Key Engineering Materials Vols 353-358 (2007) pp 2966-2969 Online: 2007-09-10

© (2007) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/KEM.353-358.2966

Hardness and Elastic Modulus of ZnO Thin Films Fabricated by PLD

Method

Han-Ki Yoon1, a and Yun-Sik Yu2, b

1
Department of Mechanical Engineering, Dong-eui University, 995 Eomgwangno, Busanjin-gu,
Busan, 614-714, Korea
2
Physics Department, Dong-eui University, 995 Eomgwangno, Busanjin-gu, Busan, 614-714, Korea
a
ahkyoon@deu.ac.kr, bbysyu@deu.ac.kr

Keywords: Zinc oxide (ZnO); Pulsed laser deposition (PLD); Substrate effect; Nano indentation (NI)
method, Hardness; Elastic modulus.

Abstract. ZnO is an n-type semiconductor having a hexagonal wurzite structure. ZnO exhibits good
piezoelectric and optical properties, and might be a good candidate for an electroluminescence device
like an UV laser diode. Then, these devices are very small, their films are very thin and they are
prepared in the limited size and shape, so they are unsuitable for the extensive mechanical testing. In
this present work, ZnO thin films are prepared on the glass, GaAs(100), Si(100) and Si(111)
substrates at various temperatures by the pulsed laser deposition (PLD) method. ZnO thin films were
evaluated by X-ray diffraction (XRD) and mechanical properties such as hardness and elastic
modulus were measured through the nano-indenter.

Introduction
Recently II-VI compound semiconductors have been attracted much attention in acoustic, electronic,
and optical applications such as surface acoustic wave (SAW) filter, acousto-optic, piezo-optic and
photoelectric devices, in particular, electroluminescent device. ZnO is a potential candidate material
for the optical devices such as light emitting diodes (LEDs) and laser diodes (LDs) due to its similar
properties to those of GaN. It has the direct band gap of 3.3eV at room temperature, the large excition
binding energy of 60meV and the high melting temperature of 2248K. So ZnO has received
considerable attention in various field[1,2]. In order to develop ZnO thin films of high quality for
device applications with good performance, it is necessary to clarify the effects of additives, the
conditions of growth and the substrate types. ZnO thin films of good quality have been prepared by
many methods, such as sputtering, thermal and electron-beam evaporation, pulsed laser deposition,
chemical vapor deposition and molecular beam epitaxy[3,4]. Among them, the pulsed laser
deposition has peculiar characteristics such as simplicity of fabrication, in-situ processing of the
multi-layer heteo-structures by using the multiple targets and stoichiometric deposition etc.
In this work, XRD and nano-indenter systems are used to evaluate the effects of the temperature
and the substrate for the mechanical properties of ZnO thin films such as hardness and elastic
modulus, because those are essential to evaluate the film quality for the device applications..

Experiment
Fabrication of ZnO thin films. In the chamber of the PLD system, there are four target holders on
one carousel and one substrate holder. The substrate holder is usually located at the opposite position
to one of the target holders. KrF excimer laser (λ=248nm) is used for the ablation of the ZnO target at
the energy density of 1J/cm2. The strong absorption of 248nm laser radiation by the target produces
an intense plasma plume in front of the target surface. The ablated material is then deposited on the
substrate kept 50mm away from the target. In the PLD experiment, the repetition rate of the laser is
5Hz, the deposition time is 30min, the ambient O2 pressure is 200mTorr, and the temperature of the
substrate varies from room termperature to 600oC. The high purity ZnO powder (99.99%) was used in

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 Key Engineering Materials Vols. 353-358 2967

Surfac e
profile
After load Indenter profile Pmax
removal Loading

Original surfac e

Load,P
profile Unloading

hf hs
S
h Surfac e profile
hc Under load

a hf h max
Displac ement,h

Fig. 1. Schematic representation

of a section Fig. 2. Schematic representationof
through an axisymmetric indentation used indentation load -displacement data during
in analysis. on complete cycle of loading and unloading.

the experiment. The disk-shaped specimen of 25mm in diameter and 5mm in thickness is obtained by
the uniaxial pressing at 100MPa, followed by the cold iso-static press at 200MPa. The disk-shaped
ZnO is sintered at 600oC for 2hrs and at 1200oC for 4hrs in order to condensate the target.
Measurement of Mechanical properties. Indentation loads of 1g and 10g are used in order to
measure the mechanical properties of ZnO thin films and substrates. Fig. 1 is a schematic of the
indentation process for an axisymmetric indenter of arbitrary profile. As the indenter is driven into the
material, both elastic and plastic deformation processes occur, producing a hardness impression that
conforms to the shape of the indenter to some contact depth, hc. The radius of the circle of contact is
A. Oliver and Pharr equation [5] is used to calculate elastic modulus Er ;
1 π S
Er = (1)
β 2 A
where Er is the reduced elastic modulus and β is a constant that depends on the geometry of the
indenter and the parameter is known as the elastic contact stiffness. S is calculated from the slope of
the upper portion of the unloading curve in Fig . 2. β is applied 1.034 for indenters with Berkovich
[6]. The elastic modulus of the specimen, E , is calculated from ;
2
1 1 −ν 2 1 −ν i
= + (2)
E E E
r i
where ν is the Poisson’s ratio for the specimen, and E and ν i are the elastic modulus and
i
Poisson’s ratio, respectively, of the diamond indenter. For diamond, elastic constants and Poisson’s
ratio are used 1141GPa, 0.07, respectively. For ZnO, Poisson’s ratio is 0.3. Then hardness, H, is
determined by the relation; H=P/A, where P is the load and A is the projected contact area at that load.
A is an experimental function of the contact depth, that is A=23.897hc2. The contact depth is
estimated by the following relation;
P
hc = h − hs = h − ε (3)
S
where ε is a constant that depends on the indenter geometry. The ε of Berkovich indenter is used 0.75
[6].

Result and Discussion

XRD analysis of ZnO. Fig. 3 shows XRD patterns of ZnO thin films fabricated at different substrate
temperatures (Ts) on glass(A), GaAs(100) (B), Si(100) (C), and Si(111) (D) substrates. It is found that
the substrate temperature Ts plays an important role in determining the structure of ZnO thin films. To
assess the quality of the thin films, the full width at half maximum (FWHM) values are measured
from XRD results. It is found that FWHM values of (002) peak of ZnO at 34.4o are around 0.2o, which
2968 Progresses in Fracture and Strength of Materials and Structures

means that the high quality thin films are fabricated by PLD method. As Ts increase to 500oC, FWHM
values of the (002) preferred orientation increase at first, but it decreases with Ts as shown in Fig.4.
Where FWHM is correlated with the grain size D by Debye-Scherrer formula [7],
0.9λ
D= (4)
β cosθ
where λ is the radiation wavelength, θ is the Bragg angle of (002) peak, and β is the FWHM value.
In Fig. 3(A), it is clear that the film deposited at Ts higher than 100oC has grown with (002)
preferred orientation. While the thin film fabricated at room temperature has an amorphous nature.
Fig. 3(B) shows XRD patterns of ZnO thin films on GaAs(100) substrates. The (002) preferred
orientation is also appeared at the fabrication temperatures above 100oC. The (002) orientation is
enhanced when Ts is increased from 100oC to 300oC. The variation of FWHM with Ts is shown in Fig.
4. Fig. 3(C) and (D) show XRD patterns of ZnO thin films on Si(100) and Si(111) substrates,
respectively. The (002) peaks in the thin films that are fabricated at high and low temperatures are
almost disappeared. In case of Si(111) substrates, the thin film fabricated at the temperature of 400oC
shows strongest diffraction peak, and simultaneously the largest FWHM is observed in this thin film.
It means that the thin film fabricated at 400oC has the smallest grain size. In case of Si(100) substrates,
the thin films fabricated at 300~500oC show intense diffraction peaks. The thin films fabricated on
Si(100) substrate exhibit lower FWHM values than those of Si(111) substrates.
XRD results indicate that the surface energy of (002) plane is lowest in the ZnO crystal. Grains of
the low surface energy will become larger as the film grows. Then the growth orientation of the thin
film is the direction of the lowest surface energy. This means that the (002) texture of the film may be
easily formed. During deposition the substrate temperature is very important. In case of the low
substrate temperature, it is difficult that atoms migrate in the film, while the high substrate
temperature causes the ad atoms to re-evaporate from the film surface.
0.30

0.28
glass
0.26 GaAs
0.24 Si(111)
Si(100)
FWHM(degree)

0.22

0.20

0.18
(a) (b)
0.16

0.14

0.12

0.10
100 200 300 400 500 600
o
Temperature( C)
Fig. 4. FWHM values of ZnO thin
(c) (d) films grown at different
Fig. 1. XRD patterns of ZnO thin films grown at different temperatures on glass, GaAs,
temperatures on glass(A), GaAs(100)(B), Si(111)(C), and Si(111) and Si(100) substrates.
Si(100)(D) substrates
Mechanical properties. Elastic modulus (A) and hardness (B) of ZnO thin films fabricated on
different substrates such as glass, GaAs(100), Si(100), Si(111) at 400oC of substrate temperature are
shown in Fig.5, respectively. Each data point shows the average values of the eight tests. Both
properties show the highest value in case of ZnO thin films fabricated on Si(100) substrate. In spite of
the same material, when the crystal axis direction of the substrate is different, the obtained values are
not same. This means that ZnO thin films fabricated on Si(100) substrates are better than ZnO thin
films fabricated on Si(111) substrate, because of Si(100) substrate have the low lattice mismatch with
ZnO. In case of Si(111) and GaAs(100), mechanical properties show similar value. In case of the glass
substrate with amorphous structure, both mechanical properties show lowest value. Therefore, these
results indicate that the crystal structure of the substrate is very important in ZnO thin films with
superior mechanical properties.
 Key Engineering Materials Vols. 353-358 2969

(A) 180 (B)

160 12
Elastic modulus (GPa)

140
10

Hardness (GPa)
120
8
100

80 Applied Load 6 A pplied Load

1g
60 1g
10g 4
40
10g
2
20

0 0
G lass GaA s(100) Si(111) Si(100) G la ss G aA s(1 00 ) S i(11 1) S i(1 00 )
Substrate Substrate
Fig. 5. Mechanical properties such as elastic modulus (A) and hardness (B) of different substrate on
applied load 1g, 10g.

Conclusions
ZnO thin films are prepared on the glass, GaAs(100), Si(100), and Si(111) substrates at different
temperatures by PLD method. XRD results indicate that the substrate temperatures of 200-500,
200-500, 300-500 and 300-500oC are good conditions for crystalline for the glass, GaAs(100),
Si(100), and Si(111) substrates, respectively. In spite of the films on the different substrates, the films
always show (002) orientation at the optimized conditions of the deposition. Mechanical properties of
the hardness and elastic modulus show the highest value in case of ZnO thin films fabricated on
Si(100) substrate. But in case of the glass substrate with amorphous structure, both mechanical
properties show the lowest values. Therefore, the crystal structure and axis orientation of the substrate
are very important for ZnO thin films with superior mechanical properties.

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[4] Jie Zhao, Lizhong Hu, Zhaoyang Wang, Yu Zhao, Xiuping Liang and Meitian Wang: Applied
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[5] E.G. Herbert, G.M. Pharr, W.C. Oliver, B.N. Lucas and J.L. Hay: Thin Solid Films Vol. 398-399
(2001), p. 331
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Progresses in Fracture and Strength of Materials and Structures
10.4028/www.scientific.net/KEM.353-358

Hardness and Elastic Modulus of ZnO Thin Films Fabricated by PLD Method
10.4028/www.scientific.net/KEM.353-358.2966