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Production of zinc oxide with variable

morphology by two novel wet-chemical methods


Ben Fulcher, Barry Tang, Dalibor Frutnik
Electron microscope Unit, Faculty of Science, University of Sydney

Abstract
Zinc oxide powders were synthesised by two wet-chemical methods featuring low temperature
(£100°C) and atmospheric pressure. We investigated a hydrothermal method using reagents
Zn(NO 3 ) 2 .6H 2O and hexamethylenetetramine (HMT) as well as an alkali precipitation method using
reagents ZnO, and NaOH. The morphologies observed by scanning electron microscopy (SEM) include
“cabbage-like”, “belt-like”, “flower-like” and “stringy-ball-like”. These morphologies were found to
vary with substrate material and initial concentration of reagents.

1. Introduction
Zinc oxide is a unique compound that demonstrates a large variety of nanostructures[1]. It is an n-
type semiconducting material with a large band gap of 3.37eV and exhibits piezoelectric, pyroelectric,
and photocatalytic properties. As such, ZnO has been investigated for potential in such diverse fields as
optics, optoelectronics, catalysis and piezoelectricity. More specifically, ZnO has also found
applications in solar cells[2-4], luminescence[5, 6], and as a rubber additive[7]. The large band gap of ZnO
implies a strong absorbance in the UV for wavelengths lower than 360nm, such that it has long been an
effective ingredient in sunscreens[8].
Among the sophisticated methods hitherto used to create ZnO structures are spray pyrolysis[9],
metalorganic chemical vapour deposition (MOCVD)[10-12], magnetron spluttering[13, 14], ethanol-in-oil
microemulsion[15], electrodeposition[16], oxidation of zinc[17], the sol-gel process[18], atomic layer
deposition[3] and pulsed laser deposition[19]. Generally, these complicated methods require specialist
machinery and expensive conditions such as elevated temperature and pressure. Recently, solution-
based methods[4, 20-23] have been reported, including alkali precipitation[9] and hydrothermal synthesis[24,
25]
. Although concerns have been raised as to the presence of water and the subsequent formation of
hydroxylated surfaces hindering catalytic performance[26], wet-chemical methods have the advantages
of convenience, low cost, low temperature, use of atmospheric pressure, and therefore the prospect of
large-scale production.
Each method used to produce nanocrystalline ZnO involves a specific set of parameters that can
be manipulated so as to modify the morphology and hence properties of the resultant ZnO powder.
Nanorings, nanohelixes, nanobows, nanobelts, nanowires and nanocages are some of the
nanostructures that have been produced via a solid-vapour phase thermal sublimation technique[1],
whilst electrodeposition techniques can produce nanocolumnar ZnO[16]. Unique structures have also
been formed by simpler thermal solution-based methods; ellipsoidal and needle aggregates, rod-like
particles[9], pencil-like, twinned pyramidal, shortened prismatic structures[24], flower-, snowflake-,
prism-, prickly sphere-, and rodlike samples[21], as well as nanorod[20, 27].
Zinc oxide is a well-known photocatalyst[28, 29]. The CO shift reaction ( CO + H 2O Æ CO2 + H 2 )
uses ZnO and copper as a catalyst[30], where the decomposition of methanoic acid is catalysed by ZnO
alone[31]. Furthermore, it has been shown that ZnO morphology has direct influence on its
photocatalytic properties[28, 29]. Enhanced catalytic properties of ZnO in the photodecomposition of
volatile organic compounds has been attributed to higher surface area and features of surface
nanostructure[27]. It is also suggested that chemical, electrical and optical properties are reliant upon
crystalline morphology and surface area. Control of surface area and morphology is a vital aspect in
other applications such as photo-emitters, sensors, varistors and transducers[27]. Singhal et al. showed
that the critical voltage of the varistor is directly related to the size of ZnO particles[15]. Further, the use
of ZnO as a humidity sensor requires a sparse, porous microstructure[32]. It is therefore vital to control
the nanostructure of ZnO to allow its use in novel applications that may demand a specific morphology
to be produced and subsequently utilised on a large-scale, with methods based on the principles
presented in this paper potentially contributing to this end.
In this paper, two aqueous solvent-based methods involving the precipitation of ZnO are
investigated to determine factors affecting the morphology of the resultant ZnO powder.

2. Experimental
2.1 Hydrothermal synthesis using a metallic substrate
A variable mass of hexamethylenetetramine (HMT) (Aldrich Chemical Company Inc., 99%) was
weighed and placed into a Teflon lined autoclave followed by 1.18g Zn(NO 3 ) 2 .6H 2O (Asia Pacific
Specialty Chemicals, Ltd., 98%). 40mL of deionised water was then added to each autoclave without
stirring, and the mixture aged at 95°C for 9 hours. Copper strips made into rings were rinsed
ultrasonically in acetone for 20 minutes and then added to each autoclave. For experiments in which
the role of silicon was investigated, a small piece of silicon metal was also attached to the top of the
copper ring. After a further 12 hours at 95°C, the solutions were allowed to cool to room temperature
in air, the substrates removed, flushed gently in deionised water and then dried at 95°C for several
hours. A sample was then prepared for scanning electron microscope (SEM) examination.

2.2 Alkali precipitation


A solution of ZnO powder (Merck, 99%) in 5M NaOH (Asia Pacific Specialty Chemicals Ltd.,
97%) was prepared. A variable volume of this solution of was taken and made up to 40mL with
deionised water. This dilution was then placed in a Teflon-lined autoclave, which itself was positioned
into a steel autoclave and then aged at 100°C for 8 hours. After being allowed to cool to room
temperature in air, the precipitate deposited at the base of the autoclave was concentrated by
centrifuging several times in water and then once in ethanol. The result was washed into a ceramic
crucible using ethanol and then dried in the oven for several hours at 95°C. The resulting thin layer of
white powder was prepared for SEM examination.

2.3 Examination
The silicon substrate was cut to an appropriate size using a diamond-tipped knife, while the
copper substrate was similarly cut using a scalpel. The powders were scraped gently and then sprinkled
onto adhesive tape in such a way as to obtain a very thin layer of powder. All samples were gold-
coated prior to examination on both the Phillips/FEI XL30 SEM and the Phillips/FEI 505 SEM.

3. Results and Discussion


3.1 Hydrothermal synthesis
The hydrothermal procedure followed here initially focused on varying the HMT concentration in
the reaction flask. No ZnO was precipitated when the HMT concentration was less than 0.8g/40mL (ie.
0.110M). The presence of a deposition was inconsistent at a concentration 0.8g/40mL, occurring in
only one of three identical trials. At HMT concentrations over this value, depositions were always
observed, the sizes of which are depicted in Table 1.
Table 1. Summary of Hydrothermal Experimental Results
Mass of HMT Substrate material Deposits observed Average particle size (microns)
0.7g Copper no N/A
0.8g Copper variable 120
0.9g Copper yes 60
1.0g Copper yes 55
1.0g Silicon yes 80
1.2g Copper yes 100
1.2g Silicon yes 60
1.4g Copper yes 100
1.4g Silicon yes 80

All morphologies produced by the hydrothermal method on either copper or silicon substrate were
found to deposit primary cabbage-like structures connected into secondary belt structures (Figure 1, 2).
As the HMT concentration increased, the belt-like linkages became less prominent, and the particles
became more particle-like and independent. This can be seen by comparing the strong belt-like
linkages of Figure 3A to the independent cabbage-like particular nature shown in Figure 3C.
Figure 1. SEM micrographs of samples prepared via hydrothermal synthesis on a copper
substrate using (A) 0.8g, (B) 0.9g HMT
These observations are consistent with the conclusion that increasing concentrations of HMT
within the reagent vessel reduce the attraction between adjacent ZnO particles. The formation of ZnO
nanorings, spirals and helixes can be explained by the minimisation of total energy due to polar
electrostatics, surface area and elastic deformation[1]. ZnO is known to form polar structures[1], and the
attraction between particles can thus be attributed to electrostatics. For two ZnO particles to attract
each other and join together in a belt-like linkage is energetically favourable due to a minimisation of
surface area and electrostatic potential. It is clear that an increased concentration of HMT inhibits this
attractive force by ‘shielding’ adjacent ZnO particles from each other.
The choice of substrate is important, as it has in some cases been shown to have a significant
impact upon crystal growth and consequential structure. ZnO has been shown to produce different
microstructures due even to different substrate orientation grown by metalorganic chemical vapour
deposition (MOCVD)[10]. Substrate materials including sapphire[10, 19], crystalline quartz and amorphous
glass[20], polycrystalline F-SnO2 glass, and Si/Si2 wafers[22, 27] have all been investigated. The substrate
material, whether quartz or glass, was claimed to have no effect on crystal structure by Wang et al.[20].
The effect of substrate in our hydrothermal method was investigated using copper and silicon
metal (lower six rows of Table 1). All other experimental variables were controlled by placing the two
substrates into the same Teflon-lined autoclave. As mentioned above, Wang et al. found no correlation
between substrate and ZnO morphology[20]. We, however, have found different structures on copper
substrate compared to those deposited on silicon substrate when prepared under the same conditions
(Figure 2). The particle sizes differed, as did the specific morphologies, although both substrate
materials gave the same general morphology, whether cabbage-like or belt-like. The most pronounced
example of this can be observed by comparison of Figure 2A,D. These were both synthesised using
1.0g HMT under the same conditions with (A) deposited onto copper and (D) onto silicon. It can be
seen that (A) is belt-like, while (D) is cabbage-like. While other morphologies obtained are similar, the
substrate material is certainly a contributing factor towards the growth and deposition of the zinc oxide
crystal.

Figure 2. SEM micrographs of samples prepared hyrothermally on either copper (A,B,C) or


silicon (D,E,F) substrate using (A,D) 1.0g, (B,E) 1.2g, (C,F) 1.4g HMT
The hydrothermal method presented here utilises zinc nitrate hexahydrate ( Zn(NO 3 ) 2 .6H 2O ) and
hexamethylenetetramine (HMT – C 6H12N 4 ) (Figure 3). These reagents have been used previously in a
number of aqueous routes[4, 9, 20, 22, 23, 27, 33], but they have never been employed via the method presented
here. Li et al.[9] reported rodlike particles, Vayssieres et al.[22, 33] synthesised nanowires and nanorods,
while Tian et al.[27] were able to produce nanorods, nanoplates and nanocolumns. Clearly the end result
is related in a sensitive way to the conditions in which the ZnO crystal is grown. It has been shown for
many different methods that the morphology and even composition of the resultant powder is
extremely sensitive to even minor changes to the conditions in which it is produced[34]. This result is
confirmed in both methods presented here, for which every tested variation in initial conditions yielded
a different final structure.

Figure 3. Structure of HMT (C6H12N4)


It has been shown by energy dispersive spectroscopy (EDS) in similar experimental procedures
that the product of the thermal treatment of Zn(NO 3 ) 2 .6H 2O and HMT is ZnO without the presence of
carbon or nitrogen contamination from the HMT[22]. Others have made use of X-ray powder diffraction
(XRD) to come to the same conclusion[20] with regard to alkali precipitation. A similar method could
have been carried out here to make certain that the product was in fact ZnO. Making use of the above
references, however, the product has been assumed to be ZnO without impurity throughout the paper.
Wither regard to length of thermal treatment we explored a secondary thermal treatment time of 2
hours, but no deposition could be recorded. Once a precipitate could be obtained by a particular
method, a variation in thermal treatment time was not altered. Although this variable could be expected
to influence the particle structures, it has previously been shown that prolonging the reaction time does
not significantly vary particle size, nor enhance crystal growth[25].
When exploring a new methodology for the formation of novel zinc oxide microstructures, every
variable must be controlled. In this case, all other variables have been controlled other than the initial
concentration of HMT. A definite effort has been made to control all variables that are suspected to
influence morphology. For example, HMT powder was always weighed out and added to the autoclave
before Zn(NO 3 ) 2 .6H 2O and the reaction flask was never stirred. Being such a delicate growth process,
changing these variables could possible influence the structure of the final ZnO crystal. We also placed
the autoclaves in the oven at room temperature and allowed it to heat up in that way every time. What
differentiates this procedure so markedly from other solution deposition methods is the addition of
powders together followed by their dilution with water. In other wet-chemical methods[9, 20-22, 24, 25, 27, 33,
34]
, the reagents are first dissolved in solution at some concentration and then added together at some
volume ratio while stirring vigorously. This detail is proposed to be one of the factors influencing the
growth of ZnO crystals in our hydrothermal method.
The benefit of investigating ZnO over other metal oxides is the convenience of its single oxidation
state of Zn2+[34]. HMT is a water soluble, non-ionic tetradentate cyclic tertiary amine[22, 35]. The
behaviour of HMT around zinc though, is relatively unexplored compared to the large amount of
research into the structure of HMT-silver complexes[36-39].
With regard to the chemistry behind the presence of HMT causing a precipitation of ZnO from
Zn2+, I propose that perhaps hydrogen ions can attach to the four lone electron pairs on the HMT
molecule forming ZnO by the reactions (1), (2) and (3) below. Reaction (4) gives the overall ionic
process, while (5) shows the entire process including the nitrate spectator ions:
2Zn 2+ + 4H 2O Æ 2Zn(OH) 2 + 4H + (1)
Zn(OH) 2 Æ ZnO + H 2O (2)
C6 H12 N 4 + 4H + Æ C6 H16 N 4 4 + (3)

2Zn 2+ + 2H 2O + C6 H12 N 4 Æ 2ZnO + C6 H16 N 4 4 + (4)


2Zn(NO3 ) 2 + 2H 2O + C6 H12 N 4 Æ 2ZnO + C6 H16 N 4 (NO3 ) 4 (5)
3.2 Alkali Precipitation
Variables explored in this method are summarized in Table 2, and representative morphologies in
Figure 4 and Figure 5. The particles of the powder produced from 1mL of supersaturated ZnO powder
in 5M NaOH solution with 39mL water (powder 1) were all primarily stringy-ball-like of about 4mm in
diameter (Figure 4A). As the concentration of this reagent solution became more concentrated, the
morphology became increasingly diverse. At 3mL of solution to 37mL of water (powder 2), there were
two main morphologies simultaneously present – both spiky- and fluffy-flower-like (Figure 4B,C). The
5mL result (powder 3) featured an average of the two forms (Figure 5D), while at 10mL (powder 4),
the structures were unstable and only fragments of flower-like particles were observed (Figure 5E).
Table 2. Summary of Alkali Precipitation Results
Name Powder 1 Powder 2 Powder 3 Powder 4 Powder 5 Powder 6 Powder 7 Powder 8
Mass of ZnO dissolved in NaOH -Supersaturated Solution- 2g 4g 2g 4g
Volume of solution used 1mL 3mL 5mL 10mL 3mL 10mL 3mL 10mL
Average particle size (microns) 4 10 7 12 5 8 6 N/A

Figure 4. SEM micrographs of samples prepared via alkali precipitation using (A) 1mL, (B,C)
3mL, (D) 5mL, (E) 10mL of supersaturated ZnO in 5M NaOH solution
The second group of powders (powders 5-9) that were created using an unsaturated solution gave
a novel result (Figure 5). There was a partial suspension of ZnO powder in the reaction mixture due to
insufficient stirring. Small, suspended particles are observed to attach themselves onto the flower-like
and rod-like ZnO nanostructures that have been precipitated from solution (Figure 5A,B,C). This is
important because it demonstrates the polar attraction between solid ZnO particles and shows that the
undissolved ZnO does not play a significant role in the crystal growth and precipitation process. From
the observations, I infer that the dissolved solution forms these morphologies and then, in a secondary
process, the suspended particles are attracted to them. This process is similar to the formation of belt
linkages in the substrate method in that the nanoparticles are created, feel an attraction to each other
and then aggregate. With regard to powders 7 and 8 (Figure 5D,E), no structural features were
observed, only large aggregates of suspended ZnO solid. It is suspected that the increased amount of
suspended ZnO solid (4g in 20mL rather than 2g in 20mL) has been attracted to what structure may
have been formed by this process and in doing so completely covered it, thereby preventing its
examination.
Figure 5. SEM micrographs of samlpes prepared via alkali precipitation using (A) 3mL, (B,C)
10mL of 2g ZnO in 20mL 5M NaOH solution; and (D) 3mL, (E) 10mL of 4g ZnO in 20mL 5M
NaOH solution
In considering the chemistry of the alkali precipitation method, we have ZnO dissolved in an
alkaline solution, and thus have a solution consisting of Zn 2+ ,O2- ,OH - , Na + for which we would
expect ZnO + 2NaOH + H 2O Æ Na2 [ Zn(OH) 4 ]. Due to heat convection and the diffusion of ions
through solution, the complex Zn(OH) 4 2- can form clusters of Zn x Oy (OH) z(z +2y -2x )- by dehydration:
OH - + OH - Æ H 2O + O2- . Such clusters will grow and eventually reach a critical size for the
[40]

formation of ZnO powder, at which point ZnO is precipitated. The following equations are those put
forward by Li et al.[41], which are used in a similar way elsewhere[20, 24]. The variables x, y, z, represent
the number of Zn2+, O2- and OH- ions respectively in the crystal:
Zn(OH) 4 2- + Zn(OH) 4 2- Æ Zn 2O(OH) 6 4 - + H 2O (6)
Zn x Oy (OH) z(z + 2y - 2x )- + Zn(OH) 4 2- Æ Zn x +1Oy +1 (OH)(zz ++22y - 2x + 2)- + H 2O (7).
But as mentioned in the introduction, this growth process is extremely sensitive to the reaction
conditions. So while other wet-chemical methods[24] feature the same complex in solution, the
conditions in which it grows and precipitates is different, and so it produces different morphologies of
ZnO.
The crystal growth process for zinc oxide is not well documented. While there have been some
success in the complicated mathematical modelling of crystal growth[42], these have been simplified to
2-dimensional growth. But while this simplification for rod-like morphologies is acceptable, to apply
the same model for the products reported here would not yield success due to their complex 3-
dimensional form.
No conclusive trends with regard to particle size could deduced from either set of experimental
results (Tables 1, 2). Thus the ultimate growth size does not simply depend on the concentration of a
particular reagent or a substrate material. There is certainly a connection between particle size and the
variables explored, but it evidently varies with such a magnitude of variables that it cannot be explicitly
realized from the set of data obtained here.

3.3 Similarities to other reported structures


The obelisk like ZnO nanorods reported by Wang et al.[20] have structural similarities to the
powders prepared here by alkali precipitation. On close examination, it can be seen that the hexagonal
obelisk-like rods are present in powders 2, 3, 4, 5 and 6 (Figure 4, Figure 5), but oriented in a flower-
like morphology. Wang et al.[20] were able to achieve a flower-like arrangement of these obelisk-like
rods using a solution of Zn(NO 3 ) 2 .6H 2O and NH 4 Cl . It was stated that a decrease in the amount of
ZnO nucleus on the substrate corresponded to the formation of this flower-like cluster, which was
achieved by lowering the concentration of zinc nitrate below 0.02M, the reaction temperature to 80-
90°C or the pH to the range 9.5-10.2 or 10.8-11.2[20]. Their reaction occurred over 30 minutes on a
quartz substrate. Our reaction occurred at a pH ranging from 13 to 14.1, at 100°C for 8 hours without
substrate. It is curious that on one hand we observe similar morphologies formed by very different
experimental methods, yet on the other hand, morphologies change dramatically with only small
changes in initial conditions.
Xu et al.[24] also report morphological similarities with those reported here by alkali precipitation.
The precipitation of ZnO from clusters of Zn x Oy (OH) z(z + 2y - 2x )- is considered the critical formation
reaction for Xu et al., as it is here. Although the structure of powder 1 was mostly stringy-ball-like as
mentioned above, it also showed unusual defects in form, exhibiting nanorods, block-like (Figure 6)
and prism-like structures. A nanorods obtained in powder 6 is similar to the rod-like morphology
reported by Xu et al. (Figure 7). Again the method was very different to ours, featuring zinc acetate
with water, KOH, or ammonia maintained at 200∞C for 2 hours without substrate.

A B

Figure 6. SEM micrograph by Xu, Wang et al. (A) with similar block-like morphology to that of
our sample (B)

A B

Figure 7. SEM micrograph by Xu, Wang et al. (A) showing similar rod-like morphology to our
micrograph (B)
Zhang et al. [21] used a simple solution-based method to create prism-like ZnO using ethanol as a
solvent at 100°C for 13 hours. We were also able to create this structure as another unusual defect in
our powder 1 (Figure 8).

A B

Figure 8. SEM micrograph by Zhang, Sun et al. (A) that shows a similar prism-like morphology
to our sample (B) through a very different experimental procedure
What can be said is that all morphologies that contained comparable features to our powders were
produced using a Zn(OH) 4 2- precursor. Since correlations were formed between the unusual defects
in our powders 1 and 6, I infer that random isolated thermochemical areas contained different
conditions during the reaction process thereby producing these defects. I claim also that the precursor is
the important species in determining the range of crystal morphologies that can be produced.
The particles deposited onto metallic substrate by our novel hydrothermal method have not to our
knowledge been reported previously. We are also the first to report ball-like nanostructures produced
alkali precipitation (powder 1).

5. Conclusions
Zinc oxide particles with variable morphology were produced by two convenient wet-chemical
methods. The growth, deposition subsequent morphology of ZnO was found to depend on the initial
concentration of reagents and the substrate material. Cabbage-like structures produced by our
hydrothermal method featured belt-like linkages with greatest prominence when the added mass of
HMT was less than 1.2 grams. It is proposed that the increased presence of HMT decreases the
adjacent electrostatic attraction between ZnO particles. Evidence for electrostatic attraction between
ZnO particles was observed also by the attraction of suspended ZnO particles to precipitated structures.
The morphologies of ZnO produced by alkali precipitation varied from ball-like through to flower-like
with variation in reagent concentration. Due to isolated areas in the reaction flask of atypical
conditions, unusual defects in uniform structure were reported in powders 1 and 6. A viable chemical
explanation for the formation of ZnO by both methods has been put forward. Ultimately it is hoped that
a particular ZnO morphology will be suited to a specific application for which ZnO could be safely and
conveniently produced by a novel wet-chemical similar to one reported here on a large scale for a
specific application.

6. Acknowledgements
We wish to thank firstly the Sydney University Science Department and the Talented Students
Program for allowing us to undertake in this investigation. In particularly Lisa Stadtmueller for
organising and overseeing the project, Mr. Zheng for spending many hours teaching and advising us
experimentally, Dr. Zhu for overseeing the project and teaching us valuable scientific techniques, and
Tony Romeo for giving up his time to teach us how the SEM works and how to use it effectively. We
acknowledge the methodology of both wet-chemical methods to Mr. Zheng.
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