Applied Surface Science 27 (1986) 355-365

North-Holland, Amsterdam

355

P R E F E R E N T I A L S P U T T E R I N G OF OXIDES: A C O M P A R I S O N
O F M O D E L P R E D I C T I O N S W I T H E X P E R I M E N T A L DATA
J.B. M A L H E R B E
Department of Physics, University of Pretoria, Pretoria 0002, Rep. of South Africa

S. H O F M A N N and J.M. SANZ *

Max-Planck-lnstitut ffir Metallforschung~ Institut fffr Werkstoffwissenschaften, Seestrasse 92, D-7000
Stuttgart 1, Fed. Rep. of Germany
Received 10 April 1986; accepted for publication 25 July 1986

Experimental data on the composition of the altered layer of some oxides bombarded with
noble gas ions are compared with different model predictions based on Sigrnund's sputtering
theory. It is shown that although the difference in mass of the metal atoms is the dominant factor
in the preferential sputtering of oxygen, the additional consideration of the surface binding
energies yields an improved agreement between theory and experiment.

I. Introduction

Although the phenomenon of sputtering is a highly complex one there is

consensus that the two main mechanisms which lead to preferential sputtering
in multicomponent targets are surface binding effects and mass difference
effects [1]. It is obvious that in certain cases only one of these mechanisms will
dominate. In the much studied C u - N i system the masses are so close to each
other that preferential sputtering can be ascribed as being mainly due to
surface binding effects. On the other hand, in the collision cascade regime, the
difference in energy and m o m e n t u m sharing between the components of
different masses will enhance sputtering of the lighter component [2]. It is,
therefore, not surprising that models have been proposed that describe preferential sputtering in terms of only one of these two mechanisms.
The aim of this paper is to propose a model which incorporates both effects
and leads to a better understanding of recent experimental results on the
preferential sputtering of anodic oxides [3-6] which were obtained by m e m bers of our group. Recently Betz and Wehner [7] summarised some of the
results reported in the literature. We also used data from their paper to
compare with the model predictions.
* Permanent address: Departamento Fisica Applicada, Universidad Autonoma, Madrid, Spain.

0378-5963/86/$03.50 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)

J.B. Malherbe et al. / Preferential sputtering of oxides

356

2. Discussion of model predictions

For a binary alloy or compound (e.g. an oxide) several authors have
developed simple models for preferential sputtering [8-10]. In the steady state,
the ratio of the surface fractional composition X,s of a metallic oxide to a bulk
fractional composition Xi b i s given by

where Y~ represents the component sputter yield [7] of the metal (M) or of the
oxygen (O).
From Sigmund's sputtering theory in the linear cascade regime [2] it follows
that the ratio of the component sputter yields can be approximated by

Yo- (AM/2m( UMI 2m

rM

Ao]

\Uo]

'

(2)

where A, and U, denote the atomic mass and surface binding energy respectively. Substitution of (2) into (1) yields

The exact value of the parameter m is uncertain since m depends on the

energy. The origin of the m in eqs. (2) and (3) comes from the particular form
of the power cross-section that Sigmund used in his theory. For this cross-section, m = 1 at high energies (Rutherford scattering) while for medium energies
(10-100 keV), m = 0.5 and for lower energies, 0 ~< m ~< 0.5. The energy of the
bombarding atoms which result in the sputtering of other atoms is usually
small. Therefore, for applications in sputtering, the relevant values for m
should lie in the range 0 ~< m ~< 0.2 [2,7].
In a recent XPS study [3] the composition of the altered surface layer in the
steady state at 3 keV Ar + ion b o m b a r d m e n t was determined for the anodic
oxides Ta 205, Nb205, H f O 2, ZrO 2, TiO 2 and A1203 . The results of ref. [3] are
summarized in table 1. An important feature is that the thickness d of the
distorted layer of ZrO 2 is appreciably smaller than that of the other oxides. If
the oxygen loss of ZrO 2 is corrected for a similar sample volume as for the
other oxides, i.e. d = 2.2 nm, then the oxygen loss would be 19%.
These results and some others on oxides are discussed in the framework of
some current sputtering theories. The data considered were obtained from refs.
[3-6,7,11].
2.1. Influence of atomic mass
To apply eq. (3) to the results obtained on oxides, we first limit ourselves to
the mass differences effect which is equivalent to setting U M = Uo in eq. (3).

J.B. Malherbe et al. / Preferentialsputtering of oxides

357

Table l
Composition and thickness d of the oxygen depletion layer of the different oxides after sputtering
with 3 keV Ar + ions in the steady state region
Oxide

Decomposition
to

A1203
TiO2
ZrO 2

.
.
TizO + TiO
ZrO + Zr
(ZrO + Zr + ZrO 2)
HfO + Hf
NbO2 + NbO
TaO 2 + TaO + Ta

HfO2
Nb205
TaeO5

Surface layer
composition
(mole fraction)

Oxygen
loss
(at%)

Surface layer
thickness d
(nm)

.
X~i = 0.43
X~r = 0.62
(0.53)
X~r = 0.62
X~b = 0.47
S ~ a = 0.50

10
29
(19)
29
18
21

1.8 _+0.6
1.3 + 0.5
(2.2)
2.0 _+0.6
2.2+0.7
2.5 + 0.7

With this condition and 2m = 0.25, eq. (3) fortuitously corresponds to an

equation derived b y H a f t [12] assuming equipartition of the beam energy and
radiation induced diffusion. It must be born in mind that this correspondence
is fortuitous because a basic assumption in Sigmund's theory [2] is nonequipartition of energy. The results are shown in fig. 1, where the experimentally determined ratio of surface atomic fraction ( X ~ / X o ) s normalized to the
respective bulk ratio ( X M / X 0 ) b for the different oxides is plotted against the
one calculated after eq. (3). However, from the figure it follows that this value
for m does not really give a significant fit between the experimental and
calculated values.
Recently H o f m a n n and Sanz [4] fitted their data to eq. (3) for the case
2m = 0.5 and U M = Uo. Since they obtained a reasonable fit, they concluded
that the effect of surface binding energies is of secondary importance compared to the mass ratio factor.
This latter value of 2m = 0.5 also represents a special case of the equation
derived by Sigmund [2] when sputtering proceeds under spike conditions, viz.

Xo ] = ( X o ]

exp~

).

(4)

It has been p r o p o s e d [13,14] that the p r e p o n d e r a n t sputtering process of

insulating oxides might be a thermal spike mechanism rather than a colhsion
cascade process. I n order to use Sigmund's equation (4) for spike sputtering,
the value of the localized temperature T of the spike region is needed. Various
estimates of T have been made. Sigmund [2] approximated the spike region as
an ideal gas at a local temperature T defined by 3 k T = 0. The energy density 0
depends on the projectile mass and energy and the target mass and density.
F r o m fig. 2.20 in ref. [2] it can be seen that typically 0 >/1 eV for 3 keV argon
sputtering. This leads to rather high temperatures and pressures which might
even induce shock waves. Kelly [13,14] proposes more modest temperatures in

J.B. Malherbe et al. / Preferential sputtering of oxides

358

2m =0.25

I v20~
2 MnO
3 BeO
4. ZnO
5 MgO
6 GazO 3
7 CrzO3/VO / V203
8 MoO3
g Sn02
10 FeO/Fe304/Fe20

c~

11

UM= Uo

HfO~

ZrO~
q

':d=13nm)

Ta2Ost

Co304

ZI.02I
(d=22nm) I Nb20,

2
0

X
i

0.5 ~
0.5

,11

1
1

L
1.5

[(XM/Xo)

s / (XM/Xo)

b] calc

Fig. 1. The experimentally determined surface composition ratios of the altered sputtered layers

[( XM/Xo)S/( XM/Xo)b]exp are plotted against the predicted ratios [( X M / X o ) S / (

XM/Xo)b]calc

as calculated from eq. (3) when only mass effects are taken into account, i.e. when UM ~- Uo for
2rn = 0.25.

the range 3500 to 4500 K (i.e. 0.3 < k T (eV) < 0.4). He explains the preferential sputtering of oxides in terms of the stability and decomposition of the
various oxides at these temperatures.
In eq. (4), the surface composition ratio of the sputtering surface depends
exponentially on the surface binding energies. Thus, a relatively small difference in the individual values taken may make a tremendously large difference in the predicted composition ratio.
However, it is unlikely that spike sputtering is the dominant process during
the sputtering of oxides. A better fit between theory (i.e. eq. (3) or (4)) and

J.B. Malherbe et aL / Preferential sputtering of oxides

359

experiment is obtained for a value of the factor 2m other than 0.5 which is the
value applicable to spike sputtering (see section 2.3).

2.2. Consideration of surface binding energies

The choice of the surface binding energies in eqs. (2)-(4) is a notoriously
difficult one due to the lack of reliable experimental data. This problem is
greatly enhanced in the case of poly-atomic compounds which do not sputter
stoichiometrically in molecular fragments. The best one can hope for in this
case is to obtain a reasonable approximation to the real energies.
To calculate the binding energies of the oxygen and metal atoms we
propose a simple model based on a gross modification of the Pauling formalism [15] for the bond energies in a covalent bond. In the Pauling formalism
the average covalent bond energy of a di-atomic oxide molecule is the
arithmetic mean of the m e t a l - m e t a l and oxygen molecule bond energies. To
account for the polarity or ionic character of the bond Pauling included
another term in the equation, viz. the difference in electronegativities e. In our
extention of this formalism to a molecule MxOy, the average bond energy is
given by
D(M~0y)=

x+y

D(M-M)+

x+y

D(0-0)+

x+y

D(M-O)

o)2,
where D ( M - M ) denotes the m e t a l - m e t a l bond energy, D ( O - O ) the dissociation energy of the oxygen molecule and D ( M - O ) the m e t a l - o x y g e n bond
energy of the di-atomic oxide MO. The mean energy required to remove only
an oxygen atom from this molecule will, to a zeroth order, exclude the
m e t a l - m e t a l bond energy term and will, therefore, be given by

Uo=

x+yXD(M-O) + x+yYD(O-O) + (

M-

2.

(5)

The bond energies in eq. (5) were obtained from ref. [16] while the electronegativities e were obtained from ref. [17].
In the case of TiO 2, BeO, MgO and ZrO 2 the dissociation energy required
to remove a single oxygen atom from the oxide molecule is tabulated by
Samsonov [18]. Therefore, for these oxides the tabulated values were taken.
In the case of binary alloys the surface binding energy U M of a metal atom
is usually taken to be equal to the sublimation energy H s of the metal [19]. In
this case of oxides the value for the surface binding energy must be modified
to account for the effect of the chemical binding energy between the metal and
oxygen atoms. Once again an approach similar to the Pauling scheme using

360

J.B. Malherbe et al. / Preferential sputtering of oxides

electronegativities [15] was used, viz.

UM ------Hs + (~M -- Co) 2"

(6)

In table 2 the values used to approximate the surface binding energies of the
metals as well as the oxygen are summarized.
For the case when mass difference effects are ignored, i.e. A M = A o, Blaise
[20] used an equation which is equivalent to setting 2m = 0 in eq. (3). It is,
however, obvious that for most of the oxides considered in this paper, the
mass difference effects cannot be ignored. This view is supported by the
results presented in fig. 2.
2.3. Combined mass and binding energy effects
In fig. 3 the results are shown for the case when both the mass difference
and surface binding effects according to Sigmund's theory of sputtering in the
linear cascade regime (eq. (3)) are included. The exponent parameter 2m = 0.33
(i.e. m = 0.165) was chosen in accordance with the range suggested in the
li.terature [2,7] and since it gives a satisfactory fit to the experimental results of
table 1.
The case of BeO, MgO and A1203 are particularly interesting since the
atomic masses of these metals are comparable to that of the oxygen atom. In
table 2 the model calculations according to eqs. (3), (5) and (6) show a
considerable enrichment of oxygen during ion b o m b a r d m e n t in the cases of
BeO and MgO. In ref. [18] the dissociation energies required to remove a
single oxygen atom from certain oxide molecules are tabulated. If these values
for BeO and MgO are taken for Uo in eq. (3) the calculated values show only a
slight enrichment of oxygen during ion bombardment. However, as pointed
out by Taglauer and Heiland [21] this enrichment probably could result in
spontaneous desorption of oxygen. Whereas no reduction effects have been
published for MgO, a light reduction of BeO has been observed [21] with AES
(where electron induced desorption can occur).
In the case of A1203 the model calculation according to eq. (5) and the
tabulated energy in Samsonov [18] give nearly the same value for the oxygen
binding energy term Uo. From table 2 it can be seen that the predicted values
are in excellent agreement with the measured value. However, in the cases of
ZrO 2 and TiO 2 better agreement between theory and experiment is obtained if
the tabulated oxygen dissociation energy is taken. Unfortunately, Samsonov
[18] lists these energies only for a few oxides.
Cr203 and Ga203 have been reported as non-reducible by ion b o m b a r d ment [22-24], which is in contrast to the prediction of 25% oxygen loss. It is
interesting to note that the lack of suboxides in both systems requires detailed
and quantitative measurements because changes in the shape of AES or XPS
peaks may not be observable.

J.B. Malherbe et al. / Preferential sputtering of oxides

361

Table 2
A compilation of the experimentally determined composition of the altered layer of different
oxides (from refs. [3-7,11] and the parameters used in the calculations
Molecule

BeO
BeO
MgO
MgO
A1203
A1203
SiO 2
TiO 2
TiOe
VO
V203
V205
Cr203
MnO2
FeO
Fe304
Fe203
CO304
ZnO
Ga203
ZrO2
ZrO 2
Nb205
MoO3
SnO 2
HfO 2
Ta205

AMa)

Se b>

EN c)

D(M-O)

Surface BE d)

(XM/Xo)S/(XM/Xo)b

(amu)

D(M-M)
(eV)

e
(eV)

(eV)

UM
(eV)

Uo
(eV)

Calc.

Exp.

9.01
9.01
24.31
24.31
26.98
26.98
28.09
47.90
47.90
50.94
50.94
50.94
52.00
54.94
55.85
55.85
55.85
58.93
65.37
69.72
91.22
91.22
92.91
95.94
118.69
178.49
180.95

3.39
3.39
1.53
1.53
3.39
3.39
4.70
4.89
4.89
5.34
5.34
5.34
4.12
2.91
4.34
4.34
4.34
4.43
1.35
2.82
6.34
6.34
7.49
6.89
3.12
6.31
8.11

1.47
1.47
1.23
1.23
1.47
1.47
1.74
1.32
1.32
1.45
1.45
1.45
1.56
1.60
1.64
1.64
1.64
1.70
1.66
1.82
1.22
1.22
1.23
1.30
1.72
1.23
1.33

4.24
0.00
4.17
0.00
4.64
0.00
8.16
7.28
0.00
6.47
6.47
6.47
4.43
4.21
4.30
4.30
4.30
3.79
2.86
3.04
7.89
0.00
7.03
5.08
5.43
7.64
8.59

5.45
5.45
4.11
4.11
5.45
5.45
6.25
7.27
7.27
7.44
7.44
7.44
6.00
4.71
6.07
6.07
6.07
6.05
3.04
4.23
8.94
8.94
10.07
9.31
4.70
8.89
10.46

6.76
4.66*
7.24
4.43*
7.01
7.07"
7.71
8.24
6.68*
7.92
7.79
7.64
6.75
6.65
6.46
6.52
6.55
6.19
5.70
5.72
8.67
7.20"
8.27
7.56
6.83
8.56
8.49

0.72
0.92
0.79
1.09
1.00
1.00
1.05
1.32
1.52
1.41
1.42
1.44
1.36
1.19
1.45
1.44
1.44
1.51
1.04
1.33
1.81
2.05
2.04
2.08
1.51
2.27
2.56

1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.50
1.50
1.00
1.00
1.67
1.00
1.34
1.05
1.05
1.05
1.33
1.00
1.00
2.26
2.26
2.22
1.50
1.00
3.26
2.50

The heats of sublimation of the metals were obtained from refs. [26,27] and the binding energies
D ( M - O ) of the di-atornic molecule MO were obtained from spectroscopic or mass spectrometric
data summarised in ref. [16]. The values indicated by an asterisk are the tabulated [18] dissociation
energy required to remove a single oxygen atom from the oxide molecule. The binding energy
D ( O - O ) of the oxygen molecule was taken to be equal to 5.16 eV. The electronegativities were
obtained from Luder [17] and the value 3.50 eV was used for oxygen.
AM := atomic mass.
b) SE = sublimation energy.
~') EN = electronegativity.
a) BE = binding energy.
a)

Although the reduction of oxides by ion bombardment was extensively

studied in recent years (see ref. [7], and references therein) in most cases only
qualitative statements have been published. Some of these results have been

J.B. Malherbe et al. / Preferential sputtering of oxides

362

AM =

I v2os
2 MnO2
3 BeO

Ao

2m =0

, ot2 ]

ZnO
5
6
7
8
9
10
11

MgO
Ga2Os
Cr203
VO
SnOz
FeO
Co30,
12 MoO3
Fe30~/Fe20~
14 V~O~

Q.

I//~d:z2nm
".0,il'r0
Ta,O~

13

2,

(d =13nm

1~i02~
J lle I

.12

~S8

0.5
[(XM/Xo)S

15

/ ( X M / X o ) b] calc

Fig. 2. The experimentally determined surface composition ratios [(XM/X0)S/(XM/Xo)b]exp a r e

plotted against the predicted ratios [ X M / X o ) S / ( X M / X o ) b ] c a l c using eq. (3) with the approximation A M ~- A o and 2 m = 0.

collected in table 3 for comparison with the predictions using eq. (3).
Results from Naguib and Kelly [25] for different oxides by high energy ion
bombardment (40 keV) and by using electron microscopy for analysis are also
included in table 3. However, it is felt that this type of study is not
representative because generally a mixture of different phases occurs which are
not distinguishable by electron diffraction.

363

J.B. Malherbe et al. / Preferential sputtering of oxides

2m = 0.33

I v20s

MnOz
3 BeO
4 ZnO
5 MgO
6 OazO 3
7 CrzO3
8 VO / V203
9 Sn02
I0 FeO/Fe30~ /Fez03
2

CL
X

to
o
X

,,o,

11 Co30,
12

MoO3

Nb20s

X
cO

le

o
X

12

2,//" 'Jll

AI20,1.,~5,

L------.J

Io

6"Tt;e 9

'SiO,

[(XM/Xo) s / (XM/Xo)b]

3
calc

Fig. 3. The experimentallydetermined surface composition ratios [( XM/Xo)S/( XM/Xo)b]exp are

plotted against the predicted ratio [(XM/Xo)S/(XM/Xo)b]ceac using eq. (3) with 2rn = 1/3 and
taking into account both mass ant1 surface binding energy effects.
A comparison with the model predictions (5) and (6) as given in table 3 and
fig. 3 can be made to the qualitative "spike" model by Kelly [13,14]. Such a
comparison reveals that the present predictions, not only being quantitative,
result also in more correct qualitative predictions than Kelly's model.
The pair-binding model [28,29] has also been used to calculate the surface
binding energies in a theoretical treatment of alloy preferential sputtering [30].
Assuming the applicability of this model to oxide sputtering, it states that the

364

J.B. Malherbe et al. / Preferential sputtering of oxides

Table 3
Comparison between predicted and qualitative observed composition changes of oxides by noble
gas ion bombardment (adapted from Betz and Wehner [7])
Oxide

Prediction
eq. (3)
2m =0.33

Observations

TiO
Ti203
CoO
C0203
NiO
Ni 203
Cu20
CuO
GeO2
NbO
NbO 2
RuO2
Ag20

Ti enrichment (AES)
No reduction (400 eV Ar + )
Co enrichment
CoO mainly
Ni enrichment (400 eV Ar + )/no reduction (3 keV Ar + )
Ni enrichment (400 eV Ar ~ )
Cu enrichment (XPS)/light O enrichment (AES)
Cu enrichment

SnO
WO2
WO3
PbO

Ti302
TiOH5
C000.65
CoO
NIO0.65
NiO
Cu00.36
CuO0.73
Oe203
Nb20
NbO
RuOo.86
Ag40
AgOo89
Sn302
WOo.72
WO
PbOo,61

PbO2

PbO1.24

Bi 203

BiOosv

Ag 203

Nb enrichment
Nb enrichment
Ru enrichment (400 eV Ar +, XPS)
Ag enrichment (400 eV Ar +, XPS)
Ag enrichment (400 eV Ar +, XPS)
W enrichment (400 eV Ar +, XPS)
WO2 + W (400 eV Ar +, XPS)/W enrichment
Pb enrichment (400 eV Ar +, XPS)/no reduction
Pb enrichment (400 eV Ar +, XPS)
Bi enrichment

ratio of the surface b i n d i n g energies is given by

VM
Vo

X ,D(M-M) + Xo D(M-O)
X D(M-O) + x b D ( o - o )

W h e n the di-atomic b o n d energies in table 2 were used to calculate this

U M / U o ratio and, after s u b s t i t u t i o n in eq. (3), the theoretical predictions were
c o m p a r e d to the experimental results, the c o r r e s p o n d e n c e was n o t as good as
w h e n using the model given by eqs. (5) a n d (6).
At present a more thorough test of the proposed model is precluded by the
lack of reliable data o n the oxygen loss a n d the depletion layer thickness.

3. Conclusions
The preferential sputtering of the oxides considered in this paper can be
q u a n t i t a t i v e l y explained to a reasonable degree of accuracy b y using S i g m u n d ' s
e q u a t i o n for cascade sputtering. It is shown that the p r e p o n d e r a n t effect for
the preferential sputtering is the difference in mass b e t w e e n the metal a n d

J.B. Malherbe et al. / Preferential sputtering of oxides

365

oxygen atoms. However, a better agreement between theory and experimental

v a l u e s is o b t a i n e d i f t h e e f f e c t o f s u r f a c e b i n d i n g e n e r g i e s is i n c l u d e d . T h e s e
energies were calculated using a rather simple model based on Pauling's
scheme with electronegativities for the calculation of covalent bond energies.
F r o m t h e r e s u l t s a n d d i s c u s s i o n it a l s o f o l l o w s t h a t f o r a q u a n t i t a t i v e t h e o r y
o n p r e f e r e n t i a l s p u t t e r i n g it is i m p e r a t i v e t o h a v e v e r y r e l i a b l e q u a n t i t a t i v e
composition analysis data.

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[5] J.M. Sanz, PhD Thesis, Stuttgart University (1982).
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