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Thin Solid Films 516 (2008) 5590 – 5596

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Effect of crystallographic orientations on electrical properties of

sputter-deposited nickel oxide thin films
Hao-Long Chen ⁎, Yao-Sheng Yang
Department of Electronic Engineering, Kao Yuan University, No. 1821, Chung Shan Road, Lu Chu Hsiang, Kaohsiung County 82151, Taiwan, ROC
Available online 13 July 2007

Abstract

Nickel oxide thin films of various preferred orientations were deposited by radio-frequency (RF) magnetron sputtering process in different gas
ratios of oxygen atmosphere at RF power 200 W on unheated and heated for (673 K) substrates. The relationships among substrate temperature,
preferred orientation and electrical properties of the NiO films were investigated. The resulting films were analyzed by grazing-incidence X-ray
diffraction, high-resolution transmission electron microscopy (HR-TEM), and ultrahigh resolution scanning electron microscopy (HR-SEM). The
electrical properties were measured using four probe and Hall effects measurements. The results show that films deposited at room temperature with
the ratio of oxygen varying from 0 to 100% develop a (111) preferred orientation. At temperature of 673 K, while the (111)-orientated film was
obtained under a low ratio of oxygen (b50% O2), a (200) preferred orientation was developed under 100% oxygen. The lowest sheet resistance
0.01 MΩ/□, resistivity 0.83 Ω-cm and higher carrier density 7.35 × 1018 cm−3 could be obtained on (111) preferred orientation samples prepared on
unheated substrates in pure oxygen atmosphere. The relationship between preferred orientation and electrical properties was proposed in this paper.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Nickel oxide; Reactive sputtering; Preferred orientation; Electrical properties

1. Introduction studied extensively [12,15–23]. Many reference data and studies

[12,15–23] have indicated that superior electric and optical
Nickel oxide (NiO) thin films with NaCl-type structure have properties of NiO films can be obtained by reactive sputtering in a
recently drawn considerable attention because they are important pure oxygen atmosphere in the range 0.1–1 Pa and using a heated
in several scientific and technological applications. They exhibit substrate. Previous studies indicated the electrical properties of
excellent chemical stability, as well as optical, electrical and NiO films depending on Ni-defective, structure and thickness
magnetic properties. They have been employed as an antiferro- [15–18,20–23]. Also, the gas ratio of O2 and substrate
magnetic material [1], p-type transparent conducting films [2], a temperature influence crystallographic orientations and micro-
material for electrochromic display devices [3], and a part of structure of the NiO films in sputtering process have been
functional sensor layers in chemical sensors [4]. Furthermore, discussed [22]. The relationships between electrical properties
(100)- and (111)-oriented NiO films can be used as buffer layers and crystallographic orientations of NiO films were not to be
that are deposited on oxide films with other orientations, such as discussed. Therefore, this paper tried to explain about the effect of
c-axis-oriented perovskite-type ferromagnetic films and super- crystallographic orientations on electrical properties of NiO films.
conducting films [5–7]. Such films have been fabricated using
various physical and chemical vapor deposition techniques, 2. Experimental methods
including spray pyrolysis [8,9], electron beam evaporation [10],
pulsed laser deposition [11], plasma-enhanced chemical vapor Nickel oxide films were deposited on the 0.7-mm thick
deposition [1,12] and reactive sputtering [3,13,14]. Reactive Corning 1737 glass substrate by a radio-frequency (RF)
sputtering is the most widely used among these methods. The magnetron sputtering system from an NiO target of 99.99%
dependence of film properties on sputtering parameters has been purity in an oxygen (99.99%) atmosphere. The distance between
the target and the substrate was approximately 80–85 mm. The
⁎ Corresponding author. Tel.: +886 7 607 7297; fax: +886 7 607 7000. chamber was evacuated to a pressure below 3 × 10− 4 Pa before
E-mail address: [email protected] (H.-L. Chen). deposition. Sputtering deposition was performed under a gas
0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2007.07.035
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Fig. 3. Scanning electron micrographs of NiO films deposited at substrate

Fig. 1. X-ray diffraction patterns of NiO films deposited at substrate temperatures of (a) 303 K and (b) 673 K with 100% O2.
temperatures of (a) 303 K and (b) 673 K with different ratios of O2 to Ar.
A conventional profilometer (Alpha-step 200) was used to
measure the thickness of the films. The electrical properties of
pressure of 1 Pa. The power of target was kept at a constant RF nickel oxide films, including resistivity, carrier concentration,
power of 200 W. The substrates were used without intentional mobility and Hall coefficient were measured with a Hall
heating (room temperature) or heated at 673 K using quartz measurement system (“Lake Shore” model 7604 Hall effect
heating lamp. The thickness of the films was about 200 nm. measurement systems). The sheet resistance of the films was
measured with a four-point probe system (Napson, RT-7) in the air
atmosphere. Then the crystal structure of the deposited films was
identified by grazing-incidence X-ray diffraction (GIXRD) using
a Rigaku D/MAX 2500 multipurpose X-ray thin film diffrac-
tometer with monochromatic high-intensity CuKα radiation
(λ = 0.15418 nm). The microstructure was observed using
ultrahigh resolution transmission electron microscope (HR-
AEM, Hitachi model HF-2000 field-emission transmission
electron microscope) and FEG-TEM (Philips Tecnai F30 Field
Emission Gun Transmission Microscope). The surface morphol-
ogy was observed with ultrahigh resolution scanning electron
microscopy (HR-SEM, Hitachi S4100, Japan) operated at 30 kV.

3. Results and discussion

3.1. Crystallographic orientations

Fig. 2. X-ray diffraction patterns of NiO films deposited at substrate temperature The crystal structure of the as-deposited NiO film was
of 673 K with the different ratios of O2 to Ar range from 60% to 100% O2. identified to be polycrystalline. The thicknesses of the films
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under investigation were consistently around 200 nm. The X- (200) while the ratios of oxygen to argon increased from 60%
ray diffraction patterns of the films deposited at the substrate O2 to 100% O2 at substrate temperature of 673 K.
temperature from 303 K to 673 K with different ratios of oxygen Fig. 3 shows SEM micrographs of NiO films deposited at
to argon are shown in Fig. 1. The diffraction peaks were substrate temperatures of 303 K and 673 K with 100% O2.
identified and compared with those of the standard 2 theta peaks Fig. 4 shows TEM images of plane view and transmission
on a JCPDS card (Bunsenite, NaCl-type structure, 2003 JCPDS electron diffraction patterns of NiO films prepared at different
database No: 89-7130). Fig. 1 (a) shows X-ray diffraction substrate temperatures with 100% O2. Fig. 5 shows TEM
patterns of the films deposited at the substrate temperature of micrographs of the cross sections. All the films exhibit a
303 K with different ratios of oxygen to argon. The film columnar structure with the growth direction perpendicular to
deposited in pure argon atmosphere shows (111) and (200) the surface. Figs. 6 and 7 show HR-TEM lattice images and
peaks while the films deposited in different fractions of oxygen diffraction pattern of NiO films prepared at substrate temper-
show (111), (220) and (311) peaks. The peak intensity of (111) ature of 303 K and 673 K under pure oxygen atmosphere.
increases with an increasing ratio of oxygen. Fig. 1 (b) shows NiO film texture depends on both the oxygen content in the
patterns from films deposited at a substrate temperature of film and the deposition temperature [1,2,9,14,19,20]. The
673 K with different fractions of oxygen to argon. The films crystal orientation of the film is controlled by the nucleation
deposited in Ar (0% O2) and 50% O2 show dominating (111) and growth of the grains [23]. The crystallographic orientations
peak. However, as the fraction of oxygen increases to 100%, the of NiO films are affected by the arrangement of O2− under the
preferred orientation is changed from (111) to (200). Fig. 2 pure oxygen atmosphere at low substrate temperatures (303 K)
shows the preferred orientation gradually changed from (111) to and the low ratio of oxygen (b50% O2) at a deposition

Fig. 4. TEM images of plane view and transmission electron diffraction patterns of NiO films prepared at different substrate temperatures with 100% O2: (a) 303 K and
(b) 673 K.
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plane in order to minimize the surface energy as shown in

Figs. 7 and 8(c). Therefore, the preferred orientation is (200)
under pure oxygen atmosphere at a high substrate temperature
of 673 K.
Ventrice Jr. proposed that repulsive forces exerted between
oxygen ions and electrostatic energy of Ni–O pairs significantly
contributes to the formation of NiO [24]. The surfaces of any
ionic or partly ionic crystal have been identified by Tasker [25]
as types I, II, or III. In type I surfaces, the stacking plane is
neutral and composed of both anions and cations at a
stoichiometric ratio, resulting in no dipole perpendicular to
the surface. Type II surfaces contain a series of charged planes.
They make a symmetric repeat unit that has no net dipole

Fig. 5. TEM micrographs of cross-sectional view of NiO films deposited at

substrate temperatures of (a) 303 K and (b) 673 K with 100% O2.

temperature of 673 K. Ni2+ and O2− , which are produced by

sputtering process, collide separately onto the growing film
surface [1]. The radius of O2− (0.140 nm) is larger than that of
Ni2+ (0.069 nm). In order to minimize the surface energy of the
growing NiO film, O2− must be arranged in the most densely
packed plane; (111), as shown in Figs. 6 and 8(b). Therefore, the
preferred orientation is (111) under the pure oxygen atmosphere
at low substrate temperatures (303 K) and the low ratio of
oxygen (b50% O2) at a high substrate temperature of 673 K.
However, under pure oxygen atmosphere at a high deposition
temperature of 673 K, Ni2+ and O2− collide onto the growing Fig. 6. HR-TEM lattice image and diffraction pattern of NiO films prepared at
NiO film at the same time. They are then arranged in the (200) substrate temperature of 303 K under pure oxygen atmosphere.
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then be understood that (111) will be the preferred orientation

under the low sputtering temperature or the low ratio of oxygen
at high temperature.
When the NiO film is deposited under high temperature, Ni2+
and O2− collide onto the growing NiO film at the same time. It is
more likely for the film to be formed with stoichiometric ratio,

Fig. 7. HR-TEM lattice image and diffraction pattern of NiO films prepared at
substrate temperature of 673 K under pure oxygen atmosphere.

perpendicular to the surface. Type III charged surfaces have a

dipole moment in the repeat unit perpendicular to the surface.
When the NiO film is deposited under the low temperature or
the low ratio of oxygen at high temperature, Ni2+ and O2−
collide separately onto the growing film surface and not enough
energy or oxygen is provided for the Ni2+ and O2− to
recombine. It is more likely for the film to be formed with
non-stoichiometric ratio, which is electrostatically polar.
According to Fisher [26], the surface of the (111) crystal Fig. 8. Schematic illustrations of nickel and oxygen atoms arrange in the unit cell
plane of NiO is a Type III surface in Tasker's scheme [25]. It can of NiO.
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which is electrostatically neutral. According to Fisher [26], the Table 1

surface of the (200) crystal plane of NiO is a Type I surface in Hall effect data for different preferred orientation of NiO films prepared on
different substrate temperatures under pure oxygen atmosphere
Tasker's scheme [25]. It can then be understood that (200)
will be the preferred orientation under the high sputtering Substrate Preferred Resistivity Carrier Hall Hall
temperature [K] orientation [Ω-cm] density mobility coefficient
temperature. [1/cm3] [cm2/Vs] [cm3/C]
303 (111) 0.83 7.35E + 18 1.03 0.85
3.2. Electrical properties
473 (111)/(200) 0.94 1.90E + 18 3.50 3.29
673 (200) 14.70 6.01E + 16 7.07 103.8
The sheet resistance and resistivity of NiO films were
measured using four probe and Hall effect measurements,
respectively. Fig. 9 shows that the sheet resistances of the as- orientation that composes were non-stoichiometric ratio
deposited films prepared on unheated substrates with different [17,22]. Non-stoichiometric nickel oxide (Ni1−δO) is known
ratios of oxygen to argon were between 1.5 and 0.01 MΩ/□. as a p-type extrinsic semiconductor [2]. The defects that are the
While for samples grown on 673 K substrates, the sheet causes of holes conductivity are Ni+2 ion vacancy. Each
resistance was between 0.05 and 1.4 MΩ/□. The sheet vacancy is replaced by two Ni+3 ions which act as electron
resistances of the films prepared on the unheated substrate of acceptors. However, crystalline NiO film with (200) orientation
303 K that are seen to decrease from 1.5 to 0.01 MΩ/□ as the is formed near stoichiometric ratio. Pure stoichiometric nickel
ratios of oxygen to argon are increased from 0 to 100% O2. oxide is an insulator with high resistivity (ρ N 1013 Ω-cm) at
Comparatively, the sheet resistances of the films prepared on the room temperature. In this study, the (111) oriented NiO films
heated substrate of 673 K that are seen to increase from 0.05 to were developed at different deposition temperatures with
1.4 MΩ/□ as the ratios of oxygen to argon are increased from 0 different ratios of oxygen to argon. As an exception, the
to 100% O2. Hall effect data for different preferred orientation (200)-oriented NiO films were formed at the deposition
of NiO films prepared on different substrate temperatures under temperature of 673 K and under the ratio of 100% O2. These
pure oxygen atmosphere are shown in Table 1. The films results show that the values of sheet resistance and resistivity of
exhibited a (111) preferred orientation at a low substrate the (200)-orientated NiO films are higher than those (111)-
temperature (303 K). The preferred orientation gradually orientated NiO films.
changed from (111) to (200) as the substrate temperature
(473 K) increased. Finally, the films exhibited a (200) preferred 4. Conclusion
orientation when the substrate temperature reached 673 K [22].
The resistivity and carrier density of the as-deposited films The relation between the crystallographic orientations of NiO
prepared on unheated substrate under pure oxygen atmosphere films and electrical properties is discussed. Those films
was 0.83 Ω-cm and 7.35 × 1018 cm−3, and 0.94 Ω-cm and deposited at a substrate temperature of 303 K, with a ratio of
1.90 × 1018 cm−3 for the sample prepared on 473 K, and oxygen ranging from 0% to 100%, have displayed a (111)
14.70 Ω-cm and 6.01 × 1016 cm−3 for the sample prepared on preferred orientation. For films deposited at substrate temper-
673 K under pure oxygen atmosphere. ature of 673 K, the (111)-orientated NiO film was obtained under
The conduction mechanism of the NiO film is believed to a low ratio of oxygen (b50% O2), the (200) preferred orientation
relate to the vacancies existing in the structure. The electrical was developed under a ratio of 100% oxygen. The NiO films
properties of NiO films are associated with their microstructure with (111) preferred orientation that composes were non-
and composition, and consequently, on the deposition environ- stoichiometric ratio. The NiO films with (200) orientation are
ment [15–18,20–23]. The NiO films with (111) preferred formed near stoichiometric ratio. The defects that are the causes
of holes conductivity are Ni+2 ion vacancy. Consequently, the
values of sheet resistance and resistivity of the (200)-orientated
NiO films are higher than those (111)-orientated NiO films.

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