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Nanoindentation characterization of ZnO thin

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Materials Science and Engineering A 452453 (2007) 715720

Nanoindentation characterization of ZnO thin films

Te-Hua Fang a , Win-Jin Chang b, , Chao-Ming Lin c
a

Institute of Mechanical and Electromechanical Engineering, National Formosa University, Yunlin 632, Taiwan
b Department of Mechanical Engineering, Kun-Shan University, Tainan 710, Taiwan
c Department of Mechanical Engineering, WuFeng Institute of Technology, Chiayi 621, Taiwan
Received 14 August 2006; received in revised form 24 October 2006; accepted 3 November 2006

Abstract
The effects of the indentation load, indentation-loading time and the creep behavior of 23 m thick ZnO films deposited on a Si(1 0 0) substrate
were investigated by nanoindentation. The ZnO thin films were deposited under different sputtering powers by a radio frequency magnetron
sputtering system. The crystallographic and surface properties of the films were characterized by X-ray diffraction (XRD) and atomic force
microscopy (AFM). Results showed that Youngs modulus and the hardness of the films increased as the sputtering power was increased. The
hardness and Youngs modulus slightly decreased as the indentation rate and creep time were increased. The best ZnO film mechanical properties
were found at a sputtering power of 225 W.
2006 Elsevier B.V. All rights reserved.
Keywords: Thin films; X-ray diffraction; Mechanical properties

1. Introduction
Recently, ZnO thin films have increasingly been used for
various technological applications in sensor, surface acoustic wave (SAW) and piezoelectric devices [14], due to their
high transparency, piezoelectric properties, wide band-gap and
electro-optical characteristics [58].
Many different deposition techniques, such as spray pyrolysis [9], pulsed laser deposition [10], sputtering method [11],
metal organic chemical vapor deposition (MOCVD) [12] and
molecular beam epitaxy (MBE) [13] have been developed to
prepare ZnO thin films.
Each method has its relative advantages for certain applications. Among them, the sputtering method is one of the most
commonly used techniques due to several advantages, such as
low substrate temperature, high deposition rate, uniform surface
and excellent crystalline orientation. However, the build-up of
internal stresses has given rise to serious concerns about the
mechanical properties of sputtered ZnO films. It has been a challenge to understand what effects the load, the loading rate and
the creep behavior have on the mechanical properties of these
films. The condition that will subject the ZnO thin films to tri-

bological interaction is caused by rubbing damage during the

piezoelectric component manufacture.
Nanoindentation techniques have been developed for probing
mechanical properties, such as the hardness and Youngs modulus of thin films [14]. Mayo et al. studied the effect of grain size
on the hardness strain-rate sensitivity of nanocrystalline bulk
ZnO and showed that lower sintering temperatures, which provide finer grain sizes, tended to promote strain rate sensitivity
[15]. Recently, a number of researchers have used the nanoindentation technique to study the indentation-produced deformation
and dislocation mechanisms of bulk single-crystal ZnO [1619],
but the influence of the indentation load, the indentation-loading
time and the creep behavior during nanoindentation still warrant
further research and discussion.
In this article, the nanoindentation-induced behavior of polycrystalline ZnO thin films deposited at various sputtering powers
was investigated. The microstructural properties of ZnO films
were investigated by X-ray diffraction (XRD) and atomic force
microscopy (AFM). The influence on a nanometer-scale that
the indentation loads, the indentation-loading time, the creep
behavior and the sputtering power had on the deposited films
were also investigated.
2. Experimental details

Corresponding author. Fax: +886 2050883.

E-mail address: changwj@mail.ksu.edu.tw (W.-J. Chang).

0921-5093/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.11.008

In this study, ZnO thin films were produced on a Si(1 0 0)

substrate by a radio frequency magnetron sputtering system,

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T.-H. Fang et al. / Materials Science and Engineering A 452453 (2007) 715720

using a 99.99% pure, 2 -diameter Zn target, and was deposited

at sputtering powers of 150, 175, 200 and 225 W. The films
thickness was measured using a stylus profiler (Tencor Alpha
Step 200, USA). The thicknesses of the films were between 2
and 3 m. The detailed growth conditions of the ZnO films have
been reported in a previous study [20].
X-ray diffraction (Rigaku D/MAX-RA, Japan) was used to
analyze the crystallographic structure of the ZnO films. Crystallographic orientation was determined by XRD rotation over
2 degrees. The morphological properties of the ZnO films
surface were measured by atomic force microscopy (Shimadzu
SPM-9500J2, Japan). Typical scans were taken over an area of
1 m 1 m at a constant scan speed of 2 m/s.
The mechanical properties of ZnO thin films were characterized by nanoindentation (Hysitron Triboscope, USA) using
a Berkovich diamond indenter with a radius of 50 nm [21]. All
indentation tests were performed at room temperature.
Loadunloading experiments were performed to understand
the effects of different loads. A loading time of 10 s, a hold time
of 1 s and an unloading time of 10 s were used. The loads ranged
from 1000 to 3000 N. For the loading rate tests, the indentationloading and unloading times ranged from 10 to 50 s at a constant
load of 1000 N, the hold time was constant at 1 s. Hold time
creep behavior experiments were performed using hold times of
30, 60 and 120 s at the peak load and kept at a constant load of
1000 N using loading and unloading times of 10 s.
3. Analysis
The hardness and Youngs modulus as a function of
the displacement of the indenter were measured from the
loadingunloading of the indenter. A loadingunloading curve
is shown in Fig. 1. In the AFM micrograph of Fig. 1a, trian-

Fig. 1. The indentation loadingunloading curve and the associated ZnO thin
film AFM indentation image.

gular indent can be clearly seen, with plastic behavior pile-up

around the indentation. The hardness of a material is defined
as its resistance to plastic deformation. Thus, hardness H is
determined from maximum indentation load Pmax divided by
the actual projected contact area Ac and written as:
H=

Pmax
Ac

(1)

In depth-sensing nanoindentation, the composite modulus E* is

calculated by [22]:
E =

2 Ac

(2)

where S is the measured stiffness and is a shape constant of

1.034 for the Berkovich tip. Youngs modulus Em is defined by:
1

2
1

1
2
i
)

(3)
Em = (1 m
E
Ei
where is Poissons ratio, E the Youngs modulus, and the
subscripts i and m refer to indenter and test material, respectively. Indenter properties used in this studys calculations were
Ei = 1141 GPa and i = 0.07 [22] and m is assumed to be 0.3.
In Fig. 1, the area under the unloading curve represents the
elastic energy deformation and is represented by the area designated as We . The area between the loading and unloading
curve represents the energy dissipated into the film due to plastic
deformation and is represented by the area designated as Wp .
4. Results and discussion
4.1. Structural and surface characterizations
The XRD patterns for the ZnO films deposited on Si(1 0 0)
substrates at different sputtering powers are shown in Fig. 2 [20].
In Fig. 2, the intensities of the (0 0 2)-orientation can be seen
to have been enhanced as the sputtering power was increased,
indicating that the crystalline film is more uniformly oriented at
higher sputtering powers.
In Fig. 2(a), the film deposited at 150 W had the poorest crystallinity. As the sputtering powers increased, the (0 0 2)-peaks
of ZnO films became sharper. Base on the XRD data, the ZnO
films started to gain better crystallization when the sputtering
power was above 200 W. In addition, the best crystalline structure appeared at 225 W and did not have different crystallite
orientations of the same phase. The use of sputtering powers
larger than 225 W led to a higher deposition rate causing the sputtered atoms to pile-up on the surface of the film and to not have
enough time to diffuse. The film also exhibited poor substrate
adhesive properties at sputtering powers greater than 225 W.
The average grain size (D) of the ZnO films was calculated
from the full width at half maximum (FWHM) of the XRD
(0 0 2)-peak at around a diffraction angle of 34.4 , using the
Scherrer formula [23]. The average grain size (D) on the ZnO
films ranged from 34 to 42 nm as shown in Table 1. It was found
that the size of the grains increased slightly as the sputtering
power was increased and the surface roughness appeared to

T.-H. Fang et al. / Materials Science and Engineering A 452453 (2007) 715720

717

Fig. 3. Three-dimensional AFM image of a ZnO film for a sputtering power of

225 W. The surface region: 1 m 1 m, Zmax = 97 nm.
Fig. 2. XRD spectra of ZnO thin films for various sputtering powers of: (a) 150,
(b) 175, (c) 200 and (d) 225 W.

decrease as the grain size got larger. Since the grains are generally cone-like in shape, the structure can be characterized by the
surface area of the grains.
An AFM image of a 1 m 1 m surface region of a ZnO
film deposited at 225 W is shown in Fig. 3. Cone-like grains
covering the ZnO surface can be seen. The average surface
roughness (Ra ) and root-mean-square surface roughness (RMS)
are listed in Table 1. The average surface roughness of the ZnO
films at the sputtering powers of 150, 175, 200 and 225 W were
12.7, 12.0, 12.4 and 12.3 nm, respectively. There are no special statistical differences between these surface roughness for
films formed at different sputtering powers. The smoothest surface was created at the highest sputtering power of 225 W. High
frequency surface acoustic wave devices function much better
when the surface of the film is smoother [24]. This could be very
useful in further SAW application development.
4.2. Investigation of loadingunloading behaviors
Fig. 4(ac) shows the (Ph) curves and creep behavior (penetration depth versus indentation load) of ZnO films deposited
at 225 W and indented at various loads, loading times and hold
times. In this current study, pop-ins were not observed. However, pop-ins have been observed in previous studies [1518].
Table 1
Grain size (D) and surface roughness (Ra , RMS) of ZnO films for different
sputtering powers
Sputtering powers (W)

D
Ra
RMS
Unit: nm.

150

175

200

225

34 5
12.7 1.3
16.4 1.6

37 6
12.0 1.0
15.7 1.1

40 6
12.4 1.0
15.9 1.1

42 7
12.3 0.8
14.3 0.5

This most likely can be attributed to the preparation methods of

the different films used.
In Fig. 4(a), it was found that as the indentation loads
increased, the penetration depths, the plastic deformation and the
area Wp all increased. The deepest plastic depth was produced
under the larger indentation loads. It was also discovered from
the overlapping loading curves of all three indentation loads that
all the ZnO films surface properties were similar.
The effect of the indentation-loading time on a nanoscale
level is shown in Fig. 4(b). The indentation-loading time was
defined as the time from the beginning of the indentation loading
to when the maximum indentation load was reached. It can be
seen that the slope of the loading curve decreased, the penetration
depths and the area Wp both increased as the indentation-loading
time was increased, i.e. as the loading rate was decreased. These
results could be explained by the dislocation and slip behaviors
causing larger plastic deformation depths to take place at the
longer indentation-loading times.
The creep behavior at three different hold times can be seen in
Fig. 4(c). It was found that the loading curves were quite similar,
but the unloading curves started from slightly greater values of
hmax as the hold times were increased. In this study, the maximum indentation depth was less than 200 nm, i.e. approximately
1/10th of the films thickness and the mechanical properties were
not influenced by the presence of the silicon substrate. At shorter
hold times, a slightly steeper unloading curve occurred, which
would reduce the calculated elastic surface deformation and the
area Wp increased as the hold time was increased. This implies
that the longer hold times allowed for more energy to be dissipated and therefore caused the creep behavior to extend further
out, which in turn created the larger indentation deformations
[25].
4.3. Youngs modulus and hardness
Fig. 5(a) shows the Youngs modulus and the hardness of ZnO
thin films measured under different indentation loads. The ZnO

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T.-H. Fang et al. / Materials Science and Engineering A 452453 (2007) 715720

Fig. 4. Loaddisplacement curves of ZnO films sputtered at 225 W under various indentation: (a) loads, (b) loading times and (c) hold times.

films Youngs modulus ranged from 68 to 125 GPa and the hardness ranged from 4 to 6 GPa. The hardness and Youngs modulus
slightly decreased as the indentation loads were increased. Similar nanoindentation tests for ZnO materials have been performed
by previous studies, such as Lucca et al. [18] and Klopfstein et
al. [19] studied mechanical responses for the chemomechanically polished single-crystal ZnO and obtained that the values
of elastic modulus and hardness ranged from 104 to 134 GPa and
2 to 7 GPa, respectively. The greater values for Youngs modulus
and hardness were achieved at the higher sputtering powers due
to the ZnO films having had better crystalline structures. The
ZnO film deposited at the sputtering power of 225 W appeared
to have had the best mechanical properties in this study. The
previous study showed that the wear volume decreased as the
sputtering power was increased [20]. Thus, the combined data

from this study and that found in ref. [20] show that the films
with higher E and H have greater wear resistance.
The ZnO films Youngs modulus ranged from 61 to 123 GPa
and the hardness ranged from 4 to 5 GPa at different indentationloading times as shown in Fig. 5(b). As the indentation-loading
time was decreased both the Youngs modulus and the hardness
of the films increased. This was due to the longer indentationloading times, and leading to dislocation slip to the materials
surface causing a larger degree of plastic deformation.
Youngs modulus and hardness of the thin films under the
different hold times of 30, 60 and 120 s are shown in Fig. 5(c).
Youngs modulus and hardness ranged from 70 to 90 GPa, and
from 4 to 6 GPa, respectively. As seen in Fig. 5(c), the indentation creep tests showed that the hardness and Youngs modulus
slightly decreased as the hold time was increased. These results

T.-H. Fang et al. / Materials Science and Engineering A 452453 (2007) 715720

719

Fig. 5. Youngs modulus and hardness for ZnO films subjected to various indentation: (a) loads, (b) loading times and (c) hold times.

might be due to the surface diffusion and reorganization processes that occurred at the longer holding times and caused
the larger indentation depths. In addition, the variation of the
hardness with the sputtering powers for different hold times in
Fig. 5(c) is not obvious when the powers range from 175 to
225 W. However, it appears a relatively large variation when the
sputtering power of 150 W is used. This because the ZnO film
deposited at sputtering powers of 150 W has a larger roughness
as listed in Table 1, and that induced a higher uncertainty and
error of measurement. In order to reduce the measurement error,
a longer hold time in the experiment may be used, such as 120 s.

thin films are well ordered with a high (0 0 2)-orientation. The

films exhibited higher quality crystalline structures as the sputtering power was increased. At sputtering powers that ranged
from 150 to 225 W during depth-sensing indentation recording,
the Youngs modulus of the films ranged from 61 to 125 GPa and
the hardness ranged from 4 to 6 GPa. In addition, the nanoindentation characteristics affected by the indentation loads, loading
rates and creep behaviors are presented. In summary, the results
confirmed that various sputtering powers played an important
role in the nanomechanical characteristics of the ZnO film and
that the films deposited at 225 W appeared to have the best
mechanical properties.

5. Conclusion
Acknowledgements
The mechanical properties of ZnO films deposited at various sputtering powers were investigated by nanoindentation. At
higher sputtering powers, the crystalline structures of the ZnO

The author would like to thank Mr. Sheng-Rui Jian, ChunChin Chang and Shi-Cheng Liao for their technical support. This

720

T.-H. Fang et al. / Materials Science and Engineering A 452453 (2007) 715720

work was partially supported by the National Science Council

of Taiwan, under Grant Nos. NSC94-2212-E150-045, NSC942212-E150-046 and NSC95-2221-E-168-008.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]

F. Hossein-Babaei, F. Taghibakhsh, Electron. Lett. 36 (2000) 1815.

W. Water, S.Y. Chu, Mater. Lett. 55 (2002) 67.
P. Sharma, S. Kumar, K. Sreenivas, J. Mater. Res. 18 (2003) 545.
K.H. Kim, K.C. Park, T.Y. Ma, J. Appl. Phys. 81 (1997) 7764.
Y.R. Park, K.J. Kim, Solid State Commun. 123 (2002) 147.
T. Nagata, T. Shimura, A. Ashida, N. Fujimura, T. Ito, J. Cryst. Growth
237239 (2002) 533.
H.M. Kim, S.K. Jung, J.S. Ahn, Y.J. Kang, K.C. Je, Jpn. J. Appl. Phys. 42
(2003) 223.
K. Funk, T. Fabula, G. Flik, F. Larmer, J. Micromech. Microeng. 13 (2003)
353.
J. Ebothe, A.El. Hichou, P. Vautrot, M. Addou, J. Appl. Phys. 93 (2003)
632.
M. Sumiya, S. Fuke, A. Tsukazaki, K. Tamura, A. Ohtomo, M. Kawasaki,
H. Koinuma, J. Appl. Phys. 93 (2003) 2562.
K.H. Bang, D.H. Hwang, J.M. Myoung, Appl. Surf. Sci. 207 (2003) 359.

[12] K.H. Bang, D.K. Hwang, M.C. Jeong, K.S. Sohn, J.M. Myoung, Solid State
Commun. 126 (2003) 623.
[13] M. Fujita, N. Kawamoto, T. Tatsumi, K. Yamagishi, Y. Horikoshi, Jpn. J.
Appl. Phys. 42 (2003) 67.
[14] R. Bahl, A. Kumar, M. Vedawyas, D. Patel, Appl. Phys. A 69 (1999) S643.
[15] M.J. Mayo, R.W. Siegel, Y.X. Liao, W.D. Nix, J. Mater. Res. 7 (4) (1992)
973.
[16] S.O. Kucheyev, J.E. Bradby, J.S. Williams, C. Jagadish, M.V. Swain, Appl.
Phys. Lett. 80 (2002) 956.
[17] J.E. Bradby, S.O. Kucheyev, J.S. Williams, C. Jagadish, M.V. Swain, P.
Munroe, M.R. Phillips, Appl. Phys. Lett. 80 (2002) 4537.
[18] D.A. Lucca, M.J. Klopfstein, R. Ghisleni, G. Cantwell, Ann. CIRP 51
(2002) 483.
[19] M.J. Klopfstein, D.A. Lucca, G. Cantwell, Phys. Status Solidi (a) 196
(2003) R1.
[20] T.H. Fang, S.R. Jian, D.S. Chuu, J. Phys. D Appl. Phys. 36 (2003) 878.
[21] T.H. Fang, W.J. Chang, Microelectron. J. 35 (2004) 595.
[22] W.C. Oliver, G.M. Pharr, J. Mater. Res. 7 (1992) 1564.
[23] B.D. Cullity, Elements of X-ray Diffraction, Addison-Wesley, Reading,
MA, 1978, p. 102.
[24] S.H. Seo, W.C. Shin, J.S. Park, Thin Solid Films 416 (2002) 190.
[25] T. Chudoba, F. Richter, Surf. Coat. Technol. 148 (2001) 191.