X-ray elastic constants of chromium nitride films deposited by arc-ion plating

Takao Hanabusa, Kazuhiro Miyagi, and Kazuya Kusaka

Citation: Journal of Vacuum Science & Technology A 22, 1785 (2004); doi: 10.1116/1.1705648
View online: http://dx.doi.org/10.1116/1.1705648
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Published by the AVS: Science & Technology of Materials, Interfaces, and Processing
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X-ray elastic constants of chromium nitride films deposited by arc-ion

plating
Takao Hanabusa
Faculty of Engineering, Tokushima University, 2-1, Minamijousanjima, Tokushima 770-8506, Japan

Kazuhiro Miyagi
Graduate Student of Tokushima University, 2-1, Minamijousanjima, Tokushima 770-8506, Japan

Kazuya Kusaka
Faculty of Engineering, Tokushima University, 2-1, Minamijousanjima, Tokushima 770-8506, Japan

Received 3 November 2003; accepted 23 February 2004; published 22 July 2004

Thin films have been successfully utilized to improve the property of mechanical components.
However, it is generally known that mechanical properties, such as elastic constants and tensile
strength of thin films, are different from those of bulk material, and they are not known in the
present state. In many times, x-ray stress measurement revealed a very high compressive residual
stress state in the film when bulk elastic constants were used in the stress calculation. The purpose
of this research is to investigate the elastic constants of chromium nitride CrN films. The film was
deposited on austenitic stainless steel JIS: SUS304 substrates by the arc-ion-plating AIP method
under the following conditions: the pressure of nitrogen atmosphere was maintained at 2.63 Pa, the
substrate temperature of about 573 K, the arc discharge current of 100 A, the bias voltage between
300 and 100 V, and the substrate rotating rate at 3 rpm. The lattice strain of CrN films was
measured by x-ray method at various loading stages and the x-ray elastic constants of CrN films
were evaluated. 2004 American Vacuum Society. DOI: 10.1116/1.1705648
I. INTRODUCTION
Recently, many studies of TiN and CrN films, which are
typically used as hard coatings, have been actively carried
out.1 4 TiN and CrN films prepared by physical vapor deposition PVD and chemical vapor deposition CVD have
greater heat resistance than films deposited by electroplating.
These films are used to coat cutting tools5 and in
die-casting.6 CrN films are considered to be useful for piston
rings and connecting rod in engines because such films are
very hard and durable.4
Residual stresses always develop in the films, because the
film and the substrate differ in atomic distance, thermal expansion coefficient, and cooling conditions. Large residual
stresses may cause micro-cracks in the film or peeling of the
film from the substrate. Therefore, control of residual stress
is essential for synthesizing mechanically stable CrN films.
An x-ray elastic constant of the film is needed for stress
measurement. Usually, the elastic constant of the film differs
in that of the bulk. In addition, x-ray elastic constant, which
changes against diffraction plane, differs in mechanical one.
In this investigation, we prepared CrN films deposited on
austenitic stainless steel by arc-ion-plating AIP system.
And, we investigated x-ray elastic constants of CrN films at
various bias voltages (V B).

The stainless-steel substrates was washed with acetone for

5 min in an ultrasonic cleaning device and mounted on the
substrate holder. After the chamber was evacuated down to
2.6103 Pa, nitrogen gas was introduced into the chamber
to an initial gas pressure of 1.0 Pa. Next, the table-mounted
substrate holder was loaded with a negative bias voltage
of 700 V and rotated at 3 rpm. The surface of the substrate was cleaned for 1 min by the bombardment of accelerated energetic Cr ions created by arc discharge near a
chromium target. After cleaning, the CrN film was deposited
on substrate under the conditions shown in Table I. The CrN
films were deposited by AIP at a constant arc current (I A) of
100 A and various bias voltages (V B) between 100 and
300 V. The thickness of the CrN films was constant at
about 3 m.

II. PREPARATION OF CrN FILMS

We used an AIP system, Kobe Steel Ltd., as shown in Fig.
1, for CrN films preparation. The substrate materials were
austenitic stainless steel JIS: SUS304 in the form of 9
605 mm3 plates. The substrates were polished before the
deposition. The average roughness of the substrate surface
(Ra) was 0.03 m.
1785

J. Vac. Sci. Technol. A 224, JulAug 2004

FIG. 1. Schematic diagram of arc-ion-plating system.

0734-2101200422417853$19.00

2004 American Vacuum Society

1785

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Hanabusa, Miyagi, and Kusaka: X-ray elastic constants of chromium nitride films

1786

TABLE I. Conditions of CrN film preparation.

Arc current I A , A
Bias voltage V B , V
Substrate temperature, K
N2 gas pressure, Pa
Revolution of table, rpm
Film thickness, m

100
100, 200, 300
573
2.63
3
3

III. X-RAY ELASTIC CONSTANT OF 110-ORIENTED

CrN FILM Refs. 7 and 8
The x-ray elastic constant was determined from the sin2
diagram taken under the application of known values of mechanical strains in a four-point bending device. The two-tilt
method8 was used to obtain a sin2 diagram in the 110oriented film because adequate diffraction intensity could
only be obtained at two angles, which were the angles
between the normal axis of the 110 planes and the normal
axis of the surface, namely 1 0 and 2 60. Stresses in
CrN films were determined by the 220 diffraction peaks,
using the following equation:

2 1
,
sin2 2 sin2 1

EX
cot 0
.
2 1 X
180

The x-ray compliance, s 2 , is determined from the change of

M , which is the slope of the 2 -sin2 diagram, by the applied stress M :
s 2

M
2 1 X
.
cot 0
EX
M 180

M M E M .

In this investigation, the mechanical Youngs modulus of

CrN film, E M , is 250 GPa.4 The applied strains are between
800106 and 3000106 .

IV. EXPERIMENTAL RESULT

1

where K is a stress constant related to the x-ray values of

Youngs modulus E X , Poissons ratio X , and Braggs angle
0 in strain-free state as
K

FIG. 3. 2 -sin2 diagram of CrN film deposited at V B100 V.

A. Structure development of CrN films

Texture development was examined by x-ray diffraction

with Cr K characteristic x rays. Figure 2 shows the diffraction patterns for CrN films deposited on austenitic stainlesssteel substrate at various bias voltages between 100 and
300 V. In all films, only the 220 diffraction peak from CrN
crystal appears at 2102.9. From the result, all the films
can be said to be 110-oriented. As bias voltage becomes
increasingly negative, the intensity of the CrN 220 diffraction increases. Diffraction peaks occur at 2110.5 for the
film deposited at V B300 V. It is thought to be attributable to 103 diffraction of Cr2 N crystal.

The change of the intercept of the 2 -sin2 diagram,

2 0 , with M yields the x-ray compliance, s 1 , as
s 1

cot 0 2 0
X

.
EX
2
M 180

The applied stress, M , is given by the product of the applied strain and the mechanical Youngs modulus

FIG. 2. Diffraction patterns of CrN films deposited on austenitic stainlesssteel substrates.

FIG. 4. Change in slope and intercept of the 2 -sin2 diagram with applied
strain for CrN films deposited at V B100 V.

J. Vac. Sci. Technol. A, Vol. 22, No. 4, JulAug 2004

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Hanabusa, Miyagi, and Kusaka: X-ray elastic constants of chromium nitride films

1787

TABLE II. Results of x-ray elastic constants measurement.

Bias voltage V B , V

100

200

300

X-ray elastic constants E X , GPa

X-ray Poissons ratio X

25731
0.310.7

26119
0.410.5

27733
0.430.8

B. Measurement of x-ray elastic constants of CrN films

The mechanical strains M were applied by a four-point

bending device. The applied strains of the film were measured by a strain gauge which was pasted on the reverse side
of the sample. In this investigation, the tensile stresses of 5
steps from 200 to 750 MPa were applied in the CrN film.
Figure 3 shows the 2 -sin2 diagram when the applied
stress was 200 and 750 MPa. The lines of the 2 -sin2
diagram had the large positive slopes because of large compressive residual stress in the CrN film deposited by AIP.
Figure 4 show the changes of the slope M and the intercept 2 0 by the applied stress M for the film deposited at
V B100 V. The slope M and the intercept 2 0 have a
linear relationship with the applied stress M . The slope of
the line in the M - M and 2 0 M diagram was 7.33
104 and 1.73104 deg/MPa, respectively. The x-ray
elastic constants E X and X were calculated by using these
values and Eqs. 3 and 4. Table II shows the results of
x-ray elastic constants measurement for the CrN films deposited by AIP at various bias voltages between 100 and 300
V. Figure 5 shows the effect of bias voltage V B on x-ray
elastic constant E X of the CrN films. The error bands indicate
the values which are calculated by the 68.3% confidence
limit. The x-ray elastic constant slightly increased with increasing bias voltage V B .

FIG. 5. Effect of bias voltage V B on x-ray elastic constant of the CrN films.

At high bias voltage of 300 V, crystal grains of Cr2 N are

formed in the films because many chromium ions are forcibly drawn toward the substrate due to the high negative bias.
X-ray elastic constant, E X , slightly increased with increasing negative bias voltage. The reason for this was
thought to be the different of 110 orientation and the existence of Cr2 N, but it is difficult to clarify.
VI. CONCLUSION
The effect of bias voltage on film structure and x-ray elastic constants was investigated in CrN films deposited by AIP
on austenitic stainless-steel substrates. X-ray diffraction patterns revealed that the films are all 110-oriented CrN films
deposited by AIP. The intensity of 220 diffraction increased
with increasing negative bias voltage.
We could obtain the x-ray elastic constants of the CrN
films deposited by AIP at various bias voltages between
100 and 300 V. The x-ray elastic constant, E X , slightly
increased with increasing negative bias voltage.
T. Matsue, T. Hanabusa, and Y. Ikeuchi, Mater. Sci. Res. Int. 5, 45 1999.
M. J. Staia, B. Levis, J. Cawley, and T. Hudson, Surf. Coat. Technol. 76,
231 1995.
3
H. Uchida, S. Inoue, Y. Nakano, and K. Koterazawa, Mater. Sci. Res. Int.
5, 265 1999.
4
K. Yamamoto, T. Satoh, and E. Iwamura, J. Surf. Finish. Soc. Jpn. 50, 52
1999.
5
I. J. Smith, D. Gillibrand, J. S. Brooks, W.-D. Munz, S. Hervey, and R.
Goodwin, Surf. Coat. Technol. 90, 164 1997.
6
O. Knotek, F. Loffler, and B. Bosserhoff, Surf. Coat. Technol. 62, 630
1993.
7
K. Tanaka, K. Suzuki, and R. Kawase, in Residual Stresses III, edited by
H. Fujiwara, T. Abe, and K. Tanaka Elsevier Applied Science, New York,
1992, p. 704.
8
T. Hanabusa, Mater. Sci. Res. Int. 5, 63 1999.
1

V. DISCUSSION
At low negative bias voltage (V B100 V), the chromium ions created at the target arrive at the substrate with
low energy because they cannot be accelerated between the
target and the substrate. At high negative bias voltage (V B
300 V), the ions accelerated between the target and the
substrate arrive at the substrate with high energy, and hence
with high mobility, facilitating crystal growth. As a result,
the intensity of 220 diffraction for the film deposited at V B
100 V was smaller than that for the film deposited at
V B300 V.

JVST A - Vacuum, Surfaces, and Films

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