Materials Letters 93 (2013) 52–55

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Facile and fast synthesis of flower-like ZnO nanostructures

Parthiban Ramasamy, Jinkwon Kim n
Department of Chemistry and GETRC, Kongju National University, 182 Singkwan, Kongju, Chungnam 314-701, Republic of Korea

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

Article history: A fast and facile method has been developed to synthesise flower-like ZnO nanostructures at room
Received 8 October 2012 temperature without using any capping agent. ZnO nanoflowers could be easily prepared by adding
Accepted 11 November 2012 ethanol to the precursor solution having higher concentration of hydroxide ions. The amount of ethanol
Available online 20 November 2012
plays an important role in the formation of ZnO nanoflowers. The products were characterized by field
Keywords: emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and transmission electron
ZnO microscopy (TEM). The room-temperature photoluminescence (PL) spectrum of the sample consists of
Flower-like near-band edge emission at  385 nm as well as a strong and broad green–yellow emission band due to
Nanocrystalline materials the presence of defect states in the sample. A reasonable growth mechanism is also proposed for the
Photoluminescence
formation of flower-like ZnO nanostructures.
& 2012 Elsevier B.V. All rights reserved.

1. Introduction without using any external capping agent is hardly available in

Nanostructured zinc oxide (ZnO) an exceptionally important
semiconductor materials to study due to its attractive physical
properties such as wide band gap (3.37 eV) and large exciton
binding energy (60 meV) at room temperature [1]. Because of its
unique optical and electrical properties it has potential applica-
tions in UV lasers [2], light-emitting diodes (LED) [3], field-effect
transistors [4], solar cells [5], and sensors [6]. The tremendous
interest in ZnO is due to its unique ability of possessing structure-
dependent properties. Therefore, the design and synthesis of ZnO
nanomaterials with different structures are very important. In
recent years, ZnO nanostructures with diverse morphologies such
as nanowires [7], nanotubes [8], nanorods [9], nanodisks [10], and
3D hierarchical architectures [11] have been synthesized via
various techniques. Among these hierarchical architectures, 3D
ZnO nanostructure that consists of 1D and 2D ZnO nanoscale
building blocks has attracted much attention since the structure
is often associated with a large surface area which is highly
desirable for solar cell, photocatalysis and gas sensing applica-
tions. The most common methods to synthesize ZnO nanostruc-
tures fall into either vapor-phase synthesis [12–14] such as
chemical vapor deposition (CVD), vapor–liquid–solid (VLS)
growth, and thermal evaporation or solution-phase synthesis
[15–17] like hydrothermal, sol–gel processes and microemulsion.
Among these solution-phase techniques are simple and cost
effective. Most of the solution based techniques require capping
agents, high temperature and higher growth time. The room-
temperature (RT) synthesis of hierarchical ZnO nanostructures
the literature.
In this work, we report a facile way for the fast synthesis of
ZnO nanoflowers at room temperature without using any capping
agent. The morphology and optical properties of the as-prepared
ZnO sample have been investigated by using XRD, SEM, TEM,
Raman and PL spectroscopy. The possible reaction mechanism for
the formation of flower-like ZnO nanostructure is proposed.
2. Experimental
All reagents used in the experiment were of AR grade and ultra
pure water (18 MO cm) was used throughout the process. In a
typical procedure to synthesize flower-like ZnO nanostructures,
0.2 g of Zn(NO3)  6H2O was dissolved in 15 mL of water and to this
0.8 g of NaOH in 10 mL of water was added slowly under constant
stirring. After stirring for 5 min at room temperature, 100 mL of
ethanol was added slowly and stirred for further 5 min. The final
white precipitate was separated by centrifugation, and washed with
water and ethanol several times and dried in vacuum.
The products were characterized by field emission scanning
electron microscopy (FE-SEM, Hitachi S-4800 UHR), Transmission
electron microscopy (TEM,), energy-dispersive X-ray analysis
(EDS, Tecnai G2F30), X-ray diffraction (XRD, Rigaku D/MAX-
2000). Raman spectrum and Photoluminescence (PL) measure-
ments were carried out on a Jobin Yvon-Labram spectrometer
using He–Cd laser (lex ¼ 325 nm) as excitation source.
3. Results and discussion

n
Corresponding author. Tel.: þ82 41 850 8496; fax: þ82 41 856 8613. Fig. 1 shows the FESEM images and XRD pattern of the
E-mail address: jkim@kongju.ac.kr (J. Kim). as-prepared ZnO nanostructures. A low-magnification view

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.11.042
 P. Ramasamy, J. Kim / Materials Letters 93 (2013) 52–55
Fig. 1. FESEM images and XRD pattern of ZnO nanoflowers synthesized at room-temperature for 5 min: (a) low magnification FESEM image (b, c) high-magnification
FESEM images and (d) XRD pattern.
(Fig. 1a) shows the high yield and uniformity of the synthesized
products. The magnified SEM images in Fig. 1b and c show that the
morphology of ZnO product is well-defined flower-like hierarchical
structure. The diameters of the flowers are around 1 mm, assembled
by many nanosheets as ‘‘petals’’. XRD characterization (Fig. 1d)
indicated that as synthesized flower-like structures, consisted of
pure hexagonal ZnO with wurtzite structure (JCPDS card no. 36-
1451). The flower-like ZnO nanostructures were further confirmed
by TEM results. The typical TEM image (Fig. 2a) confirms the
flower-like ZnO structure with diameter around 1 mm, which
consisted of large number of nanosheets. The corresponding
HRTEM image (Fig. 2b) confirmed that the nanoflowers are well
crystalline in structure and the spacing between two lattice planes
is 0.19 nm, can be ascribed to the adjacent (102) planes of wurtzite
ZnO phase. The chemical stoichiometry of the obtained ZnO nano-
flowers is further confirmed with the EDS method. Fig. 2c shows the
typical EDS spectrum which consists of only O and Zn elements,
confirming the formation of pure ZnO. Fig. 3 shows the FESEM
images of the products obtained from different volume ratios of
H2O and EtOH. From Fig. 3, one could find that the volume of
ethanol added plays a key role in the formation of ZnO nanoflowers.
In the absence of ethanol the reaction took more than 5 h to form
ZnO and the products appear as rhombus-shaped ZnO particle. The
flower-like ZnO started to form when the ratio of H2O:EtOH is 1:3,
shown in Fig. 3d. On increasing the ratio to 1:4, the flower-like ZnO
structures formed (Fig. 3e). The as synthesized ZnO samples were
nanograined and contained the well developed free surfaces and
grain boundaries. It has been shown that the presence of defects
such as grain boundaries have strong influence in the physical
properties of nanograined ZnO [18,19].
Based on the above results the formation mechanism of ZnO
nanoflowers can be explained as follows. Two kinds of reaction
can take place in alkali solutions. The initial reaction between
Zn(NO3)  6H2O and NaOH leads to the formation of ZnO22  by
Eq. (1) and that these anions then further react with water to give
ZnO nuclei by Eq. (2). As we all know, ZnO is an amphoteric
compound, which can be dissolved in acid or alkali solution.
53
When the Zn2 þ /OH  molar ratio is 1:20, the ZnO can be dissolved
in highly concentrated NaOH solution by Eq. (2), in which the
chemical equilibrium tends to proceed towards the left. The
reaction can readily be shifted to the right by deactivation of
OH  in Eq. (2) using ethanol solvent.
Zn2 þ þ4OH  - ZnO22  þ2H2O (1)
ZnO22  þH2O $ ZnO þ2OH  (2)

Ethanol can effectively shield the OH of Eq. (2) by forming
solvent cages [20], which reduce the OH  activity in the reaction
and favor the formation of ZnO. When there is sufficient amount
of ethanol to mask the activity of OH  , more ZnO nuclei would
form and aggregate together. After that, due to Ostwald ripening
more and more spherical sub-micrometer particles were pro-
duced at the cost of nano-aggregations [21]. Because of the
intrinsic anisotropic character of hexagonal ZnO, the aggregated
nanoclusters would rearrange themselves and orientedly attach
along the c-axis to each other to decrease the energy of the
system [22]. Further it is speculated that each nanocluster in
the nano-aggregations grew preferentially along its c-axis during
the reaction which results in flower-like ZnO nanostructures.
ZnO crystal exhibits the hexagonal wurtzite structure, which
belongs to the space group C46V. According to the selection rules of
phonon resonance modes, Raman-active modes for wurtzite ZnO are
A1 þ2E2 þE1 [23]. The Raman spectrum of ZnO nanoflowers is shown
in Fig. 4a. A dominated and strong intensity peak at 440 cm  1 is
attributed to the E2 mode of the non-polar optical phonons. The peak
at 333 cm  1 is attributed to the 2E2 mode. The peaks at 388 and
585 cm  1 correspond to the polar transverse A1 and longitudinal E1
optical phonon mode, respectively. In general, the E1 (LO) mode is
associated with the structural defects such as oxygen vacancies and
zinc interstitials in ZnO [23,24]. The room temperature PL spectrum
of the ZnO nanoflowers is shown in Fig. 4b. The PL spectrum shows a
sharp UV emission peak around 385 nm and broad green–yellow
peak centered at 586 nm. The UV emission is usually attributed to
recombination of free excitons, that is, near band-edge emission [25].
54 P. Ramasamy, J. Kim / Materials Letters 93 (2013) 52–55

Fig. 2. (a) TEM (b) HRTEM images and (c) EDS spectrum of ZnO nanoflowers.

Fig. 3. FESEM images of the samples synthesized at different volume ratios of H2O/EtOH: (a) 1:0 (b) 1:1 (c) 1:2 (d) 1:3 (e) 1:4 and (f) 0:1.

The broader visible emission peak originates from defect-state interstitials (Oi) in ZnO, and it may also be associated with oxygen
luminescence. It is known that the yellow emission is associated adsorbed in ZnO grain boundaries, which can also act as an electron
with electron acceptor defects such as Zn vacancy (VZn) or O acceptor [26].
 P. Ramasamy, J. Kim / Materials Letters 93 (2013) 52–55
Fig. 4. (a) Raman spectrum and (b) room temperature PL spectrum of the as synthesized ZnO nanoflowers.
4. Conclusion
A facile and fast method has been developed to fabricate
uniform flower-like ZnO nanostructures at room temperature.
Ethanol was used to precipitate ZnO from the precursor solution
having high concentration of hydroxide ions. The amount of
ethanol added plays an important role in the formation of ZnO
nanoflowers. XRD pattern and Raman measurement confirm that
the products have good crystallinity with hexagonal wurtzite
phase. From the experimental results, a possible formation
mechanism of the ZnO nanoflowers was proposed. The room-
temperature photoluminescence spectrum of the sample shows a
near-band edge emission at  385 nm and a broad defect related
emission around 586 nm.
Acknowledgment
The authors gratefully acknowledge financial support from the
Priority Research Center Program (2012-0006682), the Basic
Science Research Program (2012R1A1A2043731) and the Human
Resource Training Project for Regional Innovation through the
National Research Foundation of Korea.
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