414 Current Nanoscience, 2012, 8, 414-416

Preparation of ZnO Microstructures by Facile Hydrothermal Route, Their PL and

PEC Properties

Sajad Hussain, Chuanbao Cao*, Ghulam Nabi, Waheed S. Khan, Zahid Usman, Faheem K. Butt, Zulfiqar Ali
and Tariq Mahmood

Research Centre of Materials Science, Beijing Institute of Technology, Beijing 100081, People’s Republic of China

Abstract: ZnO flower like and doubly pointed microneedles (DPNs) were prepared on Cu2O and glass substrates respectively via facile
hydrothermal route. Cu2O substrate was prepared through thermal oxidation method from the Cu sheet. The structure and morphologies
of ZnO microstructures were characterized by X-ray diffraction and scanning electron microscopy. The average size of flower-like struc-
ture was measured to be 2 μm, whereas the doubly pointed microneedles (DPNs) exhibited a tip diameter of 150-250 nm. The flower-like
ZnO microstructures showed the photoluminescence emission spectra UV band at 383 nm along with a strong yellow emission band at
580 nm. Correspondingly, the DPNs ZnO microstructure showed UV emission peak at 396 nm associated with a blue emission peak at
469 nm. The photon-to-hydrogen efficiency was found to be 0.04% for flower like microstructure.
Keywords: Double pointed microneedles, flower like, hydrothermal process, luminescence, PEC solar cells, ZnO microstructures.

1. INTRODUCTION
One-dimensional nano-/microscale materials are attractive ex-
tensively due to their outstanding physical properties, which have
lead to their potential applications in nano-/microdevices. It is pre-
dicted that the piezoelectricity, photon-to-electron conversion effi-
ciency and photonic performance would be improved by reducing
the dimensions of ZnO due to an increase in the surface area and
the quantum captivity effect. Owing to their possible application,
ZnO nano-/microcrystals with different morphologies and function-
alities (nanolasers, piezoelectric nanogenerators, solar cells, gas
sensors and photocatalysts) have been prepared by different meth-
ods such as vapor phase transport [1], hydrothermal process [2],
chemical solution [3], metal-organic CVD [4] and chemical vapor
deposition [5]. The chemical solution method has been used to syn-
thesize ZnO nanostructures such as tube, tower, Tetrapods, needle
like [6, 3, 7, 8] and oriented helical ZnO nanorod arrays [9]. In light
,photoelectrochemical (PEC) cells have ability to split water into
hydrogen and oxygen. Such cells can be used as photo electrodes in
aqueous electrolytes. Previously ZnO nanorods have been grown on
ITO substrate to fabricate PEC and photovoltaic solar cell (p-
Cu2O/n-ZnO) by electrochemical deposition [10].
For the first time, we have prepared ZnO micro flowers and
DPNs grown on the Cu2O and glass substrate respectively via hy-
dro-thermal method. It is predicted that the solar cell fabricated on
Cu2O substrate via thermal oxidation method would show better
solar efficiency due to high charge carrier concentration of substrate
used. We have also measured the PEC property of flower like mi-
crostructures. Furthermore, only two precursors are used in this
scheme, which can effectively avoid the contaminations frequently
observed in other complicated chemical reactions.
2. EXPERIMENTAL
In order to prepare the flower-like microstructures and DPNs on
Cu2O and glass substrate respectively, equimolar (50mM) and
equimass ratio (0.5gm) of Zn(NO3)2·6H2O and C6H12N4 were used.
The seeding layer of 5 mM zinc acetate in ethanol [11] was pre-
pared on Cu2O substrate. The Cu2O substrate was placed vertically
in beaker and glass substrate was positioned at the bottom in
*Address correspondence to this author at the Research Centre of Materials
Science, Beijing Institute of Technology, Beijing 100081, People’s Republic
of China; Tel: +86 10 6891 3792; Fax: +86 10 6891 2001;
E-mail: cbcao@bit.edu.cn (Chuanbao Cao)
autoclave. Both the substrates were kept in regular laboratory oven
at 93 °C for 4 hrs, and then allowed to cool down to room tempera-
ture. The Cu2O substrate was prepared by oxidizing approximately
1 μm thick copper sheet in muffle furnace at 1000 °C for 4 hours
[12].
The phase purity of the products was examined by X-ray pow-
der diffraction (XRD, Philips X'Pert Pro MPD) whereas the mor-
phologies were determined by scanning electron microscopy (FE-
SEM Hitachi S4800). Photoluminescence properties at room tem-
perature were studied using PL spectrum with Fluorescence Spec-
trophotometer (Hitachi F-4500). The PEC measurements were car-
ried out on a potentiostat (ZAHNER IM6e) in a three-electrode cell
with light intensity of 90 mW/cm2.
3. RESULTS AND DISCUSSION
3.1. Structural and Morphological Characterization
Fig. (1a and b) show the XRD pattern of the flower-like and
DPNs like microstructures, respectively. In the inset of Fig. (1a)
most of the diffraction peaks of the spectrum with 2
values of
42°.31, 61°.36 and 43°.32, 50°.49 are indexed to the Cu2O and Cu
substrate respectively. In Fig. (1a), all the peaks are indexed to
typical hexagonal wurtzite ZnO, with calculated cell parameters
a=3.2435 Å and c=5.1989 Å for the flower like except Cu2O and
Cu peaks resulting from the substrate. In Fig. (1b), the lattice pa-
rameters for DPNs are a=3.25 Å and c=5.2159 Å consistent with
the standard values for bulk ZnO (JCPDS card No. 01-089-0511).
The higher intensity of ZnO (0 0 2) peak in flower like microstruc-
ture strongly suggests its formation along c-axis. But in DPNs no
sharp diffraction of ZnO along (002) plane is detected, which may
be related to the fact that most DPNs are grown parallel to the sub-
strate and their growth direction is not along (0 0 2) plane as previ-
ously reported [13]. In the XRD of both morphologies, sharp dif-
fraction peaks have indicated good crystallinity of the prepared
crystals and no diffraction peaks from mineral such as Zn(OH)2 or
impurities were detected.
Typical SEM images shown in Fig. (2a-c) present a large num-
ber of ZnO flower-like microstructures dispersed on Cu2O sub-
strate. ZnO flower-like microstructures consist of numerous straight
microrods emerging out radially from one central point having
thickness of 100-200 nm with an average length of 1 μm. The aver-
age size of the flower lies within the range of 2 μm. The magnified
image 2(c) exhibits that microrods with circular cross section, but

1875-6786/12 $58.00+.00 © 2012 Bentham Science Publishers

Preparation of ZnO Microstructures by Facile Hydrothermal Route
Fig. (1). (a) Shows the typical XRD of ZnO flower-like microstructures, the
inset Cu2O (b) shows the XRD of ZnO DPNs.
their diameter is not uniform along their length. Moreover the tip of
flower like microstructures is not sharp like DPNs. Fig. (2d-f) indi-
cates small, medium and high magnification images of ZnO DPNs
grown on glass substrate. The microneedles are isolated from each
other and their average length is 5–6 μm. The tips at both ends of
the DPNs are very sharp with an average diameter of 150-250 nm.
The diameter of tips is almost two and half times less than the di-
ameter of the rod at the centre. These microrods are very long due
to the high concentration of precursors.
3.2. Growth Mechanism
To describe the growth mechanism, the chemical reaction con-
tains cation Zn2+ and anion OH- , these play an important role for
the conversion of Zn(OH)2 into ZnO nuclei as described in the fol-
lowing reactions [14].

the valance band [18]. This is strong evidence that the concentration

Zn 2+ + 2OH
 Zn (OH )2 (1)
Zn (OH )2
ZnO + H 2 O (2)
If the concentration of ZnO nuclei increases, they arrange them-
selves in a flower-like structure, due to low surface energy. The
hexagonal microrods with six definite facets appear to maintain the
minimum surface energy as to keep the symmetry of the crystal
structure (wurtzite ZnO). The radii of newly formed crystal increase
linearly with the passage of time after nuclei formation. As the
fresh crystals grow, due to increase in boundaries they attach with
each other, forming the base of structure. The Zn+ is catalytically
active while the O - is inert [15]. So the top surface is energetically
active as compared to the bottom surface. That helps in growing the
flower like structures transverse to the Cu2O substrate.
Current Nanoscience, 2012, Vol. 8, No. 3 415
Fig. (2). (a-c) show low, medium and high magnification SEM images of
ZnO flower-like microstructures whereas 2(d-f) exhibit low, medium and
high magnification images of ZnO doubly pointed microneedles.
The freshly formed ZnO nuclei in the solution are highly reac-
tive and provoke the growth of larger particles. When the ZnO nu-
clei are formed, a very rapid root growth of microrods occurs. After
achieving the certain length of the microrods, the growth process
stops due to the complexity in material transfer to the tip of the
microrods [16] and finally DPNs are formed.
3.3. Photoluminescence Properties
Fig. (3a) and (b) show the room temperature photolumines-
cence (PL) spectrum of ZnO flower-like and DPNs microstructures,
which indicate a UV emission band at 383 nm and 396 nm respec-
tively. The UV emission (or NBE) may originate from free exci-
tonic emission in the ZnO materials [17], as ZnO has a high exci-
ton-binding energy of 60 meV at room temperature. In flower-like
microstructures a strong and broad yellow emission band occurs at
580 nm, which is generally attributed to the recombination of elec-
trons in the oxygen vacancies (Vo) with the photo-excited holes in
of oxygen vacancies is sufficient in flower like microstructures.
In the case of doubly pointed microneedles weak blue emission
at 469 nm is observed, which is also previously reported [2]. This
weak peak in the blue band arises due to electron transition from
the ionized oxygen vacancy level to the valence band [13].
3.4. PEC Characterization
Fig. (4) shows PEC response of flower like microstructure. The
electron–hole pairs are generated by the absorption of photons with
energies greater than the band gap of ZnO and depleted by the elec-
tric field of the depletion region. The excited electrons move
through bulk region to the counter electrode where reduction takes
place. The generated holes move towards semiconductor/electrolyte
interface where water oxidation occurs. The flower like microstruc-
tures provides high surface area and superior carrier transport along
416 Current Nanoscience, 2012, Vol. 8, No. 3
Fig. (3). Shows the room-temperature PL emission spectrum of (a) ZnO
flower-like microstructures (b) Doubly pointed microneedles.
Fig. (4). Shows the Photocurrent-voltage curve of flower like microstruc-
ture.
the c-axis, leading to the increased interfacial reaction sites as com-
pared to thin films. As a result, the PEC performance of the flower
like microstructures is greatly enhanced. The water splitting have
been observed at an applied potential of +0.8 V and active area of
PEC solar cell is 0.25cm2 resulting in a photon-to-hydrogen effi-
ciency of 0.04%.
CONCLUSION
In summary, ZnO microstructures with interesting morpholo-
gies have been successfully prepared at large scale by a simple
aqueous approach that only involves the reaction of zinc nitrate
hexahydrate in the presence of methenamine at 93°C for four hours.
Room-temperature PL spectra shows UV emission band at 383 nm
along with yellow emission at 580 nm for ZnO flower-like struc-
tures and UV emission at 396 nm with blue emission at 469 nm for
ZnO DPNs. These optical characteristics indicate that ZnO micro-
structure might have potential application in photovoltaic and PEC
solar cells.
Received: March 23, 2011 Revised: October 28, 2011 Accepted: January 13, 2012
Hussain et al.
CONFLICT OF INTEREST
None declared
ACKNOWLEDGEMENT
This work was supported by National Natural Science Founda-
tion of China (20471007
50972017) and the Research Fund for
the Doctoral Program of Higher Education of China
(20101101110026).
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