Thin Solid Films 519 (2011) 3497–3500

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Thin Solid Films

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Preparation of Cr(N,O) thin films by RF reactive unbalanced magnetron sputtering

Jun Shirahata a,⁎, Tetsutaro Ohori a, Hiroki Asami b, Tsuneo Suzuki a, Tadachika Nakayama a,
Hisayuki Suematsu a, Yoshiharu Nakajima a, Koichi Niihara a
a
Extreme Energy-Density Research Institute, Nagaoka University of Technology, Japan
b
Department of Mechanical Engineering, Tomakomai National College of Technology, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Chromium oxynitride thin films were deposited by radio-frequency (RF) reactive unbalanced magnetron
Received 8 January 2010 sputtering at various O2 flow rates onto Si(100) and glassy carbon substrates. The compositions of the thin
Received in revised form 27 December 2010 films were analyzed by Rutherford backscattering spectroscopy. The thin films were found to contain up to
Accepted 5 January 2011
44 at.% oxygen. In Fourier-transform infrared spectra, a peak attributed to the Cr–N bond of CrN was observed,
Available online 19 January 2011
but no peak attributable to the Cr–O bond of Cr2O3 was found. The textures of the thin films were observed by
Keywords: transmission electron microscopy, which revealed that samples had a columnar structure. The hardness of the
Chromium thin films was measured by nanoindentation. The hardness increased from 20 GPa to a maximum value of
Nitrides 31 GPa with increasing oxygen content.
Oxides © 2011 Elsevier B.V. All rights reserved.
Hardness
Sputtering

1. Introduction low friction coefficient [4]. However, the dependence of these

Ceramics are used in a wide variety of applications because of their
high hardness. High hardness is particularly important for cutting tools;
consequently, ceramic-coated cemented carbide tools have been widely
used. Recently, machining industries have been switching from
lubricated processes to dry processes to reduce pollutants. Furthermore,
machining centers and other machine tools are being rapidly developed,
resulting in increasingly high tool feed speeds being used. Therefore,
cutting tools are being used at increasingly high temperatures because
the cooling speed and the chip disposal rate are being reduced.
Many hard coatings that can be used at high temperatures have
been studied. Chromium nitride (CrN) is a superior hard coating with a
high oxidation resistance, a low friction coefficient, and good
protection against welding. Therefore, CrN-based coatings are being
used to improve the properties of cutting tools, and CrN has been
doped with many metallic elements to give compounds such as (Cr,Al)
N [1], Cr–Si–N [2], and (Ti,Cr)N [3]. However, these coatings require
expensive alloy targets and/or target replacement mechanisms; thus,
lower cost and simpler methods are desirable. To achieve this, we have
focused on chromium oxynitride thin films, since they have superior
properties in comparison with the CrN thin film and they are produced
by only a Cr target and N2 and O2 gases as raw materials.
Various deposition methods have been used to produce chromium
oxynitride thin films. Above all, thin films deposited by pulsed laser
deposition exhibit high hardness, excellent oxidation resistance, and a
⁎ Corresponding author. Tel.: +81 258 47 9898; fax: +81 258 47 9890.
E-mail address: shirahataj@etigo.nagaokaut.ac.jp (J. Shirahata).
properties on the oxygen content of the films has not been clarified.
Furthermore, it is very difficult to control the oxygen content by
residual gas in a chamber. Even if thin films prepared by pulsed laser
deposition have superior properties, they could not be widely used in
commercial applications because they could not be mass-produced
and the film quality is inhomogeneous. In the other case, Wilhartitz
et al. [5] deposited chromium oxynitride thin films by magnetron
sputtering. At that point, they also varied the residual gas content in
the sputtering chamber to change the oxygen content in the film. They
have reported many results of specific analysis, although the oxygen
content has not been controlled on purpose.
In the present study, chromium oxynitride thin films with precisely
controlled oxygen contents were prepared by RF reactive unbalanced
magnetron sputtering. They were deposited at various O2 flow rates
using a mass flow controller. The oxygen contents of the films were
accurately determined by Rutherford backscattering spectroscopy (RBS).
The purpose of the present study is to investigate the effects of oxygen
content on the microstructure and hardness of chromium oxynitride thin
films under the intentional controlling of oxygen content in the films.
2. Experimental
Chromium oxynitride thin films were deposited on Si(100) and
glassy carbon substrates by RF reactive unbalanced magnetron
sputtering. For comparison, Cr2O3 thin films were also prepared by
the same coating apparatus. Fig. 1 shows the experimental setup used
in this study. The target was Cr (purity: 99.9%) and was 200 mm long,

0040-6090/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2011.01.106
3498 J. Shirahata et al. / Thin Solid Films 519 (2011) 3497–3500

Turbomolecular
Mass flow pump
controllers

Heater

Table
rotation
Target RF power
supply
Ar
Heater
N2

Ar + 3% O 2 Substrate

Heater DC power
supply

Gas inlet

Fig. 1. Experimental setup.

88 mm wide, and 5 mm thick. The sputtering gas was Ar gas and the
reactive gases were N2 and Ar + 3% O2 gases. The gas flow rates were
precisely controlled by three mass flow controllers. The oxygen partial
pressure in the chamber was varied by changing the Ar + 3% O2 flow
rate in the range 0 to 400 sccm. The O2 flow rates (calculated using
the conversion factor of the mass flow controller and the mixing ratio
of Ar + 3% O2 gas) were approximately 0 to 10.8 sccm. The N2 flow rate
was controlled to maintain the working pressure at 6.0 × 10− 1 Pa. At
that point, the Ar and N2 flow rates were approximately 400 and
200 sccm, respectively. When depositing Cr2O3 thin films, Ar was used
as the sputtering gas and O2 was used as the reactive gas. During
deposition, the working pressure was maintained at 6.0 × 10− 1 Pa by
controlling the Ar flow rate. At that point, the Ar and O2 flow rates were
approximately 600 and 100 sccm, respectively. Prior to deposition, the
chamber was pumped to less than 1.0 × 10− 3 Pa using a rotary pump
and a turbomolecular pump, and the substrates were heated to
approximately 450 °C. The substrates were then cleaned by Ar ion
bombardment for 20 min with a substrate bias of −650 V, which was
supplied by a DC power supply in pulsed DC mode at 250 kHz. Films
were deposited at a total pressure of 6.0 × 10− 1 Pa in a mixed
atmosphere of Ar, N2, and O2 and an RF source supplied a power of
1000 W to the target and the substrate. During deposition, a DC voltage
of − 100 V was applied as the substrate bias and the substrate table
were rotated at 1 rpm. The deposition time was varied to prepare
samples with suitable film thicknesses for each measurement; we
performed several depositions to check the deposition rate before
preparing samples. Table 1 shows typical experimental conditions. The
thin film compositions were determined by RBS (NHV Corp., NT-
Table 1
1700HS) using 2-MeV He+ ions; samples of approximately 200-nm-
thick films on glassy carbon substrates were used in this measurement.
The crystal structures of the thin films were investigated by X-ray
diffraction (XRD; Rigaku, RINT2500HF+/PC) using Cu Kα radiation
(0.15418 nm) under operating conditions of 50 kV and 300 mA. The
chemical bonding was examined by Fourier-transform infrared (FT-IR;
Jasco, FT/IR-4200) spectroscopy. Data were recorded from 400 to
1400 cm− 1 with a resolution of 4 cm− 1. FT-IR spectra were corrected
by subtracting the absorbance of the Si substrate. The thin film texture
was observed by transmission electron microscopy (TEM; JEOL, JEM-
3010) at an operating voltage of 300 kV. These samples were prepared
using a focused ion beam (FIB; Hitachi, FB-2000S) apparatus. The
hardness was measured using a nanoindenter (Fischer Instruments,
HM2000) with a load of 25 mN. The hardness measurements were
performed nine times; the hardness was determined based on five
values by omitting the two highest and lowest values to reduce the
measurement error.
3. Results and discussion
Fig. 2 shows the thin film compositions determined by RBS. It
shows that the oxygen content of the thin films increased from b1 to
44 at.% when the O2 flow rate was increased from 0 to 10.8 sccm. This
demonstrates that the oxygen content of the thin films can be
50 Oxygen
Composition (at.%)

Typical experimental conditions. 40

Target Cr (purity: 99.9%)

30
Chromium
Cathode power (W) 1000 (RF)
Sputtering gas Ar (400 sccm)
Reactive gases N2 (approximately 200 sccm) 20
O2 (0, 2.7, 5.4, 8.1, and 10.8 sccm)
Base pressure (Pa) 1 × 10− 3 Nitrogen
Pressure in process (Pa) 6 × 10− 1 10
Bias voltage (V) −100 (DC)
Substrates Si(100) and glassy carbon
Distance between cathode 80 0 2 4 6 8 10 12
and substrate (mm) O2 flow rate (sccm)
Substrate temperature (°C) Approximately 450
Film thickness (μm) 0.2 and 2.5
Fig. 2. Compositions of thin films prepared using different O2 flow rates.

controlled by varying the O2 flow rate. In previous studies, the oxygen
content in the films was affected by residual gas in the chamber and
leakage gas and so could not be accurately controlled [4,6]. In this
study, the chamber was evacuated to 1 × 10− 3 Pa before the
substrates were heated to approximately 450 °C for 1 h while
maintaining evacuation. The O2 flow rate was accurately controlled
by the mass flow controller during deposition. Therefore, we could
eliminate any influences of residual oxygen by measures. During
deposition, the working pressure was maintained at 6.0 × 10− 1 Pa to
minimize changes in the film preparation conditions. Fig. 2 reveals
that the chromium and nitrogen contents decrease gradually with
increasing O2 flow rate. The ratio of the chromium content to the non-
metallic element content varied between about 1:1 (for CrN) and 2:3
(for Cr2O3). According to Suzuki et al. [6], chromium oxynitride thin
films contain two phases (Cr(N,O) and Cr2O3) when the oxygen
content exceeds the solid solubility limit. In the present compositional
analysis, the oxygen content reached to approximately 44 at.%, which
likely exceeded the solid solubility limit according to previous reports.
Therefore, we expected that chromium oxynitride thin films would be
divided to the above two phases.
Fig. 3 shows the XRD patterns of thin films with various oxygen
contents. The bottom of Fig. 3 shows powder diffraction data for CrN,
Cr2N, and Cr2O3 from the International Center for Diffraction Data. No
diffraction peaks due to Cr2N or chromium oxides were observed. For
oxygen contents in the range b1–22 at.%, the XRD patterns show
strong diffraction from the {200} plane and weak diffraction from the
{111} plane [assuming that the thin films have crystal structures that
are close to that of B1(NaCl) structured CrN]. The diffraction patterns
from thin films with oxygen contents of 37 and 44 at.% did not contain
any sharp diffraction peaks but had broad peaks at around 63°.
According to Wilhartitz et al. [5], chromium oxynitride becomes
amorphous when the oxygen content exceeds 25 at.%; consequently,
the above broadening of diffraction peaks could be caused by an
influence of the amorphous phase. On the other hand, Suzuki et al. [6]
reported that the chromium oxynitride was divided to two phases of
Cr(N,O) and Cr2O3 when the oxygen content exceeds 43 at.%, but also
maintains a crystallized B1 structure less than 43 at.% oxygen; there is
possibility that chromium oxynitride contains a crystallized B1
structure even if oxygen content exceeds the solid solubility limit.
In the present study, we did not clarify this question. However, based
on experimental observations in this study, it is inferred that thin
37 at.%
B1-200
44 at.%
Oxygen content
B1-111
Si sub.
Intensity (arb. units)
(Crystallite size) 61 62 63 64 65 66
<1 at.% (25 nm)
9 at.% (20 nm)
22 at.% (15 nm)
37 at.% (8 nm)
44 at.% (7 nm)
Cr2O3 thin film
30 40 50
Diffraction angle 2θ (deg.)
Fig. 3. XRD patterns of Cr(N,O) thin films with oxygen contents ranging from 1 to 44 at.
% and of a Cr2O3 thin film. The lamp voltage was 50 kV and the current was 300 mA.
J. Shirahata et al. / Thin Solid Films 519 (2011) 3497–3500 3499
films with oxygen contents of 37 and 44 at.% consist of amorphous
and/or nanocrystalline phases. Fig. 3 also shows the crystallite sizes,
which were calculated from the diffraction peak of CrN 200 using the
Scherrer equation. The calculated crystallite size decreased from 25 to
7 nm when the oxygen content increased from b1 to 44 at.%. If this
broadening was not caused by an existence of an amorphous phase,
we can assume that the crystallite size decreases with increasing
oxygen content on chromium oxynitride.
In a previous section for XRD analysis, we discussed phases under
the high oxygen contents, but it was not clarified from the result of
XRD alone; so, we investigated chemical bonding and microstructure.
Fig. 4 shows the FT-IR spectra of a Cr(N,O) thin film with an oxygen
content of 22 at.% and of a Cr2O3 thin film; for reference, it also shows
the spectra of CrN and Cr2O3 [7]. According to Suzuki et al. [4], CrN has
a broad absorption peak at 550 cm− 1 and Cr2O3 has an additional
absorption peak at 620 cm− 1. In the present study, the FT-IR spectra
of Cr(N,O) thin films have only a single broad peak and do not contain
any clear peaks attributable to Cr2O3. We thus conclude that oxygen
does not exist as Cr2O3 and that a substitutional solid solution of B1-
CrN and B1-CrO was formed.
Fig. 5(a) and (b) shows bright-field TEM images of thin films with
oxygen contents of b1 and 22 at.%, respectively. From the observation,
the thin film with b1 at.% oxygen shows a clearly columnar structure,
and that of 22 at.% oxygen also shows a columnar structure. In
addition, Fig. 5 also shows selected-area diffraction patterns;
relatively clear ring patterns are observed with sharp diffraction
spots from B1-type CrN. This implies that both samples contain
polycrystals that have a B1-type structure. In regard to the existence
of an amorphous phase, it remains unanswered; since it is very
difficult to prove the evidence of an amorphous phase. However, in
the present study, we can say with fair certainty that samples contain
a nanocrystalline phase based on the B1-type structure.
Fig. 6 shows the indentation hardness of thin films. In the present
study, the hardness of Cr(N,O) thin films increased from 20 to 31 GPa
with increasing the oxygen content. In general, the hardness of the
CrN thin film is approximately 1800 HV (approximately 18 GPa) [8],
and Cr(N,O) thin films deposited by pulsed laser deposition showed a
higher hardness of 3300 HV (approximately 33 GPa) [4]. This
hardness improvement with increasing oxygen content was also
observed in previous studies [4,6]; it might be an influence of the
solution hardening of oxygen and/or Hall–Petch relationship. After
this, in the present study, the hardness of thin films decreased above
an oxygen content of 37 at.%. In regard to this phenomenon, we
expected as the following from the above observations; when the
Oxygen content
22 at.%
Absorption (arb. units)
Cr 2 O 3 thin film
CrN
Cr2N CrN [7]
Cr2O3 Cr 2O 3 [7]
60 70
1400 1200 1000 800 600 400
Wave number k (cm-1)
Fig. 4. FT-IR spectra of a Cr(N,O) thin film with 22 at.% oxygen and a Cr2O3 thin film.
3500 J. Shirahata et al. / Thin Solid Films 519 (2011) 3497–3500

40

Indentation hardness (GPa)

30

20

10

0
0 10 20 30 40 50
Oxygen content (at.%)

Fig. 6. Indentation hardness of Cr(N,O) thin films as a function of oxygen content.

Acknowledgments

The authors wish to thank Mr. Obata, Mr. Katagiri, and Mr.
Sekimoto of Nagaoka University of Technology for the RBS analysis.
We are also grateful to Mr. Matsui, Mr. Kimoto, and Ms. Yu of the
National Institute for Materials Science for fabricating the TEM
samples. We thank all the students at the Extreme Energy-Density
Research Institute for discussions on this research.

Fig. 5. Bright-field TEM images and selected-area diffraction patterns of Cr(N,O) thin
films with various oxygen contents. (a) b1 at.% oxygen; and (b) 22 at.% oxygen.
References
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(2006) 2161.
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chromium oxynitride has high oxygen content, thin films contain a

large amount of amorphous phases and/or nanocrystalline phases,
which possibly cause softening by the inverse Hall–Petch relation-
ship [9].
Based on the above results, we supposed as follow. Cr(N,O) thin
films with oxygen contents below 22 at.% are considered to be
substitutional solid solutions. On the other hand, thin films with
oxygen contents of 37 and 44 at.% consist of a nanocrystalline phase or
an amorphous phase because of the limited solution range.

4. Conclusions

Chromium oxynitride thin films were deposited by RF reactive

unbalanced magnetron sputtering under various gas conditions. The
oxygen contents of the thin films could be controlled by varying the
O2 flow rate and careful evacuation. These thin films have a B1
structure. FT-IR spectroscopy reveals that chromium oxynitride thin
films do not have a crystalline Cr2O3 phase. From the TEM
observations, chromium oxynitride thin films have a columnar
texture. The hardness of the thin films increases up to a maximum
value of 31 GPa with increasing oxygen content. Consequently, we
have prepared Cr(N,O) thin films with the controlling of oxygen
content and revealed the function of oxygen content on chromium
oxynitride thin films.