (17) distributions of 2p levels from the spectral data of three types
IAr(2pi →1sl ) 2pi →1sl (n1sl ) · A2pi →1sl
of plasmas, as shown in figures 7(b), (d) and (f ).
Note that we have tens of equations like (17) for the 2p–1s The next step is to calculate the population ratio as
transitions and thus the densities of four 1s levels can be a function of Te and ne from the rate balance equations,
easily obtained. This method is called the branching fraction which contain the dominant production and depopulation

9
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Figure 7. Experimental emission spectra of argon plasmas: (a) ICP at 1 Pa, (c) CCP at 120 Pa and (e) SRR at 105 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 ). n2p and g2p are the population density and the degeneracy degree of 2p levels, respectively. The values of n2p /g2p are normalized
to 100.

Table 4. Operating parameters and plasma parameters for several mechanisms under these discharge conditions. In the following
types of argon plasmas. part of this section, we discuss the effects of Te and ne on the
ICP CCP SRR excited level population ratios in detail, assuming a constant
gas temperature and the plasma dimension (listed in table 4).
Driving frequency 13.56 MHz 27.12 MHz ∼0.9 GHz
Discharge pressure 1–15 Pa 4–120 Pa 103 –105 Pa
The effects of variation in these parameters, even though may
Absorbed power 75 W 50 W ∼1 W not be as significant as Te and ne , are still very important under
Plasmas’ dimension 15 cm 4 cm ∼0.1–1 mm certain conditions (section 3.2).
Gas temperature ∼400 K ∼400 K ∼500 K In figure 8, where the pressure is 1 Pa, we find that Te
is very sensitive to the population ratio 2p9 /2p10 . Both these
levels have large excitation cross sections from the metastable
processes. At low pressures (∼1–10 Pa), atoms in the 2p level 1s5 (Boffard et al 1999), and thus, under the discharge
levels are produced mainly by the electron-impact excitations conditions shown in this figure, the dominant production
from the ground state as well as from the metastables sources of 2p9 and 2p10 are the excitations from 1s5 . The ratio
(1s3 and 1s5 ). The dominant depopulation process is the of the rate of these excitation processes is nearly a constant,
spontaneous radiation. At medium pressures (∼102 –103 Pa), due to their similar excitation threshold energies from 1s5 .
the densities of the resonance levels (1s2 and 1s4 ) become The significant increase in the ratio 2p9 /2p10 with Te is caused
of the same order as those of the metastables, due to the by the depopulation mechanisms—the spontaneous radiations
strong radiation trapping by the ground state. As a result, and the self-absorption processes. Not that the selection rule
the excitations from these resonance levels to the 2p levels of the optically allowed transition from a 2p level to a 1s level
also play important roles. At high pressures (∼104 –105 Pa), is
J = 0, ±1 except J = 0 → J = 0. Thus 2p9 (J = 3)
the atom–atom collisional processes and the three-body can only decay to 1s5 (J = 2) but 2p10 (J = 1) can decay
collisions are important, owing to the high gas densities to 1s5 (J = 2), 1s4 (J = 1), 1s3 (J = 0) and 1s2 (J = 1).
(Zhu and Pu 2010). When Te increases, the density of 1s5 increases due to the
Figures 8, 9 and 10 show the contour graphs of the ground-state excitation due to the high-energy electrons. As a
population ratios versus Te and ne at 1 Pa, 120 Pa and 105 Pa, result, the self-absorption by 1s5 is largely enhanced and the
respectively. In each contour graph, we show two population effective decay rate from 2p9 to 1s5 is largely reduced. On
ratios—one is more sensitive to the variation of Te and the the other hand, the decay of 2p10 by spontaneous radiation is
other is more sensitive to ne . Different population ratios are not much affected by this process, since it can also decay to
selected at different pressures, owing to the different kinetic the resonance levels (1s2 and 1s4 ), whose densities are much

10
J. Phys. D: Appl. Phys. 43 (2010) 403001
Figure 8. Contour graph of population ratios of argon 2p levels at
1 Pa: 2p3 /2p1 and 2p9 /2p10 , calculated from a CRM (Zhu and Pu
2010). The gas temperature Tg is assumed to be 400 K, and the
plasma dimension d is assumed to be 15 cm.
Figure 9. Contour graph of population ratios of argon 2p levels at
120 Pa: 2p1 /2p5 and 2p3 /2p10 . Tg = 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 2p9 /2p10
increase with Te .
Figure 8 also shows that the population ratio 2p3 /2p1
has a strong ne dependence. As mentioned before, the level
2p1 (J = 0) has a relatively large excitation cross section
from the ground state and its excitation cross section from the
resonance level 1s2 is quite small. However, the opposite is
true for 2p3 , whose ground-state excitation cross section is
small and its excitation cross section from 1s2 is quite large
(Zhu and Pu 2010). Under the discharge conditions shown
in figure 8, the density of 1s2 significantly increases with ne ,
due to the electron-impact population transfer processes from
the metastables. As a result, the population ratio 2p3 /2p1 also
increases with ne .
In figure 9, where the pressure is 120 Pa, the population
ratio 2p1 /2p5 shows its variation with Te . With J = 0, these
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Topical Review
Figure 10. Contour graph of population ratios of argon 2p levels at
105 Pa: 2p1 /2p5 and 2p9 /2p6 . Tg = 500 K and d = 100 µm are
assumed.
two levels have relatively large ground-state excitation cross
sections, as discussed above. Thus, even at low Te s (∼1–2 eV),
as found in many medium-pressure plasmas (∼102 –103 Pa)
(Kano et al 2000, Vries et al 2006, Iordanova and Koleva 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 2p1 has a larger rate
coefficient than 2p5 for the ground-state excitation but 2p5 has
larger excitation rate coefficients from the 1s levels, the ratio
2p1 /2p5 increases with Te , as seen in figure 9.
However, for the other 2p levels with J = 0, only the
excitations from the 1s levels are important. Their population
ratios (such as 2p3 /2p10 ) are nearly independent of Te , due to
the close excitation threshold energies from the 1s levels. But it
can have a strong dependence on ne , as shown in figure 9. The
ne dependence comes from two different production sources
of 2p3 and 2p10 , even though both are excited mainly from the
1s levels: 2p3 from the resonance level 1s2 and 2p10 from the
metastable level 1s5 . Due to the electron-impact population
transfer from 1s5 to 1s2 , the density ratio 1s2 /1s5 increases
with ne . As a result, the population ratio 2p3 /2p10 increases
with ne .
In figure 10, at atmospheric pressure, the population
ratio 2p1 /2p5 also varies with Te for the same reasons as in
figure 9. On the other hand, the population ratio 2p9 /2p6
is selected to show its variation with ne . This is because
their depopulation processes have different dependence on
ne . At atmospheric pressure (gas temperature ∼500 K, plasma
dimension ∼100 µm), the 2p6 level is depopulated mainly by
the collisional quenching with the electrons, while 2p9 has
an additional important destruction channel—the collisional
quenching with the ground-state atoms. Therefore, for the
2p9 level, its rate of decrease with ne is slower than that for
2p6 level. This causes the population ratio 2p9 /2p6 to increase
with ne .
At atmospheric pressure, the gas temperature, Tg , can
affect the rate of the atom–atom collisional quenching process,
J. Phys. D: Appl. Phys. 43 (2010) 403001
Figure 11. Te and ne versus neutral gas pressure, determined by fitting the calculated population ratios of argon 2p levels with those
obtained from the experimental line ratios: (a) ne for an argon ICP at pressures 1–15 Pa, (b) ne for an argon CCP at pressures 4–120 Pa,
(c) ne for an argon SRR at pressures 103 –105 Pa, (d) Te for ICP, (e) Te for CCP and (f ) Te for SRR. The ‘probe’, ‘IEDF’ and ‘broadening’
refer to the Langmuir probe method (Zhu and Pu 2008), the method of deriving ne 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, ng (∼Tg−1 ), and that
on the collisional quenching rate coefficient
1/2
(∼Tg , Rolin
et al (2007) and Zhu and Pu (2010)). When Tg increases,
the reduction in the rate of atom–atom collision process
1/2 −3/2
(∼n2g × Tg ∼ Tg ) is faster than that of the electron–atom
process (∼ng ∼ Tg−1 ). As a consequence, the population ratio
2p9 /2p6 increases with Tg . For example, the ratio of 2p9 /2p6 at
a gas temperature of 1000 K is larger than that at 500 K (used
in figure 10) by ∼5%. This will cause the variation in the value
of ne , 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 figures 8, 9 and 10, the values of Te and ne
can be simultaneously obtained from the intersection of two
contour lines. However, the most accurate values of Te and ne
can be obtained by fitting 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. They agree well with the data from a Langmuir probe,
ne 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
12
Topical Review
scattering data (Crintea et al 2009). Otherwise, the TRG-
high
OES method to determine Te and Telow 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 (∼102 –105 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 ∼10–105 Pa, the corona
model is invalid, due to the collision processes between
metastable molecules, excited molecules and vibrationally
excited ground-state molecules, as well as the electron collision
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 Te or ne , one should use
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Table 5. The excited states and processes considered in several nitrogen CRMs used for the line-ratio techniques. e–N2 or e–N2+ represents
the collision processes between electrons and nitrogen molecules or molecular ions; N2 –N2 and N2 –O2 are for the molecule–molecule
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) N2 (X), N2 (C), e–N2 , rad, wall, N2 (X)–N2 (X) DCGD Te
N2+ (B) (N2 , ∼10–30 Pa)
Kozlov et al (2001) N2 (X), N2 (C), e–N2 , rad, N2 (C)–N2 /O2 , DBD E/N
N2+ (B) N2+ (B)–N2 /O2 (air, ∼105 Pa)
Lebedev and Shakhatov (2006) N2 (X), N2 (A), e–N2 , rad, wall, N2 (X)–N2 (X), DCGD, MDb E/N , ne
N2 (B), N2 (C)a N2 (A)–N2 (A), N2 (A/B/C)–N2 (X) (N2 , ∼102 –103 Pa)
Zhu and Pu (2008) N2 (X), N2 (A), e–N2 , rad, wall, N2 (X)–N2 (X), ICP Te , ne
N2 (B), N2 (C) N2 (A)–N2 (A), N2 (A/B)–N2 (X) (N2 , ∼0.1–10 Pa)
Isola et al (2010) N2 (X), N2 (C), e–N2 , e–N2+ , rad pulsed DCGD Te , ne
N2+ (B) (N2 , ∼300 Pa)
a
The model also includes some other species, such as N2 (a 1 u− ), N2 (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 (N2 , C 3 u → B 3 g ); (c) part of the first positive system, FPS
(N2 , B 3 g → A 3 u+ ). Partial energy diagrams of states N2 (A 3 u+ ), N2 (B 3 g ) and N2 (C 3 u ) are given in (b) and (d).

more detailed CRMs (Bibinov et al 1998), which are also called
nitrogen kinetic models (Guerra and Loureiro 1997, Guerra
et al 2001, 2004, Sá et al 2004).
Table 5 lists several works of using nitrogen CRMs to
determine Te and ne 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 (N2 , C 3 u →
B 3 g ) and the first positive system (N2 , B 3 g → A 3 u+ ), as
shown in figure 12. For low-pressure ICP and CCP discharges
(<∼103 Pa), the important production processes for the
excited molecules N2 (C 3 u ) and N2 (B 3 g ) are the electron-
impact excitation from the vibrationally excited ground-
state molecules N2 (X 1 g+ ,v) and the reactions between

13
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

N2 (X 1 g+ ,v) and N2 (A 3 u+ ) (see table 6). As a result, to in table 6. The self-absorption processes are not considered
calculate the line ratios of those two emission band systems, for the optical transitions from N2 (B 3 g ) to the metastable
we should solve the rate balance equations of N2 (X 1 g+ ,v), state N2 (A 3 u+ ), due to the small Einstein B coefficients for
N2 (A 3 u+ ), N2 (B 3 g ) and N2 (C 3 u ): absorption (equation (15)). For the nitrogen ICP discharges


+1→v,v
investigated here (Zhu and Pu 2005), the vibration–translation
→v
ne nX,v Qve−N 2
+ nX,v−1 nX,v +1 Qv−1,v
N2 (X)−N2 (X) relaxation processes by nitrogen molecules are not as important
v =v w as the vibration–vibration transfer processes and can be
 →v,v +1 ignored (Zhu et al 2006). The nitrogen atoms and their relevant
+ nX,v+1 nX,v Qv+1,v v+1→v
N2 (X)−N2 (X) + Kwall nX,v+1
processes, including the energy transfer with N2 (A 3 u+ ) and
v
  the vibration–translation relaxation with N2 (X 1 g+ ,v > 0),

+1→v+1,v
= ne nX,v Qv→v
e−N2 + nX,v nX,v +1 Qv,v
N2 (X)−N2 (X)
are not included in the model, due to the low dissociation ratio
v =v v of nitrogen molecules in this ICP discharge (<0.1%). In the
 →v−1,v +1 case of a relatively high dissociation ratio, ∼1–10%, these
+ nX,v nX,v Qv,v v→v−1
N2 (X)−N2 (X) + Kwall nX,v , (18) processes and the kinetic modelling of nitrogen atoms should
v be included, such as that for a nitrogen ECR plasma (Bibinov
  et al 2005).
 
ne nX,v QX,v→A
e−N2 + nB nX,v QB→A
N2 (B)−N2 (X)
By solving the rate balance equations (18)–(21), the
v v population ratios N2 (C 3 u )/N2 (B 3 g ) and N2 (C 3 u ,v =
1)/N2 (C 3 u , v = 0) can be calculated, as plotted in figure 13
+ AB nB = ne nA QA→X
e−N2 (at 1 Pa) and figure 14 (at 10 Pa). In the calculation, one also
 
 needs the plasma dimension and the gas temperature, due to
+ nA  nX,v  QA→B
N2 (A)−N2 (X)
the presence of diffusion-controlled deactivation at the wall
5
v
14 and collisions between heavy species (Zhu and Pu 2008).
 According to the nitrogen CRM above, the electron-
+ 2n2A QA,A→B
N2 (A)−N2 (A) + Q A,A→C A
N2 (A)−N2 (A) + Kwall nA , (19) impact excitation processes from the ground state are important
for both N2 (C 3 u ) and N2 (B 3 g ). In addition, these two
 
  states have an energy difference,
E, ∼3.7 eV (figure 12).
ne nX,v QX,v→B
e−N2 + nA  nX,v  QA→B
N2 (A)−N2 (X)
Therefore, the population ratio of N2 (C 3 u )/N2 (B 3 g ) is
v 5
v
14 sensitive to the variation of Te in the range 1–4 eV, as
 seen in figures 13 and 14. The
E between vibrational
+ n2A QA,A→B
N2 (A)−N2 (A) + AC,v nC,v levels N2 (C 3 u ,v = 1) and N2 (C 3 u , v = 0) is much
v smaller than the Te values. Thus their population ratio is
  insensitive to the variation of Te . The low-lying vibrational
  →B
+ nX,v N2 (C)−N2 (X) = ne nB Qe−N2
nC,v QC,v B→X
levels, N2 (X 1 g+ ,v = 1–8), are produced mainly by the
v v electron-impact vibrational excitation from N2 (X 1 g+ ,v = 0)
  and depopulated by both electron collisions and vibration–

+ nB nX,v QB→A
N2 (B)−N2 (X) + AB nB , (20) vibration transfer processes (note that the vibration–vibration
v transfer is dominant in both the production and depopulation

of intermediate vibrational levels with v ∼ 10–40, Guerra
ne nX,v QX,v→C,v
e−N2 + n2A QA,A→C,v
N2 (A)−N2 (A) et al (2004)). Owing to the electron-impact excitation, the
v concentration of molecules N2 (X 1 g+ , v = 1–8) significantly
 
  →C,v
C,v →X
increases with ne , which, according to the Franck–Condon
+ nX,v N2 (C)−N2 (X) =ne nC,v Qe−N2
nC,v QC,v principle, can lead to the increase in ratio N2 (C 3 u ,v =
v v >v 1)/N2 (C 3 u , v = 0) versus ne , as shown in figures 13 and
  14. Unlike the vibrational levels of the ground state, these
  →C,v
+ nX,v nC,v QC,v
N2 (C)−N2 (X)
levels do emit light.
v v <v For the first positive system (N2 , B 3 g → A 3 u+ ), the
  self-absorption processes can be ignored due to the small
 C,v →B
+ nX,v nC,v QN + AC,v nC,v . (21) Einstein B coefficients. For the second positive system (N2 ,
2 (C)−N2 (X)
v C 3 u → B 3 g ), they are ignored since the lower state
Here v and v refer to the vibrational levels in the ground state, N2 (B 3 g ) is an excited state and has a very low density.
v and v refer to the vibrational levels of state N2 (C 3 u ). Therefore, the measured emission line ratios are related to the
nX , nA , nB and nC are the densities of states N2 (X 1 g+ ), excited state population ratios by
N2 (A 3 u+ ), N2 (B 3 g ) and N2 (C 3 u ), respectively. Just as IN2 (C) AC · nC
= , (22)
defined in section 2.2, Q is the rate coefficient for gas-phase IN2 (B) AB · n B
collisions, K is the diffusion-controlled reaction coefficient
and A is the Einstein A coefficient. The superscripts and IN2 (C,v=1) AC,v=1 · nC,v=1
= . (23)
subscripts denote the species involved in each process, as listed IN2 (C,v=0) AC,v=0 · nC,v=0

14
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Table 6. Major processes in the nitrogen CRMs used for the emission line-ratio methods. Here v and v refer to different vibrational levels
high
in an electronic state. The parameters involved in calculating the rates of processes are Te and Telow , the electron temperatures
corresponding to the high-energy and low-energy electrons, respectively, ne , the electron density, Tg and ng , the gas temperature and density
and d, the plasma dimension.
Processes Parameters References
high
e–N2 e + N2 (X) ↔ e + N2 (A/B/C/a /a) Te , ne , ng Itikawa et al (1986), Itikawa (2006),
e + N2 (X) → e + e + N2+ (X/B) Majeed and Strickland (1997)a
e + N2 (X, v) ↔ e + N2 (X, v ) Telow , ne Mihajlov et al (1999)
e–N2+ e + N2+ (X) ↔ e + N2+ (B) Telow , ne Tabata et al (2006)
N2 (X)–N2 (X) N2 (X, v) + N2 (X, v ) ↔ Tg Adamovich et al (1998),
N2 (X, v + 1) + N2 (X, v − 1) Ahn et al (2004)
N2 (A)–N2 (A) N2 (A) + N2 (A) → N2 (B) + N2 (X) Tg Piper (1988a, 1988b)
N2 (A) + N2 (A) → N2 (C) + N2 (X)
N2 (A)–N2 (X) N2 (A) + N2 (X, 5
v
14) → Tg Piper (1989)
N2 (B) + N2 (X)
N2 (B)–N2 (X) N2 (B) + N2 (X) → N2 (A) + N2 (X) ng , Tg Guerra et al (2004)
N2 (C)–N2 /O2 N2 (C, v) + M → N2 (C, v )/N2 (B) + M ng , Tg Dilecce et al (2006, 2007),
v < v, M = N2 /O2 Lebedev and Shakhatov (2006)
N2+ (B)–N2 /O2 N2+ (B) + M → N2+ (X) + M ng , Tg Dilecce et al (2010)
M = N2 /O2
rad N2 (B) → N2 (A) + hν Gilmore et al (1992)
N2 (C) → N2 (B) + hν
N2+ (B) → N2+ (X) + hν
wall
wall N2 (X, v) −→ N2 (X, v − 1) ng , Tg , d Black et al (1974)
wall
N2 (A) −→ N2 (X) ng , Tg , d Augustyniak and Borysow (1994)
a
The state-to-state excitation cross sections can be calculated according to the Franck–Condon principle, with the
Franck–Condon factors from Lofthus and Krupenie (1977).

Figure 13. Contour graph of population ratios of nitrogen Figure 14. Contour graph of population ratios of nitrogen
molecules at 1 Pa: N2 (C 3 u )/N2 (B 3 g ) (×100) and N2 (C 3 u , molecules at 10 Pa: N2 (C 3 u )/N2 (B 3 g ) (×100) and N2 (C 3 u ,
v = 1)/N2 (C 3 u , v = 0), calculated using a nitrogen CRM (Zhu v = 1)/N2 (C 3 u , v = 0) · Tg = 400 K and d = 15 cm are assumed.
and Pu 2008). Tg = 400 K and d = 15 cm are assumed.

the results of this method in a nitrogen ICP discharge (Zhu and

IN2 (C,v=0) and IN2 (C,v=1) are the emission intensities from
vibrational levels 0 and 1 of state N2 (C 3 u ), similar to IAr(2p1 )
and IXe(2p5 ) used in equation (6). IN2 (B) and IN2 (C) are the
sum of emission intensities from all the vibrational levels of
states N2 (B 3 g ) and N2 (C 3 u ), respectively. A and n are
the Einstein A coefficients 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 figures 13 and 14, the values of
Te and ne in nitrogen plasmas are obtained. Figure 15 shows
Pu 2005, 2008, Zhu et al 2006). In figure 15(a), Te is tuned
by varying the pressure at a constant power. ne increases with
power at a constant pressure in figure 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
high
determine both Te (for electrons with energies >11 eV) and
high
Telow (for electrons in the energy range 1.5–4.5 eV). Te is
obtained using the line ratio of two excited states N2 (C 3 u )

15
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Figure 15. Te and ne obtained by fitting the measured with the calculated population ratios N2 (C 3 u )/N2 (B 3 g ) and N2 (C 3 u ,
v = 1)/N2 (C 3 u , v = 0): (a) Te for a nitrogen ICP versus pressure at constant power 600 W, (b) ne 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 N2+ (B 2 u+ ). These excited species are produced mainly

by the excitation processes due to high-energy electrons. Telow
is determined by the line ratio N2 (C 3 u ,v = 4)/N2 (C 3 u ,
v = 0). At low pressures (0.1–100 Pa), this line ratio
depends on the population ratio of N2 (X 1 g+ ,v = 4-7)
and N2 (X 1 g+ ,v = 0–1), according to the Franck–Condon
principle (Levaton et al 2004). This population ratio is
significantly affected by the vibrational excitation processes
due to low-energy electrons. In addition,
E between
N2 (X 1 g+ ,v = 4–7) and N2 (X 1 g+ ,v = 0–1) is as large as
∼1.5 eV. Therefore, this ratio can be sensitive to the variation
of Telow .

3. Conditions of using line-ratio methods

The conditions of using each line-ratio method have been
briefly discussed in section 2—the 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.
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).

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 figures 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 determined using the argon and nitrogen CRMs in section 2,
together with the experimental results in the reference works
in tables 1, 2 and 5, and figures 16 and 17.
In figure 16, there are four application regions for low-
temperature argon plasmas in the pressure range ∼0.1–105 Pa
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 CRM to determine
both Te and ne (Iordanova and Koleva 2007, Crintea et al 2009).
In the H-region (high-pressure region), the excitations out of
excited levels, the atom–atom 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
J. Phys. D: Appl. Phys. 43 (2010) 403001
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 figures 8–10. 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 method—deriving Te from the excitation
temperature of excited atoms—can be used in this region
(Garcı́a et al 2000). However, a non-Boltzmann ASDF
is caused due to the atom–atom collisions in atmospheric-
pressure plasmas with a low ionization ratio (Zhu and Pu 2009).
The Boltzmann-plot method is invalid in this case and a CRM
is needed in the determination of Te and ne , 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 figure 16, the corona model can be valid if special
excited levels are chosen, such as Ar(3p1 ) and Ar(5p5 ), as
described in section 2.1.2. This is because the electron-
impact excitation processes from metastable levels to 3p1 and
5p5 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, ne can be determined
by the line ratio Ar(3p1 )/Ar(5p5 ) (Zhu and Pu 2007a).
The region diagram for nitrogen plasmas is shown in
figure 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 N2 (A 3 u+ ) and
N2 (X 1 g+ ,v > 0) and the collisional processes between these
molecules (Bibinov et al 1998, Zhu and Pu 2008). In addition,
the latter CRM includes N2 (a 1 u− ), N2 (a 1 g ), N(4 S), N(2 D)
and N(2 P), owing to their collisional processes with N2 (A 3 u+ )
17
Topical Review
and N2 (X 1 g+ ,v > 0), which can be important at medium
pressures (∼103 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 (figures 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 identification of dominant
processes in a very significant way (Zhu and Pu 2010). This
is particularly true around the borderline between two regions
in figures 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-
high
state excitation is sensitive to the variation of EEDF tail (Te )
while the metastable-level excitation is sensitive to the EEDF
high
bulk (Telow ). Therefore, in figures 16 and 17, if Te > Telow ,
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.
Both the plasma dimension, d, and the gas temperature, Tg ,
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 Tg ,
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 Te at low pressures (see the above
discussion about figure 8), is enhanced by increasing d or by
decreasing Tg , since Tg can affect the broadening width of
emission lines.
At atmospheric pressure, the atom–atom collision
becomes a very important process (see the above discussion
on figure 10), whose rate increases with Tg (Zhu and Pu 2010).
Therefore, in figure 16, the high-pressure nonequilibrium
region—the H-region—is expanded to higher ionization ratio
regions with an increase in Tg .
3.3. Gas-mixture discharges
Although the region diagrams—figures 16 and 17—are 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) + O2 → Ar(1 S) + O + O, (24)
Ar(1s, 2p, 3p, 5p) + CF4 /CH4 /C2 H2 /SF6
→ Ar(1 S) + product, (25)
N2 (A) + O2 → N2 (X) + O + O, (26)
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

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 coefficients, such as Ar(2p), these
kinds of processes should be included in the CRM at high
pressures (>103 –104 Pa). For those with small Einstein
coefficients, 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),
Figure 18. A schematic energy diagram for some argon atomic
He(2 S, 2 S) + N2 (X) → He(1 S) +
1 3 1
N2+ (B) + e. (27) levels, with the resonance radiation and the cascade process shown.

When this kind of process is present, one should make a careful
examination—whether 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 N2+ (B 2 u+ ) has
sensitive functions on the densities of the metastable atoms,
He(21 S) and He(23 S) (DeJoseph et al 2007). In this case,
the Penning ionization process, as well as the other relevant
processes of He(21 S) and He(23 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 Te and ne (see figures 2 and 4). As mentioned
before, one should select excited species with suitable energy
difference (
E, equation (7)) and characteristic electron
density (neC , equation (10)) according to the Te and ne values
in the plasmas to be investigated (therefore, one needs a rough
estimation of these ‘to be measured’ parameters at first). 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 Te and ne
(see figures 8–10 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 reflection
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
optical transition of Ar(2p2 ) → Ar(1s5 ) are re-absorbed by the
Ar(1s5 ) atoms in plasmas (figure 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(3s2 ) → Ar(1 S)
are re-absorbed by the ground-state atoms Ar(1 S) (figure 18).
Obviously, the effective decay rate by resonance radiation, for
example, Ar(3s2 ) → Ar(1 S), can be significantly reduced
by increasing the pressure (thus Ar(1 S) density). As a
result, the cascade processes out of resonance levels, for
example, Ar(3s2 ) → Ar(2p2 ), 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
−1/2
of ng ×Tg ×leff at low pressures <100 Pa (leff is an effective
path length, of the order of the plasma dimension). Thus,
with ng , Tg and leff 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 reflected on the
discharge chamber walls, which, sometimes, contribute to

18
J. Phys. D: Appl. Phys. 43 (2010) 403001 Topical Review

Table 7. Spectroscopic systems used to record the emission lines in references. CCD refers to charge-coupled device, ICCD refers to
intensified CCD and PMT refers to photomultiplier tube. TRL means tungsten ribbon lamp, SR means synchrotron radiation and D2 lamp is
deuterium lamp.

Lines Spectrometer Wavelength (nm) Resolution (Å) Detector Calibration References

Ar, TRIAX550, 330–500 ∼0.5 PMT TRL Zhu and Pu (2007a)
5p → 1s Jobin Yvon
Ar, SPEX 1870c 335–925 ∼1 ICCD TRL Boffard et al (2004)
3p → 1s
Ar, HR4000, 735–915 ∼2 CCD TRL Chen et al (2009a)
2p → 1s Ocean Optics
Xe, Avaspec2048, 600–1100 ∼4 CCD TRL Zhu et al (2009a)
2p → 1s Avantes Inc.
N2+ , AS50, 110–400 ∼3 PMT D2 lamp, Bibinov et al (2008)
B 2 u+ → X 2 g+ Jobin Yvon TRL
N2 , SQ2000, 200–530 ∼6 CCD SR, Zhu et al (2006)
C 3 u → B 3 g Ocean Optics TRL
N2 , Avaspec2048, 200–1100 ∼8 CCD TRL Cicala et al (2009)
B 3 g → A 3 u+ Avantes Inc.

the emission intensities recorded by a spectroscopic system.

The reflectivity of some stainless steel chamber walls may
be wavelength dependent. The observed emission line ratios
are thus affected. This reflection effect can be enhanced due
to the films deposited by CH4 /N2 plasmas (Pu et al 2005a),
owing to the interference between the light reflected from the
film surface and that which re-emerged from the surface after
being reflected by the stainless steel chamber wall. Pu et al
(2005b) find that this effect can cause errors ∼20% in the Te
measurement by the line ratio of lines 391.4 nm and 762.6 nm
(see figure 12). They use a practical method to eliminate the
optical reflection effect. It is to arrange a black-surface plate
with a very small reflection coefficient 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 figure 19), for which a photomultiplier
tube (PMT) or an intensified 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
∼2000–3000 K are suitable for intensity calibration in the
wavelength range 300–1100 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 N2+ (B 2 u+ ,v = 0) and
N2 (C 3 u ,v = 2). Crolly and Oechsner (2001) use the 454.5
and 451.1 nm lines from Ar + (4p2 P3/2 ) and Ar(3p5 ). In this
Figure 19. Experimental emission spectra containing the weak
emission lines out of argon 4p and 5p levels (CCP,
Ar/O2 = 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 Å. 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 time–space dependent CRMs. In these
models, the rate balance equation of an excited state, x, is
written as
∂nx (r , t)
+ ∇r · (−Dx · ∇r · nx (r , t))
∂t 
= Ri [ne (r , t), Te (r , t), nx (r , t), ny,y=x (r , t),
i
Tg (r , t)]. (28)

19
J. Phys. D: Appl. Phys. 43 (2010) 403001
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 coefficient,
R is the rate of the collisional–radiative processes, which is
a function of plasma parameters (ne , Te , nx , ny , Tg ). Using
these kinds of rate balance equations, one can obtain the
time–space 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, ∼0.1–0.2 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 (Te , ne , 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 fine collimator. By moving a light collecting optical fibre
step by step, Chen et al (2007) do a spatially resolved OES
investigation of low-pressure Ar/N2 plasmas, with a spatial
20
Topical Review
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 ∼0.1–1 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 µm (Tian et al 2010). Figure 21 compares these
spatial resolution values with the energy-loss mean free path of
some species in low-temperature plasmas, which are calculated
using the argon and nitrogen CRMs assuming ionization ratio
10−4 and Tg 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 ∼1–10 µm, as seen in
figure 21.
Sometimes, the spatial distribution of the metastable
species, such as the vibrationally excited ground-state nitrogen
molecules, N2 (X 1 g+ , v > 0), also affects the spatial
resolution in determining Te and ne . This is because their
vibrational distribution can be very much spatially uniform,
due to their extremely long energy-loss mean free paths (see
figure 21). Such an example is the line-ratio method of using
N2 (C 3 u ,v = 1)/N2 (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 Te and ne . Thus the
emission intensities from these levels vary strongly with Te
and ne . 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
Franck–Condon factors. On the other hand, according to the
Franck–Condon principle, the population ratio N2 (C 3 u , v =
1)/N2 (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 Te and ne . Therefore,
using the nitrogen CRMs for vibrationally excited ground-state
molecules, one can only obtain the volume-averaged Te and
ne . For this reason, this line-ratio method is not suitable for
spatially resolved optical diagnostics (Zhu et al 2006).
J. Phys. D: Appl. Phys. 43 (2010) 403001
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 model—the corona model or the CRM—for excited
species in the plasmas to be investigated. The emphasis of
these models is the identification 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 coefficient data for the
collisional–radiative processes. Owing to the tremendous
progress in this field (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 coefficient 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.
References
Adamovich I V, Macheret S O, Rich J W and Treanor C E 1998
Vibrational energy transfer rates using a forced harmonic
oscillator model J. Thermophys. Heat Transfer 12 57–65
Ahn T, Adamovich I V and Lempert W R 2004 Determination of
nitrogen V–V transfer rates by stimulated Raman pumping
Chem. Phys. 298 233–40
Akatsuka H 2009 Excited level populations and excitation kinetics
of nonequilibrium ionizing argon discharge plasma of
atmospheric pressure Phys. Plasmas 16 043502
Augustyniak E and Borysow J 1994 Kinetics of the (A, v = 0) state
of N2 in the near afterglow of a nitrogen pulsed discharge J.
Phys. D: Appl. Phys. 27 652–60
Bartschat K and Zeman V 1999 Electron-impact excitation from the
(3p5 4s) metastable states of argon Phys. Rev. A 59 R2552–4
Behringer K 1991 Diagnostics and modelling of ECRH microwave
discharges Plasma Phys. Control. Fusion 33 997–1028
Behringer K and Fantz U 1994 Spectroscopic diagnostics of glow
discharge plasmas with non-Maxwellian electron energy
distributions J. Phys. D: Appl. Phys. 27 2128–35
21
Topical Review
Benoy D A, Mullen J J A M, Sijde B and Schram D C 1991 A novel
collisional–radiative model with a numerical bottom and an
analytical top J. Quant. Spectrosc. Radiat. Transfer 46 195–210
Bibinov N K, Bolshukhin D O, Kokh D B, Pravilov A M,
Vinogradov I P and Wiesemann K 1997 Absolute calibration of
the efficiency of a VUV-monochromator/detector system in the
range 110–450 nm Meas. Sci. Technol. 8 773–81
Bibinov N K, Kokh D B, Kolokolov N B, Kostenko V A, Meyer D,
Vinogradov I P and Wiesemann K 1998 A comparative study
of the electron distribution function in the positive columns in
N2 and N2 /He dc glow discharges by optical spectroscopy and
probes Plasma Sources Sci. Technol. 7 298–309
Bibinov N K, Bratsev V F, Kokh D B, Ochkur V I and
Wiesemann K 2005 Spectroscopic determination of the cold
electron population in very low pressure ECR discharges in
N2 /He mixtures Plasma Sources Sci. Technol. 14 109–28
Bibinov N K, Halfmann H and Awakowicz P 2008 Determination of
the electron energy distribution function via optical emission
spectroscopy and a Langmuir probe in an ICP Plasma Sources
Sci. Technol. 17 035004
Black G, Wise H, Schechter S and Sharpless R L 1974 Measurement
of vibrationally excited molecules by Raman scattering: II.
Surface deactivation of vibrationally excited N2 J. Chem. Phys.
60 3526–36
Boffard J B, Piech G A, Gehrke M F, Anderson L W and Lin C C
1999 Measurement of electron-impact excitation cross sections
out of metastable levels of argon and comparison with
ground-state excitation Phys. Rev. A 59 2749–63
Boffard J B, Lin C C and DeJoseph C A 2004 Application of
excitation cross sections to optical plasma diagnostics J. Phys.
D: Appl. Phys. 37 R143–61
Boffard J B, Chiaro B, Weber T and Lin C C 2007 Electron-impact
excitation of argon: optical emission cross sections in the range
of 300–2500 nm At. Data Nucl. Data Tables 93 831–63
Boffard J B, Jung R O, Lin C C and Wendt A E 2009 Measurement
of metastable and resonance level densities in rare-gas plasmas
by optical emission spectroscopy Plasma Sources Sci. Technol.
18 035017
Bogaerts A, Gijbels R and Vlček J 1998 Collisional–radiative model
for an argon glow discharge J. Appl. Phys. 84 121–36
Britun N, Gaillard M, Ricard A, Kim Y M, Kim K S and Han J G
2007 Determination of the vibrational, rotational and electron
temperatures in N2 and Ar–N2 rf discharge J. Phys. D: Appl.
Phys. 40 1022–9
Bultel A, Ootegem B, Bourdon A and Vervisch P 2002 Influence of
Ar+2 in an argon collisional–radiative model Phys. Rev. E
65 046406
Chang R S F and Setser D W 1978 Radiative lifetimes and two-body
deactivation rate constants for Ar(3p5 , 4p) and Ar(3p5 , 4p )
states J. Chem. Phys. 69 3885–97
Chen Y, Guo Z G, Zhu X M, Mao Z G and Pu Y K 2007 Spatially
resolved optical emission spectroscopy investigation of E and
H modes in cylindrical inductively coupled plasmas J. Phys. D:
Appl. Phys. 40 5112–6
Chen Z, Donnelly V M, Economou D J, Chen L, Funk M and
Sundararajan R 2009a Measurement of electron temperatures
and electron energy distribution functions in dual frequency
capacitively coupled CF4 /O2 plasmas using trace rare gases
optical emission spectroscopy J. Vac. Sci. Technol. A
27 1159–65
Chen W C, Zhu X M, Zhang S and Pu Y K 2009b Reconstruction of
ion energy distribution function in a capacitive rf discharge
Appl. Phys. Lett. 94 211503
Chilton J E and Lin C C 1999 Measurement of electron-impact
excitation into the 3p5 3d and 3p5 5s levels of argon using
Fourier-transform spectroscopy Phys. Rev. A
60 3712–21
Chilton J E, Boffard J B, Schappe R S and Lin C C 1998
Measurement of electron-impact excitation into the 3p5 4p
J. Phys. D: Appl. Phys. 43 (2010) 403001
levels of argon using Fourier-transform spectroscopy Phys.
Rev. A 57 267–77
Cicala G, Tommaso E De, Rainò A C, Lebedev Yu A and
Shakhatov V A 2009 Study of positive column of glow
discharge in nitrogen by optical emission spectroscopy and
numerical simulation Plasma Sources Sci. Technol. 18 025032
Crintea D L, Czarnetzki U, Iordanova S, Koleva I and
Luggenhölscher D 2009 Plasma diagnostics by optical
emission spectroscopy on argon and comparison with Thomson
scattering J. Phys. D: Appl. Phys. 42 045208
Crolly G and Oechsner H 2001 Comparative determination of the
electron temperature in Ar- and N2 -plasmas with electrostatic
probes, optical emission spectroscopy OES and energy
dispersive mass spectrometry EDMS Eur. Phys. J. Appl. Phys.
15 49–56
DeJoseph C A, Demidov V I, Blessington J and Koepke M E 2007
Investigation of a radio-frequency inductive-coupled-plasma
discharge afterglow in noble gases J. Phys. B: At. Mol. Opt.
Phys. 40 3823–33
Deutsch H, Becker K, Grum-Grzhimailo A N, Bartschat K,
Summers H, Probst M, Matt-Leubner S and Märk T D 2004
Calculated cross sections for the electron-impact ionization of
excited argon atoms using the DM formalism Int. J. Mass
Spectrom. 233 39–43
Dilecce G, Ambrico P F and Benedictis S De 2006 OODR-LIF
direct measurement of N2 (C 3 u , v = 0–4) electronic
quenching and vibrational relaxation rate coefficients by N2
collision Chem. Phys. Lett. 431 241–6
Dilecce G, Ambrico P F and Benedictis S De 2007 New
N2 (C 3 u , v) collision quenching and vibrational relaxation
rate constants: II. PG emission diagnostics of high-pressure
discharges Plasma Sources Sci. Technol. 16 S45–S51
Dilecce G, Ambrico P F and Benedictis S De 2010 On the collision
quenching of N2+ (B 2 u+ ,v = 0) by N2 and O2 and its influence
on the measurement of E/N by intensity ratio of nitrogen
spectra bands J. Phys. D: Appl. Phys. 43 195201
Donnelly V M 2004 Plasma electron temperatures and electron
energy distributions measured by trace rare gases optical
emission spectroscopy J. Phys. D: Appl. Phys. 37 R217–36
Donnelly V M and Schabel M J 2002 Spatially resolved electron
temperatures, species concentrations, and electron energy
distributions in inductively coupled chlorine plasmas,
measured by trace-rare gases optical emission spectroscopy J.
Appl. Phys. 91 6288–95
Dyatko N A, Ionikh Y Z, Kochetov I V, Marinov D L,
Meshchanov A V, Napartovich A P, Petrov F B and Starostin S
A 2008 Experimental and theoretical study of the transition
between diffuse and contracted forms of the glow discharge in
argon J. Phys. D: Appl. Phys. 41 055204
Fantz U 2006 Basics of plasma spectroscopy Plasma Sources Sci.
Technol. 15 S137–S147
Foissac C, Dupret C and Supiot P 2009 Electrical and spectroscopic
characterizations of a low pressure argon discharge created by
a broad-band helical coupling device J. Phys. D: Appl. Phys.
42 015206
Fons J T and Lin C C 1998 Measurement of the cross sections for
electron-impact excitation into the 5p5 6p levels of xenon Phys.
Rev. A 58 4603–15
Fuller N C M, Malyshev M V, Donnelly V M and Herman I P 2000
Characterization of transformer coupled oxygen plasmas by
trace rare gases-optical emission spectroscopy and Langmuir
probe analysis Plasma Sources Sci. Technol. 9 116–27
Garcı́a M C, Rodero A, Sola A and Gamero A 2000 Spectroscopic
study of a stationary surface-wave sustained argon plasma
column at atmospheric pressure Spectrochim. Acta B
55 1733–45
Gargioni E and Grosswendt B 2008 Electron scattering from argon:
data evaluation and consistency Rev. Mod. Phys.
80 451–80
22
Topical Review
Gilmore F R, Laher R R and Espy P J 1992 Franck–Condon factors,
r-centroids, electronic transition moments, and Einstein
coefficients for many nitrogen and oxygen band systems J.
Phys. Chem. Ref. Data 21 1005–19
Godyak V A 2006 Nonequilibrium EEDF in gas discharge plasmas
IEEE Trans. Plasma Sci. 34 755–66
Griem H R 1997 Principles of Plasma Spectroscopy (Cambridge:
Cambridge University Press)
Guerra V and Loureiro J 1997 Self-consistent electron and
heavy-particle kinetics in a low-pressure N2 –O2 glow discharge
Plasma Sources Sci. Technol. 6 373–85
Guerra V, Sá P A and Loureiro J 2001 Role played by the
N2 (A 3 u+ ) metastable in stationary N2 and N2 –O2 discharges
J. Phys. D: Appl. Phys. 34 1745–55
Guerra V, Sá P A and Loureiro J 2004 Kinetic modeling of
low-pressure nitrogen discharges and post-discharges Eur.
Phys. J. Appl. Phys. 28 125–52
Hu D W and Pu Y K 2009 Experimental investigation of emission
intensities in an inductively coupled afterglow neon plasma J.
Phys. D: Appl. Phys. 42 115203
Inoue G, Setser D W and Sadeghi N 1982 Radiative lifetimes and
collisional energy transfer rate constants in Ar of the Ar(3p5 5p)
and Ar(3p5 5p ) states J. Chem. Phys. 76 977–83
Iordanova S and Koleva I 2007 Optical emission spectroscopy
diagnostics of inductively-driven plasmas in argon gas at low
pressures Spectrochim. Acta B 62 344–56
Isola L M, Gómez B J and Guerra V 2010 Determination of the
electron temperature and density in the negative glow of a
nitrogen pulsed discharge using optical emission spectroscopy
J. Phys. D: Appl. Phys. 43 015202
Itikawa Y 2006 Cross sections for electron collision with nitrogen
molecules J. Phys. Chem. Ref. Data 35 31–53
Itikawa Y, Hayashi M, Ichimura A, Onda K, Sakimoto K,
Takayanagi K, Nakamura M, Nishimura H and Takayanagi T
1986 Cross sections for collisions of electrons and photons
with nitrogen molecules J. Phys. Chem. Ref. Data
15 985–1010
Jung R O, Boffard J B, Anderson L W and Lin C C 2007 Excitation
into 3p5 5p levels from the metastable levels of Ar Phys. Rev. A
75 052707
Kang N, Oh S and Ricard A 2008 Determination of the electron
temperature in a planar inductive argon plasma with emission
spectroscopy and electrostatic probe J. Phys. D: Appl. Phys.
41 155203
Kano K, Suzuki M and Akatsuka H 2000 Spectroscopic
measurement of electron temperature and density in argon
plasmas based on collisional–radiative model Plasma Sources
Sci. Technol. 9 314–22
Kano K, Suzuki M and Akatsuka H 2001 Spectroscopic
measurement of electron temperature and density in an argon
plasma jet based on collisional–radiative model Contrib.
Plasma Phys. 41 91–102
Khakoo M A et al 2004 Electron impact excitation of the argon
3p5 4s configuration: differential cross-sections and
cross-section ratios J. Phys. B: At. Mol. Opt. Phys. 37 247–81
Kim J H, Choi Y H and Hwang Y S 2006 Electron density and
temperature measurement method by using emission
spectroscopy in atmospheric pressure nonequilibrium nitrogen
plasmas Phys. Plasmas 13 093501
Kozlov K V, Wagner H-E, Brandenburg R and Michel P 2001
Spatio-temporally resolved spectroscopic diagnostics of the
barrier discharge in air at atmospheric pressure J. Phys. D:
Appl. Phys. 34 3164–76
Lebedev Yu A and Shakhatov V A 2006 Diagnostics of a
nonequilibrium nitrogen plasma from the emission spectra of
the second positive system of N2 Plasma Phys. Rep.
32 56–71
Levaton J, Amorim J, Monna V, Nagai J and Ricard A 2004 A
detailed discussion of the N2 (C 3 u ) and N2 (X 1 g+ )
J. Phys. D: Appl. Phys. 43 (2010) 403001
vibrational temperatures in N2 glow discharges Eur. Phys. J.
Appl. Phys. 26 59–64
Lofthus A and Krupenie P H 1977 The spectrum of molecular
nitrogen J. Phys. Chem. Ref. Data 6 113–290
Loureiro J and Ferreira C M 1986 Coupled electron energy and
vibrational distribution functions in stationary N2 discharges J.
Phys. D: Appl. Phys. 19 17–35
Ma J and Pu Y K 2003 Tuning the electron temperature of a
nitrogen plasma by adding helium and argon Phys. Plasmas
10 4118–22
Majeed T and Strickland D J 1997 New survey of electron impact
cross sections for photoelectron and auroral electron energy
loss calculations J. Phys. Chem. Ref. Data
26 335–49
Malyshev M V and Donnelly V M 1997 Determination of electron
temperatures in plasmas by multiple rare gas optical emission,
and implications for advanced actinometry J. Vac. Sci. Technol.
A 15 550–8
Malyshev M V and Donnelly V M 1999 Trace rare gases optical
emission spectroscopy: nonintrusive method for measuring
electron temperatures in low-pressure, low-temperature
plasmas Phys. Rev. E 60 6016–29
Mihajlov A A, Stojanović V D and Petrović Z Lj 1999 Resonant
vibrational excitation/de-excitation of N2 (v) by electrons J.
Phys. D: Appl. Phys. 32 2620–9
Neeser S, Kunz T and Langhoff H 1997 A kinetic model for the
formation of Ar2 excimers J. Phys. D: Appl. Phys.
30 1489–98
NIST 2010 Atomic Spectra Database http://physics.nist.gov/
PhysRefData/ASD/index.html
Palmero A, van Hattum E D, Rudolph H and Habraken F H P M
2007 Characterization of a low-pressure argon plasma using
optical emission spectroscopy and a global model J. Appl.
Phys. 101 053306
Paris P, Aints M, Valk F, Plank T, Haljaste A, Kozlov K V and
Wagner H-E 2005 Intensity ratio of spectral bands of nitrogen
as a measure of electric field strength in plasmas J. Phys. D:
Appl. Phys. 38 3894–9
Petrov G M et al 2000 Numerical modeling of a He–N2 capillary
surface wave discharge at atmospheric pressure Plasma Chem.
Plasma Process. 20 183–207
Piper L G 1988a State-to-state N2 (A 3 u+ ) energy-pooling reactions:
I. The formation of N2 (C 3 u ) and the Herman infrared system
J. Chem. Phys. 88 231–9
Piper L G 1988b State-to-state N2 (A 3 u+ ) energy-pooling reactions:
II. The formation and quenching of N2 (B 3 g , v = 1–12)
J. Chem. Phys. 88 6911–21
Piper L G 1989 The excitation of N2 (B 3 g , v = 1–12) in the
reaction between N2 (A 3 u+ ) and N2 (X, v > 5) J. Chem. Phys.
91 864–73
Pokrzywka B 2002 Electron induced collisional population decay
rates for levels of 3p5 4s and 3p5 4p manifolds of Ar I in plasma
Phys. Scr. 66 437–43
Pu Y K, Ren Y F, Yang S Z, Dywer D, Zhang X G and Jia X J 2000
The dependence of GaN growth rate on electron temperature in
an ECR plasma Surf. Coat. Technol. 131 470–3
Pu Y K, Yu Z D and Guo Z G 2005a Optical interference induced by
deposited wall-film in inductively coupled plasmas J. Phys. D:
Appl. Phys. 38 3457–60
Pu Y K, Yu Z D and Guo Z G 2005b Effect of wall reflection on the
determination of electron temperature by the line-ratio method
in inductively coupled plasmas Phys. Plasmas
12 113301
Pu Y K, Guo Z G, Aman-ur-Rehman, Yu Z D and Ma J 2006 Tuning
effect of inert gas mixing on electron energy distribution
function in inductively coupled discharges Plasma Phys.
Control. Fusion 48 61–70
Rolin M N, Shabunya S I, Rostaing J C and Perrin J M 2007
Self-consistent modelling of a microwave discharge in neon
23
Topical Review
and argon at atmospheric pressure Plasma Sources Sci.
Technol. 16 480–91
Sá P A, Guerra V, Loureiro J and Sadeghi N 2004 Self-consistent
kinetic model of the short-lived afterglow in flowing nitrogen J.
Phys. D: Appl. Phys. 37 221–31
Sadeghi N, Setser D W, Francis A, Czarnetzki U and Döbele H F
2001 Quenching rate constants for reactions of Ar(4p [1/2]0 ,
4p[1/2]0 , 4p[3/2]2 , and 4p[5/2]2 ) atoms with 22 reagent gases J.
Chem. Phys. 115 3144–54
Schabel M J, Donnelly V M, Kornblit A and Tai W W 2002
Determination of electron temperature, atomic fluorine
concentration, and gas temperature in inductively coupled
fluorocarbon/rare gas plasmas using optical emission
spectroscopy J. Vac. Sci. Technol. A 20 555–63
Schulze M, Yanguas-Gil A, Keudell A and Awakowicz P 2008 A
robust method to measure metastable and resonant state
densities from emission spectra in argon and argon-diluted low
pressure plasmas J. Phys. D: Appl. Phys. 41 065206
Schulze J, Schüngel E, Donkó Z, Luggenhölscher D and
Czarnetzki U 2010 Phase resolved optical emission
spectroscopy: a non-intrusive diagnostic to study electron
dynamics in capacitive ratio frequency discharges J. Phys. D:
Appl. Phys. 43 124016
Shakhatov V A and Lebedev Yu A 2008 Kinetics of excitation of
N2 (A 3 u+ , vA ), N2 (C 3 u , vC ), and N2 (B 3 g , vB ) in nitrogen
discharge plasmas as studied by means of emission
spectroscopy and computer simulation High Energy Chem.
42 170–204
Stafford L, Khare R, Donnelly V M, Margot J and Moisan M 2009
Electron energy distribution functions in low-pressure oxygen
plasma columns sustained by propagating surface waves Appl.
Phys. Lett. 94 021503
Stewart M D, Chilton J E, Boffard J B and Lin C C 2002 Use of
radiation trapping for measuring electron-impact excitation
cross sections for higher resonance levels of rare-gas atoms
Phys. Rev. A 65 032704
Tabata T, Shirai T, Sataka M and Kubo H 2006 Analytic cross
sections for electron impact collisions with nitrogen molecules
At. Data Nucl. Data Tables 92 375–406
Tian W, Zhu X M and Pu Y K 2010 Different patterns of
high-energy and low-energy electrons in an
atmospheric-pressure microplasma generated by a hairpin
resonator J. Phys. D: Appl. Phys. 43 062002
Velazco J E, Kolts J H and Setser D W 1978 Rate constants and
quenching mechanisms for the metastable states of argon,
krypton and xenon J. Chem. Phys. 69 4357–73
Vlček J 1989 A collisional–radiative model applicable to argon
discharges over a wide range of conditions: I. Formulation and
basic data J. Phys. D: Appl. Phys. 22 623–31
Vries N, Iordanova E, Hartgers A, Veldhuizen E M, Donker M J and
Mullen J J A M 2006 A spectroscopic method to determine the
electron temperature of an argon surface wave sustained
plasmas using a collision radiative model J. Phys. D: Appl.
Phys. 39 4194–203
Wang Q, Koleva I, Donnelly V M and Economou D J 2005
Spatially resolved diagnostics of an atmospheric pressure direct
current helium microplasma J. Phys. D: Appl. Phys.
38 1690–7
Weber T, Boffard J B and Lin C C 2003 Electron-impact excitation
cross sections of the higher argon 3p5 np (n = 5, 6, 7) levels
Phys. Rev. A 68 032719
Wu Y, Li Y H, Jia M, Song H M, Guo Z G, Zhu X M and Pu Y K
2008 Influence of operating pressure on surface dielectric
barrier discharge plasma aerodynamic actuation characteristics
Appl. Phys. Lett. 93 031503
Yanguas-Gil A, Cotrino J and González-Elipe A R 2006 Measuring
the electron temperature by optical emission spectroscopy in
two temperature plasmas at atmospheric pressure: a critical
approach J. Appl. Phys. 99 033104
J. Phys. D: Appl. Phys. 43 (2010) 403001
Zhu X M and Pu Y K 2005 Determining the electron temperature in
inductively coupled nitrogen plasmas by optical emission
spectroscopy with molecular kinetic effects Phys. Plasmas
12 103501
Zhu X M and Pu Y K 2007a A simple collisional–radiative model
for low-pressure argon discharges J. Phys. D: Appl. Phys.
40 2533–8
Zhu X M and Pu Y K 2007b A simple collisional–radiative model
for low-pressure argon–oxygen mixture discharges J. Phys. D:
Appl. Phys. 40 5202–5
Zhu X M and Pu Y K 2008 Using OES to determine electron
temperature and density in low-pressure nitrogen and argon
plasmas Plasma Sources Sci. Technol. 17 024002
Zhu X M and Pu Y K 2009 Nonequilibrium excited particle
population distribution in low-temperature argon discharges J.
Phys. D: Appl. Phys. 42 182002
Zhu X M and Pu Y K 2010 A simple collisional–radiative model for
low-temperature argon discharges with pressure ranging from
1 Pa to atmospheric pressure: kinetics of Paschen 1s and 2p
levels J. Phys. D: Appl. Phys. 43 015204
24
Topical Review
Zhu X M, Pu Y D, Guo Z G and Pu Y K 2006 A novel method to
determine electron density by optical emission
spectroscopy in low-pressure nitrogen plasmas Phys. Plasmas
13 123501
Zhu X M, Chen W C, Zhang S, Guo Z G, Hu D W and Pu Y K 2007
Electron density and ion energy dependence on driving
frequency in capacitively coupled argon plasmas J. Phys. D:
Appl. Phys. 40 7019–23
Zhu X M, Chen W C and Pu Y K 2008 Gas temperature, electron
density and electron temperature measurement in a
microwave excited microplasma J. Phys. D: Appl. Phys.
41 105212
Zhu X M, Chen W C, Li J and Pu Y K 2009a Determining the
electron temperature and the electron density by a simple
collisional–radiative model of argon and xenon in low-pressure
discharges J. Phys. D: Appl. Phys. 42 025203
Zhu X M, Pu Y K, Balcon N and Boswell R 2009b Measurement of
the electron density in atmospheric-pressure low-temperature
argon discharges by line-ratio method of optical emission
spectroscopy J. Phys. D: Appl. Phys. 42 142003