Arabian Journal of Chemistry (2019) 12, 5173–5179

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Piezoelectric nanogenerator based on ZnO

nanorods
Majid S. Al-Ruqeishi *, Tariq Mohiuddin, Butheina Al-Habsi, Fatma Al-Ruqeishi,
Ahmed Al-Fahdi, Ahmed Al-Khusaibi

Department of Physics, College of Science, Sultan Qaboos University, P.O. Box 36 P.C. 123, Al-Khoudh, Oman

Received 27 September 2016; accepted 15 December 2016

Available online 26 December 2016

KEYWORDS Abstract A piezoelectric nano-generator (PZG) based on in-house ZnO nanorods (ZnO NRs) was
Piezoelectric device; constructed and utilized. ZnO NRs were synthesized by tube-in-tube chemical vapor deposition
ZnO nanorods; (CVD) technique for large production. To produce large harvested rods, the inner side of a horizon-
CVD tal quartz tube was used as growth platform directly without the aid of substrates or catalysts. The
production is about 3–5 g each trail, which is considered as a large scale production in nano-field
synthesis. The fabricated nano-rods are polycrystalline in structure and it has (57 ± 11)nm and
(3.9 ± 0.8)lm in average diameter and length, respectively. Piezoelectric properties of ZnO NRs
were studied by building a real piezoelectric nano-generator, which show the proportional relation
between exerted mechanical forces and their outcome voltages. It was found that as the stress force
increases more current will flow and the maximum voltage has reached 0.7 V. The nano-generator
exhibited Schottky-like I–V characteristics and constructively generated harvesting currents. Cur-
rent jumps by 4.14 lA when the applied force was increased by about 20 N. Correspondingly,
the voltage signal exhibited a similar output of
0.25 V. This device can be utilized to generate elec-
tricity while walking to charge mobile electronic devices such as hand phones for instance.
Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Zinc oxide nanostructures with a wide direct band gap (3.37 eV) and
an efficient excitation emission at room temperature due to large exci-
ton bonding energy (60 MeV) (Wang, 2004; Tang and Zhou, 2004 and
* Corresponding author. Fax: +968 24414228.
E-mail address: majidruq@squ.edu.om (M.S. Al-Ruqeishi).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
Look and Reynolds, 1998) make it proper for opto-electric applica-
tions for short wavelengths. Other properties like fast photo-
response for ultraviolet (UV) light in the photo-detectors and transpar-
ent to visible light was reported by (Tang and Zhou, 2004). Now many
applications depend on ZnO nanostructures such as optical pumped
laser, light emitting diodes, UV photoelectric devices, biosensors, solar
cells, and piezoelectric nanogenerators (Youfan and Chang, 2010;
Dhara and Giri, 2013; Zhuo and Feng, 2008; Dagdeviren, 2010 and
Dagdeviren and Hwang, 2013). The structure of ZnO crystal consists
of alternating planes in which each atom is tetrahedrally coordinated,
with the O2 and Zn2+ ions stacked alternatively along the c-axis, and
the center of gravity of the charges is at the center of the tetrahedron
where positive and negative charges cancel each other. The lack of

http://dx.doi.org/10.1016/j.arabjc.2016.12.010
1878-5352 Ó 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
5174
center of symmetry combined with the large electromechanical cou-
pling results in a strong piezoelectric response (Wang, 2004 and
Özgür and Aliviv, 2005).
ZnO piezoelectric nano-generator (PZG) transfers mechanical
energy to kinetic energy and vice versa and hence is utilized for many
applications such as transducers, sensors and actuators (Wei and Pan,
2011; Arya and Saha, 2012 and Chen and Choe, 2012). But the chal-
lenge here is to produce ZnO nanostructures with the same morphol-
ogy in relatively large quantity in order to build portable PZG
devices. Several morphologies of ZnO such as nanorods, nanocombs,
nanobelts, nanowires, nanosheet and nanorings (Consonni and
Sarigiannidou, 2014; Lee and Minegishi, 2008 and Elias et al., 2008)
have been reported. The variety of nanostructures can be synthesized
by various techniques including gel–sol process (Tay and Li, n.d;
Shan and Xiao, 2006), hydrothermal growth and chemical vapor depo-
sition (CVD) (Sun and Liu, 2006; Patil and Pawar, 2012; Zhang and
Ram, 2012; Umar and Kim, 2005 and Wu and Yang, 2001).
The most important drawbacks of various ZnO nanostructures
synthesis methods are their low quantity and physical stability. Unsta-
ble produced nanostructures in the hydrothermal aqueous solution for
instance may cause the nanostructures to recombine, aggregate and
accumulate to form bigger structure instead, while CVD solves this
problem and produces stable, high crystalline quality nanostructures
with defined size and shape and it can be controlled for relative large
mass production. Formation of ZnO nanomaterial in the CVD tech-
nique from a mixture of ZnO and graphite was used as source of
growth precursors in long horizontal quartz tube. Therefore, the
amount of evaporated gases delivered to growth sites such as silicon
wafers at cooler locations could allow nanostructures nucleation
growth to begin. But due to the limitation sizes of the silicon wafers,
growth platforms, inside the horizontal quartz tube the total harvested
nanostructures will not be suitable to build working piezoelectric
device. Therefore, in this study an alternative solution was achieved
by utilizing the inner side of horizontal quartz tube as the favorite
nanostructure growth platform for large production and hence a piezo-
electric device was designed and built.
2. Experimental setup
In this process we design tube in tube chemical vapor deposi-
tion (CVD) system to produce large scale, mass in grams, pro-
duction of ZnO NRs. Firstly, powders from Sigma Aldrich of
graphite (99.99%, <45 lm) and ZnO (99.9%, <5 lm), with
mass ratio of (1:1) were mixed and grained well. Then an
amount of 20 g of the mixture was added each time into a com-
bustion boat and used as source material. The source material
was loaded into a 3.8 cm-inner diameter quartz tube (large
tube), which was placed at the center of a 45 cm long horizon-
tal tube furnace as shown in Fig. 1. And another small quartz
tube (D = 2.6 cm and L = 12 cm) was loaded inside the hor-
izontal quartz tube to work as growth platform or locations
near the boat directly. The inner sides of both large and small
Large quartz
tube
Pump 38 mm
26 mm
Small quartz
tube
Figure 1 Tube in tube CVD growth process for large scale production of ZnO nanowires.
M.S. Al-Ruqeishi et al.
quartz tubes are the locations where expected to grow large
scale ZnO nanowires. The horizontal quartz tube was con-
nected to argon (99.999%) gas supply and a flow rate control
system at one end while the other end kept opened as it is
shown in Fig. 1. The Ar gas was then flushed inside the quartz
tube to get rid of all other gases and kept at 10 sccm, standard
centimeters cubic per minutes. After that, the system is con-
nected to normal ventilation vacuum pump, 101 mbar. Then
the furnace was switched on and the temperature was raised up
to (1000 ± 15 °C) at a heating rate of 1.2 °C/s. The tempera-
ture is constant at the middle area of the furnace but gradually
decreases near its edges, as illustrated in temperature distribu-
tion curve shown in Fig. 1c. After the source material was
completely evaporated, the furnace was turned off and kept
to cool down to room temperature under same Ar flow rate.
The inner side of the short quartz tube was covered with a
white-gray color thin layer at locations near to the source
material place. Then the thin layer was scratched out for five
trials. Finally, the nanostructures in powder form were taken
for further analysis and characterizations.
3. Results and discussions
The experiments were carried using one large quartz tube or
large tube embedded with smaller one, see Fig. 1. In all large
tube trails high yield grown nanostructures with different sizes
and morphologies were obtained in the non-catalytic quartz
tube inner side surface as it can be revealed in Fig. 2(a). The
various obtained nanostructures morphologies can be attribu-
ted to different growth temperatures due to deposition loca-
tions far from the source material. The other thinner rods
were grown at close distance to the source materials. The
growth precursor concentration and temperature profile are
playing a more vital role in the morphology control. In
Fig. 2(b), EDX spectrum reveals that these nanostructures
consist of major elements of Zn and O and a small amount
of platinum, which is normally due to the imaging process
requirement. Because in order to produce clearer images with-
out any disruption from interface between incident electron
beam and secondary reflected electrons the nanostructures
were sprayed with Pt layer to absorb the extra electrons and
reduce the charging effects.
To produce ZnO NRs only, which is preferable shape of
ZnO nanostructures in piezoelectric devices (Khan and
Abbasi, 2012 and Soomro and Hussain, 2012), smaller quartz
tube was placed inside the lager tube as illustrated in Fig. 1.
The small tube will accumulate more growth precursors, near
the source material, under almost 1000 °C heating tempera-
ture. In Fig. 2 (c), the scratched ZnO NRs from the small
Ar
Source Material
Piezoelectric nanogenerator 5175

X 1900
(b) Element Wt%
(a) Zn 78 0.7
O 22.0 0.7

10µm

X 11000 X 18,000
(c) (d)

1µm 1µm

Figure 2 FESEM image of ZnO nanostructures with different morphologies grown at various locations inside the large quartz tube,
(a) EDX spectrum for Fig. 2(a) image, (c) low magnification of grown ZnO NRs inside the small quartz tube and (d) magnified image.

quartz tube were randomly distributed with uniform shape.
The base of the NR has hexagonal shape with direction growth
along crystal c-axis as shown in Fig. 2(c and d) and the rod
diameter decreases to form narrow needle as can be seen in
Fig. 2d. The rods have typically (3.9 ± 0.8)lm. average length
and (57 ± 11)nm. average diameter, measured at middle point
of rod base. Fig. 3 shows the Gaussian distribution of the
length and diameter of the obtained nano-rods.
The XRD pattern of synthesized NRs in Fig. 4 shows a
poly crystalline orientation with wurtzite ZnO structure. The
grown ZnO NRs have 9 diffraction planes, (100), (002),
(101), (102), (110), (103), (200), (112) and (201) at different
2hs with dominant diffraction peak. Also, the ZnO’s XRD pat-
tern indicates the pure phases with no characteristic peaks for
other impurities. The strong intensity and narrow width of
ZnO diffraction peaks indicate that the resulting products were
of high purity and high crystallinity.
We believe that the vapor-solid (VS) growth mechanism
can be used to explain the nucleation and evolving of ZnO
NRs at the surface of quartz tube. The self-seeding of ZnO
material is taken place in different orientations. Zn atoms were
evaporated from the source material and were nuclei with

10 12

8 10

8
6
Frequency
Frequency

6
4

4
2

2
0

0
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 0.04 0.05 0.06 0.07 0.08 0.09
Length (µm) Diameter (µm)

Figure 3 The Gaussian distribution of (a) the length and (b) diameter of ZnO NRs.
5176
(101)
(100)
(002)
Figure 4
oxygen. The increase in the concentration of deposition layers
of Zn and O causes the upward growth of ZnO crystal along
(0001). ZnO crystal is a polar crystal due to the Zn+2 and
O2 ions. The positive plane (0001) of the crystal contains
the Zn atoms that the growth rate in this plate is the fastest
than the negative plate (0001) where it has the slowest growth
rate. This forces the growth along the c-axis direction. Differ-
ent crystal faces have a different rate of growth as follows:
(0001) > (01 1) > (01 0) > (0001).
The piezoelectric phenomenon is described as the ability of
the material to convert the mechanical energy into electrical
energy. We have demonstrated an approach for converting
mechanical energy into electric power using our fabricated
ZnO NRs. The net charge of ZnO crystal is balanced and each
positive charge cancels nearby negative charge. When the
piezoelectric crystal squeezes, the structure will deform and
as a result net positive and negative charges will appear on
opposite crystal faces. This produces a potential difference
Aluminum Electrode
ZnO NRs
Insulate (paper)
Cupper Electrode
(b)
Figure 5 (a) The device setup, (b) scope photo of the device and (c) the connection view for taking measurements.
M.S. Al-Ruqeishi et al.
(110)
(102) (103) (200)
(112) (201)
The XRD spectrum of ZnO NRs.
across the material. In-house built-in device was designed with
a conductive material of cupper (Cu) disc, 0.05 mm thick alu-
minum (Al) disc, paper (insulator) and the synthesized ZnO
NRs as shown in Fig. 5(a and b). The insulated paper was
shaped in ring shape and was placed between Al and Cu disk
boundaries. The ZnO NRs in powder form were inserted in the
inner area centered between two electrodes of Al and Cu discs.
Then, special glow was used to stick the materials together.
The circular contact area between two electrodes and ZnO
NRs is about 4.52 cm2.
The piezoelectric device design depends on an unique cou-
pling between piezoelectric and semiconducting properties of
the ZnO NRs (Song and Zhou, 2006 and Wang and Zhou,
2006). The asymmetric piezoelectric potential and the Schottky
contact between the metal electrode and the NRs are the two
key factors for creating, separating, preserving, accumulating,
and outputting the charges (Wang and Song, 2006). The Al
(/ = 4.08 eV) disk not only enhanced the conductivity of the
(c)
(a)
Device
Voltmeter
Piezoelectric nanogenerator 5177

Table 1 (a) The I–V measurements of piezoelectric device.

Mass (g)  ¼ mgðNÞ
Weight, w Mechanical force/area (N/m2) Compression voltage 0:01ðVÞ Relaxation voltage 0:01ðVÞ
1022 10.016 22,140 0.74 0.57
944 9.251 20,449 0.70 0.54
824 8.075 17,849 0.66 0.48
715 7.007 15,489 0.52 0.43
630 6.174 13,647 0.46 0.37
521 5.106 11,286 0.38 0.32
214 2.097 4635 0.28 0.24

electrode, but also created an ohmic contact at the interface
with n-type ZnO NRs, which has electron affinity Ea = 4.5 eV
(Hasegawa and Nishida, 2005). Therefore, there is no barrier
at the interface of Al-ZnO contact and electrons can move
freely both sides, i.e. from electrode to ZnO NRs and vice
Current (µA)
versa (Mead, 1965). At the bottom electrode, Cu has /
= 4.53–5.10 eV (Xu and Shin, 2010); therefore, Cu-ZnO con-
tact is a Schottky barrier and dominates the entire transport
process. Because the compressed side of the semiconductor
ZnO NRs has negative potential and the stretched side has
positive potential, two distinct transport processes will occur
across the Schottky barrier.

In practice, the device becomes like a battery with a positive

charge on one face and a negative charge on the opposite face
when pressed and relaxed. The circuit was completed by con-
necting the device with the voltmeter as illustrated in Fig. 5c,
and the measured voltage was recorded at various stress forces.
The force was obtained by measuring and estimating finger
pressed force over a weigh balance and then multiplied with
the gravity acceleration g = 9.8 m/s2. The mechanical force
Voltage (V) per circular area was measured and all results are illustrated
in Table 1.
It is noticed that as the stress force increases more current
will flow and the maximum voltage has reached 0:7 V:.
Fig. 6a shows current-voltage characteristics (I–V) of the
piezoelectric device or nano-generator was measured twice,
directly after preparing the piezoelectric device (t = 5 min)
Figure 6 Output I–V characteristic lines of the nano-generator and at time (t = 2 h), to make sure of the device work stability.
at t = 5 min and 2 h. These measurements were conducted under compressed mode,

Figure 7 (a) Schematic drawing of a piezoelectric device with compression and relaxation modes, (b) output voltage in both compressed
and relaxation modes due to an external applied mechanical stress forces and (c) the same voltage fluctuations at both modes and
mechanical forces.
5178
the mechanical force being turned on, and relaxation mode
regularly. The nano-generator exhibited Schottky-like I–V
characteristics and constructively generated harvesting cur-
rents. Current jumps were by 4.14 lA when the applied force
was increased by about 20 N. Correspondingly, the voltage sig-
nal exhibited a similar output of
0.25 V. Similarly, at nano-
generator relaxation mode voltage output increased in oppo-
site direction correspondingly. The energy harvester generated
0.74 V of the maximum output voltage and 1.2  1005 A/cm2
of the maximum current during compression and relaxation
periodic motion. Therefore, our device maximum power is
about 8.97 lW/cm2. This efficiency considered to be in the
middle domain of piezoelectric devices when compared with
others groups’ published work (Gu and Cui, 2013; Chen and
Xu, 2010; Chun and Kang, 2015 and Xu and Hansen, 2010).
In Fig. 7 the physical principal behind the discharge energy
in the piezoelectric device arises from how the piezoelectric and
semiconducting properties of ZnO are coupled. The ZnO NRs
deformation create strain field along the nano-rod, its outer
surface being stretched (positive strain e) and the inner surface
compressed (negative e), so while positive strain (+e) causes
positive electric field (+E). When this happened for each
nano-rod the collective electric fields among all nano-rods will
create common electric field, which depends on the alignment
of these nano-rods.
The collective potential (V) is created by the relative dis-
placement of the Zn+2 cations with respect to the O2 anions,
a result of the piezoelectric effect in the wurtzite crystal struc-
ture; thus, these ionic charges will cause a potential difference
(DV) across the nano-rods, see Fig. 7(a and b), and this is
because these ions cannot move or recombine without releas-
ing the strain. In Fig. 7(b) the output voltage measured after
compression and relaxation modes is directly proportional to
the applied mechanical press force. This voltage will fluctuate
depending on the force applied and which mode is measured,
see Fig. 7(c).
4. Conclusion
An in-house piezoelectric nano-generator (PZG) based on ZnO NRs
was built and utilized successfully as an alternating electric current
producer. It was found that tube-in-tube CVD technique produces
3–5 g of ZnO NRs each cycle, which are required for construction of
PZG. The PZG responds to mechanical stress force by producing
direct current on one direction in compression mode and in opposite
direction in the relaxation mode and the maximum voltage has reached
0.7 V. This voltage will fluctuate depending on the force applied and
which mode is measured.
Acknowledgments
Authors wish to express their sincere thanks to Mr. Ibrahim
Al-Khosabi from CARUU, Central Analytical and Applied
Research Unit, Collage of Science, SQU.
References
Arya, S.K., Saha, S., 2012. Recent advances in ZnO nanostructures
and thin films for biosensor applications: review. Anal. Chim. Acta
737 (6), 1–21.
Chen, Shih-Jui, Choe, Y., 2012. Edge-released, piezoelectric MEMS
acoustic transducers in array configuration. J. Micromech. Micro-
eng. 22 (2), 25005.
M.S. Al-Ruqeishi et al.
Chen, X., Xu, S., 2010. 1.6 V nanogenerator for mechanical energy
harvesting using PZT nanofibers. Nano Lett. 10, 2133–2137.
Chun, J., Kang, N., 2015. Highly anisotropic power generation in
piezoelectric hemispheres composed stretchable composite film for
self-powered motion sensor. Nano Energy 11, 1–10.
Consonni, V., Sarigiannidou, E., 2014. Selective area growth of well-
ordered ZnO nanowire arrays with controllable polarity. ACS
Nano 8, 4761–4770.
Dagdeviren, Canan, 2010. Dielectric behavior characterization of a
fibrous-ZnO/PVDF nanocomposite. Polym. Compos. 31 (6), 1003–
1010.
Dagdeviren, Canan, Hwang, S.-W., 2013. Transient, biocompatible
electronics and energy harvesters based on ZnO. Small 9 (20),
3398–3404.
Dhara, Soumen, Giri, P.K., 2013. ZnO nanowire heterostructures:
intriguing. Rev. Nanosci. Nanotechnol. 2, 1–24.
Elias, J., Tena-Zaera, R., Lévy-Clément, C., 2008. Effect of the
chemical nature of the anions on the electrodeposition of ZnO
nanowire arrays. J. Phys. Chem. C 112 (15), 5736–5741.
Gu, L., Cui, N., 2013. Flexible fiber nanogenerator with 209 V output
voltage directly powers a light-emitting diode. Nano Lett. 13, 91–
94.
Hasegawa, S., Nishida, S., 2005. Field electron emission from
polycrystalline GaN nanorods. Journal of Ceramic Processing
Research. 6 (3), 245–249.
Khan, A., Abbasi, M., 2012. Piezoelectric nanogenerator based on zinc
oxide nanorods grown on textile cotton fabric. Appl. Phys. Lett.
101, 193506.
Lee, S.H., Minegishi, T., 2008. Ordered arrays of ZnO nanorods
grown on periodically polarity-inverted surfaces. NANO LETTER
8 (8), 2419–2422.
Look, D.C., Reynolds, D., 1998. Electrical properties of bulk ZnO.
Solid State Commun. 105 (6), 399–401.
Mead, C., 1965. Surface barriers on ZnSe and ZnO. Phys. Lett. 18 (3),
218.
Özgür, Ü., Alivov, Y.I., 2005. A comprehensive review of ZnO
materials and devices. J. Appl. Phys. 98, 41301–41404.
Patil, S.L., Pawar, S., 2012. Structural, morphological, optical, and
electrical properties of PANi–ZnO nanocomposites. Int. J. Polym.
Mater. 61 (11), 809–820.
Shan, G., Xiao, X., 2006. Growth mechanism of ZnO nanocrystals
with Zn-rich from dots to rods. J. Colloid Interface Sci. 298, 172.
Song, J.H., Zhou, J., 2006. Piezoelectric and semiconducting coupled
power generating process of a single ZnO belt/wire. A technology
for harvesting electricity from the environment. Nano Lett. 6,
1656–1662.
Soomro, M.Y., Hussain, I., 2012. Piezoelectric power generation from
zinc oxide nanowires grown on paper substrate. Phys. Status Solidi
(RRL) – Rapid Res. Lett. 6, 80–82.
Sun, Z.P., Liu, L., 2006. Rapid synthesis of ZnO nano-rods by one-
step, room-temperature, solid-state reaction and their gas-sensing
properties. Nanotechnology 17, 2266–2270.
Tang, Qun, Zhou, W., 2004. A template-free aqueous route to ZnO
nanorod arrays with high optical property. Chem. Commun. 6,
712–713.
Tay, Y.Y., Li, S., n.d., Growth mechanism of spherical ZnO
nanostructures synthesized via colloid chemistry. Phys. B: Phys.
Condens. Matter 394(2), 372–376.
Umar, A., Kim, S., 2005. Catalyst-free large-quantity synthesis of ZnO
nanorods by a vapor–solid growth mechanism: structural and
optical properties. J. Cryst. Growth 282 (1), 131–136.
Wang, Z.L., 2004. Zinc oxide nanostructures: growth, properties and
applications. J. Phys.: Condens. Matter 16, R829–R858.
Wang, Z.L., Song, J., 2006. Piezoelectric nanogenerators based on zinc
oxide nanowire arrays. Science 312, 242–246.
Wang, X.D., Zhou, J., 2006. Piezoelectric field effect transistor and
nanoforce sensor based on a single ZnO nanowire. Nano Lett. 6,
2768–2772.
Piezoelectric nanogenerator
Wei, Ang, Pan, L., 2011. Recent progress in the ZnO nanostructure-
based sensors. Mater. Sci. Eng. B 176 (18), 1409–1421.
Wu, Yiying, Yang, P., 2001. Direct observation of vaporliquidsolid
nanowire growth. J. Am. Chem. Soc. 123 (13), 3165–3166.
Xu, S., 2010. Piezoelectric-nanowire-enabled power source for driving
wireless microelectronics. Nat. Commun., 1098
Xu, Chengkun, Shin, P., 2010. Preferential growth of long ZnO
nanowire array and its application in dye-sensitized solar cells. J.
Phys. Chem. C 114 (1), 125–129.
5179
Hu, Youfan, Chang, Y., 2010. Designing the electric transport
characteristics of ZnO micro/nanowire devices by coupling piezo-
electric and photoexcitation effects. ACS Nano 4, 1234–1240.
Zhang, Yangyang, Ram, M.K., 2012. Synthesis, characterization, and
applications of ZnO nanowires. J. Nanomater., ID 624520
Zhuo, R.F., Feng, H.T., 2008. Morphology-controlled synthesis,
growth mechanism, optical and microwave absorption properties
of ZnO nanocombs. J. Phys. D Appl. Phys. 41, 185405.