Superlattices and Microstructures 42 (2007) 444450

www.elsevier.com/locate/superlattices
A novel deposition method to grow ZnO nanorods:
Spray pyrolysis
T. Dedova, M. Krunks

, M. Grossberg, O. Volobujeva, I. Oja Acik

Department of Materials Science, Tallinn University of Technology, Ehitajate tee 5, Tallinn 19086, Estonia
Available online 5 June 2007
Abstract
ZnO layers were deposited by chemical spray pyrolysis (CSP) using zinc chloride aqueous solutions
onto indium tin oxide (ITO) glass substrates at growth temperatures in the region of 400580

C. The layers
were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and low-temperature
(T = 10 K) photoluminescence (PL) measurements. The at lm of ZnO obtained at 400

C evolves to a
structured layer by raising the temperature up to 500

C. Deposition around 550

C and above results in a
layer comprising well-shaped hexagonal ZnO nanorods with diameter of 100150 nm and length of up to
1 micron. XRD shows strong c-axis orientation of ZnO being in accordance with the SEM study. Deposition
of nanorods was successful using ITO with grain size around 100 nm, whereas on ne-grained ITO (grain
size < 50 nm) with smooth surface fat crystals with diameter up to 400 nm and length of about 300 nm
were formed. Sharp near band edge (NBE) emission peaks centered at 3.360 and 3.356 eV dominated the
PL spectra of ZnO at T = 10 K, originating from the exciton transition bound to neutral donors. PL and
XRD results suggest that ZnO rods prepared by spray pyrolysis are of high optical and crystalline quality.
c 2007 Elsevier Ltd. All rights reserved.
Keywords: Zinc oxide; Nanorods; Spray pyrolysis; Surface morphology; Photoluminescence
1. Introduction
Nanostructured materials have attracted considerable interest in recent years due to their
potential application in nanoscale electronic and optoelectronic devices. ZnO nanostructures
have potential applications in solar cells, gas sensors, short-wavelength light-emitting and eld-
effect devices, Schottky diodes, etc. [1]. Much effort has been devoted to the development of

Corresponding author. Tel.: +372 620 3363; fax: +372 620 3367.
E-mail address: malle@staff.ttu.ee (M. Krunks).
0749-6036/$ - see front matter c 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.spmi.2007.04.010
T. Dedova et al. / Superlattices and Microstructures 42 (2007) 444450 445
ZnO nanostructures by different methods. Well-aligned single-crystalline ZnO nanorod arrays
have been prepared by VLS [2], CVD [3] and MOCVD [4] techniques. Wet chemical techniques
such as solution deposition [5,6] and hydrothermal process [79] are promising options for large-
scale production at low cost. However, it has been noted that without suitable treatment of the
substrates highly orientated nanorods have been rarely grown. Independent of the deposition
technique applied, usually the ZnO seed layers on different substrates [69] have been used to
grow well-aligned ZnO nanorod arrays. In some works, thin lms of conductive oxides [1,5] or
metals [10] have been used for this purpose.
In this work we present chemical spray pyrolysis as a new simple route for the synthesis of
ZnO nanorods. To our knowledge, no studies on ZnO nanostructured lms comprising nanorods
grown by pneumatic spray deposition have been reported until now. Morphological changes of
ZnO on the indium tin oxide (ITO) covered glass substrates were systematically investigated as
a function of the growth temperature and the underlayer structure. The phase composition and
orientation of ZnO crystals were characterized by XRD. Photoluminescence measurements (PL)
were used to evaluate the optical and crystalline quality of sprayed ZnO.
2. Experimental
ZnO layers were prepared by the spray pyrolysis technique using an aqueous solution of
zinc chloride (ZnCl
2
, Aldrich, purity 98%) with concentration of 0.05 mol/l. The precursor
solution was pulverized with the help of compressed air onto indium tin oxide (ITO) covered
glass substrates placed on a soldered tin bath. Two types of ITO glass (A and B) with similar
thickness of about 1 mm have been used. Type A: ITO with rough surface and nonuniform grain
size (thickness of 140 nm, medium grain size of about 100 nm). Type B: ITO with smooth surface
and uniform grain size (thickness of 200 nm, medium grain size of about 50 nm). The deposition
temperature (T
s
, temperature at substrate surface) in the range of 400580

C was varied through
the tin bath temperature using an electronic temperature controller. The amount of the solution
sprayed was 50 ml and the spray rate was kept at 2.5 ml/min.
X-ray diffraction (XRD) patterns were recorded on a Bruker AXS D5005 diffractometer using
CuK radiation ( = 0.1542 nm). ZnO phase was identied and the preferred orientation
was evaluated using the JCPDS les. The surface morphology and cross-sectional images of the
layers were examined by high-resolution scanning electron microscopy (SEM) on a Leo Supra
35. The optical properties were investigated by low-temperature (T = 10 K) photoluminescence
(PL) measurements using a HeCd laser (325 nm) as an excitation source.
3. Results and discussion
3.1. Temperature-induced morphological changes of ZnO
The morphology of spray-deposited ZnO has been investigated as a function of the growth
temperature. In this part of the study, the ITO substrates with rough surface (type A) were
used. Fig. 1(a)(d) shows typical surface images of ZnO grown in the temperature region of
400580

C. Signicant changes in the morphology of ZnO layers can be observed. The lm
deposited at 400

Cconsists of densely packed but irregularly shaped grains with a size of 50500
nm (Fig. 1(a)). The increase in the growth temperature up to 450

C supports the formation of
regularly shaped grains with size of 50100 nm (Fig. 1(b)). Further increase of the substrate
temperature up to 500

C leads to the formation of a layer consisting of hexagonal prisms with
446 T. Dedova et al. / Superlattices and Microstructures 42 (2007) 444450
Fig. 1. SEMmicrographs of ZnOlayers prepared at different substrate temperatures (T
s
) using the solution concentration
of 0.05 mol/l. (a) T
s
= 400

C, (b) T
s
= 450

C, (c) T
s
= 500

C, (d) T
s
= 580

C.
diameter of 100 nm, and the layer is not more densely packed as shown by SEM (Fig. 1(c)).
Well-shaped elongated hexagonal prisms have been formed at temperatures around 550

C and
higher. Hexagonal prisms with a diameter of 100200 nm (Fig. 1(d)) and a length of 800900
nm, showing an aspect ratio (length to diameter) of 49, are formed at 580

C. For comparison,
the spray deposition onto bare glass substrates under similar growth conditions results in crystals
with a diameter of 100300 nm and length up to 1.5 m. According to SEM, the size of the ZnO
rods on ITO substrates is smaller, but they are packed more densely than on glass.
The development of at lm into structured layer comprising nanorods could be, to some
extent, compared to the growth of nanorods in the MOCVD process [4]. In the MOCVD process,
on changing the growth temperature from 300 to 600

C ZnO gradually evolves from at to
pillar and nally to needle shaped crystals [4]. In the spray process, at ZnO lm transforms
to a structured layer consisting of nanorods by increasing the growth temperature from 400 to
550

C, whereas the size of the rods increases with the temperature.
Compared to other solution deposition techniques, ZnO nanorods similar in morphology
to those deposited by spray at 580

C were prepared by the hydrothermal process onto ZnO
premodied substrates [7,8] and the CBD technique onto ITO or SnO
2
[1,5].
Irrespective of the various morphologies of sprayed ZnO at different temperatures, the XRD
patterns of the samples are similar. The XRD pattern of the sample deposited at 560

C is
presented in Fig. 2. All diffraction peaks were identied as belonging to the ITO substrate and
ZnO (wurtzite, PDF 361451). It could be seen that the (002) reection is very strong compared
to the other reections of the wurtzite. The ratio of the intensities of (002) and (101) reections
T. Dedova et al. / Superlattices and Microstructures 42 (2007) 444450 447
Fig. 2. XRD diffraction pattern of ZnO layer deposited onto ITO at Ts = 560

C.
(I
002
/I
101
) is around 10, indicating the preferred c-axis orientation of ZnO nanorods on the ITO
substrate.
The XRD patterns as well as the alignment of spray-deposited ZnO nanorods on ITO are
similar to those of nanorod arrays produced by hydrothermal growth on ZnO premodied
substrates by Guo et al. [7,9]. Sprayed ZnO nanorods show somewhat better c-axis alignment
than those grown in solution on conductive electrodes [1,5], or by hydrothermal and solgel
processes on ZnO seed layers [8,11].
3.2. Underlayer structure-induced morphological changes of ZnO
Efforts to deposit ZnO nanorods on ITO glasses acquired from different producers sometimes
proved unsuccessful. It has been observed that the ITO microstructure has a strong effect on the
ZnO morphology. SEM micrographs of two different types of ITO and ZnO deposited on them
at 560

C are presented in Fig. 3. The deposition onto different ITO substrates was carried out in
the same run, placing the substrates side by side on a soldered tin bath.
According to the SEM surface views (Fig. 3(c), (d)), a structured lm consisting of
hexagonally shaped crystals is formed on both types of underlayer, but the width of the ZnO
crystals is about three times larger on ne-grained ITO (type B, Fig. 3(b)). SEM cross-sectional
micrographs (Fig. 3(e), (f)) show that ZnO rods with length of 800 nm are formed only on ITO
with larger grains and rough surface (type A, Fig. 3(a)). Using ne-grained ITO, the layer of ZnO
is composed of densely packed crystals (Fig. 3(f)) and no formation of rods has been observed.
Similar results are obtained, for example, for RF-sputtered ZnO on copper seed layer covered
glass substrates [10]. ZnO nanorod growth was observed on granular copper, whereas ZnO lm
was obtained on the smooth seed layer.
The results obtained indicate that the development of nanorods is strongly dependent on the
underlayer microstructure. It is well known that the most successful approach to grow well-
aligned nanorods is the use of a seed layer for site-selective nucleation. In our experiment, the
density of nuclei was denitely higher in the case of ne-grained ITO, and thus the number of
crystals formed in the early stage of growth can also be high. Obviously, the coalescence of
adjacent crystals occurs during the growth, resulting in the layer composed of fat crystals.
448 T. Dedova et al. / Superlattices and Microstructures 42 (2007) 444450
Fig. 3. SEM micrographs of two different types of ITO (a, b) and ZnO layers (c, d, e, f) grown on those at T
s
= 560

C
using zinc chloride aqueous solution with concentration of 0.05 mol/l. SEM micrographs: (a) surface view of type-A
ITO (large grain); (c) surface view and (e) cross-sectional view of the layers deposited onto type-A ITO; (b) surface
view of type-B ITO (small grain); (d) surface view and (f) cross-sectional view of the layers deposited onto type-B ITO.
3.3. Photoluminescence properties of ZnO
Photoluminescence measurements were used to evaluate the optical and crystalline quality of
the ZnO layers deposited at different substrate temperatures. For all samples, strong near band
edge (NBE) emission dominates the PL spectra at T = 10 K. High-resolution PL measurements
were used to determine the position and the FWHM value of NBE peaks (Fig. 4). The FWHM
value of the dominant peaks at 3.360 and 3.356 eVare about 45 meV. These peaks are tentatively
ascribed to the exciton transition bound to neutral donors (D

X) [12]. Weak free-exciton emission

at 3.375 eV is also observed. The peak at 3.332 eV originates from two-electron transitions
T. Dedova et al. / Superlattices and Microstructures 42 (2007) 444450 449
Fig. 4. High-resolution PL spectra of ZnO layers deposited at different substrate temperatures (Ts) of 400, 500 and
560

C. Dominant emission peaks at 3.360 and 3.356 eV are related to donor bound excitons. A weak free exciton peak
at 3.375 eV is also observed. Changes in relative intensities of the dominant peaks can be seen, indicating changes in
particular donor concentration with substrate temperature.
(TETs) [13] or can be attributed to the exciton transition bound to neutral acceptors (A

X) [14].
Changes in relative intensities of the dominant peaks are observed. The relative intensity of the
peak at 3.360 eV decreases with the substrate temperature. This is because the concentration of
the particular donor decreases.
Weak deep level emission, generally attributed to the presence of oxygen vacancies and other
structural defects, peaking at 2.4 eV, was also detected. This green emission band has been
assigned to the transition between the photoexcited holes and a singly ionized oxygen vacancy.
It has also been attributed to antisite oxygen and donoracceptor complexes [15]. The relative
intensity of the defect peak at 2.4 eV decreases slightly with substrate temperature (gure not
shown), indicating the better crystalline quality of the samples deposited at higher substrate
temperatures comprising nanorods. Compared to low-temperature wet chemical methods used
for the growth of ZnO nanorods [8,16], spray deposition allows one to grow rods of high optical
and crystalline quality.
4. Conclusions
ZnO nanorods were grown on indium tin oxide covered glass substrates by chemical spray
pyrolysis using zinc chloride aqueous solutions. It has been shown that the at ZnO lm
450 T. Dedova et al. / Superlattices and Microstructures 42 (2007) 444450
evolves to a structured layer by raising the growth temperature from 400 to 500

C. Well-shaped
hexagonal rods of ZnO showing preferred c-axis orientation were grown at temperatures around
550

C and above.
The formation of nanorods strongly depends on the underlayer microstructure, and thus
further studies on the growth of ZnO nanorods on different seed layers are of great importance
for preparing ZnO nanorod arrays by the spray technique.
Photoluminescence spectra, showing strong and sharp near band edge emission and negligible
emission caused by deep levels, suggest that ZnO rods prepared by spray are of high optical and
crystalline quality. This result, together with the spray procedure simplicity and low cost, makes
the technology promising.
Acknowledgements
Financial support by the Estonian Science Foundation (grants 5612 and 6954) is gratefully
acknowledged. Prof. J. Krustok is thanked for useful discussions.
References
[1] M. Willander, O. Nur, Y.E. Lozovik, S.M. Al-Hilli, Z. Chiragwandi, Q.-H. Hu, Q.X. Zhao, Microelectr. J. 36 (2005)
940.
[2] M.H. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind, E. Weber, R. Russo, P. Yang, Science 292 (2001) 1897.
[3] G.-C. Yi, C. Wang, W.I. Park, Semicond. Sci. Technol. 20 (2005) S22.
[4] J.Y. Park, I.O. Jung, J.H. Moon, B.-T. Lee, S.S. Kim, J. Cryst. Growth 282 (2005) 353.
[5] A.M. Peiro, C. Domingo, J. Peral, X. Domenech, E. Vigil, M.A. Hernandez-Fenollosa, M. Mollar, B. Mari,
J.A. Ayllon, Thin Solid Films 483 (2005) 79.
[6] Q. Li, V. Kumar, Y. Li, H. Zhang, T.J. Marks, R.P.H. Chang, Chem. Mater. 17 (2005) 1001.
[7] M. Guo, P. Diao, S. Cai, Appl. Surf. Sci. 249 (2005) 71.
[8] R.B.M. Cross, M.M. De Souza, E.M. Sankara Narayanan, Nanotechnology 16 (2005) 2188.
[9] M. Guo, P. Diao, X. Wang, S. Cai, J. Solid State Chem. 178 (2005) 3210.
[10] T.-L. Chou, J.-M. Ting, Thin Solid Films 494 (2006) 291.
[11] B. Lo, J.-Y. Chang, A.V. Ghule, S.-H. Tsing, Y.-C. Ling, Scripta Mater. 54 (2006) 411.
[12] D.Y. Lee, C.H. Choi, S.H. Kim, J. Cryst. Growth 268 (2004) 184.
[13] H.J. Ko, Y.F. Chen, T. Yao, K. Miyajima, A. Yamamoto, T. Goto, Appl. Phys. Lett. 77 (2000) 537.
[14] F. Jiang, J. Dai, L. Wang, W. Fang, Y. Pu, Q. Wang, Z. Tang, J. Lumin. 122123 (2007) 162.
[15] V.A.L. Roy, A.B. Djuri sic, W.K. Chan, J. Gao, H.F. Lui, C. Surya, Appl. Phys. Lett. 83 (2003) 141.
[16] L. Wu, Y. Wu, X. Pan, F. Kong, Opt. Mater. 28 (2006) 418.