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Lacona1999 XPS
Lacona1999 XPS
Citation: Journal of Vacuum Science & Technology A 17, 2771 (1999); doi: 10.1116/1.581943
View online: http://dx.doi.org/10.1116/1.581943
View Table of Contents: http://scitation.aip.org/content/avs/journal/jvsta/17/5?ver=pdfcov
Published by the AVS: Science & Technology of Materials, Interfaces, and Processing
Kinetic study of GeO disproportionation into a GeO2/Ge system using x-ray photoelectron spectroscopy
Appl. Phys. Lett. 101, 061907 (2012); 10.1063/1.4738892
Surface segregation of boron in B x Ga 1−x As/GaAs epilayers studied by x-ray photoelectron spectroscopy and
atomic force microscopy
Appl. Phys. Lett. 82, 1830 (2003); 10.1063/1.1561164
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X-ray photoelectron spectroscopy study of bombardment-induced
compositional changes in ZrO2, SiO2, and ZrSiO4
Fabio Iaconaa)
CNR-IMETEM, Stradale Primosole 50, 95121 Catania, Italy
Roger Kelly
INFM and Dipartimento di Fisica, Universitá di Trento, 38050 Povo (Trento), Italy
Giovanni Marletta
Dipartimento di Scienze Chimiche, Universitá di Catania, Viale A. Doria 6, 95125 Catania, Italy
共Received 7 August 1998; accepted 5 March 1999兲
We have studied the chemical and compositional modifications induced by 8 keV Ar° irradiation at
the surface layers of ZrO2, SiO2, and ZrSiO4 共zircon兲. The surfaces were examined by in situ x-ray
photoelectron spectroscopy 共XPS兲. We have found that while pure SiO2 evolved to SiO1.95 and pure
ZrO2 evolved to ZrO1.85, involving the appearance of reduced Si and Zr species in the XPS spectra.
On the other hand, ZrSiO4 underwent a major loss of SiO2, to yield a final Si/Zr ratio of 0.63, and
a strong degree of ZrIV reduction 共to yield ZrO1.70兲 with respect to pure ZrO2. The experimental
results are discussed in terms of several possible mechanisms, including the kinetic loss of O due to
high diffusivity in the perturbed collision cascade volume, the occurrence of
‘‘bombardment-induced segregation’’ 共BIS兲 phenomena, the occurrence of redox reactions, as well
as the ‘‘lattice relaxation with chemical guidance,’’ related to the thermodynamic stability of
irradiation-induced compounds. In particular, the compositional modifications for simple oxides
seem to be well explained mainly in terms of the model of lattice relaxation, i.e., in terms of the
‘‘thermodynamically allowed’’ formation of the intermediate valence species ZrIII and SrIII, clearly
demonstrated by XPS. For the effects seen in the mixed oxide ZrSiO4, the preferential depletion of
SiO2 has been tentatively explained in terms of BIS phenomena, while the enhanced ZrIV reduction
共with respect to pure ZrO2) is explained in terms of competing O–Zr and O–Si recombination
reactions. © 1999 American Vacuum Society. 关S0734-2101共99兲00205-5兴
2771 J. Vac. Sci. Technol. A 17„5…, Sep/Oct 1999 0734-2101/99/17„5…/2771/8/$15.00 ©1999 American Vacuum Society 2771
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2772 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2772
TABLE I. Previous work on the radiation stability of the oxides studied here.
equilibrium condition, is justified by considering that the fi- The experiments were performed in situ in a Kratos ES
nal steady state, i.e., the stable composition of the irradiated 300 XPS apparatus. The spectrometer had a base pressure of
layers, is the result of a long term equilibration, well after the 1⫻10⫺9 Torr and was equipped with a dual anode 共Al/Mg兲,
intrinsically nonequilibrium step of energy deposition related a hemispherical analyzer, and a preparation chamber, held at
to the collision cascade physics and sputtering. In particular, the same vacuum of the main chamber, used for the in situ
the energy deposition step produces a more or less large bombardment of the oxides. The analyses have been per-
volume in which the bonds are broken within a collision formed by using Al K ␣ 1,2 radiation at 1486.6 eV.
cascade, with a subsequent ‘‘equilibration step’’ consisting The irradiation treatments were performed by using a fast
in bond formation or recombination, vacancy formation, atom gun 共Ion Tech Ltd. FAB 11NF兲, operated with Ar° at 8
short and long term diffusion processes, including the imme- keV and with the particle flux incident at 45° with respect to
diate escape of small gaseous species or segregation phe- the sample normal. A fast atom beam 共FAB兲 was used in
nomena. The final results of this complex set of processes order to minimize the errors in the particle fluence, as far as
can reasonably be rationalized in term of ‘‘energy-limited’’ the neutral projectiles are not affected by the possible forma-
rearrangement, i.e., in a thermodynamical framework. tion of strong positive fields, built as a consequence of the
Overall conclusions from this work will be seen to be 共a兲 secondary electron emission in highly insulating samples. In
that pure SiO2 loses small amount of O, 共b兲 pure ZrO2 shows
each case, specimens smaller than the FAB spot were at-
the partial reduction of ZrIV ions 共about 23% of the total兲 to
tached with silver cement to a copper heating stage. The
lower oxidation states, while 共c兲 ZrSiO4 shows both an un-
effective ‘‘current density’’ calculated as if the Ar° were
expected loss of SiO2 as well as the massive reduction of
Ar⫹, was about 共6.0⫾0.5兲/␥ A/cm2, where ␥⬇1.3 is the
ZrIV cations 共about 50% of the total兲. It is to stress the
secondary electron yield of bombarded Cu.37 The corre-
marked difference observed between the degree of Zr cation
sponding fluence per minute was about (2.4⫻1015)/ ␥
reduction respectively in ZrO2 共consistent with a final com-
position ZrO1.85兲 and zircon 共final composition ZrO1.70兲. ions/cm2 min. The projected ranges for 8 keV Ar° were esti-
Finally, it will be concluded that the instability of SiO2, mated to be about 85 Å for SiO2, and 60 Å for ZrO2 and
ZrO2, and ZrSiO4 can be understood if compounds like Si2O3 ZrSiO4. These values are comparable with the XPS sampling
and Zr2O3, produced under irradiation, are metastable at low depth, ensuring that the analyzer layers are homogeneously
enough temperatures. irradiated.
Compositions were determined by monitoring the Zr 3d,
Si 2p, and O 1s XPS lines. Environmental carbon contami-
II. EXPERIMENT nation was a general problem, so the samples were first
The SiO2 targets consisted of thick and polished amor- brought to 400 °C, the vacuum was allowed to reach the
phous slices of optical grade fused silica obtained from Dow 10⫺8 Torr scale, and then a preliminary FAB irradiation was
Corning. The ZrO2 and ZrSiO4 targets were prepared by performed 共irradiation time 20 s兲. A strong indication that
compacting high purity powders 共99.99%, obtained from Al- such a procedure was adequate to minimize carbon without
drich, 325 mesh for zircon兲. significantly modifying the ZrO2 and SiO2 surfaces was that
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2773 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2773
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2774 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2774
TABLE II. The enthalpy increase per atom for oxygen loss from the oxides
studied here and in Ref. 35. Note that substances which lose O when bom-
barded typically show an enthalpy increase of 0.7–1.0 eV/atom 共see Refs.
33,34兲.
Enthalpy increase
Assumed final per atom
Substance solid phase 共eV/atom兲a
TABLE III. Observed compositional changes for the systems studied here and in Ref. 35, as well as for related
fixed-valence systems 共see Ref. 26兲.
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2775 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2775
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2776 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2776
ballistic processes, except for the very special case of near- guidance. The occurrence of the chemical reduction process
threshold effects occurring for large mass difference between in this case would depend on the possibility that the substo-
the projectile and the target atoms, i.e., He⫹on Ta2O5, ichiometric Zr2O3 and/or ZrO compounds are metastable if
prompts the partial reduction of the oxide to TaO, while the formed, due to the recombination processes in the perturbed
irradiation with Ar⫹ promotes the return of the system to the volume after the collision cascade, at a low enough tempera-
initial composition.49 ture.
At variance of this, it is known that a very large number The energetics of the whole process can be discussed in
of systems, like Fe2O3, TiO2, MoO3, CuO, Nb2O5, etc. are the following terms:
strongly reduced to lower oxidation states under particle ir- We require that ⌬H be negative for
radiation, while others 共very close in mass兲 like for instance,
2ZrO⫽Zr⫹ZrO2,
ZnO, Al2O3, MgO, CaO, Sc2O3, Cu2O, etc. are totally stable
under the same irradiation conditions. Furthermore, a num- and therefore obtain a limit for the heat of formation 共‘‘f’’兲:
ber of systems, like CoO and NiO, have been shown to have
a borderline behavior, being reduced to metal state under ⫺⌬H ZrO
f
⬍5.71 eV.
irradiation at high temperature 共about 400 °C兲 and stable at
room temperature.36 The same reasoning can be applied to the reaction,
This reduction of the cation oxidation state has been in-
terpreted in terms of various mechanisms, including model Zr2O3⫽ZrO2⫹ZrO,
like 共a兲 thermal spike,50 共b兲 bombardment-induced gibbsian
to yield
segregation,35,51 共c兲 random lattice relaxation 共or stochastic
rearrangement兲,21 共d兲 point defect accumulation,52 共e兲 diffu- ⫺⌬H Zr
f
⬍17.12 eV.
2O3
sional transport of O,33 and 共f兲 lattice relaxation with chemi-
cal guidance.33 All these models are based on thermody- This is sufficient information to evaluate the enthalpy
namical arguments, basically considering the reorganization changes for O loss from ZrO2:
of the disturbed network at very long term. These models are
exhaustively discussed with respect to available experimen- ZrO2⫽ 21Zr2O3⫹ 41O2, 1
⌬H⬎0.95 eV/atom; 共1a兲
3
tal results in Refs. 21 and 33.
In the following, we will mainly use the model of lattice
ZrO2⫽ZrO⫹ 12O2, 1
3 ⌬H⬎1.90 eV/atom. 共1b兲
relaxation with chemical guidance to analyze the irradiation-
induced reduction of ZrO2 and SiO2. In addition, we will We have already pointed out that available experimental
show that the peculiar behavior of ZrSiO4, mainly consisting data for other oxides suggest that there is a tendency to lose
in the higher degree of reduction observed for ZrIVcations O when the enthalpy change, defined as in Eqs. 共1a兲 and
with respect to ZrO2 and in the preferential loss of SiO2, 共1b兲, is 0.7–1.0 eV/atom or less.33,34 Accordingly, being the
cannot be explained only in terms of the above quoted formation of Zr2O3 under the conditions of a collision cas-
model, involving the occurrence of more complex phenom- cade clearly demonstrated by our XPS data, then O loss from
ena. ZrO2 can be explained as a purely thermodynamic effect.
A. ZrO2 and SiO2 Our estimate for O loss from SiO2 (SiO0.95), is also in
agreement with most experimental work 共Table I兲. Again
Our estimate for irradiation-induced O loss from ZrO2, there is a major conflict with respect to the supposed ther-
producing a ZrO1.85 composition, is similar to that found in modynamic stability of SiO2 共Table II兲. As in the ZrO2 case,
some previous studies 共Table I兲, also if some author reports a the conflict is removed by considering, in agreement with
catastrophic reduction of irradiated ZrO2 up to the formation our XPS data, the irradiation-induced formation of partially
of metallic Zr.28,40 In any case, there is a major conflict with reduced metastable species like Si2O3.
respect to the supposed thermodynamic stability of ZrO2 The existence of lower oxidation states of SiO2 has been
共Table II兲. widely reported in literature. Charge states intermediate be-
One possibility33 is that the existence of O loss with ZrO2 tween Si0and SiIV were found when Si was bombarded with
lies in the O loss being kinetic rather than thermodynamic. It O⫹2.
41
It is important to recognize, however, that the bom-
would thus occur in spite of the thermodynamic stability bardments were such that the quantity of oxygen was not
because of the unusually high diffusivity of O in substoichio- sufficient to saturate the bonds. Intermediate Si oxidation
metric or doped ZrO2,53,54 an explanation that has been pro- states have been found by using XPS also in bombarded
posed also for HfO2, Nb2O5, Ta2O5, and WO3.33 One envis- Cr–Si–O layers42 as well as at the SiO2 /Si interface,43 and in
ages that O produced in the collision cascade is quickly evaporated,44 sputter deposited,45 or chemical vapor
diffusing to the surface, before undergoing recombination at deposited46 substoichiometric silicon-oxygen mixtures.
the defective sites, and then is desorbed as O2. As already shown for ZrO2, the enthalpy change for the
An alternative description of why ZrO2 loses O in spite of reduction of SiO2 can be evaluated as
the supposed thermodynamic stability can be given in terms
of the above quoted model of lattice relaxation with chemical SiO2⫽ 21Si2O3⫹ 41O2, 1
3 ⌬H⬎0.79 eV/atom. 共2兲
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2777 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2777
B. ZrSiO4
The present results show that zircon undergoes a strong
reduction process for ZrIV cations and a partial loss of SiO2.
Thus, like for pure SiO2 and ZrO2, there is a conflict with
respect to the supposed thermodynamic stability 共Table II兲.
A first fact can be figured out from Fig. 5 above, where
FIG. 6. Comparison of the relative amount of residual ZrIV species vs fluence
the reduction trend of ZrIV species and the progressive deple- for ZrO2 and ZrSiO4 bombarded with 8 keV Ar° at 400 °C. The experimen-
tion of SiO2 species from zircon are reported vs fluence. It tal values are derived from XPS peak fitting analysis of the Zr 3d lines.
seems apparent that the two phenomena are not kinetically
related, as far as the SiO2 depletion process is continuously
occurring for increasing fluence, while the ZrIV reduction is
characterized by a sudden increase at about 1⫻1017 the reduced SiOx species formed by the bombardment, that
Ar°/cm2, similarly to the result found for pure ZrO2 共see obviously cannot occur in pure ZrO2. However, it should be
above兲. noted that such a redox mechanism should involve a relevant
Let us discuss at first the ZrIV reduction process. Consid- amount of reacting reduced SiOx species, for which no ex-
ering a kinetic mechanism, we note that too little is known perimental evidence exists at moment. Hence, further experi-
about the nature of defects in zircon to draw any firm con- mental and theoretical work is needed in order to properly
clusion. We do not know, for example, whether zircon will account for the described effect.
be found to resemble ZrO2 and have a high O diffusivity. Let us turn now to the possible mechanism producing the
On the other hand, the thermodynamic argument for zir- relevant preferential sputtering of the Si-containing species
con is exactly the same as for ZrO2, based on the assumption from zircon, as revealed by the marked decrease of the Si/Zr
that the reduced forms Zr2O3 and ZrO are metastable if atomic ratio from 1 to 0.63 at the highest irradiation fluence.
formed at low enough temperature 共Table II兲. However, the At the present state of the investigation we can only pro-
higher degree of reduction shown by the ZrO2 sublattice in pose that BIS mechanism may concur to the observed effect,
zircon (ZrO1.70) with respect to that observed in ZrO2 as already seen in the case of MgAl2O4, where the preferen-
(ZrO1.85) deserves a separate discussion. This effect is re- tial depletion of MgO component was observed under FAB
called in Fig. 6, where the percentage of residual ZrIV spe- irradiation, and explained in terms of the sputtering of the
cies, derived by peak fitting procedure, is plotted against the surface segregated MgO component, seen by angular re-
irradiation fluence for the two systems. The figure clearly solved XPS measurements.35 In the present case, such mea-
demonstrates the higher efficiency of the bombardment- surements have not been possible due to the powdered form
induced reduction process exhibited by the ZrO2 sublattice in of the samples.
zircon along all the explored fluence range with respect to On the other hand, it could be objected that zircon is a
the reduction effect in pure ZrO2. line compound at all temperatures55 and segregation like that
Actually, other examples of the correlation between occurring in systems without fixed composition is not pos-
beam-induced chemistry and the chemical environment in sible. We note, however, that zircon amorphizes 共Table I兲.
oxides have been already observed. In particular, it has been The fact that zircon is a line compound is therefore probably
found that TiIV is more easily reduced in pure TiO2 than in not relevant in deciding whether or not segregation can oc-
titanates, while, on the contrary, NiII is more easily reduced cur. The amorphization would probably occur even for a
in NiTiO3 共where it is quantitatively reduced to the metallic bombardment at 400 °C, as the crystallization temperature is
state兲 than in pure NiO.47,48 These peculiar behaviors have significantly higher, i.e., 760 °C20 or more.10 Furthermore,
been explained with the occurrence of redox reactions in the we have no evidence about segregation in zircon, though
framework of the model of lattice relaxation. In particular, would pointing out that Y2O3 segregates in Zr0.72Y0.28O1.86.1
for the NiII case, it has been suggested the occurrence of a Apropos to zircon being a line compound, one might be
reaction of the type: tempted to argue that mixed oxides tend to undergo demix-
ing when bombarded.47 Demixing in bombarded zircon has,
NiOx ⫹TiOy ⫽Ni⫹TiOz 共 x⬍1, y⬍2, z⬎y 兲 共3兲
however, been explicitly sought and found not to occur.56
that is able also to account for the observed lower degree of Therefore, the suitable interpretation of the SiO2 preferen-
reduction of TiIV in NiTiO3 with respect to TiO2. tial sputtering from zircon still remains an open problem. A
A similar approach can be applied also to the present clarifying experiment would involve the use of angular re-
experimental results. Indeed, the higher degree of reduction solved XPS measurements onto atomically flat zircon sur-
shown by the ZrIV species in zircon could be due to a redox faces, in order to check the relevant profile of Si species
reaction involving the preferential recombination of O with under irradiation.
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2778 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2778
16
V. CONCLUSIONS P. J. Martin, R. P. Netterfield, and W. G. Sainty, J. Appl. Phys. 55, 235
共1984兲.
In this work, we have shown that O loss from bombarded 17
L. Cartz, F. G. Karioris, and M. S. Wong, Radiat. Eff. 97, 235 共1986兲.
SiO2 and ZrO2 surfaces, due to partial ZrIV and SiIV cation 18
Hj. Matzke, Phys. Status Solidi 18, 285 共1966兲.
reduction, can be explained by using thermodynamic argu- 19
M. S. Wong, F. G. Karioris, and L. Cartz, Radiat. Eff. 106, 107 共1988兲.
ments. In particular, we have demonstrated by using XPS 20
C. Jech and R. Kelly, J. Phys. Chem. Solids 31, 41 共1970兲.
21
analysis that in both cases the O loss is not due to the reduc- I. Bertóti, R. Kelly, M. Mohai, and A. Tóth, Surf. Interface Anal. 19, 291
tion of SiIV and ZrIVspecies to their metallic states, but to the 共1992兲.
22
I. Bertóti, R. Kelly, M. Mohai, and A. Tóth, Nucl. Instrum. Methods
formation of intermediate oxidation states, corresponding re-
Phys. Res. B 80/81, 1219 共1993兲.
spectively to Zr2O3 共and partially also to ZrO兲 and Si2O3. 23
J. E. Greene, R. E. Klinger, T. L. Barr, and L. B. Welsh, Chem. Phys.
The results have been discussed in terms of the model of Lett. 62, 46 共1979兲.
‘‘lattice relaxation with chemical guidance,’’ considering the 24
J. H. Thomas and S. Hofmann, J. Vac. Sci. Technol. A 3, 1921 共1985兲.
25
recombination processes occurring after the collision cascade S. S. Chao, J. E. Tyler, Y. Takagi, P. G. Pai, G. Lucovsky, S. Y. Liu, C.
as thermodynamically driven phenomena. In particular, we K. Kong, and M. J. Mantini, J. Vac. Sci. Technol. A 4, 1574 共1986兲.
26
find that the empirically established limit of 0.7–1.0 eV/atom D. F. Mitchell, G. I. Sproule, and M. J. Graham, Surf. Interface Anal. 15,
487 共1990兲.
for the enthalpy increase, already proposed for the observa- 27
S. Hofmann and J. H. Thomas, J. Vac. Sci. Technol. B 1, 43 共1983兲.
tion of reduction effects 共or preferential O loss兲 in simple 28
S. Hofmann and J. M. Sanz, J. Trace and Microprobe Tech. 1, 213
oxides,33 holds also for ZrO2 and SiO2 systems, as demon- 共1982–83兲.
strated by the experimental observation of irradiation- 29
P. J. Martin, H. A. Macleod, R. P. Netterfield, C. G. Pacey, and W. G.
induced Zr2O3 and Si2O3 metastable oxides. Also the process Sainty, Appl. Opt. 22, 178 共1983兲.
of O loss from ZrSiO4, essentially due to the reduction of 30
G. E. McGuire, Surf. Sci. 76, 130 共1978兲.
ZrIV species, can be explained by the same thermodynamic
31
R. Kelly, Nucl. Instrum. Methods 182/183, 351 共1981兲.
32
arguments used for the simple oxides. R. Kelly, in Ion Bombardment Modification of Surfaces: Fundamentals
and Applications, edited by O. Auciello and R. Kelly 共Elsevier, Amster-
However, two further unexpected effects have been ob-
dam, 1984兲, p. 79.
served in irradiated ZrSiO4, namely 共1兲 a remarkable de- 33
R. Kelly, Mater. Sci. Eng., A 115, 11 共1989兲.
crease of the Si/Zr atomic ratio from 1 to 0.63, due to the 34
R. Kelly, I. Bertóti, and A. Miotello, Nucl. Instrum. Methods Phys. Res.
preferential sputtering of SiO2 with respect to ZrO2, and 共2兲 B 80/81, 1154 共1993兲.
a higher degree of reduction of the ZrIV species with respect 35
G. Marletta, F. Iacona, and R. Kelly, Nucl. Instrum. Methods Phys. Res.
to the pure ZrO2 case 共ZrO1.70 vs ZrO1.85兲. The first effect is B 65, 97 共1992兲.
discussed in terms of the possible occurrence of BIS mecha-
36
M. A. Langell, Surf. Sci. 186, 323 共1987兲.
37
D. Hasselkamp, K. G. Lang, A. Scharmann, and N. Stiller, Nucl. Instrum.
nism, similar to that found for the bombardment of
Methods 180, 349 共1981兲.
MgAl2O4. The second effect is discussed by invoking the 38
G. M. Ingo and G. Marletta, Nucl. Instrum. Methods Phys. Res. B 116,
possible occurrence of a redox reaction due to competing 440 共1996兲.
recombination processes of O, respectively, with Si and Zr in 39
R. Holm and S. Storp, Appl. Phys. 12, 101 共1977兲.
the relaxation step during the quenching of the collision cas- 40
C. Morant, J. M. Sanz, and L. Galán, Phys. Rev. B 45, 1391 共1992兲.
cade.
41
W. Reuter, Nucl. Instrum. Methods Phys. Res. B 15, 173 共1986兲.
42
I. Bertóti, A. Tóth, M. Mohai, R. Kelly, and G. Marletta, Thin Solid Films
241, 211 共1994兲.
ACKNOWLEDGMENTS 43
F. J. Grunthaner, P. J. Grunthaner, R. P. Vasquez, B. F. Lewis, J. Maser-
The authors gratefully acknowledge the financial support jian, and A. Madhukar, Phys. Rev. Lett. 43, 1683 共1979兲.
provided by MURST 共National Project on ‘‘Crescita, strut-
44
T. P. Nguyen and S. Lefrant, J. Phys.: Condens. Matter 1, 5197 共1989兲.
tura e reattivitá di superfici di materiali e di film
45
J. Finster, D. Schulze, and A. Meisel, Surf. Sci. 162, 671 共1985兲.
46
F. Iacona, S. Lombardo, and S. U. Campisano, J. Vac. Sci. Technol. B 14,
superficiali’’-1997兲 and CNR 共Rome兲 to the research.
2693 共1996兲.
47
A. R. Gonzáles-Elipe, J. M. Sanz, A. Fernández, J. P. Espinós, and G.
1
M. Cotter and R. G. Egdell, J. Solid State Chem. 66, 364 共1987兲. Munuera, Surf. Interface Anal. 19, 286 共1992兲.
2
S. Nagai and Y. Shimizu, J. Nucl. Mater. 128/129, 605 共1984兲. 48
D. Leinen, A. Fernández, J. P. Espinós, and A. R. Gonzáles-Elipe, Surf.
3
S. Thomas, J. Appl. Phys. 45, 161 共1974兲.
4 Interface Anal. 20, 941 共1993兲.
J. R. Pitts and C. W. Czanderna, Nucl. Instrum. Methods Phys. Res. B 13,
245 共1986兲.
49
E. Taglauer, Appl. Surf. Sci. 13, 80 共1982兲.
5
L. Calliari, Nucl. Instrum. Methods Phys. Res. B 58, 199 共1991兲.
50
R. Kelly, Surf. Sci. 90, 280 共1979兲.
51
6
L. W. Hobbs, Ultramicroscopy 3, 381 共1979兲. A. Torrisi, G. Marletta, A. Licciardello, and O. Puglisi, Nucl. Instrum.
7
R. Kelly, Nucl. Instrum. Methods Phys. Res. B 39, 43 共1989兲. Methods Phys. Res. B 32, 283 共1988兲.
8
M. C. Wittels and F. A. Sherrill, Phys. Rev. Lett. 3, 176 共1959兲. 52
H. J. Fecht and W. L. Johnson, Nature 共London兲 334, 50 共1988兲.
9
M. C. Wittels, J. O. Stiegler, and F. A. Sherrill, Reactor Sci. Technol. 16, 53
D. L. Douglass, in Corrosion of Reactor Materials 共Intern. Atomic En-
237 共1962兲. ergy Agency, Vienna, 1962兲, p. 223.
10
E. R. Vance and J. N. Boland, Radiat. Eff. 26, 135 共1975兲. 54
T. Smith, J. Electrochem. Soc. 112, 101 共1977兲.
11
M. C. Wittels and F. A. Sherrill, Phys. Rev. 93, 1117 共1954兲.
12
55
W. C. Butterman and W. R. Foster, Am. Mineral. 52, 884 共1967兲; See
F. W. Clinard, D. L. Rohr, and W. A. Ranken, J. Am. Ceram. Soc. 60,
also E. M. Levin, C. R. Robbins, and H. F. McMurdie, Phase Diagrams
287 共1977兲.
13
M. C. Wittels and F. A. Sherrill, J. Appl. Phys. 27, 643 共1956兲. for Ceramists, Vol. II 共American Ceramic Society, Columbus, OH, 1964兲,
14
M. C. Wittels and F. A. Sherrill, in Advances in X-ray Analysis, edited by Fig. 2400.
56
W. M. Mueller 共Pitman, London, 1959兲, Vol. 3, p. 269. T. Murakami, B. C. Chakoumakos, R. C. Ewing, G. R. Lumpkin, and W.
15
H. M. Naguib and R. Kelly, J. Nucl. Mater. 35, 293 共1970兲. J. Weber, Am. Mineral. 76, 1510 共1991兲.
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