Desorption Cross Section of an Adsorbed Oxygen Atom

on an Al Surface by Ar

Bombardment
Raita WADA and Seiji TSURUBUCHI
+
Department of Applied Physics, Faculty of Technology,
Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588
(Received July 8, 2002)
The intensity of light emission from excited Al atoms sputtered from a metal surface strongly depends
on the degree of oxygen coverage of the target surface. Desorption cross section of an adsorbed oxygen
atom by Ar

bombardment was obtained for a polycrystalline Al surface by means of a time transient

spectroscopic technique. The results obtained is (3.7 0.2) 10
16
cm
2
for the Al polycrystalline target
at the projectile energy of 40 keV. The initial sticking probability s
0
of an adsorbing oxygen atom was
estimated and the value obtained agreed to the reported values within experimental errors. A very sharp
spike in intensity was found to appear for the resonance line of Al atom sputtered from the Al surface in a
transient experiment when the oxygen coverage becomes large ( 1) in addition to a decay curve
usually observed with a large time constant.
KEYWORDS: desorption cross section, sticking probability, surfaceoxygen coverage, polycrystalline Al, Ar

bombardment, sputtering, transient spectroscopy

DOI: 10.1143/JPSJ.71.2886
1. Introduction
It is well known that the light emission of excited atoms
sputtered from a metal surface is strongly inuenced by
chemical conditions of the target surface or surrounding
atmospheric conditions.
18)
In the previous work, it was
shown that the steady state surfaceoxygen coverage
o
can
be quantitatively well dened even under the condition that
the projectile ions bombard a target surface.
1)
Therefore, it is
possible to investigate in situ surface chemical character-
istics as well as particlesurface interactions such as
quantum tunneling or quenching of an electron of excited
atom near the surface by observing emitted spectral
intensities from excited Al atoms produced by sputter-
ing.
912)
An observed change of spectral intensities reects the
change of surface conditions due to chemisorptions of
oxygen atoms or successive surface oxidation. The rate of
survival for excited atoms to escape from a surface without
having undergone radiationless transition is delicately
aected by the change of surface-band structure due to
adsorption of oxygen on a target surface.
9)
The intensities of
secondary ions and backscattered projectile ions are also
inuenced by the surface condition and correlation with light
emission were discussed.
1317)
In many applications of handling pure surfaces, it is
important to know chemical or electrical conditions of the
surface and an ion-beam bombardment is frequently used as
a tool for surface purication. Therefore, it is important to
have quantitative understanding for the desorption process of
chemically adsorbed oxygen atoms from a substrate. The
desorption cross section is dened as a number of desorbed
oxygen atoms from unit area of a target surface per incident
projectile ion in unit time.
Hupkens and Fluit
13)
and de Wit et al.
14)
reported that the
intensity of backscattered projectile ions with keV energies
depends strongly on the surfaceoxygen coverage and
discussions were given for the sticking probability and
desorption cross sections of adsorbed oxygen atoms on a Cu
surface.
Ghose et al.
5,6)
and Lee et al.
18)
observed spectral
emission intensities from sputtered substrate particles and
obtained sputtering coecients for an adsorbed oxygen atom
under various oxygen atmospheres for Si and Al surfaces by
Ar

bombardment in time transient experiments. Surface

conditions were usually estimated by considering a so called
exposed factor L (10
6
Torrs) and the initial sticking
probability s
0
for oxygen gas. Although the factor L is
proportional to the total number of incoming collisions of
oxygen molecules, it does not include information about
collision frequency. Therefore, it should be in mind that if a
process is dependent on the collision frequency or exposed
time interval, the factor L is not necessarily a good factor to
describe quantitatively surface conditions. A large scattering
still exists among the values s
0
even in the recent works
using scanning tunneling microscopy (STM)
19,20)
or Auger
electron spectroscopy (AES).
21)
Therefore, we have to be
careful when we estimate a value for the sputtering yield of
adsorbed oxygen atoms on the basis of the initial sticking
probability s
0
.
In the present work, a cross section was obtained for an
adsorbed oxygen atom to desorb from a polycrystalline Al
substrate surface by Ar

bombardment without using s

0
values so far reported. Spectral intensities were measured for
excited Al (396.15 nm, 4s
2
S
1,2
3p
2
P

3,2
) atoms sputtered
from a polycrystalline Al substrate under time transient
conditions as well as steady-state conditions.
2. SurfaceOxygen Coverage
If a target surface is bombarded by ions in the atmosphere
of oxygen gas, the balancing equation for adsorption and
desorption of oxygen atoms is given by
d(N
s
)
dt
=
J
e
oN
s
2vP
O
2
S() (1)
where is the oxygen coverage of a target surface, N
s
is the
+
E-mail: turubuti@cc.tuat.ac.jp
Journal of the Physical Society of Japan
Vol. 71, No. 12, December, 2002, pp. 28862890
#2002 The Physical Society of Japan
2886
surface density of substrate atoms, J is the current density of
the projectile beam, e is the charge of electron, o is the
desorption cross section, vP
O
2
is the collision frequency of
incoming oxygen molecules with a surface, P
O
2
is pressure
of oxygen gas and S() is the sticking probability of an
oxygen atom.
1,2,5,8,13,16)
The second term of the right hand is
multiplied by 2 because of dissociative adsorption of an
oxygen molecule on the Al target.
2022)
Assuming the
Langmuir model, the factor S() is given by
S() = s
0
(1 ) (2)
where s
0
is the initial sticking probability for adsorption of
an oxygen atom. The expression holds well for _ 1.
1)
The surfaceoxygen coverage is obtained from eqs. (1)
and (2) and given by
(T) = 1 (1 (0)) exp
2vP
O
2
s
0
N
s
T

(3)
where T is the exposure time of a target surface in oxygen-
gas atmosphere with beam o, (0) is the oxygen coverage
immediately after beam o. Dening t as the time interval of
ion-beam bombardment after the exposure of T, then, (T
t) is given by the following equation,
(T t) = (T)
2vP
O
2
s
0
J
e
oN
s
2vP
O
2
s
0
!
exp
J
e
o
2vP
O
2
s
0
N
s

t

2vP
O
2
s
0
J
e
oN
s
2vP
O
2
s
0
.
(4)
After sucient time of beam irradiation, i.e. after t o,

o
(t o) is given as,
1)

o
=
kP
O
2
J,e kP
O
2
, k =
2vs
0
oN
s
. (5)
Equation (4) is rewritten as
(T t) = ((T)
o
) exp(o(J,e P
O
2
k,e)t)
o
.
(6)
A similar expression is given in terms of sputtering yield of
oxygen atom.
2,5,6,8,18)
In Fig. 1 is shown the time evolution
of .
3. The SurfaceOxygen Coverage and Intensity of
Emission Lines
The emission intensity Y() of sputtered excited atoms
depends on the sputtering yield of an Al atom from an Al
surface and on the excitation probability near a surface as
well as survival probability for excited atom to escape from
the surface without having undergone a resonant ionization.
These factors are delicately aected by surface conditions,
especially by the degree of surfaceoxygen coverage .
1)
Although Kelly and Kerkdyjik assumed that the emitted
light intensity from sputtered excited atoms depends linearly
on ,
2)
it is more general to consider that the signal intensity
Y is the sum of Y
MO
, the contribution coming from the
excited atoms interacting with oxygen-adsorbed part of the
surface (o) and Y
M
, the contribution from those excited
atoms interacting with pure surface of bulk metal (o(1 )).
The total intensity Y() is, then, given by
Y = Y
MO
Y
M
,
Y
M
=
J
e
S
M
(1 ),
i
M
P
M
and
Y
MO
=
J
e
S
MO
,
i
MO
P
MO
, (7)
where sux M and MO stand for pure metal part and
oxygen chemisorbed part respectively, S
M
and S
MO
is the
sputtering yield of substrate atom, ,
i
M
and ,
i
MO
is the
excitation probability to the i-state of sputtered substrate
atom, P
M
and P
MO
is the survival probability of excited
atoms to escape from a surface without having undergone
the resonance ionization.
1)
Accordingly,
Y() = Y
M
Y
MO
=
J
e
(a b),
(a = S
MO
,
i
MO
P
MO
S
M
,
i
M
P
M
, b = S
M
,
i
M
P
M
). (8)
Putting eq. (5) into (8), the intensity Y is given by
Y(
o
) =
akP
O
2
J,e
J,e kP
O
2
bJ,e, (9)
the factor akP
O
2
, kP
O
2
, and b can be determined by tting eq.
(9) to the experimentally obtained Y(
o
) using the method
of the least-squares minimum to give the value of
o
at each
value of oxygen pressure.
1)
Actually, for large J, we have
Y - akP
O
2
bJ,e, which gives the value of b from the
slope of the line. The intensity of radiation should change
nonlinearly at small J values.
When the ion beam is switched on after exposure of the
target surface in an oxygen-gas atmosphere for time T
without ion-beam bombardment, the Y() of sputtered
excited atoms in a time transient mode is obtained by
introducing eq. (6) into eq. (8) and given as
0 200 400 600
0
0.1
0.2

0.3
0.4
t (sec)
T (exposure time)
off on on
t
Fig. 1. Time evolution of in a transient experiment.
J. Phys. Soc. Jpn., Vol. 71, No. 12, December, 2002 R. WADA and S. TSURUBUCHI 2887
Y(T t) =
J
e
(a(T t) b)
=
J
e
"
a
(
((T)
o
)
exp o
J
e
kP
O
2

t

o
)
b
#
.
(10)
4. Experimental Setup
A detail of the present setup is described in the previous
works.
1,11,12)
Briey, projectile Ar

ions were extracted

from an ion source of duoplasmatron type. The ion beam
was, after mass analyzed, collimated to the diameter of 5 mm
and bombarded a target surface at normal incidence. The
vacuum chamber was evacuated below 2 10
10
(Torr)
by turbo-molecular pumps and oxygen gas was introduced
into the chamber through a needle valve.
A polycrystalline Al target was mounted on a sample-
holder disk which was controlled from outside of the
chamber. In front of the target holder, there attached a
collector to measure the emission yield of secondary
electrons and negatively charged ions. The temperature of
the target was monitored by a thermocouple (Chromel
Almel) attached just behind of the target during beam
bombardment.
The observed spectrum is AlI 396.15 nm (4s
2
S
1,2

3p
2
P

1,2
) resonance line emitted by sputtered excited Al
atoms and its intensities were measured from the perpendi-
cular direction to the ion beam axis through a condenser lens
followed by a 50 cm monochromator equipped with a
photomultiplier.
5. Results and Discussion
5.1 Currentdensity dependence of Y(
o
)
Under a steady-state condition of adsorption and deso-
rption of oxygen atoms, the intensity Y(
o
) is given by eq.
(9). Figure 2(a) shows measured intensities Y(
o
) as a
function of J for sputtered excited Al atoms produced by
Ar

bombardment at 40 keV. A solid line is the best-tted

result by the method of the least squares minimum.
1)
It can
be said that eq. (9) describes fairly well the experimental
results for
o
- 1.
In Fig. 2(b) is shown the emission intensities Y(
o
) as a
function of . It is shown that the linearity does not hold
above
o
0.8, which may imply that the target surface
starts to change its surface characteristic from the chemi-
sorbed single-layer oxygen islands of AlO type into Al
2
O
3
type.
12)
Arranz and Palacio showed that the onset of
oxidation starts after the surface is completely covered by
chemisorbed oxygen. The fact was evidenced by the
appearance of Al
3
species indicating formation of Al
2
O
3
in AES and X-ray photoelectron spectroscopy (XPS)
spectra.
23)
The present work was carried out under the condition of

o
- 1. The measurement of
o
is dicult for an insulator
target because the light intensity of sputtered excited atoms
is linearly proportional to J and the non-linear part does not
appear. Therefore, it is impossible to determine the factor
kP
O
2
as a function of J.
5.2 Desorption cross section
In Fig. 3 is shown the result of a time transient
measurement for excited Al atoms sputtered in the excited
states from the target surface. A solid line shows calculated
results of eq. (10) which was tted by the method of the least
squares minimum. It can be said that eq. (10) describes fairly
0 0.02 0.04 0.06 0.08
0
2
4
6
8
J (A/m
2
)
Y




(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)
(a)
0 0.2

0.4 0.6 0.8 1

0
1
2
3
4
5
6
Y

/

J




(

a
r
b
i
t
r
a
r
y

u
n
i
t
s

)
(b)

Fig. 2. (a) spectral intensity of sputtered excited Al atoms (396.15 nm,

4s
2
S
1,2
3p
2
P

3,2
) as a function of J;
1)
(b) Emission intensity of
sputtered excited Al atoms as a function of
o
. The relation (10) does not
hold above
o
0.8.
12)
0 50 100 150
0
5
10
t (sec)
Y




(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)
Fig. 3. Emission intensity of sputtered excited Al atoms when the
projectile beam was switched on after T = 300 s of exposure of the
target surface in oxygen gas atmosphere of 1.8 10
7
Torr.
2888 J. Phys. Soc. Jpn., Vol. 71, No. 12, December, 2002 R. WADA and S. TSURUBUCHI
well the time transient aspect of the spectral intensities.
Kelly and Kerkdijk analyzed transients intensity variations
in bombardment of Al and Al
2
O
3
surfaces by Ne

with
10 keV energy using a similar equation as (10) but with
b = 0.
2)
Because the time constant of the decaying curve is
given as
t =
1
o(J,e kP
O
2
)
(11)
and kP
O
2
is given from Fig. 2(a), we obtain the cross section
o for an oxygen atom to desorb from the surface upon being
bombarded by an Ar

ion. The obtained o in the present

work is (3.7 0.2) 10
16
cm
2
for the Al polycrystalline
target at the projectile energy of 40 keV. The obtained value
is the mean of 22 times of measurements. In Table I are
listed the results of other works although direct comparison
is rather dicult due to dierent experimental conditions.
In considering the sputtering yield of adsorbed O atoms on
an Al substrate as discussed by Ghose et al.
5,6)
and Lee et
al.,
18)
we have
O
= 0.56 from
O
= oN
s
if the value
N
s
= 1.5 10
15
atoms/cm
2
is used for a polycrystalline Al
target.
2)
5.3 Initial sticking probability s
0
The initial sticking probability s
0
can be estimated from
the relation
s
0
=
oN
s
kP
O
2
2vP
O
2
. (12)
The value of vP
O
2
was estimated by the equation of state for
the ideal gas with T = 288 K. The increase of target
temperature was not recognized with the thermo couple
when the projectile beam was switched on probably due to a
large heat of capacity of the target holder and the chamber.
The result obtained is s
0
= 0.010 0.001. It is surprising
that the value obtained in situ without giving any eect on
the target surface agrees fairly well with those results
obtained by use of STM, AES, XPS, and high resolution
electron energy loss spectroscopy (HREELS) techniques as
shown in Table II.
1921,24)
5.4 A decay mode with a short time constant
It may be worthwhile to point out here that the decay
curve observed in time transient experiments can not be well
expressed by a single exponential function when
approaches 1 as shown in Fig. 4(a). A careful inspection
of the decay curve shows that the curve consists of two
components. A very sharp spike was observed for excited Al
atoms sputtered from the Al target in a transient experiment
at large in addition to a decay curve usually observed with
a large time constant.
If the decay curve with the long time constant is
subtracted from Fig. 4(a), the resultant curve, as shown in
Fig. 4(b), is very similar to the observed curve for an o-type
(11
"
220) Al
2
O
3
surface [Fig. 5(a)] exposed for 300 s in
oxygen-gas atmosphere of 5.3 10
7
Torr. A typical decay
time is about 3.2 s which is much shorter than that of
transient aspect observed for the case of an Al surface at
Table I. Desorption cross sections and sputtering yield for an adsorbed oxygen atom on varous surfaces.
Authors o (cm
2
)
O
A. G. J. de Wit et al.
14)
Ar

(5 keV) Cu(110) 2 10
15
7 10
15
A. G. J. de Wit et al.
14)
Ne

(7 keV) Cu(110) 1 10
15
2.5 10
15
E. Taglauer et al.
16)
He

(1.2 keV) Ni(110) 6 10

17
D. Ghose et al.
5)
Kr

(300 keV) Si(100) 1.2, 0.87

C. S. Lee et al.
18)
Ar

(20 keV) Al(111) 0.20

Present result Ar

(40 keV) Al (3.7 0.2) 10

16
0.56
(polycrystalline)
Table II. Initial sticking probability s
0
of an oxygen atom on Al surfaces.
Authors Experimental methods s
0
H. Brune et al.
20)
STM 0.005
L. O

sterlund et al.
21)
AES (O
2
molecular beam) 0.01
V. Zhukov et al.
24)
XPS, HREELS 0.02
Present result Optical spectroscopy 0.010
0 50 100 150
0
10
20
30
t (sec)
Y




(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
) (a)
(b)
Fig. 4. (a) A decay curve of spectral intensity of sputtered excited Al
atoms from a polycrystalline Al surface in a transient experiment. A sharp
decay with a small time constant is overlapped on the decay curve with a
large time constant. Under a condition of 1.0 10
6
Torr and T = 300 s;
(b) the resultant curve obtained by subtracting the decay curve with a long
decay constant in (a).
J. Phys. Soc. Jpn., Vol. 71, No. 12, December, 2002 R. WADA and S. TSURUBUCHI 2889
small (see Fig. 3). This kind of decay curve with a small
decay constant was also observed for a GaAs (100) surface
as shown in Fig. 5(b). The rapid decay at the initial stage of
beam-on may represent the same feature observed for the
Al
2
O
3
target, which means that the observed decay
component with a short time constant for an Al target can
be interpreted as the detachment process of physically
adsorbed oxygen molecules formed, probably on the
Al

layer or on partially formed Al

2
O
3
because the
feature starts at large . It will be worthwhile to point out
here that the decay curve shown in Fig. 3 does not include
such a curve with a small decay constant.
The constant a in eq. (10) is dened as a =
S
MO
,
i
MO
P
MO
S
M
,
i
M
P
M
. The sign of the constant should
be positive because the observed spikes showed positive
increase when the projectile beam was switched on.
Acknowledgement
The authors thank Dr. T. Nimura for his useful
discussions. This work was carried out under the 21 Century
COE Program on Future Nano-Materials.
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0 50 100 150
0
20
40
60
80
100
t
(sec)
(a)
0 50 100 150
0
1
2
3
4
t
Y






(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)
Y






(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)
(sec)
(b)
Fig. 5. (a) A spike observed for the o-type (11
"
220) Al
2
O
3
surface under a
condition of 4.7 10
7
Torr and T = 300 s; (b) A spike observed for a
GaAs (100) surface at 1.4 10
6
Torr with T = 1200 s.
2890 J. Phys. Soc. Jpn., Vol. 71, No. 12, December, 2002 R. WADA and S. TSURUBUCHI