OpenNano 4 (2019) 100025

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Synthesis and characterization of CuO/ZnO/CNTs thin films on

T
copper substrate and its photocatalytic applications
D. Saravanakkumara, Hicham Abou Oualidb, Younes Brahmic, , A. Ayeshamariama,d, ,
⁎ ⁎

M. Karunanaithyd, A. Mohamed Saleeme, K. Kaviyarasuf,g, S. Sivaranjanih,

M. Jayachandrani
a
Research and Development Centre, Bharathiyar University, Coimbatore, 641046, Tamilnadu, India
b
Faculty of Sciences & Technologies, Hassan II University, Casablanca, Morocco
c
Materials Science and Nanoengineering Department, Mohamed VI Polytechnic University, Lot 660 – Hay Moulay Rachid, 43150 Benguerir, Morocco
d
Department of Physics, Khadir Mohideen College, Adirampattinam – 614 701, Tamilnadu, India
e
Department of Physics, Jamal Mohamed College (Auto), Tiruchirappalli, 620 020, Tamilnadu, India
f
UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA),
Muckleneuk Ridge, P O Box 392, Pretoria, South Africa
g
Nanosciences African network (NANOAFNET), Materials Research Department (MRD), Themba LABS-National Research Foundation (NRF), 1 Old
Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province, South Africa
h
Department of Physics, SBM College of Engineering and Technology, Dindigul- 624 005, Tamilnadu, India
i
Department of Physics, Sethu Institute of Technology, Pullor, Kariapatti, India

ARTICLE INFO ABSTRACT

Keywords: In this work, Jet nebulizer technique was used to prepare thin films of CuO (1%) doped with ZnO-
Jet nebulizer carbon nanotubes (CuO/ZnO/CNTs). The morphology, surface roughness, surface pattern, and
CuO/ZnO/CNTs elemental composition of the thin films were examined by X-ray diffraction, scanning electron
Morphology microscopy, atomic force microscopy, Raman analysis, PL emission and transmission electron
Surface roughness
microscopy, respectively. The photocatalytic activity of pure CuO/ZnO/CNTs was examined
Surface pattern photocatalytic
using the rate of degradation of Rhodamine-B (RhB) under the effect of UV-B irradiation. UV–Vis
Uv-b irradiation
Rhb degradation and crystal size analysis revealed that the average crystal sizes were uniform with values of 24.89, 24.412, and
23.711 nm. The maximum absorptive energy of RhB was found to be at 551 nm.

1. Introduction

CuO is a promising material due to its photoconductive and photochemical properties., CuO exhibits p-type semiconductivity,
with narrow bandgap of 1.2 eV, and low electrical resistance values. The electrical conductivity of CuO decreases when it is exposed
to reducing-gas species. In its ground state, CuO has a 3d9 electronic configuration and is an antiferromagnetic material with a
bandgap of about 1.4 eV. The bandgap is identified as being of charge-transfer origin rather than arising from d → d transitions.
Nanoparticles (NPs), nanopowders, nanowires, and flower-like three-dimensional nanostructures have been obtained form these
copper oxides through different synthesis approaches. Some techniques include the direct heating of copper metal in ambient air,
ultrasonic spray pyrolysis, and typical chemical routes. CuO nanowires have been synthesized by Xia et al. [1] by heating pure copper
wire in air for 4 h at 500 °C. This method is the simplest one to synthesize copper oxide nanowires. Zhang et al. [2] reported the

⁎
Corresponding authors.
E-mail address: aismma786@gmail.com (Y. Brahmi).

https://doi.org/10.1016/j.onano.2018.11.001
Received 15 September 2018; Received in revised form 4 November 2018; Accepted 4 November 2018
Available online 07 November 2018
2352-9520/ © 2018 Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

synthesis of CuO with 3D flower-like nanostructures through a template-free-solution route on copper surface. Nanocrystalline CuO
powders have also been prepared by ultrasonic spray-pyrolysis technique [3]. These oxide particles have been obtained at various
calcination temperatures and have different crystallite sizes and morphologies [4].
ZnO is a candidate photoelectrical nanomaterial for the photocatalysis and degradation of various organic pollutants due to its
high sensitivity, high stability, wide bandgap, and environmental friendliness. Nanomaterials with unique features such as quantum
effect and optical behavior render them suitable for biomedical applications. Several methods have already been reported for the
determination of pharmaceutical formulations and clinical samples, including high-performance liquid chromatography and spec-
trophotometry. Compared with other methods, electrochemical sensors are attracting attention for biological environmental de-
termination due to their accuracy, lowcost, high dynamic range, and simplicity of use [5].
Carbon nanotubes (CNTs) and graphene oxide (GO) show wide-ranging potential applications that capitalize on their unique
properties [55–57]. MWCNTs and GO are broadly used as heterogeneous catalyst supports because they possess a large surface area,
good mechanical strength, and stability under harsh conditions. CNTs and GO comprise layers of carbon atoms arranged in six-
membered rings. They have structures that are distinct from one another and have an amorphous structure consisting of aromatic
sheets and strips with slits of various molecular dimensions that form porosity. CNTs are composed of curved sp2-hybridized carbon
atoms arranged in an axial alignment of concentric cylindrical planes, whereas GO is a flat monolayer of carbon atoms tightly packed
into a two-dimensional honeycomb [6]. The oxygen functional groups present on the supports have been found to play a key role in
determining their applications [7]. Many researchers have reported ionic/liquid/CNT paste electrodes as a novel electrochemical
sensor for the rapid and sensitive voltammetric determination of morphine. Novel CuO doped with ZnO/CNTs as a novel nanosensor
and 1-methyl-3-butylimidazolium bromide as a suitable binder in carbon paste matrix have also been reported for the voltammetric
determination of morphine [8]. Some properties of Rhodamine-B (RhB), especially their absorption spectra, solubility, and dichroic
ratios, are important for the realization of high-performance analysis. Accordingly, dyes with different chemical structures, parti-
cularly those with RhB, have been studied as a compound inside it. RhB dyes are also attractive because of their high chemical, photo,
and electrochemical stabilities, and they are usually characterized by high solubility and order parameters. Usually, CuO doped with
ZnOeCNTs is separately doped with two differently structured dyes. Their solubility, order parameters, textures, and phase-transition
temperatures have been determined and discussed by comparing them with one another [9].
One of the most promising applications of NPs such as CuO doped with ZnOeCNTs is for the establishment of biosensors for in
vivo usage because these carbon-derived materials has almost no toxicity [10]. CNTs are also gaining considerable attention because
of their unique fundamental physical structures, mechanical, and electronic properties that enable potential high-technology ap-
plications [11,12]. ZnO is one of the most important functional metal oxides given its versatile practical applications, such as in the
manufacture of photodetectors [13] transparent electrodes [14] spintronic devices [15], surface acoustic wave devices [16], and thin-
film gas sensors [17,47–54] . This versatility can be attributed to ZnO's outstanding properties, including a wide direct optical
bandgap and large exciton binding energy, as well as excellent chemical and thermal stability and piezoelectric properties [18]. In
recent years, nanostructured materials such as ZnOeCuO: CNT composites have also been incorporated into electrochemical sensors
for biological and pharmaceutical analyses [19]. They have many properties similar to other types of materials, but they offer unique
advantages such as enhanced electron transfer, large edge plane/basal plane ratios, and rapid kinetics of the electrode processes [20].
Nanocomposites of various shapes, sizes, and compositions are also changing modern bioanalytical measurement systems [21].
Copper plate is one of the most exploited organometallic plates in the development of carbon molecules owing to its stable redox
chemistry. The attractive characteristics of copperplate, i.e., low oxidation potential, and its derivatives are well known and com-
monly used as mediators. Thus, ZnOeCNT composite powders have been synthesized by deposition on copper plates during the
growth of ZnO NPs through a spray-pyrolysis method. As afore mentioned, CNTs and GO show wide-ranging potential applications
seeking to capitalize on their unique and fascinated properties [22].
Chen et al. [27] reported the very first vibration analysis of novel composite nanotubes (NTs) synthesized by coating CNTs with
piezoelectric ZnO. The composite NTs are found to have promising use for gigahertz/terahertz electromechanical nanoresonators
whose frequency can be even higher than those using core CNTs [23]. Chris santhopoulos et al. [24] reported ZnO/CNT hetero-
structures can be formed by thermal evaporation. The formation of the nanorods, whose self-assembling results in various structures
such as polypods and nanohedgehogs, depends on various factors and on the location of the ZnOeCNT junction. Semiempirical
molecular-orbital calculations provide evidence for the nature of binding between ZnO and CNTs [24]. Yu et al. [25] reported that
CNTs with different orientations and lengths have been grafted onto carbon fibers by catalytic chemical vapor deposition to produce
hybrids that are used to reinforce carbon/carbon (C/C) composites. Compressive property tests indicate that the C/C composites have
obvious improvements in out-of-plane compressive strength compared with pure C/C composites. Furthermore, the improvement is
strongly influenced by the orientation and length of CNTs. Compared with entangled CNTs and radially grown straight CNTs with
smaller length, CNTs with a radial grafting morphology and greater length can reinforce the F/M interface and the entire matrix more
efficiently and increase the compressive strength [25].
Carbon nanotubes (CNTs) have interesting and important properties, such as high length-to-diameter ratio, unique conductivity,
and high strength and flexibility [26]. CNT-supported catalysts have been used as electrodes in lithium-ion batteries [27]and as
materials for hydrogen storage [28,29]. Liu et al. [30] used Ni/CNTs as catalysts to synthesize CNTs with high quality and purity.
They have shown that CNTs can be a good catalyst support, so investigations on effectively impregnating metal/metal oxide onto the
surface of CNTs are important. Ang et al. [31] showed that metals can be coated onto CNTs in a single step of activation, yielding a
layer of copper or nickel on the surface of NTs. The extent of metal decoration depends on the age of the sensitizing solution via a
two-step sensitization-activation approach. Wu et al. [32] also used this method to prepare CuO on CNTs. They found that CuO on
NTs can reversibly store 268 mA h Li/g. Most CNT catalysts have been prepared by this method, in which metals are coated as a layer

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

on the NT surface. Here, the amount of metal supported cannot be easily controlled. Additionally, the pretreatment of CNT cannot be
ignored in preparing catalysts because pretreatment forms the functional groups on the CNT surface [33]. Hence, more effective
methods for accurately loading desired metals onto CNTs are required. Hydrogen is a very important component of fuel cells and is
their raw material. Methods of producing hydrogen from methanol include partial oxidation, decomposition, and steam reforming.
Among them, partial oxidation and steam reforming are the most conducive for hydrogen production. Wang et al. [34] and Alejo
et al. [35] utilized Cu-based catalysts containing a binary or ternary metal to catalyze the partial oxidation of methanol.
Herein, we demonstrate a facile way to fabricate CuO/ZnO/CNTs

2. Method of preparing CuO/ZnO/CNTs on copper substrate

Zinc nitrate dihydrate (Zn(NO3)2•2H2O (4.734 g), glycine (NH2–CH2–COOH), single-walled CNTs (SWCNTs; 0.5 mg), and cupric
chloride dihydrate (CuCl2•2H2O) (0.17 g), all analytically grade and not subjected to further purification, were used to prepare the
mother solution of the nanocomposite. Glycine consisted of CH2, CH, OH, C = O, C–C, COH, C–N, and NH2. A solution containing Zn
(NO3)2, glycine, and dimethanalamine was dissolved in 25 ml of deionized water for 2 h under magnetic stirring with a hot plate at
30 °C. Then, cupric chloride was dissolved separately with H2O2, and this solution was mixed into a beaker containing Zn(NO3)2 and
SWCNTs. The combined solution was stirred again vigorously for 2 h at 60 °C, and the mixture was cooled to ambient temperature.
Afterwards, the mixture solution was poured into 50 ml wells cleaned with a jet nebulizer bottle by spraying. A copper plate with
dimensions of 10 × 8 × 0.5 cm3 at 100 °C was mounted onto a hot-plate oven for 4 h. After spraying, the hot copper plate with
sample was cooled at room temperature. The sample, as solid powder, was collected from the plate using a stainless knife and was
placed in crucibles, which were then subjected to calcinations at 300 and 600 °C in a muffle furnace for 1 h.

2.1. Characterization techniques

The crystalline phases of the materials were investigated by powder X-ray diffraction (XRD; PAN analytical X-ray diffractometer)
with CuKα radiation at λ = 1.5406 nm. A transmission electron microscopy (TEM) system (JEOL, JEM-2010-F) was used to char-
acterize the CuO/ZnO/CNTs. A Raman spectrometer (Raman, Dongwoo, Optron, Co.) and an electron spectroscopy system for
chemical analysis (ESCA, VG Scientific Microlab 310F) were used to investigate the surface chemical composition and characteristics
of the samples.The filtrate was analyzed with a UV–Vis spectrometer (UC-2450-Shimadzu).

3. Results and discussion

3.1 XRD. analysis of CuO/ZnO/CNTs

The as-prepared CuO/ZnO/CNTs thin films were annealed at three different temperatures [room temperature (RT), 300 °C, and
600 °C] to study the changes in crystal orientation and dislocation of the nanocrystals. The powder XRD patterns of the film samples
annealed at the three specified temperatures are also shown in Fig. 1. Notable changes were observed in the crystal parameters at 300
and 600 °C denoting phase transitions, whereas the intensity of peaks varied considerably at 600 °C, denoting a significant increase in

Fig. 1. X-ray diffraction data taken from as-prepared CuO doped ZnOeCNT thin films at room temperature (RT) and two thermal treatments at 300
and 600 °C illustrating phase transformations.

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Table 1
Structural analysis of CuO doped ZnOeCNT thin films at RT, 300 °C and 600 °C.
Temperature Compound Observed 2θ (deg) hkl FWHM (deg) FWHM (rad) Grain Size Micro δ x 1014 lines/ Thickness (µm)
10−3 (nm) strain m2

RT ZnO 36.241 1 0 1 0.3549 6.191 23.565 0.084 18.008 0.52

CuO 38.181 2 0 0 0.2564 4.472 32.791 0.060 9.3002
CNT 26.305 0 0 2 0.4457 7.774 18.321 0.108 29.792
300 °C ZnO 36.246 1 0 1 0.3645 6.358 22.944 0.086 18.996 0.61
CuO 38.015 2 0 0 0.2754 4.804 30.528 0.065 10.734
CNT 26.139 0 0 2 0.4127 7.199 19.765 0.100 25.598
600 °C ZnO 36.243 1 0 1 0.3695 6.445 22.634 0.087 19.521 0.69
CuO 38.901 2 0 0 0.3025 5.276 27.853 0.071 12.892
CNT 26.305 0 0 2 0.3955 6.899 20.646 0.096 23.462

crystallinity. The XRD patterns at all temperatures were comparable for the three film samples with all peaks assigned to ZnO (JCPDS
File # 36–1451), CuO (JCPDS File # 80–0076), and CNT (JCPDS File # 26–1076), respectively, as shown in Fig. 1. The film annealed
at 600 °C was highly crystalline, with an average crystallite size of 24 nm for the three samples.
Table 1 summarizes the crystal parameters obtained by analyzing the XRD patterns. Crystallite size (D;in nanometer) was cal-
culated with the Debye–Scherrer formula:

0.9
. cos
0.9
D= cos
, K K
where D is the crystallite size, λ is the wavelength of the X-ray using Cu Kα radiation (0.154 nm), β is the full
. cos . cos
width at half-maximum (FWHM) of the peaks, and θ is the Bragg angle obtained from 2θ. The dislocation densityδdenotes the amount
of defects and vacancies in the crystal and can be determined using the crystallite size (D) with the formula:

1
=
D2

Meanwhile, the strain (ε) of the nanocomposite was determined by:

cos
=
4

The FWHM of the sample CuO/ZnO/CNTs at 600 °C was higher than that at RT.
Comparing all diffraction peaks in the patterns, variations in their intensity were observed due to the polycrystalline phase
assorted together. The 2θ position and the corresponding h, k, and l values of CuO/ZnO/CNTs were determined to be 31.85° (1 0 0),
34.52° (0 0 2), 36.24° (1 0 1), 47.568° (1 0 2), 56.613° (1 1 0), 62.894° (1 0 3), 67.902° (1 1 2), and 69.125° (2 0 1). The peaks at
2θ = 38.181° (200), 48.891° ( 2 0 2 ),53.389° (0 2 0), and 65.925 (0 2 2) were related to the copper oxide phase. The XRD patterns of
1

the CuO/ZnO/CNTs samples showedan additional one-dimensional diffraction peak at 2θ = 26.305°, which matched the (0 0 2)
hexagonal structure of CNTs. The structural parameters are shown in Table 1.

3.2. FTIR analysis of CuO/ZnO/CNTs

The functional vibrationpropertiesof the as-prepared materials were further characterized. FT-IR spectra were obtained within
400–4000 cm−1 under conventional conditions. Fig. 2 showsthe FT-IR spectra of CuO/ZnO/CNTs at RT, 300 °C, and 600 °C. All
samples exhibited the same vibrational bands, and the peak observed at 3579 cm−1was due to the O–H stretching mode. The peak at
2358 cm−1was probably due to CO2 physiosorbed on the surface of the materials [39], and the bands at 1386 cm−1 were assigned to
the C–O stretching vibration [40]. The absorption band at 523 cm−1exhibited Cu–O bondbending [41].The absorption band at 443
cm−1was attributed to the Zn–O stretching mode vibration of CuO/ZnO/CNTs at RT (low intensity), 300 °C(medium intensity), and
600 °C(strong intensity) [42-44]. This phenomenon was due to the crystallinity of ZnO in the sample as confirmed by the XRD
analysis of all samples.

3.3. Photoluminescence (PL) spectroscopy

We further carried out PL emission analysis of CuO/ZnO/CNTs at RT, 300and 600 °C samples. As shown in Fig. 3, three essential
bands were observed. The band at 539 nm (blue emission) was due to this band, and the emission band was at 544 nm (red emission).
In addition, an emission band at 610 nm,a broad band in this region, was not observed in the case of CuO/ZnO/CNTs at RT. Hence,
we observed an increase in intensity by increasing the annealing temperature from 500 to 3400 u.a for CuO/ZnO/CNTs at 300and
600 °C, respectively. Table 2 shows the structural data, angles of diffraction 2θ, FWHM, microstrain, and dislocation density of CuO/
ZnO/CNTs calculated from the XRD data and thickness of films.

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

RT
140
300 °C
600 °C
130

Transmittance (a.u)
120

110

100

90

80
537 1286 2358 3579
70
500 1000 1500 2000 2500 3000 3500 4000

Wavenumber cm-1
Fig. 2. FTIR Analysis of CuO doped with ZnOeCNT at RT, 300 °C and 600 °C.

Fig. 3. PL Analysis of CuO doped with ZnOeCNT at (i) RT, (ii) 300 °C and (iii) 600 °C.

3.4. Raman analysis of CuO/ZnO/CNTs

To confirm the composite formation, Raman analysis of CuO/ZnO/CNTs at RT, 300 °C, and 600 °C samples was carried out. For
simplistic comparison, all spectra are presented in Fig. 4.We clearly observed that all spectra were similar and exhibited several bands
in the range of 300–800 cm−1. The strong peak at 438 cm−1 was attributed to E2 mode of ZnO [45]. The peak at 583 cm−1 was
attributed to E1 mode. The peaks at 377 and 331 cm−1 were attributed to A1 modes [46]. The coexistence of CuO and ZnO was not
confirmed by RAMAN analysis due to the low loading of CuO.

3.5. Electrical studies of the CuO/ZnO/CNTs

The parameters ε andε0are the relative dielectric permittivity and permittivity of free space, respectively; μ0is the zero-field
mobility; L is the thickness of the active layer; γ is the field-activation factor; and V = (Vap − Vbi)is the voltage drop across the active
layer of the sample. According to the Fig. 5, the measured space-charge limited currents very well agreed with the equation pre-
diction [26]. Generally, mobility decreased with increased concentration of CuO/ZnO/CNTs in the photoactive medium, with the
exception of 8% loading. This finding was partly due to the formation defect clusters associated with the high concentration of CNTs
in the medium. The negative sign of the field-activation factor indicated that the mobility in the medium decreased with increased
electric field because the strong electric field in the medium imposed a unidirectional flow of charges, thereby preventing the flow
along the percolation pathways and reducing the mobility. Resistivity with respect to temperature is shown in Fig. 6, and mobility
and carrier concentration at 600 °C are plotted in Fig. 6.

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 D. Saravanakkumar, et al.

Table 2
Photocatalytic analysis of CuO doped ZnOeCNT thin films at RT, 300 °C and 600 °C.
Name of the dye moleculesRhodamine B Final conc. dye Final conc. of NaBH4 Volume of ZnOeCNT doped Time for full First order rate constant Correlation Standard deviation
(RhB) (M) (M) with CuO nanowires (mL) reduction(min) (k) (min−1) coefficient (R) (SD)

6
RT 8.0 × 10−6 1.75 × 10−2 0.25 130 2.02 × 10−2 0.94 0.370
300 °C 8.2 × 10−6 1.75 × 10−2 0.25 81 3.83 × 10−2 0.95 0.358
600 °C 8.6 × 10−6 1.95 × 10−2 0.25 69 4.15 × 10−2 0.95 0.418
OpenNano 4 (2019) 100025
D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Table 3
Electrical parameters of the samples of CuO doped with ZnOeCNT (RT), 300 °C and 600 °C.
Temperature Resistivity (Ohm Cm) Mobility Cm2/Vs Carrier Concentrations Cm−3

CuO doped with ZnOeCNT (RT) 7.1 × 10−4 7 1.2 × 1021

CuO doped with ZnOeCNT (300 °C) 6.89 × 10−4 7.9 1.01 × 1021
CuO doped with ZnOeCNT (600 °C) 5.69 × 10−4 8.3 0.963 × 1021

80000
438 (ZnO) RT
70000 300 °C
600 °C
60000
Intensity (A.U)

50000

40000 (ZnO)(ZnO) (ZnO)

331 377 583
30000

20000

10000

300 350 400 450 500 550 600 650 700

-1
Raman shift (cm )
Fig. 4. Raman Analysis of CuO doped ZnOeCNT (i) RT (ii) 300 °C and (iii) 600 °C.

Fig. 5. Resistivity vs. temperaturefor 600 °C.

3.6. Scanning electron microscopy and EDAX analysis

Fig. 7(a)–7(c) show that the CuO/ZnO/CNTs nanocomposite are agglomerated, with the grains poorly observable in the analysis
scale [27]. From the FESEM images, we inferred that the NPs were regularly shaped, and the crystallite structure was uniformly

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Fig. 6. Mobility and carrier concentrationvs.Temperature for 600 °C.

Fig. 7. (a-c) FESEM Analysis of ZnO doped with CuO and CNT at RT, 300 °C and 600 °C.

arranged on the surface. The compositions of the present compound were clearly displayed, and the signals corresponding to Zn, C,
and O appeared with minimum intensity. By contrast, no impurities were identified with the maximum intensity. These results
indicated that complete nano crystals formed with sufficient doping concentration, and that Zn distribution was observed in and the C
was about 10%.

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Fig. 8. (a-c) Scanning waveform of the Analysis of ZnO doped with CuO and CNT at RT, 300 °C and 600 °C.

At the highest annealing temperature of 300 °C, heat radiation arranging the uneven shaped smoothened CuO/ZnO/CNTs was
applied for both samples. We found that a substantial amount of CuO/ZnO/CNTs at RT and annealed at 300 °C had different
morphologies and lengths that were slightly small. Although the number discs combined to form a cylinder or rod like that number of
CuO/ZnO/CNTs combined to form the small NPs. Moreover, CuO/ZnO/CNTs combined to formed hollow semicylindrical NT mor-
phology whose length and cross-sectional area were larger than those of the small rods, as shown in Fig. 7(a).
There is possible to make the completely closed CuO/ZnO/CNTs from it by applying further heat at the highest annealing
temperature of 300 °C or by maintaining the pH of the precursor solutions values, as observed in Fig. 7b and 7c. In addition, with the
many number of CNT combined to form the rod containing rough surface with active crusts of pH 8. In other places, stacked
nameplates were observed at pH 7, so systematic agglomeration occurred in this manner. Sharp, elongated grains of CuO/ZnO/CNTs
were observed. These needle-like CNTs had diameters of approximately 40 and 50 nm, and this kind of reduction in grain size was
due to the applied heat energy that produced compressibility of crystalline grains. This result well agreed with the result of elemental
analysis.
Fig. 8(a)–8(c) show the waveform analysis of CuO/ZnO/CNTs at RT, 300 °C, and 600 °C from which the roughness of the sample
surfaces can be inferred. As shown in Fig. 9, the EDX spectrum of CuO/ZnO/CNTs confirmed the existence of expected elements such

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Fig. 9. EDAX Analysis of CuO doped with ZnOeCNT.

as Zn, O, Cu, and CNTs in the composite. Given that a small amount of doped CuO was added with starting solution for heat-energy
transformation to the composite to obtain the expected morphology. These assistant metal elements are highly stable in nature at
high temperature and we thus expected their low amount in the precursor solution. Given that these assistant metal elements were
the higher element, the presence of their low amount of them in the as-prepared composite was detected by this analysis. The atomic
proportion of Zn, O, C, Ni, Na, and Cu was observed to be 68.21%, 29.32%, 1.60%, 0.52%, 0.33%, and 0.02% for this sample,
respectively. Quantitative analysis confirmed that the entitled compound existed in the samples synthesized by simplified and
conventional spray techniques. No considerable changes were observed for the samples annealed at 300 and 600 °C.

3.7. Sensing measurements

Thin-film substrate was prepared under a pressure of 15 MPa, and gold lead was mounted on both sides of the substrate to form
the sensing element. The element was enclosed in a quartz tube, which was heated to a certain temperature in a tubular furnace. A
constant current was applied across the element. The steady-state resistance of the element was measured in air and in the presence of
a target gas in air. Ethanol sensitivity (response magnitude) was defined as the ratio of sensor resistance in air (R-air) to that in an
air–gas mixture (R-gas) to that in air. The substrate was kept at a constant temperature using a flat panel heater, and temperature was
monitored using a Cr–Al thermocouple. The Al/Au electrodes placed on the surface of the pellet made ohmic contact with the pellet
and acted as resistance-measuring electrodes. Initially, the chamber was evacuated to a base pressure of 10–2 Torr using a rotary
pump, and electrical measurements were performed at a fixed temperature of 100 °C in a vacuum. The response, i.e., the resistance
value, was considered as the reference response for the calculation of sensitivity. The temperature was controlled by varying the
current flow through the heater and measured with an accuracy of ± °C using a temperature controller with indicator [30].
The entire system was covered with a glass chamber fitted with a rubber tube at its base to ensure complete vacuum in the
chamber through suction by using a high-capacity vacuum pump. The chamber and electrical-measurement systems were well
developed for controlled variations in the inner atmospheric temperature and pressure for controlled gas-sensing analysis. The
resistance variations are shown in Fig. 12. ZnO is a well-known n-type semiconducting oxide that is widely used for reducing gases
within the operating range of 273–443 K. This oxide material has high reactivity toward reducing gases at relatively low operating
temperature, ability to easily adsorb oxygen on its surface because of its natural non stoichiometry, stable phase, and low cost, and
simple to operate. For monolayer coverage, the C–O bond cleavage process was favored, which was in contradiction to the ex-
perimental results discussed above where ethoxide and acetaldehyde production was observed.
From the Fig. 12,we also observed that the ZnO nanorods on the surface slightly deformed the shape of CuO/ZnO/CNTs. Basically,
ZnO has high sensing and photocatalytic action for RhB, so CuO/ZnO/CNTs scan sense well [31,58].

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Fig. 10. (a-c). AFM Analysis of CuO doped ZnOeCNT.

3.8. TEM analysis of CuO/ZnO/CNTs

The EDX spectrum of the hybrid nanostructure showed the presence of ZnO with CNTs. The selected area electron diffraction
(SAED) patterns shown in Fig. 9(e) confirmed the presence of crystalline hexagonal ZnO with (101), (002), and (100) faces. Copper
substrate was sprayed by CuO/ZnO/CNTs at the nanoscale, and the size increased with increased doping concentration of Cu and Zn.
This finding well agreed with the XRD results. In addition, the surface micrographs of CuO/ZnO/CNTs exhibited a nanocrystalline
and continuous dense microstructure (no pores were observed) due to the composition of NPs. Different shell-structure shapes of
CuO/ZnO/CNTs were observed in the TEM images (Fig. 11). The shape of the particles varied from nearly spherical to cylindrical,
ellipsoidal, hexagonal, and polyhedral. The average particle size varied from 40 nm to 60 nm for temperatures of 300 °C, in agreement
with XRD results. However, different shapes were present in powders, indicating that the growth habitat was independent of tem-
perature. SAED analyses of CuO/ZnO/CNTs are shown in Fig. 10(d), in which several signals originated from Cu, Zn, and O. After
thermal decomposition, only Cu, Zn, and O signals came from the CNT formation, as shown in Fig. 11(b). The SAED patterns were
entangled with one another and showed the cross-sectional HRTEM images of CuO/ZnO/CNTs The stacking sheet structure and
individual monolayers were clearly observed. The thickness of CuO/ZnO/CNTs was about 10–15 nm, which corresponded to ap-
proximately two layers of stacked individual monoatomic CNTs [36–38].

3.9. AFM analysis of CuO/ZnO/CNTs

The crystals deposited with a lattice constant 0.3251 nm have an atomically flat surface [43]. The beginning of a constructive
grain structure on the surface was visible only for the CuO/ZnO/CNTs. AFM images also revealed the surface roughness of the crystal
by noting the height deviations from the least fitted line on the 2D micrograph. Height calibrations were performed using the step
heights of freshly cleaved CuO/ZnO/CNTs. Due to the super-roughness of the samples, the laser interference pattern along the slow-
scan axis was sometimes difficult to avoid and more noticeable in the large-area scanning, having a period of twice the wavelength of

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Fig. 11. (a-d). Transmission Electron Microscopy of CuO doped with ZnOeCNT.

the laser [44, 45]. This result was due to the constructive interference of laser reflected from the sample surface and that reflected
from the cantilever. The two samples investigated in the present work were obtained based on the micromechanical behavior of CuO/
ZnO/CNTs. They were mechanically exfoliated and transferred to this copper substrate (I Method) and glass plate (II Method), which
were covered with 1.04 µm of thermal oxide. We identified the single and spherical shapes by the color influence in the optical
microscope, and CuO/ZnO/CNTs was imaged by atomic force microscopy (AFM) to ensure the uniformity of the surface layer.
Fig. 10(a)–10(f) shows the notable AFM images of CuO/ZnO/CNTs, which represented the formation of different grain-size variation
as observed from their representative corresponding HR TEM images. This image clearly represented the roughness of the sample.
Next to this, the surface morphology of the entitled compound reflected topography similar to those in HR TEM images. The sharp
crust in the AFM images indicated that samples had potential with reactive edges.

3.10. Photocatalytic activity

The photocatalytic activity of pure CuO/ZnO/CNTs was examined by the rate of degradation of RhB under the effect of UV-B
irradiation Fig. 13. All photocatalytic reactions were performed in a photocatalytic reactor system, which consisted of a cylindrical

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

(a) (b)

(c) (d)
Fig. 12. (a): Sensitivity Analysis of CuO doped ZnOeCNT at Room temperature, 300 °C and 600 °C. (b). Variation of time (Sec) with Sensitivity (%)
(c). Variation of ethanol concentration with sensitivity (%) (d). Variation of Time (Sec) with sensitivity (%).

borosilicate glass reactor vessel with a volume of 200 mL, a cooling water jacket, and a UV-B lamp (10 W of medium-pressure
mercury lamp; Institute of Electric Light Source, Beijing, China) positioned axially at the center as visible light. The reaction tem-
perature was kept at 30 °C by circulating the cooling water. A special glass frit as an air diffuser was fixed at the reactor to uniformly
disperse air into the solution. For each run, the reaction suspension was freshly prepared by adding 200 g of catalyst into 200 mL of an
initial concentration of 2.0 mg/L of RhB. After the degradation reaction, filtration was done for all samples using a syringe and a
0.50 µm syringe filter to remove any precipitated particles. The maximum characteristic absorption wavelength of RhB was posi-
tioned. To investigate the photocatalytic degradation properties of the as-prepared CuO/ZnO/CNTs, RhB was used as a model pol-
lutant to study the photocatalytic performance of– CuO/ZnO/CNTs. The absorptive intensity of RhB gradually decreased with
prolonged irradiation time when the mixed solution of RhB and CuO/ZnO/CNTs were exposed to UV-B light irradiation at RT Fig. 14.
These results indicated that RhB dye achieved optimum degradation behavior under the catalysis of CuO/ZnO/CNTs.

4. Conclusions

This improvement was due to enhanced photon harvesting and the creation of better charge percolation paths in photoactive
medium. The charge mobility derived from the space–charge limited current very well agreed with Mott–Gurney's law, and the values
were within the expected range for the polymer medium. Furthermore, the doping level of ZnO in the synthesis of CuO/ZnO/CNTs
played a critical role in the effectiveness of CNTs in the active layer of solar cells. According to the current experiment, the doping
level of ZnO must be kept low in the synthesis of CuO/ZnO/CNTs for efficient device fabrication. In particular, of the epithelial cells,
upon the CuO/ZnO/CNTs are exposed human pulmonary epithelial cells (A549) to various concentrations of composition.

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

(a) (b)

(c) (d)
Fig. 13. (a-d) Degradation analyses with respect to time at RT, 300 °C and 600 °C.

Fig. 14. Schematic diagram of the mechanism for the degradation of Rh-B on the CuO doped with ZnOeCNT composite.

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D. Saravanakkumar, et al. OpenNano 4 (2019) 100025

Declaration of Competing Interest

The authors declare that there is no conflict of interest.

Supplementary materials

Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.onano.2018.11.001.

References

[1] Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim, H. Yan, Adv. Mater. 15 (2003) 353.
[2] X. Zhang, Y.-G. Guo, W.-M. Liu, J.-C. Hao, J. Appl. Phys. 103 (2008) 114,30.
[3] S.W. Oh, H.J. Bang, Y.C. Bae, Y.-K. Sun, J. Power Sources 173 (2007) 502.
[4] G Eranna, Metal Oxide Nanostruct. Gas Sens. Device (2011).
[5] R. Du, Q. Zhao, N. Zhang, J. Zhang, Macroscopic carbon nanotube-based 3D monoliths, Small 11 (2015) 3263.
[6] Q. Li, J. Sheng, Q. Wei, Q. An, X. Wei, P. Zhang, L. Mai, Nanoscale 6 (2014) 11072.
[7] Y. Dong, K. Md, Y.-S. Chui, Y. Xia, C. Cao, J.-M. Lee, J.A. Zapien, Electrochim. Acta 176 (2015) 1332.
[8] Q. Zhang, J.-Q. Huang, W.-Z. Qian, Y.-Y. Zhang, F. Wei, Small 9 (2013) 1237.
[9] D Bauman, J Moryson H, Mol. Struct. 404 (1997) 113–120.
[10] S. Xin, L.-J. Wan Yu-Guo Guo, Nanocarbon networks for advanced rechargeable lithium batteries, Acc. Chem. Res 45 (2012) 1759.
[11] X. Zhao, C. Johnston, P.S. Grant, J. Mater, Chem 19 (2009) 8755.
[12] C. Xu, J. Sun, L. Gao, J. Power Sources 196 (2011) 5138.
[13] W. Wan, C. Wang, W. Zhang, J. Chen, H. Zhou, X. Zhang, Funct. Mater. Lett 7 (2014) 1450005.
[14] Z. Cao, B. Wei, ACS Appl, Mater. Interfaces 5 (2013) 10246.
[15] Z. Fang, W. Xu, T. Huang, M. Li, W. Wang, Y. Liu, C. Mao, F. Meng, M. Wang, M. Cheng, A. Yu, X. Guo, Mater. Res. Bul 48 (2013) 4419.
[16] M. Xu, F. Wang, Y. Zhang, S. Yang, M. Zhao, X. Song, Nanoscale 5 (2013) 8067.
[17] L. Noerochim, J.-Z. Wang, S.-L. Chou, D. Wexler, H.-K. Liu, Carbon 50 (2012) 1289.
[18] Z. Wang, G. Chen, D. Xia, J. Power Sources 184 (2008) 432.
[19] C. Ban, Z. Wu, D.T. Gillaspie, L. Chen, Y. Yan, J.L. Blackburn, A.C. Dillon, Adv. Mater 22 (2010) 145.
[20] Z. Xiong, Y.S. Yun, H.-J. Jin, Materials 6 (2013) 1138.
[21] K. Elumalai, S. Velmurugan, S. Ravi, V. Kathiravan, S. Ashokkumar, Spectrochimica Acta A, Mol. Bio. Mol. Spectrosc., 143 (2015) 158.
[22] W. Wang, S. Guo, I. Lee, K. Ahmed, J. Zhong, Z. Favors, F. Zaera, M. Ozkan, C.S. ` Ozkan, Sci. Rep 4 (2013) 4452.
[23] S. Chen, R. Yuan, Y. Chai, L. Zhang, N. Wang, X. Li, Biosens. Bioelectron. 22 (2007) 1268.
[24] A. Chrissanthopoulos, S. Baskoutas, N. Bouropoulos, V. Dracopoulos, D. Tasis, S.N. Yannopoulos, Thin Solid Films 515 (2008) 8524.
[25] J.G. Yu, X.H. Zhao, H. Yang, X.H. Chen, Q. Yang, L.Y. Yu, J.H. Jiang, X.Q. Chen, Sci. Total Environ. 482 (2014) 241.
[26] V.N. Popov, Mater. Sci. Eng. R 43 (2004) 61.
[27] J.R. Dahn, T. Zheng, Y. Liu, J.S. Xue, Science 270 (1995) 590.
[28] R.T. Yang, Carbon 38 (2000) 623.
[29] F.L. Darkrim, P. Malbrunot, G.P. Tartaglia, Int. J. Hydrogen Energy 27 (2002) 193.
[30] H. Liu, G. Cheng, R. Zheng, Y. Zhao, C. Liang, J. Mol, Catal. A 230 (2005) 17.
[31] L.M. Ang, T.S.A. Hor, G.Q. Xu, C.H. Tung, S.P. Zhao, J.L.S. Wang, Carbon 38 (2000) 363.
[32] G.T. Wu, C.S. Wang, X.B. Zhang, H.S. Yang, Z.F. Qi, W.Z. Li, J. Power Sources 75 (1998) 175.
[33] M.S.P. Shaffer, X. Fan, A.H. Windle, Carbon 36 (1998) 1603.
[34] Z. Wang, J. Xi, W. Wang, G. Lu, J. Mol, Catal. A 191 (2003) 123.
[35] L. Alejo, R. Lago, M.A. Pena, J.L.G. Fierro, Appl. Catal. A 162 (1997) 281.
[36] M. Chakraborty, A. Ghosh, R.J. Thangavel, Sol..-Gel. Sci. Technol. 74 (2015) 756.
[37] adbbc, Sundaramurthy Jayaraman, P. Suresh Kumar, D. Mangalaraj, D. Rajarathnam, Seeram Ramakrishnad, M.P. Srinivasan, RSC Adv. 4 (2014) 11288.
[38] Sadia Ameen, M.Shaheer Akhtar, Minwu Song, HyungShik Shin, ACS Appl. Mater. Interfaces 4 (2012) 4405.
[39] Kim Hyoun Woo, Kim Nam Ho, Lee Chongmu, J. Korean Phys. Soc. 44 (2004) 1417.
[40] BharatiPanigrahy, D. Bahadur., RSC Adv. 2 (2012) 6222.
[41] K.S. Brink, R.R. Reisz, A.R.H. Leblanc, R.S. Chang, Y.C. Lee, C.C. Chiang, T. Huang, D.C. Evans, Sci. Rep 5 (2015) 1.
[42] M. Moradi, M. Haghighi, S. Allahyari, Process Saf. Environ. Prot 107 (2017) 414.
[43] P.K. Raul, S. Senapati, A.K. Sahoo, I.M. Umlong, R.R. Devi, A.J. Thakur, V. Veer, CuO nanorods: a potential and efficient adsorbent in water purification, RSC Adv
4 (2014) 40580.
[44] D. Saravanakkumar, S. Sivaranjani, K. Kaviyarasu, A. Ayeshamariam, B. Ravikumar, S. Pandiarajan, C. Veeralakshmi, M. Jayachandran, M. Maaza, Synthesis and
characterization of ZnO–CuO nanocomposites powder by modified perfume spray pyrolysis method and its antimicrobial investigation, J. Semicond 39 (2018) 33001.
[45] M.T. Qamar, M. Aslam, I.M.I. Ismail, N. Salah, A. Hameed, Synthesis, characterization, and sunlight mediated photocatalytic activity of CuO coated ZnO for the
removal of nitrophenols, ACS Appl. Mater. Interfaces 7 (2015) 8757.
[46] R. Cusco, E. Alarcon-Lladó, J. Ibanez, L. Artus, J. Jimenez, B. Wang, M.J. Callahan, Phys. Rev. B. 75 (2007) 165202.
[47] Krishnakumar Lokesh, et al., Effective ammonia detection using n-ZnO/p-NiO heterostructured nanofibers, IEEE Sensors J. 16.8 (2016) 2477–2483.
[48] Madhukar Poloju, et al., "Enhancement of the isopropanol gas sensing performance of SnO 2/ZnO core/shell nanocomposites, J. Mater. Chem. C 5.10 (2017)
2662–2668.
[49] B.W. Mwakikunga, et al., Self assembly and properties of C: WO 3 nano-platelets and C: VO 2/V 2 O 5 triangular capsules produced by laser solution photolysis,
Nanoscale Res. Lett. 5.2 (2010) 389.
[50] G. Kavitha, K. Thanigai Arul, P. Babu, "Enhanced acetone gas sensing behavior of n-ZnO/p-NiO nanostructures, J. Mater. Sci. 29.8 (2018) 6666–6671.
[51] E. Manikandan, et al., Nanoflower rod wire-like structures of dual metal (Al and Cr) doped ZnO thin films: Structural, optical and electronic properties, Mater.
Lett. 131 (2014) 225–228.
[52] E. Manikandan, et al., Hybrid nanostructured thin-films by PLD for enhanced field emission performance for radiation micro-nano dosimetry applications, J.
Alloys Compound. 647 (2015) 141–145.
[53] E. Manikandan, G. Kavitha, J. Kennedy, "Epitaxial zinc oxide, graphene oxide composite thin-films by laser technique for micro-Raman and enhanced field
emission study, Ceram. Int. 40.10 (2014) 16065–16070.
[54] A. Diallo, et al., Physical & enhanced photocatalytic properties of green synthesized SnO2 nanoparticles via Aspalathus linearis, J. Alloy. Compound. 681 (2016) 561–570.
[55] Valentine Saasa, et al., "Optical and structural properties of multi-wall-carbon-nanotube-modified ZnO synthesized at varying substrate temperatures for highly
efficient light sensing devices, Sensors Transducers 195.12 (2015) 9.
[56] E. Manikandan, et al., Zinc oxide epitaxial thin film deposited over carbon on various substrate by pulsed laser deposition technique, J. Nanosci. Nanotechnol.
10.9 (2010) 5602–5611.
[57] DavidEdmond Motaung, et al., "In situ optical emission study on the role of C 2 in the synthesis of single-walled carbon nanotubes, J. Appl. Phys. 107.4 (2010)
044308.
[58] K. Kaviyarasu, et al., Well-aligned graphene oxide nanosheets decorated with zinc oxide nanocrystals for high performance photocatalytic application, Int. J.
Nanosci. 14.03 (2015) 1550007.

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