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 Mater. Res. Express 7 (2020) 025026 https://doi.org/10.1088/2053-1591/ab727b

PAPER

Growth of ZnO nanorods on FTO glass substrate

OPEN ACCESS
Hamza Slimani1, Noureddine Bessous2, Sawsan Dagher3 , Ali Hilal-Alnaqbi4, Maisa El Gamal5,
RECEIVED
15 November 2019
Boshra Akhozheya6 and Mudasir Mohammed3
1
Department of Physics, University of El Oued, Fac. Exact Sciences, 39000 El Oued, Algeria
REVISED 2
6 January 2020 Department of Electrical Engineering, University of El Oued, Fac. Technology, 39000 El Oued, Algeria
3
Electromechanical Engineering Technology, Abu Dhabi Polytechnic, Abu Dhabi, United Arab Emirates
ACCEPTED FOR PUBLICATION 4
3 February 2020
Abu Dhabi Polytechnic, Abu Dhabi, United Arab Emirates
5
College of Natural and Health Sciences, Zayed University, Abu Dhabi, United Arab Emirates
PUBLISHED 6
Department of Building & Architectural Engineering, Polytechnic University of Milan, Milan, Italy
17 February 2020
E-mail: [email protected]
Original content from this Keywords: ZnO nanorods, spray pyrolysis, FTO/ZnO, thin films
work may be used under
the terms of the Creative
Commons Attribution 4.0
licence.
Abstract
Any further distribution of
this work must maintain A simple and direct method has been developed to grow zinc oxide (ZnO) nanorods (NRs) on a
fluorine-doped tin oxide-coated glass (FTO) substrate. Firstly, spray pyrolysis deposition method is
attribution to the
author(s) and the title of
the work, journal citation applied followed by dipping the substrate in a solution of ZnO growth reagents. The morphology,
and DOI.
structure, and optical properties of the obtained thin film are investigated. The results demonstrate the
successful synthesis of the ZnO NRs on FTO substrate. The NRs have a hexagonal rod like structure
with diameter and length of 240 nm and 670 nm, respectively. FTO/ZnO NRs exhibited absorption of
UV wavelengths and high transmittance in visible light region, with energy bandgap (Eg) of 3.2 eV.
The characteristics of the FTO/ZnO NRs film can be explored in photovoltaic applications such as
dye-sensitized solar cells.

1. Introduction

Zinc oxide (ZnO) is a semiconductor with unique electrical and optical properties. This fact is due to its wide
direct energy bandgap (Eg) of 3.37 eV, as well its large exciton binding energy (60 meV), and high electron
affinity and mobility [1, 2]. ZnO can be synthesized into diverse nanostructure configurations such as
nanoparticles, nanowires, nanobelts, nanotubes and nanorods (NRs), in which its properties can be tailored to
be utilized for wide range of specific applications. ZnO nanosized are used in photocatalysis [3], hydrogenation
of carbon dioxide to methanol [4], gas and bio sensors [5, 6], solar cells, and light-emitting diodes [7, 8].
The size and shape, and consequently the properties of ZnO nanomaterial depends on the synthesis method,
the precursor solution and the type of substrate [9, 10]. The most common methods to prepare ZnO NRs are;
(i) Hydrothermal method: Zn(NO3)2.6H2O and Hexamethylenetetramine (HMTA) are used as precursors to
grow ZnO NRs with diameter of 30 nm and length of 250 nm on a glass substrate [11], in another study zinc
acetate (Zn(CH3COO)2.2HO), diaminopropane, and HMTA are used to synthesize ZnO NRs of 33 nm diameter
and 1000 nm length on an alumina substrate [12]. Hydrothermal reactions occur at a relatively low temperature
(200 °C) with long duration of synthesis (from about 10 h to several days), moreover, the hydrothermal method
is widely used to synthesize metal oxides nanostructures [13, 14] (ii) Sonochemical method: Zn(NO3)2.6H2O
and HMTA are used as precursors to grow ZnO NRs of 50 nm diameter and 500 nm length on an ITO coated
glass substrate [15], in another study Zn(CH3COO)2.2HO in paraffine oil is used to prepare ZnO NRs with
diameter in the range of 40–80 nm and length in the range of 150–300 nm [16]. (iii) Electrochemical deposition:
ZnCl2 and KCl are used to synthesize ZnO NRs on porous silicon with diameter and length of 200 nm and
700 nm, respectively [17]. (iv) Spray pyrolysis: rods with diameter of 250 nm and length of 376 nm are
synthesized on glass substrate using precursor solution of ZnCl2 in distilled water [18]. (v) Chemical vapour
deposition produces ZnO NRs with good crystallinity and high purity in a short time compared to other
techniques, nevertheless, the vapour-phase reactions require a very high temperature (1400 °C) and require a

© 2020 The Author(s). Published by IOP Publishing Ltd

 Mater. Res. Express 7 (2020) 025026
Table 1. Common synthesis methods of ZnO NRs, with their respective precursors, substrates, size range, and some other growth characteristics.

Diameter/
Preparation method Precursors Substrate length (nm) References Characteristics

Hydrothermal Zinc acitate, HMTA Glass/FTO — [25] Reactions occur at a temperature of ∼200 °C and high-pressure reaction conditions (e.g.
autoclave). Duration of synthesis is10 hours to several days.
2

Hydrothermal Zn(NO3)2.6H2O, HMTA Alumina 100/1620 [26]

Hydrothermal Zn (NO3)2·6H2O, HMTA Si wafer 200/3000 [27]
Hydrothermal, calcination Zinc acetylacetonat, urea 65/250 [28]
Sonochemical Zn (NO3)2·6H2O, HMTA Glass/Ti 65.2/668.2 [29] Ultrasound radiation is applied by means of acoustic cavitation. (high temperature and
pressure is generated)
Electrochemical deposition Zn(NO3)2·6H2O, K2SO4 Glass/Indium Tin diameters of 100–200 [30] Temperature is <100 °C. Constant or pulsed current or potential can be applied. Ions from
Oxide (ITO) aqueous metal salt solutions (electrolyte) are deposited on the substrate (electrodes) to
form ZnO.
Electrochemical deposition Zn (NO3)2·6H2O, HMTA, KCl Glass/FTO 198–306/287–545 [31]
Spray pyrolysis zinc acetate solution Glass 90–80 nm [32] Operating at temperatures of 100 °C–500 °C. Involves atomization of precursor solution
then evaporation and decomposition.
Spray pyrolysis Zn (NO3)2·6H2O, HMTA Glass 50–150/750–780 [33]

H Slimani et al
Mater. Res. Express 7 (2020) 025026 H Slimani et al

complex vacuum system [19, 20]. Less common methods for ZnO NRs synthesis are pulsed laser deposition
[21], RF magnetron sputtering [22], molecular beam epitaxy [23], and thermal evaporation [24]. However, these
methods require specialized and complex equipment, or involve extremely high temperature, pressure or
vacuumed system. Some examples on ZnO NRs’ synthesis are shown in table 1 with few characteristics.
The synthesis of ZnO NRs on the fluorine-doped tin oxide-coated glass (FTO) substrate is essential for
several photovoltaic and optoelectronic applications. However, there are few studies done on the growth of ZnO
NRs on FTO substrate [25, 31], which is an effective transparent layer in solar cell structure that absorbs UV light
and transfers electrons. In this study, we have proposed a simple, direct, and environment-friendly method to
grow ZnO NRs on FTO substrate through two steps. This method offers several advantages such as the non-
vacuum deposition, use of inexpensive equipment, relatively less complex and moderate temperatures are
required for the growth of ZnO NRs compared to other deposition techniques. To the best of the authors’
knowledge this is the first time to use Zn(CH3COO)2.2H2O and NaOH solution to synthesize ZnO NRs layer on
FTO substrate, following a spray pyrolysis deposition step. As well, the morphological, structural and optical
properties of the as synthesized FTO/ZnO NRs thin film are studied.

2. Experimental methods

ZnO NRs were deposited on fluorine-doped tin oxide (SnO2/F) glass substrate. Initially the FTO substrate was
cleaned by successive sonication in acetone and methanol, then the substrate was rinsed with deionized water
(H2O) and dried with nitrogen gas (N2).
In the first step; The precursor material zinc acetate dehydrated (Zn (CH3COO)2·2H2O) was dissolved in
H2O/methanol (1/2). With a concentration of 0.3 M. and 2 drops of glacial acetic acid (CH3COOH) was added
to avoid flakes formation. The solution was deposited on the FTO substrate using spray pyrolysis method to
initiate the ZnO seed layer. The substrate temperature was fixed at 450 °C and the substrate to nozzle distance
was 5 cm, then the substrate was sprayed on using a solution which was atomized by compressed ambient air at
the pressure of 2 bar. The solution’s flow rate was kept at 1 ml min−1 and the number of deposition sequences
was 7. Then the substrate was left to cool at room temperature.
In the second step, 1.81 mmol of each of the Zn(CH3COO)2.2H2O and NaOH were dissolved in 100 ml of
ethanol under rigorous magnetic stirring. The substrate was dipped in the solution for 1 h at constant
temperature of 65 °C which simulates the growth of NRs. Finally the substrate was washed in H2O and dried
with N2. The chemical reaction for ZnO NRs growth can be described as follows [34]:
5Zn (CH3 COO)2 : 2H2 O  Zn5 (OH)8 (CH3 COO)2 + 2CH3 COOH
Zn5 (OH)8 (CH3 COO)2 + 2NaOH  5ZnO + 2NaCH3 COO + 5H2 O
The formation mechanism of the ZnO NRs can be explained as follows; during spray pyrolysis process, when
precursor solution droplets arrive close to the FTO substrate which is heated at 450 °C, the droplets undergo
thermal decomposition, leading to the formation of the highly adherent (to the substrate) seed layer of ZnO
nanocrystals. The ZnO seed layer surface has a high reactivity because of the energy supplied via the heat
treatment at 450 °C during the synthesis process. Therefore, in the second stage; as the substrate dipped into the
solution of precursors the Zn2+ and OH− ions (present in the solution) are diffused in the ZnO seeds, resulting
in the increase of their length and diameter to develop the ZnO NRs structure. Thus, in this process, the ZnO
nanocrystals in the seed layer served as nucleation centers for the subsequent growth of ZnO NRs.
The morphology and crystallographic structure of synthesized FTO/ZnO NRs was characterized using
scanning electron microscope (SEM) with an energy dispersive x-ray spectroscopy (EDS) facility (JSM-5600;
JEOL, Japan), Fourier transform infrared spectroscopy (FTIR, Nexus TM 670), and powder x-ray diffractometer
(XRD, Shimadzu, 6100, Japan) using Cu Kα radiation (λ=1.5405 A°). The absorption and transmission
spectra were measured using UV–vis-NIR spectrophotometer (Perkin Elmer LAMBDA 950).

3. Results and discussion

3.1. Morphology and structure of the FTO/ZnO NRs

Figure 1 displays the SEM images of the ZnO layer deposited on FTO glass substrates. Figure 1(a) shows a side
view of the FTO/ZnO film, results indicate that ZnO is will coated on FTO surface with thickness of 680 nm.
Figures 1(b)–(d) show the formation of rod-like nanostructure with a hexagonal columnar structure. The
approximate diameter and length of the rods is 240 nm and 670 nm, respectively. The ZnO NRs have grown in
multiple directions to the substrate.
Figure 2(a) shows XRD patterns as 2θ in the range of 10°–70° for the FTO/ZnO NRs. The 2θ values of
31.61°, 34.33°, 36.10°, 47.36°, 56.31°, 62.64°, 67.64°, and 68.73° are related to the crystal planes (100), (002),

3
Mater. Res. Express 7 (2020) 025026 H Slimani et al

Figure 1. SEM images Of FTO/ZnO nanorods.

Figure 2. (a) XRD patterns of FTO/ZnO film, (b) FTIR spectra of FTO/ZnO NRs, and the insets are their energy-dispersive x-ray
spectroscopy elemental analysis.

(101), (102), (110), (103), (112) and (201), respectively. The assigned diffraction peaks specify the hexagonal
crystal structure of ZnO with cell parameters of a =3.249 Å and c =5.206 Å (JCPDS card no. 79–0208). It
indicates a high orientation in the c-axis. The diffraction peaks at 2θ of 26.5, 37.9, 51.6, and 54.6 are assigned to
tin oxide (SnO2) from FTO substrate (JCPDS card no. 41–1445). Very few additional weak peaks appeared
(with insignificant intensity), which could be attributed to the remaining organic components such as:
C4H6O4Zn2H2O, C2O4Zn2H2O, Zn(OH)2 or zinc acetate, and this is anticipated in wet-chemical reactions due
to the salts and solvents used.
Figure 2(b) shows FTIR spectrum of FTO/ZnO in the range of 4000–400 cm−1. The broad band at
3433 cm−1 is corresponding to the O–H stretching mode of the hydroxyl group. The hydroxyl groups are found
on the surface because of the hygroscopic nature (i.e., adsorption of water molecules from the surrounding
environment) of the ZnO NRs, the substrate was also washed with H2O in the final stage of ZnO NRs growth.
The observed peaks at 1703, 1624, 1124, 927, and 700 cm−1 are attributed to the symmetric and asymmetric
stretching of the zinc hydroxyl group. The weak peak at 1415 cm−1 might be assigned to the symmetric

4
Mater. Res. Express 7 (2020) 025026 H Slimani et al

Figure 3. (a) UV–visible absorption spectrum of FTO/ ZnO thin film, the inset is its Tauc plot, (b) Transmittance spectra of
FTO/ ZnO thin film.

stretching of carboxylate group (COO–), and the weak peaks at 1550 cm−1 and 1665 cm−1, are due to
asymmetric C=O bonds vibrations, possibly originated from reaction intermediates such as a minor residue of
zinc acetate used in the reaction. The peak at 482 cm−1 is assigned to the stretching vibrations of ZnO. The peak
at 735 cm−1 is due to the Zn–O bonding, are clearly represented [35]. Collectively, these observations confirm
the formation of the ZnO layer.
The spectra in the bottom inset shows the elemental two-dimensional energy-dispersive spectroscopy
analysis for FTO/ZnO surface. The mass percentage of these elements are shown in the table (above inset). Sn
and F elements can be seen, in addition to Zn and O elements, which indicates the migration of these elements to
the surface and could be a result of uncoated areas. Also, XRD patterns indicated few diffraction peeks resulted
from FTO.

3.2. Optical properties

Figure 3(a) shows UV- UV–vis light absorption spectrum of the prepared FTO/ZnO NRs. It is clear that the film
exhibits absorption in the UV light region. The spectrum can be used to estimate the optical energy band gap
(Eg) in eV based on the Tauc’s formula [36]:

(ahn)n = B (hn - E g)

Where α is the absorption coefficient (cm−1), hν is the photon energy (eV), B and n are constants, n is 2 for direct
electronic transition. The Eg can be calculated by creating a graph of (αhν)2 versus hν, thus the Eg value is the
intersection of the extended straight line of the linear portion of the curve to the X axis, as shown in the inset in
figure 3(a). The linearity of the curve indicates that the ZnO NRs have direct band gap transitions. The estimated
Eg for FTO/ZnO NRs is 3.2 eV. The Eg values of these NRs are less than the Eg of their bulk (3.37), even though
usually as crystal size decreases the Eg increases because of the quantum confinement effects [1, 34]. However,
the results in this study show a decrease in the Eg value in comparison to the bulk. This can be attributed to the
effect of FTO substrate, which indicates that few oxygen (O) atoms are replaced by Fluorine (F) atoms in ZnO.
EDS analysis for FTO/ZnO surface (shown in the inset of figure 2(b)) indicate the presence of F element on the
film surface, with a mass percentage of 2.02%. The integration mechanism of F into the surface, can occur via
three main routes; (i) F bonds to OH groups onto the surface by the formation of intermolecular hydrogen
bonds (OH-F), (ii) F atoms occupy the oxygen vacancies, (iii) Some O atoms might be substituted by F atoms
into oxygen lattice sites because their ionic radii are the same. Thus, the small reduction in Eg might be due to the
creation of energy levels in the band gap near the conduction band.
Figure 3(b) shows the transmittance spectra of Pure FTO and FTO/ ZnO NRs thin films. The films
demonstrated extraordinary transmittance values in the visible range (380–780 nm), while remarkable decrease
in transmission in the UV domain is observed. Pure FTO and FTO/ZnO film showed transmission of 87% and
78%, respectively, in the visible wavelength light. The high optical transparency of the FTO/ZnO film confirms
the high crystallinity of the as synthesized ZnO NRs [37].
In summary, the synthesized ZnO NRs showed hexagonal wurtzite structure which is more stable than zinc
blende structure at ambient temperatures. It is known that the ZnO has a strong ionic bond with the radii of
Zn2+ being 0.074 nm and for O2− being 0.140 nm. This property further enhances the formation of hexagonal
wurtzite structure, and the tendency of crystallization along c-axis, thus, a rod-liked structure is obtained. The
synthesized ZnO NRs exhibited a lattice constants ratio c/a of 1.60, mostly similar to that of the hexagonal cell’s

5
Mater. Res. Express 7 (2020) 025026 H Slimani et al

ideal value (c/a=1.633). Thus, the high crystallinity degree of the ZnO NRs is indicated by the high intensity of
the XRD peaks [38].
The optical analysis also verified the structural characteristics. Due to the fact that the transmittance
increases with increasing crystalline quality, FTO/ZnO film demonstrated an excellent transmittance in visible
and IR wavelength. In addition, the red shift in the Eg value indicates the enhanced crystallinity of the thin film
[39]. Several researches have been done to decrease the Eg of ZnO by doping with other metals such as Fe, Cu, Al
Ag. However, in this method the obtained FTO/ZnO NRs demonstrates optical band gap of 3.2 eV value. This
decrease in Eg value could be related to changes in the electronic structure of ZnO such as the presence of closely
sited acceptor levels in the region between the valence and conduction bands (i.e., forbidden bandgap).

4. Conclusions

Successful growth of ZnO NRs on FTO substrate was achieved via a simple yet efficient method; firstly, ZnO seed
layer is initiated by spray pyrolysis method, then the complete growth of ZnO NRs is achieved by using
Zn(CH3COO)2.2H2O and NaOH solution at relatively low temperature. The obtained film is investigated by
various characterization techniques. SEM images and XRD patterns confirm the formation of hexagonal crystal
structure ZnO NRs, with diameter of 240 and length of 670 nm. The Eg of ZnO NRs exhibits a slight red-shift
compared to their bulk, due to the effect of FTO substrate layer. Moreover, FTO/ZnO NRs thin film shows high
visible light transmittance. The produced FTO/ZnO could be used as an effective electron transport layer and
UV detector for photonic, optoelectronic and photovoltaic applications.

ORCID iDs

Sawsan Dagher https://orcid.org/0000-0002-3048-1146

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