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1991 Phys. Scr. 43 430

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Physica Scripta. Vol. 43, 430-433, 1991.
Oxidation of Rare Earth/Magnesium Interfaces
N. A. Braaten and S . Raaen
Department of Physics, University of Trondheim, NTH N-7034 Trondheim, Norway
Received August 28, 1990; accepted in revised form November 27, I990
Abstract
A photoemission study of formation and oxidation of rare earth/magnesium
interfaces is presented. Our results indicate that a thin, rare earth rich
amorphous surface alloy forms when the rare earths Ce or Pr are evaporated
onto a magnesium substrate at room temperature. When these systems
subsequently were exposed to oxygen, only weakly enhanced substrate oxi-
dation was observed. This differs from previous observations on e.g., A1 and
Ta substrates, where strongly enhanced oxidation was seen. Differences in
the Mg and A1 systems are thought to be related to different oxide structures.
1. Introduction
Most of the early experimental work on oxygen uptake in
metals and semiconductors have focused on clean substrates
[l]. During the last several years, the interest has partly
turned to overlayer systems, where thin overlayers of reactive
materials act as to increase the uptake of oxygen ions in the
substrate material [2-41. Recent studies have shown that the
rare earths Ce and Pr act as catalysts on the oxidation of A1
and Ta [5,6]. Several other studies confirm that alkali metals
have a similar effect on both metals and semiconductors
[7-lo].
A common feature of rare earths and alkali metals is their
low work function. Most of the recent theoretical studies of
alkali metals on semiconductor and free electron metal sub-
strates assume that the rate limiting step for the initial oxi-
dation is the dissociation of the oxygen molecule [l l-131. The
surface dipole induced lowering of the system work function
will facilitate a downshift and increased filling of the oxygen
2n* antibonding states, which results in a reduced barrier for
oxygen dissociation. The work function is, however, not
always the critical parameter for reaction rates. This has been
demonstrated in oxidation studies of rare earth/Cr and rare
earth/Ni interfaces [ 141. Polycrystalline chromium and nickel
surfaces have fairly large work functions (4.5 and 5.15eV,
respectively), but Ce and Pr (work functions G3.0eV)
showed no appreciable effects on these substrates. It is con-
venient, in this context, to divide the substrates into two main
categories according to whether the initial oxidation proceeds
by a surface limited process (including oxygen dissociation),
or bulk like processes limited by e.g., anion (oxygen ion) or
cation (metal ion) diffusion. Low temperature oxidation of
elements like Si, Ge, Ta and Nb, produces an amorphous,
open network structure, with tightly bonded cations. Hence,
they are typical network formers in the classification system
after Sun [15], in which the metal oxides are grouped into
network formers, intermediates and network modifiers,
depending on the oxide bond strengths [15, 161. The oxides of
the elements listed above should therefore be good anion
conductors. Oxidation of these elements is therefore often
thought of as being limited by incorporation of oxygen at the
surface. Cr and Ni, on the other hand, are typical network
Physica Scripta 43
modifiders according to this classification, and should pri-
marily grow and be limited by cation diffusion [15, 161.
Aluminium represents an intermediate case where both types
of ionic transport through the oxide have been reported
[l, 151. As Ce is deposited onto an aluminium surface, an
interface alloy forms [5]. A similar type of solid state reaction
is observed for the Pr/A1 system [6]. The catalytic activity of
the rare earth in this case is related to the high oxidation rate
of the mixed interface [5].
In this paper we present an oxidation study of interfaces
between the early lanthanides and magnesium. A1 and Mg
form quite different oxide structures. A1 oxide, A1,03, may be
classified as an intermediate oxide, in which both AI- and
0-ions may be transported through the oxide, whereas MgO
may be classified as a network modifider, in which metal ions
are transported through the oxide [16]. The initial oxide
nucleation has been reported to be quite different for poly-
crystalline surfaces of the two metals. The aluminium oxide
growth proceeds by a transformation of a chemisorbed phase
into an amorphous oxide, whereas the magnesium oxide
grow by island formation directly on the surface [17, IS]. A
recent study concluded that chemisorbed oxygen as well as
oxide were present in the initial stages of Mg oxidation [19].
The present photoemission study of oxidation of rare earth
covered magnesium was motivated by recent results obtained
from oxidation of rare earth on A1 systems [5, 61, which
showed large enhancements in A1 oxide growth, as compared
to oxidation of the bare A1 substrate.
2. Experimental procedures
All photoemission spectra were recorded using a twin anode
(Al/Mg) X-ray source from Vacuum Science Workshop
(VSW), in conjunction with an HA-50 electron energy analy-
zer (VSW). A total resolution of about 1 eV was obtained.
The base pressure in the vacuum chamber was near 1 x
lO-'Ombar. Rare earths and Mg were evaporated using resis-
tively heated tungsten baskets, which were thoroughly out-
gassed prior to evaporation. The relative attenuation of Mg
substrate peaks during evaporation of rare earth elements,
were used to estimate the amount of rare earths deposited.
The substrate emission intensities were obtained by integrat-
ing the Mg 1s peak after subtracting a linear background. A
careful calibration of evaporation rates was performed,
before and after each measurement series, in order to check
that the evaporation rates of the rare earths were constant.
3. Results and discussion
Very similar core level shifts are observed when Ce and Pr are
deposited onto a magnesium substrate. The Mg 1s level shifts
 Oxidation of Rare EarthlMagnesium Interfaces 43 1

Ce/Mg - Relative attenuation of Mg 1s intensity

a)
1-
Mg 1s
0.8 -
0.8
5 0.6-
/ 9

0.4 -

0.2 ~
0

.. . -...._
....
_,

0 1 2 3 4 5 6
Ce evaporation time [min.]

P r N g -Relative attenuation of Mg 1s intensity

0.8

1304 1302
BINDING ENERGY (eV) Pr evaporation time [min.]
Fjg. 1. Mg Is spectra from bare (bottom curve) and rare earth covered
Fig. 2. Curves showing the attenuation of M g Is level during evaporation of
magnesium films. Evaporation of approximately one monolayer of Ce or Pr
(a): Ce and (b): Pr. The circles are measured points, the solid lines are fits to
results in a 0.2eV shift of the Mg Is peak to lower binding energy.
- -
eq. (I), and the dashed lines show exponential decay. The evaporation rates
were 3 k, min-' and 2 A min-' for Ce and Pr, respectively.
0.2eV to lower binding energy when the first monolayer of
rare earth is deposited; see Fig. 1. No further shifts of this
peak were observed as the evaporation continued. The corre- PrMg [22]. The solid solubility in magnesium is very low
sponding Mg 2s levels did not exhibit such marked shifts. for these elements; less than 0.03at. YO at 340°C for Ce.
This was the case even after a relatively thick film, about Therefore, a surface alloy, which is amorphous due to the low
20-30 A, was deposited. Our experimental resolution makes temperature at which it has formed, seems to be present.
it difficult to resolve shifts of order 0.1 eV. The mean free path These results are quite similar to those obtained in an earlier
for the Mg 1s electrons are, however, substantially smaller as study of Ce on Cu [20].
compared to the Mg 2s case, and hence the analysis of the After having established some understanding of the kind
former peak represent a more surface sensitive probe of the of interface which forms between the involved elements, the
thin intermixed layer. next step was to expose the surface to relatively light doses of
To get more information about the interface, we per- high purity oxygen. The clean and rare earth covered sub-
formed an intensity analysis of the attenuated Mg 1s levels as strate were given oxygen doses ranging from 0 to 150L.
rare earths were deposited. A simple model for the mixed rare Figure 3 shows the Mg 1s emission after a 30 L exposure to
earth/Mg layer on top of the Mg substrate, in which a mixed both a clean Mg surface, and a Mg-surface covered with
homogeneous overlayer is assumed, gives the following approximately one monolayer (ML) of the rare earths. The
expression for the relative attenuation of the substrate peaks Mg 1s metal emission is shown as a reference. At this stage,
[20, 211: the surface is almost completely oxidized within a thickness
limited by the probing depth. A 1.3 eV shift in the Mg 1s peak
-
ZMg = (1 - a) + a exp [ - tr/Za] (1) for the oxidized sample, is interpreted as a sign of bulk
where a is the volume fraction of the rare earth mixed into the magnesium oxide, MgO. The size of the oxide shift in the 1s
magnesium substrate, t is evaporation time, Y is calibrated level is in good agreement with earlier studies of polycrystal-
evaporation rate and I is the electron mean free path. The line magnesium films [ 181. No dramatic effect of the rare earth
resulting intensity curves for the Mg 1s level are shown in on the oxygen uptake can be seen. In Fig. 4 we show Mg 1s
Figs. 2 (a) and (b), for Ce and Pr, respectively. Judging from spectra for heavier oxygen exposures to the Ce/Mg system.
these estimates, the Ce/Mg interface contains about 20% Initially the Mg 1s peaks are shifted to higher binding energy,
magnesium, and the Pr/Mg interface a little less. This model but for higher doses of oxygen these peaks move back almost
does not account for concentration gradients across the inter- 1 eV. These latter shifts to lower binding energies are likely to
face, and electron mean free paths are considered only to be related to how the core levels should be referenced (i.e., the
depend on the kinetic energy. degree of Fermi level equilibration) [23], and has previously
According to phase diagrams for binary alloys, the most been observed on oxidized rare earth as well as alkali metal
rare earth-rich Mg compounds that exist are CeMg and overlayer systems [23]. These core level shifts to lower binding
Physica Scripta 43
432 N . A . Braaten and S. Raaen

OJCelMg XPS
XPS
Mg Is
Mg 1s

- 1306 1304
BINDING ENERGY (ev)
1302

Fig. 3. Mg 1s spectra taken after oxygen exposure to the same samples as

shown in Fig. 1. Curve (A) shows the clean Mg substrate, curve (B) corre-
1305
BINDING ENERGY (eV)
1301

Fig. 4. Photoemission spectra showing the development of the Mg 1s peak

sponds to 30 L oxygen exposure to Mg, curve (C) corresponds to 30 L oxygen
exposure to Ce/Mg, and curve (D) corresponds to 30 L oxygen exposure to
Pr/Mg.
was estimated to be -A
8 (EKIN= -
as a 3 8, Ce on Mg-system is exposed to oxygen. The electron escape depth
180eV).

energies occur near the same oxygen exposure where formally
tetravalent Ce-oxide first occurs. We believe that this is coinci-
dental since similar shifts have been observed in the Ce/Al
system [ 5 ] , in which only trivalent Ce-oxide was present even
for large oxygen doses, > 200 L.
Estimates of oxide thicknesses for the various overlayers
are shown in Fig. 5. The estimates are obtained from moni-
toring attenuation of the metallic component of the Mg 2s
emission. The electron mean free path was estimated to be
near 20 A. The oxide thickness estimates are relatively inaccu-
rate due to the nature of the mixed rare earth/magnesium
interface. Figures 3 and 5 show quite clearly that the rare
earth overlayers have little effect on the magnesium substrate
oxygen uptake.
Oxide growth on the clean magnesium substrate was tested
for pressure dependence by using three different oxygen
pressures from 1 x 10-7mbar to 6 x 1OP7mbar.No change
in the rate of oxide development was seen. When Ce was
evaporated onto aluminium, and the system subsequently
oxidized, no sign of formally tetravalent Ce oxide was seen,
as long as the substrate was kept at room temperature [5].
This is, however, not the case on a magnesium substrate. In
Fig. 6 we show how the Ce 3d region develops during oxi-
dation of the Ce/Mg system. The Ce 3d3,*4fopeak associated
with formally tetravalent Ce oxide, CeO,, at about 916eV
binding energy [24], is present already at 60 L exposure, and
grows stronger from there on. As the oxygen exposure is
increased, a change in valence occurs from trivalent to for-
mally tetravalent.
In the case of Ce and Pr, the conversion from tetravalent
8-
6-
4-
2-
0-
0
Oxygen exposure [L]
- -
Fig. 5. Estimates of Mg oxide thicknesses from Mg 2s emission intensities
(EKIN 1400 eV, corresponding to an eIectron escape depth of 20 A) for
various oxygen exposures to a bare Mg film as well as rare earth covered
samples. The rare earth covered samples are the same as the ones showed in
Figs. 1, 2 and 4.

Physica Scripta 43

l l l I ~ I J I
OJCelMg
iI
J l l l I l l l l l
910 900
BINDING ENERGY (eV)
Fig. 6 . Ce 3d spectra from an oxidized Ce/Mg system, with approximately
one monolayer Ce coverage. The distinct feature around 916eV binding
energy is characteristic of formally tetravalent Ce oxide, CeO,.
to trivalent oxides is an important part of the suggested
model for the catalytical mechanism on N b for both over-
layers [3]. In that case the N b oxide grows by anion diffusion
across the thin oxide film. The absence of an appreciable
effect on the magnesium oxygen uptake, may suggest that
MgO grows by cation diffusion. If this is the case, the rate-
determining barrier would be at the metal/oxide interface,
associated with metal-metal bonding energies, and would be
rather insensitive to changes at the surface, like, in this case,
depositions of thin overlayers of rare earth materials. Such a
model is supported by the fact that the magnesium oxide
growth did not show dependence on oxygen partial pressure,
which is often considered as a sign of cation migration limited
oxide growth [16]. We should point out, however, that the
limited range of oxygen pressures employed in this study,
does not conclusively rule out a possible pressure dependence
on the rate of oxidation.
Oxidation of Rare EarthlMagnesium Interfaces 433
I ~ I I I I ( I I I I ~ I I
4. Summary
XPS This work has shown that evaporation of thin overlayers of
Ce 3d
C or Pr on a Mg substrate, results in a rare earth rich
amorphous alloy at the interface. The effect of the rare earths
on the Mg substrate oxidation is negligible. This observation
is in contrast to the Ce/A1 case, where a substantial enhance-
ment in the substrate rate of oxidation was present. These
differences are likely to be related to the different structures
of MgO and A1,0,: Al-oxide has an open stucture and may
be classified as an intermediate oxide in which oxidation
continues by anion migration. Mg-oxide has a denser struc-
ture and may be classified as a network modifier in which
oxidation is likely to proceed by cation migration. Therefore,
in the case of magnesium a modification of the surface barrier
for oxygen penetration (by rare earths) is not important for
continued oxide growth. Further work on the A1 and Mg
systems may be in order to clarify some of these aspects.
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Physica Scripta 43