X-ray photoelectron spectroscopy study of bombardment-induced compositional

changes in ZrO 2 , SiO 2 , and ZrSiO 4

Fabio Iacona, Roger Kelly, and Giovanni Marletta

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

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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

I. INTRODUCTION ion-bombarded SiO2,30 when the ion energy is low enough,

Radiation effects in ZrO2, SiO2, and ZrSiO4 共zircon兲 have
a long history of study including the following results 共see
Table I兲:
共a兲 Electrons. With incident low-energy electrons, ZrO21
and SiO22–5 surfaces lost O, an effect probably due to pref-
erential sputtering of electronic origin while crystalline SiO2
共quartz兲 amorphized.6 A far more significant observation,
however, was that SiO2 showed a bombardment-induced
segregation 共BIS兲 profile.5 Such a profile contains very ex-
plicit mechanistic information.7
共b兲 Neutrons. With incident neutrons ZrO2 retained its
monoclinic crystal structure,8,9 zircon was also unchanged,10
whereas SiO2 amorphized readily.11 These results are re-
flected also in the neutron-induced swelling, with that for
ZrO2 共⭐2%兲12 being significantly less than that for SiO2
共⬃15%兲.11 Contrary claims regarding the stability of ZrO2
and zircon13,14 are due to U impurities 关see footnote 共a兲 to
Table I兴.
共c兲 Ions. Heavy ion effects were severe, with ZrO2 show-
ing both an amorphous-to-cubic transition15,16 and a
monoclinic-to-cubic transition,9,13 and SiO217,18 and
zircon10,17,19,20 amorphizing. In addition, ZrO2 and SiO2
showed varying extents of O loss.4,16,21–29 In so far as SiO2
loses O, it appears to show a BIS profile.4 The loss of O from
a兲
Electronic mail: iacona@imetem.ct.cnr.it
is most likely a near-threshold effect such that the difference
in energy transfer to O and Si becomes important.31,32
In spite of the abundant information with the ZrO2 and
SiO2 systems, currently there is conflict with regard to what
extent ZrO2 and SiO2 are stable with respect to O loss. Ther-
modynamically, they should both be totally stable.33,34 Ac-
cordingly, we have undertaken a new study of their stability
with respect to heavy-particle impact in comparison with
ZrSiO4 共zircon兲 in order to investigate the response of the
simple oxides with respect to the corresponding mixed oxide
system. In fact, it has been shown that mixed oxide systems
may undergo unexpected compositional change, like that
found with MgAl2O4.35
In particular, in the present article we mainly focus our
interest on the phenomena related to particle–surface inter-
action, by performing in situ experiments using x-ray photo-
electron spectroscopy 共XPS兲. A special feature of the present
set of experiments consists of the fact that the samples have
been irradiated at 400 °C, because it has been shown that ion
irradiation at analogous temperature allows to identify intrin-
sic O loss in systems such as CoO and NiO, which are stable
at room temperature.36
According to a well-established mechanistic analysis,21,33
we make use of thermodynamical arguments to discuss the
beam-induced compositional modifications at the steady
state. This approach, implicitly requiring the existence of an

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.

Ion impact Ion impact

Substance Electron impact Neutron impact 共structure兲 共composition兲

ZrO2 ••• ••• amorph.˜cubic 共Refs. 15,16兲 •••

共amorphous兲
ZrO2 ••• monoclinic 共Refs. 8,9兲a mono.˜cubic 共Refs. 9,13兲 ZrO1.77 共Ref. 26兲
共crystalline兲 ZrO1.81 共Ref. 22兲
O loss 共Refs. 16,29兲
ZrO2 O loss 共Ref. 1兲 ⬍2% swelling 共Ref. 12兲 no change ZrO⬍1.8 共Ref. 23兲
共stabilized兲
SiO2 surface of Si 共Refs. 2,3兲 ••• no change SiO1.8 共Ref. 24兲
共amorphous兲 SiO⬍0.95共Ref. 4兲 O loss 共Ref. 25兲
BIS profile 共Ref. 5兲 SiO1.59 共Ref. 4兲
SiO1.97共Ref. 26兲
SiO1.86共Ref. 22兲
stable 共Refs. 25,27兲
BIS profile 共Ref. 4兲
SiO2 amorphous 共Ref. 6兲 amorphous 共Ref. 11兲 amorphous 共Refs. 17,18兲 •••
共quartz兲 ⬃15% swelling 共Ref. 11兲
ZrSiO4 ••• normal crystal 共Ref. 10兲a amorphous 共Refs. 10,17,19,20兲 •••
共zircon兲
a
The contrary claims, that monoclinic ZrO2 became cubic 共see Ref. 13兲 and zircon amorphized 共see Ref. 14兲 due to neutron bombardment, can be understood
in terms of U impurities 共see Refs. 8–10兲.

equilibrium condition, is justified by considering that the fi-
nal steady state, i.e., the stable composition of the irradiated
layers, is the result of a long term equilibration, well after the
intrinsically nonequilibrium step of energy deposition related
to the collision cascade physics and sputtering. In particular,
the energy deposition step produces a more or less large
volume in which the bonds are broken within a collision
cascade, with a subsequent ‘‘equilibration step’’ consisting
in bond formation or recombination, vacancy formation,
short and long term diffusion processes, including the imme-
diate escape of small gaseous species or segregation phe-
nomena. The final results of this complex set of processes
can reasonably be rationalized in term of ‘‘energy-limited’’
rearrangement, i.e., in a thermodynamical framework.
Overall conclusions from this work will be seen to be 共a兲
that pure SiO2 loses small amount of O, 共b兲 pure ZrO2 shows
the partial reduction of ZrIV ions 共about 23% of the total兲 to
lower oxidation states, while 共c兲 ZrSiO4 shows both an un-
expected loss of SiO2 as well as the massive reduction of
ZrIV cations 共about 50% of the total兲. It is to stress the
marked difference observed between the degree of Zr cation
reduction respectively in ZrO2 共consistent with a final com-
position ZrO1.85兲 and zircon 共final composition ZrO1.70兲.
Finally, it will be concluded that the instability of SiO2,
ZrO2, and ZrSiO4 can be understood if compounds like Si2O3
and Zr2O3, produced under irradiation, are metastable at low
enough temperatures.
II. EXPERIMENT
The SiO2 targets consisted of thick and polished amor-
phous slices of optical grade fused silica obtained from Dow
Corning. The ZrO2 and ZrSiO4 targets were prepared by
compacting high purity powders 共99.99%, obtained from Al-
drich, 325 mesh for zircon兲.
The experiments were performed in situ in a Kratos ES
300 XPS apparatus. The spectrometer had a base pressure of
1⫻10⫺9 Torr and was equipped with a dual anode 共Al/Mg兲,
a hemispherical analyzer, and a preparation chamber, held at
the same vacuum of the main chamber, used for the in situ
bombardment of the oxides. The analyses have been per-
formed by using Al K ␣ 1,2 radiation at 1486.6 eV.
The irradiation treatments were performed by using a fast
atom gun 共Ion Tech Ltd. FAB 11NF兲, operated with Ar° at 8
keV and with the particle flux incident at 45° with respect to
the sample normal. A fast atom beam 共FAB兲 was used in
order to minimize the errors in the particle fluence, as far as
the neutral projectiles are not affected by the possible forma-
tion of strong positive fields, built as a consequence of the
secondary electron emission in highly insulating samples. In
each case, specimens smaller than the FAB spot were at-
tached with silver cement to a copper heating stage. The
effective ‘‘current density’’ calculated as if the Ar° were
Ar⫹, was about 共6.0⫾0.5兲/␥ ␮A/cm2, where ␥⬇1.3 is the
secondary electron yield of bombarded Cu.37 The corre-
sponding fluence per minute was about (2.4⫻1015)/ ␥
ions/cm2 min. The projected ranges for 8 keV Ar° were esti-
mated to be about 85 Å for SiO2, and 60 Å for ZrO2 and
ZrSiO4. These values are comparable with the XPS sampling
depth, ensuring that the analyzer layers are homogeneously
irradiated.
Compositions were determined by monitoring the Zr 3d,
Si 2p, and O 1s XPS lines. Environmental carbon contami-
nation was a general problem, so the samples were first
brought to 400 °C, the vacuum was allowed to reach the
10⫺8 Torr scale, and then a preliminary FAB irradiation was
performed 共irradiation time 20 s兲. A strong indication that
such a procedure was adequate to minimize carbon without
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

the Zr 3d and Si 2p XPS line shapes and relative intensities

obtained by merely heating the samples were in all cases
identical to those obtained after the initial 20 s bombard-
ment. This was not true for ZrSiO4 samples, which showed a
detectable reduction of ZrIV species already after this initial
bombardment. Accordingly, in this case, we have chosen as
the starting surface the one obtained after heating.
Zr 3d and Si 2p peaks were analyzed by a fitting proce-
dure using Gaussian peak shapes and Shirley-type back-
ground subtraction. To analyze the Zr 3d peaks of ZrO2 and
ZrSiO4, the following constraints were imposed: the spin or-
bit splitting, derived experimentally, was fixed at 2.4 eV; the
3d 5/2 :3d 3/2 intensity ratio was taken as 3:2 for each doublet;
the full width at half maximum 共FWHM兲 of the peaks was
maintained constant at 1.8 eV for ZrO2 and 2.0 eV for
ZrSiO4. With these constraints, the Zr 3d doublet could be
fitted initially with one component and, after the bombard-
ment, with at most three components, corresponding to three
different oxidation states. Peak fitting was simpler with Si 2p
FIG. 1. XPS Zr 3d bands including the peak fitting of 共a兲 unbombarded
lines. Indeed, since the spin orbit splitting between the 2p 3/2 ZrO2, and ZrO2 bombarded at 400 °C to 共b兲 5.6⫻1016 Ar°/cm2 and 共c兲
and 2p 1/2 components is too small 共about 0.6 eV兲 to be re- 1.5⫻1017 Ar°/cm2.
solved by using the unmonochromatized K ␣ 1,2 radiation, the
Si 2 p peaks of unbombarded oxides were fitted by using a
single Gaussian 共FWHM⫽2.1 eV for SiO2 and 2.5 eV for oxygen content, leading to a final composition of ZrO1.85, a
ZrSiO4兲; after bombardment, a second Gaussian correspond- loss which constitutes a significant problem in view of the
ing to a different oxidation state, is needed. thermodynamic stability of ZrO2 共Table II兲.
The O/Zr atomic ratio of bombarded ZrO2 may also be
derived from the quantitative analysis of the relative XPS
III. RESULTS
peaks, by correcting peak areas for the calculated photoion-
A. ZrO2 ization cross sections and for the transmission function of the
The ZrO2 is assumed to be initially stoichiometric, as spectrometer. We have found that for ZrO2, it is not possible
shown by the fact that the fitting of the corresponding Zr 3d to obtain a reliable evaluation of this ratio by using this
XPS band, reported in Fig. 1共a兲, exhibits only one well- method. The starting ZrO2 surface indeed results strongly
resolved 3d 3/2 and 3d 5/2 doublet, the binding energy of the affected by O contamination 共O/Zr⫽2.25兲, probably due to
3d 5/2 component being 182.2⫾0.1 eV, in good agreement the presence of water and hydroxides; the cleaning procedure
with literature for the tetravalent Zr cations.28,38 The heating described in the experimental section is only partially effec-
at 400 °C and a short Ar° bombardment do not change the tive in eliminating the excess oxygen 共O/Zr⫽2.05兲. After
peak shape, being on the other hand very effective in elimi- bombardment, the O/Zr ratio evolves following a trend that
nating surface carbon contamination and possibly adsorbed is qualitatively very similar to that obtained from peak fit-
oxygen-containing species. As the bombardment proceeds, ting, confirm the occurrence of ZrIVreduction; however, the
additional components are developed, being assigned to par- O/Zr ratio values are probably still affected by errors due to
tially reduced Zr species. The response of ZrO2 to 8 keV Ar° residual O contamination, being the used ZrO2 samples a
bombardment at 400 °C is shown in detail by the XPS Zr 3d
peaks in Figs. 1共b兲 and 1共c兲. Figure 1共b兲 refers to a 5.6
⫻1016 Ar°/cm2 bombardment and shows the formation of a
new doublet, shifted from the one due to ZrIV by 1.3 eV.
Such a new doublet is assigned to ZrIII species, 共i.e., to a
substoichiometric oxide Zr2O3兲.38,39 Finally, Fig. 1共c兲 refers
to a 1.5⫻1017 Ar°/cm2 bombardment, and shows an in-
creased content of ZrIII and a third doublet, shifted from the
one relative to ZrIV by 3.1 eV and assigned to ZrII species
共i.e., to a possible form ZrO兲; it is to stress that the observed
chemical shift is remarkably smaller than that reported in
literature for ZrIVand Zr0, i.e., 4.1–4.4 eV.39,40
Figure 2 plots the evolution with increasing particle flu-
ence of the O/Zr atomic ratio, as derived from the Zr 3d peak FIG. 2. O/Zr atomic ratio, derived from XPS Zr 3d peak fitting analysis, vs
fitting. It is possible to note a continuous decrease of the fluence for ZrO2 bombarded with 8 keV Ar° at 400 °C.

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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

ZrO2 共here兲 Zr 共s兲 3.80

ZrO 共s兲 ⬎1.90
1
2 Zr2O3 共s兲
⬎0.95
SiO2 共here兲 Si 共s兲 3.15
SiO 共s兲 ⬎1.58
1
2 Si2O3 共s兲
⬎0.79
FIG. 3. O/Si atomic ratio derived from XPS Si 2p peak fitting analysis and
ZrSiO4 共here兲 Zr 共s兲⫹Si 共s兲 3.52 from the (O 1s)/(Si 2p) peak area ratio, vs fluence for SiO2 bombarded
ZrO 共s兲⫹SiO2共s兲 ⬎1.25 with 8 keV Ar° at 400 °C.
1
2 2O3 共s兲⫹SiO2共s兲
Zr ⬎0.77
MgO 共Ref. 35兲 Mg 共s兲 3.12
Al2O3共Ref. 35兲 Al 共s兲 3.48
MgAl2O4 共Ref. 35兲 Mg 共s兲⫹2 Al 共s兲 3.43 lower binding energy 共chemical shift⬇1.5 eV兲 observed after
the bombardment is due to the reduced species Si2O3.41–46
a
Obtained by dividing the enthalpy change for oxygen loss by the number of This is probably due to the different nature of this sample 共a
atoms in the formula of the starting substance. For example, for MgO⫽Mg
1 polished slice兲 with respect to ZrO2 共powder compact, easily
共s兲, this number is 2 and for ZrSiO4⫽ 2Zr2O3 共s兲⫹SiO2 共s兲, it is 6.
subjected to massive adsorption of O-containing species兲.
The results shown in Fig. 3 and Table III demonstrate that
powder compact, easily subjected to massive adsorption of both methods of O content determination reveal a definite O
O-containing species. On the other hand, the presence of loss from SiO2. In particular, Fig. 3 shows that, at variance of
excess oxygen cannot affect in any way the peak fitting re- the ZrO2 case, characterized by a continuous decrease of the
sults for Zr 3d bands; therefore, we have decided to use this O/Zr ratio up to about 2⫻1017Ar°/cm2, the bombarded SiO2
last procedure to describe the composition of bombarded readily reaches a steady state composition of SiO1.95 already
ZrO2. The obtained data are reported in Table III, where they at 2.7⫻1015 Ar°/cm2 bombardment. Also for SiO2, the oxy-
are also compared with literature data. gen loss constitutes a significant problem in view of its ther-
modynamic stability 共Table II above兲.
B. SiO2
C. ZrSiO4
SiO2 samples were bombarded at 400 °C with 8 keV Ar°
after the same cleaning procedure already described for Zircon samples were bombarded at 400 °C with 8 keV
ZrO2, i.e., heating at 400 °C and a 20 s bombardment. At Ar° after a heating process at 400 °C to eliminate surface
variance with the ZrO2 case, there is an excellent agreement carbon and adsorbed oxygen. As mentioned above, we could
between the XPS results expressed both as the atomic ratio not use in this case the short bombardment to improve sur-
O/Si, derived from peak areas corrected for the calculated face cleanliness because fluences lower than 1015 Ar°/cm2
photoionization cross sections and for the transmission func- have been found to induce reduction of ZrIV species in zir-
tion of the spectrometer, and as the results of the fitting of con. However, the simple heating was sufficient to minimize
the Si 2p peaks, under the hypothesis that the shoulder at the carbon content.

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.

Results of Mitchell et al. 共see Ref. 26兲 for

Result of 8 keV Ar° related fixed-valence systems
Substance bombardment 共here and in Ref. 35兲 共3 keV Xe⫹ 兲

MgO MgO1.00共Ref. 35兲 CaO, MgO, SrO, ZnO are stable;

BaO0.98, BeO0.97, CdO0.98,
NiO0.79, PbO0.82 evolve as shown.
Al2O3 AlO1.50 共Ref. 35兲 Al2O3, Ga2O3, In2O3, La2O3
Sc2O3, Y2O3 are stable; B2O2.94 ,
Cr2O2.85 evolve as shown.
MgAl2O4 0.70MgO•Al2O3 共Ref. 35兲 •••
ZrO2 ZrO1.85 HfO1.51, ThO1.72, ZrO1.77
SiO2 SiO1.95 GeO1.98, SiO1.97
ZrSiO4 ZrO1.70•0.63SiOx •••

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 2775 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2775

Two main points have to be considered with bombarded

zircon: 共a兲 if the SiO2 and ZrO2 sublattices undergo reduc-
tion as in the simple oxides and to what extent for a given
fluence; 共b兲 if there is a change in the Si/Zr atomic ratio, i.e.,
if one component of the mixed oxide is sputtered preferen-
tially, as already found in spinel.35
Let us address point 共a兲. First, we are unable to clearly
identify the real behavior of the SiO2 sublattice in zircon.
This is because the peak fitting procedure in this case is more
difficult than in pure SiO2, due to the increased FWHM of
the Si 2p peaks 共from 2.1 to 2.5 eV兲, which prevents a rea-
sonable fitting procedure, also if an extensive reduction can
be excluded on the basis of the symmetric peak shape. Fur-
thermore, upon the compositional point of view, the relevant
O/Si atomic ratio cannot be properly evaluated because, as
already observed for pure ZrO2, our starting sample of zircon
still contains an excess of oxygen, due to its nature of pow-
der and to the mild cleaning process before the bombard-
ment. This makes very hard to understand if a small O loss
was induced by irradiation for the SiO2 sublattice, or if, at FIG. 4. XPS Zr 3d bands including the peak fitting analysis for 共a兲 unbom-
variance of the pure SiO2, the oxidation state SiIV is stable in barded ZrSiO4, and ZrSiO4 bombarded at 400 °C with 共b兲 3.8
⫻1016 Ar°/cm2 and 共c兲 7.6⫻1016 Ar°/cm2.
zircon.
On the other hand, our results show that the irradiation
induces very significant reduction phenomena for Zr species. ratio decreases from the initial value of 1.00, to a final value
Indeed, in this case the fitting procedure of the Zr 3d peaks of 0.63. This indicates that particle irradiation induces a
remains a very powerful tool to determine their oxidation strong preferential sputtering of the SiO2 component with
state, as much as the whole Zr 3d peak shape is drastically respect to ZrO2 in bombarded zircon.
modified by irradiation. Figure 4共a兲 reports the results of According to the described data, we can express the final
peak fitting for unbombarded zircon, showing that only the composition of bombarded zircon, as reported in Table III, as
ZrIV doublet is present. After irradiation, the formation of ZrO1.70•0.63SiOx , where x is expected to be in the range
significant amount of reduced species is observed. In particu- 1.90–2.00.
lar, Fig. 4共b兲 refers to a sample irradiated to 3.8
⫻1016 Ar°/cm2 fluence and it shows that the formed ZrIII IV. DISCUSSION
species constitute as much as the 26% of the whole Zr 3d
band, while the amount of the same component for pure The mechanism of beam-induced chemical or composi-
ZrO2 irradiated at a very close fluence (5.6 tional modifications is still unclear. In fact, a large literature
⫻1016 Ar°/cm2 ) is only 12%. Figure 4共c兲 finally refers to a body denies that the compositional modification in oxides
zircon sample irradiated at a slightly higher fluence, i.e., can be explained in terms of the sputtering process intended
7.6⫻1016 Ar°/cm2, showing that the total percentage of re- as mere ballistic effects.26,33,47,48 As matter of fact, these
duced Zr species, including both ZrIII and ZrII contributions, compositional effects in general do not fit in any way with
is about 50% of the total 3d peak, while for pure ZrO2, also
at fluences higher than 1⫻1017 Ar°/cm2, the reduction
amount is only slightly higher than 20%.
The results of peak fitting are summarized in Fig. 5共a兲,
showing that ZrO2 sublattice in ZrSiO4 evolves towards a
final composition of ZrO1.70. According to the above discus-
sion, this value is remarkably lower than that one observed
for pure ZrO2, corresponding to ZrO1.85.
Concerning point 共b兲, the Si/Zr atomic ratio has been
carefully investigated. Obviously, this information can be de-
rived only from the relevant ratio between the Si 2p and
Zr 3d peak areas. Due to the fact that the total area for each
peak is needed, the results we obtained are completely reli-
able, also taking into account the above described problems FIG. 5. 共a兲 Oxygen content of ZrO2 sublattice, and 共b兲 Si/Zr atomic ratio vs
fluence, for ZrSiO4 bombarded with 8 keV Ar° at 400 °C. In 共a兲 the values
with Si 2p peak fitting, which indeed do not affect the Si/Zr for x are calculated from the peak fitting analysis of the relative XPS Zr 3d
ratio. The modification trend with Ar° fluence of the Si/Zr peaks, while in 共b兲 the Si/Zr atomic ratios are calculated from the
atomic ratio is plotted in Fig. 5共b兲. The figure shows that the (Si 2p)/(Zr 3d) peak area ratios.

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 2776 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes
ballistic processes, except for the very special case of near-
threshold effects occurring for large mass difference between
the projectile and the target atoms, i.e., He⫹on Ta2O5,
prompts the partial reduction of the oxide to TaO, while the
irradiation with Ar⫹ promotes the return of the system to the
initial composition.49
At variance of this, it is known that a very large number
of systems, like Fe2O3, TiO2, MoO3, CuO, Nb2O5, etc. are
strongly reduced to lower oxidation states under particle ir-
radiation, while others 共very close in mass兲 like for instance,
ZnO, Al2O3, MgO, CaO, Sc2O3, Cu2O, etc. are totally stable
under the same irradiation conditions. Furthermore, a num-
ber of systems, like CoO and NiO, have been shown to have
a borderline behavior, being reduced to metal state under
irradiation at high temperature 共about 400 °C兲 and stable at
room temperature.36
This reduction of the cation oxidation state has been in-
terpreted in terms of various mechanisms, including model
like 共a兲 thermal spike,50 共b兲 bombardment-induced gibbsian
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-
sional transport of O,33 and 共f兲 lattice relaxation with chemi-
cal guidance.33 All these models are based on thermody-
namical arguments, basically considering the reorganization
of the disturbed network at very long term. These models are
exhaustively discussed with respect to available experimen-
tal results in Refs. 21 and 33.
In the following, we will mainly use the model of lattice
relaxation with chemical guidance to analyze the irradiation-
induced reduction of ZrO2 and SiO2. In addition, we will
show that the peculiar behavior of ZrSiO4, mainly consisting
in the higher degree of reduction observed for ZrIVcations
with respect to ZrO2 and in the preferential loss of SiO2,
cannot be explained only in terms of the above quoted
model, involving the occurrence of more complex phenom-
ena.
A. ZrO2 and SiO2
Our estimate for irradiation-induced O loss from ZrO2,
producing a ZrO1.85 composition, is similar to that found in
some previous studies 共Table I兲, also if some author reports a
catastrophic reduction of irradiated ZrO2 up to the formation
of metallic Zr.28,40 In any case, there is a major conflict with
respect to the supposed thermodynamic stability of ZrO2
共Table II兲.
One possibility33 is that the existence of O loss with ZrO2
lies in the O loss being kinetic rather than thermodynamic. It
would thus occur in spite of the thermodynamic stability
because of the unusually high diffusivity of O in substoichio-
metric or doped ZrO2,53,54 an explanation that has been pro-
posed also for HfO2, Nb2O5, Ta2O5, and WO3.33 One envis-
ages that O produced in the collision cascade is quickly
diffusing to the surface, before undergoing recombination at
the defective sites, and then is desorbed as O2.
An alternative description of why ZrO2 loses O in spite of
the supposed thermodynamic stability can be given in terms
of the above quoted model of lattice relaxation with chemical
J. Vac. Sci. Technol. A, Vol. 17, No. 5, Sep/Oct 1999
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2776
guidance. The occurrence of the chemical reduction process
in this case would depend on the possibility that the substo-
ichiometric Zr2O3 and/or ZrO compounds are metastable if
formed, due to the recombination processes in the perturbed
volume after the collision cascade, at a low enough tempera-
ture.
The energetics of the whole process can be discussed in
the following terms:
We require that ⌬H be negative for
2ZrO⫽Zr⫹ZrO2,
and therefore obtain a limit for the heat of formation 共‘‘f’’兲:
⫺⌬H ZrO
f
⬍5.71 eV.
The same reasoning can be applied to the reaction,
Zr2O3⫽ZrO2⫹ZrO,
to yield
⫺⌬H Zr
f
⬍17.12 eV.
2O3
This is sufficient information to evaluate the enthalpy
changes for O loss from ZrO2:
ZrO2⫽ 21Zr2O3⫹ 41O2, 1
⌬H⬎0.95 eV/atom; 共1a兲
3
ZrO2⫽ZrO⫹ 12O2, 1
3 ⌬H⬎1.90 eV/atom. 共1b兲
We have already pointed out that available experimental
data for other oxides suggest that there is a tendency to lose
O when the enthalpy change, defined as in Eqs. 共1a兲 and
共1b兲, is 0.7–1.0 eV/atom or less.33,34 Accordingly, being the
formation of Zr2O3 under the conditions of a collision cas-
cade clearly demonstrated by our XPS data, then O loss from
ZrO2 can be explained as a purely thermodynamic effect.
Our estimate for O loss from SiO2 (SiO0.95), is also in
agreement with most experimental work 共Table I兲. Again
there is a major conflict with respect to the supposed ther-
modynamic stability of SiO2 共Table II兲. As in the ZrO2 case,
the conflict is removed by considering, in agreement with
our XPS data, the irradiation-induced formation of partially
reduced metastable species like Si2O3.
The existence of lower oxidation states of SiO2 has been
widely reported in literature. Charge states intermediate be-
tween Si0and SiIV were found when Si was bombarded with
O⫹2.
41
It is important to recognize, however, that the bom-
bardments were such that the quantity of oxygen was not
sufficient to saturate the bonds. Intermediate Si oxidation
states have been found by using XPS also in bombarded
Cr–Si–O layers42 as well as at the SiO2 /Si interface,43 and in
evaporated,44 sputter deposited,45 or chemical vapor
deposited46 substoichiometric silicon-oxygen mixtures.
As already shown for ZrO2, the enthalpy change for the
reduction of SiO2 can be evaluated as
SiO2⫽ 21Si2O3⫹ 41O2, 1
3 ⌬H⬎0.79 eV/atom. 共2兲
 2777 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes
Also this value is lower than 1 eV, the empirically estab-
lished limit for O loss from bombarded oxides, suggesting
that O loss from SiO2, as for ZrO2, would be possible as a
purely thermodynamic effect.
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
the reduction trend of ZrIV species and the progressive deple-
tion of SiO2 species from zircon are reported vs fluence. It
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
Ar°/cm2, similarly to the result found for pure ZrO2 共see
above兲.
Let us discuss at first the ZrIV reduction process. Consid-
ering a kinetic mechanism, we note that too little is known
about the nature of defects in zircon to draw any firm con-
clusion. We do not know, for example, whether zircon will
be found to resemble ZrO2 and have a high O diffusivity.
On the other hand, the thermodynamic argument for zir-
con is exactly the same as for ZrO2, based on the assumption
that the reduced forms Zr2O3 and ZrO are metastable if
formed at low enough temperature 共Table II兲. However, the
higher degree of reduction shown by the ZrO2 sublattice in
zircon (ZrO1.70) with respect to that observed in ZrO2
(ZrO1.85) deserves a separate discussion. This effect is re-
called in Fig. 6, where the percentage of residual ZrIV spe-
cies, derived by peak fitting procedure, is plotted against the
irradiation fluence for the two systems. The figure clearly
demonstrates the higher efficiency of the bombardment-
induced reduction process exhibited by the ZrO2 sublattice in
zircon along all the explored fluence range with respect to
the reduction effect in pure ZrO2.
Actually, other examples of the correlation between
beam-induced chemistry and the chemical environment in
oxides have been already observed. In particular, it has been
found that TiIV is more easily reduced in pure TiO2 than in
titanates, while, on the contrary, NiII is more easily reduced
in NiTiO3 共where it is quantitatively reduced to the metallic
state兲 than in pure NiO.47,48 These peculiar behaviors have
been explained with the occurrence of redox reactions in the
framework of the model of lattice relaxation. In particular,
for the NiII case, it has been suggested the occurrence of a
reaction of the type:
NiOx ⫹TiOy ⫽Ni⫹TiOz 共 x⬍1, y⬍2, z⬎y 兲
that is able also to account for the observed lower degree of
reduction of TiIV in NiTiO3 with respect to TiO2.
A similar approach can be applied also to the present
experimental results. Indeed, the higher degree of reduction
shown by the ZrIV species in zircon could be due to a redox
reaction involving the preferential recombination of O with
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2777
FIG. 6. Comparison of the relative amount of residual ZrIV species vs fluence
for ZrO2 and ZrSiO4 bombarded with 8 keV Ar° at 400 °C. The experimen-
tal values are derived from XPS peak fitting analysis of the Zr 3d lines.
the reduced SiOx species formed by the bombardment, that
obviously cannot occur in pure ZrO2. However, it should be
noted that such a redox mechanism should involve a relevant
amount of reacting reduced SiOx species, for which no ex-
perimental evidence exists at moment. Hence, further experi-
mental and theoretical work is needed in order to properly
account for the described effect.
Let us turn now to the possible mechanism producing the
relevant preferential sputtering of the Si-containing species
from zircon, as revealed by the marked decrease of the Si/Zr
atomic ratio from 1 to 0.63 at the highest irradiation fluence.
At the present state of the investigation we can only pro-
pose that BIS mechanism may concur to the observed effect,
as already seen in the case of MgAl2O4, where the preferen-
tial depletion of MgO component was observed under FAB
irradiation, and explained in terms of the sputtering of the
surface segregated MgO component, seen by angular re-
solved XPS measurements.35 In the present case, such mea-
surements have not been possible due to the powdered form
of the samples.
On the other hand, it could be objected that zircon is a
line compound at all temperatures55 and segregation like that
occurring in systems without fixed composition is not pos-
sible. We note, however, that zircon amorphizes 共Table I兲.
The fact that zircon is a line compound is therefore probably
not relevant in deciding whether or not segregation can oc-
cur. The amorphization would probably occur even for a
bombardment at 400 °C, as the crystallization temperature is
significantly higher, i.e., 760 °C20 or more.10 Furthermore,
we have no evidence about segregation in zircon, though
would pointing out that Y2O3 segregates in Zr0.72Y0.28O1.86.1
Apropos to zircon being a line compound, one might be
tempted to argue that mixed oxides tend to undergo demix-
ing when bombarded.47 Demixing in bombarded zircon has,
共3兲
however, been explicitly sought and found not to occur.56
Therefore, the suitable interpretation of the SiO2 preferen-
tial sputtering from zircon still remains an open problem. A
clarifying experiment would involve the use of angular re-
solved XPS measurements onto atomically flat zircon sur-
faces, in order to check the relevant profile of Si species
under irradiation.
 2778 Iacona, Kelly, and Marletta: XPS study of bombardment-induced compositional changes 2778

16
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21
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ACKNOWLEDGMENTS 43
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