INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS

J. Phys. D: Appl. Phys. 35 (2002) 22812290 PII: S0022-3727(02)33024-9

Spectroscopic diagnostic of an
argonhydrogen RF inductive thermal
plasma torch at atmospheric pressure
used for silicon hydrogenation
F Bourg
1
, S Pellerin
2,3
, D Morvan
1
, J Amouroux
1
and J Chapelle
2
1
LGPPTSENSCP, 11, rue Pierre et Marie Curie, 75005 Paris, France
2
LASEP, Centre Universitaire de Bourges, BP 4043, 18028 Bourges Cedex, France
E-mail: stephane.pellerin@univ-orleans.fr
Received 25 January 2002, in nal form 15 July 2002
Published 4 September 2002
Online at stacks.iop.org/JPhysD/35/2281
Abstract
Hydrogenation of silicon materials has great advantages for its photovoltaic
properties and is the key to elimination of crystalline defects during basaltic
growth of the crystal. It is therefore interesting to characterize the plasma by
optical emission spectroscopy methods in order to study hydrogenation of
silicon particles during their treatment by an inductive thermal plasma
burning in the ArH
2
mixture.
Excited states of atomic hydrogen n
/
= 38, which are responsible for
silicon hydrogenation, have been detected by the optical emission
spectroscopy of the Balmer series lines. These hydrogen lines have been
used to determine electronic density on the plasma axis. Furthermore, Ar I
lines were used to estimate the electronic temperature by the Boltzmann plot
method. The deviation from the local thermodynamic equilibrium of the
plasma has also been estimated.
1. Introduction
Silicon is one of the main semiconductor materials for
photovoltaic applications [13]. Hydrogenation of a silicon
material has great advantages for its photovoltaic properties
[4, 5] and is the key to elimination of crystalline defects during
basaltic growth of the crystals.
Previous papers [6, 7] have shown that the highly excited
states of atomic and molecular hydrogen produced by an
inductive thermal plasma burning in the ArH
2
mixture, react
with the melted silicon at 2500 K, leading to a photovoltaic
grade silicon. The highly excited zone of the plasma is
located between the four-turn coils which are connected to
the generator. The calculations according to the model, and
the measurements of the velocity of the plasma gas [8, 9]
lead to a residence time of the excited species in this reactive
zone, which is close to 5 10
3
s. In order to be sure
that correlation exists between results of the optical emission
3
Author to whom correspondence should be addressed.
spectroscopy (OES) and material properties it is better to use
deuterium instead of hydrogen. Then the exodiffusion of
deuterium from the silicon treated by the RF plasma allows
an accurate measurement of the hydrogen concentration in the
material. This hydrogen is connected to the dangling bonds
of the silicon. The measurement of physical properties of
the silicon deposit shows a large diffusion length (200 m)
despite a high dislocation density (10
6
cm
2
) generated during
the recrystallization of liquid silicon. These two values seemto
be different from that for the usual silicon crystalline material,
which has simultaneously lowdislocation densities (10
4
cm
2
)
for a large diffusion length (100200 m) [10]. This is due to
the high hydrogen content in the silicon (2 10
15
at. cm
3
) as
measured by the exodiffusion technique
Earlier studies on the hydrogenation of silicon show that
atomic hydrogens passivate the high density of dangling bonds
in the crystal defects [10]. The efciency of this mechanism
can be improved with highly excited atomic hydrogens. In
order to understand this phenomenon in more detail, we have
decided to characterize the plasma gas. The aim of this paper
0022-3727/02/182281+10$30.00 2002 IOP Publishing Ltd Printed in the UK 2281
F Bourg et al
is the characterization of the applied inductive plasma torch
by OES in order to understand mechanisms of hydrogenation
of silicon during its interaction with the plasma. Furthermore,
we study the validity of the local thermodynamical equilibrium
state (LTE) generally assumed in the numerical simulations
[8, 9].
2. Experimental set-up
A new set-up was used to study the plasma jet. The
spectroscopic study has been realized with the plasma torch
described in gure 1. The plasma jet is generated by a
RF generator (5.2 MHz) operating with xed power in the
range 57 kW. The torch, composed of a quartz tube (internal
diameter d
int
= 30 mm; external diameter d
ext
= 33 mm), is
placed in the centre of four water-cooled copper coils (3 mm
diameter section; spire diameter: 44 mm; step: 7 mm) spaced
4 mm apart.
The gas mixture (Ar+H
2
), controlled by mass-owmetres
(Ar: 29.430 Lmin
1
, H
2
: 0.60 Lmin
1
), is introduced
tangentially at atmospheric pressure (10
5
Pa) in the upper part
of the torch and ows in the quartz tube with a swirling
trajectory. The average residence time of the gaseous species
in the plasma is close to 5 ms on the axis.
The emission spectrum of the plasma is simultaneously
recorded side-on at three points on the axis (step of 12 mm)
by three optical bres (diameter: 200 m) placed in a water-
cooled teon support. The optical bre is set perpendicular
to the plasma axis and the extremity is located at 6 mm of the
quartz tube to limit heating from the plasma. The position of
the bre (x, y, z) xed on its support depends on a manual
micrometre stage. Measurements can be made along the
Axial flow
Z axis
Ar+H
2
Gas inlet Gas inlet
Emission
spectrometer
(CCD detector)
1200 gr.mm
1




Optical fibre
(= 200 m)

water
water
Moving table by
micrometric screws

Quartz tube
(30 mm x 33 mm)
Water cooled
copper coils
Teflon support
Air knife
Z = 0 cm
Z = 1.2 cm
Z = 9.6 cm
x
y
z
Copper crucible
Figure 1. Experimental set-up.
plasma column by moving the table. The origin of the plasma
jet length (Z = 0) was xed in the centre of the inductive coils
between the second and third turn, where the temperature of
the plasma is supposed to be maximum [8]. Three successive
measurements are performed along the axis in order to cover
the entire plasma length, from Z = 0 to 96 mm by steps
of 12 mm.
The acceptance angle of the optical bre was reduced to
0.044 St. To increase the spatial resolution, the plasma volume
covered by each optical bre is close to a cylinder of diameter
1.99 mm and allows characterization of the plasma all along
the jet axis, thus, avoiding the problem of hiding by the copper
coils.
The signal is transmitted to a SpectruMM Spectrapro 500i
spectrometer of 0.5 m focal length (grating: 1200 gr mm
1
,
dispersion R = 0.108 nmmm
1
for 400 nm) equipped
with an OMAhead (1024128 pixels). The exposure time t
exp
is typically taken to be in the range 1535 ms. The images of
the three optical bres are well separated on the CCD detector.
The spectral sensitivity of the optical set-up was calibrated
using a tungsten-ribbon lamp. Calibration in wavelength
and determination of the apparatus function
app
(full-width
at half-maximum), presumed Gaussian, were made using
different low-pressure lamps (argon, mercury, helium, etc).
3. Preliminary observations
Preliminary observations have been made in an ArH
2
mixture
plasma (Ar (29.4 Lmin
1
)H
2
(0.6 Lmin
1
)) withpower xed
toP = 6.5 kW. The argonspectrumhas beenrecordedbetween
400 and 800 nm and revealed many intensive Ar I lines, but no
ionized argon lines.
2282
Diagnostic of an ArH
2
inductive plasma
Furthermore, excited states of atomic hydrogen from H
(n
/
= 3 n = 2) to H8 (n
/
= 8 n = 2) of the Balmer
series, responsible for the silicon hydrogenation, have been
detected by optical emission spectroscopy (see gures 27).
The main results can be summarized as follows: along the
axis, the maximum of the intensity of the hydrogen lines is
measured at the middle of the coils, and it decreases along the
axis to the end of the plume. We can see, at 10 cmdownstream
of the last turn of the coil, that H emission is still important
and taking into account the average temperature and velocity
of the plasma, we can consider that the residence time of the
species in the plasma is close to 510
3
s. The emission lines
H , H, H and H8 are also detected, but in the inductive zone,
they are hidden by the high continuumradiation of the plasma.
The electromagnetic eld, on the axis of the plasma, is
able to polarize the electronic states of atomic hydrogen and
limit the de-excitation [11]. The polarization of this hydrogen
excited atom depends on the polarity of the target (anodic
H (656.279) nm
200000
300000
400000
500000
600000
654 654.5 655 655.5 656 656.5 657 657.5 658 658.5 659
[nm]
I
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Z= 0 mm
1.2 cm
2.4 cm
3.6 cm
4.8 cm
6.0 cm
7.2 cm
8.4 cm
9,6 cm
0
100000
Figure 2. Intensity of H lines along the axis of the plasma jet (entrance split: 20 m, t
exp
= 15 ms scan
1
).
H (486.133) nm
480 482 484 486 488 490 492 494
[nm]
I
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Z= 0 mm
1.2 cm
2.4 cm
3.6 cm
4.8 cm
6.0 cm
7.2 cm
8.4 cm 9.6 cm
0
5000
10000
15000
20000
25000
30000
Figure 3. Intensity of H lines along the axis of the plasma jet (entrance split: 28 m, t
exp
= 15 ms scan
1
).
or cathodic). In the particular case of silicon treatment by
RF plasma with our experimental set-up, melted silicon in
the copper crucible is equivalent to a cathode polarized by
a oating potential generated by the plasma, and on which
the excited atomic hydrogen reacts. However, the distance
between the coil and the crucible permits the control of
residence time of the atomic hydrogen species, and thus
control their concentration and their reactivity with the melted
material.
Observation of the Balmer series spectral lines along the
plasma column, proves the particularityof the inductive plasma
source used, which is able to generate highly excited states of
atomic hydrogen reacting with melted silicon. Particularly,
even if these species have a low concentration in the plasma
jet, they have a high reaction rate with dangling bonds and
stabilize the ArSi link up to 1100 K [6, 7].
The Fulcher bands of molecular hydrogen (transition
d
3
a
3
, close to 610 nm) were also observed in low
2283
F Bourg et al
H (434.047) nm
[nm]
I
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Z= 0 mm
1.2 cm
2.4 cm
3.6 cm
4.8 cm
6.0 cm
7.2 cm
8.4 cm
9.6 cm
Ar (433.356 nm)
Ar (433.534 nm) Ar (433.356 nm)
432 432.5 433 433.5 434 434.5 435 435.5 436
0
2000
4000
6000
8000
10000
12000
14000
Figure 4. Intensity of H lines along the axis of the plasma jet (entrance split: 26 m, t
exp
= 15 ms scan
1
).
H (410.174) nm
[nm]
I
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Z = 0 mm
1.2cm
2.4 cm
3.6 cm
4.8 cm
6.0 cm
7.2 cm
8.4 cm
9.6 cm
405 406 407 408 409 410 411 412 413 414 415
0
1000
2000
3000
4000
Figure 5. Intensity of H lines along the axis of the plasma jet (entrance split: 31 m, t
exp
= 35 ms scan
1
).
temperature regions, at the extremity of the jet, where the
electric eld is not sufcient to increase the lifetime of
atomic radicals. These bands are generally not observed
at atmospheric pressure, but at very low pressure [12, 13]
where they are used to determine the rotational temperature
in hydrogen discharge. Their detection is another proof of the
particularity of the inductive plasma torch.
4. Determination of the electron number density
A rst estimation of the maximum electron density in
the plasma jet, can be made using the Inglis and Teller
equation [14], giving the higher atomic hydrogen energy level
n
max
that could be obtained in a plasma with electron density
N
e
(in (cm
3
)):
log(N
e
) = 23.26 7.5 log(n
max
)
In our case n
max
= 8, and we obtain N
e
= 3 10
16
e

cm
3
in the inductive zone.
The H line has been used to determine the electronic
density through the estimation of the Stark broadening.
The electronic density is given by the equation [15]
N
e
= C(N
e
, T
e
)
3/2
S
where
S
is the Stark broadening (full-width at half-
maximum) of the hydrogen atomic line and C(N
e
, T
e
) is a
coefcient giveninthe literature [15] for different temperatures
T
e
. In our case, its dependance on T
e
is weak. This method is
independent of the equilibrium state of the plasma.
We have veried that the apparatus function
app
of
the optical set-up, is always negligible compared to the Stark
broadening
S
of the hydrogen lines (
S
2 nm

app
0.1 nm), and we have not taken it into account.
For the temperature range used here (close to 10 000 K) the
Doppler broadening is also very weak and can be neglected.
The accuracy of the electron number density is determinated
from data for C(N
e
, T
e
) given in [15] and the error in
the measurements of the full-width at half-maximum of
the hydrogen lines. In the case of H, the error in the
2284
Diagnostic of an ArH
2
inductive plasma
3.6 cm
2000
4000
6000
4.8 cm
H

(397.007nm)
H

(397.007nm) H

(397.007nm)
H

(397.007nm)
H

(397.007nm)
1000
2000
3000
6.0 cm 7.2 cm
H

(397.007 nm)
400
500
600
700
800
900
8.4 cm
200
300
400
500
9.6 cm
395.5 396.5 397.5 398.5 395.5 396.5 397.5 398.5
[nm]
395.5 396.5 397.5 398.5
[nm]
395.5 396.5 397.5 398.5
[nm]
[nm]
395.5 396.5 397.5 398.5
[nm]
395.5 396.5 397.5 398.5
[nm]
7000
9000
11000
13000
600
900
1200
1500
1800
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
Figure 6. Intensity of H lines along the axis of the plasma jet (entrance split: 31 m, t
exp
= 35 ms scan
1
).
measurements is around 2%, and those in the spectroscopic
data C(N
e
, T
e
) are in the range of 5%.
The mean electron number density N
e
obtained as a
function of the axis length Z, is shown in gure 8 for the
experimental conditions summarized in the table 1. The results
show a decrease in the electronic density from N
e
= 4.2
10
16
cm
3
in the middle of the inductive coils (Z = 0 mm), to
N
e
= 2.3 10
16
cm
3
at Z = 96 mm. This conrms that the
inductive coils are the most reactive zone of the plasma.
We have tried to compare these results with the electron
density obtained from the prole measurements of the Ar I
lines. In this case, Stark broadening is proportional to electron
density [15, 16]:
N
e
=
N
0
e
w
0
S
w
S
The coefcients = N
0
e
/w
0
S
are listed in the literature
[16,17] with accuracy from15%to 50%for the different argon
lines that we could use. But they were very narrow and the
apparatus functionwas close totheir Starkwidth. The accuracy
of this method was quite poor and without real signicance.
Nevertheless, taking the average of the values measured at the
same location, the results obtained are similar to the electron
density taken from the hydrogen lines (see gures 8 and 9).
We must note that when we increase the hydrogen content
in the plasma, it is necessary to increase simultaneously the
power applied in order to stabilize the plasma. Then, the higher
observed electron density is due to the increase of the power
and not due to the higher hydrogen concentration in the gas
mixture. This is conrmed by the same effect observed in the
pure argon plasma (see gure 9).
5. Determination of the electronic temperature
The intensive Ar I lines can be used to determine the electronic
temperature. Two different methods were applied: a modied
atomic Boltzmann plot and the ratio of the intensity line to the
continuum.
2285
F Bourg et al
H
8
(388.905 nm) H
8
(388.905 nm)
6500
7500
8500
9500
10500
387 388 389 390
[nm]
387 388 389 390
[nm]
[nm]
387 388 389 390
[nm]
3.6 cm
ArI (389.466 nm)
H
8
(388.905 nm) H
8
(388.905 nm)
H
8
(388.905 nm) H
8
(388.905 nm)
3000
3500
4000
4500
4.8 cm
ArI (389.466 nm)
1000
1500
2000
6.0 cm
600
900
1200
7.2 cm
400
500
600
700
387 388 389 390
[nm]
387 388 389 390
[nm]
387 388 389 390
8.4 cm
200
300
400
500
9.6 cm
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
I
n
t
e
n
s
i
t
y

[
a
.
u
]
Figure 7. Intensity of H8 lines along the axis of plasma jet (entrance split: 61 m, t
exp
= 35 ms scan
1
).
5.1. The Boltzmann plot method
The atomic Boltzmann plot method [18] can be used
to determine the excitation temperature of a plasma jet.
Assuming the LTE state, the plasma temperature can be
obtained by plotting the equation
y ln

ki

ki
A
ki
g
k

= ln K
E
k
kT
e
where
ki
is the line intensity,
ki
is the wavelength and E
k
and
g
k
are the excitation energy and statistical weight of the upper
atomic state respectively; k is the Boltzmann constant and K is
a constant for all the considered lines. Then, the slope of the
straight line obtained is inversely proportional to the electronic
temperature. This method does not require a standard source
for calibration, but to increase the accuracy, a maximumenergy
area must be covered.
However, in our case, the intensity of several optically
narrow lines of Ar I, in the wavelength region 300700 nm,
were recorded along a given line of sight chord in the plasma
source. Application of the atomic Boltzmann method in
such a case of spatially integrated measurements cannot give
the central axis temperature without application of the Abel
inversion technique.
A method has been proposed by Marotta [19] and used,
for example, by Joshi et al [20] in an arc plasma and
Albinski et al [21] in electro-discharge machining, to obtain
the temperature on the axis of the plasma without performing
the calculations of the Abel inversion. It is applicable also to
plasma torches where the plasma column has a high-gradient
Gaussian temperature prole. According to the results of the
numerical model [9], this hypothesis seems to be available in
the RF plasma torch, except between the inductive coils (for
Z = 0) where there exists a temperature maximumout of axis.
Furthermore, the method used here is valid if the line
emissivity increases with rising temperature, i.e. for the case
T
e
< T
m
(where T
m
is the norm temperature of the consid-
ered line). In our experimental condition, it is always the case,
because norm temperatures of Ar I lines are generally close to
15 000 K, a limit above which the Ar II lines must appear.
So, we used this modied atomic Boltzmann technique
to determine the central axis temperature of a plasma column.
2286
Diagnostic of an ArH
2
inductive plasma
1.5E+16
2.0E+16
2.5E+16
3.0E+16
3.5E+16
4.0E+16
4.5E+16
5.0E+16
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
N
e

[
c
m

3
]
N
e

[
c
m

3
]
1,5E+16
2,0E+16
2,5E+16
3,0E+16
3,5E+16
4,0E+16
4,5E+16
5,0E+16
(a)
(b)
Figure 8. Electron density N
e
in ArH
2
plasma as a function of the
plasma length Z from (a) H line, (b) Ar lines.
Table 1. Experimental plasma conditions used for the plasma
diagnostic.
Argon Hydrogen Power
(Lmin
1
) (Lmin
1
) (kW) Symbols
29.4 0.6 (2.0%
vol
) 6.3 .
29.6 0.4 (1.3%
vol
) 5.9 .
29.8 0.2 (0.7%
vol
) 5.6
30 0 6.6
30 0 5.4
30 0 4.5
10 ms acquisition
1
1 acquisition (r eseau: 1200 tt mm
1
)
In this technique, a plot of
y ln

ki

ki
E
k
A
ki
g
k

= ln K
E
k
kT
e
as a function of E
k
, gives the central axis temperature; in this
case,
ki
is the spatially integrated line intensity, and K is a
constant for all Ar I lines. This expression differs from the
well-known classical atomic Boltzmann plot method [18] by
the presence of the energy term (E
k
) present in the logarithm
(see the comparison between results from the classical and
modied Boltzmann plots shown in gure 10).
Seven optically narrow lines were chosen (namely
415.859, 425.936, 430.010, 451.073, 470.232, 696.543 and
750.387 nm) in order to cover the maximum energy difference
and to increase the precision of the method. The slope of
the straight lines obtained is inversely proportional to the
electronic temperature.
The accuracy of this method is quite close to that of
the data available in the literature (1530%, in [22]), and
the method was sensitive in the determination of intensity
of lines that were sometimes not well resolved. Particularly,
1.5E+16
2.0E+16
2.5E+16
3.0E+16
3.5E+16
4.0E+16
4.5E+16
5.0E+16
Z [cm]
N
e

[
c
m

3
]
0 1 2 3 4 5 6 7 8 9 10
Figure 9. Electron density N
e
in pure Ar plasma as a function of the
plasma length Z.
7000
8000
9000
10000
11000
12000
13000
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
T
e

[
K
]
Figure 10. Comparison between results from classical () and
modied () Boltzmann plot obtained with argon lines in an ArH
2
plasma (Ar (29.4 Lmin
1
)H
2
(0.6 Lmin
1
); P = 6.3 kW).
R
2
=0.99
2.05E18 2.10E18 2.15E18 2.20E18 2.25E18 2.30E18 2.35E18
Energy [J]
[
a
.
u
.
]
T
e
=11300 K
at Z=2.4 cm
45.5
45.0
44.5
44.0

43.0
42.5
43.5
Figure 11. Typical Boltzmann plot obtained with argon lines in an
ArH
2
plasma (Ar (29.4 Lmin
1
)H
2
(0.4 Lmin
1
); P = 6.3 kW).
when measurements are made at the extremity of the plasma
plume where there is a poor signal-to-noise ratio, the error in
temperature can be close to 1100 K. Nevertheless, this method
gives a good estimate of the equilibrium plasma state, because
points in the Boltzmann plots were generally well aligned (see
the example in gure 11).
The variation of the electronic temperature along the
plasma axis, for different powers (4.46.4 kW) and different
amounts of hydrogen (02%
vol
), are shown in gure 12.
The difference in temperatures between the middle of the
coils and the end of the plasma plume (Z 90 mm) is
around 10001500 K, depending on the power injected into the
plasma. These results are in good agreement with calculations
obtained by numerical modelling [9]. Particularly, we can
underline that the axial temperature repartition obtained by the
modied Boltzmann plot method is very close to the results of
numerical models [23].
2287
F Bourg et al
7000
8000
9000
10000
11000
12000
13000
7000
8000
9000
10000
11000
12000
13000
(a)
(b)
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
T
e

[
K
]
T
e

[
K
]
Figure 12. Axial variation of T
e
as a function of the power from the
modied Boltzmann plot method (a) pure argon plasma, (b) ArH
2
plasma.
The electronic temperature of the plasma seems to be
directly dependent on the power and independent of hydrogen
content. The addition of hydrogen in an argon plasma modies
signicantly the plasma properties (electron density, thermal
conductivity, enthalpy, diameter of the plasma) but does not
seem to have an inuence on the plasma temperature. The
presence of hydrogen increases thermal conductivity, which
is responsible for an improvement in the thermal treatment
of silicon particles in deposition processes with an important
phenomenon of evaporation [10].
5.2. Line-to-continuum ratio method
When the LTE hypothesis is valid in the one-time ionized
one-component plasma, the Saha law allows us to write the
population N
u
of an energy level u as a function of the electron
density N
e
;
N
2
e
N
u
= 2
U
1
(T
e
)
g
u

2m
e
kT
e
h
2

3/2
exp

E
u
kT
e

where h and k are the Planck and Boltzmann constants,

respectively; m
e
is the mass of the electron; E
u
and g
u
are
the energy and statistical weights of the considered level,
respectively; E

and E

are the atom ionization energy

and lowering of the ionization potential and U
1
(T
e
) is the
ion partition function for the atom. Under our experimental
conditions, U
1
(T
e
) is close to the statistical weight g
I
of the
fundamental level of the Ar II ion, and E

is small. The
emission coefcient of a transition from the level u, can be
written in the frame of the Boltzmann equilibrium:

u

hC
4
A
ul

u
N
u

hC
8
u
A
ul
N
2
e
g
u
g
I

h
2
2m
e
kT
e

3/2
exp

+
E

E
u
kT
e

1
E

kT
e

where
u
and A
ul
are the wavelength and the atomic transition
probability, respectively, and the term
E

2.953 10
11

N
e
T
e
may be neglected since it is very small.
Furthermore, in the one-time ionized one-component
plasma with a Maxwellian velocity distribution, the continuum
emission coefcient in the visible range, can be approximated
by [18]

R

C
1

2
u
N
2
e

T
e
(
u
, T
e
)
C
1
=
16e
6
3C
2
(4
0
)
3

6m
3
e
k
= 1.63 10
43
J m
4
K
1/2
s
1
st
1
where C
1
is a constant for all Ar I lines; the argon Bibermans
factor (
u
, T
e
) can be found in the literature for different
wavelengths
u
and temperatures T
e
[24].
The line-to-continuum ratio in the wavelength range ,
is quite independent of electron density N
e
and is only a
function of the temperature T
e
[25]:
y

u

R
C
2
A
ul
g
u
g
I

exp(+(E

E
u
)/kT
e
)
T
e
(
u
, T
e
)
C
2
=
h
4
C
8C
1
(2m
e
k)
3/2
= 2.00 10
5
MKSA
where C
2
is a constant for all the Ar I lines.
This equation can be theoretically solved using the
Bibermans factor (, T
e
) given in [24] for Ar I lines. It
gives the value of T
e
versus the ratio of the line intensity,
at the wavelength , to the adjacent continuum intensity in
a given spectral range = 1 nm. This ratio has been
determined from the experimental data for three Ar I lines:
415.859, 430.010 and 451.073 nm, for which the Bibermans
factor is independent of temperature T
e
.
The accuracy of this method is quite good, essentially
because measurements of
R
and
u
are time-simultaneous.
Results obtained from the average of values measured at
the same location are presented in gure 13. The plasma
temperature distribution is similar to those obtained by the
modied Boltzmann plot method; it decreases from 11 500 K
in the inductive zone, to 950010 000 K at the extremity of
the plasma jet, without any real inuence on the hydrogen
concentration or power.
6. Departure from the LTE state
6.1. Conclusions on the experimental results
All Boltzmann plots constructed with our experimental data,
show a good alignment of the points, except at the extremity
of the plasma jet. But there, the signal-to-noise ratio is bad
and experimental errors are quite large. So, we can conclude
that the Boltzmann equilibrium is realized in the plasma.
This remark is reinforced by the similarity of temperature
distributions obtained from the Boltzmann plot method and
the line-to-continuum ratio.
2288
Diagnostic of an ArH
2
inductive plasma
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
0 1 2 3 4 5 6 7 8 9 10
Z [cm]
7000
8000
9000
10000
11000
12000
13000
T
e

[
K
]
7000
8000
9000
10000
11000
12000
13000
(a)
(b)
T
e

[
K
]
Figure 13. Axial variation of T
e
as a function of the power from the
line-to-continuum ratio method (a) pure argon plasma, (b) ArH
2
plasma.
1.5E+16
2.0E+16
2.5E+16
3.0E+16
3.5E+16
4.0E+16
4.5E+16
5.0E+16
N
e

[
c
m

3
]
Z [cm]
0 1 2 3 4 5 6 7 8 9 10
Figure 14. Comparison of the axial electron density distributions
obtained from the spectral lines: Stark width ( N
S
e
) and from the
line-to-continuum ratio method with LTE hypothesis (. N
S
e
) in an
ArH
2
plasma (Ar (29.4 Lmin
1
)H
2
(0.6 Lmin
1
); P = 6.3 kW).
Validity of the LTE assumption has been veried by
comparison of N
e
determined experimentally from the Stark
broadening of hydrogen lines (independent of any equilibrium
assumption) with the electron density calculated from the
plasma composition at equilibrium(with Ar, Ar
+
, Ar
2+
, H, H

,
H
+
, H
2
, H
+
2
andelectronconcentrations takenintoaccount [26])
and with temperature T
e
given by the line-to-continuum ratio.
Results show that the plasma is very close to the LTE (see
gure 14).
6.2. Estimation of the temperature difference between
electrons and heavy particles
In order to evaluate the difference between the electron
temperature T
e
and the temperature of the heavy particles T
h
in the plasma jet, we assume that the energy E
2
given to
electrons in a unit of volume in the electric eld E is used to
warmthe heavy particles (atoms and ions) by collisions. Then,
neglecting the contribution due to thermal conduction, we have
E
2
= 4
m
M
(
ea
+
ei
) N
e
k(T
e
T
h
)
where
ea
,
ei
are electronatom and electronion collision
frequencies, respectively; and m
e
and M are the electron and
heavy particle masses.
The electronion collision frequency
ei
is given by

ei
= Q
ei
(T
e
)v
e
)N
e
with
v
e
) =

8kT
e
m
Q
ei
(T
e
) =
e
4
36
2
0
(kT
e
)
2
ln

3/2
0
(kT
e
)
3/2
e
3
N
1/2
e

where v
e
) is the electron mean velocity at temperature T
e
; and
Q
ei
is the electronion collision cross section.
In the same way, the electronatom collision frequency

ea
is given by

ea
= Q
ea
(T
e
)v
e
)N
h
with
v
e
) =

8kT
e
m
Q
ea
(T
e
) = 4 10
24
T
e
+ 0.353 10
20
where Q
ea
is the electronatom collision cross section.
Considering that the departure from the thermal equilibrium
is rather small (T
e
T
h
T ), the heavy particle density
N
h
can be estimated from the Dalton equation in a one-time
ionized plasma:
P = k[(N
h
+ N
e
)T
h
+ N
e
T
e
] k(N
h
+ 2N
e
)T
e
= 10
5
Pa
Thus, the difference between the electron temperature T
e
and the heavy particle temperature T
h
in the plasma jet can be
calculated as
T
e
T
h
=
E
2
4(m/M)(
ea
+
ei
)N
e
k
The results obtained, for a plasma volume taken to be a
cylinder of length 10 cm and diameter 10 mm, are shown in
table 2. In the inductive zone, the temperature difference is
small incomparisontothe electrontemperature. The extremity
of the plasma jet is characterized by lower electron densities
and temperature. It corresponds to a turbulent zone, where
cold gas can enter into the plasma. There, the departure from
thermal equilibrium is more.
The same results are obtained with pure argon plasma.
So, it seems that the addition of a small quantity of hydrogen
into the gas ow, does not disturb the LTE state in the plasma
column.
2289
F Bourg et al
Table 2. Departure between electron T
e
and the heavy particle temperatures T
h
.
Plasma ArH
2
(2%
vol
) ArH
2
(2%
vol
) ArH
2
(2%
vol
) Pure argon Pure argon Pure argon
P (kW) 6.3 6.3 6.3 6.6 6.6 6.6
Z (mm) 0.0 4.8 9.6 0.0 4.8 9.6
T
e
(K) 11 500 11 150 10 700 11 050 10 700 10 200
N
e
(cm
3
) 4.2 10
16
3.1 10
16
2.7 10
16
2.2 10
16
1.7 10
16
1.8 10
16
N
h
(cm
3
) 5.44 10
17
5.88 10
17
6.23 10
17
6.12 10
17
6.43 10
17
6.74 10
17

ei
(s
1
) 3.28 10
11
2.60 10
11
2.42 10
11
1.94 10
11
1.61 10
11
1.78 10
11

ea
(s
1
) 1.54 10
10
1.58 10
10
1.57 10
10
1.62 10
10
1.62 10
10
1.58 10
10
(T
e
T
h
) (K) 76 129 158 237 366 314
7. Conclusion
The energetic characterization of an inductive thermal plasma
torch, burning in the ArH
2
mixture, has been obtained by
OES. The free electron density and temperature have been
determined for supplied power varying from 4.4 to 6.4 kW
with different hydrogen contents. The measured maximum
temperature in the plasma is around 11 00011 500 K in the
middle of the inductive coils for an electronic density close to
N
e
4 10
16
e

cm
3
.
The introduction of hydrogen into an argon plasma does
not modify the temperature repartition in the plasma, which
only depends on the power injected into the plasma gas.
Under our experimental conditions (side-on spatially
integrated measurements), the local thermodynamic equilib-
rium assumption, which is supposed to be reached in the
numerical modelling, has been veried.
To validate results of plasma models and numerical
calculations, it is now necessary to determine the radial
distributions of temperature and electron density in the plasma
column, and to estimate the gas temperature using the
molecular bands of hydrogen. We are continuing to study
these problems.
Acknowledgments
We are grateful to Professor K Musiol (M Smoluchowski
Institut Physics, Jagellonian University, Krakow, Poland) for
fruitful discussions and for his interest in our work. This work
was supported in part by ADEME.
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