Journal of Alloys and Compounds 619 (2015) 378–382

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Journal of Alloys and Compounds

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

CuO nanostructures grown by the SILAR method: Influence of Pb-doping

on the morphological, structural and optical properties
F. Bayansal a,b,⇑, Y. Gülen c, B. Sß ahin b, S. Kahraman a,b, H.A. Çetinkara b
a
Department of Metallurgical and Materials Engineering, Faculty of Technology, Mustafa Kemal University, Hatay, Turkey
b
Department of Physics, Faculty of Arts and Sciences, Mustafa Kemal University, Hatay, Turkey
c _
Department of Physics, Faculty of Arts and Sciences, Marmara University, Istanbul, Turkey

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

Article history: CuO nanostructures with and without Pb were synthesized by the Successive Ionic Layer Adsorption and
Received 2 July 2014 Reaction method. The films were characterized by scanning electron microscopy, energy dispersive X-ray
Received in revised form 8 September 2014 spectroscopy, X-ray diffraction and ultraviolet–visible spectrophotometry. Scanning electron microscopy
Accepted 8 September 2014
results showed that the morphology of the film surface was changed from plate-like to coral-like nano-
Available online 16 September 2014
structures with increasing Pb concentration. The X-ray diffraction patterns showed the monoclinic crystal
 1 1Þ and (1 1 1). Furthermore, ultraviolet–visible spectra showed
structure with preferential planes of ð1
Keywords:
that the band gap of the films was tailored by Pb doping.
CuO
Nanostructure
Ó 2014 Elsevier B.V. All rights reserved.
Doping
Optical properties
Electron microscopy

1. Introduction [12,16,19]. But generally in most of the low temperature methods

In the recent years many efforts have been devoted to grow,
characterize and describe the physical and chemical properties of
transition-metal oxides because of their potential applications in
a variety of functional devices. Among these transition-metal oxi-
des copper oxide (CuO), one of the important p-type semiconduc-
tors with a narrow band gap of 1.2–1.9 eV [1–3], has attracted
much attention. It has potential applications in many fields such
as catalysts [4], field emission devices [5], gas sensors [6], biosen-
sors [7], high temperature superconductors [8], photovoltaic
devices [9], energy storage [10] and spintronics [11]. Most of these
applications require copper oxide on nanoscale size. Therefore
many recent efforts have been concentrated on the fabrication
techniques that could change the nanostructure and thus enhance
the performance of the devices.
CuO films have been synthesized by many different methods
which are thermal oxidation [12], electrodeposition [13], dip coat-
ing [14], chemical vapor deposition [15], magnetron sputtering
[16], chemical bath deposition (CBD) [17] and Successive Ionic
Layer Adsorption and Reaction (SILAR) [18]. In these methods
one of Cu, CuO, Cu2O and Cu(OH)2 phases were obtained
⇑ Corresponding author at: Department of Metallurgical and Materials
Engineering, Faculty of Technology, Mustafa Kemal University, Hatay, Turkey.
Tel.: +90 326 2455845; fax: +90 326 2455867.
E-mail address: fbayansal@gmail.com (F. Bayansal).
these four phases were obtained together. Therefore, in order to
convert the other phases into CuO further annealing processes in
oxygen or air atmosphere were applied to the samples after the
growth. On the other hand, among these techniques SILAR is a
promising technique because it is a simple, safe, environmental
friendly, suitable to mass production, low temperature and cost
effective solution method.
The microstructure and growth steps reasonably affect the
physical and chemical properties of the metal oxide films. More-
over, doping of semiconductors with some certain elements offers
an effective approach to adjust their properties which is crucial
for their practical applications [20]. Although a number of
researchers performed doping, it is still remains a challenge to
achieve high quality of crystalline films with excellent physical
and chemical properties of doped CuO nanostructures. Pb is one
of the doping elements that were used in many metal oxide
growth processes [21,22]. But, to the best of our knowledge there
are no reports on the synthesis and properties of Pb-doped CuO
thin films.
In the present paper we report for the first time synthesis of
CuO nanostructures with different doping concentrations of Pb
by the SILAR method. The morphological, compositional, structural
and optical properties of the films have been investigated by
scanning electron microscopy (SEM), energy dispersive X-ray
spectroscopy (EDS), X-ray diffraction (XRD) and UV–vis.
spectrophotometry.

http://dx.doi.org/10.1016/j.jallcom.2014.09.085
0925-8388/Ó 2014 Elsevier B.V. All rights reserved.
 F. Bayansal et al. / Journal of Alloys and Compounds 619 (2015) 378–382
Fig. 1. Scanning electron microscopy images and energy dispersive spectroscopy results of pure and Pb-doped nanostructures.
2. Experimental details
Synthesis of pure and Pb-doped CuO nanostructured thin films were carried out
in a solution containing Cu2+ (for pure samples) or Cu2+:Pb2+ (for doped samples)
ions. The raw materials used in the experiments were analytical grade reagents,
purchased from Sigma–Aldrich Company and Merck KGaA and used without further
purification. In order to deposit pure films first 0.1 M copper chloride solution was
prepared with copper(II) chloride dehydrate (CuCl22H2O) and 100 ml double dis-
tilled water (18.2 MX cm). Then it was stirred in a magnetic stirrer at room temper-
ature for a few min. in order to get a transparent and well-dissolved solution. After
stirring, pH value of the solution was adjusted to 10.0 by adding aqueous ammo-
nia and then it was heated up to 90 °C. During the experiments the temperature
was kept as constant. Microscope glass slides which were cleaned with a certain
recipe given in [17] are used as substrates. In order to get 1–2 lm thick films 10
cycles of SILAR were applied. A SILAR cycle can be described as follows: the sub-
strates were dipped into the solution for 30 s. Then they were taken out from the
bath and immediately dipped into hot water (90 °C) for another 30 s. Finally the
films were dried at room temperature for a day. After drying, the samples were
cleaned ultrasonically for 5 min. in order to detach bigger and tightly bonded par-
ticles. For the doped samples the same procedure was applied, but this time differ-
ent concentrations of Pb(NO3)2 were added to 0.1 M copper chloride solutions. In
order to get 1, 2, 4, 8 and 16 at.% of Pb in the solutions the molarities were adjusted
379
to 0.001, 0.002, 0.004, 0.008 and 0.016 respectively. The rest of the experiments
were remained as the same.
A PhilipsXL30S FEG scanning electron microscope (SEM) was operated at an
acceleration voltage of 15 kV for morphological imaging. The compositions of Pb
ions were investigated through energy dispersive X-ray spectroscopy. The crystal
structures of the samples were examined by Rigaku SmartLab X-ray diffractometer
(Cu Ka radiation, k = 1.540056 Å). A scan rate of 0.01°/s was applied to record the
patterns in the 2h range of 30–80°. Optical studies were conducted at room temper-
ature by using a Thermo Scientific Genesys 10S UV–vis. spectrophotometer.
3. Results and discussion
3.1. Morphological studies
Scanning electron microscopy was employed to analyze the
morphological properties of pure and Pb-doped samples. Fig. 1
shows the morphologies of pure and Pb-doped (1, 2, 4, 8 and
16 at.%) films. The insets in the figures show the elemental distri-
bution (EDS results) of the films. From these graphs it is obvious
380 F. Bayansal et al. / Journal of Alloys and Compounds 619 (2015) 378–382

_ are much stronger than that of the other peaks which indicate that
(111) (111)
they are preferential crystal planes of the nanostructures. As seen
(110) _
_ (311)
from the figure Pb doping (even in small percentages) caused a
_
(202) (020) (113)
 1 1Þ and (1 1 1) peak intensities. But further
great decrease in the ð1
(220) 16% doped
increase in doping concentration caused an increase in the ð1  1 1Þ
and (1 1 1) peak intensities. These mean that the crystalline quality
8% doped of the films first was decreased suddenly with a small Pb doping
and then increased slowly with increasing doping percentages.
None of the patterns showed any of Pb phases which mean the
4% doped
Intensity (a.u.)

Pb phases were very small and disappeared in the noise signal.

30 40 50 60
2θ (degree)
Fig. 2. X-ray diffraction patterns of pure and Pb-doped CuO films.
that the Pb concentrations of 1, 2, 4, 8 and 16 at.% in the growth
solutions provided dopings of 0.27, 0.37, 0.36, 0.46 and 0.75 at.%
of Pb in the films, respectively. If we further increase the concen-
tration of Pb in the growth solution we can obtain highly Pb-doped
CuO films just by looking at this linear behavior. As seen from the
SEM figures the obtained films are crack free with nano-sized
particles.
As the Pb doping increases the film morphology changes from
plate-like nanostructures as in [23] to coral-like nanostructures.
From the SEM figures it is clear that a small amount of Pb
(0.27 at.%) changed the surface morphology. Further dopings had
very little effects on the morphology but they caused a decrease
in the thickness of the nanostructures that is they became thinner
with increasing Pb doping. As seen in the following sections this
change affected the band gap of the films strongly.
The average grain sizes (D) of the structures was calculated
2% doped
from the peak full width at the half maximum (FWHM) of a peak
(b), using the Debye–Scherrer’s equation [24]:
1% doped
0:94k
D¼ ð1Þ
b cos h
where k is the wavelength of X-ray radiation, h is the Bragg’s angle
of the peaks and b is the angular width of peaks at FWHM. Each X-
ray diffraction peak obtained in a diffractometer is broadened due
to instrumental and physical factors (grain size and lattice strains).
The microstrain (e) and dislocation density (q) for the CuO films
Pure were calculated using the following equations [24]:
b cos h
70 80 e¼ ð2Þ
4
and
15e
q¼ ð3Þ
aD
where a is the lattice constant. The calculated average grain sizes
(D) of the CuO nanostructures are given in Table 1. As seen from
the table, grain sizes of the films were first increased (0.27 at.%
Pb) suddenly then decreased slowly with increasing Pb doping. This
result can also be supported by the SEM measurements. As
expected, both the behavior of microstrain and dislocation density
values of the films are in reverse manner with the grain size values.
For all the calculations (grain size, microstrain and dislocation den-
sity) the first dominant five peaks that are (1 1 0), ð1  1 1Þ, (1 1 1),
 0 2Þ and (0 2 0) are used. From a detailed investigation of XRD pat-
ð2
terns, a shift in peak positions was determined towards lower 2h
values with increasing Pb doping. This shift indicates the presence
of a decrease in lattice strains in the structures [25].
3.3. Optical studies

3.2. Structural studies
The crystal structure and phase purity of the films has been
characterized by a Rigaku SmartLab X-ray diffractometer (Cu Ka
radiation, k = 1.540056 Å). Fig. 2 shows the XRD patterns of pure
and Pb-doped (1, 2, 4, 8 and 16 at.%) films obtained at an operating
voltage and current of 40 keV and 30 mA respectively. The 2h range
of 30–80° was recorded with the scan rate of 0.01°/s.
All the major diffraction peaks in the patterns can be indexed to
monoclinic CuO crystal structure (JCPDS Card Number: 01-080-
0076). It is found that the intensities of ð1 1 1Þ and (1 1 1) peaks
Studying the optical absorption provide us simple methods for
explaining properties related to the band structure and band gap
energy of the materials. In order to measure the band gap energies
of the films a Thermo Scientific Genesys 10S UV–vis. spectropho-
tometer was used in the wavelength range of 190–1100 nm.
The optical absorption in the UV–vis. region is dominated by the
optical band gap (Eg) of a semiconductor that is related to the opti-
cal absorption coefficient (a) and the incident photon energy (ht)
by the following relation

m
ðahtÞ ¼ C ht  Eg ð4Þ

Table 1
Pb concentration, band gap and structural parameters of the films.

Pb concentration (at.%) Eg (eV) Average grain size (nm) Microstrain (103) Dislocation density (1012/cm2)
0.00 1.43 9.94 3.896 143.20
0.27 1.80 17.22 2.150 41.85
0.37 1.76 16.21 2.254 45.43
0.36 1.72 15.79 2.297 46.79
0.46 1.68 13.07 4.083 253.20
0.75 1.65 8.98 5.119 281.30
 F. Bayansal et al. / Journal of Alloys and Compounds 619 (2015) 378–382 381

Pure, Eg=1.43 the figure it is seen that the band gap was increased suddenly with
0.27% Pb, Eg=1.80 a small Pb doping (0.27 at.%) and then decreased slowly with
0.37% Pb, Eg=1.76 increasing doping. These results are also found to be parallel to
0.36% Pb, Eg=1.72 the results obtained by SEM and XRD analysis.
0.46% Pb, Eg=1.68
0.75% Pb, Eg=1.65 4. Conclusions

As a conclusion the authors have presented the first report on

the morphological, structural and optical properties of Pb-doped
CuO nanostructured thin films. The films were synthesized by
the SILAR method on the glass substrates successfully. By changing
the doping percentages CuO nanostructures of different morpholo-
( α hv)2(a.u.)

gies were grown. Also the XRD results showed that the crystal
quality of the films was modified by Pb doping. From the UV–vis.
spectra it can be concluded that the band gap of the films can be
changed by tailoring the morphology and Pb doping concentra-
tions of the films.

Acknowledgement

This work is partially supported by the Scientific Research Com-

mission of Mustafa Kemal University (Project No. 279).

References

[1] Iqbal Singh, R.K. Bedi, Studies and correlation among the structural, electrical
and gas response properties of aerosol spray deposited self assembled
nanocrystalline CuO, Appl. Surf. Sci. 257 (2011) 7592–7599.
1 1.2 1.4 1.6 1.8 2 2.2 [2] R. Sahay, J. Sundaramurthy, P. Suresh Kumar, V. Thavasi, S.G. Mhaisalkar, S.
Eg (eV) Ramakrishna, Synthesis and characterization of CuO nanofibers, and
investigation for its suitability as blocking layer in ZnO NPs based dye
2
Fig. 3. Comparison of (aht) vs. ht plots of pure and Pb-doped CuO films. sensitized solar cell and as photocatalyst in organic dye degradation, J. Solid
State Chem. 186 (2012) 261–267.
[3] Likun Zheng, Xinjian Liu, Solution-phase synthesis of CuO hierarchical
nanosheets at near-neutral pH and near-room temperature, Mater. Lett. 61
1.9 (2007) 2222–2226.
[4] Hanbo Zou, Shengzhou Chen, Zili Liu, Weiming Lin, Selective CO oxidation over
CuO–CeO2 catalysts doped with transition metal oxides, Powder Technol. 207
1.8 (2011) 238–244.
[5] Woo-Yong Sung, Wal-Jun Kim, Seung-Min Lee, Ho-Young Lee, Yong-Hyup Kim,
Kyung-Ho Park, Soonil Lee, Field emission characteristics of CuO nanowires by
1.7 hydrogen plasma treatment, Vacuum 81 (2007) 851–856.
Eg (eV)

1.6
1.5
1.4
0 4 8 12
Pb concentration in the solution (%)
Fig. 4. Band gap values of the CuO films as a function of Pb concentration.
where C is an energy independent constant and m is an index which
depends on the kind of optical transition that prevails. Specifically,
n is 1/2, 3/2, 2 and 3 when the transition is direct-allowed, direct-
forbidden, indirect-allowed, and indirect-forbidden, respectively.
CuO is known to be a direct-allowed semiconductor [26], and hence
a graph was plotted (Fig. 3) with (aht)2 (where m = 1/2) vs. photon
energy (ht) as a function of Pb doping. By using this graph the band
gap values can be determined by extrapolating the straight line por-
tion. The Eg of pure CuO film was found to be 1.43 eV which is in
accordance with [17].
On the other hand the Eg values were found to be 1.80, 1.76,
1.72, 1.68 and 1.65 eV for the films having 0.27, 0.37, 0.36, 0.46
and 0.75 at.% of Pb, respectively. The band gap values vs. Pb
concentration in the growth solution are plotted in Fig. 4. From
[6] Manish Kumar Verma, Vinay Gupta, A highly sensitive SnO2–CuO multilayered
sensor structure for detection of H2S gas, Sens. Actuators, B 166– 167 (2012)
378–385.
[7] Kajal Jindal, Monika Tomar, Vinay Gupta, CuO thin film based uric acid
biosensor with enhanced response characteristics, Biosens. Bioelectron. 38
(2012) 11–18.
[8] T. Jarlborg, Effects of spin–phonon interaction within the CuO plane of high-Tc
superconductors, Physica C 454 (2007) 5–14.
[9] C.C. Vidyasagar, Y. Arthoba Naik, T.G. Venkatesh, R. Viswanatha, Solid-state
synthesis and effect of temperature on optical properties of Cu–ZnO, Cu–CdO
16 and CuO nanoparticles, Powder Technol. 214 (2011) 337–343.
[10] Zhigang Yin, Yunhai Ding, Qingdong Zheng, Lunhui Guan, CuO/polypyrrole
core–shell nanocomposites as anode materials for lithium-ion batteries,
Electrochem. Commun. 20 (2012) 40–43.
[11] Wenli Gao, Shuhu Yang, Shaoguang Yang, Liya Lv, Youwei Du, Synthesis and
magnetic properties of Mn doped CuO nanowires, Phys. Lett. A 375 (2010)
180–182.
[12] L. De Los Santos Valladares, D. Hurtado Salinas, A. Bustamante Dominguez, D.
Acosta Najarro, S.I. Khondaker, T. Mitrelias, C.H.W. Barnes, J. Albino Aguiar, Y.
Majima, Crystallization and electrical resistivity of Cu2O and CuO obtained by
thermal oxidation of Cu thin films on SiO2/Si substrates, Thin Solid Films 520
(2012) 6368–6374.
[13] Nillohit Mukherjee, Bibhutibhushan Show, Swarup Kumar Maji, Utpal Madhu,
Sanjib Kumar Bhar, Bibhas Chandra Mitra, Gobinda Gopal Khan, Anup Mondal,
CuO nano-whiskers: electrodeposition, Raman analysis, photoluminescence
study and photocatalytic activity, Mater. Lett. 65 (2011) 3248–3250.
[14] T. Serin, A. Yildiz, S
ß .H. Sßahin, N. Serin, Multi phonon hopping of carriers in CuO
thin films, Physica B 406 (2011) 3551–3555.
[15] F. Pola-Albores, W. Antunez-Flores, P. Amezaga-Madrid, E. Rios-Valdovinos, M.
Valenzuela-Zapata, F. Paraguay-Delgado, M. Miki-Yoshida, Growth and
microstructural study of CuO covered ZnO nanorods, J. Cryst. Growth 351
(2012) 77–82.
[16] Takahiro Itoh, Kunisuke Maki, Preferentially oriented thin-film growth of
CuO(1 1 1) and Cu2O(0 0 1) on MgO(0 0 1) substrate by reactive dc-magnetron
sputtering, Vacuum 81 (2007) 904–910.
382 F. Bayansal et al. / Journal of Alloys and Compounds 619 (2015) 378–382
[17] F. Bayansal, H.A. Çetinkara, S. Kahraman, H.M. Çakmak, H.S. Güder, Nano-
structured CuO films prepared by simple solution methods: plate-like, needle-
like and network-like architectures, Ceram. Int. 38 (2012) 1859–1866.
[18] M.T.S. Nair, Laura Guerrero, Olga L. Arenas, P.K. Nair, Chemically deposited
copper oxide thin films: structural, optical and electrical characteristics, Appl.
Surf. Sci. 150 (1999) 143–151.
[19] K.V. Gurav, U.M. Patil, S.W. Shin, G.L. Agawane, M.P. Suryawanshi, S.M. Pawar,
P.S. Patil, C.D. Lokhande, J.H. Kim, Room temperature chemical synthesis of
Cu(OH)2 thin films for supercapacitor application, J. Alloy. Compd. 573 (2013)
27–31.
[20] Mashkoor Ahmad, Caofeng Pan, Wang Yan, Jing Zhu, Effect of Pb-doping on the
morphology, structural and optical properties of ZnO nanowires synthesized
via modified thermal evaporation, Mater. Sci. Eng., B 174 (2010) 55–58.
[21] Sajid Butt, Yaoyu Ren, Muhammad Umer Farooq, Bin Zhan, Rizwan Ur Rahman
Sagar, Yuanhua Lin, Ce-Wen Nan, Enhanced thermoelectric performance of
heavy-metals (M: Ba, Pb) doped misfit-layered ceramics: (Ca2xMxCoO3)0.62
(CoO2), Energy Convers. Manage. 83 (2014) 35–41.
[22] Amel F.M. Ismail, Mamdouh M. Ali, Laila F.M. Ismail, Photodynamic therapy
mediated antiproliferative activity of some metal-doped ZnO nanoparticles in
human liver adenocarcinoma HepG2 cells under UV irradiation, J. Photochem.
Photobiol., B 138 (2014) 99–108.
[23] F. Bayansal, S. Kahraman, G. Çankaya, H.A. Çetinkara, H.S. Güder, H.M. Çakmak,
Growth of homogenous CuO nano-structured thin films by a simple solution
method, J. Alloy. Compd. 509 (2011) 2094–2098.
[24] Y. Gülen, B. Sahin, F. Bayansal, H.A. Çetinkara, Solution-phase synthesis of un-
doped and Pb doped CdO films, Superlattices Microstruct. 68 (2014) 48–55.
[25] G.G. Rusu, A.P. Râmbu, V.E. Buta, M. Dobromir, D. Luca, M. Rusu, Structural and
optical characterization of Al-doped ZnO films prepared by thermal oxidation
of evaporated Zn/Al multilayered films, Mater. Chem. Phys. 123 (2010) 314–
321.
[26] Arrak Klinbumrung, Titipun Thongtem, Somchai Thongtem, Characterization
and gas sensing properties of CuO synthesized by DC directly applying voltage,
Appl. Surf. Sci. 313 (2014) 640–646.