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Materials Chemistry and Physics 115 (2009) 172–178

Contents lists available at ScienceDirect

Materials Chemistry and Physics


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

Synthesis of assembled ZnO structures by precipitation method in


aqueous media
S. Sepulveda-Guzman a,b,∗ , B. Reeja-Jayan c , E. de la Rosa d , A. Torres-Castro a,b ,
V. Gonzalez-Gonzalez a,b , M. Jose-Yacaman e
a
Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, UANL Km. 10 de la nueva carretera al Aeropuerto Internacional de Monterrey,
PIIT Monterrey, Apodaca NL, Mexico
b
Facultad de Ingeniería Mecánica y Eléctrica de la UANL, Ciudad Universitaria San Nicolás de los Garza, Nuevo León C.P. 66451, Mexico
c
Texas Materials Institute, The University of Texas at Austin, 1 University Station C0803, USA
d
Centro de Investigaciones en Óptica, A.C. Loma del Bosque #115 Col. Lomas del Campestre, León Gto. C.P. 37150, Mexico
e
Physics and Astronomy Department, University of Texas at San Antonio, 1604 Campus San Antonio, TX 78249, USA

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

Article history: In this work, arrays of submicron ZnO structures were successfully synthesized using a one-step
Received 5 August 2008 aqueous precipitation method. Snowflake-like and flower-like morphologies were obtained by chang-
Received in revised form 15 October 2008 ing the reaction temperature. X-ray diffraction (XRD) patterns indicated that the ZnO arrays have a
Accepted 16 November 2008
wurtzite crystal structure. A possible growth mechanism based on the analysis done by scanning elec-
tron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron
Keywords:
microscopy (HRTEM), and high-angle annular dark field (HAADF) is proposed. Our findings suggest that
Zinc oxide
the growth mechanism of the ZnO arrays is by self-aggregation, and that such an oriented aggregation is
Microstructure
Nanomaterials
enhanced by increasing the reaction temperature. The results also revealed that the aggregation process
Chemical growth introduces several structural defects such as differences in mass distribution and crystalline structure.
In order to study the surface chemical composition the samples were also characterized by XPS. The
results showed the presence of Zn(OH)2 and absorbed carbon species on the ZnO surface. In addition, the
photoluminescence characterization showed that on UV excitation ( = 360 nm) all samples present the
characteristic UV emission centered at 390 nm, and for the sample synthesized at 60 ◦ C, a visible emission
was also observed.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction properties of nanowires are modified by varying morphological fac-


tors such as diameter and length. On the other hand, the design of
Zinc oxide (ZnO) is a direct band gap semiconductor with a structures by the assembly of nanoparticles has also received great
room temperature wide band gap of 3.37 eV and a large excitonic attention in recent years because their resulting properties depend
(electron–hole) binding energy of 60 meV, larger than the thermal on their microstructure, morphology and surface. Branched struc-
energy at room temperature (26 meV). In addition, ZnO is biocom- tures are also very important because of the increased number of
patible, and can be used in bio-applications without coating [1]. connection points, providing a means for parallel connectivity and
These properties make ZnO an interesting material with poten- interconnection of functional elements in applications like solar
tial applications such as sensors [2], UV lasers [3], piezoelectric cells. Higher conversion efficiencies have recently been reported
[4], luminescent phosphor, photonic crystals [5], and photovoltaics for dye sensitized solar cells when flower-like ZnO particles were
[6]. A lot of research has been conducted on tuning the electrical used as electrode material [9]. In addition, the process of assem-
and optical properties of ZnO. Sadhu et al. studied the doping of bly of structures allows the study of several growth mechanisms,
ZnO with rare earth ions such as Eu3+ in order to produce white such as the self-aggregation processes in ZnO structures, which
light emission, but also observed that the optical properties were are difficult to elucidate in isolated particles [10]. Several methods
altered by changing morphological parameters such as particle size like chemical vapor deposition (CVD) and physical vapor deposi-
and shape [7]. Chang et al. [8] also reported that photoluminescence tion (PVD) have been developed to assemble ZnO nanoparticles
into complex structures such as flower-like and web-like agglom-
erates [11–13]. However, in order to obtain the final structure
∗ Corresponding author. these methods usually require multiple steps, high temperature and
E-mail addresses: ssepulveda@mail.uanl.mx, selenura@gmail.com sophisticated equipment. In contrast, low-temperature wet chem-
(S. Sepulveda-Guzman). ical processes such as precipitation, hydrolysis, and hydrothermal

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.11.030
S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178 173

process are cost-effective and scalable and have been used in the
synthesis of a wide variety of ZnO nanostructures. The precipitation
method in particular has been successfully used to design differ-
ent structures of ZnO. Kawano et al. [14] observed a change in the
growth mechanism when the preparation method changed from
acidic to basic route. One-dimensional nanoparticles (rods) were
prepared by changing the addition sequence of reagents. The con-
trolled growth of ZnO structures by the assembly of particles has
also been reported using a precipitation method assisted by poly-
mers or surfactants [15–17]. In addition, arrays of tower-like and
tube-like ZnO structures have also been synthesized by wet chem-
ical methods. However, in order to obtain such structures a harsh
process was required [18]. The effect of reaction parameters such
as pH and reaction time on morphology has also been elucidated
[19–21]. Nevertheless, the synthesis of assembled ZnO structures in
large volumes using simpler and economical wet chemical meth-
ods is still a challenge. In this work we prepared ZnO assemblies
by a wet chemical approach without any template or surfactant.
The morphology of the assembled ZnO structures was modified by
the change of reaction temperature. In addition, structural char-
acterization of the synthesized assemblies was studied by X-ray
diffraction (XRD), scanning electron microscopy (SEM), transmis-
sion electron microscopy (TEM) and high-angle annular dark field
(HAADF) techniques. Surface chemical composition was also ana-
lyzed by X-ray photoelectron spectroscopy (XPS).

2. Experimental Fig. 1. X-ray diffraction (XRD) patterns of the as-synthesized ZnO powders obtained
at different temperatures.
Zinc nitrate (Zn(NO3 )2 ) and sodium hydroxide (NaOH) reagents were purchased
from Aldrich and used without any purification. In a typical process 12.5 ml of 0.2 M
Zn(NO3 )2 solution was added to 25 ml of deionized water. The mixture was trans- bled ZnO structures. The morphology and the average size of the
ferred to an oil bath at the reaction temperature. Once the temperature was stabilized assemblies were very uniform in each case, as seen in the SEM
12.5 ml of 4 M NaOH solution was added immediately to the mixture under vigor-
images acquired at lower magnification (Fig. 2a, c, and e). How-
ous stirring. After the addition, the mixture was heated and stirred continuously
for 3 h. To study the effect of temperature, several experiments were carried out at ever the general morphology of the assembled ZnO structures was
60 ◦ C, 70 ◦ C and 80 ◦ C. Each experiment produced an uniform ZnO precipitate that strongly influenced by the reaction temperature. The ZnO arrays
was separated by centrifugation and washed with deionized water. The ZnO samples obtained at 60 ◦ C seem to resemble flakes growing out of a common
were analyzed by SEM using a Hitachi S-4500II operating at 10 kV. TEM, HRTEM, and
nucleus (Fig. 2b). The sample obtained at 70 ◦ C contains flower-
HAADF were performed on a Philips Tecnai F20 and JEOL 2010F at 200 kV. Samples
were dispersed in ethanol at room temperature and sonicated for 10 min. Aliquots
like structures very different from those synthesized at 60 ◦ C. The
were dropped on 3-mm diameter lacey carbon copper grids. The XRD patterns were growth pattern of the particles seems to have a preferential direc-
acquired using a SIEMENS D-5005 equipment provided with a Cu tube with K␣ radi- tion, resembling leaves sticking out of a nucleus (Fig. 2d). This
ation at 1.54 Å, scanning in the 25–75◦ 2 range with increments of 0.03◦ and a swept morphology is evident in the sample synthesized at higher tem-
time of 8 s. The samples were analyzed by XPS on a PHI 5700 system equipped with
perature (Fig. 2e), which contains more defined structures, and
dual Mg X-ray source and monochromated Al X-ray source with depth profile and
angle-resolved capabilities. The charging effect was corrected by shifting the binding the pattern of growth is similar to that obtained at 70 ◦ C (Fig. 2c).
energies, considering the C 1s signal at 284.6. Nonlinear fit, using Gaussian curves, However, the structure is formed by uniform rods with common
was performed, maintaining the full-width at half-maximum (FWHM) constant for nuclei, rather than leaf-like structures. These observations suggest
all components in a particular spectrum. The photoluminescence (PL) characteriza- that the precipitation process can be a successful method to obtain
tion was performed at room temperature on a Jovin Yvon fluorometer under 360 nm
excitation from a 75 W UV Xe lamp. The spectra were acquired from ZnO powder
different ZnO arrays under milder conditions, in contrast to those
dispersed in ethanol in a quartz cuvette. In order to correct the electronic noise obtained at longer reaction time and higher temperature [18,19].
Savitzky-Golay algorithm was applied to all spectra and finally normalized to the In addition, the average size of the resulting arrays decreased from
maximum value. 1 ␮m to 500 nm when the reaction temperature was increased from
60 ◦ C to 80 ◦ C. This might have been promoted by a higher number
3. Results and discussion of ZnO nuclei formed at the higher temperature during the pre-
cipitation process. The subsequent particle growth was restricted
Fig. 1 shows the XRD patterns of as-synthesized powders at dif- resulting in a smaller particle size. In order to study the structure
ferent temperatures, all diffraction peaks can be indexed to the and find evidence about the growth mechanism of the assembled
hexagonal phase of ZnO and agree very well to the reported data ZnO structures, analyses of HAADF, TEM and HRTEM were done.
(JCPDS 05-0664). This indicates that even the samples synthesized Fig. 3 shows the HAADF images acquired from the ZnO assemblies.
at lower temperatures have a well-defined crystalline structure. In The HAADF images show little diffraction effects, and hence con-
addition, no other peak related with impurities was detected in the tain very useful information about the chemical composition and
XRD patterns. However, differences in the relative peak intensities the mass distribution [22]. The ZnO assemblies show a heteroge-
of the diffraction pattern of the three samples were observed, which neous mass distribution according to the differences in brightness
can be associated with a particular orientation for each sample. observed in the respective HAADF images (Fig. 3). This observa-
tion is also related to some irregularities on the surface [23]. This
3.1. Morphology and structural characterization characteristic is stronger in the assembly synthesized at lower tem-
perature as was revealed by the irregular brightness in the flake-like
Fig. 2 shows the SEM images of the ZnO samples synthesized structure (Fig. 3a). The TEM images can provide details about the
at 60 ◦ C, 70 ◦ C, and 80 ◦ C revealing high-yield growth of assem- structure of the ZnO assemblies. Fig. 4 shows bright-field TEM
174 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178

Fig. 2. Scanning electron microscope (SEM) images at low and high magnifications of the assembled ZnO structures synthesized at (a and b) 60 ◦ C; (c and d) 70 ◦ C, and (e and
f) 80 ◦ C.

images of the flake-like, leaf-like and rod-like structures obtained ture (Fig. 4a). The image also shows a fairly smooth surface as was
at different temperatures. Regular fringes spaced at 0.28 nm, which previously observed by HAADF analysis, which is attributed to the
corresponds to the (1 0 0) interplanar distance are clearly visible random attachment of ZnO nanoparticles to the flake-like structure,
in the HRTEM image of the sample synthesized at lower tempera- resulting in a rough surface. This effect is less evident in the sam-

Fig. 3. High-angle annular dark field (HAADF) images of the ZnO assemblies obtained at (a) 60 ◦ C, (b) 70 ◦ C and (c) 80 ◦ C.
S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178 175

ple synthesized at 70 ◦ C. The HRTEM image clearly shows a fringe reaction temperature. This in turn changes the morphology of the
spacing of 0.513 nm and 0.283 nm which corresponds to (0 0 1) and resulting ZnO arrays formed under different reaction conditions.
(1 0 0) planes, respectively. Nevertheless, the sample synthesized at A growth mechanism is proposed in Fig. 5. During the precipi-
80 ◦ C in contrast to that synthesized at lower temperature shows tation process ZnO nuclei were produced and in the absence of
a smooth surface and the corresponding HRTEM image revealed any stabilizer agent, regular array-like structures were formed by
that the arrays are formed by crystalline rods with a lattice spac- self-aggregation process as was indicated by HRTEM analysis. This
ing of 0.287 nm, which corresponds to the (1 0 0) planes in ZnO. self-aggregation can proceed either by a randomly oriented or by a
The HRTEM image also shows that the rods grow along the [0 0 0 1] highly oriented process, as reported in several works [25,26]. In this
direction, the polar c-axis of the ZnO crystal lattice (Fig. 4f) [24]. case the oriented aggregation was highly favored by increasing the
These observations revealed that the growth mechanism of ZnO reaction temperature as was observed in the sample synthesized at
structures in aqueous solution can be modified by changing the 80 ◦ C. This either resulted from the aggregation of primary nanopar-

Fig. 4. Transmission electron microscope (TEM) images of the ZnO arrays synthesized at (a) 60 ◦ C, (b) 70 ◦ C, and (c) 80 ◦ C. High-resolution transmission electron microscope
(HRTEM) images of the structure base of the arrays obtained at (d) 60 ◦ C, (e) 70 ◦ C, and (f) 80 ◦ C.
176 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178

ples as a function of the reaction temperature. Fig. 6a, b and c shows


the XPS deconvoluted spectra for Zn 2p3/2 core level for the samples
synthesized at 60, 70 and 80 ◦ C, respectively. In all cases the peak
was deconvoluted into two peaks, the dominant peak at 1021.2 eV
is associated with the Zn2+ in ZnO wurzite structure and the weaker
peak at 1022.3 eV is associated with some zinc hydroxide species
[28,29]. The deconvolution of XPS spectra for the O 1s core level
line shows the presence of three different peaks (Fig. 6). The main
peak centered at 530.2 eV is attributed to the O 1s level in the ZnO
wurzite structure surrounded by the Zn atoms with their full com-
plement of nearest-neighbor O2− ions [30]. The peak at 531.5 eV is
associated with the O 1s in the zinc hydroxide species and agrees
very well with the O 1s binding energy in other metal hydroxides
and oxyhydroxides [31]. The peak at 532.5 eV is associated with
adsorbed or chemisorbed oxygen species such as O2 , H2 O or CO
due to surface hydroxyl groups [32,33]. This suggests that besides
chemisorbed hydroxyl species due to the polar face of ZnO, Zn(OH)2
is also present on the surface. However, the Zn(OH)2 is present
Fig. 5. Schematic representation of ZnO arrays formation by precipitation method
in aqueous solution. in low concentration and only on the surface, since no evidence
of this compound was observed by XRD. In addition, the relative
abundance of Zn(OH)2 obtained from the Zn 2p3/2 spectrum, using
ticles in an oriented mode or the particles may have first aggregated the atomic sensitive factors, indicates that the sample synthesized
randomly and then reoriented during the reaction to produce crys- at lower temperature contains a higher concentration of Zn(OH)2
talline rods. However, this process is less likely to occur at lower (11%) when compared to that synthesized at higher temperature
temperatures, in which case the randomly oriented aggregation or (8%). It is possible that during the reaction at lower temperature a
imperfect oriented attachment process promoted the incorpora- partial ZnO precipitation occurred, forming other Zinc oxyhydrox-
tion of structural defects on the ZnO as can be seen in the HRTEM ide species [34]. In addition to the Zn 2p3/2 and O 1s high-resolution
image of flake-like arrays. This observation is in agreement with spectra, C 1s core level spectrum was also acquired. The deconvo-
other reports and has been widely explained by Penn et al. [27]. lution of the C 1s peak is shown in Fig. 7. The peak at 284.6 eV is
indexed to C 1s whereas the peak at about 288.5 eV is associated
3.2. XPS characterization with C 1s of chemisorbed carbon species on the ZnO surface [30].
This observation is in agreement with the analysis of O 1s high-
XPS characterization of the ZnO arrays was performed in order resolution spectrum. The values of relative abundance for different
to investigate the variation of the chemical composition of the sam- carbon species calculated from the high-resolution C 1s spectra sug-

Fig. 6. High-resolution Zn 2p3/2 XPS spectra and high-resolution O 1s XPS spectra for the samples synthesized at different temperatures.
S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178 177

(NBG) of ZnO and is associated with the free recombination of exci-


tons. Whereas, for the arrays synthesized at 60 ◦ C besides the UV
emission centered at 390 nm a broad green visible emission cen-
tered at 580 nm is observed. The green visible emission bands in
ZnO samples has been observed before and commonly attributed
to the recombination of electrons in oxygen vacancies. The origin
of oxygen vacancies is still not fully understood. However, in this
case they could be produced by the structural defects incorporated
during crystal growth through self-aggregation process at low tem-
perature and by the presence of zinc oxyhydroxide species on the
surface of ZnO arrays which in turn creates nonstoichiometric ZnO.
These assumptions are in agreement with other reports [28,35,36]
and are in concurrence with the XPS results described before.

4. Conclusions

In this work, the assembly of submicron ZnO structures has


been demonstrated by a simple precipitation method in aqueous
medium within a considerably low reaction temperature range.
SEM analysis indicated a strong effect of the reaction temper-
ature on the morphology of the ZnO arrays. HAADF, TEM and
HRTEM analysis further clarified that morphological and structural
changes were introduced by changing the reaction temperature.
These results suggest that the growth mechanism was by self-
Fig. 7. High-resolution C 1s spectra for the sample synthesized at different temper- aggregation. These oriented and random aggregation processes
atures.
were dependent on the reaction temperature. A random aggrega-
tion process resulted in ZnO flake-like arrays with surface defects
gest that the flake-like arrays, which were synthesized at lower and a high concentration of Zn(OH)2 , which created a reactive sur-
temperature, are more likely to interact with carbon species like face as was shown by the XPS analysis. In addition, on UV excitation
dissolved carbonic anhydride present in the water or solvent used ( = 360 nm) all samples presented a UV emission peak character-
to purify the ZnO powder after reaction. This was possibly favored istic of ZnO. In addition, a visible emission band was observed for
by both the presence of Zn(OH)2 and the surface defects observed in the arrays synthesized at 60 ◦ C and it was attributed to structural
this sample during the morphological and structural analysis. XPS defects and the presence of oxyhydroxide species.
results also indicate that the ZnO arrays have a potential for use in
catalytic reactions due to the high abundance of reactive sites, pro-
Acknowledgments
moted by surface defects. However, additional studies focused on
this application must be done.
The authors wish to thank Dr. Y. Sun for XPS measurements, Dr. X.
Gao for TEM assistance and M. Ramirez for helping with sample syn-
3.3. Photoluminescence characterization
thesis. We acknowledge financial support by the Welch foundation
and the ICNAM-CIMAV program. We are also thankful to Industrias
Fig. 8 shows the room temperature photoluminescence spectra
Penoles for support this project.
for the arrays synthesized at 60, 70 and 80 ◦ C. For the arrays synthe-
sized at higher temperature, 70 and 80 ◦ C, the spectra showed a UV
emission band (390 nm) which is the characteristic near band gap References

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