Mikrochim.
Acta 133, 191±196 (2000)
Preparation of Cr2O3-Al2O3 Solid Solutions by Reactive
Magnetron Sputtering
Mirjam Witthaut , Rainer Cremer, Klaus Reichert, and Dieter Neusch
Lehrstuhl fur Theoretische H
uttenkunde, RWTH Aachen, Kopernikusstr. 16, D-52056 Aachen, Germany
Abstract. (Al,Cr)2O3 layers were deposited on
cemented carbide insert tips at a substrate temperature
-phases [5 ± 9]. For many applica-
of 500  C by means of reactive magnetron sputtering.
An Al target was sputtered in RF mode and a Cr target
in DC mode simultaneously in an oxygen/argon
plasma. The in¯uence of the Al and Cr sputter power
and of the oxygen partial pressure on composition and
structure of the (Al,Cr)2O3 layers as well as on the
binding states of their components were investigated.
Special attention was paid to the interpretation of
the O ls and O-KLL ®ne structure and peak shifts. For
the binary phases
-Al2O3 and Cr2O3, a good the moderate temperatures applied by PVD.
agreement with literature values was observed in
each case. In case of the ternary phases a continuous
shift of the energetic position of the O1s peak, the O-
KL23L23 transition and the modi®ed Auger parameter
 0 of oxygen between the two binary phases
-Al2O3 Al2O3, which is deposited in cubic Fd
and Cr2O3 could be detected, indicating a wide range
-Al2O3) at low temperatures and shows a phase
of solid solubility between Al2O3 and Cr2O3. As
revealed by grazing incidence X-ray diffraction, the
crystallinity of the ternary phases is less pronounced
as compared to the binaries and increases with
- to -Al2O3
increasing oxygen ¯ow rate.
-Al2O3 ®lms as deposited by
Key words: (Al,Cr)2O3; PVD; metastable solid solutions.
In the last years alumina has gained increased attention
as a hard coating material [1 ± 4]. This interest is based
on the high performance of -Al2O3 coatings as
deposited by thermal chemical vapour deposition
(CVD) processes. In contrast to thermal CVD the
deposition of alumina by physical vapour deposition
 To whom correspondence should be addressed
-Al2O3 and Cr2O3 at lower temperatures
utz
(PVD) in general leads to the formation of amorphous
or nanocrystalline
tions, -Al2O3 is favoured because of its hardness,
wear resistance, and thermal stability. On the other
hand, its deposition by thermal CVD is limited to
temperature resistant substrates like cemented carbides,
whereas the deposition of crystalline alumina by PVD
at substrate temperatures of less than 550  C would
allow to coat heat-sensitive substrates like tempered
steels. It is therefore desirable to ®nd suitable
deposition conditions for crystalline -Al2O3 ®lms at
Because a deposition of pure -alumina at substrate
temperatures below 550  C is not possible yet [10, 11],
the effect of chromium additions resulting in ternary
®lms has been investigated in this work. In contrast to
3m structure
(
transition to the stable R 3c structure (-Al2O3) at
temperatures of about 1000  C, Cr2O3 always forms
the stable rhombohedral R 3c structure at any condi-
tions. The phase transition from
induces lattice stresses and may lead to the spallation
of the ®lm. Thus,
magnetron sputtering seem to be unsuitable for high
temperature applications. The deposition of single-
phase (Al,Cr)2O3 ®lms in rhombohedral R 3c structure
could thus lead to hard and oxidation resistant
coatings for operation at elevated temperatures.
While complete solid solubility between -Al2O3
and Cr2O3 can be observed at temperatures above
950  C, a miscibility gap occurs at lower temperatures
[12]. No determination of the ranges of solid solution
between
192 M. Witthaut et al.

under the non-equilibrium conditions of PVD has

been made up to now.

Experimental

(Al,Cr)2O3 Deposition
The ®lms were deposited on cemented carbide insert tips
(Kennametal K313) in a Leybold L 560 HV reactive magnetron
sputtering system (residual gas pressure < 1  10ÿ4 Pa) at a
substrate temperature of 500  C. Aluminum was sputtered in RF
and chromium in DC mode simultaneously, both targets mounted
on PK9O magnetron cathodes. The argon and oxygen partial
pressures were adjusted by mass ¯ow controllers. The deposition
Fig. 1. Cathode voltages as a function of the oxygen ¯ow rate
time for all coatings was 120 min. A substrate bias of ÿ 90 V
during ®lm deposition for combined DC and RF sputtering
(140 W RF) was applied. In series 1 the coatings were deposited
with different compositions using varied RF and DC powers
between 0 and 300 W. The Ar partial pressure was held constant at
3.4  10ÿ1 Pa, the oxygen partial pressure was 3.9  10ÿ2 Pa. In linity of the Al2O3 ®lms. Consequently, a ®rst series
series 2 the DC/RF power ratio was held constant at 150/300 W was deposited at an oxygen ¯ow rate of 9 sccm, which
and the oxygen ¯ow rate varied between 5 and 50 sccm,
corresponding to 2.4  10ÿ2 to 1.9  10ÿ1 Pa.
is low enough to avoid target poisoning, but on the
other hand high enough to ensure the formation of a
pure oxide without metallic components. A second
Film Characterization by XPS, XAES, and GID series should illustrate the in¯uence of the oxygen
The composition of the ®lms as well as the chemical binding states ¯ow rate on the crystallinity and structure of the
of the components were analyzed by X-ray photoelectron ternary ®lms.
spectroscopy (XPS) and X-ray induced Auger electron spectro-
scopy (XAES) in a combined XPS/AES spectrometer Cameca The composition of the ®lms of series 1 corre-
Nanoscan 50 using non-monochromatized Mg K X-rays (200 W). sponds to the quasibinary section Al2O3-Cr2O3 with a
The spectra of the sputter-cleaned ®lms were recorded using a slight substoichiometry regarding oxygen (Table 1).
MAC3 analyzer in pulse counting mode with constant energy
resolution. Calibration was carried out on the Ag-M4N45N45
The XPS results of series 2 show that between 7.5 and
transition at 358.2 eV and the Au-M5N67N67 transition at 50 sccm oxygen ¯ow rate the aluminum content of the
2015.7 eV. Charge correction was made using the Ar 2p3/2 peak ®lms decreases with increasing oxygen ¯ow rate at
at 241.2 eV. Survey spectra were taken in the range of 0 ± 620 eV constant oxygen content. This can be explained by the
binding energy, step 0.5 eV, resolution 1 eV, dwell time 20 ms,
cycles 100. The spectra of the O-KLL group, superimposed with higher conductivity of chromium oxide in comparison
the Cr-LMM, were taken with step 0.2 eV, resolution 1 eV, dwell to alumina, both formed at the surface of the targets.
time 40 ms, cycles 100. The O1s peak was measured with step The resistivity differs by several orders of magnitude,
0.2 eV, resolution 1 eV, dwell time 20 ms, cycles 100. For
quanti®cation the Cr 2p3/2, Al 2s, and the O1s peaks were
107
cm for chromium oxide and 1014
cm for
considered. The background was subtracted according to the alumina [13]. Figure 1 shows that the DC cathode
method of Shirley and the relative sensitivity factors were voltage (Cr) is above 7.5 sccm less effected by
determined using pure -Al2O3 and Cr2O3 as standards.
increasing oxygen ¯ow rate than the RF one (Al),
The crystallographic structure of the ®lms was analyzed by
means of grazing incidence X-ray diffraction (GID) in a Siemens although a stronger change in case of a DC cathode
D 500 goniometer at an angle of incidence of 3 to the surface. should be expected due to charge effects. At an
Spectra were taken in the 2 range of 30 ± 80 using 900 W Cu K oxygen ¯ow rate of 5 sccm the Cr/Al ratio is much
radiation (0.154186 nm).
higher as compared to 7.5 sccm and simultaneously
the oxygen content revealed a distinct substoichio-
metry, probably indicating the deposition of a mixed
Results and Discussion
oxidic-metallic ®lm.
Figure 1 shows the voltages of the DC and RF cathode The O1s peaks of series 1 are shown in Fig. 2. The
in dependence of the oxygen ¯ow rate. Based on the line position of the Al2O3 ®lm corresponds well with
experiences with Al2O3 ®lms [10] the breakdown of the literature values of 530.8 ± 531.05 eV for -Al2O3
the RF cathode voltage indicates the formation of [13,14], the position of the O1s line in Cr2O3 is
alumina at the target surface. This effect leads to a slightly shifted to a lower binding energy as compared
decrease in sputtering rate and to a drop in crystal- to the literature value of 530.0 eV [15]. The difference
Preparation of Cr2O3-Al2O3 Solid Solutions by Reactive Magnetron Sputtering 193

Table 1. Composition of the sputtercleaned ®lms

Cr/at.-% Al/at.-% O/at.-%

PDC(Cr) /PRF(Al) /W
Series 1 0/300 0 40.8 59.2
O2 ¯ow rate: 70/300 9.5 35.2 55.3
9 sccm 150/300 25.2 16.1 58.7
230/150 37.5 6.6 55.9
150/0 42.6 0 57.4
O2 ¯ow rate/sccm O2 partial
pressure/mbar
Series 2 5 2.4  10ÿ4 27.5 20.5 52.0
PDC(Cr) /PRF(Al): 7.5 3.3  10ÿ4 16.1 25.0 58.9
150/300 W 9 3.9  10ÿ4 25.2 16.1 58.7
12.5 5.2  10ÿ4 27.5 14.1 58.4
50 1.9  10ÿ3 30.9 11.2 57.9

Fig. 2. XPS spectra of the O1s peak of the ®lms of series 1 Fig. 3. XAES spectra of the O-KL23L23 transition of the ®lms of
series 1

in the binding energy of the O1s electrons can be
explained by the difference in a) electrical conductiv-
ity and b) polarizability of Al2O3 and Cr2O3. The
emission of a photoelectron results in a core hole that
polarizes the surrounding of the atom. Depending on
the chemical and structural properties of the material,
the extraatomic relaxation energy signi®cantly in¯u-
ences the kinetic energy of the photoelectron. This
electrostatic interaction can be directly connected to
the dielectric relative permittivity of the material,
which is lower for Al2O3 as compared to Cr2O3
leading to the shift in O1s photoelectron energies. The
continuous shift of the O1s peak between the
constituent binaries and the absence of double peaks
indicates that the ternary ®lms have been deposited in
a single-phase structure. Evaluation of the O-KL23L23
Auger transition revealed that in case of the
participation of valence electrons the peak shift bet-
ween Al2O3 and Cr2O3 is distinctly marked (Fig. 3).
The kinetic energies of the O-KL23L23 Auger
electrons are somewhat higher than literature values
of 508 eV for Al2O3 [14] and 511.4 eV for Cr2O3 [15],
but in the same range. The continuous shift of this
transition between the binaries without any presence
194 M. Witthaut et al.

Fig. 4. Modi®ed Auger parameter of oxygen in the ®lms of series 1

of a shoulder in the peak shape revealed that the

ternary ®lms consist of single-phase (Al,Cr)2O3, i.e.
obviously Al atoms substitute Cr atoms. The modi®ed
Auger parameter 0 of oxygen in the ®lms of series 1
is represented in Fig. 4. This value can be used for
Fig. 6. XAES spectra of the O-KL23L23 transition of the ®lms of
identi®cation of chemical binding states especially of series 2
insulating materials, where additional charge effects
lead to peak shifts in electron spectra. The continuous
decrease of the Auger parameter with increasing
aluminum content from 1042.0 in case of Cr2O3 to
1039.2 in case of Al2O3 shows the continuous change
in the chemical binding state of oxygen in the ternary
®lms, attributed to the decreasing conductivity and
polarizability of the material [16,17,18].
The XPS and XAES analyses of the ternary ®lms of
series 2 (Figs. 5 and 6) also exhibit a continuous shift
of the O1s peak and the O-KL23L23 transition between
Fig. 7. Modi®ed Auger parameter of oxygen in the ®lms of series 2
7.5 and 50 sccm oxygen ¯ow with increasing Cr/Al

ratio. This observation again con®rms that oxygen in

Fig. 5. XPS spectra of the O1s peak of the ®lms of series 2
the ternary ®lms exists in only one binding state as
(Al,Cr)2O3. The O1s and O-KVV line positions of the
®lm deposited at an oxygen ¯ow rate of 5 sccm are
placed between those of the ®lms deposited at 7.5 and
9 sccm, according to the Cr/Al ratio detected.
Evaluation of the Auger parameter of the ®lms
(Fig. 7) again revealed a continuous shift with
decreasing Cr/Al ratio to lower values.
To explain the higher Cr/Al ratio and the
substoichiometry of the ®lm deposited with 5 sccm
oxygen ¯ow rate, the Al 2s and Cr 2p peaks have been
interpreted. The shape of the Al 2s was the same as
compared to the other ternary ®lms, indicating a
single binding state of aluminum. The Cr 2p peaks of
series 2 are shown in Fig. 8. In contrast to the O1s and
O-KL23L23 line positions the Cr 2p1/2 and Cr 2p3/2
peaks exhibit no characteristic shift with different
Preparation of Cr2O3-Al2O3 Solid Solutions by Reactive Magnetron Sputtering 195

Fig. 8. XPS spectra of the Cr 2p doublet of the ®lms of series 2 Fig. 9. GID spectra of the constituent binaries and a ternary
(Al,Cr)2O3 ®lm

compositions: In a (Al,Cr)2O3 ®lm the binding state of

oxygen is strongly in¯uenced by the polarizability of
the nearest neighbours, which varies with the Cr/Al
ratio. In case of Cr or Al, no change of their nearest
neighbours occurs, assuming that Al substitutes Cr
sites in the lattice. The Cr 2p1/2 as well as the Cr 2p3/2
peak of the 5 sccm ®lm exhibit a main line at lower
binding energy and distinct shoulders at the position
of the Cr 2p peaks of the other ®lms. Obviously the
5 sccm ®lm consists of two chromium containing
phases. The energetic distance of the main Cr 2p1/2
and Cr 2p3/2 lines is 9.1 eV and corresponds well with
literature data for metallic chromium of 9.2 eV [17].
Furthermore, the energetic distance of the Cr 2p3/2
between metallic chromium and Cr in Cr2O3 is given
in [19] as 2.5 eV, which is slightly higher than the
2.4 eV measured here, possibly due to the Al content
in the oxidic phase. Fig. 10. GID spectra of two ®lms of series 2
Figure 9 shows the GID spectra of the Al2O3 and
Cr2O3 ®lm and of the ®lm deposited with 12.5 sccm
oxygen ¯ow rate. Because of the relatively low deposited with 5 and 50 sccm oxygen ¯ow rate (series
substrate temperature (500  C) the alumina ®lm has 2). A comparison with the ternary ®lm in Fig. 9
been crystallized in the cubic
-modi®cation. The indicates that the crystallinity of the ®lms slightly
Cr2O3 ®lm has grown in the stable rhombohedral increases with increasing oxygen ¯ow rate, which is
modi®cation. The spectrum of the ternary ®lm and contrary to pure Al2O3 ®lms investigated in a previous
evaluation of the lattice parameters revealed, that it paper [10]. Furthermore, the GID spectrum of the
has grown as (Al,Cr)2O3 in the rhombohedral R 3c 5 sccm ®lm con®rms the XPS results that this ®lm
structure of Cr2O3 and -Al2O3, respectively. consists of metallic chromium and nanocrystalline
Figure 10 shows the diffraction spectra of the ®lms (Al,Cr)2O3 or an amorphous phase.
196 Preparation of Cr2O3-A12O3 Solid Solutions by Reactive Magnetron Sputtering
Conclusions
Ternary Al-Cr-O ®lms have been deposited by
magnetron sputtering at substrate temperatures of
500  C. Although only a small region of solid solution
between Al2O3 and Cr2O3 exists under stable condi-
tions, the nonequilibrium conditions of reactive magne-
tron sputtering resulted in the formation of single-phase
(Al,Cr)2O3 ®lms with compositions along the complete
quasibinary section Al2O3-Cr2O3, as revealed by XPS
and XAES measurements. The crystallinity of the ®lms
increased with increasing oxygen partial pressure. At
very low oxygen partial pressures of 2.4  10ÿ2 Pa a
codeposition of metallic chromium and (Al,Cr)2O3 was
observed.
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