Appl. Phys.

B 48, 73-84 (1989)

A~)Ji~:~ photo-
physics
Physics B "' Laser
Chemistry
9 Springer-Verlag 1989

Spectroscopic Investigation of the Ionization Kinetics

in XeCl Laser Discharges
by Xe* Density Measurements
Th. Hammer and W. Biitticher

Institut ffir Plasmaphysik, Universit/it, D-3000 Hannover, Fed. Rep. Germany

Received 5 April ~988/Accepted 9 June 1988

Abstract. Time and spatially resolved absorption measurements of Xe* particle number
densities performed at an X-ray preionized self-sustained XeCl*-laser discharge were used
to investigate the reaction kinetics of such discharges and to test the validity of the
commonly-made assumption that they are fit well by spatially homogeneous numerical
models. It turned out that the Xe* density distribution over the discharge cross section
remains homogeneous for less than 100 ns only. Comparing the experimental results of the
homogeneous discharge phase with zero-dimensional model calculations, we conclude that
induced emission modeled using two excited xenon levels must be taken into account for the
quantitative interpretation of the absorption measurements. For the interpretation of the
Xe 6 s ' - 6p' absorption measurements even a multilevel model will be necessary. Further we
conclude from the relative courses and the absolute values of the Xe* particle number
densities that realistic HC1 kinetics should contain three vibrationally excited levels and
stepwise excitation processes as proposed by Dem'yanov et al. [8].

PACS" 42.55G, 52.65, 52.70

During the last few years several XeCI* laser models
[1-10] and spectroscopic investigations of excited
state population densities [-8, 11-13] of the discharge
pumped XeCI* laser have been published. But there
are some questions which have not yet been answered:
- There is no quantitative interpretation of the mea-
surements by model calculations.
- As a background light source for the absorption
experiments pulsed dye lasers were used. Because of
the limited pulse width and the jitter of the synchroni-
zation, the time resolution was not good enough to
investigate the first rise of the excited state population
densities.
- Nothing is known about the excited state particle
density distribution within the discharge gap. This
information is necessary to prove the applicability of
zero-dimensional discharge models.
To gain insight into the reaction kinetics of self-
sustained high pressure glow discharges in Ne/Xe/HC1
mixtures, we performed end-on absorption measure-
ments at the xenon 6s-6p and 6s'-6p' transitions
(Fig. 1) in an X-ray preionized XeCl* laser discharge
containing various mixtures of Ne, Xe, and HC1
(Table 1). As a background light source we used a Kr
ion laser (Coherent CR2000K) pumped cw single-
mode dye laser (Coherent CR 599-03). We obtained a
time resolution of about 2 ns and a spatial resolution
transverse to the laser beam of less than 1 mm (Sect. 1).
To calculate particle number densities from the optical
depth, the f-values and the line profiles of the tran-
sitions are to be known (Sect. 2). Induced emission
must not be neglected. In Sect. 3 an estimation of
systematic errors caused by limited temporal and
spatial resolution follows. For the use in model
calculations various atomic energy levels are summed
up to model levels. The assumptions under which this
has been done with xenon are checked experimentally
(Sect. 5). More-dimensional effects are described in
Sect. 4. In Sect. 6 the experimental results are com-
pared with those of our model calculations. After that
the kinetic model of the XeCI* laser discharge is
established: The importance of a second, higher
74 Th. Hammer and W. B6tticher

5ps zP~tz 13./,5 eV 5p5 2P~s2 12.13eV is 20 ram. The discharge is driven by a peaking-circuit.
nI ' ns'
13/2] It/2] 0/21
ns no 1[ 3 / 2 The load capacitance of 20.5 nF can be charged up to
.&.j.j.j.....0..!. 1 o ! 2
30 kV. The discharge chamber can be filled with total
pressures up to 3 bar. Table 1 gives an overview of the
investigated discharge conditions.
-7- - L Figure 2 shows the set-up of the absorption experi-
-L ~ ment [15]. As a laser dye we used Styryl 9 M (Lambda
11 ---7 .27 ~L .2- .y_ ._7_ _ L _fi_ ..L
Physik) in a solution of propylene carbonate and
-.7- ___7 .2.
tu i 83/*.91 820.86 ethylen glycol. Pumping with 3.6W Kr ion laser
i~I radiation (Coherent CR 2000 K all line red) we ob-
tained more than 30 mW single mode dye laser radi-
- -
L . y ......
82g,2/~ 82339
ation (Coherent CR 599-03) for all transitions under
investigation. Using the 10cm confocal Fabry Perot
interferometer the bandwidth was estimated to be less
than 40 MHz. The optogalvanic effect with a Cu-Xe
hollow cathode discharge was used to tune the dye
Sp6 150 laser to the line centers of the xenon transitions at
Fig. 1. Transitions used for the absorption experiments, vacuum- 823.4nm, 820.2nm, 820.8nm, and 834.9nm vacuum
wavelength given in nm. The levels marked with * and ** are wavelength.
collected to give the model levels Xe* and Xe**, respectively A grating spectrograph, linear dispersion
24 pm/mm, gave the possibility to detune the dye laser
from the line centers of the transitions with 5pro
excited Xenon level for the interpretation of-the precision. This was necessary as most of the absorption
experimentally determined particle densities is shown, measurements were performed at the line wings
as well as the significance of stepwise vibrational because of the large optical depths of the laser dis-
excitation of HC1 introduced by Dem'yanov et al. [7]. charge at the line centers of the transitions. For this
reason the line profiles had to be investigated in more
detail than in previous works [12, 13].
1. Experimental Set-Up Transfering the dye laser and the transmitted
The X-ray preionized XeCI laser discharge used as test radiation by means of optical wave guides (multimode
specimen is described in detail by Stielow et al. [l 4]. Its graded-index fiber, core diameter 50 ~tm) gives high
area given by the preionization is 170 x 10 mm 2, its gap experimental flexibility and reduces the noise of the

Table 1. Parameter range investigated by absorption experiments: load voltages in kV for different gas mixtures

Pint [bar] Pxo [mbarJ/Pncl [mbar]

50/5.0 75/2.5 75/5.0 75/7.5 150/5.0

1.0 15, 20, 25, 30 15, 20, 25, 30 15, 20, 25, 30 25 15, 20, 25, 30
2.0 15, 20, 25, 30 25 15, 20, 25, 30 25 15, 20, 25, 30
3.0 20, 25, 30 25 25 20, 25, 30

BSM L
I Kr - Ion -Loser / v 'fill v,-,,.-/A II
M
N~'- - -> ~ XeOI-Loser

Grating SpectrocjrQph
r" . . . . . . .

IM o d e control ~s

I
I
I
I

Fig. 2, Set-up of the absorption experiment. BS: beam spliter; M: mirror; L: lens, f = 10 ram; GF: glass fiber; LS: lens system; UVR: UV-
reflecting mirror; A: aperture, q~< 1 mm; IF: interference filter; OGE: optogalvanic effect with a Cu Xe hollow cathode discharge; PD:
Si Pon photodiode; ac, de amplifier; OS: 275 MHz oscilloscope
 Spectroscopic Investigation of the Ionization Kinetics
signals. With the lens system L the exit plane of the
glass fiber is focused into the center of the discharge.
The apertures A (4) < 1 mm) and the interferencefilter IF
(bandwidth 10 rim) are suppressing the discharge radi-
ation to less than 2% of the intensity of the incident dye
laser radiation. The optical signal is detected in an
electrically screened cabin using a fast Si Pin photo-
diode (Hamamatsu S 1722). To get the intensity of the
dye laser beam without absorption, a slow dc amplifier
(0-5 kHz) with high input impedance is put parallel to
the avantec GDP ac amplifier (50 kHz~00 MHz). Its
amplification can be adjusted to that of the ac
amplifier. A 275 MHz storage oscilloscope
(HP 1727 A) is used to record the difference signal.
With this combination of detector, amplifiers and
oscilloscope we get a time resolution of about 2 ns. To
attach the time scales of different signals (i.e. dye laser
absorption, discharge current, discharge voltage and
XeCI* laser pulse) to each other we put a very short
electric pulse on every signal (half-width 2 ns). Further
signal processing is done by taking Polaroid photos of
the oscillographs and digitizing them with an accuracy
of 0.05 divisions. Nonlinearities of the oscilloscope
time scales and distortions of the Polaroid photos are
corrected numerically.
2. Calculation of Particle Number Densities
Under the given experimental conditions, spontaneous
emission of the discharge plasma can be neglected
[16]. Thus the particle number densities of excited
xenon atoms can be calculated from the measured
intensities 1(2, 0, lo(2) according to
v(2, t) = - In [1(2, 0/lo(2)3,
Tab.e 2. f-values of the xenon transitions used for absorption measurements. (a) Theory [17], r length-, v velocity formulation. (b)-(e)
Lifetimes from [18-21], branching ratios from [17, 183. (f)-(h) References [22-24]. The last row gives the mean values and the standard
deviations of the f-values derived from literature.
6s[3/232 - 6p[3/232 6S[3/231 - 6p[1/23o
823.39 nm 828.24 nm
(a) r 0.253 0.153
v 0.227 0.103
(b) 0.189_+ 10%
(c) 0.231 _ 10%
(d) 0.204_ 14% 0.122-+ 3.5%
(e)
(f) 0.291_+ 5% 0.117__ 7%
(g) 0.233 + 23%/-- 28% 0.136 + 39%/-- 33%
(h)
0.233 _+14% 0.126_+ 15%
"Because of the large discrepancy to the other values not included into the mean value
75
where r is the optical depth, and
Nl(t)" {1 - [gl" N2(t)]/[g2" Nl(t)]}
= z(2, 0/[0-21(2) 9L], (2)
where Ni and g~ (i=1,2) are the particle number
densities and statistical weights of the lower (1) and
upper (2) level. L is the length of the plasma, which is
assumed to be homogeneous.
Equation (2) defines the "effective" particle number
density, which takes into account that induced emis-
sion must not be neglected. The photoabsorption cross
section O-z1 of the transition is defined by
e2
a21(2) = 4ne.orn~c2 "rc2z"f21 " P21(2), (3)
where 2 o is the wavelength of the unperturbed tran-
sition, f21 the absorption oscillator strength, and P21(2)
the normalized line profile of the transition.
While ]:values of the xenon transitions can be
found from literature [17-24], partly by combining
life-time measurements with measured and calculated
branching ratios (Table 2), nothing is known of the line
broadening of the near infrared xenon lines in
Ne/Xe/HC1 mixtures. Thus we determined them with
ol~r experimental set-up by detuning the dye laser to
various wavelengths 2~ off the line center of the
transition and taking the transmission I(2i, t)/Io(2~) of
the discharge, which is reproducible to within a few
percent for about 100 ns. Because of the large optical
depths of the discharge at the line centers of the
investigated transitions most of the measurements
were performed outside the pre-ionized volume.
Evaluating the relation
(1) z(2,, t)/v(2, + J = P21(2,)/P21(2,+ 0, (4)
6S'[1/23 o-- 6p'[3/231 6s'[1/231 - 6p'[3/232
820.86 nm 834.91 nm
0.286 0.461
0.193 0.337
0.267 _+20% 0.364_+ 20%
0.217 -t- 20% 0.345 _+20%
0.333_+ 20% a 0.355-+ 20%
0.243 -+ 20% 0.399 + 20%
0.241 + 15% 0.377_+ 12%
76 Th. Hammer and W. B6tticher

F'\ we obtained normalized line profiles for different gas

mixtures (Fig. 3). The statistical methods used for this
lo~O procedure are described in detail by H a m m e r [28].
Substantial deviations between fit and measured
values occur only in the line wings ( [ 2 - 2 0 + 5 2 [
-g >0.2 nm). Thus the error in the normalization con-
Z
/f
stant is less than 15% for the high pressure (3bar)
experiments and less than 5% for those experiments
"mlOg performed at lower neon pressures. Table 3 gives line
profile values for different gas mixtures at three values
/ / of 2 - 20 + c~2used for the absorption experiments. The
I _4ro I T I 410 r i foreign gas broadening caused by neon will dominate.
-8 0 80
X-Xo [pm]
Neither the xenon nor the HC1 partial pressure has
significant influence upon the line width, but the
influence of the xenon partial pressure upon shift and
li
101o asymmetry cannot be neglected. Within the error
bounds no evidence for Stark broadening was found in
measurements at the discharge center. Nevertheless it
109 could not be excluded because of the large optical
depths in the line cores of the transitions. So one may
g have a time dependent line profile, which means that
a. 10~
particle densities are no longer proportional to optical
depths. Estimations from Ar and K r Stark broadening
[-29, 30] give maximum errors for the line profile values
-05 0 0.5 of about 30% at electron densities of 5 x 10 zl m -3 and
b X-Xo [nm]
neon pressures of 2 bar. In the further analysis we as-
Fig. 3a, b. Line profile of the Xe 6s[3/2]z-6p[3/2] 2 tran- sumed that Stark broadening of the xenon transi-
sition at 2o=823.39nm a line core, b total line profile in a tions is neglible.
gas mixture of Ne/Xe/HCl=g45/150/5mbar. The experi-
mental values are connected by full lines, the broken lines give
fits of them using (5)
3. Error Considerations
In addition to the errors of line profile and f-value,
taking weighted averages over t and fitting the line which affect the absolute value of the effective particle
cores of the measured profile with asymmetric Lorentz number densities, errors from the determination of the
profiles [-25-27] optical depth must be considered:
The signal levels of transmission "1" (al), of trans-
1 7/2 + ~" ( 2 - 2 o + 52) mission "0" (%) and the time t must be read from the
PaL(~) = --" (5)
7c (~ -- 20 -{-52) 2 q- (7/2) 2 oscillographic record. Each of these quantities has an
(7: F W H M , 52: line shift, 7: asymmetry constant), uncertainty of about 2% relative to al - a 0. According

Table 3. Line profile values P~l(fl)in 10S/mused for the evaluation of effectiveparticle number
densities

Transition P,o, [bar] 2 - 2 o [nm]

0.0 -0.04 -0.4

6s[3/2] z - 6p[3/2] 2 1.0 221 _+6% 12.1_+16% 0.26 25 %

2.0 137 22.6_+13% 0.63 _+24%
3.0 95 2% 28.4__+ 6% 1.07_+/8%
6s[3/211- 6p[1/2]o 2.0 66_+6% 36.5+/7% 1.40_+26%
6s'[1/2]o - 6p'[3/2] 1 2.0 47 _ 7% 5.59_+18%"
6s'[1/2] 1 - 6p'[3/2] 2 2.0 105 _+9% 0.67 42%

a Value at -0.2 nm instead of -0.4 nm

Spectroscopic Investigation of the Ionization Kinetics
to the law of error propagation [31] this leads to a
standard deviation of
s = 0.02/T-(2. (1 - T + T2)) '/2 ,
where T is the transmission.
The limited time resolution mentioned in Sect. 1
causes a temporal shift of the absorption signal of 2 ns
and an underestimate of the first absorption peak of
3 %. Two other systematic errors arise from the limited
diameters of dye laser beam and aperture stop: For
particle density measurements in the outer discharge
regions the particle density gradients lead to an
underestimate of the optical depths. This effect may be
amplified or reduced by the Schlieren effect, depending
on the wavelength of the dye laser radiation relative to
the line center of the transition under investigation, sO
the contours of the particle density distribution over
the discharge cross section seem to be more or less
pronounced. A quantitative estimation of this error
cannot be given, because the intensity profile of the dye
laser radiation at the exit plane of the glass fiber is
unknown. NeVertheless, one should be careful with the
interpretation of spatially resolved absorption
measurements.
4. Multi-dimensional Effects
All measurements described in this section have been
performed with the dye laser tuned to 2 = 823.0 nm in
the blue line wing of the 6s[3/2l 2 - 6p[3/2] 2 transition.
12
a 2O 40 60
~G
2
b 20 40 60
;', Ii "~
C
i ; I
20
i '~ I
40
I I
60
77
The temporal correlation between absorption signals
taken at different locations of the discharge was
achieved by relating them to discharge current signals
(6)
measured simultaneously.
Several series have been taken starting from the
center of the discharge and scanning the probe beam
step by step transverse to the electric field. The results
are presented as lines of constant optical depth (Fig.
4a-c) in the x - t plane, where x is the distance from the
discharge center and t the time since onset of absorp-
tion. The most striking features are the narrowing of
the discharge after the first current minimum and the
appearance of regions of high optical depth beside the
main discharge channel during the second current half
wave. While in absorption the optical depth grows
with the load voltage, in emission the lateral channels
get less pronounced. One reason for this unexpected
behavior may be induced emission, which lowers the
absorption with growing Xe @[3/2]2 - but constant
6s[3/2] 2 -particle number densities. At later times the
discharge channel narrows further to a width of
4-5 mm, which is consistent with emission measure-
ments [32] (Fig. 5) and may be due to inhomogeneities
of the electric field. From these results we conclude that
a comparison of experiment and model calculations
makes sense only for the first current half wave.
A few absorption measurements were performed in
the cathode region of the discharge. These experiments
show that the theories which describe the cathode fall
of low pressure glow discharges are not valid for
80 100
t [ns]
Fig. 4a--e. Temporal development
of the spatial profile of excited
80 100 xenon atoms: Lines of constant
t [ns] optical depth, x gives the distance
of the dye laser probe beam from
the discharge center, t the time
from onset of absorption at the
discharge center. Gas mixture
Ne/Xe/HC1= 1920/75/5 mbar.
Load voltages: a Uo=20kV,
\ N
/ L
80
/" f ~ I
I00
---,-*0.5~
b Uo=25kV , c Uo=30kV
t[ns]
 78 Th. Hammer and W. B6tticher

300
T=I
-~200

~" 100

-505 -505 -505 T=C

X [mm]
Fig. 5. Streak exposures of the visible light emitted from the
discharge taken with the slit at discharge center parallel to the a 20 ns/div
electrode surfaces. Discharge conditions are the same as in
Fig. 4

-~-- (a)
-~- (b) T=I
m.-J--! -~-- (c}

{!, ",. I / l'

\ p,/ r ,
o
o ,~, ~ ~, , . . . . "-~" 1'
/ ,%~' ,/ ,,, ,,'
T=r
~, \ 4, .

b 20 ns/div
Fig. 7a, b. Reproducibility of the transmission signals taken
at a 1 mm and b 2 m m distance from the cathode. Dis-
[ i , , , I i = i
charge conditions are the same as in Fig. 6
O0 20 z,O 60 80 100
t[ns]
Fig. 6. Effective particle number densities at different dis-
tances to the cathode: (a) 0.5 nm, (b) 1.0 ram, (c) 3.0 ram. Gas two excited xenon levels Xe* and Xe** using the
mixture Ne/Xe/HC1= 1920/75/5 mbar, U0 =25 kV relations [36]
N* = ~6s, 6s'Ni, N** = Z~6p' 6p,Nj, (7)
transient high pressure glow discharges: From extra-
g* = ~6s, 6s'gl, g** = Z6p,6p'gj (8)
polation of the similarity rules one would expect a
cathode fall thickness of about 10 ~tm; what is observed for the particle densities and statistical weights. These
is a 2 mm thick layer in front of the cathode with definitions are justified if the measured effective par-
different behavior compared with the discharge vol- ticle number densities can be expressed as

x,. ( 1 - ggi.Nj~
j U / -- 8 , . N . . ( 1-
ume iFig. 6). Irreproducibilities of the absorption
,* 9
signals at relatively early times (Fig. 7) confirm the u*/ . (9)
observations of Taylor [33], that the cathode region of
excimer laser discharges may trigger volume insta- So we performed absorption measurements at the
bilities (HC1 depletion instability [-34, 35]). four transitions indicated in Fig. 1 using a gas mixture
of Ne/Xe/HC1 = 1920/75/5 mbar. For the 6 s - 6p tran-
sitions this relation is valid within the error limits, but
5. Relations of the Observed Effective Particle Number for the 6s'-6p' transitions there are serious discrep-
Densities to the Model Level Populations ancies (Fig. 8): compared with the 6s[3/211 level, the
Restricted by the published excitation and ionization 6s'E1/211 level is underpopulated by a factor of 10,
cross sections in our model calculations we defined the while the 6s'[1/2]o level is overpopulated by a factor
Spectroscopic Investigation of the Ionization Kinetics 79

- t h e further course during which the discharge

-~.- (b)
t -~-- (c)
- e - (a) I changes it's width and becomes inhomogeneous.
- +- (d)40
/\ .... o
A comparison of the experimental results with the
r '., model calculations makes sense only for the first three
, . I. /,-,,\ parts of the course.
,-,, y --- ,, il;~,,,,k The first nearly exponential rise was resolved in
]'~i"
.,,,. ...... .
I ,,, \
t/..k ,,',, t ', \,;
; / measurements at three different wavelengths of the line
, ~, ,, ~ , 9 \\ ,, ,, ,
profile of the transitions under investigation. Combin-
k,--l-.I----,, ", \ lit 't,, ",,, ',,j ing these courses using simultaneously measured dis-
tf +l"+*-+-'-b," \ tli '~, ",, , charge current signals we obtained the development of
the effective particle number densities over a range of
,,~ ..... "k~+.~-%t ,t; .... ,, "~-,,4,
more than four decades (Fig. 10). At low load voltages
# .... ..T :,, +'~ -.,, the agreement with model calculations is not satis-
# l'-. ; v factory, and it gets worse with growing neon and xenon
pressures.
20 ~0 60 80 100 Figure 11 shows measured and calculated effective
t [nsI
particle number densities for the @[3/212-6p[3/212
Fig. 8. Effective particle number densities of the four xenon transition at the first current maximum for various
transitions investigated9 Gas mixture Ne/Xe/HC1 discharge conditions. Especially at high neon pressures
=1920/75/5 mbar. Uo=25 kV. (a) 6s[3/2]z-6p[3/212 , (b)
6s[3/2]~--@[11210, (c) 6s'[l12]o--6F[312]~, 6s'[U2]~ the agreement of these values is very good, but
--6p'[3/2]~, (e) average value calculated for the 6s[3/2]~ experiment and model calculation show opposite neon
- 6p [3/2]z transition using (9) pressure dependence. This, as well as the above
mentioned behavior of the rise-times, could not be
explained - the circuit model used may be responsible,
as could be the reaction kinetic model. The first
of 1.5. This may be due to collisions with xenon atoms assumption is supported by the observation that under
at thermal energies, which couple the 6s'[1/211 state some discharge conditions the experimental results
to the 6p[1/2]~ state lying only 10.4meV above. show two minima at the end of the first current half
Since the two 6s levels dominate the population of the wave, while the model calculations predict only one
first model level of xenon one can conclude that the minimum. The second assumption arises from the fact,
6s[3/2] 2 - @[3/2] 2 transition is suitable for obtaining that e-e collisions are not included in the Boltzmann
information on the population density of the whole
model level. But electron collision excitation cross
sections of single I S o - 6 S , ~ S o - 6 S ' , 6 s - 6 p , and 6s' T -- U/IO
/ ........ P" 0,55
- 6 p ' transitions, as well as electron collision ioniz- _ /i-k\ l ...... I 1102o
ation cross sections of the excited levels, are desirable f\ i \ t, I -~- Nno
to create a more realistic model which allows the !,'. /\'---7
interpretation of the above-mentioned discrepancies
between the effective particle number densities. 'm I r t.. 9 ; , , .
- 1 # I il( - ~ ,,, t \

6. Comparison o f Experimental Results with M o d e l

Calculations
9 ! t ~ !% ,,, I "

The temporal development of the effective particle , k i : ,/ /\ \

x , ~ i \ -/ / ~ ,
number density of excited xenon may be subdivided
into four parts (Fig. 9): 0
- the first very fast rise during breakdown of the
discharge voltage followed by a pronounced \
maximum, AO 60 80 100 I20 140 160
t[nsl
- a relatively flat plateau correlated with a plateau in
the discharge voltage and the first maximum of the Fig. 9. Experimental r e s u l t s o f d i s c h a r g e v o l t a g e U , c u r r e n t I,
discharge current, photon pulse P and effectiveparticle number density N of the
6s[3/212-6p[3/212 transition. The error bars give the stan-
- one or two minima which roughly coincide with
dard deviation according to (6); the shift of the error bar at the
minima or zero points of discharge voltage and first absorption maximum accounts for the correction due to
current, limited time resolution
 80 Th. Hammer and W. Bttticher

101
- - model model --- model
5 --D-- ~ -- experiment -- experiment
- - ~ - experiment
3 -~_.t o 1 bor ~ . o 1 bar /
2
;2b r , / ' 2 + 2bor /
v 3bor M
100

5 %
o
3
z
2
1(/1 1

~'E 5
~'-'3
o
~2
z 10-2

~ 50
' ' 100
' ' I; 0 ~ ' 25
I ' 5.0
' ' 75'
a pxe[m bar] b pHcj[mbar]

2 Fig. lla, b. Effective particle number densities of the 6s[3/2]z

16 3
-6p[3/212 transition at the first current maximum, load
voltage Uo=25kV. For a the HC1 partial pressure was
5

2 i,?
/
/ 5 mbar, the xenon partial pressure for b was 75 mbar. In
addition to the statistical errors (6) for the 2-bar condition the
systematic errors resulting from line profile and f-value are
shown (large error bars)
3O 40 50
a t[ns]

equation, and this may lead to errors in the high energy

10' region of the calculated E D F and hence to an underes-
-- model
5 timation of neon excitation rates.
3
2

10~
7. Justification of the Reaction Kinetic Model
I

5 A detailed description of the reaction kinetic model

3 and the used electron collision cross sections and rate
2 coefficients is given in a previous paper [14]. In this
101 section the sensitivity of the calculated discharge
voltage, current and excited xenon effective particle
5

;;/i
'E
o-- 3 number densities to the model assumptions for xenon
o excitation and HC1 vibrational excitation will be
A2
z 102
examined.
Figure 12 shows various electron collision exci-
5 tation cross sections of xenon: The curves labeled (a)
3
(b), and (c) are total excitation cross sections [37-39],
2
curve (d) gives a sum of 6p and 6p' excitation cross
153
sections containing cascade contributions from higher
level excitation [401 and curve (f) stands for metastable
excitation put on an absolute scale by Blagoev et al.
[41] using rate coefficients for superelastic electron
Lo 50 60 70 80 90
metastable collisions determined from probe measure-
b tins] ments in afterglow discharges. As the most reliable one
Fig. 10a, b. Effective particle number densities of the 6s[3/2]z we consider the cross sections of Hayashi [39] These
-6p[3/212 transition during the late avalanche phase of the were evaluated from a Boltzmann analysis of swarm
discharge. The detunings of the dye laser from the line center experiments using the most recent values for the
of the transition were 0.0nm (earliest phase), -0.04nm m o m e n t u m transfer cross sections and taking into
(medium range) and -0.4nm (fully developed discharge).
The error bars show the standard deviations according to (6). account resonance structures in the threshold region of
Discharge conditions a Ne/Xe/HCl=945/50/5mbar, Uo the excitation cross sections. Subtracting the sum of 6p
= 30 kV, b Ne/Xe/HCI= 1845/150/5 mbar, Uo = 15 kV and 6p' excitation cross sections (Xe**) we got a cross
Spectroscopic Investigation of the Ionization Kinetics 81

[ --(a} cross sections [42, 43] even large errors in the partition
.... (b)
........ (el of the total excitation cross section play a m i n o r role.
i/ //I/// J
....... (d) This can be seen from Fig. 14, where the results of four
' . . . . . . . . (e)

kO~ )
/'
/

/I
/ I
/ /I
,/ /
I' / - / I " ~ ----7/- -
./" /
/!/" different xenon excitation schemes (Fig. 13) are com-
pared: Discharge voltage and current are determined
only by the total excitation rate. In contrast to this, the
m e a s u r e d effective particle n u m b e r densities can be
E reproduced only if two excited m o d e l levels and two
.j ,/ / ../
step excitation of the higher level are t a k e n into
o i I /I i'I
ij ii / / account.
i
J
/
I // i"
/ In the literature on XeCI* laser modeling, HC1
O.E
9" I i /" vibrational excitation and dissociative a t t a c h m e n t of
:/ / ./" / ./"
/ / .// i electrons to HC1 is treated in various different m a n n e r s
(Table 4). T o verify the HC1 kinetics p r o p o s e d by
~i~\i / I S " 7 / j "
,'x~L~ .~:"- D e m ' y a n o v et al. [8] we p e r f o r m e d m o d e l calculations
,, J / ..~" using the following assumptions:
S, ,./,
9 ~0 , ,
II
E [eVl
,
I2
, , II3 |~ ' (I) Vibrational excitation and dissociative attach-
m e n t were treated using energy dependent electron
Fig. 12. Electron collision excitation cross sections of XeI. a collision cross sections. Following D e m ' y a n o v et al.
Schaper and Scheibner [37], b Specht et al. [38], c Hayashi [8], we assumed a l _ 2 = 2 . a o _ l and a 2 _ 3 = 3 . a o _ 1
[39], d 6p- and 6p'-excitation combining the values of
for the excitation cross sections. Reducing the n u m b e r
Felt'san and Zapesochnyi [40] with branching ratios from
[17], e 6s- and 6s'-excitation (difference of the cross sections of vibrational levels t a k e n into account affects the
c and d), f metastable excitation [41] discharge voltage as well as the effective particle
n u m b e r densities of excited x e n o n a t o m s (Fig. 15).
(II) In Fig. 16a-c we c o m p a r e four different m e t h o d s
Xe B Xe I~ Xe IV Xe of modeling electron-HC1 collision reactions: (a) The
m o d e l described in (I) using vibrational excitation up
to v = 3, (b) the complete reaction scheme of (I), but
using rate coefficients for HC1 vibrational excitation
and dissociative a t t a c h m e n t to HC1. These rate coeffi-
Xe + Xe + Xe + Xe
cients as functions of the m e a n electron energy were
Fig. 13. Investigated reaction schemes for the electron colli- determined from the a b o v e - m e n t i o n e d cross sections
sion excitation and ionization of XeI assuming the E D F to be Maxwellian, (c) an H C I m o d e l
restricted to v = 0 and v = i using energy dependent
section for lower level excitation (e), which was as- excitation cross sections but rate constants for dis-
signed to the 6s and 6s' states (Xe*). Indeed this is only sociative a t t a c h m e n t (k,tt(v = 0) = 2.5 x 10-16 m3/s,
a rough estimation, but because of the high values of the k, t t ( v = l ) = l . 1 x 1 0 - t 4 m 3 / s ) [44], (d) the same reac-
X e * - X e * * excitation and Xe* and Xe** ionization tion scheme as in (c) but using rate constants for

Table 4. Treatment of e-HC1 collision reactions in XeCI* laser modeling (v = vibrational quantum number of the HC1 molecule,
RCONST = rate constant, RC'(E/N)= E/N dependent rate coefficient, QS(e)= energy dependent cross section, + = included, - --not
included)

[1] [2, 3] [5] [8] [6] This

work

Vibrational 1 2 1 3 1 3
levels up to RCONST QS(e) RCONST QS(s) QS(s) QS(~)
vibrational
excitation - ? - + + +
superelastic
collisions - - - + _ +
stepwise
excitation RCONST v=0: QS(~) RC(E/N) QS(~) v=0: QS(~) QS(e)
dissociative v= 1, 2: RC v= 1, 2: RC
attachment
82 Th. Hammer and W. B6tticher

20 20
o-u(t}+- I(t) P V=3
........ V = 2
.... V=I

10

g
H
z

i I . . . . I r i , , i ,

AO 60 80 100 120 1AO 160

a AO 60 80 100 t[ns~20] %0 160
t [ns]

/ ~"'~---.---.... ./" "'-~ ..

~ y .......
V=2
... V=I
2f ........ "1
t ill. "-" /
._~ ; r
~'E t,~ ".. : '-. ,%
'....\ /
1
~1: I1 "%- #.'7 "-~. /
6 ~ If \-'i,,' ? "
,. ' i

'",,X LW:/
..-/ ",,,
J i , , , i , , . " ' ~ - - - - J . i .
z,O 60 80 100 120 1AO 160 020 60 80 100 120 ' 1~0' ' ' 160
b t[ns] b t[ns]

Fig. 14a, b. Discharge voltage U and current ! a and
effective particle number densities of the 6s[3/2]a-6p[3/212
transition b calculated using the reaction schemes shown in
Fig. 13. Ne/Xe/HC1 = 1920/75/5 mbar, Uo = 25 kV
Fig. 15a, b. Discharge voltage U a and effective particle
number densities of the 6s[3/2]~-6p[3/2] 2 transition b
calculated changing the number of HC1 vibrational levels
taken into account (v gives the upper limit of the vibrational
quantum number respectively). Discharge conditions are the
same as in Fig. 14

vibrational excitation too (kexo=2.4x 10-14m3/s) 8. Conclusions

[44]. For the superelastic collisions the rate constant
was chosen to be 1.43 times the excitation rate End-on absorption measurements of effective particle
constant. number densities N~. [1-(g~Nj)/(gjNi)] of excited
From (I) and (II) compared with the experimental xenon atoms have been performed using the 6s and 6s'
results, we conclude that rate constants are insufficient states as lower levels. As one may expect comparing the
to describe HC1 vibrational excitation and dissociative mean electron energy ( 3 ~ e V ) during the discharge
attachment of electrons to HC1. Furthermore, the HC1 phase with the energy difference between the upper and
kinetics proposed by Dem'yanov et al. I-8] - stepwise lower excited xenon levels used for the absorption
HC1 vibrational excitatio[i up to v = 3 - is confirmed by experiments (1.5 eV), the model calculations confirmed
the relative course and the absolute value of the that induced emission has to be included for the
effective particle number densities of excited xenon interpretation of the experimental results. Due to the
atoms. small number of published xenon excitation and
 Spectroscopic Investigation of the Ionization Kinetics 83

- - (<~l
20 ....... (b)
.... (c) -- (a) . 2
..... (d) ....... (b} . 2
.... (c)
.... (d)
..-0-- exp.-0.55

P'd,:
,F
10 ,

t,
8'
~-.,"..
It.' ",
",",,,'\
\'\ i
l\ i;'." " ""\
if;" f~. ",. ",\ 13_
g--,-
~". ...... --.,,
/7. /
.7: !
\ \ ..'..

i
-
"'"',
"\',
"& ~t:
;7: "'-..

AO 60 80 100
t[ns]
t20 lZ,O 160 0/~0
, , , i .
60 80 ~00
t[nsl
120
5 140 160

-- (a)
(b)
(c) ,...\ ",,\
{d) / ,,.
exp. / -,,,,
/ "% ...,#!i \,, \
: 3 \
; / :. x.
/ '\ \
"'.....
'E

"oo_
}\. \' , , L. B

Fig. 16a--c. Discharge voltage U a, effective particle number

densities of the 6s[3/212-6p[3/212 transition b and laser
photon pulse e calculated using four different methods to
model electron-HC1 collision reactions (see text for explan-
O&~o '
ation). Discharge conditions are the same as in Fig. 14
50 80 100 120 1AO 160
t[ns]

excited xenon excitation and ionization cross sections discharge as long as the xenon total excitation rate
we collected the 6s and 6s' levels and the 6p and 6p' remains constant, for HC1 stepwise vibrational excit-
levels to give Xe* and Xe**, respectively. Although the ation has to be taken into account. Calculations like
experimental results show that this doesn't describe the those of Domcke and Mfindel [45] for HC1 v = 0 - n
effective particle number densities of the 6s'-6p' excitation should be performed to justify the estimated
transitions in a sufficient way, the agreement with v = n - n + l excitation cross sections. On the other
effective particle number densities determined for hand time resolved absorption measurements of the
6s-6p transitions justifies the model as a whole. HCI(v) population densities could show the impor-
Reliable cross sections for the excitation and ioniza- tance of stepwise excitation processes directly.
tion of individual energy levels are needed to extend By scanning the dye laser beam over the discharge
the kinetic model of the xenon atom. For the interpret- cross section with a spatial resolution of better than
ation of spectroscopic measurements of other excited- 1 mm it could be shown that discharge homogeneity
state population densities (i.e. Ne*, Xe +*, CI*) further and constant cross section are given only for some ten
detailed information on excitation and ionization nanoseconds. Even if one neglects the fact that the
cross sections is necessary. discharge behavior in the cathode region differs from
While details of the xenon excitation and ioniza- that in the volume, these effects restrict the comparison
tion kinetics do not influence the impedance of the of model and experiment to the first current half wave.
84
To describe these phenomena, multi-dimensional dis-
charge models are desirable. Because the spatial distri-
bution of electrons is expected to differ significant
from that of excited xenon atoms, time and spatially
resolved measurements of the electron density should
give additional information.
The way in which the discharge becomes inhomo-
geneous and narrower may be typical for our experi-
ment. However, from the observations of other re-
search groups discharge constriction can be concluded
too [13, 34]. The works of Coutts and Webb [34] and
Osborne and Hutchinson [-35] indicate that HC1
depletion is responsible for this constriction as well as
for the filamentation of the discharge at later stages.
Inhomogeneities of the electric field and the pre-
ionization may initiate the instability observed in our
experiments.
In summary we can state that spectroscopic par-
ticle density measurements, in combination with a
discharge model including realistic multilevel struc-
tures of the atom or molecule under investigation,
provides a powerful tool for understanding the reac-
tion kinetics of transient glow discharges. Spatially
resolved measurements yield information on discharge
homogeneity and stability.
Acknowledgements. This work was supported by the Deutsche
Forschungsgemeinschaft (Bo 496/11-1, 2 and 3). We thank
Lambda Physik, G6ttingen, for the permanent loan of the
EMG50. We are especially grateful to F. Rebentrost, who
introduced one of our team (G. Stielow [-14]) to the code
PLASKIN, which was made freely available to us by the Max-
Planck-Institut fiir Quantenoptik, Garching. In running the final
model H.-H. Hehmsoth and D. Backhaus were of great help.
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