Author’s Accepted Manuscript

A New Synthesis Route of ZnO Nanonails via

Microwave Plasma-Assisted Chemical Vapor
Deposition

M.F. Meléndrez, F. Solis-Pomar, C.D. Gutierrez-

Lazos, P. Flores, A.F. Jaramillo, A. Fundora, E.
Pérez –Tijerina
www.elsevier.com

PII: S0272-8842(15)01754-X
DOI: http://dx.doi.org/10.1016/j.ceramint.2015.09.046
Reference: CERI11323
To appear in: Ceramics International
Received date: 13 July 2015
Revised date: 8 September 2015
Accepted date: 8 September 2015
Cite this article as: M.F. Meléndrez, F. Solis-Pomar, C.D. Gutierrez-Lazos, P.
Flores, A.F. Jaramillo, A. Fundora and E. Pérez –Tijerina, A New Synthesis
Route of ZnO Nanonails via Microwave Plasma-Assisted Chemical Vapor
D e p o s i t i o n , Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2015.09.046
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 A New Synthesis Route of ZnO Nanonails via Microwave
Plasma-Assisted Chemical Vapor Deposition
M.F. Meléndrez1*, F. Solis-Pomar2, C. D. Gutierrez-Lazos2, P. Flores3, A.F. Jaramillo1,
A. Fundora4 and E. Pérez –Tijerina2*
1
Advanced Nanocomposites Research Group (GINA). Hybrid Materials Laboratory (HML).
Department of Materials Engineering (DIMAT), Faculty of Engineering, University of
Concepcion, 270 Edmundo Larenas, Box 160-C, Concepcion, Chile 4070409.

2
Facultad de Ciencias Físico-Matemáticas, Universidad Autónoma de Nuevo León, San
Nicolas de los Garza, Nuevo León 66451, México
3
Department of Mechanic Engineering (DIM), Faculty of Engineering, University of
Concepcion, 219 Edmundo Larenas, Box 160-C, Concepcion, Chile 4070409.
4
Instituto de Ciencia y Tecnología de Materiales (IMRE), Universidad de La Habana,
Zapata y G, Vedado, CP 10400 La Habana, Cuba

*Corresponding author: MFM: E-mail: mmelendrez@udec.cl, Phone: +5641-2203187, Fax: +56-41-2203391,

UdeC, Edmundo Larenas 270, Concepción, Chile. EPT: E-mail: eduardo.pereztj@uanl.edu.mx

ABSTRACT

In this work, a new method to obtain zinc oxide nanonails (ZnO-NNs) via microwave

plasma-assisted chemical vapor deposition (MAP-CVD) is reported. The ZnO-NNs were

grown on cobalt seeds using He as the carrier gas. The cobalt seeds were deposited onto

alumina at different distances from the substrate to the precursor material via the sputtering

technique. The ZnO-NNs were characterized by SEM, TEM, SAED, HRTEM and EDX.

NNs growth was uniform on the substrate surface: the stem of these structures ranged

between 250 to 450 nm, the cap ranged between 25 – 150 nm, and the necks ranged

between 30-200 nm. The wide distribution of the NNs dimensions was due to the vapor

from the thermal decomposition of ZnO, which is richer in gaseous species of Zn than

oxygen, leading to the formation of oxygen vacancies. The rich Zn vapor triggers the
growth in a different direction to the shank of the cap forming the NNs, which grows in the

direction [1010]. Some structural and experimental aspects are discussed in this paper.

Keywords: Nanonails, Chemical vapor deposition, Zinc Oxide, Microwave.

1. INTRODUCTION

One-dimensional (1D) nanostructures, such as nanowires (NWs), nanorods (NRs), belts

(NBs), nanotubes (NTs) and nanonails (NNs), have attracted the attention of researchers

due to their intrinsic properties and novel applications in various fields [1]. There are

several nanostructured materials that are now widely used; these materials are based on

zinc oxide, which has excellent properties, such as a wide band gap energy (3.37 eV), a

large exciton binding energy (60 meV) at room temperature, high optical gain (300 cm-1),

high mechanical and thermal stabilities, and radiation hardness. Because of its unique

properties, ZnO has been studied for its potential applications in optoelectronic devices [2],

field emitters [3], solar cells [4], sensors [5] and transparent electrodes [6]. Many types of

one-dimensional (1D) ZnO nanostructures, including NRs [7], NWs [8], NBs [9], NTs [10]

and NNs [11], have been synthesized. The early synthesis methods include chemical vapor

deposition (CVD), metal organic CVD [12], thermal evaporation [13], the template method

[14], electrochemical deposition [15] and the hydrothermal method [16]. It is well known

that the synthesis of nanostructures remains one of the current problems in nanotechnology

and that this problem is tackled through two research approaches: i) new methods of

synthesis and ii) massive synthesis of nanostructures. This work is focused on the first

topic: a new method for the synthesis of ZnO nanostructures, particularly nanonails (NNs),

via Microwave Plasma-Assisted Chemical Vapor Deposition (MPA-CVD).

The ZnO-NNs were synthesized by thermal evaporation and condensation from ZnO

powders [17, 18]. This structure is denoted as nanonail because of its resemblance to a nail.

The above methods required a tight control of synthesis parameters in its procedures; in

addition, this equipment in most cases consumes more energy and is expensive because it

requires high temperatures. The high temperature requirement is one of the main reasons

why the MPA-CVD method presented here is simple, inexpensive, rapid and reproducible,

as the heating is realized via microwave irradiation using a conventional oven. The reaction

is performed in the presence of a He plasma previously formed by the gas ionization due to

microwave irradiation; this ionization favors the formation of NNs on alumina substrates.

Moreover, it is known that the application of nanostructures in nanodevices significantly

depends on the shape and size [19]. For example, the 1D geometry, coupled with the

dislocation-free single-crystalline nature, high refraction index and atomically smooth

surfaces, allow for sufficient end-facet reflectivity and photon confinement in a volume of

just a few cubic wavelengths of material. The strong field localization inside sub-

wavelength cubic volumes enables large emitter-field interaction strength. The

manipulation of light with a 1D-ZnO nanocrystal is an interesting interaction because the

envisioned photons within a small cavity can be experimentally verified [20]. The main

advantage of ZnO is that it allows for production of a diversity of structural geometries,

depending on the synthesis conditions, e.g., a variety of 1D nanostructures, such as NNs,

which can be very interesting due to their optical properties (e.g., optical cavity effect). It is

well known that the densities of defects and oxygen vacancies significantly affect the

physical properties of oxide nanostructures. This correlation between structure and property

was verified by a PL study [21]. However, oxygen vacancies not only affect material
properties but also play an important role in the growth process of 1D structures, possibly

leading to the formation of different type forms: flowers, tubes, tapes, wires, rods, and

nails, among others [22]. This work is focused in a new synthesis system MPA-CVD, on

alumina substrates, where microwave plasma-assisted heating produces the rapid

decomposition of ZnO. In the course of the reaction, the rich in Zn vapor leads to a possible

formation of oxygen vacancies and hence the growth in another direction. This paper also

discusses some aspects of the synthesis and the possible mechanism of formation of various

types of ZnO-NNs.

2. EXPERIMENTAL DETAILS

Synthesis: All used reagents were of analytical grade. A quartz tube of 60 cm × 4 cm was
used in the ZnO nanonails synthesis. The precursor material was ZnO powder (99.99%
Sigma-Aldrich). The target used for the cobalt seeds deposition consisted of Co (99.99%
purity, 0.15 cm thick and 2" diameter) produced by Superconductor Materials, Inc. The
synthesis was divided in two parts: i) first, the deposition of the cobalt seeds used as the
catalyst particles on the alumina substrates via conventional sputtering and ii) second, the
growth of nanonails by Microwave Plasma-Assisted Chemical Vapor Deposition (CVD-
MPA) in the device displayed in Fig. 1. Cobalt depositions were realized by DC sputtering
during 15 seconds and 220 mA. The synthesis of nanonails was realized in a ceramic
container with the ZnO (1.0 g) precursor and graphite powder (1.0 g) homogeneously
mixed. The container is placed in the center of the quartz tube of the device and alumina
substrates, with the catalyst Co seeds placed at 1, 5 and 10 cm away from the precursor
material (ZnO + graphite). A conventional microwave was used for the synthesis (Sharp
R658L). Before the experiments, the system was evacuated to 1×10-3 torr, and a continuous
flow (50 sccm) of He gas was then introduced to the system. The reaction was performed at
1000 W power during 5 minutes. Pink-colored plasma was formed immediately after
starting the reaction process. After the thermal decomposition process and the subsequent
growth of nanonails on alumina substrates, the samples were cooled to room temperature
with a He flow.

Characterization: High-resolution transmission electron microscopy was performed using

a JEM-ARM200F probe aberration corrected analytical microscope with a resolution of
0.08 nm. Selected area electron diffraction was performed in a JEOL 2010F operating at
200 kV (point resolution of 0.19 nm). Scanning electron microscopy (SEM) was performed
using a FEG Hitachi S-5500 ultra high-resolution electron microscope (0.4 nm at 30 kV)
with a BF/DF Duo-STEM detector and in a FEI-Nanonova 100 FESEM.

3. RESULTS AND DISCUSSION

In this work, ZnO nanonails were obtained using a new Microwave Plasma-Assisted

Chemical Vapor Deposition (CVD-MPA) technique. This technique is a modification of

the original procedure to obtain ZnO nanowires filled with Pb by thermal decomposition

assisted by microwave previously reported [23]. The presence of an electrical discharge (in

the form of plasma) inside the reactor allows for gas molecules to be excited to higher

energy states, thereby increasing the reaction rate. Generally, these discharges are produced

at high frequency current to increase the efficiency of the deposition process. Therefore, it

is possible to work at different frequencies within the radiofrequency and microwave range.

The excitation frequency of the discharge was 2.45 GHz, which is a frequency suitable to

dissociate gas molecules. In this microwave plasma assisted system, the working pressure

was 10-2 - 10-3 torr. In the device, it was not possible to polarize the substrates by some

potential to attract positive or negative ions from the discharge plasma and increase the

energy of the atoms to be deposited. This behavior occurs because the plasma is formed
around the quartz tube of the device, where the precursor material (in the center of the

microwave oven) and the alumina-cobalt substrates are located. The substrates are placed at

different distances from the precursor material along the quartz tube to achieve different Zn

vapor saturation indices. An outline of the synthesis process and an image of the plasma

during the growth reaction are illustrated in Fig. 1.

The results corresponding to experiments with the alumina substrate at distances of 1 cm

(Fig. 2a, b) and 5 cm (Fig. 2c, d) are displayed in Fig. 2. These experiments were realized

without plasma for comparison with those in which the microwave assisted plasma was

used. In the first image, no growth of any kind of ZnO nanostructures was observed

because the substrate was placed close to the container with the precursor material.

Throughout the synthesis process, the ZnO mixed with graphite is thermally decomposed, a

process promoted by the vacuum system. The decomposition and subsequent evaporation

of species start between 5 and 10 seconds of microwave treatment. The graphite absorbs

most of the incident radiation on the sample container, thus increasing the temperature in

the reactor to over 1000 ° C. Initially, the heating is a robust process, and vapor is carried

by the ionizing gas to the substrates. For this reason, if the substrate is placed very close to

the container, the deposition of material is not achieved. As a result, in the images of Fig.

2a and Fig. 2b the growth of any ZnO structure on the substrate was not observed because

the growth depends greatly on the gas flow; for a greater flow, there is a higher vapor drift

that prevents the deposition on the substrates near the sample container. Furthermore, at a

distance of 5 cm (Figs. 2c, 2d), the growth of ZnO structures shows a shaped tip, for which

the diameter in its narrowest part is 40 nm and that at its widest part is 300 nm. The growth

of these structures is likely to occur through the vapor-liquid-solid mechanism (VLS),

however, seeds cobalt on the ZnO-NNs cap were not observed in the analysis. The VLS

mechanism seems to be the most successful in the generation of large quantities of

nanowires with single crystalline structures. This process was originally developed by

Warner and Ellis to produce micrometer-sized whiskers in the 1960s [24]. Subsequently,

the mechanism was demonstrated thermodynamically and kinetically and recently

reexamined by Lieber, Yang, and other researchers to generate nanowires and nanorods

from a rich variety of inorganic materials [25]. In the catalyst assisted VLS mechanism,

catalyst nanoparticles serve as a preferential site for the absorption of reactants from the

vapor phase and, under supersaturation conditions, serve as a nucleation site for

crystallization, as controller of the nanostructures growth direction, and they also favor the

supersaturation of the eutectic melt, which is established by catalytic absorption of the

gaseous reactants and acts as the driving force for growth in a highly anisotropic manner.

The inherent 1D self-organized structures combine crystalline quality with high

controllability of both length and diameter, which may vary over a wide range according to

the template used [26, 27]. The ZnO nanotips (shown in Figs. 2c, 2d) also have been

obtained by other authors [22] using conventional CVD and by sublimation of ZnO powder

without introducing a catalyst [28, 5]. Such materials can be used to build field effect

transistors (FET) [29] and nanocantilevers [30], among other devices.

Moreover, when performing the CVD reaction with microwave-assisted plasma, the

formation of ZnO-NNs was observed on alumina substrates placed 10 cm from the

precursor material container (Fig. 3). These NNs were obtained with a He flow of 50 sccm

and a microwave oven power of 1000 W. The reaction time was 5 minutes, which is one of

the advantages of this method compared with the conventional CVD. The ZnO-NNs were
formed homogeneously on all surface of the alumina substrate placed at 10 cm from the

precursor material, as shown in the low magnification micrograph displayed in Fig. 3a.

With the greater details shown in the image at higher magnification (Fig. 3d), the ZnO-NNs

are found to be formed by a hexagon-shaped upper head and a body also of hexagonal

shape but of smaller size.

Such nanostructures have also been obtained by wet methods and deposited onto ITO

(Indium Tin Oxide) [21] by physical methods, such as PVD, and deposited onto Si

substrates [31], and they have also been obtained by CVD with conventional heating [32].

Most of the used methods are similar, and some parameters are genearally modified, such

as gas flow in the range of 50 to 200 sccm, the type of gas (Ar, N2, and He), the mixture of

inert gas with oxygen (Ar / O2, Ar / N2 , and He / O2), substrates (Al2O3, Si, and ITO),

heating temperature (600-1100 °C), distance from the substrates to the precursor material

container (1 to 20 cm), heating rate (10 to 25 °C / min) and growth times. In some cases,

seed growth is used, as in the case of this work; in other cases, the growth is performed

without a specific catalyst [6, 33].

The typical TEM image, shown in Fig. 4 (c), reveals that the diameters of the cap, cone-like

shape below the cap (neck), and the stem are approximately 150, 50, and 25 nm,

respectively. The detailed structures of the ZnO-NNs were characterized using HRTEM, in

this case; Fig. 4 (d) is a HRTEM image taken from the stem of nanonail, which shows its

perfect lattice structure and confirms that the ZnO-NNs has the wurtzite type structure. The

lattice constant measured from the lattice fringes was 0.28 nm, which further confirms that

the ZnO-NNs grows along the [0001] c-axis direction.

Figures 4b and 4c show two ZnO-NNs with cap diameters of 50 and 150 nm, respectively.

The stem of the ZnO-NNs always had the same diameter (25 nm). Usually such

nanostructures are found to have diameters of the cap between 50-600 nm [34, 35] and

diameters of the stem between 25-200 nm [36, 37]. Most of the ZnO-NNs show the same

stem diameter; this diameter is similar to the size of the cobalt seeds deposited by

sputtering, which can be seen in Fig. 5 (b); this could be a clue that the growth of these

nanostructures can be via of VLS mechanism. The diameter of the seed catalyst increased

after of the growth of ZnO-NNs due to their coalescence when the temperature of the

substrate was raised. This synthesis is particularly interesting because the alumina substrate

used in the synthesis is rough, as shown in Fig. 5 (a). Because of this roughness, the

formation of ZnO nanorods is evident at the bottom of the substrate because 1) the vapor

rich in zinc, 2) oxygen does not reach all these sites, and 3) these nanorods are smaller than

the ZnO-NNs. Note that, at the top of these rods, particles of cobalt are found (red frame in

Fig. 5b), above provides further evidences about of VLS growth mechanism of these

nanorods.

The nanonail structure consists of a nanorod stem and a lotus-shaped head (the cap). This

structure is exceptional because it indicates that the growth along the [0001] direction is not

always dominant, as in the case of nanorods. The growth process can be described in two

steps: first, a nanorod grows along the [0001] axis by alternatively stacking O and Zn

atomic layers over the top facet; second, the growth along the axial direction slows down

and the radial growth starts to become dominant, leading to the formation of a hexagonally

shaped nanonail head (cap). Hence, there was a change in the growth conditions that

suddenly hastened the radial growth and gradually increased the thickness of nanorod,
while the epitaxy over the top facet continued. The formation mechanism of ZnO nanonails

still remains unclear. Nevertheless, Liu and Motta [20] studied a single nanonail and they

revealed that the tapered neck section has more oxygen vacancy defects; this characteristic

also has been confirmed by Fan et al. [38] and Li et al. [39], which indicates that the change

of Zn/O ratio in growth species could be a trigger for the formation of nanonails. However,

the controversy over the mechanism of formation of these nanonail nanostructures remains.

To investigate the nanostructure morphology, it is very important to understand the factors

that determine the speed of growth along different orientations and their relative ratios. It is

well known that, in most situations, the growth rates of the different family of planes follow

the sequence (0001) > (1011) > (1010) [40]. There are several reasons why the (0001)

plane shows the highest growth speed, thus promoting the one-dimensional growth. One is

that the Zn (0001) plane has the lowest surface energy, which tends to be the most stable

against oxidation [41]. Because the temperature of the growth zone is above the Zn melting

temperature, this liquid-phase growth front is highly effective to absorb the incoming Zn

vapor and maintains a high growth speed. Another factor is that the top area of nanorods

always receives a higher flux of Zn vapor than the shaft due to the shadow effect intrinsic

to all physical vapor processes. If the growth along the [0001] direction dominates, then

nanorods often grow continuously with homogeneous diameters; this proves the growth

direction found in the HRTEM analysis (Fig. 4c).

Moreover, we should mention that ZnO is decomposed by a microwave-assisted thermal

reaction. The reaction is so strong that, at the first 5 seconds of treatment with 1000 W of

microwaves, the process of decomposition and vaporization of the Zn species begins,

according to the following reaction.

Carbothermal reduction of ZnO at 900-1000 °C resulted in Zn and suboxides ZnOx.

Reaction (1) in the MPA-CVD method is quite fast, so the vapor is transported in the

carrier gas (He) through the quartz tube. However, as the reaction proceeds, the vapor

becomes rich in Zn species, which can be better absorbed in the catalyst (Co-Seeds) than

the species of CO and CO2. This process results in a lack of oxygen atoms, thus producing

more oxygen vacancy defects in the nanostructures grown on the substrate. Increasing the

number of oxygen vacancies triggers the growth of the nanorod stems in the direction

[1010]. In conclusion, we think that there are at least two factors that promote the formation

of nanonails. One factor is that the top surfaces of nanonails always receive the incoming

source vapor at a higher rate than that of the underneath stems due to the shadow effect.

This trend further accelerates as the caps of the nanonails grow larger. The other factor is

the abrupt increase of the O/Zn ratio as the Zn vapor runs out near the end of evaporation.

This change may significantly boost the lateral growth along the [1010] direction and

promotes the formation of caps on the nanorod necks [20]; the above process is influenced

by the inert gas (He) used in the reaction (I) and the plasma assisted by microwave

irradiation due to the possible alignment of the deposited Zn atoms on the substrate.

However the growth process of NNs, at least by this technique, is not entirely controlled,

although the preferential shape is the nanonail structure. The uniformity of the caps, necks

and shank of the NNs do not suggest that there is an equal distribution of vapor species in

the entire alumina substrate; this unequal distribution leads to the formation of NNs with

different dimensions in their caps, necks and shank, as illustrated in Figures 6a-f. In these

micrographs, neck sizes of 50 and 60 nm (Fig. 6a) and 320 and 380 nm (Fig. 6b) were

observed; nanonails with two necks also were observed (Fig. 6d) as well as stake-shaped
NNs without necks (Fig. 6f). These micrographs prove that the gaseous species are not

uniform across the substrate surface, leading to growth of different types of NNs.

Finally, in Fig. 7, SEM micrographs of ZnO-NNs on alumina substrates are displayed. The

observed defects above the caps of NNs could be a further indication that these

nanostructures grew via VLS. These structural defects in the caps of NNs indicated that the

growth of ZnO nanorods continues from the stem of the NNs; when steam is poor in

oxygen, it leads to growth in another direction [1010]; at this time, the growth of the cap

begins, as the catalytic seed is liquid above the cap of NNs, and the growth of the cap may

slow due to the inclination of the NNs and generate the defects that are shown in Figure 7,

even this seed due to the high temperature of the reaction system could also fall off the cap.

4. CONCLUSIONS.

ZnO-NNs were synthesized by MAP-CVD catalyzed by seeds of cobalt on alumina

substrates. The obtained NNs presented different sizes in three main parts, i.e., caps, necks,

and shank, and their values ranged between (25-150 nm), (30-200 nm), and (250-450 nm),

respectively. The formation of this type of nanostructure can be due to the formation of

oxygen vacancies during the growth. Microwave-assisted reaction is fast and vigorous

compared to conventional CVD. Employing the MAP-CVD approach, the produced vapor

is richer in Zn than oxygen, allowing for the growth of NNs instead of NWs. The inert gas

plasma with the vapor produced by the thermal decomposition of ZnO facilitates the

formation of NNs due to the stabilization of the reactant species of the ionized gas. Defects

presented in the caps of NNs provide evidence that possibly the growth mechanism of this
type of nanostructures may be via VLS; however the results are inconclusive regarding the

above. Through this new technique, the homogeneous growth of ZnO nanonails on alumina

substrates was demonstrated.

ACKNOWLEDGEMENTS

MFM thanks FONDEF No. CA12I10308 for financial support of this work and the Government of
Chile. The authors are also grateful to the electronic microscopy laboratory of the International
Center for Nanotechnology and Advanced Materials at the University of Texas in San Antonio,
USA, and the Advanced Nanocomposites Research Group (GINA) at the Materials Engineering
Department (DIMAT), University of Concepcion, Concepcion - Chile. The authors would like
to thank the National Commission for Scientific and Technological Research,
CONICYT (Ministry of Education Government of Chile) by PhD scholarship grant Nº 63140015
of A.F. Jaramillo.

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FIGURE CAPTIONS

Fig. 1. Microwave Plasma-Assisted Chemical Vapor Deposition (MPA-CVD) synthesis

device used for the growth of ZnO nanonails.

Fig. 2. SEM images of a) and b) alumina substrates after synthesis via CVD without
microwave plasma assistance, with the distance from the substrate to the sample container
of 5 cm. c) and d) 20 cm growth without plasma.

Fig. 3. SEM images of the ZnO-NNs obtained with MPA-CVD at 1000 W and 5 minutes of
reaction. a) and b) low magnification image, which shows NNs of uniform growth
regarding the length and width on the alumina substrate. c) and d) image of high
magnification NNs, where the form of this type of nanostructures is observed.

Fig. 4. HRTEM analysis of ZnO-NNs obtained with MPA-CVD. a) Low-magnification

image of NNs, b) and c) high magnification image, where the different diameters of the cap
and stem are observed, d) HRTEM image showing the preferential direction of growth of
the stem of NNs in the direction [0001].

Fig. 5. SEM image showing the alumina substrate surface roughness. a) In the background,
the formation of ZnO nanorods can be observed. b) Contrast image, where the seeds of
cobalt catalyst (25 nm) are observed, and ZnO nanorods grown via the VLS mechanism.

Fig. 6. ZnO-NN with MPA-CVD grown on alumina substrate. The caps, necks and shank
of NNs with different dimensions. a) 50 - 60 nm, b) 320-380 nm, d) 30 - 40 nm, d) no
conically NNs neck, f) TEM image e) ZnO-EDX of NNs.

Fig. 7. SEM images of the ZnO-NNs grown via MPA-CVD, based on a VLS growth
mechanism. The observed defects of the caps of the NNs indicate the possible mechanism
of growth of such nanostructures.
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7