Vous êtes sur la page 1sur 6

Journal of Alloys and Compounds 476 (2009) 513518

Contents lists available at ScienceDirect

Journal of Alloys and Compounds


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

Room temperature anodic deposition and shape control of one-dimensional


nanostructured zinc oxide
Srimala Sreekantan , Lee Ren Gee, Zainovia Lockman
School of Materials and Mineral Resource Engineering, Universiti Sains Malaysia (Engineering Campus), 14300, Nibong Tebal, Seberang Perai Selatan, Malaysia

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

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.

1. Introduction with ZnO is not comparable to TiO2 , as the efciency of such


devices merely reached 2% [3]. Hence, the properties of ZnO is
Rapid development in the eld of wide band gap semiconduct- yet to be perfected and further investigated. One way in which
ing oxides has stimulated intensive research efforts due to their ZnO can be further improved is through the engineering of ZnO
importance in fundamental scientic studies and potential appli- crystals dimensions and morphologies by utilizing synthesizing
cations. In recent years, wide band gap semiconducting oxides processes. It is known that nanoscale one-dimension (1D) semi-
have been perceived as an attractive material for renewable energy conductor materials are currently drawing considerable interest.
devices. Titanium dioxide (TiO2 ) for example is used as an active Obviously, nanoscale 1D ZnO is preferred in photoanode applica-
component (photoanode) in several devices, namely, photocatal- tions. It is not only the materials band gap which can be altered
ysis, photoelectrolysis, and photovoltaics [1]. Several other wide due to the quantum connement effect, but in addition the 1D
band gap semiconducting oxides have also been identied. In par- nanoscale ZnO in the form of nanowires, nanoneedles, nanoporous,
ticular, zinc oxide (ZnO) has been extensively investigated [2,3] due and nanorods can offer larger surface areas. Hence, higher photons
to its numerous attractive characteristics, such as large excitation absorption is expected. However, in attaining the right dimen-
binding energy (60 meV) [2] at room temperature, rich chemistry sions and morphologies, a control synthesis procedure for the
effect which translates to ease of doping the oxide, and wide band production of 1D nanoscale ZnO must be sought and optimised.
gap of 3.37 eV [3]. These characteristics make ZnO nanostructures Various methods such as thermal evaporation [10], hydrothermal
potentially applicable in room temperature ultraviolet lasing [4], process [11], microemulsion growth [12], chemical vapor deposi-
blue-ultraviolet (UV) light emission [5], photocatalysts [6], eld tion (CVD) [13], and metal-organic CVD [14] have been applied to
emissions [7], and fabrication of piezoelectric transducers, actua- grow 1D ZnO nanostructures. Nevertheless, most of these meth-
tors [8], and solar cells [9]. However, the performance of devices ods suffer from two shortcomings: rstly, they require extreme
conditions and expensive equipment; and also they are not suit-
able for controllable synthesis. Thus, developing room temperature
Corresponding author. Tel.: +60 4 5995255; fax: +60 4 5941011. approaches for fabricating 1D nanostructures of ZnO still remains
E-mail address: srimala@eng.usm.my (S. Sreekantan). a challenge.

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

In this paper, we describe a room temperature electrochemi-


cal process for preparing 1D nanostructure via anodic deposition
of a zinc foil in NaOH. Anodic deposition is a process that com-
bines simplicity, cost-effectiveness, and ease in morphology control
[1517]. This paper will further describe a comprehensive experi-
mental setup on the anodic deposition process for the construction
of 1D ZnO nanostructures such as nanoneedles, nanoowers, and
nanoakes by simply varying electrochemical deposition condi-
tions, mainly the time of deposition and the concentration of the
electrolyte. After considering the mechanistic model of the ZnO
formation via anodic deposition, a separate experiment was con-
ducted to investigate the effect of adding zincate (Zn(OH)4 2 ) to
the oxide structure on the Zn foil. Finally, the effect of surface treat-
ment of the foil before deposition was investigated to explore its
effect on the formation of ZnO nanostructures.

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 ).

3. Results and discussion

3.1. Phase and crystallinity of the deposit

Anodic deposition of ZnO initially occurs through the dissolution


of Zn in a NaOH solution [18]. This will lead to the formation of
a zinc ion complex which will be deposited onto the surface of
the anode. The process of dissolution of Zn and the formation of
the complex is related to the current density applied to the anode
and on the pH of the solution [1519]. The complex may be in the
form of zincate. In this study, the reaction sequence is proposed
after considering the morphology of the oxide formed at different
experimental parameters.
Fig. 1 shows the FESEM micrograph of the sample prepared at Fig. 2. EDX spectrum of ZnO nanoneedles.
8.33 mA/cm2 current density in 4.0 M NaOH solution for 60 min.
The condition is chosen based on our preliminary studies which
indicated that successful deposition can be produced when current
density is maintained around this value. As illustrated in Fig. 1, the
formation of the nanostructured deposit can be seen, which at this
point is speculated to be ZnO.
The nanostructure is in the form of nanoowers which upon
closer examination can be seen to consist of a bundle of
nanoneedles (the inset micrograph in Fig. 1) growing at random
orientations. Such morphology covers the entire surface of the foil.
The length of the ower petal is between 500 and 700 nm. Aver- Fig. 3. XRD pattern of the foil anodized with a current density of 8.33 mA/cm2 in
age base diameter of the nanoneedles is 100 nm and the tip is 4.0 M NaOH for 60 min.
S. Sreekantan et al. / Journal of Alloys and Compounds 476 (2009) 513518 515

Fig. 4. Typical FTIR spectrum of the nanoowers.

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

To investigate the effect of reaction time on the formation of the


nanoower, current density was xed at 8.33 mA/cm2 and elec-
trolyte molarity was set to 4 M while deposition times were varied
from 15 to 60 min. Fig. 6a and b shows the nanostructures formed
on the zinc foil at 15 and 30 min, respectively. Fig. 6 also provides
a summary of the possible mechanism of the formation of ZnO
nanostructures during deposition. Initially, at the rst 15 min, there
was a formation of small ZnO particles with a diameter of 40 nm
deposited on the foil. The inset in Fig. 6a shows the presence of
spherical-shaped nanoparticles. After 30 min, it was noticed that
the ZnO particles grew to form nanoneedles, which were arranged
in unidirectional and aligned positions. The inset in Fig. 6b shows
the mechanically fractured surface, indicating that the length of the
nanoneedles formed is approximately 300 nm. When the deposi-
tion time was prolonged to about 60 min, the nanoneedles grew
Fig. 5. PL spectrum of ZnO nanoneedles with (a) self-aligned structure and (b)
longer (500700 nm) and nally formed a ower-like structure
ower-like structure. (Fig. 1). The thickness of the deposition at 15 and 30 min was 0.03
516 S. Sreekantan et al. / Journal of Alloys and Compounds 476 (2009) 513518

and 0.4 m, respectively. Based on this observation, the reaction


process can be expressed as follows [17]:

Zn Zn2+ + 2e

Zn2+ + 2OH Zn(OH)2 (p)

Zn(OH)2 + 2OH (aq)

Zn(OH)4 2 (aq) ZnO(p) + 2H2 O(aq) + 2OH

At the initial stage of the reaction, ZnO spontaneously nucleated


from the Zn(OH)4 2 solution to form nanoparticle on the Zn foil. The
formed ZnO nanoparticles are expected to be the building blocks in
the formation of nanoneedles and nanoowers. Wahab et al. pub-
lished an explanation on nanoower formation [20] and stated that
the radius of a newly formed nanoparticle increases linearly with
Fig. 7. FESEM micrograph of the annealed zinc foil anodized in 4.0 M NaOH with
reaction time after particle formation. As the new particle grows,
Zn(NO3 ) addition with a current density of 8.33 mA/cm2 . (The inset micrograph is
there is an increase in the phase boundaries and the particles even- at a magnication of 50,000 shows the presence of coarse aky type ZnO.)
tually touch one another, thus forming the base structure of the
self-aligned nanoneedle. Once the base is formed, the growth rate
begins to decrease along the transverse direction and the growth
in the radial direction continues to form nanoowers, with the top
surface being the energetically favored surface.

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
ide ions (2 M) concentration through which denser lms are formed
[1] B. Oregan, M. Gratzel, Nature 353 (1991) 737.
(Fig. 8c). [2] M. Guo, P. Diao, S. Cai, Appl. Surf. Sci. 249 (2005) 71.
[3] W.J. Lee, A. Suzuki, K. Imeda, H. Okada, A. Wakahara, A. Yoshida, Jpn. J. Appl.
3.4. Effect of surface treatment Phys. 1 43 (2004) 152.
[4] M.H. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind, E. Weber, R. Russo, P. Yang,
Science 292 (2001) 1897.
It is worth noting that most of the ZnO nanostructures formed [5] J. Johnson, H. Yan, P. Yang, R. Saykally, J. Phys. Chem. B 107 (2003) 8816.
from the zinc surface without any surface treatment resulted in a [6] B. Pal, M. Sharon, Mater. Chem. Phys. 76 (2002) 82.
[7] X.D. Bai, E.G. Wang, P.X. Gao, Z.L. Wang, Nano Lett. 3 (2003) 1147.
non-uniform structure with varying thickness due to the heteroge-
[8] X.Y. Kong, Z.L. Wang, Nano Lett. 3 (2003) 1625.
neous nucleation of air-formed native oxide. Hence, in the following [9] M. Law, L.E. Greene, J. Goldberger, J.C. Johnson, R.J. Saykally, P. Yang, Nat. Mater.
set of experiments, the foils have been etched in a solution of 5% 4 (2005) 455.
HCl for 30 s followed by annealing in a furnace at 190 C for 3 h [10] A. Umar, S.H. Kim, J.H. Kim, A. Al-Hajry, Y.B. Hahn, J. Alloys Compd. 463 (2008)
516.
prior to anodization to purposely form a thin ZnO layer with thick- [11] J.M. Jang, C.R. Kim, H. Ryu, M. Razeghi, W.G. Jung, J. Alloys Compd. 463 (2008)
ness 0.2 m (Fig. 9) on the Zn before deposition. Fig. 10 shows 503.
the SEM micrograph of the foil anodized with a current density of [12] L. Guo, Y.L. Ji, H.B. Xu, P. Simon, Z.Y. Wu, J. Am. Chem. Soc. 124 (2002) 14864.
[13] C.L. Wu, L. Chang, H.G. Chen, C.W. Lin, T.F. Chang, Y.C. Chao, J.K. Yan, Thin Solid
1.0 mA/cm2 in 6.0 M NaOH for 60 min. It resulted in well-aligned Films 498 (2006) 137.
nanorods (inset in Fig. 10) which uniformly covered the substrate [14] J.Y. Park, H. Oh, J.J. Kim, S.S. Kim, J. Cryst. Growth 287 (2006) 145.
518 S. Sreekantan et al. / Journal of Alloys and Compounds 476 (2009) 513518

[15] F.F. Wang, R. Liu, A. Pan, L. Cao, K. Cheng, B. Xue, G. Wang, Q. Meng, J. Li, Q. Li, Y. [20] R. Wahab, S.G. Ansari, Y.S. Kim, H.K. Seo, G.S. Kim, G. Khang, H.S. Shin, Appl.
Wang, T. Wang, B. Zou, Mater. Lett. 61 (2007) 2000. Surf. Sci. 253 (2007) 7622.
[16] C. Lin, H. Lin, J. Li, X. Li, J. Alloys Compd. 462 (2008) 175. [21] D.M. Bengal, Y.F. Chen, Z. Zhu, T. Yao, Appl. Phys. Lett. 70 (1997) 2230.
[17] X. Wu, G. Lu, C. Li, G. Shi, Nanotechnology 17 (2006) 4396. [22] B.K. Choi, D.H. Chang, Y.S. Yoon, S.J. Kang, J. Mater. Sci. 10854 (2006) 9036.
[18] J. Zhao, Z.G. Jin, T. Li, X.X. Li, Appl. Surf. Sci. 252 (2006) 8287. [23] M. Izaki, T. Shinagawa, H. Takahashi, J. Phys. D Appl. Phys. 39 (2006) 1481.
[19] S.H. Yi, S.K. Choi, J.M. Jang, J.A. Kim, W.G. Jung, J. Colloid Interface Sci. 313 (2007) [24] M. Izaki, S. Watase, H. Takahashi, Appl. Phys. Lett. 83 (2003) 4930.
705.