Characterization and Analysis of Nanomaterials - Nanomaterials and Devices

5/14/2018 7.
Electro-Optical and Piezoelectric Applications of Zinc Oxide - Nanomaterials and Devices
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Electro-Optical and Piezoelectric

Applications of Zinc Oxide
ZnO is an emerging nanoscale material due to its exciting optoelectronic and
piezoelectric properties. In Chapter 7, ZnO is discussed in detail. The growth
of nanoscale ZnO films is presented, along with the resulting optoelectronic
properties of these materials. The principles of piezoelectricity are
introduced, along with ZnO-based generation of electricity through force.
K EY WO R DS
ZnO; epitaxial growth; ZnO nanowires; piezoelectricity; ZnO nanogenerator
CHA PTE R O U TL I NE
7.1 Optoelectronic Applications 175
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5/14/2018 7. Electro-Optical and Piezoelectric Applications of Zinc Oxide - Nanomaterials and Devices
7.1.1 Optical Properties of Zinc Oxide 175
7.1.2 Epitaxial Growth of ZnO 179
7.1.2.1 MBE Technique with Microwave 179
7.1.2.2 L-MBE Growth Technique 179
7.1.3 Optical Properties of ZnO Quantum Dots 181
7.1.4 Controlled Synthesis of the Ordered ZnO Nanowire Arrays 183
7.1.4.1 VLS Growth 183
7.1.4.2 VS Growth 184
7.1.4.3 The Hydrothermal Method 184
7.2 Piezoelectric Applications of Zinc Oxide 185
7.2.1 Piezoelectric Effect 185
7.2.2 Piezoelectric Application of Zinc Oxide: Nanogenerators 187
7.2.2.1 Why Do We Need Nanogenerators? 187
7.2.2.2 Principle of Piezoelectric Nanogenerators 188
References 190
7.1 Optoelectronic Applications
7.1.1 OPT IC A L PROPERT IES OF ZIN C OX IDE [1]

Apart from III–V nitrides and II–VIII–VI selenium compounds, the unique
nature of zinc oxide (ZnO) makes it a much anticipated material for the next
generation of wide band-gap semiconductor laser devices. Although the
methods for preparing ZnO of higher quality have yet to be further explored,
ZnO has shown great superiority over other materials. Zinc oxide is considered
to be an important direct wide band-gap semiconductor material. At room
temperature, it can have a band-gap width of 3.37 eV and exciton binding
energy of up to 60 meV, with rotation properties from the blue to ultraviolet
bands. ZnO has high chemical and thermal stability and is not easily oxidized
in the atmosphere. Compared with III–V nitrides and II–VIII–VI selenium
compounds, it has unmatched material stability.
Because the ZnO grain size goes down to the nanoscale, significant changes
will occur on its surface electronic structure and crystal structure, and thus it
will show nanoscale size effect, surface effect, dielectric confinement effect,
and quantum size effect that macro-block materials do not have. Meanwhile, it
may have characteristics unparalleled in normal ZnO materials. Many of its
special features can be applied in a variety of areas, including chemistry,
electronics, biology, and medicine.
Zinc oxide-based semiconductor optoelectronic devices, including UV

detectors, light-emi ing diodes (LEDs), and semiconductor laser diodes (LDs),
are widely used in optical communication networks, optical display and
storage, conversion, and optical detection. In the field of optoelectronic
displays, for example, the technology for flat panel displays is a basic
requirement for the terminal display in the information age. Currently, it is
available with key technologies, including liquid crystal display, cathode ray
tube, plasma display panel, vacuum fluorescent display tube, and LED. The
LED for flat panel displays exhibits the advantage of low drive voltage.
Combined with IC design, it is secure in use, featuring a multicolor display,
long life, and quick response. As an ideal flat panel display device, it has a
wide range of potential applications for scientific instruments, portable
computers, and aerospace and military fields. Commercialized red and green
LED monochrome display devices have been available, yet color displays are
not commercialized. The main reason is that the brightness and color purity of
blue electroluminescence is lower than required, making it unable to display
true colors with three primary colors, whereas white electroluminescent
materials are mostly in the broadband radiation, which cannot satisfy the
practical requirements because of lower effective radiation intensity of three
primary colors from the filter chips. This is known as the blue
electroluminescence problem in the field of electroluminescence. The
development of the zinc oxide-based LED makes it possible to produce full-
color LED displays, launching a blue electroluminescence boom worldwide.
The key technology for ZnO-based optoelectronic devices is the preparation

of high-quality p-type ZnO thin films. Intrinsic ZnO is an n-type
semiconductor, which must be doped with the acceptor before p-type
transformation is achieved. However, there are more donor intrinsic defects in
zinc oxide; they may produce a high degree of self-compensation effects on
acceptor doping. Also, acceptor impurities in solid solution are very low; it is
difficult to achieve p-type transformation, resulting in failure in making the
core of semiconductor devices with a zinc oxide p–n junction structure. This
greatly limits the development and application of zinc oxide-based
optoelectronic devices. At present, p-type ZnO research has become an
international focus, and a series of breakthroughs have been made accordingly.
A ZnO homogeneous p–n junction with a two-tier structure of p-ZnO/n-ZnO
has been created. In addition, some proposals like the donor–acceptor co-
doping method that can be used to reduce acceptor ionization energy,
resulting in the formation of shallow acceptors in ZnO, have been proven to
be feasible [2]. These results have great significance for new a empts at
making zinc oxide short-wavelength light-emi ing devices, performing in-
depth studies, and applying the doped ZnO thin-film crystal growth
mechanism to broaden the application areas of zinc oxide thin films.
In recent years, blue–green lasers have become popular in semiconductor laser

research. As early as 1991, the US-based 3M Company achieved the first II–VI
ZnSe-based quantum-well laser (77 K), which was breaking news in the field
of science. After that, the joint study group of Brown at Purdue University in
the United States, Philips in the Netherlands, and Sony Corporation in Japan
made lasers that could work continuously at room temperature. By 1996, Sony
Corporation showed its II–VI blue–green laser, with ZnSe/ZnCdSe as
quantum wells and ZnMgSSe as the restriction layer, had a continuous
working life at room temperature up to 100 h. However, the development of
ZnSe-based lasers has not been as fast as many had expected. A full 5 years
were spent improving the laser’s working life from 1 to 100 h, but further
enhancements might lead to even greater difficulties. The main reason lies in
the fact that ZnSe crystals have strong ionic and weak covalent characteristics.
It is very “soft” and easily damaged. Under stimulated emission, it can easily
have a large number of defects in proliferation due to an increase in
temperature. It generated many doubts among researchers, who wondered if
ZnSe, with its inherent shortcomings, is suitable for making a blue–green
laser. In particular, after 1996, with the emergence of GaN blue LEDs and
LDs, the ZnSe material series was facing bleaker prospects. Since the success
of GaN lasers in continuous operation at room temperature, negative views of
the blue–green laser in the ZnSe system have prevailed.
Are the II–VI semiconductors in dire straits regarding creating a blue–green

laser? Some research groups still continue to improve the quality of ZnSe
epitaxial material (such as the use of a ZnSe single crystal as the substrate,
reducing the misfit dislocation of the ZnSe/GaAs interface) and increase the
concentration of p-type doping and perfection of the ohmic contacts of the
electrode. In addition, there are still two ways for new exploration. One is the
use of the beryllium compound ZnMgBeSe. However, many people might
hold back considering its highly toxic nature. The second way is to use ZnO
materials.
Currently, zinc oxide at room temperature can be observed to have stimulated

emission by optical pumping. Yet the observation of stimulated emission at
low temperatures by using electron beams in ZnO bulk materials has been
seen for many years. However, because of the fact that stimulated emission
intensity is rapidly reduced with an increase in temperature, ZnO
optoelectronic material has long been neglected by researchers. Because the
GaN system has provoked more a ention in recent years, ZnO material has
been used as a buffer layer between the GaN epitaxial layer and the SiC
substrate. The reasons are a ributed to the following basic properties. First,
ZnO shares the same wur ite-type la ice structure as that of GaN. Its a-axis
la ice constant is 0.325 nm, which is less than 2% of the la ice mismatch with
GaN, and its c-axis la ice constant is 0.527 nm. Second, ZnO has an n-type
19 3 2
19 3 2
doping concentration up to 10 /cm and mobility of 260 cm /Vs, showing
excellent electrical properties. Third, according to the common anion rule of
electron affinity and energy band offsets, ZnO has a conduction band
minimum that is lower by 0.7 and 0.4 eV respectively than those of GaN and
SiC. Therefore, its use as a buffer layer between GaN and SiC will not cause a
barrier to block electron motion. In the usual GaN/AlN/SiC structure, the
buffer layer of AlN has a conduction band offset of 2.1 and 2.4 eV from GaN
and SiC respectively, resulting in the buffer layer AlN becoming a potentially
high electronic barrier. Finally, compared with the nitride semiconductor,
ZnO material is quite soft and has a relatively small shear modulus. Its use as a
buffer layer can prevent the dislocation caused by the la ice mismatch
extending to the GaN active layer.
7.1.2 EP I TAXI AL GR O WTH O F ZNO

Because ZnO bulk material tends to have some flaws, stimulated emission can
only be achieved under low-temperature conditions. Therefore, it is not
appropriate to use it for making different devices. The use of epitaxial thin
films or a low-dimensional quantum structure is thus necessary to improve the
crystal quality and the bound exciton energy. So far, high-quality growth of
ZnO is accomplished by the use of molecular beam epitaxy (MBE)
technology, with (0001) Al 2O3 as the substrate. Although ZnO and Al 2O3 may
have a la ice mismatch of up to 16%, strain release could lead to a three-
dimensional growth of ZnO quantum dots. In the process of growing ZnO in
MBE, one of the greatest problems is the O2 that may find a way into the
growth chamber. The following is a brief overview of two kinds of
technologies for MBE growth of ZnO.
7.1.2.1 MBE Technique with Microwave
Because the binding energy of oxygen molecules is as high as 5.16 eV, the
traditional methods for material growth, for example MBE and chemical vapor
deposition, are unlikely to decompose oxygen molecules into atoms. Here,
one of the simplest ways is to decompose oxygen molecules into atoms before
they react with Zn and, in this way, the flow of O2 will also be reduced. A
research team in Japan at the Tohoku Institute of Metallic Materials made a
clever use of microwave methods that allowed oxygen molecules to be
ionized into the plasma before passing into the growth chamber, where the
microwave source power was 120 W, gas flow was controlled by a drain valve,
the selected substrate was (0001) sapphire, and growth temperature was
maintained at 500–550°C.
7.1.2.2 L-MBE Growth Technique
Another growth technique is the high-power laser ablation of the ZnO target
with a purity of 99.999%, so that ZnO can be spu ered onto (0001) sapphire
substrates at a temperature of 500°C. In this growth process, ZnO
decomposition is inevitable under high-power laser and high local
temperature. To ensure the quality of crystals, the growth chamber requires an
oxygen-rich environment. In general, we can use the beam pressure of oxygen

to increase the level of oxygen.
These two methods for epitaxial ZnO on sapphire are executed by using the
Stranski–Krastanov growth mode. The whole process is monitored by high-
energy electron diffraction. In the initial stage of epitaxial ZnO, the thin
stripe-like RHEED pa ern shows that the growth is in a two-dimensional
layer. As the ZnO thickness increases, strain energy in the epitaxial layer
accumulates to a certain degree and will be released by way of dislocation,
thus forming a three-dimensional growth nucleus. At this point, some dots in
the RHEED pa ern will be distributed on the thin line as shown in Figure 7.1.
Epitaxial ZnO may have the [ ] and [ ] crystal orientations that
are, respectively, parallel to the [ ] and [ ] of Al 2O3. Because

ZnO thickness is 55 nm, images under the atomic force microscope show the
regularly ordered microcrystalline islets formed in three-dimensional growth
with a diameter of approximately 50 nm and fluctuation of 10%. Compared
with the bulk material, these two methods can reduce the concentration of
impurities and defects so that stimulated emission may occur at room
temperature. It should be made clear that in the growth of InAs on GaAs
substrates, the la ice constants of both have a difference of 7%. Because the
InAs layer thickness is approximately 0.5 nm, the formation of islets starts. The
mismatch between the ZnO and Al2O3 may be 16%, whereas the critical
thickness of the formed islets is 55 nm. This might be determined by three
factors: ZnO surface energy, Al 2O3 substrate surface energy, and the interfacial
energy between the two.
FIGURE 7.1 RHEED patterns of ZnO epitaxial layer: (A)

(0001) sapphire substrates after annealing treatment; (B) the
growth after 10 min; (C) the growth after 20 min; (D) growth
after 1 h (growth rate: 1.5 nm/min). Taken from Ref. [3].
7.1.3 O PTI C AL P R O P ERTI ES O F ZNO Q UANTUM DOTS

With the ZnO band gap of 3.37 eV, stimulated emission may be achieved at
low temperatures. Nonetheless, such stimulated emission has never been
observed at room temperature, and thus it is of li le scientific interest to the
research community. By the time ZnO quantum dots were successfully grown,
the optically pumped stimulated emission observed at room temperature may
achieve an exciton binding energy of 60 meV. Such high energy at low
temperatures makes it possible to significantly reduce the lasing threshold.
The following is a brief description of optically pumped stimulated emission
of ZnO quantum dots.
With the cwHe–Cd (355 nm, 15 ps) laser as the excitation light source, a
different composite process can be observed at different excitation intensity,
as shown in Figure 7.2.
FIGURE 7.2 Stimulated emission peak at different excitation

intensities. Taken from Ref. [3].
The free exciton peak A in Figure 7.2 corresponds to the stimulated emission
peak E ex at low-intensity excitation. In the case of higher excitation intensity,
the free exciton peak may be gradually replaced by a new P 2 peak of
approximately 70 meV, which is lower than E ex. This is a spontaneous emission
peak in the collision process of two excitons, the intensity of which presents a
linear increase as the optical pump intensity increases. In the collision process
of the two excitons, one of the excitons will absorb energy from another
exciton and complete the transition to the high-energy state P n. The exciton
will release a photon in the transition from an unstable high-energy state back
to the ground state.
(7.1)
Here, ≈60 meV is the binding energy of the ZnO exciton, k is
the Bol mann constant, and T is the temperature. When the optical pump
intensity reaches the threshold , the P 2 peak is

gradually replaced by the new stimulated emission peak P, with the optical
pump intensity increased further to the threshold
, and a new stimulated emission peak N will

appear. For the relationship between stimulated emission intensity L and
optical pump intensity I, see Figure 7.3. As the excitation intensity exceeds
the threshold , the peak P intensity may decrease with the increase of
excitation intensity. This is because the excitation light source is too strong,
thus resulting in high concentrations of plasma.
FIGURE 7.3 Peak intensity of the stimulated emission on

changing the optical pump intensity. Taken from Ref. [3].
7.1.4 CO NTR O LLED SY NTH ESI S O F TH E O R DER ED ZNO

NANO WI R E AR R AYS
As one of the one-dimensional ZnO nanomaterials, ZnO nanowire plays a key
role in the development of devices using ZnO-based nanomaterials. The
process of producing ZnO nanowires is a key issue worldwide. To date,
scientists have invented many new techniques and new methods for preparing
ZnO nanowires. The growth mechanism of ZnO nanowires can be categorized
in the following ways: (1) vapor–liquid–solid (VLS) growth method, (2)
vapor–solid (VS) growth method, and (3) hydrothermal method. These
methods can be classified as follows.
7.1.4.1 VLS Growth
In the 1960s, R. S. Wagner and associates first proposed the VLS growth
method in their research on the growth process of silicon whiskers. This is the
traditional method for the growth of one-dimensional material. It is based on
the catalyst of liquid metal clusters as the active sites of gas-phase reactant. The
source material for preparation of the one-dimensional material is heated into
vapor form. After the vapor is spread onto the surface of the catalyst to form
saturated clusters, one-dimensional nanostructures will grow and take shape on
the catalyst surface. The VLS method has been widely used for the preparation
of nanowires of various inorganic materials, including ZnO nanowires. In the
thermal evaporation VLS growth method for preparation of one-dimensional
zinc oxide nanomaterials, catalysts are often made from copper or gold, or
nanoparticles or nanofilms prepared with other transition metals.
Based on the catalytic VLS growth mechanism, ZnO nanowires can be

synthesized using a simple chemical vapor transport and condensation method.
Here, the catalyst plays a vital role in the growth of ZnO nanowires. By
controlling the starting position and size of the catalyst, control of the location
and diameter, respectively, of ZnO nanowires can be achieved, whereas the
density of nanowires can be controlled by the density of catalyst particles.
However, using the current catalyst VLS method, we cannot control the size
and density distribution; therefore, we cannot control the diameter, location,
and density distribution of ZnO nanowires.
7.1.4.2 VS Growth
The VS method includes one or several reactants heated to form vapor at high
temperatures. The vapor in an inert gas flow is transported to the low-
temperature zone in the reactor or vapor is rapidly cooled to achieve growth
in one-dimensional structural materials. In 1997, Yang and colleagues used the
improved VS method and successfully prepared an MgO nanorod array with a
diameter of 7–40 nm and height of 1–3 µm. The preparation of one-
dimensional zinc oxide nanomaterials using the VS growth mechanism is also
very common. Lee and colleagues, by controlling the atmosphere, prepared
ZnO nanowires by way of thermal evaporation, where zinc oxide powder was
used as raw material with no catalysts and thermal evaporation temperature
was 1,380°C. Nanowire growth substrate was placed at the export end of an
alumina tube at a temperature of approximately 450°C. Xu and associates
prepared ZnO nanowires and nanowhiskers with calcined ZnC2O4
nanoparticles and powders. Surface-active agent was used in the calcination
process. In a tube-type furnace, the quar boat had a temperature of 920°C and
access to ammonia. The growth of ZnO nanowires is also interpreted as the VS
mechanism in this preparation method.
The VS method has the advantage of requiring no catalyst; however,

considering the complexity of the equipment for the synthetic process, the
higher reaction temperature, very limited choice of substrate, the expense,
and difficulty in controlling the size and shape of one-dimensional material, it
is greatly limited in applications in the manufacture of devices.
7.1.4.3 The Hydrothermal Method
The hydrothermal method is in the liquid-phase synthesis method category.
The liquid-phase synthesis method, compared with VLS and VS, which
require high temperatures (800–1,400°C), is a low-cost, low-temperature
synthetic method. The hydrothermal method was first used for synthesis of
ZnO nanorods. Zn nitrate solution (Zn(NO3)2•4H2O), mixed with
hexamethylene tetramine, is placed inside a hydrothermal reactor at 95°C and
heated for 1–10 h. From sediment on the F–SnO2 glass after cleaning and air-
drying, a large number of aligned ZnO nanorods can be obtained; however,
the size of the product is a bit too large. There are improved methods, such as
the two-step hydrothermal method. The two-step hydrothermal method is as
follows. First, ZnO grains with a diameter of 5–10 nm are evenly sca ered on
an Si (100) chip as a crystal seed. When the silicon chip is uniformly covered,
ZnO nanorods can be synthesized at 90°C by shaking the chip suspension for
0.5–6 h in an open crystalline plate of zinc-filled nitrate solution. After the
chip is removed with salt ions, cleaned, and dried, we can get ZnO nanorods
with a diameter of approximately 90 nm. In addition, the hydrothermal
synthesis method can also be used to prepare ZnO nanowires. Currently
reported array films of single-crystal ZnO nanorods created by a hydrothermal
preparation have a highly consistent orientation, with an average diameter of
approximately 40 nm. The film of approximately 390 nm emits strong
fluorescence. A ZnO nanocolumn array created by hydrothermal synthesis has
a nanocolumn length of 230 nm and a diameter of 38 nm. ZnO nanowire
created by hydrothermal synthesis has a diameter of 50–80 nm and a length of
more than 6 mm.
Compared with the preparation method of ZnO nanowires as described in

Sections 7.1.4.1 and 7.1.4.2, the hydrothermal method has the unique
advantages of being simple and economical and requiring no special large-
scale equipment or high reaction temperature. If the size and location of ZnO
grains (precursor of ZnO nanowires) can be controlled, then the ZnO nanowire
size, location, and orientation, which are ultimately obtained with the
hydrothermal method, can be controlled by the homoepitaxy principle.
7.2 Piezoelectric Applications of Zinc Oxide
7.2.1 PIEZOELECT RIC EFFECT

In physics, a number of dielectric ionic crystals (e.g., quar , Rochelle salt,
barium titanate) will have polarization not only under an electric field but
also under mechanical stress.
In a certain direction, as the dielectric experiences a mechanical force to

deformation, it will cause the relative transfer of its internal positive and
negative charge centers to polarize. As a result, two of its relative surfaces
(polarization surfaces) will be found with the bound charge Q with the
opposite symbols, and its electric displacement D (the charge density σ in the
MKS system of units) is proportional to the external stress tensor T:
(7.2)
In this equation, d is the piezoelectric constant matrix. This process indicates a

conversion from mechanical energy to electrical energy, called the positive
piezoelectric effect.
If the aforementioned dielectric is applied with an electric field, then the

relative displacement of the positive and negative charge centers inside the
dielectric will also lead to dielectric deformation, with its strain S being
proportional to the external electric field strength E:
(7.3)
Dt is the converse piezoelectric constant matrix.
This phenomenon is known as the converse piezoelectric effect, also known as

electrostriction, a process in which electrical energy is converted to
mechanical energy. The piezoelectric effect is the effect of a charge
polarization caused by the mechanical deformation of materials; it is an
important physical process to achieve mechanical and electrical coupling and
sensing.
Piezoelectric materials were discovered by the Curie brothers (Pierre Curie

and Jacques Curie). They first demonstrated how to generate electricity
through movement in 1880, and they constructed the world’s first
piezoelectric sensor. In the following year, Jacques Curie discovered the
function that converted the electric energy created by movement to another
type, called the converse effect. The piezoelectric technology demonstration
led to the building of the world’s first ultrasonic submarine detector by French
military scientists in 1917. This was the prototype of sonar.
At that time, piezoelectric material had to be extracted from quar ; these

quar bodies may act as a frequency reference and flexibility tester and so on.
In acoustic holographic technology, they can be used to detect small structural
defects. Today, however, the piezoelectric material can be manufactured in
the laboratory and can also be made into various synthetic compounds, which
include ceramic converters, microphones, accelerometers, starters to the filter
of surface acoustic waves, and others. The synthesized piezoelectric materials
also can be used as solid-state devices to replace the solenoid and the static
“muscle” in computer motor systems.
The piezoelectric effect is one of the most important physical effects that has
been applied to the sensing and control of subjects. When applied with stress,
some of the crystals with the special structure can generate a voltage
difference. Conversely, under the influence of an external electric field, the
crystal can produce elastic deformation. The piezoelectric effect demonstrates
an important physical process through which stress is converted to electrical
signals.
7.2.2 P I EZO ELECTR I C AP P LI C ATI O N O F ZI NC OXI DE:

NANO GENER ATO RS
7.2.2.1 Why Do We Need Nanogenerators?
A nanodevice is small, uses less power, has high sensitivity in reflecting, and
has all the unique advantages of macroscale devices. Nanodevices have been
at the forefront of research in academia. To make these tiny devices work
properly, they must be driven with electricity. However, only self-powered
nanodevices can be regarded as a true nanosystem. Because a nanosystem must
be very tiny (so it can be implanted into the human body, for example), its
power supply system must be miniaturized. Nonetheless, the current study is
only focused on the nanoscale device itself, without considering the issues of
power-inpu ing systems.
Energy is needed for generating power. For example, wireless sensors that are
planted into organisms require a ba ery to supply the power directly or
indirectly. Many nanodevices are used for health care and, in such
circumstances, conventional ba eries that contain lithium and cadmium and
other toxic substances cannot be candidates for biomedical devices to be
implanted in the human body.
Alternatively, people are aware of recycling and reuse. In fact, there is much
wasted energy around us, such as the vibration of passing vehicles, electric
heat, a variety of acoustic and electromagnetic waves, and so on. If we can
develop a technology to recycle that wasted energy, then it will be a truly
remarkable contribution to improving energy efficiency.
In fact, people generate energy when walking and breathing. So, can we
convert the energy in the human body into the electric power for nanoscale
devices? In other words, can the tiny vibrating mechanical energy in the
surrounding environment be collected and transformed into electricity to
provide energy for nanodevices such as sensors and detectors? The vibration of
mechanical energy exists in the natural world and in people’s daily lives, such
as the various frequency noises caused by air or water flow, engine rotation,
air-conditioning, or the functioning of other machines, as well as energy used
to stretch the muscles in people when walking or the compression energy
from the feet stepping on the ground. Even in the human body, subtle changes
in pressure caused by breathing, the heart beating, or blood flow somewhere
in the body can also be used to drive nanogenerators. A tiny device that could
transform the body’s bioenergy into electricity for nanodevices so we can
achieve the miniaturization of nanodevices and its power supply system
would be most ideal.
The concept of the nanogenerator is proposed just in this context. By using the
unique nature of zinc oxide nanowires with the vertical structure, nanoscale
mechanical energy can be successfully converted into electrical energy. The
development of nanogenerators of this kind is based on zinc oxide nanowires
with a vertical structure. By using a conductive atomic force microscope probe,
the vertical zinc oxide nanowires can be bent and input with mechanical
energy, whereas the piezoelectric effect in the zinc oxide nanowires may
result in the polarization of charge. Thus, mechanical energy is transformed
into electrical energy. Because of the semiconductor features of zinc oxide,
the semiconductor metal Scho ky barrier can be used for the temporary
storage of electrical energy in nanowires. The conductive atomic force
microscope probe is applied to access the power for transmission to the
outside. Thus, a perfect nanoscale-generating function is made ready.
Presently, the power-generating efficiency of nanogenerators can reach 17–
30%. The invention of nanogenerators opened a new chapter in nanoscience
and technology. Principally and theoretically, it laid the foundation for self-
generating nanodevices.
7.2.2.2 Principle of Piezoelectric Nanogenerators [4–6]
The principle of the nanogenerator is based on the piezoelectric effect by the

use of one-dimensional nanomaterials (nanowires or nanobelts); that is, a
longer (micron level) nanowire is pushed using an electron microscopy (e.g.,
atomic force microscopy, ATM) probe to produce a charge. Also, as the probe is
moved away, the charge is released as current. Thus, mechanical energy is
converted into electrical energy to enable the normal operation of a
nanogenerator. Here, the piezoelectric effect is a result of the bending of the
nanowire, so it can be called the bending-electric effect. Macrobending is
quite difficult, and the bending-electric effect is not so significant. But
nanoscale one-dimensional bending is relatively easier, so the bending-
electric effect is manifested more easily. Of the known one-dimensional
materials, ZnO is the most important. The main advantages of ZnO are that it is
a semiconductor with a piezoelectric effect, a basic feature that allows it to be
used as electrical and mechanical coupling sensors and inverters; in addition,
in the current nanostructures that have been invented, ZnO has the most
varieties, such as nanowires, nanobelts, nanosections, nanorings, nano-arched
structures, and nanohelical structures [3, 7 ,8]. People have gained
experience in how to control and grow high-quality ZnO nanostructures. As

mentioned, a nanogenerator may find its major application in biological
systems, which require relatively higher biosafety and biocompatiblity of the
materials involved. ZnO meets these requirements.
It is vital that zinc oxide is featured in semiconductors with a piezoelectric

effect. This guarantees that zinc oxide nanowires are able to complete the cost-
effective transition from mechanical energy to electrical energy.
Conventional piezoelectric materials, such as PZT, are usually insulators. Their
bending or compression can also generate electric potential changes.
Nevertheless, because they cannot work with metal to form a Scho ky barrier
with a one-way conductive feature, the transition from charge accumulation to
release cannot be achieved. Thus, while there are some studies that tend to use
conventional piezoelectric materials as a power source, they require complex
external circuitry to achieve the accumulation of charge, making it really
difficult to miniaturize the devices. More importantly, conventional
piezoelectric materials, due to the higher complexity of their chemical
composition and crystal structure, are difficult to synthesize into high-quality
nanoscale structures. Therefore, the high output power can only be achieved
by increasing the size and external forces, thus making it impossible to achieve
small size and high power at the same time. On the contrary, as a new type of
semiconductor piezoelectric material, zinc oxide has a relatively simple
chemical composition and crystal structure. Nanowire produced from this has a
small diameter, usually less than 100 nm, but its length can reach a few
microns. This favorable aspect ratio makes it able to be bent and able to
produce electrical potential difference with very li le force. As long as we
can perform this process, for example bend a large number of vertical
nanowires continuously, then nanogenerators with high output power are
likely to be made.
Experimental devices and processes using a conductive AFM tip to bend a

piezoelectric nanowire to generate electricity are shown in Figure 7.4. The
corresponding voltage signals are shown in Figure 7.5, where y is the bending
amplitude of the nanowire from the vertical.
FIGURE 7.4 Experimental device and the process using a

conductive AFM tip to bend a piezoelectric nanowire to generate
electricity. From Ref. [9].
FIGURE 7.5 Life profile of voltage output signal obtained by

AFM tip scanning along a vertical nanowire. From Ref. [9].
References
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Press; 2006.
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semiconductors. IBM J Res Dev. 1970;14(1):61–65.
3. Ke L, Miao XY, Wei YF, Wang J, Wang X. New materials for II–VI
semiconductor lasers—ZnO quantum dots. Physics. 1999;28:30–34.
4. Tamargo MC, ed. II–VI Semiconductor Materials and Their Applications

[M]. New York, NY: Taylor & Francis Inc.; 2002; 132.
5. Fan XW, Lv YM. Research progress of ZnSe semiconductor blue light-

emi ing and laser devices. Physics. 1994;23:393.
6. Pelekanos NT, Ding J, Hagero M, et al. Quasi-two-dimensional excitons in

(Zn,Cd)Se/ZnSe quantum wells: Reduced exciton–LO–phonon coupling due
to confinement effects. Phys Rev B. 1992;45(11):6037.
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based on InxAl yGa1−x−yN quaternary alloys. Appl Phys Le . 2000;77(6):791.
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InxAl yGa1−x−yN quaternary alloys. Appl Phys Le . 2001;78(1):62.
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applications. Physics. 2006;35:897.
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5/14/2018 7.

Electro-Optical and Piezoelectric Applications of Zinc Oxide - Nanomaterials and Devices

 Nanomaterials and Devices

Electro-Optical and Piezoelectric

7.1 Optoelectronic Applications 175

7.1.1 Optical Properties of Zinc Oxide 175

7.1.2 Epitaxial Growth of ZnO 179

7.1.2.1 MBE Technique with Microwave 179

7.1.2.2 L-MBE Growth Technique 179

7.1.3 Optical Properties of ZnO Quantum Dots 181

7.1.4 Controlled Synthesis of the Ordered ZnO Nanowire Arrays 183

7.1.4.1 VLS Growth 183

7.1.4.2 VS Growth 184

7.1.4.3 The Hydrothermal Method 184

7.2 Piezoelectric Applications of Zinc Oxide 185

7.2.1 Piezoelectric Eﬀect 185

7.2.2 Piezoelectric Application of Zinc Oxide: Nanogenerators 187

7.2.2.1 Why Do We Need Nanogenerators? 187

7.2.2.2 Principle of Piezoelectric Nanogenerators 188

7.1 Optoelectronic Applications

7.1.1 OPT IC A L PROPERT IES OF ZIN C OX IDE [1]

Zinc oxide-based semiconductor optoelectronic devices, including UV

The key technology for ZnO-based optoelectronic devices is the preparation

In recent years, blue–green lasers have become popular in semiconductor laser

Are the II–VI semiconductors in dire straits regarding creating a blue–green

Currently, zinc oxide at room temperature can be observed to have stimulated

7.1.2 EP I TAXI AL GR O WTH O F ZNO

7.1.2.1 MBE Technique with Microwave

7.1.2.2 L-MBE Growth Technique

oxygen-rich environment. In general, we can use the beam pressure of oxygen

Epitaxial ZnO may have the [ ] and [ ] crystal orientations that

are, respectively, parallel to the [ ] and [ ] of Al 2O3. Because

FIGURE 7.1 RHEED patterns of ZnO epitaxial layer: (A)

7.1.3 O PTI C AL P R O P ERTI ES O F ZNO Q UANTUM DOTS

FIGURE 7.2 Stimulated emission peak at different excitation

intensity reaches the threshold , the P 2 peak is

, and a new stimulated emission peak N will

FIGURE 7.3 Peak intensity of the stimulated emission on

7.1.4 CO NTR O LLED SY NTH ESI S O F TH E O R DER ED ZNO

7.1.4.1 VLS Growth

Based on the catalytic VLS growth mechanism, ZnO nanowires can be

The VS method has the advantage of requiring no catalyst; however,

7.1.4.3 The Hydrothermal Method

The hydrothermal method is in the liquid-phase synthesis method category.

Compared with the preparation method of ZnO nanowires as described in

7.2 Piezoelectric Applications of Zinc Oxide

7.2.1 PIEZOELECT RIC EFFECT

In a certain direction, as the dielectric experiences a mechanical force to

In this equation, d is the piezoelectric constant matrix. This process indicates a

If the aforementioned dielectric is applied with an electric ﬁeld, then the

Dt is the converse piezoelectric constant matrix.

This phenomenon is known as the converse piezoelectric eﬀect, also known as

Piezoelectric materials were discovered by the Curie brothers (Pierre Curie

At that time, piezoelectric material had to be extracted from quar ; these

7.2.2 P I EZO ELECTR I C AP P LI C ATI O N O F ZI NC OXI DE:

7.2.2.1 Why Do We Need Nanogenerators?

7.2.2.2 Principle of Piezoelectric Nanogenerators [4–6]

The principle of the nanogenerator is based on the piezoelectric eﬀect by the