ORIGINAL PAPER

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Effects of Cu–K Co-Doping on the Morphological, Optical,

and Electrical Properties of NiO Films Deposited by Spin-
Coating Sol–Gel Method
Meng-Si Song, Chao-Qian Liu,* Nan Wang,* Ting-Ting Lun, Xiao-Na Zhai, Qing Ge,
and Xiao-Yang Zhang

reduced significantly by creating nickel

Cu–K co-doped NiO films (Ni1–2xCuxKxO and x ¼ 0–0.05) are deposited on vacancies or forming interstitial oxygen
common glass substrates by the spin-coating sol–gel method. The phase and atoms in NiO crystallites.[11] It is well
the morphological, optical, and electrical properties of NiO films as a function of known that the electrical properties can
be adjusted by doping appropriate dopants
the Cu–K co-doping concentration are explored by X-ray diffraction, scanning
into the NiO crystal lattice. Most of the
electron microscopy, and ultraviolet–visible spectrophotometer and Hall effect researches focused on single-element
measurement systems, respectively. All the films are pure phases of the cubic doping for NiO films, such as K,[12] Cu,[13]
rock-salt structure. As the doping concentration increases, the preferred orien- Na[14], and Li,[15] but there are limited
tation of the Ni1–2xCuxKxO films changes from (200) to (111). Moreover, the studies on the effect of several elements
co-doping on the electrical properties of
surface morphologies of the films are obviously affected by the Cu–K co-doping
NiO thin films. The single-element doping
concentration. The absorption coefficients of the Cu–K co-doped NiO films are usually optimized only the electrical prop-
relatively higher than that of the undoped film on the whole in the visible region erties of NiO but deteriorated its optical
except x ¼ 0.02. With the increase in doping concentration, the resistivity of the properties. Therefore, how to coordinately
films decreases on the whole. Finally, the figures of merit (FOM) of the films are improve the electrical and optical proper-
considered, and the maximum FOM of the films is achieved at x ¼ 0.02. ties of NiO films is an important issue
to be explored. Chen et al.[1] reported that
LixCu0.1Ni0.9
xO thin films with different
Li contents were prepared by the chemical
1. Introduction solution deposition method and found that Cu–Li co-doping
can coordinately enhance the optical and electrical properties
In recent years, NiO as a p-type transparent conductive oxide of NiO films.
(TCO) has attracted extensive interest because it possesses some Both K and Li belong to main-group element in the chemical
specific properties, such as excellent chemical stability, a wide element periodic table and have similar chemical properties, but
direct energy gap of 3.6–4.0 eV,[1] a wide spectral range of trans- K has lower costs than Li. Moreover, Cu–Li co-doping had a ben-
parency, and low material cost.[2] In addition, NiO thin films have eficial impact on the optical and electrical properties of NiO
a wide range of applications in various areas, including gas films.[1] Therefore, research on the optical and electrical proper-
sensors,[3,4] photocatalysis,[5,6] electrochromic display devices,[7] ties of Cu–K co-doped NiO films was carried out in the present
and solar cells.[8–10] However, it is difficult to obtain NiO films work, where the spin-coating sol–gel method was used to prepare
with both excellent conductivity and high transmittance in the the Cu–K co-doped NiO films, and the effects of the Cu–K
visible-light region, which restricts the expansion application co-doping concentration on the properties of the NiO films were
of NiO films in the field of TCO. systematically considered.
The ideal stoichiometric NiO is an insulator with high electri-
cal resistivity (about 1013 Ω cm). Generally, its resistivity can be
2. Results and Discussion
2.1. X-Ray Diffraction Patterns
M.-S. Song, Dr. C.-Q. Liu, Dr. N. Wang, T.-T. Lun, X.-N. Zhai, Q. Ge,
X.-Y. Zhang
Engineering Research Center of Optoelectronic Materials and Devices The X-ray diffraction (XRD) patterns of the Ni1–2xCuxKxO
School of Materials Science and Engineering (x ¼ 0–0.05) films are shown in Figure 1a, where the scan mode
Dalian Jiaotong University is θ
2θ scan. There was no secondary phase detected by compar-
Dalian 116028, China ing with the standard PDF card (PDF# 47–1049), and the crystal
E-mail: cqliu@djtu.edu.cn; nwang@djtu.edu.cn
structure of the films belonged to cubic rock-salt structure.
The ORCID identification number(s) for the author(s) of this article Moreover, the preferred orientations that existed in the films
can be found under https://doi.org/10.1002/pssa.201900803. can be observed. To clearly observe the variation tendency of
DOI: 10.1002/pssa.201900803 the preferred orientations, the diffraction intensity ratios between

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Figure 1. a) XRD θ
2θ scan patterns of the Ni1–2xCuxKxO films, b) the diffraction intensity ratios (I(111)/I(200)) of the (111) and (200) reflections, and
c) the fitted peak position values of the (200) reflections.

(111) and (200) (labeled as I(111)/I(200)) were calculated and are relax the residual stress in the films. Therefore, the residual ten-
shown in Figure 1b, where the diffraction intensities of the crystal sile stress of the films with x ¼ 0.04 and 0.05 was lower that of the
planes are fitted by the Pearson-VII function. When the doping other films, and then the shifts of the (200) peak position were
concentration was in the range of x ¼ 0–0.03, the diffraction inten- smaller for the films with x ¼ 0.04 and 0.05.
sity ratios of I(111)/I(200) were lower than that of the standard XRD
spectrum pattern, which indicated that (200) was the dominant ori-
2.2. Morphologies
entation of the diffraction peak. The film had a minimum diffrac-
tion intensity ratio at x ¼ 0.02, which indicated that the preferred
Figure 2 shows the morphologies of the Ni1–2xCuxKxO films
orientation of (200) was enhanced with increasing doping concen-
measured by scanning electron microscopy (SEM) and the insets
tration in the range of x ¼ 0–0.02. When the doping concentration
are the corresponding cross-section images. Although the surface
was more than x ¼ 0.03, the preferred orientation changed to
morphologies of the films with x ¼ 0–0.03 were commonplace, the
(111), and the preferred orientation of (111) was enhanced with
surface of the films with x ¼ 0.4 and 0.5 presented some circular
increasing doping concentration. Berezin et al.[16] have reported
bulges. Especially, some bulges were broken at their top for
that NiO thin films with (111) orientation could be used as buffer
x ¼ 0.05. Moreover, it can be found from the insets that the com-
layers to deposit other oriented oxide thin films such as perovskite
pactability of the films with x ¼ 0–0.03 increased with increasing
ferromagnetic films and superconducting thin films.
doping concentration. Otherwise, the connection among layers in
To further analyze the effect of Cu–K doping on the crystal
the films with x ¼ 0.4 and 0.5 became loose with increasing doping
structure of NiO films in detail, the peak position values of
concentration, and clear gaps can be observed. This case is consis-
the (200) reflections were fitted by the Pearson-VII function
tent with bulge morphologies of the films with x ¼ 0.4 and 0.5.
and are shown in Figure 1c. It can be found that all the fitting
The surface morphologies of the Ni1–2xCuxKxO (x ¼ 0.04,
values are higher than that of the standard XRD pattern. Because
0.05) films should be mainly related to the K doping concentra-
the ionic radius of Cuþ (i.e., 0.77 Å) or Cu2þ (i.e., 0.73 Å) and
tion and can be explained according to a previous study.[12] In the
Kþ (i.e., 1.38 Å) are all larger than that of Ni2þ (i.e., 0.69 Å),
process of rapid pyrolysis, for the films with a higher K doping
when Cu and K ion places Ni2þ at the lattice site of NiO or
concentration, the pyrolysis gas would be more difficult to release
enters the interstitial site of NiO lattice, the lattice constant
from the coating layer and then would induce swelling of the
of Ni1–2xCuxKxO should increase with increasing doping con-
coating layer. In the study of Cu-doped NiO films,[13,17,18] there
centration. Therefore, the diffraction peak positions of the
did not appear circular bulges or broken and cracked bulges,
Ni1–2xCuxKxO films should move to lower angles with increasing
although the Cu doping concentration reached 10 atm% or even
doping concentrations. Obviously, the above state is reversal to
higher. However, there were some maze-like bulges, and the
the actual result. Therefore, according to Poisson’s effect, the
bulges were even broken or cracked in the films with a higher
residual tensile stress should exist in the prepared films, whether
K doping concentration.[12] Therefore, the surface morphologies
doped or not. Further, it can be observed that the variation of the
of the films with x ¼ 0.04 and 0.05 should be mainly caused by
peak positions shown in Figure 1c is not monotonic. This case
the high doping concentration of K.
suggests that the residual stress state in the films was not affected
only by doping. Combining the morphologies of the films shown
in Figure 2, it can be deduced that the morphology of the films 2.3. Composition
was also one key factor affecting the residual stress state. As the
doping concentration was higher (i.e., x ¼ 0.04 and 0.05), wrin- Obviously, the letter x in the earlier text only represents the
kled and broken morphologies can be observed, which should theoretical doping concentration of Cu and K in the films.

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Figure 2. SEM images of Ni1–2xCuxKxO films: a) x ¼ 0, b) x ¼ 0.01, c) x ¼ 0.02, d) x ¼ 0.03, e) x ¼ 0.04, and f ) x ¼ 0.05. The insets are the corresponding
cross-sectional images.

There may be some differences between the theoretical doping

concentration and the actual doping concentration. Therefore,
it is significant to measure the actual doping concentration of
Cu and K in NiO-based films. In this study, the composition
of the NiO-based films was measured by an energy-dispersive
spectrometer (EDS). The results of the analyzed molar ratios
of [Cu] to [Ni] þ [Cu] þ [K] and [Cu] to [Ni] þ [Cu] þ [K] (labeled
as [Cu]/([Ni] þ [Cu] þ [K]) and [K]/([Ni] þ [Cu] þ [K]), respec-
tively) are shown in Figure 3. As the same as a previous study[12]
the EDS measurement was carried out at three different regions
for every sample to measure as accurately as possible the com-
position, and the results of every sample shown in Figure 3 are an
arithmetic average of the three measured results. Clearly, the
measured results shown in Figure 3 reveal that the actual doping
concentration of Cu and K is well consistent with the theoretical
doping concentration. Figure 3. Measured a) K and b) Cu doping concentrations in the
Ni1–2xCuxKxO films against the theoretical Cu–K doping concentration (x).
2.4. Optical Properties

Figure 4a shows the optical transmittance spectra of the those of the undoped film on the whole in the visible region
Ni1–2xCuxKxO films. It is observed that the transmission except x ¼ 0.02. In order to eliminate the effect of thickness
values of the Cu–K co-doped films were relatively lower than on the optical properties of the films, the absorption coefficient

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Figure 4. a) Transmittance spectra, b) calculated absorption coefficient based on transmittance spectra, and c) (αhυ)2 versus hυ plots of the Ni1–2xCuxKxO
films. The inset in part (c) is the fitted bandgaps of the films.
of the Ni1–2xCuxKxO films is calculated by Lambert’s
formula[12,19]
1
α ¼ ln =d
T
where T is the transmittance and d is the thickness of film. The
calculated absorption coefficients of the films are shown in
Figure 4b. It is observed that its values were in the magnitude
order of 103 cm
1 in the visual light range. Moreover, the
absorption coefficients increased on the whole with increasing
doping concentration.
In general, NiO is considered as a direct energy-gap semicon-
ductor. Hence the relation between the absorption coefficient
and photon energy is
ðαhυÞ2 ¼ Aðhυ
E g Þ
where A is a constant and hυ and Eg are the photon energy and
the direct energy gap, respectively.[12], The (αhυ)2 versus hυ plots
of the films are shown in Figure 4c and the fitted bandgaps of the
films are shown as an inset. Clearly, the bandgaps decreased with
the increase in Cu–K co-doping concentration. The change was
mainly due to the increase in Cu doping concentration and can
be understood as follows. In the study of K-doped NiO films,[12] it
was found that doping of K has little effect on the bandgaps of the
NiO films. However, the bandgaps of the NiO films decreased
with the increase in Cu doping concentration in previous
studies[13,17,18]. Therefore, it can be inferred that the variation
in Ni1–2xCuxKxO films on the bandgaps should be mainly deter-
mined by the Cu doping.
2.5. Electrical Properties
The variation in the resistivity, carrier concentration, and carrier
mobility for the Ni1–2xCuxKxO films as a function of the doping
concentration is shown in Figure 5. The undoped and Cu–K
co-doped NiO films were all p-type semiconductors. It is shown
clearly that the carrier concentration remained almost invariable
with the increase in doping concentration.
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(1)
Figure 5. Carrier concentration, carrier mobility, and resistivity of the
Ni1–2xCuxKxO films.
(2)
According to the analysis on the electrical properties of the
K-doped films in a previous study[12], the invariableness in carrier
concentration should be due to the doping saturation in the pres-
ent work, at least because the saturation doping concentration of
Kþ is very limited in NiO.
Moreover, carrier mobility increased with increasing doping
concentration on the whole. This result should be determined
mainly by the morphologies of the films. Our previous work indi-
cated that the compactability of the NiO films increased with
increasing K doping concentration.[12] According to the earlier dis-
cussion on the cross-section morphologies, the compactability of
films with x ¼ 0–0.03 also increased with increasing doping con-
centration. Furthermore, the in-plane compactability of every layer
in the films with x ¼ 0.04 and 0.05 should increase also, although
there were wrinkles and cracks among layers in the film. In fact,
the decrease in the residual tensile stress in the films with x ¼ 0.04
and 0.05 also suggested the increase in the in-plane compactability
of every layer. The increase in compactability should induce
the increase in carrier mobility. Therefore, the carrier mobility
increased on the whole with doping concentration.
The resistivity of the films decreased on the whole with the
increase in doping concentration. The minimum value of the
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Figure 6. The figure of merit of the Ni1–2xCuxKxO films with different Cu–K
doping concentrations.
resistivity was about 90.44 Ω cm at x ¼ 0.03. Actually, resistivity
is proportional to the inverse of the product of carrier mobility
and carrier concentration. As mentioned earlier, carrier concen-
tration was almost invariable on the whole. Therefore, it can be
considered that the variation of resistivity was opposite with that
of the carrier mobility on the whole, as shown in Figure 5. That
is to say, the variation of resistivity was mainly determined by
carrier mobility.
2.6. Figures of Merit of the Films
For TCO materials, it is hoped that both their conductivity and
transmission are as high as possible. To evaluate synthetically the
conductivity and transmission of the TCO film, the figure of
merit (FOM) is considered generally. The most widely used
formula of FOM was first defined by Haacke[20] and is written as
FOM ¼ T 10
r =RS (3)
where Tr is the transmittance at λ ¼ 550 nm (the wavelength
at which solar power conversion is maximized)[20] and RS is
the sheet resistance. The calculated values of FOM for the
Ni1–2xCuxKxO films are shown in Figure 6. It is noteworthy that
these FOM values were three orders larger than those of non-
doped NiO films reported by Benramache and Aouassa.[21]
Moreover, it is found from Figure 6 that the maximum FOM
value among the samples was obtained at x ¼ 0.02, which indi-
cated that the Ni0.96Cu0.02K0.02O film had a better balance
between transmission and sheet resistance. Also, the FOM of
the Ni0.96Cu0.02K0.02O film was larger than that of the Li-doped
NiO film.[22] Overall, the above analyses suggest that the Cu–K
co-doped NiO film has a certain potential application in the field
of TCO films.
3. Conclusion
Ni1–2xCuxKxO (x ¼ 0–0.05) thin films were deposited on common
glass substrates by the spin-coating sol–gel method. The phase and
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the morphological, optical, and electrical properties of the films
were explored. All the films were pure phase with cubic rock-salt
structure. As the doping concentration increased, the preferred
orientation of the films changed from (200) to (111). The residual
tensile stress exists in the prepared films, whether doped or not.
The surface morphology was seriously affected by the doping
concentration of Cu and K. The surface morphologies of the films
with x ¼ 0–0.03 were flat, but the surface of the films with x ¼ 0.4
and 0.5 presented some circular bulges. Especially, some bulges
were broken at their top for x ¼ 0.05. In addition, the transmit-
tance of the Cu–K co-doped films was relatively lower than that
of the undoped film on the whole in the visible region except
x ¼ 0.02. The minimum value of resistivity was about 90.44 Ω cm
at x ¼ 0.03. The Ni0.96Cu0.02K0.02O film exhibited the maximum
value of FOM among the samples. The present results indicate
that the Cu–K co-doped NiO films have potential applications
in the field of TCO films.
4. Experimental Section
The spin-coating sol–gel method was adopted to prepare Ni1–2xCuxKxO
(x ¼ 0–0.05 with interval of 0.01) thin films on the common glass
substrates with the area of 2.5  2.5 cm2. The concentration of metal ions
in each precursor solution was controlled at 0.75 M. Every precursor solu-
tion was prepared using nickelacetate tetrahydrate, potassium acetate, and
copper (II) chloride dehydrate as the source materials of metal ions,
2-methoxyethanol as solvent, and ethanolamine as the complexing agent
and stirred at 60  C for 2 h. All the prepared precursor solutions were aged
for 1 day at room temperature. The substrates were cleaned by hydro-
chloric acid, deionized water, and ethanol two times in sequence, and
the cleaning time of every step was 10 min at room temperature. The pre-
cursor solution was spin coated on glass substrates at 3000 rpm for 15 s.
Then, the precursor film was pyrolyzed by a homemade tube furnace at
500  C for 1.5 min. The abovementioned process was repeated ten times.
The details of the homemade tube furnace are described in our previous
work.[19] Finally, all the deposited films were annealed at 500  C for 1 h in
the tube resistance furnace in air ambience.
The crystal structure of the films was examined by XRD (PANalytical
X’pert) with Cu–Kα1 radiation (λ ¼ 1.54056 Å). The morphology was char-
acterized using an SEM (SEM, Zeiss Supra55 [VP]). The thicknesses of the
prepared films were obtained from the cross-section SEM images and
were 350 nm. The compositions were acquired using EDS in the condi-
tion of an acceleration voltage of 20 kV and the scan time is 60 s. The
optical transmittances were observed by a UV–visible spectrophotometer
(U-3900, Htachi) in the wavelength range of 300–900 nm, where a blank
common glass was used as reference. A Hall effect instrument (Hall 8800)
was used to investigate the electrical properties of the prepared films.
Acknowledgements
This work was supported by Guiding Project of the Liaoning Natural
Science Foundation, China (grant nos. 2019-ZD-0091 and 2019-ZD-0097),
Project of Department of Education of Liaoning Province, China (grant
nos. JDL2017005 and JDL2017013), Natural Science Foundation of
Liaoning Province, China (grant nos. 2015020191 and 2015020653), and
National Natural Science Foundations of China (grant nos. 51002018 and
51302024).
Conflict of Interest
The authors declare no conflict of interest.
© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Keywords
Cu–K co-doping, morphology, NiO films, optical and electrical properties,
sol–gel method
Received: September 22, 2019
Revised: November 29, 2019
Published online: January 29, 2020
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