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Journal of Non-Crystalline Solids 354 (2008) 28432848

www.elsevier.com/locate/jnoncrysol

ZnO nanorod growth by chemical bath method

P. Hari a,b,*, M. Baumer a, W.D. Tennyson c, L.A. Bumm c
a

Department of Physics and Engineering Physics, University of Tulsa, 600 South College Avenue, Tulsa, OK 74104, USA
b
Nanomaterials Institute, University of Tulsa, 600 South College Avenue, Tulsa, OK 74104, USA
c
Homer L. Dodge Department of Physics and Astronomy, University of Oklahoma, Norman, OK 73019, USA
Available online 12 February 2008

Abstract
Controlled growth of ZnO nanorods on various substrates is of great interest in photonic and electronic device applications. Among
the various growth techniques developed, wet chemical processes hold great promise as a low cost, low temperature deposition technique.
In this study we report properties of ZnO nanorods grown on indium tin oxide coated glass substrates by heating an equimolar solution
of zinc (II) nitrate and hexamethylenetetramine solution. The morphology of ZnO nanorods exhibited both open and closed hexagonal
shapes under various deposition conditions above 90 C. At 95 C, growth of equimolar ratio of zinc (II) nitrate and hexamethylenetetramine after 4 h examined by scanning electron microscope exhibited mainly open hexagonal structures. The same equimolar ratio at
95 C grown at 9 h and longer duration of chemical bath exhibited closed hexagonal structure. The ratio of the open area of nanorods
to the closed surface decreases dramatically as the deposition time is increased from 4 h to 26 h. Peak shape analysis of ZnO nanorods
under X-ray diraction spectrum suggests average crystallite size domains of 200 nanometers. Surface morphology measured using
Atomic Force Microscope (AFM) indicates that the 26 h sample is slightly rougher than the 4 h grown ZnO sample.
2008 Elsevier B.V. All rights reserved.
PACS: 73.61.Ga; 73.63.Fg; 78.66.Hf
Keywords: IIVI Semiconductors; Nanocrystals; X-ray diraction; Atomic force and scanning tunneling microscopy; Scanning electron microscopy;
Nano-clusters

1. Introduction
Nanocrystalline zinc oxide has wide range of devices
such as high power transparent thin lm transistors, optical
waveguides, conductive gas sensors and transparent electrodes for photo-electrochemical applications [1]. For
developing ZnO nanorods for these and other important
technological applications, a simple cost-eective method
of deposition is highly desirable. Among the various
growth techniques developed, wet chemical processes [2
5] hold great promise as a low cost, low temperature deposition technique. For device applications, it is essential to
*
Corresponding author. Address: Department of Physics and Engineering Physics, University of Tulsa, 600 South College Avenue, Tulsa,
OK 74104, USA. Tel.: +1 918 631 3128; fax: +1 918 631 2995.
E-mail address: hari@utulsa.edu (P. Hari).

0022-3093/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2007.09.097

have a thorough understanding of the growth mechanism

and morphology of ZnO nanorods fabricated by chemical
bath deposition techniques. Typically, the controllable
growth parameters in a chemical bath deposition technique
are the molar ratio, pH of solution, temperature of the
chemical bath and the substrate on which the nanorods
are deposited. Previous studies using chemical bath deposition techniques have yielded crystalline hexagonal rods of
length ranging from 110 lm in length and 10 nm to
1 lm in diameter [6,7]. The chemical bath technique we
used in this study was based on the novel deposition technique developed by Vayssieres and Yan [4,5]. The main
goal of our study was to monitor changes in ZnO nanorod
morphology as the deposition bath time is varied, keeping
all other parameters identical. In previous studies [46],
nanorods were typically examined after heating the precursor solutions for 9 h in a chemical bath. In this study we

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P. Hari et al. / Journal of Non-Crystalline Solids 354 (2008) 28432848

monitored changes in the ZnO surface during the intermediate stages of the chemical bath deposition leading to a
fully developed nanostructured lm made of hexagonal
shaped ZnO nanorods.
2. Experimental procedures
The chemical bath deposition technique (CBD) used in
this study for fabricating ZnO nanorods comprised of an
equimolar solution of zinc nitrate hexahydrate (Zn(NO3)

6H2O) and hexamethylenetetramine (C6H12N4), obtained
from Aldrich chemicals. The solution was stirred for 3
24 h, depending on the volume of the solution used. The
substrates used in this study were indium tin oxide coated
unpolished glass slides purchased from Delta Technologies
Limited, with typical substrate resistance in the range of
14 ohms per square. To make samples of ZnO nanostructures, equimolar (1:1) solution of zinc nitrate hexahydrate
and hexamethylenetramine was used. Starting with a
desired volume of high purity type 1A water from Millipore ltration system, the proper amount of hexamethylenetetramine was added to make 1 molar solution. Once
the hexamethylenetetramine is dissolved completely in
water, the mass of zinc nitrate hexahydrate was added so
that the solution becomes equimolar. For 200 ml of water,
mass of hexamethylenetetramine used was 2.80 g and zinc
nitrate hexahydrate was 5.94 g. The substrate was suspended in a jar containing the equimolar solution of the

precursors with a copper wire for the duration of the chemical bath. The jar containing the substrate and the precursor solutions were immediately taken after each chemical
bath deposition time and the entire contents were allowed
to reach equilibrium at room temperature for about 10
12 h. The substrate was rinsed with high purity water,
and after drying in air, a portion of the sample was sputter
thick for scanning electron
coated with gold of 150 A
microscopy (SEM) measurements. SEM measurements
were done using a Hitachi S-2300 SEM and JEOL JSM840. The samples generally needed 824 h to dry. The main
experimental variable used in this study was the time of
growth under CBD for ZnO nanorods. We performed
two experiments to make sure that temperature variation
of 5 of the chemical bath did not aect the nanorod
growth in any signicant manner. One experiment was conducted with precursor solution in each jar individually
heated for the duration of the CBD, by placing one jar at
a time in the furnace. A second experiment was conducted
with the precursor solution distributed equally in three jars
and jars were taken out of the furnace sequentially after 4,
5 and 6 h. When the furnace was opened after each prescribed time, there was a time period (typically 20 min) during which the temperature uctuated by 5. SEM
inspection afterwards showed no signicant dierences in
surface morphology between the samples produced by the
two techniques. For X-ray diraction (XRD) and atomic
force microscopy (AFM) measurements, samples from

Fig. 1. SEM images of ZnO nanorods taken at 4 h (a), 5 h (b), 6 h (c) and 26 h (d) are shown.

P. Hari et al. / Journal of Non-Crystalline Solids 354 (2008) 28432848

3. Experimental results and analysis

4.0

Ratio of area of open rods to

area of closed rods

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3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0

10

15

20

25

30

Deposition Time (hours)

Fig. 2. Analysis of SEM images of ZnO nanorods to show the progressive

lling of nanorod surface with time. Details of the image analysis
procedure are given in the main text.

the main ITO coated glass were used without any surface
coating. XRD measurements were done using a 25 keV
Scintag diractometer and AFM measurements were performed using a Topometrix Explorer using a MikroMasch
NSc35/no Al silicon tip with radius of curvature of 10 nm.
We also prepared several samples by placing the jar containing precursors and substrate in an oil bath, to maintain
a more uniform temperature. SEM measurements showed
no remarkable dierence in the surface morphology
between samples heated in a conventional oven and by
the oil bath technique.

ZnO samples prepared by CBD were taken out of the

temperature bath after 4, 5, 6 and 26 h. SEM images of
the samples are shown in Fig. 1((ad), respectively). Typically, ZnO nanorods prepared by CBD grow in a direction
perpendicular to the surface of the substrate (along the caxis direction) exhibiting the well known hexagonal cross
section [7]. In addition to the typical hexagonal shaped
nanorods with closed ends, Fig. 1 also indicates that the
SEM images of ZnO nanorods prepared at 4, 5, and 6 h
exhibit a signicant number of incomplete or open nanorods. We examined the digital images of ZnO nanorods to
gain a quantitative understanding of the ratio of the open
structures to closed structures as the deposition time is varied. For digital image analysis we used DIAS 2.0 software
program provided by Sun Angstrom Inc., Boston. The procedure employed for image analysis is as follows: a grid was
used to dene regions of the image. The area occupied by
open structures and closed nanorod surfaces were calculated using the software for this grid. The ratio of the area
occupied by the open ended nanorods to closed nanorods
was computed form this procedure. Using a random number generator, the location of the grid was selected at dierent regions of the SEM. The above procedure was repeated
and we obtained an average ratio of the area occupied by
open ended nanorods to closed nanorods for a given
SEM digital image. The results of our image analysis on
ZnO nanorod SEM images are shown in Fig. 2. Each point
in the graph is an average of 10 random grid locations

Fig. 3. XRD data of ZnO nanorods deposited at 4, 26, 7 and 6 h are displayed respectively from top to bottom as the rst four traces. For comparison
purpose XRD crystalline data of raw ZnO crystal and ITO are also displayed. ZnO nanorods were attached to a Cu wire for chemical bath suspension.
XRD data on Cu are also displayed as the last trace.

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P. Hari et al. / Journal of Non-Crystalline Solids 354 (2008) 28432848

Fig. 4. (a) Top: AFM image of the 4 h ZnO nanorod surface. Bottom: The graph is a topographic cross section extracted from the AFM image along the
path shown by the dark line in the image. (b) Top: AFM image of the 26 h ZnO nanorod surface. Bottom: The graph is a topographic cross section
extracted from the AFM image along the path shown by the dark line in the image.

P. Hari et al. / Journal of Non-Crystalline Solids 354 (2008) 28432848

across the SEM image. As it is evident from Fig. 2, the

ratio of the area of open ended surface to closed surface
decreases as the deposition time increases. From Fig. 2,
we can infer that at 4 h of deposition, the ratio of open
to closed nanorods is roughly 3. The ratio of area occupied
by open rods to closed rods is reduced to approximately 0.5
as the deposition time is increased to 6 h. We have also
conducted SEM studies on samples prepared by CBD at
9 h. The surface of the 9 h sample was very similar to the
26 h sample, with signicant number of nanorods exhibiting closed hexagonal structures. This may be an indication
that ZnO nanorods by CBD reach equilibrium around 9 h.
The ratio of the area occupied by open nanorods to closed
ones is about 0.3 at 26 h of deposition.
We also examined the nanorods by XRD to obtain an
estimate of the size of the nanorod cluster size from the
width of the XRD diraction peaks from the (0 0 2) planes.
Analysis was performed using standard software for the
diractometer based on the Scherrer formula. Our analysis
shows that all the ZnO samples prepared at various CBD
times have clusters of width in the range of 150200 nm.
XRD for various ZnO nanorods are shown in Fig. 3.
In addition to SEM and XRD measurements, we performed AFM studies on two ZnO samples. The results of
AFM measurements on the 4 h and 26 h sample are shown
in Fig. 4(a) and (b). AFM micrographs were analyzed using
Gwyddion 2.7 software. A topographic cross section was
extracted from the AFM image (shown by the dark line
in Fig. 4(a) and (b)) along the direction indicated by the
line. The root mean square (RMS) topographic roughness
of the surface, extracted from the image area, is 0.259 lm
for the 4 h sample and 0. 383 lm for the 26 h sample. Even
though these values are only rough estimates across a representative portion on each sample, for comparison purpose, we may say that the 26 h sample has a slightly
rougher surface compared to the 4 h sample. It is interesting to note that ZnO nanorods have layers built on the typical hexagonal surface as the deposition time is increased
beyond 9 h. As evident in Fig. 1(d), the 26 h sample exhibits stairs or stacks built on the top of the regularly
observed hexagonal surface. This layered structure could
explain why the surface roughness is higher for the 26 h
sample as suggested by our AFM measurements.
4. Discussion
The main advantage of using CBD over conventional
methods in fabricating metal oxides is that we have better
control over the morphology, texture and orientation of
nanostructures. Thin lms made up of nanorods are grown
at very low temperatures directly from the substrate dictated by nucleation and thermodynamics of the aqueous
precursors. The experimental approach we have adopted
in this study is to take snap shots at the building process
of ZnO nanorods for better understanding of the growth
mechanism by which the rods are assembled. SEM micrographs (Fig. 1(a) and (b)) of ZnO nanorods fabricated the

2847

early period of nanorod formation, appears to have incomplete termination of nanorod ends. This eect is manifested
in open structures of ZnO nanorods at 4 h and 5 h of
CBD. By examining the SEM images of ZnO nanorods
at longer deposition times, it is apparent that the frequency
of incomplete or open structures decreases signicantly
with time (Fig. 2).
Pancholski et al. [8], Penn and Baneld [9], and Li et al.
[3] have observed coalescence phenomena involving nanostructures that result in the formation of nanorods and
nanowires. A growth mechanism involving fusing of tiny
nanorods rods (typically less than 60 nm in diameter) was
inferred from SEM study of ZnO [3] grown by CBD at
88 C for 10 h. From SEM images, tiny nanorods appear
to coalesce over time and form a bundle that results in a
single nanorod of 150200 nm diameters. From previous
SEM studies of these tiny nanorods it is evident that several incomplete structures of un-fused bundles along with
fused bundles of regular hexagonal structures are present
during various stages of ZnO nanorod growth. A growth
mechanism involving fused tiny nanorods giving rise to
hexagonal ZnO nanorods could explain the patterns we
observed in this study. In order to explain the presence of
incomplete or open nanorods, it is quite likely that the
fusing of tiny rods takes place to form the outer wall of
the hexagonal manifold rst. This is consistent with our
observation that all of the ZnO structures at 4 h and 5 h
appear to have the hexagonal outline on the outer wall.
Our observation that at earlier times of CBD there are
incomplete or open structures or tube like structures
could very well indicate that the fusing of tiny nanowires
inside the shell has not been completed. As the nanorods
are allowed to grow, the fusing takes place uninterrupted,
resulting in the hexagonal shaped nanorods we observe at
higher CBD times. This interpretation could be tested by
growing ZnO rods at lower temperatures and monitoring
the growth process at specic intervals of time.
It is quite interesting to note that if we continue to grow
ZnO nanorods by CBD beyond the customary 9 h period
required for fabricating regular hexagonal shaped structures, we observe layers accumulating on the top of nanorod surface (Fig. 1(d)). This could very well be an
indication that the lling of the nanotubes continue even
after the formation of the regular hexagonal structures.
The appearance of stacked layers could explain the slight
increase in surface roughness for the 26 h ZnO sample in
comparison with the 4 h sample.
5. Conclusions
ZnO nanorods grown on indium tin oxide glass substrate by chemical bath deposition method at 95 C exhibit
open tube like structures at low deposition times along
with closed hexagonal nanorod cross sections. SEM study
of the surface of nanorods deposited at 4, 5, 6 and 26 h
indicates that there is a progression of lling of open
structures with time. AFM measurements of surface rough-

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P. Hari et al. / Journal of Non-Crystalline Solids 354 (2008) 28432848

ness indicate that there is a slight increase in the surface

roughness of ZnO nanorods deposited at 26 h compared
to the ZnO nanorods deposited at 4 h. The appearance of
open tube like structures could be explained by a growth
mechanism in which nanorods are built from tiny nanowires of smaller diameter fused together.
Acknowledgements
The support of Oklahoma State Regents Funds for
Higher Education and NSF-EPSCoR funds are gratefully
acknowledged for sponsoring this work. L.A. Bumm and
W.D. Tennyson were supported by NSF CAREER Grant
No. CHE-0239803, the Center for Physics in Nanostructures, NSF MRSEC No. DMR-0520550, AFOSR
FA9550-06-1-0365. M. Baumer was supported by the
TURC and SURPP program at the University of Tulsa.

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