Atomic oxygen recombination at the wall in a time
afterglow
L. Magne, H. Coitout, G. Cernogora, G. Gousset
To cite this version:
L. Magne, H. Coitout, G. Cernogora, G. Gousset. Atomic oxygen recombination at the
wall in a time afterglow. Journal de Physique III, EDP Sciences, 1993, 3 (9), pp.1871-1889.
<10.1051/jp3:1993247>. <jpa-00249050>
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Submitted on 1 Jan 1993
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J.
Phys.
Fiance
III
j1993)
3
1871-1889
1993,
SEPTEMBER
1871
PAGE
Classification
Ph_vsics
Absfi.acts
52.20
Atomic
Magne,
L.
recombination
oxygen
Laboratoire
Cedex,
Coitout,
H.
Physique
de
Gaz
des
4
ieiised
L'dvolution
de
la
exponentielles.
ddcharge est
ddduite
ddcroissances
h
j2,4±1-1)x10~~.
Abstract.
afterglow
time
a
Gousset
G.
Plasmas,
Paris-Sud,
Universitd
value
during
j2.4
is y
brought
are
wall
pyrex
up
in
±
accepted
J993,
Bit.
212,
Orsay
91405
1993)
28,time
atomique dans l'dtat
fondamental
mesurde
dans la postest
spectroscopie
d'absorption
rdsonante
dans
l'ultraviolet
densitd
atomique pendant la post-ddcharge est la
de
deux
somme
La probabilitd
de
rdassociation
des
h la paroi en
du
atomes
pyrex
de la
ddcroissance
la plus rapide.
La
valeur
ainsi
obtenue
est
interprdtations de la
ddcroissance
plus lente en
de gain
terme
la
par
discussion.
oxygen
resonant
the
dans
June
ground state density
absorption
in
spectroscopy
the afterglow is a
of
sum
Atomic
obtained
gain
dvoqudes
sont
discharge with
atomic
density
probability at
1.
Des
=
atomique
Jo
d'oxygbne
ddcharge pulsde
densitd
La
d'une
lointain.
J993,
Marc-h
Rdsumd.
ddcharge
tube
des
et
and
in
wall
France
(Receii>ed
y
Cemogora
G.
the
at
of
the
1.1)
x
measured
is
the
two
discharge tube is
Interpretations
10~ ~
in
time
the
afterglow
of
pulsed
a
ultraviolet
vacuum
exponential
The
evolution
of
range.
decays. The
recombination
deduced
from
of the
slowest
the
fastest
decay
as
decay.
possible
The
so
atomic
discussion.
the
Introduction.
Atomic
oxygen
atomic
species
simulate
catalytid
simulated
Surface
technology
atomic
sources
are
exposure.
flux
on
of
For
interest for the study of
great
fast
instance,
atom
oxygen
surfaces,
in
the
low
Earth
orbital
behaviour
materials
beams
conditions
are
under
required
[1, 2].
The
in
to
problems
of
oxidation
during the atmospheric
erosion,
reentry
or
can
hypersonic flows of active species [3].
by plasma device are spreading out as industrial
applications
treatments
materials.
The
application field of low
discharges
pressure
oxygen
recombination,
reactive
order
also
be
using
broadening to
depend on the
by oxidation
for
high
is
now
supraconductor
realization
[4].
Conductive
properties of thin films strongly
Oxygen
stoichiometry.
deficiency
in
YBaCUO
samples can be corrected
oxygen
carried by the flowing afterglow of a radio
by oxygen
caused
frequency
atoms
discharge [5]. In order to improve wettability and adhesion properties, surface
of
treatment
polymers can also be performed in the flowing afterglow of
microwave
discharge [6].
JOURNAL
1872
PHYSIQUE
DE
N° 9
III
studies
of
production
atomic
experimental
optimize
to
atoms
sources,
oxygen
Thus,
discharges, as well as their transport in flowing afterglows, are essential.
many
density in flowing
efficient.
Atomic
diagnostics for atomic density
measurements
are
now
calorimetry [7-9], NO [10] or NO~ [11-14] titration,
afterglow
measured
by
be
can
[17],
silver-coated
spectroscopy
O~ synthesis in a liquid nitrogen trap [15, 16], mass
quartz
[18] or
ultraviolet
(V.U.V.)
monitor
absorption
in the
resonant
spectroscopy
range
vacuum
obtaining in situ
also
of
for
[5,19, 20].
techniques
Laser
great
spectroscopy
use
are
with a good spatial
resolution.
The spatial
distribution
of atomic
ground state
measurements
established
density in an
effusive
beam
from a D-Cdischarge, has recently been
using
ionization
multiphoton
(R.M.P.I.) and two photon laser induced
fluorescence
(L.I.F.)
resonant
density
be performed by L-I-F.
[21]. Within
discharges,
atomic
measurements
oxygen
can
absorption
[19, 21, 23].
[22], actinometry [21] and V-U-Vspectroscopy
numerous species coexist,
discharges are a complex medium
where
Low
pressure
oxygen
kinetics
positive
The
such
metastable
molecules,
negative ions and
and
atoms.
as
ozone,
involving the heavy particles depend on the working
conditions
of the discharge
and
many
elaborated
[24-31]. In spite of the
difficulties
of obtaining a forecasting
models
have
been
model for the heavy particles densities,
fixing the atomic density are known
the main
processes
wall [23]. So the
dissociation
by
electronic
collisions
recombination
the
and
the
at the
to be
recombination
probability at the wall y is an all-important data in order to predict
value of the
the
atomic
density available
within
well as losses during transport in a flowing
the
sources
as
afterglow.
Concerning
Numerous
works
devoted
determination
of y for
several
materials.
to the
are
glass,
of
which
is
the
materials
for
confining
commonly
used
low
temperature
most
one
pyrex
plasmas or flowing afterglows, the published values for y range from 2 x10~~ [32] to
5 x 10~ ~ [28]. The higher values
obtained
for pyrex
from a kinetic
under plasma
are
exposure,
model for a D-C- low
discharge under steady state
conditions
[28]. All experimental
pressure
given for pyrex in flowing afterglows. These results are always smaller than the
values
are
estimated
under discharge
conditions.
ones
The aim of this work is to
evolution
the
of atomic ground state density in a static
measure
time
afterglow, using the
V-U-Vabsorption
technique, in order to
resonant
spectroscopy
determine
experimental value of the
recombination
probability at the wall, for pyrex under
an
plasma
exposure.
order
In
within
Experimental
2.
set-up.
experimental
The
Pure
and
MgF~
In
oxygen
1.5
windows
order
diameter
inside
cm
maintained
set-up is shown in figure 1.
dissociation
and
excitation
obtained
are
to
in
gradient along
tube.
pyrex
V.U.V,
radiations
allowing
impurities,
remove
the discharge
tube.
the
observation
weak
a
direction.
Under
conditions,
the
gas
with
a
pulsed discharge
of
extremities
gas
regulated
flow,
this
flux
is
with
These
tube
in
are
Upstream,
pressure
using a throttle
appliances allow
is
time
in the
us
observation
to
measured
valve
to
flow
mass
a
enough
low
limited
residence
this
a
50
long
cm
closed
with
transmission.
However,
pumping efficiency is
Downstream,
capacitance gauge.
with an
absolute
these
The
and
pressure
adjust flowing
zone
controller,
neglect the
by a pirani
varies
from
is
is
pressure
gauge.
measured
conditions.
0.5
s
to
duration,
discharge
The
current
generator supplies high voltage pulses with adjustable
[33]
Previous
have
shown
that
for
long
repetition frequency.
pulses (5 ms)
measurements
high current (300 mA), the interpretation of results is not easy because of gas heating and
which
of long life species,
complicate
atomic
kinetics
creation
in
of the
because
can
problems,
the
pulse
width
and
the
discharge
avoid
these
order
afterglow. In
to
current
must
3
s.
and
and
also
the
be
N° 9
ATOMIC
RECOMBINATION
OXYGEN
AT
THE
WALL
1873
P-u
I
M-F-c
+
Oi
M
C-G
O,
~'~'
D-s
'
',
'.
p-u
~_
l~
p-u
M-T
M-c
D-o
Fig. I.
Experimental set-up. M-F-CFlow
P-GMass
Controller,
Pirani Gauge, C-GCapacitance
Gauge, T-V- : Throttle Valve, P-UDischarge Tube, W
Pumping Unit, D-SDamany Source, D-TMgF~ Windows, V. U-V-M- : Vacuum Ultra Violet
P-M- : Solar Blind
Photomultiplier,
Monochromator,
M-TMaster
Trigger, H-V-P-GHigh Voltage Pulse
D-ODigital Oscilloscope, M. C.
Generator,
Microcomputer.
as
low
as
presented
characteristic
possible.
this
in
decay
The
value
and
paper,
time of the
of
pulse
the
current
duration
current
is
about
is
value
I
~s.
30
~s
ranges
Pulses
for
the
from
repetition
major
part
30mA
to
frequency
of
results
the
200mA.
must
The
be
slow
density is returned to zero before the following pulse. This is
conditions,
Under
these
the
chose
frequency
why
this
between 0. I and I Hz.
we
can
reason
we
obtain
discharges for pressures
ranging from 2 x 10~~ to 5 Torr.
radiations
by a low pressure
The
emitted
discharge tube is lighted at one side by V-U-Vdischarge in
Penning discharge (Damany Source). This V,U.V,
is
constituted
by
source
a D-Celectrons
confined
field.
The
three
lines of the
in
which
steady
magnetic
by
pure
oxygen
are
a
O(~S°)-O(~Pj)+hv,
figure
2,
emitted
with
high
atomic
triplet
in
shown
resonant
are
diagnostic
requires
the
intensity and good stability. The
absorption
resonant
spectroscopy
incident
of
this
triplet,
been
of
the
lines
shapes.
The
high
resolution
has
measurement
spectrum
Meudon
(France). The
Observatoire
de
measured
with a 10 m focal length
spectrometer
at the
high resolution profiles of the three lines are reported in figure 3 for working conditions of the
fixed to P
200 mA. In this figure we can
Damany source
4 x 10~ ~ Torr and 1
strong
see
a
self absorption of the J
2
component.
V-U-Vradiations,
transmitted
through the discharge tube, are analyzed in wavelength by a
50 cm focal length
(ASM 50 Jobin Yvon). A solar blind photomultiplier (EMI
monochromator
94138)
transmitted
light for the
with a MgF2
window
and a CSI
photocathode
detects
the
selected
efficient
wavelength.
This
detector
is
for
wavelengths ranging from
120nm
to
enough
to
make
sure
that
atomic
=
=
=
JOURNAL
1874
PHYSIQUE
DE
N° 9
III
(eV)
E
°(~S~)
9.52
130.614
nm
130.417
nm
130,21i
nm
0~0281
J=O
O.O196
J=I
O(~Pj)
J=2
Fig.
2.
Resonant
triplet O(~S")
atomic
~o
=130.487
O(~Pj)
-
+
hp.
nm
(J"I)
~o=1500217
(J=2)
~Uo=130.604
(J"0)
nm
nm
g
(
~
a
4
-3
-6~10
-3
-3
-3
-2.lO
-4~lO
2.10
~-~~
Fig.
3.
P
4
High
x
10~
resolution
Ton
and 1
profiles
200
=
of the
mA.
three
lines
in
of the
-3
4.lO
-3
6~10
nm
atomic
triplet
emitted
by the Damany
source
for
ATOMIC
N° 9
210
The
nm.
the
of
without
function
apparatus
of the
plotted in figure 3
J=2,
J=
overlapping
will
J=0
be
10~
x
spite
In
As
monochromator.
3.43
are
and
I
x10~~nm~
5.4
detector
allows
of
taken
2. 81
nm,
10~
x
~
lines
nm
the
and 2, I
the
10~
~
A
our
emission
of the
nm
order
order.
experimental
broadened
by the
with
widths
x
second
first
the
and
strongly
are
of fact,
matter
a
with
work
us
obtained
and
1875
WALL
triplet
atomic
any
of the
atomic
spectrum
device is presented in
THE
AT
for high wavelengths
overlapping
between
the
triplet emitted by the source,
figure 4. We can see that the
off of this
cut
grating
RECOMBINATION
OXYGEN
for the
function
respectively
while
the
has
apparatus
that
broadening, the three lines are well
resolved.
into
diagnostic
in the
calibration.
account
a
lines
component
width
The
of
weak
J= i
J=o
~
b
129~9
130
130~3130~4130~5
130~2
130,1
Spectrum
4.
device
for
P
4
of the
10~~
x
=
triplet
atomic
Ton
and
by
emitted
200
1
the
130~?
(nm)
Wavelength
Fig.
130~6
Damany
source
obtained
with
our
experimental
mA.
=
oscilloscope (Le Croy 9400) in order to average
numeric
output signal is connected
to a
microcomputer.
transferred
digitalize the transmitted signal. The recorded
to a
traces
are
discharges, strongly depends
in oxygen
reproducibility of atomic density
The
measurements
of the wall.
This
second point is due to the fact that
surface
state
gas purity and on the
P-M-
and
on
recombination
probability
discharge
discharge
During
this
very
and
to
with
a
wall
is
the
main
sensitive
to
the
surface
the
at
is
keep
high
treatment,
the
gas
the
surface
same
flux
is
loss
state
during
maintained
discharge
tube
Recombination
of
atomic
oxygen.
process
of the
cleanliness
In order to improve the
experiment, a D-Cbefore
each
of the wall,
state.
is
heated
about
by hot
one
hour
before
resistive
wires.
the
pulsed
mode~
JOURNAL
1876
Diagnostic
3.
typical plot
figure 5. We
(t
0),
~
is
we
is
itself
density
choose
instant
the
the
not
visible
beginning
the
0 at
=
increases
It
until
it
and
up
retums
to
it
N° 9
From
the
over
afterglow. Before the pulse
independent. The
This signal is time
afterglow,
the signal
scale. During the
time
the
to
lines, is reported in
three
for the
of the
atoms.
retums
zero.
afterglow
the
of time,
function
a
signal without
plot because of the
in this
signal during
transmitted
t
as
transmitted
detect
decreases
signal
transmitted
of the
dependent.
time
III
calibration~
A
pulse
PHYSIQUE
DE
time
without
value
these
measurements,
signal
before
atoms,
we
discharge
the
the
as
define
the
atomic
ratio
of
:
i~(A, t)
Rexp(A, t)
where
A
Before
the
is
the
which
source
is
i~(A,
t
~
by
o)
=
j~
°~
the
ground
function,
y)
F
component.
constituted
is
in
apparatus
io(A
selected
the
molecules
device
the
of
signal
the
occurs,
absorbed
with
convolution
wavelength
central
discharge
(i)
~~
~~
=
the
intensity emitted by
Taking
into
account
state O~(X~IY).
signal is given by :
transmitted
of the
«x(A
~y) exp(-
incident
io~ix)i(t
y)
o) L) dy.
~
the
the
(2)
70
~°
l 50~21 7
nm
50
130~487
nm
$Z
absorption
from
level
j=2
absorption
from
level
j=1
absorption
from
level
j=0
E
40
~j
~
30
nm
20
transmitted
the
10
~~°°
Fig.
to
signal through
discharge.
Because
Transmitted
5.
the
end
of the
~°
°
the
of
Tim~°(ms)
discharge
the
time
tube
scale,
for the
the
~~°
~°°
three
lines.
discharge
(30
The
~s
~°°
instant
t
width) is
O
not
corresponds
visible.
N°
9
In
this
ATOMIC
RECOMBINATION
OXYGEN
AT
THE
WALL
1877
expression, «~ (A is the absorption cross section on the molecular ground state given in
reported in table I. [O~(X )](t
0 is the initial density of
molecules
the ground
on
L is the length of the absorbing
medium
equal to 50 cm. F (A is the apparatus
function
Io(A ) is the incident
intensity
emitted
by the
(Fig.
3).
source
[34] and
state.
and
Table
~
I.
for
used
Data
(J)
Level
calibration.
the
bEi
$tatisticd
Weight
2
During
the
I~(A, t)
Io(A
Oscillator
Strength
130~217
4~19x10.~~
0~048
3
228.6
130.487
3.74x10.'~
0.048
317.8
130.604
3~56x10.~~
0~048
afterglow,
molecular
signal can be expressed
j~~
=
ax~X) in
cm~
nm
0
time
transmitted
in
5
0
The
in K
g~
as
y)F~y)exp(-
ground
atomic
and
absorb
both
states
f
light.
incident
:
y) jO~(X)i
«~(A
(t)L
K(A
y,
t)L)dy
(3)
-«
where
of
K(A,
atomic
t
oxygen
coefficient
of the
during
dependent.
The
phenomenon
its
application to
described
in [23].
The
absorption
coefficient
the
afterglow, the
) is the
of
resonant
atomic
an
Therefore
for
atomic
i
Ko
=
where
the
first
Ko gives the
factor
emitted
line
and
experimental
our
absorption profile can
P
Within
the
convolution
Since
we
independent.
of
the
assume
The
Doppler
a
time
fixed
due
to
the
ground
the
on
recombination
state
is
time
shape
(P
w
neglected [36].
broadening
with
independent
the
effect
the
shape
The
of
is
of
the
profile of
300K,
profile
for the
the
wavelength
broadening on
pressure
is then given by the
line
the
Doppler
calculated
then
central
line.
absorption
Lorentzian
T=
Voigt
coefficient
absorption
the
of
Tow ),
5
temperature
gas
(4)
P (A
absorption
of the
value
(A ) is the
conditions
be
Here,
line.
molecules
of
transitions
absorption for atomic
is well
described
in [35], and
density
in
steady
discharge
is
measurement
state
a
oxygen
only briefly explain the results used for the
calibration.
we
absorption can be written as the product of two factors [35] :
K (A
Ao of the
atomic
density
broadening.
natural
broadening is time
using the following
formula
~
Ill aii~lw ~l
i
~
~
~~~
)~
with
6v~
a
=
6v~-,
In
(2)
(6)
and
"~
w
"°~
2
=
~D
,fi
(7)
JOURNAL
DE
respectively
the
878
6v~
where
6v~
and
are
central
frequency
vo is the
For a Voigt profile, the
by [35]
absorption
and
natural
absorption
the
N° 9
III
broadening
Doppler
the
and
line.
coefficient
the
at
central
wavelength
,fi
f IO (~PJ)]
of the
line
is
given
:
Ko
f is
absorbing
permittivity
where
order
In
of
PHYSIQUE
and
into
of
the
are
e
light
the
take
~
strength
and
m~
c
)j~~
~
oscillator
atoms,
to
)
2
of
(8)
~,
line
the
and
mass
reported in table I, [O(~Pj)]
the charge of the
electron,
is
density
the
po is
the
of
vacuum
speed.
the
account
evolution
time
of the
signal during the afterglow (Eq. (3)), the
molecular
ground state at the time t of
transmitted
density
the
=
io~(x )i(t
io~ ix )i(t
=
ground
molecular
state
to be
pressure is assumed
the afterglow is given by
~
density
constant.
19)
io i(t )
o
in the
So the
where
jw~
ioi(t)
=
iol'Pj)i
z
no)
(t).
jwj,
The
population
of
atoms
distribution
Boltzmann
at
each
sub-level
temperature
T
on
of the
=
state
is
supposed
to
be
6Ej
~- [O(P2)lexpi-j
gj
~
[O(Pj)]
ground
given by
a
(11)
~
g2
6Ej
Ej
E~ and gj is the statistical weight of level J.
Fixing the total
atomic
density on the ground state and taking into
the
weak
account
overlapping seen in figure 4, we can
calculate
numerically the ratio R)(j( (A for the component
function
of the density on the
J as a
Those
calculations
corresponding
sub-level
J.
be
can
simplified assuming that the absorption
section
is
by
molecular
ground
«~(A
)
state
cross
for a wavelength
the
emission
line
width.
R)(j[(A
is
equal
Then,
)
given
by
constant
to
range
:
where
=
~°
I
Rjjjj(A)=exp(«j(A)jOiL)
j~~ll(A
-v)F(y)exp(-KOP(A
-y)L)dy
(12)
~"
~
z j~~ll(A
l=0
-y)F~y)dy
-CC
wavelength of the
considered
component.
R)jj[
130.487 nm) and
ratio
(A
130.217
nm), R)(j[ (A
presents
so
130.604
functions
of
density
of
sub-level
R)(j( (A
the
each
nm) as
[O(~P~ II, [O(~Pj )] and
[O(~Po)] respectively. All the required data for those
calculations
reported in table I.
are
density
For the low value of R)$j( (A ) (strong absorption), it is not possible to
atomic
measure
higher than an upper limit. However, within our experimental conditions, for atomic densities
during the afterglow is still good.
deduced
densities
of the
lower than 10'~ cm~ ~ the
accuracy
variation
of density leads to a strong
lower
than lo ' ' cm~ ~ a small
Reciprocally, for densities
signal
determined
noise ratio. Typically,
by
the
is
then
variation in R)(/~ (A ). The
over
accuracy
where
F (A ) is
Figure
centred
6
on
the
calculated
the
=
=
densities
under
2
x
lo
'°
cm~
~
are
uncertain.
=
9
N°
OXYGEN
ATOMIC
RECOMBINATION
THE
AT
WALL
1879
2
(Tg
300
=
-1
~~
11
lo
13
12
10
lo
10
O(~PJ)
Fig. 6.
R)(]~ jA
IO (~P2)1,
lO(~Pi)I
The
and
hypothesis of a
point for the
Boltzmann
of the
atomic
triplet
deduced
from
component
sub-level
can
be
130.487
=
[O(~Po)I respectively.
The
equilibrium
calibration
critical
a
nm), R)[]~ (A
130.217
=
under
with
a
in
our
good
lo
Cm
nm)
of
130.604
nm
)
assumed
to
be
=
is
distribution
conditions.
(Fig. 4)
corresponding
resolution
R((/~(A ) for the
gas
sub-levels
experimental
lo
~
and R)$j[ (A
temperature
for the
15
14
10
and
made
Indeed,
then,
the
component.
functions
as
T
300
in (I
detect
we
of
K.
=
is not
each
population of each
But the hypothesis
Under
state density.
ground
dissociation
low
current),
molecular
conditions
pulse
width
and
experimental
(short
stays
our
leads
correction
factor
(Eqs.
(9)
and
(10))
the
hypothesis of constant
low.
The
to
pressure
correction
factor
be neglected in
exp(«x[O IL ). This factor does not exceed 1.02. This
can
comparison with experimental
fluctuations.
calibration
be
influence
The
of the long life species O~ and O~I'A~) on the
must
now
in
discussed.
The
absorption of incident light by these two species can be taken into
account
transmitted
signal IT(A, t) given in (3) by multiplying this expression by a factor
the
sections
exp(- «~[O~I'A~)j it ) L
cross
ma [O~](t) L). Here, «~ and «o~ are the absorption
of
a
Boltzmann
equilibrium
is
used
for the
calculation
of
sections
These
by O~('A~) and O~ respectively.
cross
The
line
width.
emission
equal
the
wavelength range
to
density at instant t given in (9) must also be corrected
io~(x)i(t)
The
pulses repetition
JOURNAL
DE
PHYS>QUE
l>I
=
io~(x)i(t
frequency is
-T
1,
N'9,
SEPrEMBER
low
1Wl
~o)
(from 0.
ioi(t)
I Hz to I
molecular
supposed
are
expression of
and
becomes
io~('Ag)i(t)
Hz) and
because
to
be
molecular
constant
on
ground
a
state
:
io~i(t)
of the flux,
the gas is
67
JOURNAL
j880
PHYSIQUE
DE
pulses, then, O~( ' A~) and O~ do
transmitted
of the
signal before the discharge IT(A,
ratio R(()~(A ) has to be multiplied by
remarks,
the
changed
between
"~)iO~('A~)i(t>
exp((«x
From
values
the
be
evaluated
maximum
and
of «~
published
«~
assuming a
constant
density [O~ 'A~ )]
lo
'~
1.02.
for
So O~
does
exponential
second
The
neglected
low
for
R)(j[(A ),
fact
the
overestimation
under
densities
absorption
ozone
could
densities
is
From
overestimated
this
in
significantly
be
is
calculation
but
results of
t ) and using the
density for each level of the ground
logarithmic
plots figure 7a for O(~P~),
state
«~~
the
could
reach
have
we
end
of
l.24
x
this
effect
=
that
a
keep
for
an
atomic
contribution
that
mind
be
of
involve
5
The
in
can
value
can
factor
a
cm~
'~
10~
high
the
cm~ ~.
to
can
suppose
we
calibration
density of 10'~
ozone
of
atomic
afterglow.
the
results.
ratio R~~~(A,
plotted
calibration
the
in
figure
6,
obtain
we
O(~Pj). Typical results are shown
figure 7b for O(~Pj) and figure
absolute
semi
included
the
the
in
term
exponential term is
Similarity, an upper limit
density
value
for
ozone
see
overestimation
overestimated
is
nm
If
first
in figure 6
For
density).
can
not
the
maximum
atomic
at
Experimental
the
lo
x
We
(high
atomic
the
2
0.94.
then
R)()~(A)
absorption by ozone
density. This
cm~~ assuming an
that
of
is
term
of
values
for
130
at
exponential
afterglow.
the
calibration.
a
section
these
to
(t) L).
first
of the
value
assuming
by O~
obtained
cross
limit
the
on
expression
the
on
According
:
"o,>iO,i
maximum
influence
strong
a
=
[37].
4.
have
not
second
exponential term is
10'~ cm~'
absorption
The
the
[O~]
(' A~
factor
upper
an
the
~,
~
a
influence
any
0) given in (2).
[O~(~A~)] during
for
cm~
t
exp((~rx
x
[34],
in
value
=
L)
have
not
two
N° 9
III
in the
7c
for
O(~Po).
figures
these
From
decay. In order
clear
determine
to
regression.
linear
it is
A
that
the
the
frequencies
good fit is
very
jO(~Pj)i
(t)
=
v~ and
v~
functions
the
of
and
and
8a
values
v~
of
The
7c.
results
present
two
C~ exp(-
+
fastest
the
8b
t)
atomic
of
sum
and
of the
the
the
decay
regression
slowest
linear
non
deduced
so
(13)
t)
v~
v~
and
v,
respectively.
reported in
are
frequencies as
pressure.
fixed
a
figures
7b
C~ exp(-
contribution
with
a
is not a single exponential
density decay we use a non
exponential decays
density
atomic
associated
with
frequencies.
Figures 8a and
the
are
of
obtained
associated
the
are
figures 7a,
For
C~
C~ and
where
evolution
range
the
values
of
pressure,
8b are
dispersed.
For
from
120 Hz to
290
the
so
instance,
Hz.
This
determined
concerning
scattering
frequencies
for
v~,
does
not
v~
and
pressure
a
result from
v~
presented
around
a
bad
0.3
in
Torr,
accuracy
of
frequencies
attributed
exceed
to the fit does
not
ten per
cent.
discrepancy is due to discharge
That
reproducibility.
experimental
Because
of
these
fluctuations,
and v~ seem
discharge
and no
difference
between
not to depend on the
current
v
the
is
sub-levels
observed.
For the
it is impossible to find a dependence of the
same
reason,
ratio CjC~ with the
the discharge
current.
pressure
or
densities at the end of the discharge (t
The
obtained
0
shown in figures 7a, 7b and 7c are
with a
Boltzmann
distribution
300K.
acquisitions of
transmitted
in
The
agreement
at
not
of
but
the
three
independent
simultaneous
results
signals for the three lines are not
are
reproducibility.
by the discharge
affected
experiments. So these results are
the fit.
The
error
on
the
calculated
=
Since
v~
can
the
be
main
attributed
loss
to
process
that
of
process.
atomic
oxygen
is
known
to
be
the
loss
at
the
wall,
9
N°
ATOMIC
RECOMBINATION
OXYGEN
14
0(~P
~~
in
THE
AT
1881
WALL
~
cm
13
t)
exp(-O.086
1.66xlO
12
2.l9xlO
exp(-O.027t)
~~
fit
total
i o
i i
i o
~~
160
(mS)
Time
~)
140
120
loo
80
60
40
20
O
~~
~~14
~~ ~ ~~~
~~
~
~~
0(~P~)
~~
13
~°~~~~~
12
~'~~~~~
~~
~~P~~~°~~~ °
~~P~~~'~~~
lo
total
cni~
in
3.30xlO
exp(-O,125
t)
exp(-O.031
t)
~~
~~
5.67xlO
fit
total
~~
fit
"'
"...
i o
"".".._
i i
i o
i i
i o
~~
20
O
60
40
~i~l~
b)
Fig.
7.
a)
b) [O(~P,)]jt)
[O(~Po)I(t) in
[O(~P~)](t)
in
the
140
loo120
80
lo
160
(~IIS)
in
the
afterglow
afterglow for
~~
~
~~
~~
afterglow
the
for
P
P
0.6
=
for
200
Torr,
0.6
P
=0.6
Tom,
Tom,
200
1
=
200mA
1=
mA
and
mA
=
=
and
and
a
pulse
a
a
pulse
width
~~~
~~~
~~
(~~)
~j~~
~)
pulse
width
width
of 30
of
~s.
of 30
30
~s.
~s.
d
JOURNAL
1882
PHYSIQUE
DE
III
loco
N°
~
*
J
#
2
J
=
i
J
=
o
9
+
~
°
8°
+
+
*##
j
~
+
x
~
t4
q
o
~
~~
C
+
~
[
+
+
#
0
~
f
~
~
~
O
I
C
j
+
a
%
I)
/~
~
j
0
*
~
-,~,~-~~----~-~L-~aJ
O.
I
Pressure
in
I
Torr
a)
/
+
o
J
+
J
=
I
=
o
X
C
~
~
ioo
b*
w
C
~
j
o
~
cr
,
f
w
~
L~
+
~
+
+
j
(
~
*
«
a
S
>
*
l
v
~
*
+
+
w
~
+
R+
I
f
go
I
I
I
-I
lo
in
Pressure
b)
Fig.
8.
pressure.
a)
The
fast
frequency
v~
as
a
function
of
pressure.
b)
The
slow
frequency
v,
as
a
function
of
N°
ATOMIC
9
the part of the
tube radius r, the
For
the
time
taken
distance
reach
to
wall
taken
time
the
to
=
Do
velocity.
In
Torr
this
case,
our
discrepancy
5
diffusion
is the
of
equation [14]
is
this
r~
=
@
recombination
is at
v~
when
be
can
the
atom
written
as
with
a
:
r
~
yp
in
pressure
calculate
we
10~~
r~
+
of the
higher
pressure
find a
pressure
a
cannot
range,
pressure
that
see
for
valid
we
1883
path is small in comparison
be approximated as the sum
Then
2
Torr, P is the
at I
measurements,
in
we
formula
last
the
range.
results
the
From
coefficient
T2
WALL
(14)
r~P
=
+
can
for
path [38].
free
Ti
where
free
mean
needed
r~
mean
v~
the
THE
AT
recombination
for
the
and
rj
equal
wall
the
from
time
total
which
for
measurements
the
RECOMBINATION
OXYGEN
than
0.5
Tow.
dependence
value
mean
a
and k is the
Torr
mean
of
Because
of
v~ in
loo
P~
atoms
Hz.
the
0.5
the
From
to
the
=
s.
=
v~
experimental
our
r~
1.5
=
10~
x
experimental
P~
coefficient
diffusion
The
conditions,
So
The
so
=
r~
So
we
obtained
in
oxygen
rj (s
correction
the
fluctuations.
fl
=
s.
atomic
of
due
3
=
value
is
10~
x
diffusion
to
determine
can
O~ is Do
~
P
can
cm~
222
=
(Torr),
neglected
be
'
I
at
then,
Tow
for
[39].
Within
5 Torr,
P
=
comparison with
y assuming
in
probability
recombination
the
s~
the
that
:
r
y
=
(2.4
±
I,I
)
x
10~~
deviation
estimated
using the standard
of v~.
interpretation of the
for
under 0.5 Ton is
difficult.
When
the
measurements
pressure
free path is not small in comparison with the tube radius, the wall
be
considered
cannot
plane surface and the assumptions made in relation (14) are not valid.
Moreover, if the
6y
is
The
mean
as
a
number
of
velocity
atomic
while
v~ is
collisions
could
velocity
increasing
an
in
the
increase
bulk
when
of y
is
gas
pressure
because
increases
function
of
and fi,
sufficient
not
decreases.
of the
this
The
activation
could
thermalize
to
the
threshold
explain why
v~
their
atoms,
probability
recombination
[43]. As the loss
increases
while
mean
increases
frequency
the
pressure
decreases.
Interpretation of the
decay will be brought
5.
slowest
into
the
decay
v~ is
discussion
not
in
easy.
terms
However,
of
qualitative
eventual
atomic
interpretations
gain.
of this
Discussion.
recombination
probability at the wall y for oxygen
published values of the
atoms
on
The
reported in table II. Most of them
zone.
concern
pyrex kept out of the discharge
within a D.C,
discharge. They are
published in [21, 23, 28] are
estimated
for pyrex
collisions,
is
obtained
the
dissociation
by
which
assuming the balance
between
electronic
fitting
and the
the
is
deduced
by
calculated
using a
Boltzmann
code,
losses
wall.
at
y
experimental atomic
densities
by resonant
V.U.V.
absorption
[21, 23,
measured
spectroscopy
The published
of
28] or actinometry [21]. Our value of y is close to these
results.
values
within
higher
flowing
afterglow.
discharge
T=
300K
than
for
in
The
at
are
pyrex
y
differences
recombination
in discharges and in afterglow are not explained yet
between
for
Some
pyrex
values
are
JOURNAL
1884
Table
Published
II.
PHYSIQUE
DE
N° 9
III
t.ecombination
probability
y
Excitation
Medium
ref.
1.2x10~
RF
Flowing
[9]
3, I x10.~
RF
Flowing
[40]
of
i,allies
the
at
w-all foi~
pyre.<
a
oxygen
atoms.
afterglow
2 x 10.~
Pyrolysis
1.2 x16@'
RF
Flowing
[32]
Flowing
[41]
afterglow
1. 6 x 10~
~
ioJ
~
Microwave
Flowing
afterglow
[42]
Microwave
Flowing
l14i
D. C
Flowing
afterglow
[16]
RF
Flowing
11 2]
Flowing
ill
4. 6 x 10~
9.2
x
1@~
(1.2-0. 33)
x
10~
RF
afterglow
2, I x1@~
Within
D.C
[23]
the
discharge
5 x10'~
Within
D-C
[28]
the
discharge
1.53 x10"~.T~ ~
320 K ~ T ~ 450
2.4
x
Within
D-C
10'~
Pulsed
[21]
the
afterglow
Time
present
discharge
atomic
densities
10'~ cm~~,
around
involving the
collision
probability is then proportional to the
mechanism
of
recombination
atomic
700
to
by
(including
K
the
at
dominant
the
of
surface
of
per
for
seems
surface
by heavy
bombardment
However,
As
a
matter
whole
rejected.
adsorbed
the
of
state
we
think
of fact
measurement
this
plasma
impurities
do
not
of
the
gaseous
sheath
observed
due
field
consequences
could
increasing
the
improve
the
number
of
cleanliness
oxygen
of
adatoms
to
on
not
the
that
case,
[21].
But
afterglow.
of
well
surface
known.
recombination.
decays during the
alteration
surface
the
K
modification
a
effect
is
250
that
in
flowing
The
theory
covered
are
In
atoms.
in
the
from
sites
the
modification
of atomic
permanent
modifications
like
irreversible
roughness
So
From
ranging
all
[43]
Rideal
recombination
area.
noticed
have
exposure
and
it is
surface
temperature
afterglows),
the
The
last
particles,
accelerated
in
only has reversible
exposure
process.
The
when
unit
a
is
process
adatom.
an
point is well
should be equal to y
y
could be
y in afterglow
submitted
discharge.
to the
This
charges
that
we
wall
that
discharges and
the
dentisy
in
an
the
with
[43], it
depend on
so
y
increasing
function
of the
temperature.
following that theory, in a discharge at 300 K,
difference
The
between
within
discharge and
y
adatoms,
is
y
recombination
atom
gaseous
number
of
adatoms
a
reached
temperature
does
not
work
could
could
be
by removing
increase
the
ATOMIC
N° 9
recombination
water
or
about
wall.
the
at
metallic
The
atoms
is
still
electrodes
the
is
THE
AT
poisoning
of the
influence
sputtered by
problems
these
RECOMBINATION
OXYGEN
of
WALL
by
surface
the
easily
not
1885
calculable
impurities
and
such
as
discussion
the
open.
possible absorption by ozone at
decay. Apart from that, it
atomic
an
on
gain
atomic
during
the
afterglow
could
be brought up.
seems
in the time
evolution
of atomic
The
ground state could bring about a
second
discharges and flowing afterglow.
variations
of y values
between
characteristic
the
5Torr
decay
frequency
In
0.5Torr
has
to
range,
mean
pressure
a
during
equal
Hz.
This
slower
could
by
of
time
35
decay
be
caused
gain
the
P,
atoms
to
a
afterglow.
According to the time
evolution
of
density given by equation (13) and
atomic
assuming that this gain G(t)
satisfies
the
equation :
Interpretation
the
end
slowest
of the
decay is
afterglow which
hypothesis of
that the
slowest decay
observed
explanation of those
of the
could
not
influence
Jioi(t)
obtain
time
the
(v~
=
instance,
For
gain
This
the
surface
could
density
observed
gain.
initial
low
very
a
these
it
wall
of
However,
this
adsorption.
knowledge of the
of
could
also
be
life
that
seems
The
reaction
Rl
s~
'
reactions
to
of
state
coupled with
reported in
lead
to
by
the
prove
wall.
the
bulk
~
would
iia
is
the
gain
this
properties of the
assumption
easily
could
to
enough
be
is
leave
35
Hz.
An
to
give
the
surface
and
because
it
assumes
requires
a
ruling the evolutions
complex,
because
are
of gas. The
kinetics
O in afterglows
are
gain
adatoms
this
the
7c,
frequency equal
cm~
concerning
However,
reactions.
Eliasson
of
and
numerous
III
and
7b
0.
=
kind
'~
lo
x
by
), O,
table
atomic
an
[44]
in
to ?
in the
7a,
t
This
(16)
characteristic
a
is
controlled
process
difficult
So it is
to
surface
instant
atoms.
the
t).
v~
figures
in
the
at
O~('A~), O~('lY/
as
could
reported
k~j
coefficient
due
reactions
the
presented
10'~ cm~~
weakly adsorbed
afterglow with
those
adatoms
equal
during
~pecies such
species are strongly
long
of
x
from
come
wall
v,) C~ exp(-
measurements
3.5
to
the
at
heat
very good
This gain
the
for
equal
of the
(15)
~~~~
~
evolution
G(t)
approximately
the
j~j~~~
~ t
jt
we
of the
because
easy
have
the
atoms,
efficient.
most
quenching
controversial
O('D).
of
and
However,
the
strongly
to
gain during the
be
seems
give significative atomic
O~('~/),
afterglow.
This
gain has a time
evolution
ruled
by the decay of O('D),
O~('A~ ), Oi These last two species are known for their long lifetime in afterglows. This gain
could
results.
its
contribution
the
slower
experimental
However,
decay in our
appear
as
strongly depends on the initial
densities.
No
of these species under
experimental
measurements
conditions
estimation
of the
enough to ours have been published so far. Moreover, the
close
time dependence of this gain requires a
solvation
during the afterglow
of the complete
kinetics
which
reactions
involving these species.
take
into
all the
must
account
However,
gain that we propose here seems to be in agreement
the hypothesis of atomic
with
experimental
observations
in flowing
afterglow published in [11]. In this work, the spatial
decay of atomic
ground state density is measured in the flowing afterglow of a RF
oxygen
discharge as a function of the RF power. These
from the
done for
distances
measurements
are
discharge
50 cm
between
150
Pressure
fixed
Torr
the
velocity
and
is
and
of gas is
at I
cm.
'.
55
of
density
The
slope
the
spatial
decay
atnmic
[O]
of
becomes
smaller
cm,s~
as
power
overestimated.
increases
60
cm
So
from
from
downstream
200
the
W
discharge.
flow
and
reactions
to
600
The
that
R3
W
and
and
authors
metastable
could
R4
the
also
[O('D)]/[O]
ratio
mention
O~('3/
that
is
O~(~A~)
observed
increases
is
found
existing
as
up
from
a
to
50 %
major
150
80 %
to
product
cm
in
the
in
at
the
flow.
1886
Table
Reactions
III.
for
and
creation
PHYSIQUE
DE
JOURNAL
of
loss
atomic-
reaction
O~(~Aj
O~'D)
O~
+
+
Da
+
Da
N° 9
III
o~iD)
q
+
oz
+
o
-
o
-
O~(16)
+
O~
-
O~(lZ()
+
O~
-
+
+
time
ref.
iu"
144j
Rl
loll
x
afterglow.
[45]
Ma
7 x 10"
O~~D)
the
k(cm~ K')
3
«~D)+Oz-o+o~
in
oxygen
[46]
'
Mb
O~('A)
oz(izj
7,4xlm~
[47J
3.8xl@'~
[48]
loll
[48]
WC
O
+
O~
+
Oz
O
+
O~
+
O~
R3
1. 8
R4
x
100 K'
prucnt
work
Consequently,
atomic
could
there
be
due
could
includes
oxygen
to
an
gain
be
this
increase
O
+
a
non
gain.
in
W1fl
-
R5
~O~
negligible gain
The
molecular
fact
that
the
metastable
along the
slope decreases
of O
states
and
O
flow
l'D
and
while
the
the
spatial decay
power
which
) populations
of
increases
could
spatial decay. This decay is obtained for times higher
than I s and could
correspond to our slowest decay v~. Therefore, this effect could explain a
differences
in the values of y in flowing afterglow and in discharge. For instance, in
part of the
[I I ], y is deduced from the spatial decay of [O]. As this decay could be not only due to losses
include gain
wall but also
could
could be
underestimated.
at the
process,
y
D.C,
discharges [21, 23, 28] the gain of atomic ground state by the
In the case of steady state
dissociation
by electronic
collisions.
reaction
RI, R3 and R4 can be neglected in front of the
published in [21, 23, 28] are free from this effect.
calculated
of y
values
So, the
obtained in discharge because, to a certain
determine
from v~ is close to the one
we
y that
possible
gain
by fitting the temporal evolution of atomic
have distinguished loss and
extent,
we
exponential
decay.
ground state density with a double
increase
atomic
contribution
in
the
ATOMIC
N° 9
RECOMBINATION
OXYGEN
THE
AT
1887
WALL
Conclusion.
6.
resolved
afterglow and time
constitute
experimental technique allowing us to
a good
ground state density. This technique does not require any
which
could perturb the afterglow. This first experimental
with
is in good
the
under
plasma
agreement
exposure
This
is
perhaps
due
discharges
conditions.
agreement
to a
association
The
also
good
to
method
the
time
of
for
used
we
gain
between
distinction
determination
the
and
loss
of
the
addition
of
value
of y
similar
evolution
other
species
2,4
values
~
for
of the
allows
method
titration
pyrex
steady
in
state
atomic
of
for
10~
x
=
surface
this
spectroscopy
time
calculated
Indeed,
y.
absorption
resonant
follow
state
wall
but
relatively
a
processes.
Acknowledgments.
We
with
like
would
the
lo
Touzeau,
Pr.
thank
to
for
spectrometer
Vialle
M.
Launay
F.
V.U.V.
m
Dr.
and
contribution
her
Pagnon
D.
to
Observatoire
the
at
for
the
helpful
many
of
measurements
(France)
Meudon
de
line
profiles
and
Dr.
concerning
discussions
M.
oxygen
atoms.
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