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Article history: One-dimensional (1D) nanostructures of zinc oxide (ZnO) have been synthesized through an electro-
Received 20 June 2008 chemical process via anodic deposition of a zinc foil in NaOH. X-ray diffraction (XRD) pattern and energy
Received in revised form 29 August 2008 dispersive X-ray (EDX) analysis indicate that the synthesized ZnO crystal is a wurtzite with a hexagonal
Accepted 6 September 2008
structure. Furthermore, a eld emission scanning electron microscope (FESEM) reveals several types of
Available online 30 October 2008
1D ZnO structure, such as nanoparticles, nanoneedles, nanoakes, and nanoowers, depending on the
condition of the anodization process, particularly the reaction time and concentration of the electrolyte.
Keywords:
The Zn foil deposited with 8.33 mA/cm2 current density in 4 M NaOH for 30 min resulted in the formation
Zinc oxide
Anodic deposition
of well-aligned nanoneedles. A 30 min deposition resulted in the formation of nanoparticles and a longer
Nanoowers deposition (60 min) will produce nanoowers. The molarity of the NaOH controlled the length of the ZnO.
Nanoneedles Fourier transformation infrared (FTIR) spectrum for ZnO nanoowers shows the standard peak of ZnO
Nanoakes at 500 cm1 . In addition, room temperature photoluminescence (PL) of the nanoowers demonstrates a
weak peak at 381 nm and a dominant broad peak at 515 nm. This suggests that the grown nanoowers
have high structural defect. However, the self-aligned nanoneedle structure exhibits a strong dominant
peak at 381 nm and a suppressed broad peak at 515 nm, indicating that the self-aligned nanoneedles
possess good crystal quality compared to the nanoowers.
2008 Elsevier B.V. All rights reserved.
0925-8388/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2008.09.044
514 S. Sreekantan et al. / Journal of Alloys and Compounds 476 (2009) 513518
2. Experimental procedure
The high purity (99.9%) zinc foils with 0.2 mm thickness used in this study
were obtained from Goodfellow Cambridge Limited. Prior to surface treatment, the Fig. 1. FESEM micrograph of zinc foil anodized with a current density of
foils were degreased by sonicating with acetone, rinsing with deionized water, and 8.33 mA/cm2 in 4.0 M NaOH for 60 min. (The inset micrograph is at a magnication
then drying in nitrogen steam. Electrochemical experiments were performed using of 25,000 shows the bundle of nanoneedles.)
a direct current voltage source (Zhao Xin RXN-303D) with an integrated charge
controller. Currents were varied in the experiment to explore the effect of current
density on the morphology of the grown ZnO. Zinc foils (surface area = 6.0 cm2 ) generally sharp. The thickness of the nanostructure produced was
were used as anodic electrodes while stainless steel sheets, AISI 3104 (surface determined gravimetrically by measuring the change in weight of
area = 6.0 cm2 ), were used as cathodic electrodes. The distance between anodic and the substrate due to oxide deposition, the area of deposition and
cathodic electrodes was 30 mm. The electrolyte used in this process was NaOH. Elec-
using the bulk density of ZnO (5.6 g/cm3 ). The thickness of the
trolyte solutions with varying concentrations were prepared from reagent grade
chemical and deionized water. All anodic deposition experiments were performed
deposition prepared at 8.33 mA/cm2 current density in 4.0 M NaOH
at room temperature (25 C). The temperature was carefully monitored using water solution for 60 min was 0.6 m.
bath magnetic stirrer to ensure good temperature control and uniformity of 1 C. Chemical stoichiometry of the nanoneedles was investigated
After anodizing for the specic duration, the foil was immediately removed from using energy dispersive X-ray (EDX) analysis. The results, as shown
the solution and washed with distilled water. Finally, it was dried in nitrogen stream
in Fig. 2, indicate that there are no other elements present except
prior to characterizations.
Scanning electron microscopy (using a Leo Supra 35VP FESEM) was conducted for Zn and O. The atomic ratio of zinc to oxygen of the nanoneedles
to analyze the structural and morphological characteristic of nanostructured ZnO. measured through the EDX quantitative analysis data is approxi-
A cross-section of the photographs were obtained by observing the mechanically mately 1:1, an afrmation that the nanoneedles are pure ZnO.
fractured sample. X-ray diffraction (XRD) was performed using an X-ray diffrac-
The XRD measurement was conducted to assess the crystalline
tometer model, PANalytical XRD Rontgen Diffractometer System PW 3040/60 XPert
PRO) with Cu K radiation ( = 1.5418 ). Fourier transformation infrared (FTIR) was
phases of the nanoneedles. A typical XRD pattern of a sample
recorded with a PerkinElmer. Fluorescence spectra were recorded at room temper- anodized for 60 min is shown in Fig. 3. Two sets of peaks can be iden-
ature by using an LS 55 luminescence spectrometer (Jobin-Yvon ).
tied. The rst is readily indexed to the hexagonal ZnO phase (JCPDS
36-1451) with unit cell parameters a = 3.249 and c = 5.206 . The
other peaks correspond to pure zinc which clearly originated from
the foil. The ZnO formation is conrmed to be crystalline even
without conducting post-annealing treatment. This indicates the
formation of crystalline oxide in situ at low temperature. The com-
position and quality of the anodized foil was analyzed by FTIR
spectroscopy. Fig. 4 shows the FTIR spectrum acquired in the range
of 4004000 cm1 . The band at 500 cm1 is related to the ZnO
bond. A similar observation has been made by Wahab et al. [20].
Based on the XRD, EDX, and FTIR results, it can be concluded that
the thin lm oxide produced is ZnO.
Room temperature PL spectrum of the nanoneedles with ower-
like structure is illustrated in Fig. 5. For comparison, the PL spectrum
of the self-aligned nanoneedles obtained after 30 min of anodiza- Fig. 6. FESEM micrograph of zinc foil anodized at (a) 15 min (The inset micrograph
tion was also considered. It can be observed that the sample has two is at a magnication of 50,000 shows the presence of spherical-shaped nanopar-
ticles.) and (b) 30 min. (The inset micrograph shows the mechanically fractured
emission peaks, the UV emission at 381 nm (3.2 eV) and the green
surface, indicating the length of the nanoneedles.)
emission at 515 nm. Generally, the UV emission of ZnO is attributed
to an exciton-related activity [21], and the green emission is due
to the point defects related to the surface such as oxygen vacan- nanoneedles are high compared to ower-like structure, indicating
cies or impurities [22]. The intensity ratio of the UV to the visible a 30 min deposition will produce nanoneedles with better crystal
emissions can be used to evaluate the quality of ZnO [23,24]. The quality.
intense broad green emission indicates a very high concentration
of oxygen vacancies in the ZnO with ower-like structure. It was 3.2. Effect of deposition times and proposed mechanism of
also observed that the intensity of the UV emission of self-aligned deposition
Zn Zn2+ + 2e
Fig. 8. FESEM micrograph of foil anodized using NaOH with various concentrations: (a) 1.0 M, (b) 1.5 M (The inset micrograph shows the width of the aky-like structure.)
and (c) 2.0 M.
S. Sreekantan et al. / Journal of Alloys and Compounds 476 (2009) 513518 517
Fig. 9. FESEM micrograph shows the cross section of Zn foil after annealing, indi- Fig. 10. FESEM micrograph of annealed zinc foil anodized with a current density of
cating the formation of thin ZnO layer. 0.83 mA/cm2 in 6.0 M NaOH for 60 min. (The inset micrograph shows the formation
of well-aligned nanorods.)
Zincate formation is believed to be one of the key factors in
determining the formation of ZnO nanoneedles. To examine the because it was predicted to have a homogeneous native oxide layer.
effect of zincate addition, 0.5 wt% Zn(NO3 ) was added to 4 M NaOH The thickness of deposition was 0.4 m. However, there were some
to form more zincate ions. The foil was then anodized with a current impurities present on the surface of the nanorods, which were
density of 8.33 mA/cm2 for 60 min. Fig. 7 shows the SEM micrograph proven to be sodium based on the EDX results (not shown). Never-
of the anodized foil. It can be observed that a coarse aky type ZnO theless, surface treatment of Zn before deposition is believed to be
is oriented in a perpendicular manner to the zinc foil. The thickness benecial in the formation of a more homogenous nanostructure
of the deposition was 0.8 m. This indicates that zincate addition on Zn.
can advance the formation of ZnO nanoneedles.
4. Conclusion
3.3. Effect of NaOH concentration
In summary, various 1D ZnO nanostructures can be obtained
Based on the proposed mechanism of ZnO deposition shown through anodic deposition of Zn complex ions in alkaline solution.
earlier, it is hypothesized that the morphology of ZnO will strongly EDX, XRD, and FTIR analyses conrmed that the as-deposited lm
depend on the concentration of the electrolyte. Fig. 8 illustrates consisted of pure ZnO wurtzite with a hexagonal structure, thus
the FESEM micrographs of zinc foil after anodizing it for 60 min requiring no post-annealing treatment. Electrolyte concentration,
in an electrolyte with different molarities (1, 1.5, and 2 M). For 1 M, time of reaction, current density, zincate formation and addition,
ZnO nanoparticles with diameters of 50 nm (Fig. 8a) were formed, as well as surface treatment, play important roles in the formation
whereas for 1.5 M, aky type structures with width of 80 nm were of 1D ZnO structures.
acquired (Fig. 8b). For 2 M, thick and short nanoowers with lengths
of 100300 nm were obtained (Fig. 8c). The varying morphology
Acknowledgments
and dimension of the nanostructures formed are not well under-
stood. However, it is speculated that the structure must be related
The author would like to thank the Ministry of Higher Educa-
to the degree of supersaturation of ZnO nuclei on the foil surface. At
tion for sponsoring this work through grant FRGS 6070020 and
low concentrations of hydroxide ions, there are only few hydroxide
Universiti Sains Malaysia Short Term Grant 2007: 6035226.
ions that can react with Zn2+ ions to form zincate ions. Zn(OH)4 2 ,
which nally form the thin layer of ZnO, indicate the initial stage of
ZnO growth. Obvious growth can be perceived for higher hydrox- References
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