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, Xiao-Yang

Zhang
Accepted Article
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, School of Materials Science

and Engineering, Dalian Jiaotong University, Dalian 116028, China

E-mail addresses: cqliu@djtu.edu.cn and nwang@djtu.edu.cn

Keywords: Sol-gel method; NiO film; Cu-K co-doping; Morphology; Optical and electrical

properties

Abstract: Cu-K co-doped NiO films (Ni1-2xCuxKxO, x=0-0.05) were deposited on common glass

substrate by spin-coating sol-gel method. The phase and the morphological, optical and electrical

properties of the NiO films as a function of the Cu-K co-doping concentration were explored by X-

ray diffraction, scanning electron microscope, ultraviolet-visible spectrophotometer and Hall effect

measurement system, respectively. All the films were pure phase of cubic rock-salt structure. As the

doping concentration increased, the preferred orientation of the Ni1-2xCuxKxO films changed from

(200) to (111). Moreover, the surface morphologies of the films were obviously affected by the Cu-

K co-doping concentration. The absorption coefficients of the Cu-K co-doped NiO films were

relatively higher than that of the undoped film on the whole in the visible region except x=0.02.

With the increase of doping concentration, the resistivity of the films decreased on the whole.

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doi: 10.1002/pssa.201900803.

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Finally, the figures of merit (FOM) of the films were considered, and the maximum FOM of the

films was achieved at x=0.02.

1. Introduction

In recent years, NiO as a p-type transparent conductive oxide (TCO) has attracted extensive
Accepted Article
interests because it possesses some specific properties, such as excellent chemical stability, wide

direct energy gap of 3.6-4.0 eV,[1] wide spectral range of transparency, and low material cost.[2] In

addition, NiO thin films have a wide range applications in various areas, including gas sensors,[3,4]

photocatalysis,[5,6] electrochromic display devices[7] and solar cells.[8-10] However, it is difficult to

obtain NiO films with both excellent conductivity and high transmittance in the visible-light region,

which restricts the expansion application of NiO films in the field of TCO.

The ideal stoichiometric NiO is an insulator with high electrical resistivity (about 1013 cm).

Generally, its resistivity can be reduced significantly by creating nickel vacancies or forming

interstitial oxygen atoms in the NiO crystallites.[11] It is well known that the electrical properties can

be adjusted by doping appropriate dopants into NiO crystal lattice. Most of the researches focused

on the single-element doping for NiO film, such as K,[12] Cu,[13] Na[14] and Li,[15] but there are

limited studies about the effect of several elements co-doping on the electrical properties of NiO

thin films. The single-element doping usually optimized only the electrical properties of NiO, but

deteriorated its optical properties. Therefore, how to coordinately improve the electrical and optical

properties 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 content were prepared by chemical solution deposition

method, and found that Cu-Li co-doping can coordinately enhance the optical and electrical

properties of NiO films.

Both K and Li belong to main-group element in the chemical element periodic table and have the

similar chemical properties, but K has lower cost than Li. Moreover, Cu-Li co-doping had a

beneficial impact on the optical and electrical properties of NiO films.[1] Therefore, the research on

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the optical and electrical properties of Cu-K co-doped NiO films was carried out in the present

work, where the spin-coating sol-gel method was employed to prepare the Cu-K co-doped NiO

films and the effects of the Cu-K co-doping concentration on the properties of the NiO films were

systematically considered.
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2. Experimental

Spin-coating sol-gel method was adopted to prepare Ni1-2xCuxKxO (x=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 the each precursor solution was controlled at 0.75 M. The every

precursor solution was prepared by using nickelacetate tetrahydrate, potassium acetate and copper

(II) chloride dehydrate as the source materials of metal ions, 2-methoxyethanol as solvent, and

ethanolamine as complexing agent, and stirred at 60°C for 2 hours. All the prepared precursor

solutions were aged for one day at room temperature. The substrates were cleaned by hydrochloric

acid, deionized water and ethanol for two times in sequence, and the cleaning time of every step is

10 min at room temperature. The precursor 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 above mentioned process was repeated for ten times. The details of the homemade tube

furnace have been described in our previous work.[16] Finally, all the deposited films were annealed

at 500C for 1 hour in the tube resistance furnace in air ambience.

The crystal structure of the films was examined by X-ray Diffractometer (PANalytical X’pert)

with CuKα1 radiation (λ=1.54056Å). The morphology was characterized using the scanning

electron microscope (SEM; Zeiss Supra55 (VP)). The thicknesses of the prepared films were

obtained from the cross-section SEM images and approximately 350 nm. The compositions were

acquired using the energy dispersive spectrometer (EDS) in the condition of an acceleration voltage

of 20 kV and the scan time is 60 s. The optical transmittances were observed by an UV-visible

spectrophotometer (U-3900, Htachi) in the wavelength range of 300 to 900 nm, where a blank
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common glass was used as reference. Hall effect instrument (Hall 8800) was employed to

investigate the electrical properties of the prepared films.

3. Results and discussion

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3.1. X-ray diffraction patterns

The X-ray diffraction (XRD) patterns of the Ni1-2xCuxKxO (x=0-0.05) films are shown in Figure

1(a), where the scan mode was θ-2θ scan. There was no secondary phase detected by comparing

with the standard PDF card (PDF# 47-1049), and the crystal structure of the films was belong to

cubic rock-salt structure. Moreover, it can be observed that preferred orientations existed in the

films. In order to clearly observe the variation tendency of the preferred orientations, the diffraction

intensity ratios between (111) and (200) (labeled as I(111)/I(200)) were calculated and shown in Figure

1(b), where the diffraction intensities of the crystal planes were fitted by Pearson-VII function.

When the doping concentration was in the range of x=0-0.03, the diffraction intensity rations of

I(111)/I(200) was lower than that of the standard XRD spectrum pattern, which indicated that (200)

was the dominant orientation of the diffraction peak. The film had the minimum diffraction

intensity ratio at x=0.02, which indicated that the preferred orientation of (200) was enhanced with

increasing doping concentration in the range of x=0-0.02. When the doping concentration was more

than x=0.03, the preferred orientation was changed to (111), and the preferred orientation of (111)

was enhanced with increasing doping concentration. Berzin et al.[17] have reported that NiO thin

films with (111) orientation could be used as buffer layers to deposit other oriented oxide thin films

such as perovskite ferromagnetic films and superconducting thin films.

To further analyze the effect of Cu-K doping on the crystal structure of the NiO films in detail,

the peak position values of the (200) reflections were fitted by the Pearson-VII function, and are

shown in Figure 1(c). It can be found that all the fitting values are higher than that of the standard

XRD pattern. Because the ionic radius of Cu+ (i.e. 0.77Å) or Cu2+ (i.e. 0.73Å) and K+( i.e. 1.38Å)

are all larger than that of Ni2+ (i.e. 0.69 Å). When Cu and K ion places Ni2+ at the lattice site of NiO

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or enters the interstitial site of NiO lattice, the lattice constant of Ni1−2xCuxKxO should increase with

increasing doping concentration. Therefore, the diffraction peak positions of the Ni1−2xCuxKxO films

should move to lower angles with increasing doping concentration. Obviously, the above state is

reversal to the actual result. Therefore, according to Poisson's effect, the residual tensile stress

should exist in the prepared films whether doped or not. Further, it can be observed that the
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variation of the peak positions shown in Figure 1(c) is not monotonic. This case suggests the

residual stress state in the films was not affected only by the doping. Combining the morphologies

of the films shown in Figure 2, it can be deduced that the morphologies of the films was also one

key factor affecting the residual stress state. As the doping concentration was higher (i.e., x=0.04,

0.05), wrinkled and broken morphologies can be observed, which should relax the residual stress in

the films. Therefore, the residual tensile stress of the films with x=0.04, 0.05 was lower that of the

other films, and then the shifts of (200) peak position was smaller for the films with x=0.04, 0.05.

3.2. Morphologies

Figure 2 shows the morphologies of the Ni1-2xCuxKxO films measured by SEM and the insets are

the corresponding cross-section images. Although the surface morphologies of the films with x=0-

0.03 were commonplace, the surface of the films with x=0.4 and 0.5 presented some circular bulges.

Especially, some bulges were broken at their top for x=0.05. Moreover, it can be found from the

insets that the compactability of the films with x=0 to 0.03 increased with increasing doping

concentration. Otherwise, the connection among layers in the films with x=0.4 and 0.5 became

loose with increasing doping concentration, and clear gaps can be observed even. This case is

consistent with bulge morphologies of the films with x=0.4 and 0.5.

The surface morphologies of the Ni1-2xCuxKxO (x=0.04, 0.05) films should be mainly related to

the K doping concentration and can be explained according to Ref. [12]. In the process of rapid

pyrolysis, for the films with higher K doping concentration, the pyrolysis gas would be more

difficult to release out from coating layer and then would induce the more swelling of coating layer.

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In the study of Cu-doped NiO films,[13,18,19] there did not appear circular bulges or broken and

cracked bulges, although the Cu doping concentration reached 10 at.% or even higher. However,

there were some maze-like bulges and the bulges were even broken or cracked in the films with

higher K doping concentration.[12] Therefore, the surface morphologies of the films with x=0.04 and

0.05 should be mainly caused by the high doping concentration of K.

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3.3. Composition

Obviously, the letter x in the above text only represents the theoretical doping concentration of Cu

and K in the films. 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 the NiO-based films. In this study, the composition of the NiO-based

films was measured by EDS. The result of the analyzed molar ratios of [Cu] to [Ni]+[Cu]+[K] and

[Cu] to [Ni]+[Cu]+[K] (labeled as [Cu]/([Ni]+[Cu]+[K]) and [K]/([Ni]+[Cu]+[K]), respectively)

were shown in Figure 3. As the same as Ref. [12], the EDS measurement was performed at three

different regions for every sample to measure as accurately as possible the composition, 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 revealed that the actual doping concentration of Cu

and K is well consistent with the theoretical doping concentration.

3.4. Optical properties

Figure 4(a) shows the optical transmittance spectra of the Ni1-2xCuxKxO films. It can be obtained

that the transmission values of the Cu-K co-doped films were relatively lower than those of the

undoped film on the whole in the visible region except x=0.02. In order to eliminate the effect of

thickness on the optical properties of the films, the absorption coefficient of the Ni1-2xCuxKxO films

is calculated by Lambert’s formula:[12, 16]

1
  ln d (1)
T ,

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where T is the transmittance and d is the thickness of film. The calculated absorption coefficients of

the films are shown in Figure 4(b). It can be 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 the doping concentration.

In general, NiO is considered as a direct energy gap semiconductor. Hence the relation between
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the absorption coefficient and photon energy is

(2)
2
  h   A  h  E g 

where A is 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 displayed in Figure 4(c) and the fitted bandgaps of the

films are presented as an inset. Clearly, the bandgaps decreased with the increase of Cu-K co-

doping concentration. The change was mainly due to the increase of Cu doping concentration and

can be understood as follow. In the study of K-doped NiO films,[12] it was found that the doping of

K has little effect on the bandgaps of the NiO films. However, the bandgaps of the NiO films

decreased with the increase of Cu doping concentration in the Ref. [13, 18, 19]. Therefore, it can be

inferred that the variation of Ni1-2xCuxKxO films on the bandgaps should be mainly determined by

the Cu doping.

3.5. Electrical properties

The variation of the resistivity, carrier concentration, and carrier mobility for the Ni1-2xCuxKxO

films as a function of the doping concentration are depicted in Figure 5. The undoped and Cu-K co-

doped NiO films were all p-type semiconductors. It can be seen clearly that the carrier

concentration remained almost invariable with the increase of the doping concentration.

According to the analysis on the electrical properties of the K-doped films in Ref. [12], the

invariableness in the carrier concentration should be due to the doping saturation in the present

work, at least because the saturation doping concentration of K+ is very limited in NiO.

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 Moreover, the 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 indicated

the compactability of the NiO films increased with increasing K doping concentration.[12]

According to the above discussion on the cross-section morphologies, the compactability of the

films with x=0-0.03 also increased with increasing doping concentration. Furthermore, the in-plane
Accepted Article
compactability of every layer in the films with x=0.04 and 0.05 should increase also, although there

were wrinkles and cracks among layers in the film. In fact, the decrease of the residual tensile stress

in the films with x=0.04 and 0.05 also suggested the increase of the in-plane compactability of

every layer. The increase of compactability should induce the increase of 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 of the doping concentration.

The minimum value of the resistivity was about 90.44 ∙cm at x=0.03. Actually, resistivity is

proportional to the inverse of the product of carrier mobility and carrier concentration. As

mentioned above, the carrier concentration was almost invariable on the whole. Therefore, it can be

considered that the variation of the resistivity was opposite with that of the carrier mobility on the

whole as presented in Figure 5. That is to say, the variation of the resistivity was mainly determined

by the carrier mobility.

3.6. 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 TCO film, the figure of

merit (FOM) is considered generally. The most widely used formula of FOM was first defined by

Haacke[24], and is written as

10
FO M  Tr RS (3)

where Tr is the transmittance at λ = 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

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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.[25] Moreover, it was found

from Figure 6 that the maximum FOM value among the samples was obtained at x=0.02, which

indicated the Ni0.96Cu0.02K0.02O film had a better balance between the transmission and sheet

resistance. Also, the FOM of the Ni0.96Cu0.02K0.02O film was larger than that of the Li doped NiO
Accepted Article
film.[26] Overall, the above analyses suggest Cu-K co-doped NiO film has a certain potential

application in the field of TCO films.

4. Conclusion

Ni1-2xCuxKxO (x=0-0.05) thin films were deposited on common glass substrate by spin-coating

sol-gel method. The phase and 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=0-

0.03 were flat, but the surface of the films with x=0.4 and 0.5 presented some circular bulges.

Especially, some bulges were broken at their top for x=0.05. In addition, the transmittance of the

Cu-K co-doped films were relatively lower than that of the undoped film on the whole in the visible

region except x=0.02. The minimum value of the resistivity was about 90.44 ∙cm at x=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-doping NiO films have potential application in the field of TCO

films.

Conflicts of Interest

The authors declare no conflicts of interest.

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Acknowledgements

This work was supported by Guiding Project of the Liaoning Natural Science Foundation, China

(Grant Nos. 2019-ZD-0091/0097), Project of Department of Education of Liaoning Province, China

(Grant Nos. JDL2017013/05), Natural Science Foundation of Liaoning Province, China (Grant Nos.

2015020653/191), National Natural Science Foundations of China (Grant Nos. 51002018 and
Accepted Article
51302024).

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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

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Figure 2. SEM images of Ni1-2xCuxKxO films: (a) x=0, (b) x=0.01, (c) x=0.02, (d) x=0.03, (e)

x=0.04, and (f) x=0.05. The insets are the corresponding cross-section images

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 Accepted Article
Figure 3. Measured (a) K and (b) Cu doping concentrations in the Ni1-2xCuxKxO films against the

theoretical Cu-K doping concentration (x)

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 (c) is the fitted

bandgaps of the films.

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 Accepted Article
Figure 5. Carrier concentration, carrier mobility and resistivity of the Ni1-2xCuxKxO films

Figure 6. The figure of merit of the Ni1-2xCuxKxOfilms with different Cu-K doping concentrations

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 The preferred orientation of the Ni1-2xCuxKxO films changed from (200) to (111) with increasing

doping concentration. The surface of the films with x=0.4 and 0.5 presented some circular bulge

and some bulges were broken at their top for x = 0.05. It was found that the Ni0.96Cu0.02K0.02O film

had a better balance between the transmission and sheet resistance.

Accepted Article
Keywords: Sol-gel method; NiO film; Cu-K co-doping; Morphology; Optical and electrical

properties

Meng-Si Song, Chao-Qian Liu*, Nan Wang, Ting-Ting Lun, Xiao-Na Zhai, Qing Ge, Xiao-Yang

Zhang

Effects of Cu-K Co-doping on the Morphological, Optical and Electrical Properties of NiO

Films Deposited by Spin-coating Sol-gel Method

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