Thin Solid Films, 42 (1977) 185 191

{~ Elsevier Sequoia S.A., Lausanne

Printed in the Netherlands

185

S P U T T E R I N G OF METALS IN T H E PRESENCE OF REACTIVE GASES

J. HRBEK

Czechoslovak Academy of Sciences, The J. Heyrovsk); Institute of Physical Chemistry and Electrochemistry, Mfichova 7, 12138 Praha 2, Vinohrady (Czechoslovakia)
(Received July 5, 1976; accepted October 15, 1976)

The sputtering yields of Ti, Ta, Mo and W bombarded by Ar ions were

measured in situ by a weight loss measurement as a function of the partial pressure
of reactive gas (02 or N2). The sputtering yields decreased to about 0.4-0.1 of the
initial value in the presence of a reactive gas for every gas-target combination
studied. All the curves were of sigmoidal shape with an inflection point that
depended on the primary ion current density.
The results were interpreted in terms of a monolayer chemisorption of the
reactive gas on the target surface using the assumption that the actual sputtering
yield can be expressed as a linear combination of the sputtering yield of the clean
target and the sputtering yield of the target covered with the adsorbed layer.

1. INTRODUCTION
The effect of gaseous impurities on the preparation of thin films by sputtering
was recognized a long time ago 1'2. More recently Wehner 3 and Yonts and
Harrison 4 found that the sputtering yield for both low and high energy was affected
by oxygen or reactive gas adsorption. In some recent papers the importance of the
physicochemical properties of the gas-target combination during reactive sputtering was discussed 5-12. The interaction between the reactive gas molecules and the
surface atoms of the target is of basic importance with respect to the nature and
mechanism of the sputtering process. This has been taken into account in recently
published models of reactive sputtering 10-12.
The various models of reactive sputtering can be verified by using the data from
experiments in which the deposition rate has been measured as a function of
different parameters, including the partial pressure of reactive gas. These measurements are complicated by the diversity of the interactions of both sputtered and
adsorbed particles with the substrate where the sputtered material is deposited.
Thus the sputtering yield is in general not proportional to the deposition rate 13.
A decrease in the deposition rate as the partial pressure of the reactive gas is
increased has been correlated by various authors with a decrease in sputtering
rate 6'1'12, with plasma characteristics 14 and with different physicochemical
processes on the substrate 15.
During the last fifteen years a large number of experimental data have been
published, and many models of reactive sputtering have been constructed. All these

186

J. HRBEK

models can be classified according to the position at which the interaction between
the reactive gas molecules and the target atoms takes place, e.g. on the target, in the
plasma or at the substrate 16.
Under certain experimental conditions the target surface can be considered as
the most probable interaction site 17. For this site, oxidation l, gettering 11 and
adsorption 12 were suggested as the mechanisms responsible for reactive sputtering.
In these papers the authors studied the changes in deposition rate as a function o f
the partial pressure and o f other parameters measured simultaneously, e.g. the mass
spectrum of the particles sputtered from the surface 1~ or the discharge characteristics ~o.
k

[ro,]
1.0

0.5

I
10

15

10

16

I
10

17

10

18

z(o21 [0~-2 ~~]

Fig. 1. The relative s p u t t e r i n g yield k as a function of the i m p i n g i n g rate Z (cm 2 s ~) of the reactive gas.
The Ti O2 target gas c o m b i n a t i o n was m e a s u r e d at p r i m a r y ion current densities of 250 p A cm 2 ( O )
a n d 30 p A cm -2 ().

15
10

[,e,]

16
10

17

zIN 2) [o-2 -I]

18

10

10

1.0 - -

0.5

--

I
10

15

I
10

16

I
10

17

I
1018

Fig. 2. The e x p e r i m e n t a l values o f the relative s p u t t e r i n g yield k as a function of the i m p i n g i n g rate Z of

the reactive gas for M o - O 2 ( 0 ) and M o N 2 (C)) t a r g e t - g a s c o m b i n a t i o n s . The p r i m a r y ion current
density was 150 laA cm - 2

S P U T T E R I N G OF METALS IN THE PRESENCE OF REACTIVE GASES

187

In the present work the sputtering yields o f T a , Ti, Mo and W were measured as
a function of the partial pressure of reactive gas ( 0 2, N2), and the experimental data
are explained in terms of an adsorption model.
2. EXPERIMENTAL

The experiments were carried out in an all-glass high vacuum apparatus

evacuated by oil diffusion and titanium sublimation pumps to an ultimate pressure
of less than 10 - s Pa. The residual gas, consisting mainly of CO, N 2 and H20, was
checked with a Centronic A I G 50 analytical ion gauge. The sputtering yields were
calculated from the weight losses of the metal targets caused by b o m b a r d m e n t with
Ar ions of energy 2.3 keV. The ion source with oscillating electrons and ion
extraction perpendicular to the electron beam axis was built according to the design
of K o e d a m 18. Secondary electron emission from the target was suppressed by a
combination of magnetic and electrostatic fields. The weight losses were measured
using a quartz spring balance with a sensitivity of 0.005 mg. The targets were
transferred magnetically in v a c u o from the target chamber to the balance or to the
heating cell for outgassing by electron bombardment.
The purity of the reactive gases used in this study was checked with an A I G 50.
The argon used as the inert gas for sputtering was spectroscopically pure. The metal
targets were 0.2-0.5 mm sheets of 99.7 ~o Ti, 99.9 ~o Mo, 99.99 /o Ta and 99.98 /o W.
The standard deviation of the measured sputtering yields was 13 ~ .

[re,]

15
10
I

16
10
I

17
10
I

18
10
I

1.0

0.5

10~5

1016

1017

1018
Z(O 2) [cm-2 s-1]

Fig. 3. The experimental values o f k as a f u n c t i o n o f Z f o r the Ta 0 2 ( 0 ) and T a - N 2 ( O ) target-gas

c o m b i n a t i o n s . The p r i m a r y ion current density was 150 laA cm - z.

3. RESULTS
The relative sputtering yields k (the ratio of the yield in the presence of the
reactive gas to that in the absence of the reactive gas) as a function of the impinging
rate Z of the reactive gas molecules are plotted in Figs. 1-4. The influence of the

188

[,e,]

J. HRBEK

15
10

16
10

17
10

Z(N 2) ~m-2 ~ ]
18
10

1.0

0.5

I
10

15

16
10

1
10

17

I
10

18

Z(O 2 ) ~ m - 2 ~ 1]

Fig. 4. T h e e x p e r i m e n t a l values o f k as a f u n c t i o n o f Z f o r the W 0 2 ( 0 ) a n d W N 2 ( C ) ) t a r g e t gas

combinations. The ~rimaryion current density was 150 ~Acm 2.

oxygen impinging rate on the Ti sputtering yield for primary ion current densities o f
250 laA c m - 2 and 30 ~tA cm 2 is shown in Fig. I. Figures 2, 3 and 4 show k r e r s u s Z
plots for M o O 2 and Mo N 2 target gas combinations, Ta O2 and Ta N 2
target gas combinations and W 02 and W N 2 target gas combinations respectively.
In all target gas combinations the sputtering yield was found to decrease to
about 0.4 0.1 o f the initial value. All the curves have a sigmoidal shape with an
inflection point that shifts to higher pressures when the primary ion current density
is increased.
4. DISCUSSION
With appropriate pressure and temperature conditions the reactive gas can be
chemisorbed onto the metal surface. If a target surface that is covered with a
chemisorbed layer is b o m b a r d e d by ions, the adsorbed particles will be removed
from the surface not only by desorption but also by sputtering.
The sputtered particles originate both from the surface and from the bulk of the
target. Most particles are sputtered from a very thin surface layer ~0. It is evident that
with an increasing surface coverage o f chemisorbed gas the probability that the
adsorbed particles will be sputtered will also increase 2 and simultaneously the
sputtering o f metal particles from the surface will be reduced. Thus the sputtering
yield o f gas-covered metal should be lower than the yield o f the clean metal because
part o f the primary ion energy will be used for sputtering the adsorbed layer. If this is
so, we might expect the metal sputtering yield to depend on the surface coverage, as
shown in Fig. 5.
Let us suppose that the adsorption is governed by the Langmuir isotherm.

SPUTTERING OF METALS IN THE PRESENCE OF REACTIVE GASES

e-o

o<e<l

189

o =1

Fig. 5. Two contributions to the sputtering yield can be distinguished: the surface contribution Fs and
the bulk contributionFa, Whenthe coverageO of the metal surfaceincreases, Fs is reducedand adsorbed
particles are also sputtered from the surface (contribution Fsa).

Using this approximation we can write 21

s Z ( l - O) = FAO

(1)

where s is the sticking probability, Z the impinging rate (cm- z s- 1) of gas molecules
on the surface, O the surface coverage and FA the rate (cm -2 s -1) of removal of
adsorbed particles from the surface.
If the actual sputtering rate Fe is a linear combination of the sputtering rates F1
atO=landF oatO=0weobtain
Fo = r o - ( r o - r O 0

(2)

Using F I / F o = m and F o / F o = k and rearranging eqn. (2) we can write

1-k
O= - 1-m

(3)

By substitution ofeqn. (3) into eqn. (1) we get

k=

sZ
sZ+F g(1-m)

(4)

This equation can readily be compared with the experimental data. The sputtering
yield and the sputtering rate are proportional so that the normalized sputtering
rates k and m can be determined from the measured sputtering yields together with
the values sZ. The value of the removal rate FA is determined from the condition
that k = (m + 1) because then F A = s Z .
As an example, the Ti-O 2 target-gas combination results are plotted together
with the model curve in Fig. 6. The experimental data for the W - O z and W - N z
target-gas combinations could be fitted reasonably well also. The decrease in
sputtering yield for the T a - O / a n d M o - N 2 systems is steeper than predicted by eqn.
(4). In contrast, for the Ta N z and M o - O 2 systems the inflection regions of the
experimental curves are elongated in comparison with the model curve.
The assumptions used for the derivation ofeqn. (1) are not completely fulfilled
in the sputtering process. In the course of the experiment the target is heated owing
to the ion bombardment; furthermore, when the impinging rate of oxygen or
nitrogen on the target is high, the surface coverage can be greater than unity. One of
the assumptions we made was that the surface was homogeneous with respect to
adsorption but this can be made invalid by ion bombardment 22. In spite of evident

190

J. HRBEK

[,e,]
1.0

0.5

15
10

16
10

1
10

17

10

18

Z(O 2) [cm-2 s-11

Fig. 6. The calculated k =./(Z) curves (eqn. (4)) compared with the experimental data for the Ti O z
target--gas combination : - , model: O, 250 gA cm a ; , 30 #A cm - 2.

violation o f the assumptions used in the derivation o f eqn. ( 1), this approximation is
widely used in the surface applications o f secondary ion mass spectroscopy 23, 2,,
The sputtering yield o f adsorbed gas will certainly be a function o f coverage.
Depending on the actual mechanism of adsorption and sputtering we expect that
when gas is adsorbed and sputtered in atomic form the sputtering yield o f the
adsorbed gas will be proportional to the coverage, whereas for atomic adsorption
and molecular sputtering the yield will be proportional to the second power o f the
coverage. F o r the latter mechanism we shall change the assumption o f a linear
c o m b i n a t i o n (eqn. (2)) to
fo = Fo-(fo-ft)O

(5)

and thus

sZ

k = 1-[sZ-+Z

\2
] (1-m)

(6)

This equation is a better approximation than eqn. (4) for the M o - O 2 and T a - N 2
target gas combinations.
F r o m sputtering theory it follows that the sputtered particles originating from
the bulk are characterized by a higher kinetic energy than the particles from the
surface region 19. We m a y thus expect that for the covered surface there will also be
changes in the energy distribution o f the sputtered metal particles. The m a x i m u m in
the energy distribution should be shifted to higher energy values because the
n u m b e r o f metal particles originating at the surface is reduced. So far, however,
there are no direct experimental data confirming this conclusion, but indirect
information concerning the energy spectra o f sputtered ions supports the prediction 2s.
The assumption that we have used concerning the combination of sputtering
rates has been used also in other models o f the reactive sputtering process 1 ~2.

SPUTTERING OF METALS IN THE PRESENCE OF REACTIVE GASES

191

Because there are so many other approximations there is no possibility of

comparison with the experimental data measured by other authors.
5. CONCLUSION

The influence that the partial pressure of the reactive gas exerts on metal
sputtering yields was measured and was interpreted by means of the Langmuir
isotherm using the assumption that the actual sputtering yields can be expressed as a
linear combination of the sputtering yield of the clean target and the sputtering yield
of the target covered with an adsorbed layer. Direct measurement of the sputtering
yields of the metal enabled us to exclude uncertainties about the nature of the
interaction of the substrate with the incoming particles.
The reactive sputtering mechanism is controlled simultaneously by the
adsorption-sputtering mechanism of the reactive gas adsorbed, by changes in the
surface binding energy due to adsorption and finally by collision mechanics.
ACKNOWLEDGMENTS

The author gratefully acknowledges the helpful comments made by Drs. (~.
Jech and Z. Knor.
REFERENCES
1 C.J. Corbek, J. Opt. Soc. Am., 23 (1933) 109.
2 H. Koenig and L. Heisinger, Festschrift Hereaus Platinschmelze, Hereaus Platinschmelze, Hanau,
1947, p. 202.
3 G.K. Wehner, Phys. Rev., 108 (1957) 35.
4 O.C. Yonts and D. E. Harrison, J. Appl. Phys., 31 (1960) 1583.
5 R.E. Jones, H. F. Winters and L. I. Maissel, J. Vac. Sci. Technol., 5 (1967) 84.
6 E. Hollands and D. S. Campbell, J. Mater. Sci., 3 (1968) 544.
7 H.F. Winters, J. Vac. Sci. Technol., 8 (1971) 17.
8 M. Cantagrel and M. Marchal, J. Mater. Sci., 8 (1973) 1711.
9 M. Bernheim and G. Slodzian, Int. J. Mass Spectrom. Ion Phys., 12 (1973) 93.
10 J. Heller, Thin Solid Films, 17(1973) 163.
11 F. ShinokiandA. Itoh, J. Appl. Phys.~46(1975)3381.
12 T. Abe and T. Yamashina, Thin Solid Films, 30 (1975) 19.
13 R.E. Jones, C. L. Standley and L. I. Maissel, J. Appl. Phys., 38 (1967) 4656.
14 J.B. Llounsburry, J. Vac. Sci. Technol., 6 (1969) 838.
15 H.F. Winters, D. L. Raimondi and D. E. Horne, J. Appl. Phys., 40 (1969) 2996.
16 L. Holland and G. Siddall, Vacuum, 4 (1953) 375.
17 L.I. Maissel, in L. I. Maissel and R. Glang (eds.), Handbook of Thin Film Technology, McGrawHill, New York, 1970, Chap. 4.
18 M. Koedam, Philips Res. Rep., 16 (1961) 101.
19 P. Sigmund, Phys. Rev., 184 (1969) 383.
20 H.F. Winters and P. Sigmund, J. Appl. Phys., 45 (1974) 4760.
21 D.O. Hayward and B. M. W. Trapnell, Chemisorption, 2nd edn., Butterworths, London, 1964.
22 R.S. Gvosdover, V. M. Efremenkova, L. B. Shelyakin and V. E. Yurasova, Radiat. Effects, 27
(1976) 237.
23 A. Benninghoven, Surf. Sci., 35 (1973) 427.
24 G. Blaise and M. Bernheim, Surf. Sci., 47 (1975) 324.
25 T. Ishitani, H. Tamura and T. Shinmiyo, Surf. Sci., 55 (1976) 179.