SURFACE AND INTERFACE ANALYSIS

Surf. Interface Anal. 26, 659666 (1998)

XPS and X-ray Diraction Characterization of

Thin CoAlN Alloy Films Prepared by Reactive
Sputtering Deposition
K. Asami,1,* S. Ohnuma2 and T. Masumoto2
1 Institute for Materials Research, Tohoku University, Katahira, Sendai 980-77, Japan
2 The Research Institute for Electric and Magnetic Materials, Yagiyama-minami, Sendai 982, Japan

Thin (Co Al )
N (x = 030 at.% ) alloy lms prepared by a reactive radio frequency (r.f.) sputtering
0.8 0.2 100x x
method were characterized by XPS and x-ray diraction (XRD). The lm with no nitrogen consisted of a CsCltype CoAl metallic compound, while the nitrogen-containing alloys were composed of very ne AlN and facecentred cubic (fcc) Co phases. The quantitative XPS analysis under an assumption of uniform distribution of all the
elements resulted in much lower concentrations of Co and higher concentrations of Al and N in comparison with
the bulk composition for the nitrogen-containing alloys. By taking account of the granular structure of the alloy
lms, i.e. the nanoscale particles of fcc Co embedded in the AlN compound, the results of quantitative XPS analysis
were explained successfully. Moreover, the thickness of the AlN layer and the size of the fcc Co particles were also
able to be estimated under the nanoscale structure models. The results were in good agreement with observation by
transmission electron microscopy, especially when a nanostructure model was adopted where nanoscale CoN
particles are dispersed in AlN matrix in a simple cubic-like arrangement. ( 1998 John Wiley & Sons, Ltd.
KEYWORDS : XPS ; nanogranular materials ; CoAlN ; magnetic materials ; thin lm ; nano-composite ; x-ray diraction

INTRODUCTION
Nowadays, the development of microelectronic devices
need micro-miniaturization of all parts. Thin-lm technology is a very important key factor in the realization
of the miniaturization of devices. As for semiconductor
devices, large-scale development of new technologies
such as monolithic integrated circuit technology, surface
mounting technology and hybrid integration technology is attained. On the other hand, the miniaturization of magnetic devices, which are also an essential
part of the total development of miniaturization of
microelectronic devices, is less developed. Micromagnetic devices such as thin-lm microtransformers,
thin-lm inductors and thin-lm magnetic heads have
been developed but they still rely on conventional
materials. It can thus be said that the main difficulty of
miniaturization of magnetic devices is in the lack of new
materials suitable for miniaturization.
Recently, granular materials are attracting as much
attention as new magnetic materials applicable to
micromagnetic devices such as thin lms of heterogeneous alloys having both high electrical resistivity
and soft magnetic properties. For example, FeBN,1
CoFeBN (AlN),2 Fe(Co)BF3 and CoFeAlN4
are quite useful in the very high frequency region (1500
MHz). Some of the present authors4 have investigated
the properties of CoFeAlN lms in relation to the
concentrations of Al and N, and found that the alloy

* Correspondence to : K. Asami, Institute for Materials Research,

Tohoku University, Katahira, Sendai 980-77, Japan
CCC 01422421/98/09065908 $17.50
( 1998 John Wiley & Sons, Ltd.

system showed discontinuity of saturation magnetization at Al/N \ 1 : 1, suggesting that the properties of
lms are strongly related to the concentrations of Al
and N.
The present authors5 also studied the chemical states
of elements in (Co Al )
N alloys, which also
0.2 100~x
x
show a clear peak of0.8
electrical
resistivity
at x D 20 at.% :
cobalt was in the metallic state ; aluminium was in the
metallic state at x \ 0 but it formed AlN when 22
at.% nitrogen was added ; and nitrogen was in the
nitride state. The apparent composition of every
element estimated from the XPS intensities using the
conventional uniform distribution model deviated
greatly from the bulk composition.
In this study, the deviations of the apparent compositions determined by XPS were re-examined by taking
account of the nanometre scale structure of the material
observed by transmission electron microscopy (TEM).
EXPERIMENTAL
The (Co Al )
N alloy thin lms were prepared
0.2 100~x radio
x
by using0.8a reactive
frequency (r.f.) magnetron
sputtering technique. The subscripts denote atomic percentages of components, and x designates at.% N relative to Co Al
alloy. The composition range
20030 at.%. Alloy lms D2 lm thick
examined was80x \
were prepared on water-cooled glass substrates by sputtering Co Al alloy targets. Nitrogen addition was
conducted80by 20
sputtering in an Ar/N gas mixture. The
2 was controlled
concentration of nitrogen in the alloys
by regulation of the N /Ar gas ow ratio. The compositions of the lms were2estimated from a calibration line
Received 14 January 1998
Accepted 16 April 1998

660

K. ASAMI ET AL .

between the nitrogen content and the N /Ar gas ow

2
ratio : [N ]/[N ] Ar]. The calibration curve was based
2
2
on Rutherford backscattering spectrometry (RBS) measurements of alloy lms formed on glassy carbon plates.
Photoelectrons excited by the monochromated Al Ka
line were analysed by using an SSI SSX-100 electron
spectrometer. The vacuum of the specimen chamber for
XPS measurements was D7 ] 10~8 Pa during measurements. The full widths at half-maximum of Au 4f
7@2
and Ag 3d
photoelectron peaks of pure Au and Ag
5@2
were 0.96 and 0.89 eV, respectively, under the spectrum
acquisition conditions. Binding energies of electrons
were calibrated by a method described elsewhere ;6,7
binding energies of the Au 4f
and 4f
electrons of
7@2
5@2
Au metal and the Cu 2p
and 2p
electrons of Cu
3@2
1@2
metal were taken as 84.07, 87.74, 932.53 and 952.35 eV,
respectively, and the kinetic energy of the Cu
L M M Auger electrons of Cu metal was taken as
3 4,5eV.6
4,5The angle between the specimen surface and
918.65
the direction of photoelectrons to the detector (take-o
angle) was xed at 35.
Before XPS measurements, the surface contaminant
and air-formed oxide lm were almost completely
removed by Ar` etching. The ion etching was performed under an Ar gas pressure of D6 ] 10~6 Pa and
at 2 kV accelerating voltage with an emission current of
10 mA for an etching time of 40 s. The ion beam was
scanned over an area of D2 ] 2 mm2. Alloy compositions after Ar` etching were estimated quantitatively
from the integrated XPS peak intensities by a method
proposed elsewhere,7,8 assuming uniform distribution of
all the elements (Co, Al and N).
The integrated XPS peak intensities were obtained
after subtracting the background, which was calculated
by Shirleys procedure ;9 the lower and upper limits
were taken at 775.5 and 787.5 eV, respectively, for the
Co 2p peak, at 70.5 and 78.5 eV for the Al 2p peak
and at3@2
393.5 and 402.5 eV and for the N 1s peak. As for
the photoionization cross-sections of the Co 2p , Al
3@2elec2p and N 1s electrons relative to that of the O 1s
trons, values of 4.53,10 0.18711 and 0.61412 were
adopted, respectively. The respective eective escape
depths of the photoelectrons excited by the Al Ka line
for the above levels were taken as 0.91, 1.29 and 1.13
nm at a 35 take-o angle.
The structure of thin alloy lms was examined by the
glancing-angle x-ray diraction (XRD) method : Rigaku
Rotaex RU-200B with a rotary Cu target (j \ 0.151 48
nm for Cu Ka) and a monochromator of pyrolytic
graphite, where the incidence angle a was xed at 1.
Metallurgical structure was observed by high-resolution
transmission electron microscopy (HRTEM) using a
JEOL JEM-2010F installed with a eld emission-type
electron gun for specimens prepared on an NaCl singlecrystal substrate.

RESULTS AND DISCUSSION

X-ray diraction
In Fig. 1 the x-ray diraction patterns of the alloy thin
lms are shown, where diraction patterns of AlN
deposited on glass substrate and sintered AlN powder
Surf. Interface Anal. 26, 659666 (1998)

Figure 1. X-ray diffraction patterns of the (Co Al )

N
0.8substrate
0.2 100x
alloy thin films and those of AlN deposited on glass
andx
sintered AlN containing 5% Y O .
2 3

containing a binder of 5% Y O are also included for

2 3
comparison. The diraction pattern
of Co Al alloy
80 20
shows two intense peaks and a weak peak that
are able
to be assigned to (100), (111) and (200) peaks of the
CsCl-type CoAl phase. By plotting the lattice constants
calculated from each of the above-mentioned three
peaks vs. cos2 h ] (1/sin h ] 1/h)/2, the corrected lattice
constant a \ 0.284 86 nm was obtained. Although the
0 is far removed from the stoichiometric
composition
composition for the CsCl-type CoAl phase, the lattice
constant of Co Al fell on the extrapolated line of a
80 20
0
vs. alloy composition.
All the alloys containing nitrogen show broad diraction peaks. The most intense diraction peak for all the
nitrogen-containing alloys appears at almost the same
diraction angle as that of the (110) peak of the CoAl
phase. The most intense peaks have a small swell on the
high-angle side and also a small peak at D 76 in addition to a small peak at 3040. The intensity of the peak
at 3040 increases with the nitrogen concentration in
the alloy, while that of the peak at D76 decreases.
Because there are intense peaks between 30 and 40 in
the diraction pattern of AlN, the evolution of a peak
between 30 and 40 can correspond to the formation of
AlN. As mentioned in the previous paper,5 electron diffraction of the crystalline phase of nitrogen-containing
alloys revealed the existence of a face-centred-cubic (fcc)
structure. Consequently, the peaks at D45 and 76 correspond to (111) and (220) peaks of the fcc phase,
respectively, and the high-angle-side swell of the (111)
peak can be accounted for by the (200) peak of the fcc
phase.
( 1998 John Wiley & Sons, Ltd.

XPS AND XRD OF REACTIVE SPUTTER-DEPOSITED CoAlN FILMS

In Fig. 2, the lattice spacing of the (111) plane of the

fcc phase calculated from the peak position of the (111)
peak is plotted vs. the nitrogen concentration in the
alloy. The (002) spacing of a-Co (hexagonal closepacked structure, hcp) is also plotted for comparison.
The lattice spacing of (Co Al )
N alloys
0.8 0.2 100~x x
increases with nitrogen concentration linearly, and it
can be seen that the (111) spacing of the
(Co Al )
N alloy becomes almost equal to the
0.8 0.2 100~x x
(002) spacing of hcp Co at 20 at.% N concentration.
This result means that nitrogen starts to dissolve into
the Co phase at D 20 at.% nitrogen when the nitrogen
concentration is increased. At x \ 20, [Al] \ 16 at.%,
therefore some excess nitrogen should still exist if all the
Al atoms form AlN. Oda et al.13 studied CoN lms
prepared by reactive sputtering. They found the Co N
phase with a cubic unit cell with Co atoms packed in 4fcc
and a nitrogen atom at the centre of the unit cell for
alloys with nitrogen concentrations of 5.115.5 at.%,
while Co21.7 at.%N alloy had a Co N structure with a
hexagonal unit cell. Their Co
N 3alloy had a lattice
5.47
constant of 0.3586 nm (0.2070 nm for (111) spacing).
The diraction pattern of Co
N alloy, which corre5.47 Al )
sponds to x \ 25.7 for (Co
N alloy,
0.8 0.2
100~x
showed well-dened peaks, while
(Co
Al x ) N
25
alloy in Fig. 1 gives very broad peaks 0.8
and 0.2
the75(111)
spacing is 0.2036 nm. Consequently, the Co phase in
(Co Al )
N alloys is not the Co N phase but
0.8 the
0.2fcc
100~x
x
rather
Co phase
in which nitrogen 3has dissolved.
The fcc Co phase with dissolved nitrogen is expressed as
the CoN phase hereafter.
The grain size of the fcc phase was also estimated
from the peak width of the (111) peak after correcting
for the overlapping eect of the (200) peak by using

Figure 2. The lattice spacing of the (111) plane of the fcc phase
calculated from the peak position of the (111) peak plotted vs . the
nitrogen concentration in the alloy.
( 1998 John Wiley & Sons, Ltd.

661

Scherrers equation. The average grain sizes were 2.0,

1.6 and 1.6 nm for alloys with x \ 22, 25 and 30, respectively. It is clear that the addition of nitrogen develops a
nanometre-scale granular structure.
X-ray photoelectron spectrometry
The Al 2p peak of the Co Al alloy appeared at 72.45
80 20than that of pure Al at
eV, which is slightly smaller
72.95 eV. It can be caused by the formation of CoAl,
where some electrons are transferred from Al to Co
atoms. However, the Co 2p
peak position of the
3@2
Co Al alloy (778.16 eV) is quite close to that of pure
20 though the Co forms a metallic compound
Co80even
with Al as shown in Fig. 1. It is therefore difficult to
judge simply from the peak position of the Co 2p
3@2
spectrum if some of the Co atoms are in the form of the
metallic compound.
The Co 2p electron binding energy for alloys with
3@2 ^ 0.05 eV, which is nearly equal to
nitrogen is 778.15
the Co 2p
electron binding energy for pure Co of
3@2 binding energy of the Co 2p
778.2 eV. The
electrons
3@2 of nitroalso seems not to be aected by the addition
gen.
For alloys with P22 at.%N, the binding energy of Al
2p electrons was 73.9 ^ 0.1 eV. In Fig. 3, the binding
energy of the Al 2p electrons of pure Al and Al O are
2 3
plotted vs. the formation energy. The heat of formation
gives the binding energy of the Al 2p electrons of a substance which is 92 kcal mol~1 and is close to that of
AlN (76.5 kcal mol~1), as shown in Fig. 3. It can be
said, therefore, that the Al 2p peak observed on the
CoAlN specimens corresponds to that of Al in
nitride. Moreover, the peak binding energy of the N 1s
electrons for x P 22 at.% specimens was 396.7 ^ 0.1 eV,
while the binding energies of the N 1s electrons for Ti
and Fe nitrides are 396.7 and 396.9 eV, respectively.14,15
Accordingly, it can be concluded that Al and N in the
CoAlN specimens are in the form of aluminium
nitride.
In the previous paper,5 it was shown by XPS quantitative analysis under the assumption of a uniform distribution model that the surface composition of the

Figure 3. The relationship between the binding energy of the Al

2p electrons and the formation energy.
Surf. Interface Anal. 26, 659666 (1998)

662

K. ASAMI ET AL .

alloy without the addition of nitrogen was almost the

same as that of the nominal composition, while the concentrations of Co in the specimens containing nitrogen
were much lower than the nominal compositions and
the Al/Co atomic ratios were much larger than those
expected from the average composition of the alloys.
Judging from the Al 2p peaks, specimens with 22
at.% nitrogen contained essentially no metallic Al, i.e.
all the Al in the alloy lms was in the form of nitride.
Actually, the Al/N atomic ratios estimated from the
integrated XPS intensities were 0.98, 1.03 and 1.09 for
22, 25 and 30 at.%. N specimens, respectively, under the
assumption that all the elements are distributed uniformly within the analysing region (the uniform distribution model).
In the previous paper,5 the large Al/Co atomic ratio
obtained by XPS for nitrogen containing alloys in comparison with the nominal concentration was mainly
attributed to the eect of surface cleaning by Ar`
etching. Under the ion etching conditions adopted,
etching for 40 s was enough to remove the surface contaminants. The surface composition of the Co Al
alloy was 79.7 at.% Co after 40 s of ion etching 80
but 20
it
decreased to 74.3 at.% Co after 280 s of ion etching.
Because the bulk composition is 80 at.% Co, it can be
said that Co is preferentially sputtered by Ar` under
the conditions adopted. Consequently, it can be said
that the ion etching for 40 s under the above condition
is eective to remove surface contaminant carbon and
air-formed oxide on the CoAl alloy system, but does
not give a large change in the alloy composition. The
Co concentrations of CoAlN alloys after cleaning
were all much lower than those expected from the bulk
compositions. Some reasoning other than preferential
ion etching should be examined to explain the discrepancy between the observed and the bulk compositions if
we take the sputtering rates of Co and Al to be the
same as those in CoAl and CoAlN systems.
Nanoscale non-uniformity can also give a large deviation from the average composition if the analysis was
carried out under the uniform distribution model. It
was revealed16 by HRTEM observations that CoAlN
alloy lms have a granular structure with grains of
diameter O5 nm. The nanogranular structure of the
alloys could also have a large eect on the photoelectron intensity because the sizes of the structure units are
comparable with the escape depths of the photoelectrons. Consequently, the quantitative XPS results can
be evaluated by comparison with the results of nonuniform structure model calculation.
A simple layered structure model
As one of the non-uniform structure models, the layered
structure model shown in Fig. 4 was examined. In the
model, it is simply assumed that the material consists of
layered AlN and fcc Co phases, i.e. the top surface layer
and the second layer consist of AlN compound and fcc
Co phase in which some nitrogen is dissolved (CoN
phase), respectively, and the whole material is assumed
to be in the form of a sequential stack of AlN/CoN/
AlN/CoN/ . . . , where the thicknesses of AlN layers
and CoN layers are constant throughout the material.
The concentration of nitrogen in the CoN phase,
Surf. Interface Anal. 26, 659666 (1998)

Figure 4. A simple layered structure model of reactively sputterdeposited CoAlN alloys.

[N]
, is therefore the dierence between the bulk or
CohN concentrations of N and Al, i.e. [N]
average
\ [N]
CohNratio in
[ [Al]. It is also assumed that the N/Al molar
the AlN phase is unity. The thickness ratio between
AlN and CoN layers can be calculated from the bulk
composition by considering the above assumptions for
AlN and CoN phases as follows
a o ] ([Co] ] M ] ([N] [ [Al] ] M )
Co
N
\ AlN
t
o
] [Al] ] (M ] M )
CohN
Al
N
where a and t are the thicknesses of the CoN and AlN
layers, respectively, o is the density of substance L and
M and [E] are theL atomic weight and the nominal
E
molar
concentration of element E in the alloy, respectively. For o
and o
, values of 3.26 and 8.71 g
AlN respectively.
CohN
cm~3 are adopted,
Under the uniform distribution assumption, the XPS
concentrations were calculated using the integrated
intensities of the Co 2p , Al 2p and N 1s electron
spectral peaks expected3@2from the nanoscale-layered
structure model shown in Fig. 4. In Fig. 5, the XPS concentrations of Co, Al and N for (Co Al ) N alloy
0.8 0.2 70
30 AlN
thus calculated are plotted vs. the thickness
of the
layer, t. It is clear that the XPS concentrations analysed
using the uniform distribution model depend largely on
the thickness of the AlN and CoN phases. By taking
proper thicknesses, the observed XPS intensities or the
quantitative results analysed by uniform distribution
model could be explained. For (Co Al ) N alloy
0.2 the
70 uniform
30
where the concentrations estimated0.8from
distribution model were 33.8 at.% Co, 31.7 at.% Al and
34.6 at.% N, the best t was obtained at t \ 0.50 nm
and a \ 1.16 nm ; the corresponding concentrations
( 1998 John Wiley & Sons, Ltd.

XPS AND XRD OF REACTIVE SPUTTER-DEPOSITED CoAlN FILMS

663

Figure 6. A nanoscale structure model with simple cubic-like

arrangement of CoN particles dispersed in an AlN phase matrix.

where
o
] [Al] ] (M ] M )
CohN
Al
N
o ] ([Co] ] M ] ([N] [ [Al]) ] M )
AlN
Co
N
Using the integrated intensities of the Co 2p , Al 2p
and N 1s electron spectral peaks expected 3@2
from the
simple cubic-like structure model shown in Fig. 6, the
XPS concentrations were calculated by assuming a
uniform distribution of all the elements. In Fig. 7, the
XPS concentrations of Co, Al and N expected from the
model substance shown in Fig. 6 are plotted vs. the
clearance of CoN particles in the model
(Co Al ) N
alloy. By least-squares tting, the
0.2 70 30
XPS0.8concentrations
obtained under the uniform distribution model are 33.97 at.% Co, 32.86 at.% Al and
33.18 at.% N at t \ 0.70 nm and a \ 5.47 nm for the
above alloy.
In Table 1, the results obtained under the simple
cubic-like arrangement model are summarized. It can
be seen that the calculated XPS concentrations are in
good agreement with those observed.
The sizes of AlN and CoN phases determined by
XPS under the simple cubic-like arrangement model are
compared with those obtained by using XRD and TEM
methods in Table 2. Because the AlN phase does not
give proper XRD peaks for grain size calculation, comparison of the thicknesses of the AlN phase is done
merely between the TEM and XPS results. The grain
sizes of the CoN phase determined from XRD peaks
are smallest and those from the XPS model calculation
are largest. Because XRD grain size depends on the size
of crystallites, it can be smaller than the size of the
CoN phase when the CoN grains consist of several
crystallites. In the case of TEM observation, the size of
the CoN phase is judged from the image of the CoN
phase region. The TEM image is formed by transmitted
electrons. The size estimated from the TEM image is
therefore liable to appear smaller than the actual size of
the CoN phase when the thickness of the specimen is
larger than the size of the CoN phase and several
K\

Figure 5. Change in the apparent XPS concentrations of Co, Al

and N with the thickness of the AlN layer of the (Co Al ) N
0.8 0.2 70 30
model alloy specimen shown in Fig. 4.

were 32.4 at.% Co, 26.3 at.% Al and 41.3 at.% N. The
low Co concentration in comparison with the bulk
composition may be explained by this model. However,
the N/Al molar ratio of 1.57 obtained from the layered
structure model is too large in comparison with the
observed value of 1.09. For (Co Al ) N
alloy,
0.8 0.2 78 of22the AlN
similar results were obtained : the thicknesses
and CoN layers were 0.415 and 0.916 nm, respectively,
and the concentrations for Co, Al and N from the
model were 40.1, 26.3 and 33.6 at.%, respectively. The
N/Al molar ratio of 1.28 obtained from the model calculation was also much larger than the observed value
of 0.98.
A simple cubic-like structure model
Because the layered-structure model seems to be too
simplied a model for the CoAlN alloys, a nonuniform structure model with a simple cubic-like
arrangement of CoN particles in AlN phase matrix is
considered to be a model closer to reality. A crosssection of the model material is shown in Fig. 6, where
cubes of CoN particles with side length a, are dispersed in AlN phase in a simple cubic-like arrangement.
The clearance between (or the boundary width o f) the
CoN cubes, t, is related to a and the alloy composition
as follows
a\

t
,
(1 ] K)1@3 [ 1

( 1998 John Wiley & Sons, Ltd.

Surf. Interface Anal. 26, 659666 (1998)

K. ASAMI ET AL .

664

under the simple cubic-like arrangement model can give

reasonable values for the average size of the CoN
phase and the average thickness of the AlN phase.
Uncertainty of XPS results

Figure 7. Change in the apparent XPS concentrations of Co, Al

and N with the clearance or boundary width of CoN particles for
the (Co Al ) N model alloy specimen shown in Fig. 6.
0.8 0.2 70 30

grains appear overlapped. About the thickness of the

AlN phase, the values obtained from TEM observation
are larger than those estimated from XPS measurements. This could be caused by the blurred boundary of
the TEM images. Accordingly, it can be said that the
thickness estimated from XPS quantitative analysis

Escape depths of photoelectrons. It is generally thought

that it is difficult to determine the absolute values of
thickness and so on from the XPS measurements.
However, it is possible to estimate reasonable thickness
by using the empirical escape depths as a measure of
length. For example, we found the anodizing ratios of
pure Ti and Ti60 at.% Ni alloys in a sulphuric acid
solution to be 2.1 and 0.9 nm V~1 by XPS analysis.17
The reported values for pure Ti range from 1.8 to 2.2
nm V~1.18 It was also reported11 that the anodizing
ratio of Al36 at.% Ti alloy in neutral borateboric acid
solution is 1.6 nm V~1, which is quite reasonable when
it is compared with those of pure Ti and pure Al. The
anodizing ratio for pure Al was reported to be 1.3 nm
V~1 by Hass20 and 1.4 nm V~1 by Nagayama and
Takahashi.21 We have also compared the thickness of
an anodized lm formed on pure Al estimated by XPS
analysis with that observed by TEM. From the TEM
image the thickness of the anodized lm was estimated
to be 2.8 nm, while XPS analysis gave 2.1 nm. Thus, the
thicknesses of thin surface lms on alloys and metals
estimated by XPS analysis are satisfactorily in good
agreement with the other observations as far as the
lms are solid and compact, indicating that the escape
depths used for the analysis in this paper are reasonable.
Photoionization cross-sections and the procedure used to determine peak areas. Experimental or practical photoioniza-

tion cross-sections for quantitative analyses are always

related to the procedure used to determine the peak
areas. When the procedure is specied, the experimental
photoionization cross-sections corresponding to the
peak intensities by the procedure are dened. The high

Table 1. Comparison between the observed and calculated XPS concentrations for
(Co Al )
N alloys
0.8 0.2 100x x
Nominal
composition
(at.%)

Co
Al
N
62.4 15.6 22
Co
Al
N
60.0 15.0 25
Co
Al
N
56.0 14.0 30

Observed
N

Co

Al

39.8
42.6
33.8

30.0
28.3
31.7

29.4
29.1
34.6

Calculated
N

N/Al

Co

Al

0.98
1.03
1.09

40.2
42.8
34.0

33.3
30.3
32.9

N/Al

26.5
26.9
33.2

0.80
0.89
1.01

Table 2. Comparison between the sizes of the CoN phase and thicknesses of
the AlN phase determined by XRD, TEM and XPS
Nominal composition
(at.%)

Size of CoN phase (nm)

XRDa
TEMb
XPS

Thickness of AlN phase (nm)

TEMb
XPS

Co
Al
N
2.0 0.1
3.05.0
5.19
0.81.2
0.69
62.4 15.6 22
Co
Al
N
1.6 0.3

4.37

0.57
60.0 15.0 25
Co
Al
N
1.5 0.2
2.03.5
5.48
1.01.5
0.70
56.0 14.0 30
a Obtained from Scherrers equation ; grain size 0.91/B cos h, where B full
width at half-maximum of a diffraction peak and h diffraction angle.
b Estimated from TEM photographs.16
Surf. Interface Anal. 26, 659666 (1998)

( 1998 John Wiley & Sons, Ltd.

XPS AND XRD OF REACTIVE SPUTTER-DEPOSITED CoAlN FILMS

reliability of the values of the experimental photoionization cross-sections cannot be obtained by measuring
just a single specimen. Therefore, we have determined
the experimental photoionization cross-sections of the
Co 2p
and Al 2p
electrons relative to that of
3@2
3@2`1@2
the O 1s electrons from several standard specimens.10,11
The standard deviations of the photoionization crosssections of the Co 2p and Al 2p
electrons rela3@2
3@2`1@2
tive to that of the O 1s electrons were 2.7% and 1.2%,
respectively, under the conditions where the escape
depths were xed to the values mentioned above, and
the integrated intensities of Co 2p , Al 2p
, O 1s
3@2
3@2`1@2
and N 1s photoelectron peaks were estimated by the
procedure stated in the Experimental section. The accuracy of the quantitative results is naturally dependent
on the accuracy of the values of the photoionization
cross-sections. For example, using the photoionization
cross-section ratios of the Cr 2p
and Fe 2p
elec3@2
trons relative to that of the O 1s3@2electrons determined
with standard deviations of 2.6% and 2.0%, it was
found that surface lms on FeCr alloys heated in vacuo
at 380 C consisted of Cr O , where x \ 1.97 and
x 2.00
y
y \ 3.00 for Fe20Cr, x \
and y \ 3.00 for
Fe50Cr and x \ 1.90 and y \ 3.10 for Fe80Cr, and
their thicknesses were 1.85, 1.94 and 1.75 nm, respectively.22 Because the chromium oxide stable under the
condition during measurement was Cr O , it can be
2 3surface lms
said that the estimated compositions of the
are quite reasonable. Thus, as far as we use properly
determined photoionization cross-sections for quantitative analyses, we can determine the surface compositions within the accuracy of the photoionization
cross-section ratios.
The photoionization cross-section of the N 1s electrons was taken from Scoelds paper12 because we had
no good specimens for it. However, the values calculated by Scoeld are generally taken as the best values
at present for simple peaks such as O 1s, N 1s, C 1s, etc.
For example, the photoionization cross-section ratio of
the Al 2p electrons to the O 1s electrons calculated from
Scoelds data is 0.183, which is almost the same as our
experimental value of 0.187.11 Consequently, the uncertainties of the compositions are at most 5% of the estimated composition. When the composition of Co is
34 ^ 2% (6% of the estimated value is taken as the
uncertainty for the composition of Co), then the compositions of Al and N should be D32.9 ^ 1% and
D33.2 ^ 1%, respectively, because the total composition is always 100%, i.e. there is a constraint that the
summation of all the deviations of the estimated compositions must be zero. The uncertainty in the composition leads to an uncertainty of D7% in thickness, i.e.
the thickness of the AlN layer will be 0.7 ^ 0.05 nm and
the corresponding size of the CoN phase cube will be
5.5 ^ 0.4 nm.
As for the absolute value of the thickness, we have
difficulty in dening the thickness because of its ambiguity. Observation by TEM gives information on the
spacial distribution of the substance, while XPS thickness relies merely on the attenuation of the signal or the
inelastic scattering probability. When the thickness is
dened as the spatial distribution of the substance, then
it corresponds to the TEM thickness. The XPS thickness therefore has the tendency to be smaller than the
TEM thickness, especially when the substance is less
( 1998 John Wiley & Sons, Ltd.

665

compact. As mentioned above, the TEM thickness also

contains some uncertainty, mainly because of the
blurred boundaries of particles, which causes underestimation of the size of the CoN phase and overestimation of the thickness of the AlN phase.
Consequently, the lengths observed by TEM in Table 2
should be closer to those observed by XPS if the TEM
image could be analysed properly. Because the
CoAlN alloys are expected to be dense, XPS can give
comparable values of the thickness of the AlN phase
and the size of the Co-N phase with those obtained by
using XRD and TEM methods.
It is worthy of note that an XPS quantitative analysis
of nanoscale granular materials under a uniform distribution model will result in a large deviation of composition from the bulk composition and the explanation
of the data will be misleading. For XPS analysis of such
a substance we need proper nanoscale structure models.
We can get comparable values of the sizes of AlN and
CoN phases by XPS with those obtained by using
XRD and TEM methods as long as we apply carefully
determined XPS parameters to well-controlled XPS
measurements.

CONCLUSIONS
Thin (Co Al )
N (x \ 030 at.%) alloy lms
100~x x r.f. sputtering method were
prepared 0.8
by a0.2 reactive
studied by XPS and XRD and the following conclusions
are drawn :
(1) The Co Al alloy lm consists of CsCl-type CoAl
20
metallic80
compound.
(2) (Co Al )
N (x \ 2230 at.%) alloys are
0.8 0.2granular
100~x xmaterials. They are composed of
nanoscale
fcc CoN grains of D45 nm in size embedded in
AlN compound, and the clearance between or the
boundary width of CoN particles or the thickness
of the AlN phase is D0.60.7 nm.
(3) XPS quantitative analysis of the above-mentioned
nanogranular materials under the assumption of a
uniform distribution model results in much lower
concentrations of Co and much higher concentrations of Al and N in comparison with the bulk composition.
(4) A model of simple cubic-like arrangement of CoN
particles in AlN compound matrix is a good
approximation to evaluate the nanostructure granular substance by the XPS quantitative analysis.
(5) From the XPS analysis, the thickness of the AlN
layer and size of the fcc CoN phase particles are
able to be estimated under the above-mentioned
nanoscale granular structure model. In general, the
XPS quantitative analysis for nanoscale granular
materials needs proper nanoscale structure models.

Acknowledgements
The authors wish to thank Mr Y. Murakami for helping with the
XRD measurements. The present work is supported in part by Grantin-Aid for Scientic Research (C) (2) No. 09650776 from the Ministry
of Education, Science, Sports and Culture, Japan.
Surf. Interface Anal. 26, 659666 (1998)

666

K. ASAMI ET AL .

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( 1998 John Wiley & Sons, Ltd.