Surface & Coatings Technology 315 (2017) 44–60

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Surface & Coatings Technology

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

Effects of deposition power of IGZO film and graphene layer in

IGZO/graphene + Ni/SiO2/Si wafer specimens on the mechanical
and electrical properties in tribotests
Tse-Chang Li a, Ba-Son Nguyen b, Yu-Ching Chiang a, Ching-Lin Hsiao a, Jen-Fin Lin a,c,⁎
a
Department of Mechanical Engineering, National Cheng Kung University, Tainan 701, Taiwan
b
Faculty of Mechatronics – Electronics, Lac Hong University, 10 Huynh Van Nghe Road, Bienhoa, Vietnam
c
Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan

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

Article history: In the present study, indium gallium zinc oxide (IGZO) films were deposited onto graphene + Ni/SiO2/Si wafer
Received 22 September 2016 specimens with deposition powers of 60-, 80-, and 100-W, respectively. The effects of deposition power on the
Revised 6 February 2017 microstructure and vacancy defects formed in the graphene + Ni layer are evaluated based on the electrical
Accepted in revised form 8 February 2017
and mechanical properties of as-received specimens. The role and behavior of the graphene + Ni film on the elec-
Available online 11 February 2017
trical resistance of the IGZO film with microcracks were evaluated using a tribotester. The variations of the accel-
Keywords:
eration, ay, in the direction normal to specimen contact surface and the morphology of worn surface and the
Graphene layer friction coefficient in a stroke are provided us to identify their wear styles including seizure, stick-slip motion,
Tribotest and running-in instability. After applying a number of swing cycles, the turning angle of the Ni crystalline with
IGZO film respect to the graphene orientation increases with increasing the number of cycles. The mean microcrack length
Hillock increases with increasing the turning angle. However, the electrical resistance of specimen is not elevated by in-
RF magnetron sputtering creasing the microcrack length so long as the connection of the graphene layer with the IGZO film is sustained.
Increase in the deposition power promotes the growth of hillocks in the graphene + Ni layer. These hillocks
make the graphene + Ni layer convex with an uneven film thickness and lead to void defects in the
graphene + Ni layer, they also cause the IGZO film with relatively large mean surface roughness and high friction
coefficient.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Several oxide semiconductors, such as zinc oxide (ZnO), indium zinc
oxide (IZO), zinc tin oxide (ZTO), and indium gallium zinc oxide (IGZO)
have been the promising candidates as the channel layers of the thin-
film transistors (TFTs) [1–4]. Amorphous IGZO TFTs have attracted
much attention in the application of the active-matrix flat-panel dis-
plays because of the advantages of relatively large field-effect mobility
and relatively low cost and good uniformity.
The IGZO thin films were prepared by pulsed laser deposition (PLD)
method under different pressure [5] in order to achieve high perfor-
mance in electrical properties. Transparent IGZO films prepared by
PLD indicates that InGaO3(ZnO)x with x ≤ 5 may be suitable for TFT ap-
plications [6]. Carrier concentration varied strongly dependent upon the
oxygen partial pressure. Amorphous IGZO films treated with hydrogen
⁎ Corresponding author at: 1 University Road, Tainan City 701, Taiwan ROC.
E-mail address: jflin@mail.ncku.edu.tw (J.-F. Lin).
plasma with low resistance ohmic contacts are due to the formation of
high density of oxygen vacancies and O\\H bonds [7].
For the a-IGZO with a high O content and the lower density of elec-
trons, the electrical and photosensitivity characteristics of TFT degrade
[8]. The electrical properties and TFT characteristics of a-IGZO films are
related to the reduction of the oxygen-related defects in the films [9].
The effect of the thermal annealing shows the electrical properties to
be enhanced by increasing the optical band gap and oxygen vacancies
[10].
Defects, including hillocks and nanovoids, are frequently found in
bottom-gate TFTs due to stress migration arising at a high annealing
temperature [11,12]. The deposition temperature had the most signifi-
cant effect on hillock density. The number of hillocks increases rapidly
with temperature [13]. Nathan et al. [14] carried out a systematic
study on the effect of sputter deposition conditions on hillock formation.
The threshold value of annealing stress (σan) required for the growth of
hillocks was determined [15]. The stress change parameter, σf – σan (σf:
internal stress after annealing), is a positive value increasing linearly
with σan. The hillocks occur in both the amorphous and crystalline

http://dx.doi.org/10.1016/j.surfcoat.2017.02.022
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 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
materials so long as the (σf – σan) value is beyond the critical value, and
their density increases linearly with (σf – σan).
Graphene has been studied extensively due to its unique character-
istics. Very low friction coefficient and high pressure resistance make
graphene a promising material for antiwear coatings [16]. Monolayer
graphene oxide was found to have a lower effective Young's modulus
compared to that for pristine graphene [17]. Large-area and uniform
graphene films prepared by chemical vapor deposition are polycrystal-
line and thus contain grain boundaries that may weaken the material
[18]. Graphene is stiff and strong, and exhibits brittle fracture at room
temperature. Stone-Wales defects generally deteriorate sheet strength,
which is manifested by early breakage nucleating from the defect site
and catastrophic rupture quickly afterward [19,20]. When functional-
ized graphene sheets are incorporated into epoxy, the crack propaga-
tion rate is reduced significantly and the fracture toughness is
increased by 65% [21]. In molecular dynamics simulations [22], the sp-
sp2 and sp-sp2-sp3 bonding networks were observed in graphene with
vacancy defects and Stone-Wales defects, respectively. The structural
defects may deteriorate the electronic and mechanical properties of
graphene-based devices. Graphene has the unique ability to reconstruct
its lattice around intrinsic defects [23]. The study of Usachov et al. [24]
found that the strong chemical interaction of carbon with nickel gives
rise to the ability of graphene to cost geometrically nonuniform surface
in the form of a curved continuous film. Graphene can be functionalized
through judicious manipulation of defects, impurities, and adsorbates.
The intrinsic defects in graphene including vacancies, interstitials, and
line defects, and their potential role in transport, have been overviewed
[25]. Impurities and adsorbates can be served as the dopants to enhance
carrier densities, and thus controlling n- and p-type conductions for TFT
applications. The study of Ryu et al. [26] provides a basic understanding
for the behavior demonstrated in the supported graphene on SiO2/Si.
Thermal annealing can induce a structural distortion and activate the
ability of diatomic oxygen to accept charge from graphene. The relation-
ship between structural distortion and electrical hole doping on a SiO2
substrate was established. The electric properties of single-walled car-
bon nanotubes are extremely sensitive to the chemical environment
[27]. Exposures to air or oxygen influence the electrical resistance dra-
matically. The electronic parameters can be “turned” by small concen-
trations of adsorbed gases; and a semiconducting nanotube can be
converted into an apparent metal. Residual defects in graphene are
the likely nature after long annealing, they are multivacancies and
adatom pairs in a form of 7-5-5-7 hillocks [28].
The interaction of graphene with the (111) surface of Ni, Al, Cu, etc.
has been investigated [29]. The results of the local density approxima-
tion show that Co, Ni, and Pd can bind graphene strongly. In the prepa-
ration of graphene film, the technique of using solid carbon source
shows much simpler, less expensive, and less hazardous advantages.
For a Ni catalyst, carbon atoms can diffuse into the Ni film efficiently
during a high-temperature annealing process. Some of the C atoms seg-
regate from the bulk to the Ni surface to be the graphene materials [30].
The optical and electrical properties and the performance in the anti-
fatigue wear in the IGZO/SiO2/Si wafer specimens are strongly depen-
dent upon the size and quantity of the microcracks formed in the
IGZO film during the fatigue tests. In order to improve the electrical
property and anti-fatigue behavior of specimen, the growth of graphene
layers between the IGZO and SiO2 films seems able to reach. The amor-
phous carbon deposited onto the nickel layer was turned out to be ei-
ther the graphite-like or the graphene film when the annealing
temperature by the rapid thermal annealing (RTA) is sufficiently high
[31]. The RTA provides an economic and efficient method to prepare
the graphene films in a short time. It is an incentive to adopt this tech-
nique in the present study. The use of the graphite-like or graphene
film shows several advantages including: (1) effective reductions of
specimen's electrical resistance and carrier mobility even operating in
the condition of continuous increases in the size and quantity of the
microcracks in the IGZO film; (2) the interface between the IGZO and
45
graphite-like films remains dense even after experiencing a number of
fatigue cycles in the tribo tests, it can provide a substitutive channel
with a low resistance for electrical current so long as this film is
sustained without disconnection.
The IGZO film was deposited onto graphene + Ni/SiO2/Si wafer sam-
ples at three deposition powers. Cyclically swing motions in the tribo
tests were then carried out to simulate thumb-driven wear on IGZO/
graphene + Ni/SiO2/Si wafer panels. During the test, variations of
specimen's electrical resistance with time were available. Scanning elec-
tron microscopy (SEM) and acceleration (vibration) signals and friction
coefficient variations were provided to identify the wear models arising
in a stroke and evaluate the effect of deposition power on a specimen's
microstructure and defects formed at the graphene + Ni layer. Trans-
mission electron microscopy (TEM) micrographs and X-ray photoelec-
tron spectroscopy (XPS) spectra of the C 1s and O 1s core levels were
obtained from the as-received and tested specimens to investigate the
variations and behavior of electrical resistance in the tribotests of the
three kinds of specimen. The effects of the microstructures in relation
to the C\\C and C\\O bondings and mean microcrack length on electri-
cal resistance are evaluated for these specimens operating at various cy-
cles. The effect of oxygen vacancy on the sheet resistivity of Hall
measurements is also investigated. IGZO/graphene + Ni/SiO2/Si wafer
and IGZO/glass specimens were prepared with the same deposition
powers for the IGZO film in order to identify the effect of graphene on
the distinction between them in carrier mobility, sheet resistivity, and
sheet carrier concentration.
2. Experimental
2.1. Materials and preparation
In the present study, specimens were prepared using 2 cm × 2 cm Si
wafers as the substrate material. These wafers had a pre-grown 300-
nm-thick thermal silicon oxide film. They were cleaned using the stan-
dard RCA cleaning procedures, followed by a rinse in deionized water
and hot-plate drying. A thin polycrystalline Ni layer was then deposited,
followed by the co-sputtering of a Ni and carbon (Ni, C) layer for 1 min
using a direct-current co-sputtering system (ACS-4000-C3, ULVAC,
Japan). The above procedure was repeated and then another Ni layer
was deposited. The final film stack in a form of Ni/(Ni, C)/Ni/(Ni, C)/Ni
was prepared with a total thickness of 300 nm. The purities of the Ni
and C targets were both kept at 99.99%. After deposition, the samples
were loaded into a RTA chamber for vacuum annealing. The tempera-
ture was elevated to 900 °C and the dwell time was set as 30 min. The
annealing process was performed in the RTA chamber at a pressure of
2 × 10−6 Torr. The sample was then allowed to cool to room tempera-
ture, the cooling rate of the RTA chamber was well-controlled at
10 °C/s. Fig. 1(a) shows the morphology of the graphene + Ni/SiO2/Si
wafer specimen before depositing the IGZO film. The Raman mapping
technique (MRI-532 Protrus Tech, Taiwan) was applied to obtain the
Raman spectra for the detect spots in the graphene + Ni film, which
are located in the island-shaped area with stains and the area in the
light area outside of the stain areas, respectively. The three peaks iden-
tified as the D-band (=1353 cm−1), G-band (=1593 cm−1), and 2D–
band (= 2707 cm−1) are presented in the entire area of specimen
with a difference in the intensity of each band between these two
areas. Obviously, the intensities of these three peaks in the light area
were formed to be relatively higher. The peak in Fig. 1(b) for the 2D-
band shows the evidence of the graphene layers growing in the Ni
film as the top layer of the specimen before depositing the IGZO film.
IGZO thin films were then deposited on these samples using an RF
magnetron sputter system (Helix, HLLS-87, Taiwan). A single IGZO
film with a mole ratio of In:Ga:Zn = 1:1:1 was used as the target. In
this study, deposition powers of 60-, 80- and 100-W were used respec-
tively to deposit the IGZO films, with the other deposition conditions
fixed, as shown in Table 1. The deposition power was varied to
46 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60

Fig. 2. Photograph of tribotester.

is equipped with two load cells (Futek MBA400, FSH07071, USA) for
measurements of the frictional force (Fx) parallel to the horizontal com-
ponent of the sliding direction of the reciprocating swing and the nor-
mal contact force (Fy) vertical to the component. An accelerometer
(PCB Piezotronics, Inc., 352C65, USA) was installed for the measurement
of vibrations (ay) arising at the pin in swing contact with the specimen.
This pin made of silicone (3M, USA) and with a spherical tip with a di-
ameter of 5 mm, was connected at the bottom of a rod bar to produce
pendulum-like motion. The pin material is chosen because the hardness
and Young's modulus of silicone are relatively closer to those of the
human fingers. The maximum pendulum angle was measured to be
45° (symmetrical) with respect to the vertical direction. This action
was used to simulate the fatigue and wear behavior arising at the
thumb-driven display. The other end of the rod bar was fixed at a certain
height by adjusting a screw before the tribological test such that Fy =
0.5 N in the vertical direction was obtained. The hardness (H) of the sil-
icon material varied in a range of 0.005 to 0.04 GPa and its reduced mod-
ulus (Er) varied in a range of 0.002 to 0.062 GPa; both values were
obtained from nanoindentation tests, and strongly dependent on the in-
dentation depth. A reciprocating frequency of 0.833 Hz was applied for
the swing motion. The velocity of the pendulum tip moving in one
Fig. 1. (a) SEM image of the graphene + Ni/SiO2/Si wafer specimen before coating the
IGZO film; (b) the Raman mapping of the specimen. stroke is varying with the contact position and thus the pendulum
angle. It is thus hard to measure from the complex contact deformation
behavior during the swing motion. The stroke lengths for the 60-, 80-,
investigate its effect on the thickness uniformity and flatness of the and 100-W specimens are approximated as 1.77, 1.74, and 1.62 cm, re-
graphene film between the IGZO and Ni films. These two parameters af- spectively. A data acquisition system (Orion Recorder II, 8 channels,
fect the defects in graphene and the electrical properties, including elec- USA) along with NI 9234 and NI 9237 modules (National Instruments,
trical resistance, of the IGZO film. USA) was applied to acquire ay, Fx, and Fy signals. The sampling rate of
the load cells was set at 1024 point/s in continuous recording mode.
In order to investigate the evolution of tribological behavior, two ex-
2.2. Tribological tests tension cords were adhered onto the specimen's top surface (IGZO film)
at two positions symmetrical with respect to the central line of the spec-
A self-designed tribotester, shown in Fig. 2, was applied to conduct imen in order to measure the electrical resistance variations of the IGZO
the friction and wear tests of the three kinds of specimen. This tester film. A micro electrical resistor (Picotest M3500A, USA) was employed
to acquire the electrical resistance during the cyclic testing process.
The test current was fixed at 1 mA. The electrical resistance varied in a
range of 100 to 1000 Ω. The specimens used in the tests were prepared
Table 1
to be 20 mm in length and 20 mm in width. The top and lateral profiles
Details of deposition conditions.
of the IGZO films were prepared using a dual focused ion beam (FIB, FEI
Target IGZO Nova-200, USA) and the morphology of worn surface of the IGZO films
Target diameter (mm) 75
were prepared using a dual focused ion beam (FIB, Helios Nanolab G3
Source to substrate distance (cm) 5
Substrate temperature Room temperature
CX, USA).
Power (W) 60, 80, 100 The measurements of electrical resistivity, carrier concentration and
Chamber pressure (Torr) 20 × 10−3 mobility of the as-received specimens have been carried out on a Hall
Ar flow rate (sccm) 20 effect analyzer (AHM-800A, MarChannel, Taiwan) with a magnetic
Sputtering time (s) 7200
field provided by 0.2 Tesla permanent magnets.
T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60 47

3. Results and discussion

3.1. Material characterisation

SEM images of the specimens prepared with 60-, 80-, and 100-W as
the deposition power for the IGZO film are shown in Fig. 3(a)–(c), re-
spectively. They were obtained before the specimens were subjected
to the tribotest. Numerous island-shaped bulges with different sizes
formed depending on the applied deposition power. Bulges with a
small mean area were created in the 60-W specimen. The mean areas
of bulges created in the 80- and 100-W specimens were significantly
larger than that of the 60-W specimen. These bulges directly influence
the parameters, including the mean surface roughness (Ra) of the spec-
imen before the tribological test and the normal contact and frictional
forces during cyclic testing. The Ra values of the as-received 60-, 80-
and 100-W specimens are 9.85, 10.3, and 15.6 nm, respectively. The Ra
values increase with increasing deposition power for the IGZO film.
The lateral surfaces of the IGZO/graphene + Ni/SiO2/Si wafer speci-
mens prepared with deposition powers of 60-, 80-, and 100-W are
shown in Fig. 4(a)–(c), respectively. A very thin (several nanometers)
graphene + Ni film formed between the layers of IGZO and SiO2. There-
fore, for the graphene + Ni film, its thickness uniformity and structure
perfection are governed by its two adjacent layers, especially for the
Ni layer. The images show that voids/microcracks are apt to form in
the Ni layer near the SiO2 layer and that hillocks protrude out of the
top surface of the Ni film. The growth of defects (hillocks and voids) per-
haps had occurred in the preparations of the graphene + Ni film on the
surface of the SiO2/Si wafer specimen. The differences in the size and
quantity of these defects may be enlarged by the sequential deposition
of IGZO film with different deposition power. The possibility of hillock
formation is governed by the specimen stress (σdeposit.) in the deposi-
tion and the annealing process of the carbon + Ni film, and the stress
(σafter deposit.) sometime after finishing the above process. The σafter de-
posit. value can be determined using Stoney's formula if the local radii
of curvature of specimen surface before deposition and after deposition
and annealing are available. The σdeposit. value, however, is difficult to
determine because the radius of curvature formed during the deposi-
tion and the annealing process is unavailable. A formula for the determi-
nation of σdeposit. was developed in the study of Flinn et al. [32]. Several
parameters in this expression are unavailable for some coating films, the
σdeposit. value is thus unable to obtain in this study. Nevertheless, these
two kinds of defect are related to Δσ ≡ (σdeposit. − σafter deposit.) although
they grew at different threshold value [33]. According to the results in
the literature [15], both the numbers of hillocks and voids are linearly
proportional to the Δσ values produced in the film depositions. In gen-
eral, the Δσ value increases with increasing the deposition temperature
and thus the deposition power. Therefore, the density of hillocks/voids
in this study is elevated by increasing the deposition power. The mean
size of hillocks is observed to be also proportional to the deposition
power. In Fig. 4(a), voids/microcracks form, but no hillocks appear. In
Fig. 4(b) and (c), hillocks whose height increases with increasing depo-
sition power have formed. The formation of voids/microcracks is favor-
able for the release of thermally induced residual stress in the
graphene + Ni layer, and thus impedes the growth of hillocks, which
may cause the graphene to be in a convex form. This may result in a
loss of film thickness uniformity and even lead to fracture risk in the tri-
bological test. Fig. 4(d) shows the thickness variations of the IGZO film
with deposition power. The results indicate that the film thickness of
IGZO increases almost linearly with deposition power.
Nanoindentation tests were carried out to evaluate specimens' hard-
ness (H) and reduced modulus (Er). In order to avoid the hardness and
reduced modulus values in the nanoindentations to be affected by the

Fig. 3. SEM images of IGZO/graphene + Ni/SiO2/Si wafer specimens prepared with

deposition powers of (a) 60-W, (b) 80-W, and (c) 100-W for IGZO film.
48 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
Fig. 4. SEM images of lateral surfaces of IGZO/graphene + Ni/SiO2/Si wafer specimens prepared with deposition powers of (a) 60-W, (b) 80-W, and (c) 100-W. (d) Thicknesses of IGZO film
varying with deposition power.
substrate of Si wafer, the indentation load corresponding to depth b 20%
of the minimum value of the total thickness of the IGZO/graphene ±
Ni/SiO2 composite film was applied in this study. Hardness values of
7.56 ± 0.648, 8.63 ± 0.542 and 9.17 ± 1.780 GPa and reduced moduli
of 124.9 ± 5.37, 131.0 ± 10.12, and 136.8 ± 8.46 GPa were obtained
for the 60-, 80-, and 100-W specimens, respectively. Both the H and Er
values increased slightly with increasing the deposition power for the
IGZO film. Several factors including the voids in the microstructure
and thickness in the IGZO film are combined to affect the measures of
hardness and elastic modulus. Obviously, the film thickness of IGZO be-
comes the dominant factor for these two mechanical properties. The ef-
fect of microstructure will be discussed in the later section. Increasing
the IGZO film thickness can reduce the influence of all layers (including
Ni) below this film on the hardness. Therefore, specimen hardness is el-
evated by increasing the deposition power and thus the IGZO film
thickness.
Local magnifications of the Ni layer without and with hillocks in the
as-received 80-W specimen are shown in Fig. 5(a). In Fig. 5(a) for the
area without hillock, the graphene + Ni layer, with a thickness of 3–
5 nm, is flat between the IGZO and Ni films. This layer has a sturdy
and uniform thickness before the swing test. It becomes a low-resis-
tance conductive channel for the electric current. In the area with hill-
ocks, the graphene + Ni layer is protruded upward by the hillocks and
has a variable thickness. The thickness of the graphene in hillock areas
is relatively small. Fig. 5(b) shows the lateral surfaces of the 80-W spec-
imen after the tribo tests of 300 cycles. In the area originally without
hillock, the graphene + Ni layer retained the connections with the
IGZO film but varied the thickness at different places. In the area with
hillocks, the relatively thinner graphene + Ni layer still connected
with the IGZO film even after running 300 cycles. The above character-
istic reveals that the graphene + Ni layer has exhibited its strong adhe-
sion strength with the IGZO film and good material flexibility even
under the loads for a number of cycles. TEM selected area electron dif-
fraction (SAED) patterns in Fig. 5(c) were obtained for the two small
areas in the IGZO film of the as-received 60-W specimen, where the
Ni layer below this film is presented to be a form without and with a
hillock, respectively. The Bravais-Miller indices were used to label the
diffraction spots. The diffraction spots corresponding to the point with-
out hillock below it almost form a hexagonal ring. The characteristic of
this ring indicates that the IGZO layer in this region underwent a very
small geometric distortion. The diffraction spots corresponding to the
point with a hillock below it can be regressed by an ellipse such that
L1 = 4.91 nm−1 and L2 = 5.71 nm−1 and L1/L2 ≅ 0.86. L1/L2 ≠ 1 is gen-
erally obtained from the specimen with un-flat or hump up Ni films.
Nevertheless, the IGZO films in these three kinds of specimen were pre-
pared to be the mixture of amorphous and crystalline microstructures.
Energy-dispersive X-ray spectroscopy (EDS) analyses of the O, C, Ga,
In, and Zn elements were made for the scanning line passing through all
 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
layers of the as-received 80-W specimen, including the graphene + Ni
film without and with hillocks, respectively. However, only the spectra
of the C element are presented in Fig. 6(a) (without hillocks) and (b)
(with hillocks). It should be mentioned that different non-zero cps
value of the C element are more or less distributing over the entire
depth of the lateral surface. This feature can be attributable to the con-
taminations by the carbon residuals in the chamber during the surface
cutting by the FIB. The spectrum shown in Fig. 6(a) indicates that C is
mainly concentrated in the layers of IGZO and graphene + Ni. The
mean cps value of C for the graphene + Ni layer without hillocks is
much larger than that for the IGZO layer. The spectrum shown in Fig.
6(b) indicates that C is also mainly concentrated in these two layers.
However, the mean cps value for the IGZO layer is much larger than
that for the graphene + Ni layer. This behavior may be interpreted by
the provision of the XPS spectrum of C 1s for the as-received 80-W spec-
imen, as shown in Fig. 6(c). The peaks at about 284.8 and 289.0 eV are
identified as the C\\C and C\\O bonds, respectively [34]. The C\\C
bond is produced in the graphene + Ni layer irrespective of either the
plane or distortion style of this layer. The C\\O bone is formed to have
points defect in the graphene film during the deposition of the IGZO
film; then, substitutional impurities are produced at the interface of
Fig. 5. TEM images of lateral surfaces of (a) the as-received 80-W specimen; (b) the 80-W specimen at the 300th cycle in the local areas without and with hillock, respectively, (c) the TEM
SAED patterns for the areas in the IGZO film without and with a hillock below them.
49
the IGZO and graphene + Ni layers. The effects of the C\\C and C\\O
bonds on the electrical resistance variations of specimen in the cycles
of tribo test will be discussed in the later section.
EDS analyses were conducted for the Ni layer in the 80-W specimen.
Fig. 7(a) shows the EDS spectra of the Ni, C, O, and Si elements at the po-
sition marked by the black dot in the TEM micrograph of a hillock
(inset). The content of C is 5.5 at% in the graphene + Ni layer. The con-
tent of Ni in the hillock is 90.6 at%. This implies that the quantity of
graphene in the hillock is minor compared to that of Ni. Fig. 7(b)
shows the EDS spectra of the Ni, C, O, and Si elements at the position
marked by the black dot in the TEM micrograph of the Ni layer without
hillocks (inset). The Ni and C content levels are 52.4 and 41.6 at%, re-
spectively. The graphene content in the graphene + Ni layer without
hillocks is much higher than that in the same layer with hillocks.
Fig. 8 shows the XRD patterns of the 60-, 80-, and 100-W specimens
before the tribological test. InGaO3(ZnO)3 (0 1 14), InGaO3(ZnO)3 (0 0
15), InGaO3(ZnO)3 (0 2 16), and InGaZnO4 (0 0 15) are the main crystal-
line phases in the three specimens. InGaO3(ZnO)3 (0 1 14) has the
highest peak intensity (PI) of these four phases; therefore, it is dominant
in the microstructure of the IGZO layer. The InGaZnO4 (0 0 15) peak has
the second highest intensity. The peak intensities of all crystalline
50 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
Fig. 5 (continued).
phases are strongly governed by the deposition power of IGZO. Define IR
as:
PIInGaO3 ðZnO3 Þ ðð0 1 14Þþð0 0 15Þþð0 2 16ÞÞ
IR ¼
PIInGaO3 ðZnO3 Þ ðð0 1 14Þþð0 2 16Þþð0 0 15ÞÞ þ PIInGaZnO4 ð0 0 15Þ
The IR values for the three kinds of specimen are shown in Table 2.
The values follow the sequence (IR = 0.9257)100 W b (IR =
0.9496)80 W b (IR = 0.9728)60 W. The data in Table 2 show that increas-
ing IR by decreasing the deposition power decreases the mean surface
roughness (Ra), hardness (H), and reduced modulus (Er) of the
specimen.
The deconvolutions of the XPS of O 1s core-level spectra for the 60-,
80-, 100-W specimens have been obtained. The peak at a binding
energy of ~530 eV (O1) is ascribed to the O2– ions in the IGZO structure,
it represents oxygen in the oxide lattice without oxygen vacancies. The
O2 peak (≅531 eV) represents the oxygen vacancies or OH group. The O3
peak (≅531.8 eV) reflects the existence of weakly bonded oxygen spe-
cies on the film surface, and is attributable to H2O and absorbed species
integrated into the materials [35]. The peak intensity (a.u.) results of O2
have the sequence of (IO2 = 3892.6)80 W b (IO2 = 3909.3)60 W b (IO2 =
6628.2)100 W. This sequence shows the characteristic that the rise in the
oxygen vacancy is advantageous for lowering the intensity of
InGaO3(ZnO)3.
3.2. Tribological tests and behaviors
Tribotests were carried out for the three kinds of specimen for vari-
ous durations. The experimental results of the acceleration (ay) in the y-
direction, the normal contact force (Fy) in the y-direction, and the tan-
gential (friction) force (Fx) in the x-direction for the 60-W specimen
at the 100th cycle for rightward motion are shown in Fig. 9(a)–(c), re-
spectively. In Fig. 9(a), the vertical dashed line corresponding to
0.590 s marks the lowest point of the spherical indenter, where the
greatest normal contact load is created. The horizontal dashed line cor-
responding ay = 0 is used as the border of vibrations in the y-direction
in either the acceleration or deceleration region. In the front time region,
the contacts were operating with deceleration. In the rest rear time re-
gion, the contacts were operating with acceleration and great fluctua-
tions are presented nearby the right dead point. In the entire forward
motion of this cycle, there are two medium-size ay peaks, at the time
points of 0.292 and 0.900 s, respectively, and great ay fluctuations near
the right dead point. Apart from these, ay fluctuations with small ampli-
tude are present at the durations of a short time after starting from the
left dead point and near the middle way of the stroke.
Due to the differences in the deformations and contact areas formed
on the two sides of the lowest point of the spherical indenter, the Fx and
Fy profiles with fluctuations are unsymmetrical. In the acceleration re-
gion (on the left hand side of the lowest point), Fy with a positive
value at the left dead point first decreases to zero, and then increases
in the opposite direction until it reaches its maximum value. In this re-
gion, a positive Fy is created at the large oblique angle, for which the
elastic deformation of the indenter is negligibly small. As the oblique
angle toward the lowest point continuously decreased, the spherical in-
denter was compressed, undergoing elastic deformation where a signif-
icant outward expansion of the indenter lateral surface was produced.
In this time period, the compressive force in the −y direction monoton-
ically increased. As the contact entered the deceleration region, Fy (neg-
ative value) decreased due to the variations of contact area with time
related to the elastic recovery of indenter deformation. The decreasing
trend stopped at t = 0.90 s. After this time point, the elastic recovery
is so strong that the contact area with stick-slip motion is quickly en-
larged to withstand the compressive load again. This slip motion also
caused the tangential force of the indenter to be in the same direction
as that of the forward motion, as shown in Fig. 9(b).
The wear styles in the cycles can be identified by the provisions of
the data including friction coefficient, morphology in the worn area,
and threshold value needed for a specific wear type. In this study, the
threshold value predicted by the theoretical analyses is hard to deter-
mine due to the lacks of the precise values of some parameters in the
ð1Þ
model. Therefore, only the characteristic patterns of friction coefficient
and morphology in the worn surface are combined to provide for the
rough and instinctive identification of wear style in this study. The re-
sults of |Fx/Fy | are thus obtained as the friction coefficient (μ) data vary-
ing with the stroke time. Fig. 10(a) shows the μ data of the 60-W
specimen operating at the 1st, 100th, 200th, and 300th cycles, respec-
tively. With the same specimen material, the distinctions among these
three μ curves exist in the time of having the fluctuations mentioned
previously, and the magnitude in the peaks. The two peaks nearby the
two dead points in the 1st cycle are created to be the running-in
 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60 51

Fig. 6. EDX spectra of C element distributions in local areas of the as-received 80-W specimen (a) without, and (b) with hillock; (c) the XPS spectrum for the C 1s of the 60-W, 80-W, and
100-W specimens.

behavior of two contact surfaces. The fluctuations appearing in the rear
half stroke and nearby the middle time (0.6 s) are formed due to the
elastic/plastic deformations of the two contact specimens. More details
will be discussed later. In the 100th, 200th, and 300th cycles, these two
peaks at 0.292 and 0.900 s are created due to the contact conditions sat-
isfying the criterion of stick-slip motion. It is likely that thermal or me-
chanical fluctuations in this system can generate the initial pining of the
specimen surface. When the tilt angle of the swing bar (with the indent-
er) is reduced to a critical value, the motion will stop abruptly. The mo-
tion of the indenter trip stops so long as the sliding velocity reaches the
critical velocity (v0), which is determined by the condition that the
pinned solid islands can be nucleated [36,37]. In general, the velocity
v0, which is hard to measure in practice, is obtained by the situation
that the rate of increase of the elastic force on an island equals the
rate of increase of the pinning force created by growth of the island.
The wear morphologies specimen corresponding to these two points
of time are shown in Fig. 10(b) noted by (b.1) and (b.3), they are pre-
sented in the island-shaped areas with upward protrusions. The lateral
surfaces of worn specimens had been prepared by the technique of FIB.
In each specimen, there exists a layer with a more or less thickness over
the IGZO film. This layer has been identified as the silicone material
which was due to the material transfer from the swing indenter to the
IGZO film. Define q as the tangential traction and p as the normal con-
tact pressure in the sliding contact. α is defined as the angle between
the applied oblique load by the spherical indenter and the common nor-
mal (α = 0). If the inclination of the oblique force is less than the angle
of friction, which is actually unavailable in the tribo contacts of this
study, no slip will occur and, moreover, the distribution of frictional
stress at the contact surface is everywhere proportional to the normal
contact pressure, (q = p·tanα b μp). If the inclination of the force
52 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60

Fig. 7. EDX spectra for the 80-W specimen (a) with and (b) without hillock. Insets show TEM images of scanned area (black dot).

exceeds the angle of friction, a slip motion followed closely by a stick be-
gins at once and the frictional traction is everywhere equal to its limiting
value (q = μp). It is found that the friction coefficients created at these
two time points and in one-peak form are on two sides of the time point
of the lowest point (t = 0.590 s) of the spherical indenter and roughly
symmetrical with respect to this point. The significant μ rise in a plateau
form with fluctuations appearing in the duration just a short time after
0.6 s is identified to be the wear style of seizure which is characterized
by high friction coefficients lasting for a period of time due to the in-
denter stuck by the specimen. This wear style can be further ensured
by the morphology of specimen shown in Fig. 10(b) (noted by (b.2)
for t = 0.71 s) too. In general, the critical condition of seizure is that of
the transition from mild to severe wear mode. The temperature rise
due to a moving frictional heat generation causes a decrease in hardness

Table 2
Roughness, mechanical properties, and IR values for three kinds of specimen.

Specimen Ra Skewness Kurtosis Hardness, Reduced modulus, IR

code (nm) H (GPa) Er (GPa)

60-W 9.9 −0.051 4.20 7.56 124.9 0.9728

80-W 10.3 −0.075 3.40 8.63 131.0 0.9496
100-W 15.6 0.254 3.62 9.17 136.8 0.9257
Fig. 8. XRD patterns for three kinds of as-received specimen.
 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
Fig. 9. Tribotests results for 60-W specimen. (a) Acceleration (ay) in y-direction, (b)
frictional force (Fx) in x-direction, and (c) normal contact force (Fy) in y-direction at
100th cycle.
53
near the contact surface. The decrease in hardness makes increases in
the density of asperity contact points and an expansion in plastic region
at an asperity contact. At the same instant, the sharp distribution of
hardness decreases the μ value. The expansion in plastic region may re-
sult in the increases in the ratio of shear strength (k) [38]. The increase
in k intends to the transition of mode from mild wear to seizure style. As
the morphology shows, the seizure is presented to be a pattern of cavity
surrounded by the plateaus, which was created due to the pull-off ma-
terials from the specimen. The ay (vibration signal) and Fx and Fy force
fluctuations in the rear portion of this forward motion near the right
dead points are believed to be due to the thermoelastic instability [39]
in the running-in process of the two contact surfaces. Barber [40]
showed that initial small departures from perfect conformity concen-
trated the pressure and hence the frictional heating into particular re-
gions of the interface. These regions expanded above the level of the
surrounding surface and reduced the area of real contact, thereby con-
centrating the contact and elevating the local temperature still further.
If sliding continues, the expanded spots, where the pressure is concen-
trated, wear down until contact occurs elsewhere. The new contact
spots proceed to heat, expand, and carry the load; the old ones, relieved
of load, cool, contract, and separate. This cyclic process can be observed
in these fluctuations of ay, Fx and Fy. The critical value of velocity (Vc) has
been developed [41] in the Vc = 4π/cμE⁎λ, where c is the distortivity of
the stationary solid, E⁎ is the reduced modulus defined for the two con-
tact bodies, and λ indicates the wavelength of contact surface undula-
tions. λ is varying with time, it is hard to measure during the tribo
contacts. Therefore, the Vc value in every stroke of these cycles is un-
available. As the sliding velocity approaches this critical velocity, the
fluctuations in ay, Fx, and Fy increase rapidly in their magnitude, as
shown by these three parameters near the two dead points. The mor-
phology of the area with running-in instability is shown in Fig. 10(b)
noted by (b.4). Basically, the wear pattern is presented to the plastic de-
formations involving a sequence of stick-slip instabilities. The small
fluctuations in ay start from the left end point and terminate at a time
about 0.1 s. This time interval and the one nearby the right end point
are found to be almost symmetrical with respect to the middle time of
the entire stroke. This symmetry in ay in combination with a large fric-
tion coefficient peak in this region allow us to identify them to be the
behavior of running-in instability which is appearing dependent on
the movement direction. Small ay fluctuations are created in the time
interval of 0–0.1 s in the forward movement; however, they become
large ay fluctuations when the contacts operate in the backward
movement.
The mean friction coefficient (μ) is defined as the average of the μ
values over one forward stroke. Fig. 10(c) shows the μ values evaluated
for the 60-W, 80-W, and 100-W specimens, operating at the 100th,
200th, and 300th cycles, respectively. The μ results shows the monoton-
ic behavior only when they are evaluated at the same value of swing cy-
cles. They show the following sequences: (μ)100 W, 100 cycles N (μ)80 W,
100 cycles ≅ (μ )60 W, 100 cycles and (μ )100 W, 200/300 cycles N (μ )80 W, 200/
300 cycles N (μ )60 W, 200/300 cycles. Surface roughness, Ra, and specimen
hardness, H, are two influence factors in the determination of the aver-
age friction coefficient, μ. In general, a surface with a larger value of Ra
can result in a relatively higher μ. However, an increase in H makes a re-
duction of asperity's contact area operating in plastic region, thus lower-
ing the μ value. The dominance of surface roughness in the μ
determination is obviously higher than that of specimen hardness, the
combined effect of these two controlling factors on μ is thus governed
by Ra.
The tribo contacts occurred in the specimen with a small wear depth
only. This depth is actually insufficient to penetrate through the IGZO
layer. Therefore, the frictional behavior is totally governed by the con-
tact mechanisms of pin and specimen and the material in the IGZO
film. The peak intensities (PIs) of the C\\C bond for the as-received
three specimens shown in Fig. 6(c) indicate that (PIC-C =
3040.31)6 0W N (PIC-C = 2769.15)100 W ≥ (PIC-C = 2735.57)80 W. The
54 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60 55

Fig. 11. SEM images of worn surfaces of (a) 60-W, (b) 80-W, and (c) 100-W specimens at 300th cycle. (d) Penetration depths of microcracks in lateral surface of 100-W specimen obtained
at 300th cycle. (e) Mean microcrack lengths and mean friction coefficients created in the 80-W specimen at different number of cycles.

Fig. 10. (a) The relation between friction coefficient and time; (b) the morphologies of the 60-W specimen created at the four points of the forward stroke of the 100th cycle; (c) variations
of mean friction coefficient with number of cycles for three kinds of specimen.
56 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
above results reveal that the specimen with a high PI of graphene is in-
deed helpful for the reduction of μ.
3.3. Worn surface microcracks
Fig. 11(a)–(c) show the SEM morphologies of the 60-, 80-, and 100-
W specimens, respectively, after the 300th cycle. They are the images
obtained from the areas of the worn surfaces excluding from the behav-
iors of stick-slip, seizure and instability, where microcracks are still vis-
ible. Numerous microcracks on a scale of micrometers created on the
top surface of the IGZO layer; their penetration depth was in the direc-
tion across the IGZO layer. The electrical resistance of the IGZO layer
thus increased with increasing penetration depth of microcracks. Fig.
11(d) shows an example of microcracks beneath the top surface of
IGZO, which were created in the 100-W specimen after the 300th
cycle. Solidworks software was applied to determine the mean length
(ML) of these microcracks. The mean length was obtained as the aver-
age of the microcracks formed in the coating film within a measurement
area of 250 nm × 250 nm. ML values of 4.43, 3.96, and 4.14 μm were ob-
tained for the 60-, 80-, and 100-W specimens, respectively. The ML
values follow the sequence (ML)80 W b (ML)100 W b (ML)60 W. The lateral
surfaces of the specimens after tribotests were examined. No
microcrack or delamination was observed at the interface of the IGZO
and graphene + Ni layers. Fig. 11(e) shows the variations of mean
microcrack length and mean friction coefficient (μ) at the three num-
bers (100, 200, and 300) of cycles in the 80-W specimen. The results in-
dicate the μ is one of the controlling factors in determining the mean
microcrack length; even a small rise of the μ value can result in a sub-
stantial increase in the mean microcrack length of specimen.
3.4. Electrical properties and substitutional impurities
The variations of electrical resistance (ER) in the 60-, 80-, and 100-W
specimens with the number of cycles are shown in Fig. 12(a)–(c), re-
spectively. In this study, 9800, 2050, and 1080 cycles were set for the
60-, 80-, and 100-W specimens, respectively. These numbers of cycles
were determined based on the growth rate of electrical resistance ex-
hibited in these specimens. The starting value of ER in the 60-W speci-
men was 8.86 Ω. The ER value slightly increased to 8.97 Ω after
9800 cycles. The ER increased by only 0.11 Ω despite) the mean length
and number of microcracks increasing with time. This can be attributed
to the structural stability of the graphene layer during the tests. The
graphene layer provided an alternative channel for electric current
with low electrical resistance despite noticeable increases in the mean
length and number of microcracks. The ER variations for the 80-W spec-
imen are shown in Fig. 12(b). The starting ER was 4.8 Ω. The ER curve
before the 168th cycle decreased slightly, and then exhibited a sharp
drop. After this cycle, the ER curve increased monotonically until a sec-
ond sharp drop at the 1158th cycle. It then increased monotonically
until a third sharp drop at the 1924th cycle. The maximum ER arising
in this cycle is 5.69 Ω. Therefore, there is a total increase of 0.89 Ω
after 2065 cycles. The variations of ER for the 100-W specimen are sim-
ilar to those for the 80-W specimen, as shown in Fig. 12(c). 6.9 Ω is the
starting ER for this specimen. The highest ER was 7.71 Ω. Therefore, a
total increase of 0.81 Ω occurred after 1183 cycles. The increasing rate
of ER of the 60-W specimen is the lowest of the three kinds of specimen.
For the 80-W specimen, increases in the mean microcrack length sub-
stantially decreased electrical resistance. This unusual behavior can be
attributed to the graphene + Ni layer in this time period still serving
as a good conductive channel for electric current.
Fig. 13 shows the TEM morphology of the as-received 100-W speci-
men, provided as an example of obtaining the angle (α) between the
line along the graphene layer and the line parallel to the crystal pattern
of the Ni layer. Here, the former line is defined in the positive direction if
the trend from left to right is upward; conversely, the latter line is in the
positive direction if it points with a downward orientation. Therefore,
(α0 − α) represents the turning angle of the graphene film from the
original orientation of the as-received specimen after applying a num-
ber of cycles. Here α0 denotes the initial angle before the application
of tribo tests. Based on this principle, the measurements of the α
angle were made for several specimens; the results are shown in
Table 3. The “-” symbol means that the datum is not provided. The later-
al surfaces of several specimens have been prepared by the FIB in order
to observe the deformation behavior demonstrated in the interface of
the IGZO film and graphene layer after applying the tribo tests. In the re-
gion without hillock, the graphene layer retained to be a flat pattern
with a tight connection with the IGZO film after applying a number of
cycles; however, a turning angle b180° was formed between the Ni
layer and graphene film. In the region with hillocks, the graphene
layer still connect without fracture in the places with relatively thin
thickness during the cyclic motions; furthermore, good bonding is still
sustained between the two films such that the interface can provide a
channel for electrical current. The following conclusions can be made:
(1) for the as-received specimens, the α angle decreases with increasing
deposition power for the IGZO film (it rapidly decreased when the de-
position power was increased from 80 to 100 W); (2) an increase in
the number of cycles can increase the α angle.
Fig. 14 is presented to establish the relation between the turning
angle (α0 − α) of the graphene layer and the mean microcrack length,
and the electrical resistance variations created in the 80-W specimens
operating at the 100th, 200th, and 300th cycles, respectively. The results
show that the mean microcrack length increases nonlinearly propor-
tional to the turning angle of graphene; however, the increases in the
mean microcrack length do not bring in the lowering of electrical resis-
tance like we expect. This unusual behavior is that the bending
graphene layer still connected the IGZO film tightly and the connection
had provided a channel of low resistance for the electrical current even
numerous microcracks had been formed in the IGZO film.
In order to explain the sharp drops in electrical resistance demon-
strated in Fig. 12(b) for the 80-W specimen, XPS spectra were obtained
for Ga 3d, Ga 2p, In 3d, O 1s and C 1s core levels. However, only the spec-
tra for C 1d are presented in light of the effect of structural defects in
graphene on the electrical conductivity variations in the cyclic tests.
Fig. 6(c) shows the XPS spectra of the as-received 60-, 80-, and 100-W
specimens. The C\\C characteristic peak at about 284.85 eV is identified
as the graphene-related intensity, and the C\\O peak at about 288.95 eV
is created due to the structural defects produced in the graphene layer
before the formation of graphene oxide. The data of peak intensity
(PI) for the as-received specimens show the sequence of (PIC-
C)60 W N (PIC-C)100 W N (PIC-C)80 W and (PIC-O)60 W N (PIC-O)100 W N (PIC-
O)80 W. In this study, vacancies (or defects) were initially produced dur-
ing the deposition of the IGZO film onto the graphene + Ni/SiO2/Si
wafer specimen. Point (or Stone-Wales) defects may have formed due
to plasma bombarding. Such transformations are possible even if less
than the threshold energy is transferred to carbon atoms for their dis-
placement because bond rotation for Stone-Wales defects requires less
energy than that for knock-on displacement [42], which has to be trans-
ferred to a carbon atom to leave its lattice position without immediate
recombination with the vacancy. Plasma at electron energies close to
the threshold gives rise to bond rotations. Then, the O atoms in IGZO
are captured as foreign atoms. They can be incorporated into graphene
as substitutional impurities. Oxygen serves as a natural dopant in car-
bon structures since it has two fewer electrons. Owing to the different
bond lengths of carbon and oxygen atoms, the oxygen atoms are located
slightly off the graphene layer when occupying the substitutional posi-
tion [43]. Once created, substitutional dopants are expected to be very
stable due to strong covalent bonding. Replacement of a carbon atom
by an oxygen atom shifts the Fermi level of graphene into the valence
or conduction band, and also changes its electronic structure [44,45].
Bulk substitution promotes the onset of semiconducting-metal transi-
tion [27,46]. Pyridine-like defects induce a semiconducting-metal tran-
sition. Oxygen dopant is expected to be an efficient way of introducing
 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60 57

on the electronic structure with a feature of d-wave superconductors.

The covalent bonds open the possibility for tunnel junctions between
the IGZO and graphene + Ni layers. This behavior is likely the main
cause of the intermittent and abrupt drops of electrical resistance in
the tribotests. Fig. 15 shows the XPS spectra for C 1s for the 80-W spec-
imen at the 100th, 200th, and 300th cycles. The intensities of the peaks
of the C\\O bond after 100, 200, and 300 cycles are much higher than
those of the as-received 80-W specimen. The peak intensities of the
80-W specimens show the sequence that (PIC-C)80 W, 200 cycles N (PIC-
C)80 W, 100 cycles N (PIC-C)80 W, 300 cycles, and (PIC-O)80 W, 200 cycles N (PIC-
O)80 W, 100 cycles N (PIC-O)80 W, 300 cycles. The elevation of the C\\O intensity
implies that the quantity of substitutional impurities increased but not
in proportion to the number of cycles. The electrical resistance was de-
termined to be the combined effect of the continuously growing
microcracks and the density variations of oxygen impurities. Intermit-
tent drops in electrical resistance occurred only when the effect of the
impurity density on electrical conductivity surpassed that of the
microcracks. Nevertheless, the significant drop has brought in the num-
ber of cycles an effective increase before reaching the top limitation of
electrical resistance.

3.5. Effects of the peak intensities of C\\C and C\\O bondings on electrical
resistance and its rise

The data of electrical resistance (ER) and its rise (ΔER) for these
three kinds of specimen are obtained at the 300th cycle, respectively.
In the as-received specimens, the electrical resistance results show the
sequence of (ER)60 W N (ER)100 W N (ER)80 W. The electrical resistance
before tribo tests is determined strongly dependent upon the peak in-
tensities of the C\\C and C\\O bondings and the film thickness of the
IGZO film. It is found that the sequences of (PIC-C) and (PIC-O) are consis-
tent with that of (ER)as-received. The smallest film thickness becomes the
additional factor to the 60-W specimen with the highest ER value. The
electrical resistance rise data show the sequence of (ΔER)80 W,
300 cycles N (ΔER)100 W, 300 cycles N (ΔER)60 W, 300 cycles. This ΔER sequence
is exactly opposite to those of (ER)as-received and (PIC-C) and (PIC-O). That
is, an as-received specimen with a relatively high ER will have a relative-
ly small value of (ΔER)300th cycle as a result. The ER values of the 80-W

Fig. 12. Variations of electrical resistance with number of cycles for (a) 60-W, (b) 80-W,
and (c) 100-W specimens.

reactive sites into other carbon sp2 structures. Such localized substitu-
tional impurities make the impurity sites chemically and electrically ac- Fig. 13. TEM morphology of lateral surface of as-received 100-W specimen and definition
tive [47]. It has been studied [48] in relation to the effects of impurities of α angle.
58 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60
Table 3
Results of α angle.
Number of cycles 0 100 200
Specimen code
60-W 180° – –
80-W 177° 125° 70°
100-W 58° – –
specimens obtained at different cycle show the sequence of (ER)80 W,
N (ER)80 W, 300 cycles N (ER)80 W, 200 cycles. The results of mean
100 cycles
microcrack length (CL) in the IGZO film show the sequence of
(CL)80 W, 300 cycles N (CL)80 W, 200 cycles N (CL)80 W, 100 cycles. Obviously,
the sequence of ER is not exactly opposite to that of CL. The mean
microcrack length is thus not the sole factor in determination of the
ER value of the 80-W specimen operating at different cycles. The com-
bined effect of (PIC-C) and (PIC-O) intensities, and the quality of the
graphene + Ni film, and the (CL) becomes the controlling parameter
in determination of the ER value at different cycle.
The carrier mobility, sheet resistivity, and sheet carrier concentra-
tion for the three IGZO/graphene + Ni/SiO2/Si wafer specimens are
shown in Table 4. Carrier mobility increased with increasing deposition
power for the IGZO film whereas sheet carrier concentration decreased.
The 60- and 80-W specimens had small differences in each of the
electrical properties. The differences between the 80- and 100-W
specimens were larger, especially for carrier mobility and sheet carrier
concentration.
Define the peak intensity ratio (IRO2) of O2 as
IRO2 ≡ IO2 =ðIO1 þ IO2 Þ
where I denotes the peak intensity. The results of IRO2 show the
sequence (IRO2 = 0.4228)80 W ≅ (IRO2 = 0.4252)60 W b (IRO2 =
0.5821)100 W. The sequence of sheet resistivity (SR) shows that (SR =
0.1568 Ω·cm)80 W ≈ (SR = 0.1565 Ω·cm)60 W N (SR =
0.1060 Ω·cm)100 W. The above results show that the SR value for the ox-
ygen-deficient IGZO thin films is significantly lower than that of oxy-
gen-rich one due to the effective formation of oxygen vacancies. The
behavior demonstrated in these two parameters is consistent with
that shown in the study of Kamiya et al. [49].
In order to investigate the effect of the graphene + Ni film on the
magnitudes of the three electrical properties of specimen, the as-re-
ceived IGZO/graphene + Ni/SiO2/Si wafer and IGZO/glass specimens
are prepared with the same three deposition powers for the IGZO
films. The sole difference in these two kinds of specimen exists between
Fig. 14. Electrical resistance, mean microcrack length, and turning angle, (α0 – α) of the
80-W specimen operating at 100th, 200th, and 300th cycle.
300
55°
56°
–
Fig. 15. XPS spectra for C 1s core level of 80-W specimen obtained at 100th, 200th, and
300th cycles.
the materials of the SiO2/Si wafer and glass layers. The reason of using
these two kinds of substrate materials is simply because the deposition
system was out of work at the time in the preparation of the IGZO/SiO2/
Si wafer specimen without graphene, and the IGZO/glass specimens
were then available. Since these two kinds of substrate are the materials
ð2Þ with a high electrical resistance, the measurements of specimen's sheet
resistivity and carrier concentration and mobility by the Hall effect ana-
lyzer can reflect the difference in these three electrical properties be-
tween the designs of IGZO/graphene + Ni and pure IGZO sufficiently.
The carrier mobility, sheet resistivity, and sheet carrier concentration
of the IGZO/glass specimens prepared with 60-, 80-, and 100-W as the
deposition power for the IGZO layer are shown in Table 5. It should be
mentioned that the deposition conditions for the IGZO film in the
IGZO/glass specimens are as same as those for the IGZO/graphene + Ni/-
SiO2/Si wafer specimens. For the IGZO/glass specimens, carrier mobility
and sheet resistivity decreased with increasing the deposition power for
the IGZO film, whereas sheet carrier concentration increased. The sheet
resistivity of the IGZO/graphene + Ni/SiO2/Si wafer specimen was
much lower than that of the IGZO/glass specimen, irrespective of the de-
position power. However, the sheet carrier concentration of the IGZO/
graphene + Ni/SiO2/Si wafer specimen was much higher than that of
the IGZO/glass specimen. For deposition powers of 60- and 80-W, the
carrier mobilities of the IGZO/graphene + Ni/SiO2/Si wafer specimens
were much lower than those for the IGZO/glass specimens, respectively.
For a deposition power of 100-W, the carrier mobility for the IGZO/
graphene + Ni/SiO2/Si wafer specimen had a value risen to the same
order of magnitude as that for the IGZO/glass specimen.
4. Conclusions
1. The peak intensity ratio (IR) of InGaO3(ZnO3) decreased with increas-
ing deposition power for the IGZO film. The decrease in IR increased
Table 4
Three electrical properties of as-received IGZO/graphene + Ni/SiO2/Si wafer specimens
prepared with various deposition powers.
Specimen Mobility Sheet resistivity Sheet carrier
code (cm2/V·s) (Ω·cm) concentration (cm−3)
60-W 83.8 0.1565 4.765 × 1017
80-W 91.5 0.1568 4.355 × 1017
100-W 3170 0.1060 1.419 × 1016
 T.-C. Li et al. / Surface & Coatings Technology 315 (2017) 44–60 59

Table 5
Three electrical properties of as-received IGZO/glass specimens prepared with various deposition powers.

Specimen code Mobility, MB (cm2/V·s) Mean MB (cm2/V·s) Sheet resistivity, RE (Ω·cm) Mean RE (Ω·cm) Sheet carrier concentration, CC (cm−3) Mean CC (cm−3)

60-W 6.081 × 103 7.66 × 103 1.913 × 109 7.99 × 108 5.373 × 105 3.15 × 106
3.700 × 103 2.433 × 108 6.941 × 106
1.320 × 104 2.415 × 108 1.961 × 106
80-W 1.352 × 103 2.89 × 103 1.379 × 108 3.36 × 108 3.354 × 107 1.62 × 107
3.175 × 103 7.484 × 108 2.631 × 106
4.152 × 104 1.225 × 108 1.228 × 107
100-W 2.057 × 103 2.70 × 103 3.762 × 108 1.91 × 108 8.077 × 106 1.97 × 107
4.372 × 103 7.168 × 107 1.994 × 107
1.678 × 104 1.243 × 108 3.109 × 108

in the mean surface roughness (Ra), hardness (H), and reduced mod-
ulus (Er). The highest value of Ra and the highest H of the 100-W
specimen become the dominant factor of this specimen operating
at the three cycles with the highest mean friction coefficient. The
IGZO film thickness increased with increasing deposition power for
the IGZO film.
2. Increasing the deposition power promoted the growth of hillocks in
the graphene + Ni layer. These hillocks forced bulges in the as-re-
ceived specimens with a relatively large value of the mean surface
roughness (Ra); they also made the graphene layer have a convex
form with uneven film thickness. Mean surface roughness and
mean friction coefficient increase with increasing the deposition
power. Due to these defects, carrier mobility increased and sheet car-
rier concentration decreased with decreasing deposition power for
IGZO. Significant changes in the three electrical properties were ob-
served between 80- and 100-W specimens.
3. The O atoms in IGZO serve as foreign atoms that were incorporated
into graphene as substitutional impurities. The impurities intermit-
tently affect the electric structure with a feature of superconductors
during the tribotests, resulting in a sharp drop in electrical resistance.
For the 60-W specimen, no hillocks formed and electrical resistance
increased only slightly even after a large number of testing cycles.
The sharp drops in electrical resistance for the 80- and 100-W spec-
imens lowered the electrical resistance.
4. The deposition of the graphene + Ni layer maintained the good elec-
trical properties of the IGZO/graphene + Ni/SiO2/Si wafer specimens
with a large number of microcracks so long as it has a tight connec-
tion with the IGZO film. For deposition powers of 60- and 80-W,
the carrier mobilities of the IGZO/graphene + Ni/SiO2/Si wafer spec-
imens were much lower than those for the IGZO/glass specimens, re-
spectively. For a deposition power of 100-W, the carrier mobility in
the IGZO/graphene + Ni/SiO2/Si wafer specimen had the same
order of magnitude as that for the IGZO/glass specimen. Irrespective
of the deposition power, the sheet resistivity of the IGZO/
graphene + Ni/SiO2/Si wafer specimen was much lower than that
for the IGZO/glass specimen; the sheet carrier concentration of the
IGZO/graphene + Ni/SiO2/Si wafer specimen was much higher
than that for the IGZO/glass specimen.
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