Surface Science 218 (1989) 331-345 331

North-Holland, Amsterdam

AN XI’S STUDY OF THE INTERAC’IION OF OXYGEN

WITH ZIRCONIUM

C. MORANT, J.M. SANZ, L. GALAN, L. SORIANO and F. RUEDA

Departamenio de fisica Aplicada, C-XII, Universidad Authoma de Madrid
Cantobbnco, E-28049 Madrid Spain

Received 9 January 1989; accepted for publication 4 April 1989

XPS has been used to study the initial stages of the oxidation of polycrystahine Zr at room
temperature and low oxygen pressures (PO, I 10m8 Torr). The results indicate that at exposures
< 0.6 L oxygen atoms adsorb on the surface of zirconium without formation of oxidelike bonds.
Upon further oxygen exposure the initial oxygen chemisorption leads to the formation of ZrO,
and different suboxides which remain at the Zr/ZrO, interface, while ZrOr grows continuously as
oxidation proceeds. Analysis of the spectra suggests the presence of four oxidation states of Zr
shifted about 1.1 eV per metal-oxygen bond. At lo3 L the oxide layer was estimated to be 1.6 nm
thick and ZrO,,, of average composition. Analysis of the 01s signal enabled us to distinguish
between oxidic and adsorbed oxygen, the last one being present in amounts close to the
monolayer.

1. Introduction

It is well known that the initial oxide layer which forms on any metal
surface influences the later oxidation kinetics. Thus, the knowledge of the
oxide forming at the surface of any metal exposed to oxygen is of great
importance not only from the technological point of view, but also in order to
understand the mechanisms of metal oxidation [l-3].
Although the oxidation of zirconium has been the subject of a large number
of studies employing surface-sensitive techniques [4-171, it appears that the
question about the oxidation state of zirconium and whether suboxide forma-
tion occurs during the earliest stages of the oxidation process requires further
study.
Auger electron spectroscopy (AES) studies [4,8,10,12,13] have shown that
the oxidation of zirconium at room temperature starts with dissociative
chemisorption of oxygen at exposures lower than l-2 L, (1 L = low6 Torr . s),
and follows with the formation and growth until coalescence of oxide nuclei
for exposures up to 60-100 L. Thickening of the oxide film is the final step. A
limiting thickness of 1.5-2 nm at room temperature has been estimated
[5,12,15].

0039-6028/89/$03.50 0 Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
332 C. Mot-ant et aI. / XPS study ofinteraction of oxygen with zirconium

Although changes in the shape of the Auger lines of zirconium have been
observed [10,12,15] and interpreted as due to oxide formation, a more direct
evidence of the presence of different suboxides should be gained from XPS
studies. Tapping [5] observed the broadening of the Zr3d doublet during
exposure to oxygen. The line was not analyzed in detail, and only ZrOz was
identified. Valyukhov et al. [6] using XPS and SIMS also identified only Zr4+
species. However, Sen et al, [8] using XPS and AES have reported the
formation of a suboxide labelled ZrO at oxygen exposures c 25 L. At
exposures < 10 L it appears that the oxidation state of zirconium increases
continuously until ZrO is formed. At exposures > 25 L ZrO, was detected.
Using electron energy loss spectroscopy (EELS), Corallo et al. [14] studied 40
L oxygen-exposed polycrystalline zirconium varying the primary electron
beam energy in order to alter the depth sensitivity of the technique. To explain
their results they proposed the presence of suboxides such as ZrO, Zr203, and
other nonstoichiometric oxides as well as that the oxidation state of zirconium
increased with depth. More recently, two XPS studies on the room tempera-
ture oxidation of zirconium [15,16] claiming the formation of two suboxides
during the first stages of the oxidation process, have been published, However,
they show important discrepancies in the assignment and the kinetics of
formation.
The present study reports a detailed and qu~titative analysis of the Zr3d
and 0 1s XPS spectra as a function of the oxygen exposure in order to monitor
the oxidation state of zirconium and the thickness and composition of the
corresponding oxide film. It is shown that initial chemisorption of oxygen
leads to the development of different suboxides as well as ZrO, at exposures
between 0.6 and 2 L. At higher exposures, ZrO, grows at the oxide/gas
interface whereas the suboxides remain mainly at the metal/oxide interface.
At exposures > 100 L, the saturation is reached and a limiting thickness of the
oxide overlayer of = 1.6 nm is estimated. The results also show that about a
monolayer of adsorbed oxygen 0, (i.e. not in the oxide state) is always
present during the oxidation process.

2. ExperhnentaI

Polycrystalline zirconium of 99.7% nominal purity (Goodfellow Metals) and

25 pm thick was used throughout this work. The sample was degreased in
acetone and alcohol, immersed in deionized water, and dried before introduc-
tion into the spectrometer. The foil was then annealed at about 1000 K for 5
min in vacuum (residual pressure +zlo-” Torr). XPS spectra taken after
annealing showed a clean surface with only very small amounts of sulfur
which could easily be removed by Arf sputtering. Exposures to oxygen were
then performed by introducing high purity oxygen through a leak valve at low
 C. Morant et al. / XPS stu& of interaction of oxygen with zirconium 333

pressures and keeping the sample at room temperature. For reference, ZIG,
was prepared by annealing a Zr foil at 475 K in an oxygen atmosphere
(Po, = 10m5 Torr). Surface characterization was performed in a LHS 10 ESCA
spectrometer (Leybold-Heraeus) using a non-monochromatized Mg Ka X-ray
source. The analyzer was operated in the constant pass energy mode ( Epass= 20
ev). This corresponds to a Gaussian resolution function of FWHM = 0.25 eV.
Photoelectrons were collected normal to the sample.

3. Results and discussion

Fig. la shows the raw data for the Zr 3d XPS line after different exposures
to oxygen. The spectra correspond to clean metal (0 L) and to five different
oxygen exposures at room temperature. A spectrum of ZIG, obtained after
6000 L of oxygen exposure at 475 K is included as reference. The different
oxygen exposures were strategically chosen according to the three different
stages, experimentally observed [12] in the oxidation kinetics of zirconium. As
the oxygen exposure is increased, the spectra broaden and exhibit new features
on the high binding energy side of the line.
The spectra of fig. la were used after numerical processing, to determine
the chemical composition and thickness of the films. They were smoothed by a
quadratic least-squares fitting method [18,19] with an energy interval accord-
ing to the spectrometer resolution so that no real structure would be lost
[19,20]. A smooth background was then subtracted taking into account both
secondary electrons and energy losses [21,22]. Difference spectra were then
generated by removing the corresponding contribution of the clean metal from
the spectra of the partially oxidized samples. The results are shown in fig. lb.
It is interesting to observe that at oxygen exposures Q 0.6 L the spectrum
remains essentially unchanged compared to the metal except for its intensity
which decreases as oxygen is adsorbed. At higher exposures (> 2 L) the
characteristic peaks of the metal are continuously attenuated, and new features
due to zirconium oxides start to grow at higher binding energies. The presence
of Zr4+ (i.e. ZrG,) as well as other suboxide species can be easily corroborated
comparing with the spectrum of ZrOz. However, the identification and quanti-
fication of the different oxidation states require a more detailed analysis of the
spectra and the use of fitting procedures.
The number of shifted core levels to be used in the fitting procedure
appears to be ambiguous. However, as no satisfactory fitting could be ob-
tained with two or three oxidation states, the difference spectra were analyzed
in terms of four oxidation states shifted 1.06 eV per oxidation state with
respect to the metal (i.e. one forth of the energy difference observed between
Zr4+ and Zr’). The use of four oxidation states equally spaced in energy was
firstly suggested by spectra as that shown in fig. 2 where the experimental
334 C. Morant et al. / XPS stdy ofinteraction ofoxygen with zirconium

b)

0 L

0.6 L

2.1 L
-. -..,\_
_-’
_..--
..-

,._ I*

11.5 L -- ‘-I_ --

122 L

1185 L

6000 L
475 K
,.
,.....m -
j i_._ . /I /
1 4 I I 1 I I 1
190 180 190 180

BINDING ENERGY [ev)

Fig. 1. XPS spectra of the Zr 3d line for various oxygen exposures at room temperature. The 6000
L spectrum was obtained at 475 K. (a) Raw experimental data; (b) after subtraction, smoothing,
and removal of the contribution of metallic Zr.

spectrum at 1185 L is shown after removal of the Zr 3d,,, component of each

Zr 3d 5,.2,+2 doublet. The subtraction was done according to a spin-orbit
multiphcxty ratio of 2/3 and an energy separation of 2.39 eV due to spin-orbit
splitting. Furthermore, whereas the four oxidation states Zr4+, Zr3+, Zr’+,
 C. Morant et al. / XPS sttu& of interaction of oxygen with zirconium 335

BlNDlNG ENERGY (eV)

Fig. 2. XPS Zr3d,,, spectrum of zirconium exposed to 1185 L of oxygen after removal of the
3d3,2 spin-orbit component.Equally spaced oxidation states of zirconiumare indicated.

Zr+ are well established in Zr halides [23] au energy shift of about 1.1 eV per
metal-oxygen bond would explain the suboxide structure observed by other
authors at 1 and 2 eV [16], 1.2 and 3.3 eV [17], 2 eV [8] and 1 eV [24] with
respect to the metal peaks. Approximately equally shifted integral oxidation
states have also been observed by XPS in many other thin oxide layers
[25--281. In fact the valence charge transfer (ionization energy) and the
crystalline field (Madelung energy) contributions to the chemical shift are
expected to be approximately proportional to ionic&y or oxidation state
[29,30].
On the other hand, n in Zr”+ just refers to a formal oxidation state and not
to the actual charge transfer and is an indication of the local coordination of
the metal. Thus, the four proposed oxidation states of Zr at the metal/oxide
interface would correspond to the four possible coordinations of Zr with the
oxygen atoms (i.e. ZrO,, Zr,O,, ZrO and Zr,O).
The lineshape of the individual peaks was assumed to be the same for all
the oxidation states and determined by a least-squares fit of the ZrO,
spectrum. The result was a mixed Gaussian-Lorentzian curve of FWHM = 1.80
eV which corresponds to the convolution of a Lorentzian of FWHM = 1.08 eV
with a Gaussian of FWHM = 1.25 eV. These values represent a broadening of
about 0.4 eV due to the hole lifetime and a Gaussian broadening of 1.22 eV
induced by phonons and structural effects. The energy and intensity of the
Zr4+ 3d line and the respective intensities of the other species (i.e. Zr3+, Zrzt
336 C. Morant et al. / XPS study of interaction of oxygen with zirconium

I !
190 185 180 1 i
BINDING ENERGY (eV)

Fig. 3. Normalized XPS Zr 3d difference spectra of fig. lb. Continuous line: experimental spectra
of fig. lb. Dotted line: least-squares analysis in terms of four different oxidation states and a
satellite. Dashed line: least-squares synthesis.
 C. Moranf ef al. / XPS study of interactionof oxygen withzirconium 337

Table 1
Best-fit parameters for Zr3d XS spectra (cf. fig. 3)

Binding energy of metal Zr 3d,,, 178.52

Binding energy of oxide Zr4+ 3d,,, 182.75

Metal-oxide chemical shift 4.23

Spin-orbit splitting 2.39

Shape and width of metal peaks:

width 0.7
Doniach-Sunjic
asymmetry ( 4 0.1
Gaussian width 0.5

Shape and width of oxide peaks:

Gaussian FWHM 1.25
Lorentzian FWHM 1.08
Total FWHM 1.80

Satellite:
Binding energy 186.00
Gaussian width 3.76

Reference binding energies:

Au 4f7/2 84.23
&3d,,z 368.21
Cu 3Ps/2 932.38
Energy iu eV.
Energy errors = 0.05 eV.

and Zr*) were then obtained by a non-linear least-squares curve fitting

procedure [31] applied to the spectra of fig. lb. However, as part of the
intensity on the high energy side of the spectra was systematically un-
accounted for, a small broad Gaussian labelled “satellite” was included in the
fitting procedure. Although its origin is uncertain (it could not be assigned to
any contaminant), it could be due to a metal-to-ligand charge transfer process
involving the unoccupied 4d levels of the metal ions as observed in other
transition-metal compounds [32]. The results of the lineshape fitting are shown
in fig. 3 by a dashed line only where they deviate from the experimental curve.
The individual components are shown by dotted lines. The corresponding
fitting parameters have been compiled in table 1.
The lineshape of the peak corresponding to metallic zirconium was well
fitted by convolution of a Doniach-Sunjic function (FWHM = 0.7 eV and an
asymmetry factor cy= 0.1) with a Gaussian function (FWHM = 0.5 ev). An
intrinsic width of the core level of = 0.1 eV, as expected for a metal [33] is
then obtained.
338 C. Moran? 6%al. / XPS sit&y of intern&on of oxygen with zirconium

OXYGEN EXPOSURE (L)

Fig. 4. Intensities of the Zr3d in the different oxidation states, Zr4+ (o), Zr3+ (o), Zr2+ (o),
Zr+ (A), satellite (0) and 01s (v) normalized to the intensity of the metal in the substrate (Zr’)
as a function of oxygen exposure.

In order to get more quantitative information, the intensities of the differ-

ent components were considered. They are shown in fig_ 4, where the intensity
of the oxygen 01s line has also been included. In this figure, it can be
observed that, whereas at exposures c 0.6 L the initially adsorbed oxygen
atoms appear not to form oxide-like bonds as no changes could be observed in
the shape of the Zr 3d XPS line, at exposures = 2.1 L, all the oxidation states
of Zr are readily detectable. In addition, at exposures > 2.1 L the normalized
intensities of the suboxides show an approximately constant behaviour relative
to Zr* indicating that they remain at the Zr/ZrO, interface. It is interesting to
note that ZrO, constitutes the major component of the oxide layer at ex-
posures 2 2 L.
The 0 Is spectra corresponding to different oxygen exposures are shown in
fig. 5. Except for the spectrum labelled ZrO,, at least two components can be
clearly distinguished. Furthermore, important differences in shape and binding
energies can be observed and have been sawed in table 2. However,
 C. Moran? et al. / XPS study of interaction of oxygen with zirconium 339

535 530 535 530 535 530

BINDING ENERGY lev)
Fig. 5. Normalized XPS 01s spectra for various oxygen exposures. Continuous line: experimental
spectra. Dotted line: individual components. Dashed line: least-squares synthesis.

surface charging and changes in the work function, which occur as the
oxidation proceeds [4], make an unambiguous identification and assigrrmentof
the different 0 1s peaks very difficult and controversial.
Fig. 5 shows that at 0.6 L the 01s spectrum consists of a main peak at
E, = 530.81 eV and a shoulder of simihu FWHM at E, = 532.86 eV (cf. table
2). In a first attempt, they have been assigned to adsorbed oxygen Oad, as no
oxide formation could be detected from the analysis of the corresponding
Zr 3d spectrum. In fact 0 Is peaks at E, = 531.5 eV have also been observed
in other metals and assigned to chemisorbed oxygen 1341. On the other hand,
the higher binding energy peak at Eb = 532.86 eV would be consistent with
some form of adsorbed or incorporated oxygen with a lower effective charge
(i.e. OH- species). As support for this assignment it is worth mentioning that

Table 2
Fit parameters for 0 1s XPS spectra (cf. fig. 5)

Exposure (L) Total FWHM (eV) & (ev)

0.6 2.10 530.81
2.10 532.86
2,1~z#LlO3 1.40 530.76
2.80 531.84
zm2 1.69 531.17

Energy errors = 0.05 eV.

340 C. Morant et aL / XPS study of interactionof oxygen with zirconium

Hoflund et al. [9,11] have shown that oxygen is able to attract hydrogen from
the bulk to form hydroxyl species.
At oxygen exposures larger than 2 L a new and sharper peak (cf. table 2) at
a binding energy E, = 530.76 eV can be clearly observed. It is assigned to
oxygen in an oxide state in agreement with similar peaks observed in many
other transition metal oxides [34]. This assignment is also corroborated by the
continuous increase of its intensity as the oxidation proceeds and by the
observed induced effects on the Zr3d line. The small and broad high binding
energy component should then be interpreted as due to the superposition of
the two oxygen peaks observed at 0.6 L (cf. table 2) (i.e. chemisorbed oxygen
and OH- groups remaining in an overlayer position).
The 01s spectrum after 6000 L of oxygen exposure at 475 K consists of
only one component (i.e. oxide). The high binding energy component of the
01s peak disappears but the peak becomes broader and lightly shifted in
energy compared with the corresponding component observed at room tem-
perature (cf. table 2); surface charging due to the formation of an oxide layer
thicker than 6 nm could be the origin of such changes.

3.1. Thickness

Assuming that the metal is covered with an oxide layer of uniform thick-
ness, the intensity of the signal from the metal substrate is given by:

I,, = I& exp(-d/X), (I)

where I& is the intensity of the clean metal, X is the effective escape depth of
the photoelectrons and d is the equivalent thickness of the oxide overlayer. d

16
-*
/HH
H/y
l’
14- /’
/
.‘7 /
_ /
: 12- / /’
W /
Z /
xc - l
,o / /
E lo- / ,
/
/

8 I I I 1 1 I
5 10 50 100 500 1000

OXYGEN EXPOSURE (L)

Fig. 6. Oxide layer thickness obtained from the intensity of Zr substrate (Zr’) using eqs. (1) and
(2) as a function of the oxygen exposure.
 C. Morant et al. / XPS s&y of interactionof oxygen with zirconium 341

can be determined from eq. (1) if the mean free path of the detected electrons
is known. A can be estimated from the empirical universal relation given by
Seah and Dench [35]. Taking into account the geometry of our experimental
arrangement we obtain:
x Zr= hrrOz=2nm (2)
for Zr3d electrons in the metal and the oxide.
Fig. 6 shows d as a function of the oxygen exposure. As seen in the figure a
rapid growth of d up to exposures of = 10 L is followed by a low variation of
the thickness (i.e. saturation region). At = lo3 L an oxide layer = 1.6 nm
thick has been estimated, in very good agreement with previously [5,12,16,17]
reported limiting thickness. However, in view of the oversimplified assump-
tions and the uncertainties in X, those d values must be considered as a rough
estimation of the thickness of an equivalent homogeneous oxide layer.

3.2. Composition

From the intensity of the different oxidation states of zirconium (cf. fig. 4),
the composition of 210~ can be calculated by

f (3)
where I(Zr”+) is the intensity of the signal corresponding to the different
oxidation states.
Using eq. (3) with 16 n G 3 and the intensities shown in fig. 4, an average
composition Zr0,,9 can be estimated for the interface layer (1 to 2 monolayers
thick) formed only by the suboxides. On the other hand, considering the
average composition of the whole film after = lo3 L (i.e. taking also into
account the ZrO, species), ZrO,, is obtained which indicates that even at such
exposures well above saturation, the oxide layer is still considerably different
from stoic~ome~c ZrO,. The dependence of the average composition x on
the oxygen exposure has been depicted as empty squares in fig. 7.
Alternatively, the average composition of the whole oxide layer ZrO, can
also be determined in terms of the intensities of the oxygen and oxidized
zirconium signals. The ratio of these intensities in the case of an oxide layer of
thickness d is given by

-=-I(O) S(0) N(0) 1 - exp( -d/A,)

I(ZroX) S(Zr) N(ZroX) 1 - exp( -d/A,,) ’
(4)
where 5’ refers to the XPS sensitivity factor and N to the atomic concentration
in the oxide film. Considering that ~(0)/~(Zrox) = x, x can be estimated
from eq. (4). Using the thicknesses determined in the above section and
342 C. Morant et al. / XPS st@ of interaction of oxygen with zirconium

tabulated sensitivity factors [36], the compositions shown as full circles in fig.
7 are obtained. In this case, the whole area of the 0 1s line has been used for
I(0). It is interesting to observe that the resulting values for x are well above
those obtained from eq. (3) and even higher than 2, which would correspond
to ZrOz. Therefore, it appears that x is overestimated if it is assumed that all
the oxygen atoms are bound to zirconium forming ZrO,. In other words, it
seems that the partially oxidized zirconium surfaces show an excess of oxygen
(i.e. not forming oxide) which causes such overestimation. In fact, recalling
that the oxygen signal originated from different states, we should consider
only the intensity of the peak related to the oxide state (i.e. E, = 530.76 ev).
In doing so, a better agreement with those results obtained using eq. (3) is
achieved as can be observed by comparing empty squares and circles in fig. 7.
A quantification of the 0 1s peaks assigned to chemisorbed and hydrated
oxygen (i.e. adsorbed) can also be done easily. If it is located in the outermost
layer its intensity should be directly proportional to the fractional monolayer 19
of oxygen atoms in such states. Assuming that the oxide layer of thickness d
and composition x = N(O,,)/N(ZP) already obtained is covered by a frac-
tional monolayer 8 of oxygen atoms, the ratio 1(0)/1(Zr”“) of the whole 0 1s
and oxidized Zr3d intensities is simply given by the sum of the unattenuated
(1 - t9) and attenuated (8) parts of the signals:

+e[N(o,,) exp(-a/X0) (l- exd-d/U)1

+ (I- 8) [W%,) (1 - exd-d/L))] >

x { e[iv(Zr““) exp(-a/&,) (l- exd-d/b,))]

+ (I- e) [ N(Zr““) (1 - exd -d/h))] >ml>

where a is the thickness of a monolayer and N(O,,) = up3 is the atomic
concentration of a monolayer of adsorbed oxygen. Taking a = 2 A as the
atomic size of oxygen in ZrO,, the surface density of an oxygen monolayer
would be = 2 x 1015 cm-* m . good agreement with sticking coefficient data of
Fromm [37] and the calculated saturation density given by Foord et al. [4] (i.e.
2.1.4 X 1015 cme2).
Calculation of 8 from eq. (5) for several exposures enabled us to determine
the calibration constant to convert the 0 Is signal corresponding to O,, into 8.
The results are shown in fig. 8 and indicate the existence of a fractional
monolayer of adsorbed oxygen during the whole oxidation process, reaching a
saturation value of = 1 ML at exposures > 100 L.
 C. kforant et al. / XPS st@ of interaction of oxygen with zirconium 343

3.0 .

_---____-__------________
__-- a 0

_4
0

______-D_________-D-
_*-- __--
0 _

0 0
8
L I I I 1 I
5 10 50 100 500 1000
OXYGEN EXPOSURE (L 1

Fig. 7. Composition x in ZrO, versus oxygen exposure: (0) from suboxide intensities, eq.(3); (0)
from oxygen and ZP intensities considering the whole 01s signal, eq. (4); (0) from oxygen and
Zr“” intensities considering only the intensity of 01s in the oxide state (i.e. E, = 530.76 ev), eq.
(4).

11

0.8 - /
/
/
/
0.7 - /d
/
,’
/
0.6 -
,d

oD5 ’ ’ 1 I I I
0.5 1 5 10 50 100

OXYGEN EXPOSURE ( L)
Fig. 8. Coverage of adsorbed oxygen as a function of oxygen exposure.

4. Conclusions

Previous kinetic studies [4,10,12,15,16] of the initial oxidation of zirconium

have concluded that the interaction of oxygen with zirconium at room temper-
ature involves dissociative chemisorption (X l-2 L), nucleation and growth of
344 C. Morant et al. / XPS stu& ofinteraction of oxygenwith zirconium

ZrO, until coalescence and thickening of the film to a limiting thickness of

= 1.5-2 mn. Adopting this picture, the results obtained in this work can be
interpreted easily. At exposures 6 0.6 L corresponding to the chemisorption
stage, it has been shown that oxygen atoms adsorb on the surface of zirconium
without formation of oxide-like bonds. This was characterized by an 0 1s peak
at E, = 530.81 eV whereas no noticeable change in the shape of the Zr 3d line
could be observed. The 01s photoelectron line showed also a small shoulder
at higher binding energies (i.e. E, = 532.86 ev). Although its origin appears
uncertain, the possibility of its being due to hydroxyl groups has been
suggested. The estimated oxygen coverage at 0.6 L was = 1.1 X 1015 atoms
crnm2 representing a fractional coverage of = 0.6 of a monolayer. This initial
stage appears to extend up to =0.75-l L [12,13]. Upon further oxygen
exposure, the initial oxygen chemisorption leads to the formation of different
oxides. At 2.1 L the Zr 3d line exhibits new features at the high binding energy
side which have been assigned to different zirconium oxides. Data analysis and
fitting procedures suggest the existence of four different oxidation states of
zirconium (i.e. Zr,O, ZrO, Zr,O, and ZrO,) which develop at exposures
between 0.6 and 2 L. The 01s spectrum is characterized by a sharp peak at
E, = 530.76 eV assigned to the oxide and a very broad shoulder centered at
E, = 531.84 eV which has been interpreted as a supe~osition of the two 01s
components observed at 0.6 L. Increasing the oxygen exposure, ZrO, grows
continuously whereas the other suboxides remain at the Zr/ZrO, interface,
forming an interface layer of average composition ZrO,,. At exposures > 10’
L the saturation region is reached, and at = lo3 L an 1.6 nm thick oxide layer
with an average composition of ZrO,,e is formed. Adsorbed oxygen was also
present during this stage in amounts close to the monolayer, reaching a
saturation value of about 2 X 1015 atoms cme2 at lo2 L.

Acknowledgements

This research was financially supported by the CICYT of Spain through

contract No. PR83-3304. One of the authors (J.M.S) acknowledges a grant
from the Scientific Committee of the NATO.

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