Thin Solid Films 407 (2002) 118–121

Preparation of Cr(Nx,Oy) thin films by pulsed laser deposition

Tsuneo Suzuki*, Hajime Saito, Makoto Hirai, Hisayuki Suematsu, Weihua Jiang, Kiyoshi Yatsui
Extreme Energy–Density Research Institute, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka, Niigata 940-2188, Japan

Abstract

Chromium oxynitride wCr(Nx ,Oy )x thin films have been prepared by pulsed laser deposition (PLD). The thin films were
prepared by depositing chromium metal vapor in a nitrogen ambient gas with residual oxygen. By composition analysis using X-
ray photoelectron spectroscopy and Rutherford backscattering spectroscopy, it was found that the thin films contained approximately
;46 at.% oxygen. In the Fourier transform infrared spectra, the peak originating from the Cr–N bond was found, and no peak
originating from the Cr–O bond of the Cr2O3 phase was observed. X-ray diffraction results indicated that the thin film was in a
B1 (NaCl) structure. From these results, it has been concluded that the Cr(Nx ,Oy ) thin film, which structurally resembles CrN
where nitrogen atoms were partially substituted by oxygen, has been successfully produced. It was also found that the CrN phase
maintains a B1 structure, even if 46 at.% oxygen is dissolved into the structure. By decreasing nitrogen pressure, the preferential
orientation of the thin films changes from w200x to w111x. 䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Nitrides; Laser ablation; Infrared spectroscopy; X-Ray diffraction

1. Introduction is in a B1 (NaCl) structure similar to CrN, maintains a

B1 structure even with oxygen dissolution up to 50 at.%
Since CrN has excellent properties in hardness, oxi- w4x. Therefore, it is expected that Cr(Nx,Oy) thin films
dation resistance, chemical stability and slide, it has of a B1 structure can be produced by dissolving oxygen
been used as a material for cutting tools, plastic metal atoms into a B1–CrN lattice.
molds, and frictional parts. For abrasion resistance mate- Pulsed laser deposition (PLD) is a very effective
rials, high hardness and stability at high temperature, method of thin film preparation by using the ablation
including high-temperature strength, are very important. plasma produced by the pulsed lasers. In PLD, ablated
At present, TiN, whose structure is same as that of CrN, particles arriving at the substrate have kinetic energies
is widely used as a coating material. However, the in the range of 10;100 eV, which is higher than most
thermostable critical temperature of TiN is relatively of the other methods, and therefore, more active migra-
low (approx. 500 8C). Compared with TiN, the oxidation tion on the substrate can be expected. As a result, the
resistance of CrN is higher since the Cr oxide film thin films prepared by PLD generally have better crys-
formed at high temperatures is more stable than that of tallinity. In this paper, we report our experimental results
Ti w1x. On the other hand, it is difficult to avoid of Cr(Nx,Oy) thin film preparation by PLD. The prepared
contamination of oxygen during the preparation of thin films were analyzed for crystal structure, chemical
nitride thin films. Therefore, Cr–N–O seems to be more bonding state, composition, and surface morphology.
practical. So far, Cr–N–O thin films have been produced
by sputtering w2x or arc evaporation w3x. However, the 2. Experiment
thin films prepared by these methods consist of a two-
phase mixture of CrN and Cr2O3. In other words, a thin The experimental setup is shown in Fig. 1. The
film of single-phase chromium oxynitride wCr(Nx,Oy)x ablation plasma was produced by irradiating the Ndy
has not yet been prepared. It is known that TiN, which yttrium aluminum garnet laser beam (355 nm) onto a
solid target. The laser was electro-optically Q-switched
*Corresponding author. Tel.: q81-258-49-9893; fax: q81-258-47- by a Pockels cell to produce intense, short pulses (;7
9890. ns). The laser beam was focused by lens so that the
E-mail address: [email protected] (T. Suzuki). energy density was adjusted to be 10 Jycm2 on the

0040-6090/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 2 . 0 0 0 2 3 - 8
 T. Suzuki et al. / Thin Solid Films 407 (2002) 118–121 119

Fig. 1. Experimental setup. Fig. 2. Composition of the thin films as a function of nitrogen
pressure.
target surface, within the spot area of 3 mm2. The
deposition time was 1 h at the laser-pulse repetition rate 3. Results and discussion
of 10 Hz. A chromium disk (99.9% in purity) was used
as the target. The chamber was first evacuated to The result of the composition analysis by XPS is
2=10y5 torr using a turbomolecular pump and then shown in Fig. 2. The saturated concentration obtained
filled with nitrogen gas (99.99% in purity) up to 0.1;10 after an Ar ion etching of 10 min was plotted. It is seen
torr. Since air leakage into the chamber was large, the that, when N2 pressure is increased, the nitrogen con-
ultimate vacuum was 2=10y5 torr in spite of vacuum centration slightly increases while the Cr and O concen-
drawing for 10 h. The residual air in the chamber turned trations do not show any clear dependence. In all
out to provide oxygen to the thin films. The deposition samples, 36–46 at.% oxygen was observed. The com-
surface was approximately 4 cm2 on a single-crystal, position analysis carried out by using RBS has given
(100)-oriented silicon substrate, placed at a distance of similar results as XPS.
10 mm from the target. The substrate temperature was Fig. 3 shows FT-IR spectra of the thin films prepared
controlled using a heater and a thermocouple. The under different nitrogen pressures. For comparison, spec-
typical experimental conditions are shown in Table 1. tra for CrN and Cr2O3 w5x are also presented. The
The composition of the thin film was determined by absorption spectra of each sample show a single broad
X-ray photoelectron spectroscopy (XPS) and Rutherford peak at 550 cmy1, which corresponds to the Cr–N or
backscattering spectroscopy (RBS). The surface mor- Cr–O bond. However, if the Cr–O bond of Cr2O3 phase
phology was observed by scanning electron microscopy
(SEM). The crystal structure of the thin film was studied
by X-ray diffraction (XRD) using CuKa radiation of
0.154 nm under operating conditions of 50 kV and 300
mA. The chemical bonding state was estimated by
Fourier transform infrared spectroscopy (FT-IR), where
the raw data was recorded from 1400 to 400 cmy1 with
a resolution of 4 cmy1 for 200 scans. The FT-IR
spectrum for each sample was obtained after taking into
account of the absorbance of the Si substrate.

Table 1
Experimental conditions

Fluence 10 Jycm2
Base pressure 2=10y5 torr
Target Cr
Substrate Si (100)
Distance (target–substrate) 10 mm
Substrate temperature 400 8C
Nitrogen pressure (PN2) 0.1;10 torr Fig. 3. FT-IR spectra of thin films prepared at different nitrogen
pressures.
120 T. Suzuki et al. / Thin Solid Films 407 (2002) 118–121

the structure of each thin film is in a B1 structure, based

on CrN. Diffraction peaks due to Cr or chromium oxides
were not observed. Under the base pressure of
10y5;10y6 torr, which contains a lot of oxygen, it is
usually expected that Cr oxides, not only Cr2O3 but also
CrO2 and CrO3, will be formed. In addition, under the
present experimental condition (substrate temperature
400 8C), CrO2 and CrO3 should be decomposed to
Cr2O3 w6x. However, the XRD results in Fig. 4 have
shown that all thin films are in a single-phase B1
structure, without any oxide phases of chromium,
although XPS results have indicated the existence of a
large amount of oxygen in the thin films. This result
also explains the absence of Cr oxide bond in the FT-
IR spectra.
From the above results, we have understood that
neither an amorphous nor a crystallized Cr2O3 phase
exists in the thin film. It is, therefore, presumed that, in
our Cr(Nx,Oy) thin films, oxygen atoms have simply
replaced nitrogen atoms in the CrN lattice, which has
been maintained in a B1 structure even when the oxygen
Fig. 4. XRD patterns of thin films prepared at different nitrogen concentration reaches as high as 46 at.%.
pressures. It can be seen from Fig. 4 that the thin film prepared
at PN2s10 torr seems to orientate in the w111x direction,
dominates the thin film, another peak at 620 cmy1 while the thin films prepared at PN2s0.1 and 1 torr
should be expected. Therefore, the broad peak at 550 orientate in the w200x direction. The reason for this
cmy1 was attributed only to the Cr–N bond. In other difference has not yet been understood.
words, the Cr–O bond does not massively exist in thin Fig. 5 shows the SEM image of the thin films prepared
film. under different nitrogen pressures. The surface of the
Fig. 4 shows X-ray diffraction patterns of the thin thin film prepared at PN2s0.1 torr is relatively smooth.
films prepared under different nitrogen pressure. JCPDS On the other hand, the surfaces of the thin films prepared
card data for Cr, CrN and Cr2O3 were also shown for at PN2s1 and 10 torr are rough. It is considered that
comparison. The agreement between each XRD pattern the smooth surface obtained under lower pressure is due
and the JCPDS data of CrN is evident, indicating that to direct deposition of the ablation plasma. Under higher
pressure, however, the ablated material is cooled while
colliding with the gas molecules, and as a result, starts
to aggregate before arriving at the substrate. The depo-
sition of fine solid particles may have caused the rough
surface of the thin films obtained under higher gas
pressure.

4. Conclusion

From the experimental results of Cr(Nx,Oy) thin film

preparation by pulsed laser ablation, we have obtained
the following conclusions:
1. Cr(Nx,Oy) thin films have been successfully prepared
by depositing chromium vapor in nitrogen with resid-
ual oxygen gas.
2. The CrN thin film is maintained in the B1 structure,
even when the thin films contained approximately 46
at.% oxygen.
3. The surface rough depends on the ambient gas pres-
Fig. 5. SEM images of thin films surface prepared at (a): PN2s10 sure. A relatively smooth surface was obtained only
torr, (b): PN2s1 torr (c): PN2s0.1 torr. under low pressure.
 T. Suzuki et al. / Thin Solid Films 407 (2002) 118–121 121

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