Thin Solid Films 515 (2006) 1157 1160

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Spray pyrolysis deposition of zinc oxide nanostructured layers

M. Krunks , T. Dedova, I. Oja Aik
Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5, Tallinn 19086, Estonia
Available online 20 September 2006

Abstract

Highly structured ZnO layers comprising well-shaped hexagonal rods were prepared by spray pyrolysis deposition of zinc chloride aqueous
solutions in the temperature range of 490560 C. The layers were characterised by SEM, XRD and SAED. A flat ZnO film evolves into the
structured layer consisting of single crystalline hexagonal elongated prisms at growth temperatures close to 500 C and above. The rise of both the
growth temperature and solution concentration increases rod dimensions. The deposition of the 0.1 mol/l solution at 500 C results in crystals
with a diameter of 200300 nm and length of 800 nm. However, the rods grown at 560 C indicate a width in the range of 400600 nm and a
length of up to 2500 nm. The deposition of the 0.05 mol/l solution at 560 C results in the rods with a diameter of 100300 nm and a length of
1500 nm. The increase of the concentration up to 0.2 mol/l results in branched crystals, mainly tripods with a similar leg size of 600700 nm in
width and 3000 nm in length. According to XRD, the ZnO layers grown from the 0.1 mol/l solution in the temperature range of 450560 C are c-
axis-oriented, independent of morphology. The XRD peaks intensities ratio (I002/I101) of the samples deposited at 560 C changes from 9 to 1.3 by
an increase in the solution concentration from 0.05 to 0.2 mol/l and indicates that c-axis orientation vanishes at higher concentrations. We showed
that ZnO nanorods with the length to diameter ratio of 30 can be prepared by spray technique using indium tin oxide-covered glass substrates
instead of bare glass.
2006 Elsevier B.V. All rights reserved.

Keywords: Spray pyrolysis; Electron diffraction; Nanostructures; Surface morphology; Zinc oxide scanning electron microscopy

1. Introduction Furthermore, we studied the orientation and optical properties

One-dimensional semiconductor nanostructures are of great
interest for future nanoscale electronic and optoelectronic
devices [1]. ZnO nanostructures have potential applications in
solar cells, gas sensors, short-wavelength light emitting and field
effect devices, Schottky diodes, etc. [2]. Over the past few years,
great efforts have been made to develop ZnO nanostructures by
different methods. Well-aligned single-crystalline ZnO nanorod
arrays have been prepared by vapourliquidsolid (VLS) [3]
and chemical vapour deposition (CVD) methods [2,4,5]. Wet
chemical low-temperature techniques [6,7] provide promising
options for large-scale production and a good potential for scale-
up. However, one of the drawbacks of the solution growth
methods is the relatively long processing time.
In this work, morphological changes of ZnO films grown by
spray pyrolysis technique using zinc chloride aqueous solution
were investigated as a function of the growth temperature.
Corresponding author. Tel.: +372 6203363; fax: +372 6203367.
E-mail address: malle@staff.ttu.ee (M. Krunks).
0040-6090/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2006.07.134
of the films, as well as the effects of solution concentration and
different substrates. To our knowledge, no studies on ZnO
structured films comprising nanorods by a pneumatic spray
deposition have been published.
2. Experimental
ZnO layers were prepared by spray pyrolysis method using an
aqueous solution of zinc chloride (ZnCl2, Aldrich, purity 98%).
The concentration of ZnCl2 was varied from 0.02 up to 0.2 mol/l.
The precursor solution was pulverized onto the substrates placed
on a soldered tin bath. The deposition temperature (Ts, tempe-
rature at the substrate surface) was varied in between 400
and 560 C with accuracy of 5 C using an electronic tem-
perature controller. Commercial glass and ITO-covered glass
(30 30 1 mm3) were used as substrates. Compressed air was
used as a carrier gas. The solution volume was 50 ml and the
spray rate was maintained at 2.5 ml/min.
X-ray diffraction (XRD) patterns were recorded by a Bruker
AXS D5005 diffractometer using the Cu-K radiation
1158 M. Krunks et al. / Thin Solid Films 515 (2006) 11571160

Table 1
The ratio of intensities of the (002) and (101) reflections (I002/I101) in XRD
pattern and the diameter (d), length (L), aspect ratio (L/d) of ZnO nanorods on
glass substrates depending of the deposition temperature (Ts) and zinc chloride
concentration in solution (C)
C (mol/l) Ts (C) I002/I101 d (nm) L (nm) L/d
Effect of Ts 0.10 450 7.7 500 1000 2
0.10 490 8.6 200300 700800 2.54
0.10 540 6.0 400600 15002000 24
Effect of 0.05 560 9.0 100300 1500 515
concentration 0.10 560 5.5 400600 20002500 36
0.20 560 1.3 600700 3000 45

substrates were used. According to the optical transmittance

Fig. 1. Optical transmittance spectra of ZnO layers prepared on glass slides at
substrate temperatures (Ts) of 400 C and 500 C.
( = 0.1542 nm). The optical transmittance spectra of the films
were recorded on a Varian Techtron 636 spectrophotometer in
the wavelength range of 300800 nm. The surface morphology
and the cross-section of the layers were examined by scanning
electron microscopy (SEM) using a Leo Supra 35. The selected
area electron diffraction (SAED) patterns were recorded on a
transmission electron microscope (TEM) EMV-100BR at
100 kV.
3. Results and discussion
3.1. Effect of substrate temperature
To study the effect of the deposition temperature, zinc
chloride solution with a concentration of 0.1 mol/l and glass
spectra (Fig. 1), deposition at substrate temperatures around
400 C resulted in ZnO films with an optical transparency of
70% in the visible region of the spectrum. The SEM micrograph
of the film deposited at 400 C is presented in Fig. 2a. The film
consists of densely packed grains with a size from 50 up to
500 nm. The increase of the deposition temperature above
450 C leads to hazy films with significantly decreased optical
transparency as shown in Fig. 1 for the sample deposited at
500 C. The SEM micrograph shows that the film deposited at
450 C is no more dense and consists of cylindrical crystals with
a diameter of 300 nm (Fig. 2b). Further temperature increase up
to 490 C leads to the layers consisting of well-shaped elongated
hexagonal prisms with the diameter of 200300 nm and the
length of 700800 nm (Fig. 2c). The changes observed in
morphology explain the decreased optical transmittance of the
structured layers due to the light scattering.
The dimensions and morphology of the rods formed at 490 C
are very similar to those grown onto SnO2-covered glass

Fig. 2. SEM surface views of ZnO layers deposited from zinc chloride aqueous solutions with concentration of 0.1 mol/l onto glass substrates at temperatures (Ts) of (a)
400 C, (b) 450 C, (c) 490 C and (d) 540 C.
 M. Krunks et al. / Thin Solid Films 515 (2006) 11571160
Fig. 3. XRD patterns of ZnO layers deposited onto glass substrate at 560 C
from zinc chloride solutions with concentration of (1) 0.05 mol/l, (2) 0.1 mol/l,
and (3) 0.2 mol/l.
substrates by microwave activation in aqueous solutions [8]. The
film deposited around 540 C consists of rods with diameters of
400600 nm (Fig. 2d) and lengths of up to 2.0 m. Thus,
deposition at higher temperatures increases the size of the rods
and leads to lower substrate coverage. The results of the SEM
study are summarised in Table 1.
XRD patterns of flat films and structured layers deposited
from the solution with concentration of 0.1 mol/l at tempera-
tures 400560 C, are similar. The X-ray diffractogram of the
structured layer deposited at 560 C is presented as graph 2 in
Fig. 3. The strong (002) reflection and weak reflections of the
(101) and (102) planes of the wurtzite (PDF 36-1451) can be
detected in the diffractogram. The ratio of the intensities of
(002) and (101) reflections (I002/I101) between 5.5 and 8.6 is
characteristic of the samples consisting of well-shaped
hexagonal columns (Table 1). For a powder sample, the I002/
I101 is 0.44. Thus, according to XRD, ZnO crystals in the films
are c-axis-oriented.
Our results show that the spray pyrolysis technique can be
applied to grow ZnO nanorods at temperatures higher than those
used to deposit ZnO flat films. The mechanism of highly c-axis-
oriented ZnO flat film development into mainly c-axis-oriented
ZnO nanocolumns by increasing the growth temperature is not
yet clear. To some extent, it can be compared to nanorods growth
Fig. 4. SEM micrographs of ZnO layers deposited at substrate temperature of 560 C onto the glass substrates using zinc chloride aqueous solutions with concentration
of (a) 0.1 mol/l, a cross-sectional view; (b) 0.2 mol/l, a plane view.
1159
Fig. 5. SEM cross-sectional micrograph of the ZnO layer deposited onto ITO-
covered glass at substrate temperature of 560 C using zinc chloride aqueous
solution with concentration of 0.1 mol/l.
in the MOCVD process [5]. Both technologies are characterised
by the c-axis anisotropic growth of ZnO at higher temperatures.
In the MOCVD process, ZnO gradually evolves from flat to
pillar and finally to needle-shaped crystals by changing the
growth temperature in the range of 300600 C [5]. In the spray
process, a flat film evolves also into nanocolumns but both, rod
diameter and length on glass substrates increases with the
temperature rising.
3.2. Effect of solution concentration
To study the effect of solution concentration on the
development of nanorod morphology, the growth temperature
was fixed at 560 C. The Zn2+ concentration of 0.02 mol/l in the
spray solution leads to the formation of separate crystals with a
size about of 200 200 nm2 on a glass substrate. The use of
more concentrated solutions of 0.05 mol/l results in elongated
crystals with the diameter of 100300 nm and the length of up
to 1.5 m (Table 1). Raising the solution concentration from 0.1
to 0.2 mol/l, the diameter of the columns increases from 400
600 up to 600700 nm and crystals length increases from about
2 to 3 m (see Fig. 4a and b, respectively).
SEM study also shows that solution concentration has a
significant influence on the shape and alignment of the rods.
Almost vertically standing columns can be deposited from
solutions with concentrations of 0.050.1 mol/l (Fig. 4a). The
deposition of more concentrated solutions (0.2 mol/l) results in
1160 M. Krunks et al. / Thin Solid Films 515 (2006) 11571160
Fig. 6. Selected area electron diffraction (SAED) pattern of a single spray
deposited ZnO nanorod.
the formation of the sets of branched crystals (Fig. 4b). The set of
rods mainly consists of tripod-shaped ZnO crystals with legs of
similar size, while the legs are oriented in different directions.
The rods in bundles exhibit well-shaped planes of the hexagonal
structure. Similar alignment of ZnO rods and poor substrate
coverage, as presented in Fig. 4b, is also reported for rods
prepared by hydrothermal or plasma-enhanced CVD techniques
onto bare Si wafers [9,10]. The formation of ZnO nanotetrapods
with uniform leg width and length is reported by VLS process
[11].
Fig. 3 presents XRD patterns of the layers deposited from
solutions with different concentrations. According to XRD,
highly c-axis-oriented layers with the I002/I101 ratio of 10 could
be grown from the 0.05 mol/l solutions. Deposition of more
concentrated solutions increases the relative intensity of the
(101) reflection, while the spray of the 0.2 mol/l solution results
in a sample exhibiting reflections of (101), (100), (102) and
(110) planes in addition to the (002) reflection. It could be seen
that by increasing the solution concentration, the intensities ratio
(I002/I101) decreases from 9 to 1.3 (Fig. 3 and Table 1). Thus,
SEM and XRD both demonstrate a decreased c-axis orientation
of the columns on glass substrates in the case of concentrated
solutions.
It is well-known that highly c-axis-oriented and uniform in
size rods can be produced only on substrates with a high density
of nuclei [6,12,13]. The SEM cross-sectional image of spray-
deposited ZnO rods on the ITO-covered glass is presented in
Fig. 5. It can be seen that rod diameter is between 70 and 200 nm
and length is nearly 2 m, resulting in the aspect ratio of 1030.
Substrate coverage seems to be higher and rods are thinner
(Fig. 5) than those grown on the glass substrate under similar
conditions (Fig. 4a). Compare to the CBD (chemical bath
deposition) deposited nanorods on a SnO2 electrode [8], the
spray-deposited ZnO rods on ITO have similar width, but show a
superior aspect ratio and a better c-axis alignment.
Concerning the rods deposited onto a glass substrate, it can be
proposed that the formation of an intermediate ZnO layer
supports the growth of almost vertically standing crystals
(Fig. 4a). The behaviour observed is similar to that described for
c-axis-oriented ZnO nanorod arrays on glass substrates by a
vapour phase process, where a ZnO wetting layer was formed
between the nanorods and the substrate [14].
Fig. 6 shows a typical selected area electron diffraction
(SAED) pattern of a ZnO nanorod. SAED patterns recorded for
different samples reveal that all individual nanorods indepen-
dent of the growth temperature and solution concentration are
single crystalline.
4. Conclusions
It has been shown that ZnO structured layers comprising
single crystalline nanorods can be prepared by the spray
pyrolysis deposition of zinc chloride aqueous solutions at
temperatures higher than that needed to obtain flat films. Simple
set-up, moderate deposition temperatures in the range of 490
560 C and short deposition times of about 20 min, in addition,
a possibility to cover large areas are in principle making this
technology competitive with other techniques. According to our
first results, the size of rods on glass substrates is increased by
the growth temperature and solution concentration, leading to
decreased c-axis orientation and lower substrate coverage.
Similarly to other deposition techniques, substrate type is also
highly important. ZnO nanorods with the diameter of 70
200 nm and the length of 2000 nm, resulting in the aspect ratio
up to 30 can be grown on ITO substrates. Experiments are in
progress to find out the effect of different substrates and seed
layers as well as the spray procedure parameters on the growth
of ZnO nanorods and ZnO nanorod arrays by a simple
pneumatic spray pyrolysis technique.
Acknowledgements
Financial support by the Estonian Science Foundation (grant
5612) is gratefully acknowledged. Authors like to thank Mrs. O.
Volobujeva for SEM micrographs and Dr. V. Mikli for TEM
experiments.
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