Nuclear Instruments and Methods in Physics Research B 269 (2011) 1973–1976

Contents lists available at ScienceDirect

Nuclear Instruments and Methods in Physics Research B

journal homepage: www.elsevier.com/locate/nimb

Effect of microstructure on the nanomechanical properties of TiVCrZrAl nitride

films deposited by magnetron sputtering
Zue-Chin Chang a, Shih-Chang Liang b, Sheng Han c,⇑
a
Department of Mechanical Engineering, National Chin-Yi University of Technology, 35, Lane 215, Section 1, Chung-Shan Road, Taiping City, Taichung County 41101, Taiwan, ROC
b
Department of Materials Science and Engineering, National Chung Hsing University, 250 Kuo Kuang Road, Taichung 40227, Taiwan, ROC
c
Department of Leisure and Recreation Management, National Taichung Institute of Technology, 129 San-Min Road, Section 3, Taichung 40401, Taiwan, ROC

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

Article history: This paper describes the nanoindentation behavior of TiVCrZrAl nitride films grown on Si substrates
Received 15 February 2011 by means of reactive radio-frequency magnetron sputtering at growth temperatures from 150 to
Received in revised form 2 May 2011 300 °C. We used cross-sectional transmission electron microscopy and X-ray diffraction to analyze
Available online 6 June 2011
the microstructure and crystallinity and nanoindentation techniques to study the hardness and elastic
modulus. We found that a face-centered-cubic solid-solution structure with strong (2 0 0), (1 1 1),
Keywords: (2 2 0), and (3 1 1) orientations were revealed by X-ray diffraction. Upon increasing the growth tem-
Nanoindentation
perature of the films, the hardness and elastic modulus increased to maximum values of 15.2 and
TiVCrZrAl nitride films
Hardness
203.5 GPa, respectively.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction In recent reports [26,27], we described the contact-induced struc-

Transition metal-based materials featuring one principal ele-
ment, compound, or coating have been studied extensively [1,2].
For example, hard coating films of Ti and TiCr alloys have led to
the development of new hydrogen storage alloys exhibiting higher
capacity and superior mechanical properties [3–11]. These metallic
alloy coatings often provide poor yield strengths and undergo defor-
mation because of their low hardness. To enhance the resistance of
such films, several methods have been developed, such as the use
of nitridation processes and/or the incorporation of solute elements
[12–23]. High-entropy alloys featuring additional multi-principal
elements have been suggested previously to combine simple solid
solutions with nanocrystalline and/or amorphous structures, result-
ing in improved performance in terms of hardness, strength, and
anticorrosion resistance. Taizhong et al. [24] employed the fast
melt-spinning method to prepare TiCr1.1V0.5Fe0.1Mn0.1 alloys,
which have a Laves phase-related body-centered-cubic (BCC) struc-
ture. Characteristically, high-entropy alloys consist of simple solid
solutions featuring simple BCC and face-centered-cubic (FCC) struc-
tures, forming nanoscale particles distributed in an amorphous and/
or crystalline matrix. The bulk glassy structure of the alloy usually
exhibits high strength and good fatigue resistance [14,15]. Using a
TriboLab nanoindenter (Hysitron) and a Berkovich diamond inden-
ter tip, Shieu and coworkers [25] found that the hardness of TiVCr
and TiVCrZrY films was enhanced to ca. 11 and 14 GPa, respectively.
⇑ Corresponding author. Tel.: +886 4 22195902; fax: +886 4 22195901.
E-mail address: shenghan@ntit.edu.tw (S. Han).
tural deformation behavior of Zn1 xCdxSe epilayers and the nano-
tribological behavior of alloy materials featuring Zn1 xMnxO
epilayers. The hardness and residual stress are two important
parameters affecting the applications of alloys films, particularly
for the high-entropy TiVCrZrAl alloys. Because these high-entropy
alloy films are readily deposited using sputtering processes, by
adjusting the composition or process parameters, they have poten-
tially high applicability in various fields. Therefore, we have system-
atically investigated the relationship between the mechanical
characteristics and the growth conditions used to form TiVCrZrAl ni-
tride films.
In this study, we used reactive radio-frequency (RF) magnetron
sputtering to grow the equimolar TiVCrZrAl nitride films at various
temperatures under N2/Ar, mainly at a 1:1 flow ratio. The crystal
structure was identified using X-ray diffraction (XRD). A transmis-
sion electron microscope (TEM) was used to examine the micro-
structure of some specimens. Subsequently, we determined the
values of H and M using nanoindentation techniques.
2. Experimental details
The target alloy ingots were prepared using equimolar elemen-
tal Ti, V, Cr, Zr, and Al (purity: >99.99 mass%) through repeated arc
melting (at least five times) in an Ar atmosphere, and then cut and
polished into a disk having a 2-in. diameter. The TiVCrZrAl nitride
films were deposited on Si (1 0 0) wafers through reactive RF mag-
netron sputtering at growth temperatures of 150, 200, 250, and
300 °C. To remove the contaminants formed on the target surface

0168-583X/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2011.05.027
1974 Z.-C. Chang et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 1973–1976

and to stabilize the sputtering conditions, it was necessary for pre- Upon increasing the growth temperature, the (2 0 0) peak became
sputtering to be performed for 5 min prior to each deposition pro- more obvious. Further, from measurements of the full width at half
cess. The base pressure of the deposition chamber reached less maximum, we used Scherrer’s formula to calculate the average
than 3  10 6 torr, the samples were deposited at a power of grain sizes of the films [31]. At growth temperatures of 150, 200,
150 W in a mixed Ar/N2 (1:1) atmosphere under a constant work- 250, and 300 °C, the resulting grain sizes of the TiVCrZrAl nitride
ing pressure of 5  10 3 torr. The deposition time was 90 min at film were 2.5, 2.7, 3.2, and 3.3 nm, respectively. The intensity of
room temperature with a bias of 100 V. The distance between the (2 0 0) peak increased significantly upon increasing the growth
the substrate and the target was set at 90 mm. The crystal struc- temperature to 300 °C, revealing enhanced crystallinity in the
ture and preferred orientation of the film were examined using (2 0 0) oriented plane.
glancing angle X-ray diffraction (MacScience MPX3), with an inci- Nanoindentation is a useful technique for probing the properties
dent angle of 1°, Cu Ka radiation, and operation at 40 kV and of thin films. We used the CSM mode to investigate the properties of
30 mA. The phase evolution and crystallization behavior of the
sample were observed using TEM (JEOL, JEM-2100F) and by record-
ing SAD; TEM samples were prepared through mechanical polish-
ing down to 20–30 lm, followed by Ar ion milling to electron
transparency. The observations were made at 200 kV. The values
of H and M of the TiVCrZrAl nitride films were determined using
a Nano Indenter XP instrument (MTS Cooperation, Nano Instru-
ments Innovation Center, TN, USA). The nanoindentation was per-
formed using a diamond Berkovich indenter tip (tip radius: about
50 nm); plastic deformation was generated at very small loads.
The hardness data obtained using a Berkovich indenter can be
transformed to Vickers hardness because both techniques employ
the same-shaped three-sided pyramid, which provides similar
area-to-depth functions.
The continuous contact stiffness measurement (CSM) mode,
which is executed by superimposing small oscillations on the force
signal to measure displacement responses, offers a direct measure-
ment of dynamic contact stiffness during the loading process in the
indentation test; it is insensitive to thermal drift. Hence, the CSM
mode can be used to obtain values of H and M relative to the inden-
tation depth; therefore, and was used in these experiments
[28–30]. Fig. 2. Hardness of TiVCrZrAl nitride films deposited at various growth tempera-
tures, plotted with respect to the indentation depth.

3. Results and discussion

The TiVCrZrAl nitride films revealed (1 1 1), (2 0 0), (2 2 0), and

(3 3 1) peaks for FCC packing at 36.96°, 43.1°, 62.5°, and 74.5°,
respectively, in their XRD spectra shown in Fig. 1. The TiVCrZrAl ni-
tride films exhibited crystalline structures from 150 to 300 °C. The
film had a (2 0 0) preferred orientation under the growth conditions.

Fig. 3. Young’s moduli of TiVCrZrAl nitride films deposited at various growth

temperatures, plotted with respect to the indentation depth.

Table 1
Hardness, modulus and H/E ratio of the TiVCrZrAl assembly prepared at various
growth temperature.

Temperature (°C) Hardness (GPa) Modulus (GPa) H/E

150 13.4 ± 0.6 193.5 ± 8.0 0.0692
200 13.1 ± 0.5 192.4 ± 7.8 0.0678
250 13.3 ± 0.6 193.0 ± 8.1 0.0678
Fig. 1. Typical XRD spectra of TiVCrZrAl nitride films deposited at various growth 300 15.2 ± 0.9 203.5 ± 9.2 0.0746
temperatures.
 Z.-C. Chang et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 1973–1976 1975

Fig. 4. TEM images revealing the microstructures of TiVCrZrAl nitride films deposited at growth temperatures of (a) 150, (b) 200, (c) 250, and (d) 300 °C. Insets: (top) images
of the interfacial quality of TiVCrZrAl nitride films grown on Si substrates at a thickness of ca 0.5 lm; (bottom) SAD analysis.

the TiVCrZrAl alloy in the nano-scale regime from studies of its con- 200 nm, following the method proposed by Oliver and Pharr [21].
tinuous penetration depth. Figs. 2 and 3 plot the values of H and M For indentation depths up to about 20 nm, the value of H increased
of the TiVCrZrAl film as functions of the indentation depth at upon increasing the indentation depth, such behavior is usually
1976 Z.-C. Chang et al. / Nuclear Instruments and Methods in Physics Research B 269 (2011) 1973–1976
attributed to the transition between purely elastic and elastoplastic
contact, whereby the value of H is actually equal to the contact
pressure. For indentation depths greater than about 20 nm, H be-
came a constant. The values of M followed a trend similar to that
of the hardness, except that its magnitude converged at an indenta-
tion depth smaller than that for H. Therefore, we determined the
average values of H and M from measurements performed at inden-
tation depths ranging from 100 to 200 nm—an adequate depth to
achieve a fully developed plastic zone, but not exceeding 20% of
the film thickness to avoid the substrate effect [32]. For the TiVCrZ-
rAl nitride films formed at growth temperatures of 150, 200, 250,
and 300 °C, the measured values of H and M were listed as Table
1. It is slight oscillated and discontinuous phenomena in the plot
of the values of H (Fig. 2). It was the reason that resulted from the
shear-induced dislocation slips in the TiVCrZrAl nitride film [33].
Increasing the growth temperature to 300 °C caused the values of
H and M to increase slightly, presumably because of thermal growth
effects, which essentially presented a high elastic strain to failure
capability [23]. The hardness/elastic modulus (H/E) ratio (Table 1)
is a measurement of the absorbed energy prior to destruction of a
film. Several factors affect the value of H of a film, including the
packing, stoichiometry, residual stress, preferred orientation, and
grain size. The film deposited at 300 °C possessed the highest value
of H/E might be that resulted from (2 0 0) orientation structure with
approaching stoichiometric phase. A high H/E ratio usually means
superior wear resistance in a coating [23]. The XRD with informa-
tion regarding the crystal quality resulted in the degree of indenta-
tion, because the value of H increased with the increasing
temperature. A harder layer that was relatively difficult to deform
imposed severe resistance toward the plastic deformation of the
films when the growth temperature was 300 °C. Fig. 4 displays
TEM profiles including the microstructure, cross-sectional views
and SAD assembly. It is clearly observed that these films exhibit a
typical columnar structure. The SAD patterns revealed that each
sample was polycrystalline. No precipitation or second phase was
observed, implying high mutual solubility of present alloy design.
Fig. 4d (grew at high temperature of 300 °C) finds the more crystal-
lization in the microstructure. It is suggested that the reason is con-
ducted by strongly polycrystalline as well as somewhere
crystallization of the form and that induced a preferred orientation
of the film from XRD analyzed. Its good-quality columnar micro-
structure was observed that accompanied the enhanced mechani-
cal resistance against elastic and elastoplastic deformations. This
phenomenon was shown in Figs. 2 and 3 for indentation depths be-
low 50 nm, which can reflect film-only properties. Chandra et al.
[16] found that higher sputtering and deposition rates led to a high-
er density of islands nucleating on the substrate and resulted in a
finer grain size, consistent with our observations. During the sput-
tering growth process, the effect of the temperature dominated that
of the sputtering efficiency. It was that the growth temperature not
only induced the formation of nucleation seed but also enhanced
the values of H and M of the TiVCrZrAl nitride films.
4. Conclusion
We have used a combination of nanoindentation, XRD, and TEM
analyses to investigate contact-induced structural deformation
behavior in sputtering-derived TiVCrZrAl nitride films in terms of
their surface features and nanomechanical properties. TEM images
revealed that the films had very large poly-crystalline structures.
XRD analyses revealed the crystalline nature of the TiVCrZrAl ni-
tride films. The values of H of the TiVCrZrAl nitride films increased
from 13.4 ± 0.6 to 15.2 ± 0.9 GPa and the Young’s modulus in-
creased from 193.5 ± 8.0 to 203.5 ± 9.2 GPa upon increasing the
growth temperature from 150 to 300 °C.
Acknowledgment
The authors gratefully acknowledge the financial support of this
research from the National Science Council and Ministry of Educa-
tion of the Republic of China (Taiwan) under the respective con-
tract number of NSC 97-2622-E-167-004-CC3 and 100M-24-019.
The authors would like to thank Dr. H.-C. Wen for technical assis-
tance and the National Nano Device Laboratories for experimental
support.
References
[1] S.J. Pearton, J.C. Zolper, R.J. Shul, F. Ren, J. Appl. Phys. 86 (1999) 1.
[2] J.R. Johnson, J. Less-Common Met. 73 (1980) 345.
[3] J.R. Johnson, J.J. Reilly, F. Reidinger, L.M. Corliss, J.M. Hastings, J. Less-Common
Met. 88 (1982) 107.
[4] O. Beeri, D. Cohen, Z. Gavra, J.R. Johnson, M.H. Mintz, J. Alloy Compd. 267
(1998) 113.
[5] S.N. Klyamkin, A.Yu. Kovriga, V.N. Verbetsky, Int. J. Hydrogen Energy 24 (1999)
149.
[6] X. Chu, M.S. Wong, W.D. Sproul, S.A. Barnett, Surf. Coat. Technol. 57 (1993) 13.
[7] F. Akasheha, H.M. Zbib, J.P. Hirth, R.G. Hoagland, A. Misra, J. Appl. Phys. 101
(2007) 084314.
[8] S. Veprek, Surf. Coat. Technol. 97 (1997) 15.
[9] S. Ranganathan, Res. News Curr. Sci. 85 (2003) 1404.
[10] A. Inoue, Acta Mater. 48 (2000) 279.
[11] A.L. Mackay, Crystallogr. Rep. 46 (2001) 524.
[12] J.W. Yeh, S.K. Chen, J.Y. Gan, S.J. Lin, T.S. Chin, T.T. Shun, C.H. Tsau, S.Y. Chang,
Metall. Mater. Trans. A 35A (2004) 2533.
[13] T.K. Chen, T.T. Shun, J.W. Yeh, M.S. Wong, Surf. Coat. Technol. 188/189 (2004)
193.
[14] Y.Y. Chen, T. Duval, U.D. Hung, J.W. Yeh, H.C. Shih, Corr. Sci. 47 (2005) 2257.
[15] Y.Y. Chen, U.T. Hong, J.W. Yeh, H.C. Shih, Appl. Phys. Lett. 87 (2005) 261918.
[16] R. Chandra, A.K. Chawla, D. Kaur, P. Ayyub, Nanotechnology 16 (2005) 3053.
[17] P.K. Huang, J.-W. Yeh, Surf. Coat. Technol. 203 (2009) 1891.
[18] J. Pelleg, L.Z. Zevin, S. Lungo, N. Croitoru, Thin Solid Films 197 (1991) 117.
[19] J.E. Sundgren, Thin Solid Films 128 (1985) 21.
[20] W. Ensinger, Nucl. Instr. Meth. Phys. Res. B 127/128 (1997) 796.
[21] W.C. Oliver, G.M. Pharr, J. Mater. Res. 7 (1992) 1564.
[22] H.W. Chang, P.K. Huang, A. Davison, J.-W. Yeh, C.-H. Tsau, C.-C. Yang, Thin Solid
Films 516 (2008) 6402.
[23] A. Leyland, A. Matthews, Wear 246 (2000) 1.
[24] H. Taizhong, W. Zhu, F. Shanglong, X. Baojia, X. Naixin, Mater. Sci. Eng. A 390
(2005) 362.
[25] D.C. Tsai, F.S. Shieu, S.Y. Chang, H.C. Yao, M.J. Deng, J. Electrochem. Soc. 157
(2010) K52.
[26] H.C. Wen, C.S. Yang, W.C. Chou, Appl. Surf. Sci. 256 (2010) 2128.
[27] Y.M. Chang, H.C. Wen, C.H. Tsai, C.S. Yang, J.S. Wang, W.F. Wu, C.P. Chou,
Microelectron. Reliab. 50 (2010) 1111.
[28] B.C. He, H.C. Wen, T.Y. Chiang, Z.C. Chang, D. Lian, W.F. Wu, C.P. Chou, Appl.
Surf. Sci. 256 (2010) 3299.
[29] B.C. He, C.H. Cheng, H.C. Wen, Y.S. Lai, P.F. Yang, M.H. Lin, W.F. Wu, C.P. Chou,
Microelectron. Reliab. 50 (2010) 63.
[30] P.F. Yang, H.C. Wen, S.R. Jian, Y.S. Lai, S. Wu, R.S. Chen, Microelectron. Reliab. 48
(2008) 389.
[31] H.P. Klug, L.E. Alexander, X-Ray Diffraction Procedures for Polycrystalline and
Amorphous Materials, John Wiley & Sons, New York, 1974.
[32] B.S. Li, Y.C. Liu, D.Z. Shen, J.Y. Zhang, Y.M. Lu, X.W. Fan, J. Cryst. Growth 249
(2003) 179.
[33] M.-H. Lin, H.-C. Wen, C.-Y. Huang, Y.-R. Jeng, W.-H. Yau, W.-f. Wu, C.-P. Chou,
Appl. Surf. Sci. 256 (2010) 3464.