11.1.

ZnO based materials -overview

11.1.1. Review of the most usual ZnO based materials
11.1.2. Specific properties
11.1.3. Methods of fabrication and real products

11.1.2.
REVIEW ARTICLE
Structure, microstructure and physical properties of ZnO based materials in various forms:
bulk, thin film and nano
Shubra Singh1,2,3, P Thiyagarajan1,2, K Mohan Kant1,2, D Anita1,2, S Thirupathiah1,2, N
Rama1,2, Brajesh Tiwari1,2, M Kottaisamy2 and M S Ramachandra Rao1,2,3

ZnO is a unique material that offers about a dozen different application possibilities. In spite of
the fact that the ZnO lattice is amenable to metal ion doping (3d and 4f), the physics of doping in
ZnO is not completely understood. This paper presents a review of previous research works on
ZnO and also highlights results of our research activities on ZnO. The review pertains to the work
on Al and Mg doping for conductivity and band gap tuning in ZnO followed by a report on
transition metal (TM) ion doped ZnO. This review also highlights the work on the transport and
optical studies of TM ion doped ZnO, nanostructured growth (ZnO polycrystalline and thin films)
by different methods and the formation of unique nano- and microstructures obtained by pulsed
laser deposition and chemical methods. This is followed by results on ZnO encapsulated Fe3O4
nanoparticles that show promising trends suitable for various applications. We have also reviewed
the non-linear characteristic studies of ZnO based heterostructures followed by an analysis on the
work carried out on ZnO based phosphors, which include mainly the nanocrystalline ZnO
encapsulated SiO2, a new class of phosphor that is suitable for white light emission.

The domains of interest for compounds based on ZnO and associated heterostructures
are optoelectronics and spintronics. Indeed ZnO has a unique combination of high band gap
energy (∼3.4 eV) and excitonic stability.
The high excitonic energy (∼60 meV)
-makes it a potential candidate for light emission applications [4–7].
-also gives strong resistance to high temperature electronic degradation during operation
(e.g. laser diodes).
It is also the hardest (Mohs’ hardness ∼5) in the family of II–VI semiconductors.
ZnO along with GaN has attracted intense attention in the search for high-TC
ferromagnetic diluted magnetic semiconductor (DMS) materials.
Another important aspect of ZnO is the one-dimensional ZnO nanostructures which have
attracted special attention because of their unique properties and diverse hierarchical
nanostructures [18]. Different techniques such as pulsed laser deposition (PLD), sputtering,
thermal evaporation and condensation, solid state reaction and chemical methods
have been employed to fabricate such nanostructures [19– 24].
ZnO exhibits a large family of nanostructures [25]. In addition to the conventional nanowire
(NW) and nanobelt [26] structures, many interesting morphologies have been discovered
recently, such as nanocages [27], nanocombs [28], nanorings [29], nanosprings [30, 31],
nanobows [32] and nanodiscs [33, 34].
It has been found that changing the ZnO vapour concentration during the growth can
switch the growth morphology from NW to curved nanobelts [35], thus forming a nanobow
structure. These structures not only provided valuable inputs to depict models in
understanding crystal growth mechanisms on the nanometre scale but also exhibited high
potential for fabricating novel nanodevices (electronic and optical) with enhanced
performance.

4. Piezoelectric property of ZnO

For creating and designing micro-electromechanical systems (MEMS), new functional
materials should be integrated on various substrates. Piezoelectric thin films, such as lead
zirconate-titanate (PZT), boron doped diamond and oxidized zinc (ZnO), are the key
materials for designing MEMS syatems.
Although the piezoelectric property is of major importance for the properties of MEMS, not
much attention was given to measuring the piezoelectric coefficient of the deposited thin
film. Since the piezoelectric thin film is mostly deposited by sputtering and sol/gels [98,99],
the piezoelectric coefficient is affected by the deposition conditions to improve the
properties. Very little research work has focused on the material composition and deposition
conditions. Among the above-mentioned materials ZnO exhibits both semiconducting and
piezoelectric properties that can form the basis for electromechanically coupled sensors and
transducers.
It also exhibits the most diverse and abundant configurations of nanostructures known.
The piezoelectric characteristics of the ZnO thin film were measured using the pneumatic
loading method (PLM)
For the specimens sintered below 1000 ◦C, the addition of ZnO significantly improved the
piezoelectric and dielectric constants, which the authors attributed to the improvement
in bulk density.
The crystal structure changed from rhombohedral to tetragonal with increasing ZnO
content and the dielectric, pyroelectric and piezoelectric constants of the ceramics increased
considerably with the addition of ZnO.
The piezoelectric properties of a ZnO hexagonal microtube, which has a highly symmetrical
hexagonal tubular structure, have been studied by Fu et al [105].

5. ZnO nanostructures deposited by PLD

We have already seen that ZnO is a II–VI semiconductor with properties similar to GaN. It
is therefore a potential candidate for optoelectronic applications in the short wavelength
range (green, blue, UV), information storage and sensors [107–109].
Besides these advantages, a higher resistivity, grain density and preferential growth of ZnO
films are desirable for piezoelectric device applications.
All the above properties of ZnO thin films are strongly influenced by techniques such as
PLD. PLD is an ideal technique to fabricate ZnO nanostructures and there have been a few
earlier reports on the fabrication of ZnO nanodot arrays as well as nanorods by PLD [110–
112].
ZnO pyramidal nanostructures have been reported by Angappane et al grown by using
PLD of the oxide onto a Si(1 0 0) substrate at 600 ◦C [114].
Ganesan et al reported a pulsed laser vaporization (PLV) technique to synthesize NWs of
single-crystal ZnO having a wurtzite structure by using colloidal gold nanoparticles as
seeding catalysts [115]. Okada et al succeeded in synthesizing ZnO nanorods by
nanoparticle assisted PLD without using any catalyst where nanoparticles formed by the
condensation of ablated particles play an important role [116]. Growth of crystalline ZnO
NWs by the PLD approach using a femtosecond laser as the ablation source was reported
by Zhang et al [117].

6. ZnO nanostructures prepared by other methods

Chemical methods provide a good and simple means of realizing ZnO nanostructures. Li et
al [121] synthesized ZnO rings and discs by a solution phase approach.
Wei et al [124] reported singlecrystal NWs of zinc oxide prepared by a novel self-seeded
vapour–liquid–solid (VLS) growth method using ultrasonic spray-assisted chemical vapour
deposition, in which liquid Xu et al [125] prepared ZnO NWs and nanowhiskers via a novel
approach in the presence of surfactant by using acetate zinc, oxalic acid, sodium chloride,
cyclohexane, as starting materials. Nanosized ZnO powder was synthesized by Masaki et al
by a precursor process using zinc sulfate salt and aluminum sulfate salt as starting
materials. In this case pulp and crystalline cellulose were used as precursor materials [126].

7. ZnO Coated Fe3O4 nanoparticles

It is well known that magnetic nanoparticles tend to agglomerate not only because of their
large surface energy but also due to their strong magnetic interactions. Therefore, for both
fundamental and applied oriented investigations, magnetic properties are studied by
preparing the samples in the form of nanocomposites, which is by dispersing the magnetic
particles in magnetically inert matrices or by coating the nanoparticles with non-magnetic
compounds.
In recent years, there has been intense interest in the fabrication of coreshell particles with
tailored properties for various applications in materials science [127]. The properties of the
core particles can be significantly altered by the shell surrounding the core, while the
surface properties of such particles are governed by the characteristics of the shell.
ZnO–Fe3O4 composite samples were prepared by the sol–gel method (Kunming et al )
[128]. It was shown that samples heat treated in H2 could show strong ferromagnetism at
room temperature while samples treated in air only showed very weak magnetism.
Novel homogeneous Fe3O4 core–shell polyhedrons have also been successfully fabricated
through a simple cetyltrimethyl ammonium bromide (CTAB)-modified hydrothermal
method [129].
Fe3O4 nanoparticles (FNPs) have been synthesized by the co-precipitation route at low
temperature [131–133]. The resulting core–shell nanoparticles exhibited a well-dispersed
property.

8. ZnO based heterostructures

To realize the optoelectronic applications of ZnO, an important issue is to fabricate both
high quality p-type and n-type ZnO in bulk and thin film form. Since it is rather
difficult to realize stable p-type ZnO thin films, one solution to this problem is to fabricate
n-type ZnO on p-type layers/substrates of other oxide materials [134–137]. Several
research efforts have focused on this area. ZnO NWarray-embedded n-ZnO/p-GaN
heterojunction light emitting diodes have been fabricated by growing Mg doped p-GaN
films, ZnO NW arrays and polycrystalline n-ZnO films consecutively [138].

9. ZnO based phosphors

In order to reduce the power consumption and increase the brightness of phosphors used in
flat panel displays we need to optimize the properties of phosphors (light emitting solids). To
achieve this, a basic physical understanding of the luminescence processes of the phosphor
materials is essential.
ZnO is a well-known greenish white light emitting phosphor for low-voltage vacuum display
devices with a relatively high luminescent efficiency [141]. Moreover, ZnO due to its bio-
compatible character would be a suitable phosphor material (by doping) in biological
labelling applications.
Many researchers have investigated the emitting properties of ZnO films, including
ultraviolet and green emission.
Liu et al [143] investigated the green and yellow luminescence centres in ZnO and Mn
doped ZnO.
We observed that the emission resulting from the composite is a result of the formation of a
ZnO–SiO2 nanocomposite with fibrous growth of ZnO spread on micrometre sized
amorphous SiO2 matrix.
Since nanoparticles possess an enormous surface to volume ratio, the interaction between
semiconducting nanocrystals and the surrounding materials can strongly affect the emission
spectrum and thus offer an effective means to engineer the optoelectronics properties.
Recently, it has been demonstrated that the green yellow emission from ZnO is enhanced
when ZnO is embedded or combined with different materials as composites [161–166].

Structure and Thermoelectric Properties of ZnO Based Materials

The present dissertation investigates the relationship between the structure and
thermoelectric properties of ZnO based materials, with a focus on trivalent element
doping on engineering the microstructure and altering the electrical and thermal transport
properties. Within the solubility range, the addition of trivalent elements, such as In3+, Fe3+ and
Ga3+, is observed to increase the electrical conductivity of ZnO and decrease the thermal
conductivity.

11.1.3. Methods of fabrication and real products

Issue 39, 2013
From the journal:
Journal of Materials Chemistry C

Nanofillers in ZnO based materials: a ‘smart’ technique for developing miniaturized high
energy field varistors
S. Anas,*ab K. V. Mahesh,a V. Jobin,a S. Prasantha and S. Ananthakumar*a
Abstract
The present work encompasses the strategic design, synthesis and development of high energy
field ZnO varistors. The key aspect of the study involves the chemical synthesis of ZnO based
nanorod nanofillers by a pH selective precipitation and reflux method. High field varistors were
developed out of these crystalline nanofillers by employing them as fillers to the micron sized
commercial varistor powder

G.J. Owens et al. / Progress in Materials Science 77 (2016) 1–79 primul full text
The favorable optical properties of NPs obtained by the sol–gel method have also become a
common topic of research as reflected in numerous scientific publications [136–138]. Benhebal et
al. [139] prepared ZnO powder by sol–gel method from zinc acetate dihydrate, oxalic acid, using
ethanol as solvent. Yue et al. [140] also obtained ZnO by the sol–gel method. High-filling,
uniform, ordered ZnO nan-otubes have been successfully prepared by sol–gel method into
ultrathin anodised aluminum oxide membranes. Integrating the ultrathin anodised aluminum
oxide membranes with the sol–gel technique may help to fabricate high-quality 1D nanomaterials
and to extend its application as a template for nanostructures growth.

11.1.2. Specific properties

11.1.3. Methods of fabrication and real products
Sensors (Basel). 2013 May; 13(5): 6171–6182.
Published online 2013 May 10. doi: 10.3390/s130506170031
PMCID: PMC3690049
Hydrothermal Synthesis of Various Hierarchical ZnO Nanostructures and Their Methane
Sensing Properties
Qu Zhou,1,* Weigen Chen,1,* Lingna Xu,1 and Shudi Peng2
Hierarchical flower-like ZnO nanorods, net-like ZnO nanofibers and ZnO nanobulks have been
successfully synthesized via a surfactant assisted hydrothemal method. Gas sensors based on the
as-prepared ZnO nanostructures were fabricated by screen-printing on a flat ceramic substrate.
Hierarchical flower-like ZnO nanorods and net-like ZnO nanofibers samples show higher gas
response and lower operating temperature with rapid response-recovery time compared to those of
sensors based on ZnO nanobulks. These results present a feasible way of exploring high
performance sensing materials for on-site detection of characteristic fault gases dissolved in
transformer oil.

In recent years, great efforts have been made to fabricate low-dimensional ZnO nanostructures
[23,24], since their gas sensing properties can be efficiently improved in this way.
Hitherto, low-dimensional ZnO nanostructures with different morphologies including nanobelts
[25], nanotubes [26], nanorods [27,28], nanowires [29], nanofibers [30], nanodisks [31],
nanospindles [31], and nanoneedles [32], have been successfully developed, and many exhibit
interesting gas sensing performances towards H2, CO, NO2, H2S, SO2 and some volatile organic
compounds (VOCs). Pawar et al. [31] obtained interesting morphological transformations from
rod-to-disk-to-spindle-to-flower merely by varying the pH of the growth solution. Pawar and co-
workers [32] also synthesized vertically aligned ZnO nanorods, hexagonal nanorods, faceted
microrod rods, nanoneedles and nanotowers assisted with different surfactants (polyetherimide
PEI, polyacrylic acid PAA, diammonium phosphate DAP and DAP-PAA). Chai et al. [33]
reported the synthesis of functionalized individual ZnO microwires prepared by a carbothermal
reduction vapor phase transport method. Hamedani et al. [34] applied a fast and facile microwave
assisted method to prepare various ZnO nanocrystal morphologies and investigated their response
and selectivity for CO, CH4 and C2H5OH. However, to the best of our knowledge, reports on the
hydrothermal synthesis of low-dimensional ZnO nanostructures of various morphologies and their
gas sensing properties towards CH4 have been rare.
The additive surfactants are found to play key roles in synthesizing hierarchical flower-like ZnO
nanorods and net-like ZnO nanofibers. The sensors fabricated with ZnO nanorods and nanofibers
exhibit better CH4-sensing properties than those of nanobulks. These results demonstrate a
promising approach to fabricate gas sensors to detect CH4 and other characteristic fault gases in
power transformers.

The ZnO-based gas sensor was fabricated by the screen-printing technique with a planar ceramic
substrate,

Structural Characterization
To chemically identify the phase composition and purity of the prepared samples, we first
conducted the X-ray powder diffraction measurement. It was demonstrated that we have
successfully synthesized the desirable hierarchical ZnO nanostructures via a simple and facile
hydrothermal method.

As is known to all that PVP is a non-ionic surfactant, and an easily polarized functional group “–
C=O” is universally present in its repeated unit [36,37]. The “O” atom in the “–C=O” functional
group of PVP has a negative charge and the “Zn” in the precursor particles are positively charged,
so an intense attraction occurs between “O” and “Zn” atoms when PVP was added to the mixed
solution in our experiments, and ZnO nanorods were produced. Correspondingly, these ZnO
nanorods aggregated and self-assembled toward the common centre of PVP. With the increase of
the aggregation, finally hierarchical flower-like ZnO nanostructures appeared.
When PEG was added to the mixed solution, it worked as a assembly substrate, which can easily
embed Zn(OH)42− in its long-chain orientation. As the reaction time went by, the Zn(OH)42−
crystals gradually grew with a fiber-like structure along the long chains of PEG and novel three-
dimensional net-like ZnO nanostructures were finally synthesized. When no surfactant was added
to the solvent, the Zn(OH)42− precursors nucleate and aggregate chaotically, and bulk-like ZnO
nanostructures were formed.

It is well known that ZnO is a typical n-type semiconductor gas sensing material, and its gas
sensing properties are dominated by the surface resistance.
-In ambient air, oxygen would be absorbed on the ZnO surface at first. Due to its strong
electronegativity, absorbed oxygen then acts as a trap capturing electrons from the conduction
band of ZnO. Consequently, a depletion region on the surface appears, resulting in an increase in
the ZnO resistance.
-When the sensor is exposed to ambient CH4, the CH4 molecules react with adsorbed oxygen and
trapped electrons are released back to the conduction band, thus an decreased resistance is
measured.
Compared with tranditional ZnO nanobulks, ZnO nanorods and nanofibers exhibit much higher
gas responses at a low temperature with rapid response-recovery times, long-term stability and
good repeatablity. These can be explained with the hierarchical ZnO nanostructures and
morphologies formed by flower-like nanorods and net-like nanofibers. The main factors that
influence the gas sensing behaviors of the materials are the specific surface area and pore
structure.
To further confirm the inner architectures of the as-prepared ZnO nanostructures, nitrogen
adsorption and desorption measurements were performed to estimate the texture properties.

Table 1. BET surface area and pore structure parameters of the samples.

11.1.3. Methods of fabrication and real products

Optimization of a New ZnO Nanorods Hydrothermal Synthesis Method for Solid State Dye
Sensitized Solar Cells Applications
Laurent Schlur†, Anne Carton†, Patrick Lévêque‡, Daniel Guillon†, and Geneviève
Pourroy*†
J. Phys. Chem. C, 2013, 117 (6), pp 2993–3001
We report on the growth control of zinc oxide nanorods to point out the effect of the ZnO
nanorods quality on the power conversion efficiency (PCE) of transparent conductive oxide
(TCO)/ZnO nanorods/dye/spiro-OMeTAD/metal electrode photovoltaic devices.

Ultra-Fast Microwave Synthesis of ZnO Nanorods on Cellulose Substrates for UV Sensor

Applications
Ana Pimentel *, Ana Samouco, Daniela Nunes ID, Andreia Araújo, Rodrigo Martins and
Elvira Fortunato *
In the present work, tracing and Whatman papers were used as substrates to grow
zinc oxide (ZnO) nanostructures. Cellulose-based substrates are cost-efficient, highly sensitive
and environmentally friendly. ZnO nanostructures with hexagonal structure were synthesized by
hydrothermal under microwave irradiation using an ultrafast synthesis time of 10 min.
By using ZnO nanorods, the surface area-to-volume ratio will increase and will improve the
sensor sensibility, making these types of materials good candidates for low cost and disposable
UV sensors.

Introduction
In the recent years, a huge effort has been made to produce materials that can be used in different
applications, such as nanoelectronics, optoelectronics, photonics, gas sensors, solar cells,
photocatalysis, lab-on-paper for rapid diagnostic tests and antibacterial applications using flexible,
biodegradable and green substrates, like cellulosic fiber-based substrates. The use of cellulosic
substrates in these types of applications bring some advantages as cellulose is the Earth major
biopolymer being suitable for low-cost applications, besides being flexible, lightweight,
biocompatible and biodegradable [1,2].
Properies
Zinc Oxide (ZnO) is an n-type semiconductor with a wide and direct band gap of about 3.37 eV
and a large free exciton binding energy of 60 meV at room temperature which allows it to act as
an efficient semiconductor material [11]. ZnO possesses unique electrical, optical, photocatalytic
and antibacterial properties, also being a low-cost material with a high surface reactivity. The
physical and chemical properties of ZnO nanomaterials vary as a function of size, shape,
morphology and crystalline structures.
Many efforts have been devoted to the development of different ZnO nanostructures with
improved properties. The shape and the aspect ratio of this nanostructures are key factors that
greatly influence the electrical and optical properties of ZnO material. Different techniques,
precursors and solvents can be used to prepare a vast variety of nanostructures. Thus, new green
synthesis strategies are vital for the development of novel nanomaterials [6,12].
Synthesis methods
Hydrothermal synthesis is a simple method that allows the production of uniform and well
distributed ZnO nanorod arrays, and is generally associated with conventional heating, which is
known to be inefficient, besides being time and energy consuming. Microwave irradiation, on
other hand is a low cost technology due to its unique features such as short reaction time thus
energy saving, enhanced reaction selectivity, homogeneous volumetric heating and high reaction
rate [13]. In fact, microwave synthesis has been successfully employed for several sources of
nanomaterials, shortening the synthesis reaction time [6,8,14–18].
As it is largely known, to synthesize a continuous ZnO layer using the hydrothermal synthesis
method, it is imperative to use a seed layer [19,20]. In this sense, the use of different techniques
for surface treatments have been reported by some authors to improve the surface wettability and
adhesion. Examples of techniques employed include plasma treatment [21,22], wet chemical [23]
and UV/Ozone treatment [24,25]. The UV/Ozone treatment is a simple, inexpensive and low-
temperature method that allows simultaneously the removal of some surface contaminants and the
polarization of ZnO seed layer surface.
The direct growth of ZnO nanorods on paper substrates has so far been reported by very few
authors [20,26],

Applications
Zinc oxide is frequently employed in a wide range of applications, from optoelectronics to
biological fields [20,27–31]. Nevertheless, one of the most investigated areas for ZnO is
UV/Ozone sensing, mainly due to its capacity of absorbing UV light, being transparent to visible
light, presenting a high sensitivity and selectivity [32–34]. The use of ZnO nanostructures instead
of thin films allows an increase in sensor responsivity and sensitivity due to a higher aspect ratio
of length to diameter and higher surface area of nanostructures [36].
Many authors have reported the direct growth of ZnO nanorods to act as the photoactive layer in
UV sensors on rigid (glass and silicon) [35,37] and flexible substrates (polymeric, textile and
cellulosic substrates [26,36,38]).

The synthesis of ZnO nanorods on tracing and Whatman papers by the hydrothermal synthesis
method under microwave irradiation. The influence of synthesis temperature with a fixed time and
the influence of UV/Ozone treatment on the ZnO seed layer have been studied. After an extensive
structural, morphological and optical characterization of the synthesized nanorod arrays, the
materials were tested as UV sensors.

UV/Ozone ZnO Seed Layer Treatment

After the deposition of ZnO seed layer on both cellulosic substrates, an UV/Ozone treatment was
used in order to improve the ZnO surface polarity. In Figure 3 it is possible to observe the XRD
measurement and SEM images of the ZnO seed layer, deposited by sputtering technique. It is
possible to observe that the ZnO seed layer is very smooth with a preferable orientation along the
(002) crystallographic plane.
The use of UV/Ozone systems for surface treatment have already been used by other authors in
order to increase the surface oxygen, polarity and wettability [44,45]. This UV/Ozone system
presents some advantages when compared with other systems: no vacuum is required (no need of
any sophisticated apparatus), and the absence of a wet chemistry treatment gives the advantage of
no residual solvents or other contaminants left at the substrate/sample surface; also, it can be used
at room temperature [46].
ZnO is a crystal with a hexagonal structure that grows along the c axis and possesses both polar
and nonpolar surfaces, arising from the anisotropy of the wurtzite structure. It presents high
energy polar surfaces, with a Zn2+ terminate (0001) plane and an O2− terminated (0001) plane
(this surfaces reconstruct to lower the surface energy) [45,47]. As reported by Talebian et al., the
solvents play an important role on hydrothermal/solvothermal synthesis [48]. When synthesizing
ZnO nanoparticles by the hydrothermal method, it will originate a very strong interaction between
the polar terminate plane (0001) of ZnO surfaces.
So, by exposing the ZnO seed layer to UV light, the O2 adsorbed to the surface will be
decomposed and the surface will become more polar, with a Zn terminate plane
(0001), which will promote the growth of ZnO nanorods by hydrothermal synthesis method
assisted by microwave irradiation. A more polar ZnO seed layer will improve the growth of ZnO
nanorods with a direction perpendicular to the seed layer surface. Figure 4 shows a schematic of
surface modification prior to ZnO nanorod arrays grown by hydrothermal method under
microwave irradiation [50].

Crystallographic Structure and Morphology Analysis of ZnO Nanorods

To infer the crystallographic structure and the morphology of the synthesized ZnO nanorod
arrays, XRD and SEM analysis were carried out to all materials produced on this study. The XRD
diffractograms of the ZnO nanorods grown on cellulosic substrates are presented in Figure 5. For
all of the materials produced, the observed peaks can be fully indexed to the hexagonal wurtzite
ZnO structure, with lattice constants of a = b = 0.3296 nm and c = 0.52065 nm, which is in
accordance with the literature [51]. The three peaks observed are fully assigned to the
crystallographic planes (100),(002) and (101).
The results confirm that it was possible to grow pure ZnO nanocrystals on cellulosic substrates
(tracing and Whatman papers). Nevertheless, is possible to observe that the crystallinity of ZnO
nanorods increases with the increase of synthesis temperature and with UV/Ozone treatments
prior to synthesis. These results corroborate the previous assumption that the UV/Ozone treatment
favor the growth of ZnO nanorods on the surface of cellulosic substrates.
On the tracing paper condition, a splitting of the XRD peak corresponding to the crystallographic
plane (002) is observed, and it might be due to the peak doublet of K-alpha 1 and K-alpha 2 [52].
SEM analysis for ZnO nanorod arrays synthesized on tracing paper substrate is shown on Figure
6. The effect of temperature and UV treatment prior to microwave synthesis has been
investigated. The synthesis time was constant for all samples (10 min). It is possible to observe
that without UV treatment, the ZnO nanorods grow in an inhomogeneous way, with a non-
uniform shape and size (regardless the synthesis temperature). Moreover, it is easily observed that
the ZnO nanorods do not cover fully the substrate surface. With a UV treatment prior to ZnO
nanorod array synthesis, the growth of these nanostructures becomes more homogeneous,
covering all the substrate surface. For low temperature synthesis (70 ◦C), no ZnO nanoparticle
growth is observed, but with the increase of synthesis temperature the ZnO nanorods start to
cover all of the substrate surface, becoming higher in length and well aligned, especially in the
case of the tracing paper substrate, mainly due to its very smooth surface. Thus, with the increase
of temperature, it is possible to observe that the nanorods become higher and thicker, for synthesis
with UV treatment. The ZnO nanorods present an average length of 130 nm, 300 nm and 500 nm
for synthesis temperatures of 90, 110 and 130 ◦C, respectively. Regarding the thickness, they
present an average value of 85, 100 and 110 nm for the same range of temperatures.
Figure 7 shows the SEM images of the synthesis of ZnO nanorod arrays using Whatman paper as
substrate. Also in this case the growth as a function of synthesis temperature is observed, with and
without an UV treatment prior to synthesis. As observed in tracing paper, it is possible to see that
the use of an UV treatment prior to ZnO growth will favor the growth of this type of
nanostructures. Without UV treatment, the growth is very heterogeneous, not completely covering
the substrate surface. With UV treatment, the ZnO nanorod arrays grew uniformly, covering all of
the surface. By increasing the synthesis temperature, the ZnO nanorods increased their length,
presenting average values of 120, 340 and 480 nm for synthesis temperatures of 90, 100 and 130
◦C, respectively. Regarding the thickness, they present an average value of 55, 66 and 75 nm for
the same range of temperatures.
The misalignment of nanorods with the increase of temperature is due to the high roughness of
the surface.
So, the top view SEM images (from both type of substrates) indicate that well-defined
crystallographic planes of the hexagonal single crystalline ZnO nanorods can be identified and
that they grow along the [0001] direction.
Comparing the two types of papers used, it is possible to conclude that tracing paper needs a
higher temperature for ZnO nanorods start to nucleate at the surface. On Figure 8 is possible to
observe a comparison between the length and the diameter of the ZnO nanorods as a function of
temperature, for both type of cellulosic substrates, with the corresponding SEM images.
Figure 9 shows the optical band gap calculation for ZnO nanorods synthesis with and without UV
treatment and as a function of synthesis temperature. The optical band gap was calculated by
extrapolating (αhν)2 as a function of hν. On the insets, it is possible to observe the reflectance
behavior of each sample, that is, the ZnO nanorod arrays produced absorb almost all the light in
the UV region of the spectra.
estimated optical band gap values, calculated from the Tauc equation, are discriminated on Table
1. By observing the values obtained it is possible to see that for both types of cellulosic substrates
the band gap value increased with the increase of synthesis temperature, with or without the use
of UV treatment prior to ZnO nanorods synthesis. This result is probably due to the increase of
temperature, a more homogeneous nanorod arrays cover all the substrate surface, thus the
measured band gap value become closer to the theoretical value ZnO band gap of 3.2–3 eV.

It is also possible to conclude that the same range of values was obtained, regardless of the type of
cellulosic substrate used or if a UV treatment was used prior to ZnO nanorod synthesis.
Application of ZnO Nanorods in Paper-Based UV Sensors
The ZnO nanorods arrays grown on cellulosic substrates were applied as UV sensors, and for that
only one condition from each substrate has been selected. By observing the SEM images (see
Figures 6 and 7) it was decided to test the ones with higher surface coverage and larger ZnO
nanorods—Synthesis condition of 130 ◦C.
So, for ZnO nanorod UV sensor production, carbon interdigital contacts were screen printed on
paper substrates after ZnO nanorods growth, like is exemplified in Figure 10. A polymeric mask
was used with the interdigital contacts design that allow us to ensure that the contacts were equal
for both the samples.

Synthesis of ZnO Nanostructures

An ultrafast method based on hydrothermal synthesis assisted by microwave irradiation have been
used for the synthesis of ZnO nanorod arrays on paper substrate. Two distinct types of paper
substrates coated with a ZnO seed thin film layer have been used: tracing (Canson, Annonay,
France) and Whatman (Sigma-Aldrich, St. Louis, MO, USA) no. 2 papers.
The ZnO seed layer was deposited on the two types of paper substrates by radio frequency (RF)
sputtering, at room temperature. A ceramic oxide target of ZnO with a purity of 99.99% was used
for the deposition. For the depositions, the chamber was evacuated to a base pressure of 10−6
mbar. A shutter between the substrate and the target enabled the protection of the targets from
cross contamination. For the deposition of ZnO seed layer, it was used a power density of 12.30
Wcm−2. and a deposition pressure of 4 × 10−3 mbar. The distance between the target and
substrate was fixed at 15 cm. The deposition was carried out for 90 min allowing the formation of
a 200 nm ZnO layer.
After uniformly coating the two types of paper substrates with ZnO thin films, ZnO nanorod
arrays were grown by hydrothermal synthesis under microwave irradiation with a Discover SP
microwave system, from CEM (Matthews, NC, USA). Two different approaches were tested,
UV/ozone treated or without any previous treatment.
For UV treatment, the substrates (tracing and Whatman no. 2) were placed for 5 min in a
UV/Ozone system from Novascan (Bonne, MO, USA), equipped with two UV lamps with
wavelengths of 185 nm and 254 nm. The distance between the paper and UV lamps were kept at
10 cm. For the microwave-assisted synthesis, the ZnO seeded substrates (20 × 20 mm) were
placed at an angle against the Pyrex vessel, with the seed layer facing down [16] and filled with
an aqueous solution of 25 mM zinc nitrate hexahydrate (Zn(NO3)2·6H2O; 98%, CAS: 10196-18-
6) and 25 mM hexamethylenetetramine ((C6H12N4)2; 99%, CAS: 100-97-0) [12], both from
Sigma Aldrich (St. Louis, MO, USA). Microwave synthesis was fixed at 10 min.
The use of a UV/Ozone treatment was tested before the nanorods synthesis and was optimized the
growth temperature to obtain a uniformly coated paper with ZnO nanorods. The synthesis was
done at different temperatures: 70, 90, 110 and 130 ◦C. After each synthesis process, the paper
substrates were cleaned with deionized water and ethanol and dried with nitrogen compressed air.
Figure 13 represents a schematic of the production process for ZnO nanorods arrays synthesis on
paper substrates (with and without an UV/Ozone treatment).
Characterization Techniques
Differential scanning calorimetric (DSC) measurements of tracing and Whatman paper substrates
were carried out using a Simultaneous Thermal Analyser (TGA-DSC-STA 449 F3 Jupiter,
Netzsch-Geratebau GmnH, Selb, Germany). Approximately 5–7 mg of each sample was loaded
into an open aluminium crucible and heated from room temperature to 550 ◦C with a heating rate
of 5 ◦C min−1, in air atmosphere.
Surface 3D profilometry of the paper substrate was performed using an Ambios XP-200 (Ambios
Technology, Santa Cruz, CA, USA) profiler for an area of 1 × 1 µm2.
The crystallinity of the ZnO nanorod arrays has been determined X-ray diffraction (XRD), using a
PANalytical’s X’Pert PRO MRD X-ray diffractometer, (PANalytical B.V., Almero, The
Netherlands) with a monochromatic CuKα radiation source (wavelength 1.540598 Å). XRD
measurements have been carried out from 10◦ to 90◦ (2θ), for paper analysis, and from 30◦ to 40◦,
for ZnO nanorods measurements, with a scanning step size of 0.016◦. The morphology of papers
substrates and ZnO nanorods has been characterized by Scanning Electron Microscopy (SEM)
using a Carl Zeiss AURIGA CrossBeam Workstation instrument (Carl Zeiss Microscopy GmbH,
Oberkochen, Germany) equipped with an Oxford X-ray Energy Dispersive Spectrometer (Carl
Zeiss Microscopy GmbH, Oberkochen, 0 individual nanorods, using ImageJ software [66].
Room temperature diffuse reflectance measurements of were performed using a Perkin Elmer
lambda 950 UV/VIS/NIR spectrophotometer (Perkin Elmer, Inc., Waltham, MA, USA) with a
diffuse reflectance module (150 mm diameter integrating sphere, internally coated with
Spectralon). The calibration of the system was achieved by using a standard reflector sample
(reflectance, R = 1.00 from Spectralon disk). The reflectance (R) was obtained from 250 to 800
nm.
3.3. Characterization of ZnO Nanorods on Tracing and Whatman Substrate as a UV Sensor
The synthesized ZnO nanorod arrays on tracing and Whatman paper substrates were characterized
as a UV sensor, using a potentiostat model 600, from Gramy Instruments, Inc. (Warminster, PA,
USA), in a chronoamperiometry configuration, with a constant applied voltage of
10 V. For interdigital electrical contacts, a carbon resistive ink, PE-C-774, from Conductive
Compounds (Hudson, NH, USA), was used. The ZnO nanorod arrays were subjected to UV
irradiation with an EL-Series Twin Tube UV lamps, from UVP (Upland, CA, USA) with an
intensity of 8 W at a wavelength of 365 nm. The sensor produced was irradiated for 2 min,
followed by 2 min in the off state.

Conclusions
In the present work, the synthesis of ZnO nanorod arrays was studied on two different cellulosic
substrates, tracing and Whatman papers. An ultra-fast chemical synthesis method, based on
microwave irradiation, was employed requiring just 10 min to produce ZnO nanorod arrays in
both substrates. The influence of a UV treatment prior to synthesis was studies together with the
synthesis temperature effect on the growth of ZnO nanorod arrays on paper substrates. It was
observed that without UV treatment, the growth on ZnO was heterogeneous, not covering all the
substrate surface. With the use of UV treatment and increase of synthesis temperature, larger ZnO
nanorods fully covering both cellulosic substrates could be observed. The XRD analysis
confirmed the formation of pure and crystalline wurtzite ZnO, with no other impurities detected.
The samples produced at 130 ◦C, with UV treatment prior to ZnO synthesis, were characterized as
a UV sensor, revealing an increase of 3 times in the responsivity with the use Whatman paper,
when compared with tracing paper. Bending tests revealed that decreasing the curvature radius
will also decrease the responsivity of the UV sensor. Nevertheless, the results show that these
types of sensor are stable when working in a bending mode.

11.1.3. Methods of fabrication and real products

Review
Three-Dimensional ZnO Hierarchical Nanostructures:
Solution Phase Synthesis and Applications
Xiaoliang Wang 1,*, Mashkoor Ahmad 2 and Hongyu Sun 3,*
Abstract: Zinc oxide (ZnO) nanostructures have been studied extensively in the past 20 years due
to their novel electronic, photonic, mechanical and electrochemical properties. Recently, more
attention has been paid to assemble nanoscale building blocks into three-dimensional (3D)
complex hierarchical structures, which not only inherit the excellent properties of the single
building blocks but also provide potential applications in the bottom-up fabrication of functional
devices.
This review article focuses on 3D ZnO hierarchical nanostructures, and summarizes major
advances in the solution phase synthesis, applications in environment, and electrical/
electrochemical devices.
-We present the principles and growth mechanisms of ZnO nanostructures via different solution
methods, with an emphasis on rational control of the morphology and assembly.
-We then discuss the applications of 3D ZnO hierarchical nanostructures in photocatalysis, field
emission, electrochemical sensor, and lithium ion batteries.
Throughout the discussion, the relationship between the device performance and the
microstructures of 3D ZnO hierarchical nanostructures will be highlighted. This review concludes
with a personal perspective on the current challenges and future research.

Introduction
Advanced nanomaterials, which are earth abundant and environmentally compatible, show the
potential to solve the serious energy and environment problems. As an important and widely used
wide bandgap (3.0–3.2 eV) oxide semiconductor, ZnO shows unique physical and chemical
properties [1]. The applications of ZnO materials range from room temperature nanolasers,
nanogenerators, solar cells, lithium ion batteries and photocatalysts.
ZnO crystal shows the stable structure as hexagonal wurtzite under the condition of normal
temperature and atmospheric pressure. The crystal structure of ZnO can be viewed as a number of
alternating planes composed of tetrahedrally coordinated oxygen and zinc ions stacked alternately
along the [0001] direction (Figure 1). There are two important structural characteristics in
wurtzite ZnO,i.e., the absence of inversion symmetry of the positive and negative charge centers
and polar surfaces, which are the origin of piezoelectric properties and unique growth behaviors
in the synthesized ZnO nanostructures.
The most typical polar surface in ZnO structure is the basal plane (Figure 1), in which positively
charged Zn-(0001) and negatively charged O-(000-1) polar surfaces are produced. These net
charges on the polar surfaces are ionic charges and non-mobile. The distribution of surface
charges is responsible for the minimizing the electrostatic energy of the system, which is also one
of the important driving forces for growing nanostructures with the domination of polar surfaces
[2]. In principle, by the standard Wulff construction, which depends on the relaxation energies [3].
For ZnO crystals, the kinetic parameters vary with different crystal planes and growth direction
due to different relaxation energies, which are emphasized under a given growth condition [4].
Therefore, from the viewpoint of decreasing the system total energy, a ZnO crystallite will
commonly develop into a three-dimensional morphology with well-defined and low-index
crystallographic faces (Figure 1). In addition, the surface energy can be modified by selective
adsorption of additives or surfactants on specific planes, and the morphology can be controlled
accordingly by adding suitable agents during the synthesis.
Inspired by the size- or morphology-dependent properties or device performances, numerous
efforts have been devoted to the synthesis of ZnO nanostructures with 1D morphologies, such as
nanowires, nanobelts, nanorings, nanohelices and so on [2,5,6]. Recently, more attention has been
paid to assembling low-dimensional nano-sized building blocks into three-dimensional (3D)
complex hierarchical structures [7]. Compared to mono-morphological structures, 3D ZnO
hierarchical structures usually exhibit high surface to volume ratios, a large accessible surface
area and better permeability. In addition, the hierarchical structures can increase the number of
light traveling paths and thereby facilitate light absorption. Finally, such 3D hierarchical
structures not only inherit the excellent properties of the single nano-sized building blocks but
also provide potential applications in the bottom-up fabrication of functional devices including
photocatalysts, sensors and drug release systems [8]. It is, therefore, important to develop facile
approaches to synthesize 3D hierarchical structures with controlled fashion.
Herein, we summarize the most recent progress in the synthesis of 3D ZnO hierarchical
nanostructures by using solution phase routes, and discuss the related applications. Firstly, typical
solution phase synthesis methods towards 3D ZnO hierarchical nanostructures are reviewed,
including direct precipitation, microemulsions, hydrothermal/solvothermal, sol-gel,
electrochemical deposition, and chemical bath deposition. The basic principles of the synthesis
and main factors that influence the structure and morphology of the products are analyzed. Then,
different applications based on the 3D hierarchical architectures are discussed in the context of
photocatalysis, field emission, electrochemical sensors, and electrodes for lithium ion batteries
(Figure 2). Finally, current challenges and future outlooks of the synthesis and applications of 3D
ZnO hierarchical nanostructures are briefly outlined.

Solution Phase Synthesis of 3D ZnO Hierarchical Nanostructures

The above discussion shows that the hierarchical assembly in ZnO nanostructures is related to the
electronic/optical properties and thus a wide range of potential applications. So far, many
synthesis strategies based on physical (physical and chemical vapor deposition, laser ablation, ball
milling, lithographic, etc.), chemical (gas phase reaction, various solution phase synthesis), or
biological methods have been well established to obtain 3D ZnO hierarchical nanostructures [9].
Comparing to other methods, solution phase route shows unique advantages, such as low cost
(low in energy consumption and equipment costs), scalability, and ease of handling. Most of the
solution phase reactions occur under mild condition with a relatively low temperature (<200 ◦C).
Therefore, solution phase synthesis has attracted increasing interest. Typical solution phase
synthesis includes precipitation, microemulsions, hydrothermal/solvothermal, sol-gel,
electrochemical deposition, chemical bath deposition, and so on. There are several excellent
reviews describing the synthesis of ZnO nanostructures [10–13]. In this paper, we mainly focus
on ZnO hierarchical nanostructures synthesized by different solution phase methods.

2.1. Precipitation
In a typical precipitation process, different kinds of alkalis (NaOH, KOH, ammonium, urea,
hexamethylene tetramine (HMT), etc.) and zinc sources (zinc salts, zinc foil, etc.) are used
(Figure 3a). The synthesis starts with a reaction between zinc and hydroxide ions followed by the
process of aggregation. A resultant precipitate is collected by filtration or centrifugation. The
morphology and assembly of the ZnO products can be controlled by adjusting the reaction
conditions, including the concentration of reacted solutions, temperature, time, and additives to
tune the reaction steps [14]. Kołodziejczak-Radzimska and co-workers [15] optimized the
precipitation conditions that would ensure getting the uniform particles of ZnO with the minimum
diameter. Sepulveda-Guzman et al. [16] synthesized submicron ZnO arrays by a simple one-step
aqueous precipitation method with zinc nitrate (Zn(NO3)2) and sodium hydroxide (NaOH) as the
reagents. The effect of reaction temperature on the morphology change was studied. Snowflake-
like and flower-like morphologies were obtained at 60 ◦C and 70 ◦C. The ZnO arrays are formed
through self-aggregation process, by increasing the reaction temperature. In another work,
Oliveira and co-workers [17] systematically investigated the influence of zinc salts
(Zn(NO3)2·6H2O, zinc sulfate (ZnSO4·7H2O)), pH value, temperature, additives (sodium
sulfate, sodium dodecyl sulfate) on the final ZnO morphology and size. The results show the
importance of nucleation of nanometric primary particles followed by oriented aggregation to
produce uniform submicrometric particles. Recently, López et al. [18] reported an interesting
work on exploring the synthesis of ZnO by employing zinc sources leached from alkaline
batteries, paving a new way to recycling useful nanostructures from various chemical wastes.
It should be noted that ZnO is a typical amphoteric oxide, which can be etched in either an acid or
alkali environment. The reaction between the zinc ions and alkaline ions results in the formation
of ZnO crystals. Meanwhile, the newly formed ZnO further reacts with alkaline in growth
solution until an equilibrium is achieved. Thus, tuning the precipitation (growth) and in situ
etching provides a facile approach to control the morphology of nanocrystals [19–21]. For
example, Xi et al. [19] fabricated large-scale arrays of highly oriented single-crystal ZnO
nanotubes by an in situ chemical etching of the ZnO nanorods. Yang et al. [20] have demonstrated
a novel anisotropic etching methodology for the synthesis of complex Ag nanoparticles shapes by
controlling the concentrations of etching solution, and highlighted their important applications as
highly sensitive surface enhanced Raman spectroscopy substrates. In our previous studies [8], we
reported a simple precipitation to synthesize ZnO 3D.
hierarchical structures by using Zn(NO3)2·6H2O, Zn foil, and KOH as the zinc source and
alkalis. Importantly, the morphology of the hierarchical structures can be simply selected by
changing the KOH concentrations. The morphology of the products are sheet, flower-like
microsphere assembled by nanosheets, flower-like microsphere assembled by nanoneedles, and
flower-like microsphere assembled by thinner nanoneedles when the concentration of KOH
increased from 0.5 to 2, 4, and 8 M, respectively (Figure 4a). A possible formation mechanism
based on preferential etching of KOH along the [001] direction of ZnO sheets was proposed
(Figure 4a). The growth or/and etching can be further controlled by adding suitable capping
agents that prefer to absorb on specific crystal planes, making it possible to have fine control over
the morphology. Tian et al. [22] demonstrated that citrate ions can selectively adsorb on the (001)
surfaces of ZnO crystals and thus inhibit the growth along [001] orientation. Based on this
knowledge, they synthesized large arrays of oriented ZnO nanorods with controlled aspect ratios
and a series of complex morphologies. In our studies, we combined the selective capping (citrate
ions) and etching (KOH) together to capture the intermediate of the morphology change, and
proposed a possible formation mechanism based on capping–etching competitive interactions
(Figure 4b) [23]. The strategy can also be applied to the synthesis and modification of other
materials by carefully selecting suitable capping agents and etchants.

Microemulsions

Materials synthesis via microemulsion is occurred in a stable mixed solution that contains water,
oil, and surfactant. Depending on the properties of immiscible liquid–liquid interface, the
formation of microemulsion can be in the form of oil-swollen micelles dispersed in water (oil-in-
water, or O/W) or the reverse case, i.e., water swollen micelles dispersed in oil (water-in-oil,
W/O). The two configurations are usually named as microemulsion and reverse microemulsion,
respectively [24]. Figure 3b shows a typical process for the synthesis of ZnO via microemulsion
method. The typical size of the microemulsion or reverse microemulsion is smaller than 100 nm;
therefore, the microemulsions can be used as nanoreactors for materials synthesis, which provides
a bottom-up route to control the size and morphology by adjusting the microemulsion properties.
By studying the phase diagrams of oil-water-surfactant system containing toluene, zinc acetate
solution, cetyltrimethylammonium bromide and butanol, Lin et al. [25] obtained the desired size
and shape of ZnO particles (Figure 5a–d). This study demonstrates the importance of
investigating the intrinsic properties of this multi-liquid-phase system. Jesionowski et al. [26]
made emulsion that was composed of cyclohexane as the organic phase, zinc acetate as the water
phase and appropriate emulsifiers. The obtained ZnO showed a narrow particle size distribution
and large specific surface area. In their further work [27], they synthesized a series of ZnO
materials in a similar emulsion system. ZnO structures with the morphologies of solids, ellipsoids,
rods and flakes were successfully obtained by applying modifications of the ZnO precipitation
process.

2.3. Hydrothermal and Solvothermal

Hydrothermal synthesis refers to the materials synthesis by chemical reactions of substances in a

sealed heated aqueous solution above ambient temperature and pressure, while solvothermal is
very similar to the hydrothermal route except the precursor solution is usually non-aqueous
(Figure 3c) [28–31]. Well control over the hydrothermal/solvothermal synthetic conditions is a
key to the synthesis of ZnO nanomaterials with defined structure, morphology, composition, and
assembly. Typical control experimental parameters include reagents, solvent, additives, filling
degree, temperature, time, and so on [32,33]. In addition, substrate is an important and interesting
parameter that can affect the ZnO morphology, especially the aligned ZnO nanostructures. In a
study, ZnO nanostructures on Zn foil was synthesized by hydrothermal synthesis [34]. The
morphology and assembly of ZnO arrays are dependent on the solvent properties. Specifically,
ZnO nanorod arrays and randomly scattered nanorods are obtained in the mixed solvent
containing ammonia aqueous solution (1%) and pure water, and pure water system, respectively.
Moreover, repetitive hydrothermal or solvothermal treatment can yield more complex and
hierarchical configurations. By employing this simple strategy, Ko et al. [35] synthesized high
density and long branched tree-like ZnO nanoforests (Figure 5e). In a report of Joo et al. [36],
single-crystalline ZnO nanowires were grown on substrates with zinc oxide seed layers in
aqueous solutions by hydrothermal method. The effect of specific additives on the ZnO
morphology was studied in detail. The results show that the addition of positively charged
complex ions (Cd, Cu, Mg, Ca) and negatively charged complexes (Al, In, Ga) promote low and
high aspect ratio growth of ZnO nanostructures (Figure 5f). They demonstrated that face-selective
electrostatic crystal growth inhibition mechanism governed this selective synthesis. Wysokowski
et al. [37] used β-Chitinous scaffolds as a template during the hydrothermal synthesis of ZnO
under mild conditions (70 ◦C). The obtained samples showed unique film-like morphology, which
showed good antibacterial properties against Gram-positive bacteria. Very recently, Van Thuan
and Kim et al. [38] synthesized oval-shaped graphene/ZnO quantum hybrids by employing a
facile chemical-hydrothermal method. The samples exhibited excellent catalytic properties for the
selective reduction of nitroarenes.

Sol-Gel Processing

The sol-gel process contains the formation of solid material from a solution by using a sol or a gel
as an intermediate step. The synthesis of metal oxide materials often involves controlled
hydrolysis and condensation of the alkoxide precursors or salts. Figure 3d illustrates the main
steps of preparation of metal oxides powder by the sol-gel process: (i) preparation of the precursor
solution; (ii) hydrolysis of the molecular precursor and polymerization via successive bimolecular
additions of ions, forming oxo-, hydroxyl, or aquabridges; (iii) condensation by dehydration; (iv)
solvent evaporation and organic compounds removal to form xerogel; and (v) heat treatment of
the xerogel to form powers. Properties of the final products, including the particle size, surface
area, crystallinity, and agglomeration, are highly dependent on the reaction parameters, especially
the precursors, solvents, additives, evaporation, drying, and post-treatment conditions [39] (Figure
5g). Tseng et al. [40] employed the sol-gel process to synthesize ZnO polycrystalline
nanostructures using Zn(CH3COO)2·2H2O as the zinc solute and different alcohols as solvents
(glycol, glycerol, and diethylene glycol). The morphology of the final ZnO was fiber, rhombic
flakes, and spherical particles. The formation of thorn-like ZnO nanostructures in the sol-gel
process was reported by Khan and co-workers [41]. They further modified this method by
mechanical stirring during the sol generation, and found the agitation speed was a critical value in
determining the size and aspect ratio of the particles. Higher stirring speed is favorable for
anisotropic growth of ZnO nanoparticles.

2.5. Electrochemical and Chemical Bath Deposition

Electrochemical deposition (ECD) and chemical bath deposition (CBD) methods are facile and
can produce materials or nanostructures that cannot be obtained by other deposition methods. The
CBD process only requires suitable solution containers and substrate mounting devices (Figure
3e), while for the ECD method, additional power supplies, electrodes (counter electrode/CE,
reference electrode/RE) are necessary, and the substrate (working electrode/WE) must be
conductive (Figure 3f). More importantly, the morphology and orientation of the deposited
samples can be tuned by controlling the reaction thermodynamics and kinetics, including solution
properties, additives, substrate, temperature, and electrochemical parameters (applied potential,
current density, etc.) [42–47].
-The synthesis of ZnO nanostructures via the ECD process includes the reduction of precursor at
the electrode, the supersaturation at the vicinity of the electrode, and subsequent precipitation.
Theoretically, factors that affect any step should be considered to achieve the good control of final
structures. In this regard, Illy et al. [48] systematically studied the effect of various experimental
parameters (electrolyte concentration, pH value, reaction temperature, and overpotential) on the
morphology, thickness, transparency, roughness and crystallographic orientation of the ZnO
materials. They found that ZnO nanostructures with (002) preferential orientation and controlled
thickness can be grown by using optimized parameters, which are important for organic
photovoltaic applications. Different additives can either interact with the ions in the electrolyte,
absorb on specific sites on the deposited ZnO structure, or change the electrolyte itself
(conductivity, viscosity, etc.), resulting in a different deposition pathways and thus final products.
In a study by Oekermann and co-workers [49], the addition of water soluble tetrasulfonated
metallophthalocyanines (TSPcMt), in which Mt = Zn(II), Al(III)[OH] or Si(IV)[OH], in the
electrolyte containing zinc nitrate yields completely different morphology and assembly, which is
ascribed to the preferential adsorption of the additive molecules onto the crystal planes of ZnO
(Figure 5h,i).
-Synthesis of ZnO nanostructures via CBD is based on a direct chemical reaction involving
dissolved zinc ions and oxygen precursors in the solution. Different from ECD where the
deposition only occurs on the conductive substrate, the growth of ZnO in CBD process can take
place either in the solution or on the substrate surface. The morphology and assembly of ZnO
products can also be controlled by the solution, additives, and so on [50]. Moreover, patterned or
flexible ZnO hierarchical nanostructures can be obtained by applying corresponding substrates
[51] (Figure 5j).

The above-mentioned solution phase synthesis methods have their own advantages and
disadvantages. Table 1 summarizes and compares the methods for the synthesis of 3D ZnO
hierarchical nanostructures. In addition, the different solution phase methods can be combined
together or with other treatments, such as microwave heating, sonochemistry, etc., to achieve even
more complex and interesting hierarchical nanostructures with useful applications. For example,
sol-gel processing or microemulsions are often employed with hydrothermal/ solvothermal
treatment to prepare various nanostructures [52]. The pre-synthesized ZnO nanostructures via
hydrothermal or ECD methods can be further etched to form needle or tube arrays [53]. The
assembly of ZnO architectures can be tuned by means of ECD via deformation and coalescence of
soft colloidal templates in reverse microemulsion [54]. It is worth noting that a wide range of ZnO
hierarchical nanostructures can also be synthesized from different biomass, such as
microorganisms, enzymes, bacteria, and plant extracts, which are eco-friendly alternatives
compared to the conventional synthesis methods [55–57]. In a word, solution phase synthesis
provides plenty of room to control and optimize hierarchical ZnO architectures for diverse
applications.
Applications of 3D ZnO Hierarchical Nanostructures
3D ZnO hierarchical nanostructures show unique advantages of high surface area, porous
structures, and synergistic interactions of the constituted nano building blocks. Therefore, 3D ZnO
nanostructures possess improved physical/chemical properties, such as enhanced light harvesting,
increased reaction sites, and improved electron and ion transportation, which are highly needed
for optical, electrical, and electrochemical applications. In this paper, we will review the most
recent progress in the research activities on 3D ZnO hierarchical nanostructures used for
photocatalysis, field emission, electrochemical sensors, and electrodes for lithium ion batteries.

3.1. Photocatalysis

ZnO nanostructures have attracted much attention to the fields of photocatalysis, including
photocatalytic degradation of organic contaminants, photocatalytic water splitting, and so on, due
to the notable merits such as nontoxicity, biological compatibility, and universality.
Typical steps involved in heterogeneous photocatalysis process are as follows (Figure 6) [58]: (1)
light absorption;(2) the generation and separation of photoexcited electrons and holes; (3) the
migration, transport and recombination of carriers; and (4) surface electrocatalytic reduction and
oxidation reactions. The overall catalysis efficiency is related to the cumulative effects of these
consecutive steps. For ZnO photocatalysts, the activity is limited by the intrinsic wide bandgap
(3.0–3.2 eV) and the high electron–hole recombination rate, which can be tuned by optimizing the
structural parameters of the photocatalysts, such as size, morphology, assembly, specific surface
area, and the defect density [59]. Compared to the 0D, 1D, or 2D counterparts, and 3D ZnO
hierarchical nanostructures show advantages of high surface area and porous structures, enhanced
light harvesting, and synergistic effects between the nano building blocks. All of these characters
are beneficial for the photocatalysis enhancement.
The comparison of the photodegradation of organic dye Rhodamine B (RhB) under UV-
irradiation with different 3D ZnO hierarchical nanostructures yielded by facile solution phase
method is shown in (Figure 7a,b) [8]. Under the same experimental conditions, the relative
photocatalytic activity is thin needle flowers > needle flowers > sheet flowers > nanosheets. The
significant improvement in the photocatalytic activity of the thin needle flowers structure can be
attributed to the following reasons: (1)optical quality and special structural features; (2) the large
active surface area and interspaces of the flower structure, which facilitate the diffusion and mass
transportation of RhB molecules and hydroxyl radicals; (3) the improved efficiency of electron–
hole separation.
The morphology of ZnO nanostructures dependent photocatalysis is later demonstrated in the
degradation of methylene blue in aqueous solution [60]. By coupling the strategies of elemental
doping [61], defect engineering [62], modifying the surface with visible light active materials [63]
or plasmonic-metal nanostructures (Ag, Pt, Au, etc.) [64], and the photodegradation properties of
3D ZnO hierarchical nanostructures can be further improved. For example, we evaluated
photocatalytic performance of ZnO needle flowers and Au nanoparticles/ZnO needle flowers
composite (Au/ZnO) by degradating organic dye RhB under UV irradiation (Figure 7c–e) [65].
The pure ZnO showed observable photocatalytic activity but with rather slow kinetics. Only
~60% of the RhB was decomposed within 90 min. In contrast, when the Au/ZnO composites were
applied as the photocatalyst, a significant synergistic enhancement effect was observed, i.e., RhB
was decomposed thoroughly within 90 min. The Au nanoparticles enhanced photodegradation is
also observed in ZnO sheet flowers. In these studies, besides the hierarchical morphology of ZnO
nanostructures, the improvement of photocatalytic properties can be ascribed to the presence of
noble metal nanoparticles: (1) the light absorption is increased due to the strong surface plasmon
resonance of the noble metal nanoparticles; and (2) the efficiency of charge separation of the
photo-generated electron–hole pairs is increased due to the strong electronic interaction between
strong electronic interaction and ZnO.
The above routes to improve the degradation properties in ZnO hierarchical photocatalysts
can also be applied to photosplit water to generate hydrogen. For example, elemental
doping and defect engineering are effective to narrow the bandgap of ZnO materials,
which results in an extension of light absorption range from UV into visible light range,
while generating interface structures by depositing plasmonic noble metals separates
photogenerated carriers, improves visible and near-infrared photo-absorption, and thus
achieves high-performance photocatalytic hydrogen evolution.

3.2. Field Emission

Field emission devices show several advantages, such as the resistance to temperature
fluctuation and radiation, less power consumption, low thermionic noise, low energy
spread, miniature volume and nonlinear, and the exponential current–voltage (I–V)
relationship in which a small variation in the voltage results in a large change in the
emission current instantaneously [66]. Theoretical calculations show that the external filed
induces a decrease of the surface barrier height by a value of ∆φ ~ 3.8 F1/2 (for φ in eV
and F in V/Å) (Figure 8a), and the field is off the order of ~109 V/m. If the emitter surface
is sharp configuration as shown in Figure 8b, electrons can be extracted at a considerably
lower applied field. The relationship between the field emission current density (J) and the
applied electric field (E) is described by Fowler–Nordheim equation: J = (Aβ2E2/φ)
expb−Bφ3/2(βE)−1
c, where A (1.54 × 10−6 A eV V−2) and B (6.83 × 103 eV−3/2 V µm−1) are the first and
second F-N constants, φ is the work function, and β is the field enhancement factor, which
reflects the magnitude of electric field at the emitting surface.
The field enhancement factor β can be defined as the ratio of local electric field divided to
the applied electric field. Therefore, β is a dimensionless quantity. The emission current
density at a constant cathode-anode distance is strongly dependent on the work function φ
and the field enhancement factorβ that is related to geometric configuration of the emitter,
crystal structure, conductivity, and so on. w the potential to be good candidates for field
emission. Moreover, a variety of ZnO nanostructures can be synthesized by facile solution
phase methods as discussed above, which not only reduce the cost, but also make it
possible to fabricate flexible field emission devices based on polymers or other metal
substrate materials [69,70].
Field emission studies on ZnO nanorod arrays synthesized on zinc foils by the
solvothermal route are presented by Dev et al. [71]. The effect of solvothermal parameters
including the solvent (distilled water and ethylenediamine), temperature, and time on the
morphology and field emission properties of ZnO nanostructures are studied. It was
observed that, with the increase in ethylenediamine concentrations, the alignment of the
nanorods gets better, corresponding to the increase of field enhancement factor from 850
to 1044. ZnO nanotube arrays were prepared by hydrothermal reaction in ammonia and
zinc chloride solutions by Wei et al. [72]. The turn-on field of the ZnO nanotube arrays
was extrapolated to be about 7.0 V m−1 at a current density of 0.1 A cm−2, the emission
current densities reached 1 mA cm−2 at a bias field of 17.8 V m−1, and the field
enhancement factor was estimated to be 910. Cao et al. [73] reported the field emission of
wafer-scale ZnO nanoneedle arrays synthesized by template-free electrochemical
deposition method. The field enhancement factor of the ZnO nanoneedle arrays was 657
with a working distance of 250 μm between the cathode and anode. In our studies [74], we
compared the field emission properties of ZnO nanowire arrays with flat ends and
nanoneedle arrays with sharp ends (Figure 9a). The ZnO nanowires were synthesized by
the hydrothermal method at 70 °C. Then, solution etching was employed to form ZnO
nanoneedles at room temperature. The turn-on electronic fields of ZnO nanoneedles and
nanowires are 2.7 and 5.3 V μm−1 at a current density of 10 μA cm−2. The threshold
electronic fields, which were defined as the field value at the emission current density J of
0.1 mA cm−2, of ZnO nanoneedles and nanowires are 3.9 and 6.1 V μm−1, respectively
(Figure 9b). The field enhancement factors were estimated to be 4939.3 for ZnO
nanoneedles and 1423.6 for ZnO nanowires (Figure 9c). In addition, there is no obvious
degradation of the current density, demonstrating the excellent emission stability of the
ZnO array materials (Figure 9d). This study highlights the important effect of emitter
geometry on the field emission.
Besides sample geometry, intrinsic electric conductivity in ZnO material also influences
the field emission properties. Using a simple solution reduction method, oxygen-deficient
ZnO nanorod arrays were synthesized by Su et al. [75]. The concentration of oxygen
vacancies can be effectively controlled by adjusting the reduction temperature ranging
from 30–110 °C, resulting in a controlled tailoring of the band structure of the ZnO. The
final oxygen-deficient ZnO nanorod arrays with optimized topography show excellent
field emission properties, the threshold electronic field was as low as 0.67 V μm−1, the
field enhancement factor was as large as 64,601, and the stability was also favorable. In
addition, doping with metal [76] or non-metal elements [77] through facile solution phase
methods is also an effective method to improve the field emission properties of ZnO
nanostructures. Doping induced conductivity enhancement and electron increase in the
conduction band are the possible reasons for the emission properties improvement.

Electrochemical Sensors

Continuous monitoring of biological molecules and metal ions has attracted much interest
due to the significant use in biotechnology, medicines, food and processing industry, and
as a valuable biological marker for many oxidative biological reactions. In this regard,
electrochemical sensors show unique advantages of high sensitivity, wide range of
detection, real-time monitoring, ease of fabrication and control, reproducibility, and low
cost, which can not be simultaneously achieved by other techniques, such as radioisotope
tracing and nuclear magnetic resonance.
The principle of electrochemical sensors is based on electroanalytical chemistry
techniques in which quantitative investigating sensing is made by varying the potential
and measuring the resulting current as an analyte reacts electrochemically with the
working electrodes surface (nanostructures modified glass carbon electrode, (GCE),
Figure 10). The frequently used electrochemical techniques employed in sensors include
cyclic voltammetry (CV), linear scan voltammograms (LSV), differential pulse
voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and so on.
Thanks to the biocompatible and nontoxic nature and high sensitivity to chemical species,
ZnO nanostructures have been intensively studied as different kinds of electrochemical
sensors to monitor important biological molecules and metal ions in organism, typically
including glucose, dopamine, uric acid, L-lactic acid, L-Cysteine, hydrogen peroxide,
potassium, sodium, calcium, magnesium, and iron ions. Due to the large surface area and
porous nature, 3D ZnO hierarchical nanostructures based electrochemical sensors
generally show good sensitivity, low detection limit, long-term stability, and repeatability.
Yang et al. [78] prepared ordered single-crystal ZnO nanotube arrays on indium-doped tin
oxide coated glass by combining electrochemical deposition and subsequent chemical
etching methods. The samples were used as a working electrode to fabricate an enzyme-
based glucose biosensor, which exhibited high sensitivity of 30.85 µA cm−2 mM−1 at an
applied potential of +0.8 V vs. saturated calomel electrode (SCE), wide linear calibration
ranges from 10 µM to 4.2 mM, and a low limit of detection at 10 µM for sensing of
glucose. We studied electrochemical sensing of hydrogen peroxide by using noble metal
nanoparticle-functionalized ZnO nanoflowers. Firstly, the hierarchical flower-like ZnO
structures were synthesized by a co-precipitation method in a solution containing Zn
(NO3)2·6H2O and KOH. Au or Ag nanoparticles were decorated on the surface of ZnO
nanoflowers by subsequent hydrothermal treatment. Au/ZnO, Ag/ZnO and bare ZnO
nanostructures modified GCE were fabricated and used as H2O2 sensors. The electrodes
were tested in 0.05 M Phosphate buffered saline at pH = 7.2 with a platinum counter
electrode and a saturated calomel electrode (SCE) reference electrode. CV results show
that the electrochemical oxidation of H2O2 started at about −0.68 to −0.1 V versus SCE
(Figure 11a), and the CV response for Ag/ZnO electrode was much higher than Au/ZnO
and bars ZnO electrodes. In addition, the Ag/ZnO electrode also exhibited rapid and
sensitive response to the change in concentration of H2O2 and the amperometric current is
noticeably increased upon successive addition of H2O2 (Figure 11b). The linear range of
calibration curve for these modified electrodes was from 1 to 20 µM (correction factor, R
= −0.998) with a low limit of detection (LOD) of about −2.5 µM (Figure 11c). The
sensitivity of the H2O2 sensor for Ag/ZnO modified electrode is 50.8 µA cm−2 µM−1,
which is much higher than that of Au/ZnO and bare ZnO electrodes.
Stability test showed that Ag/ZnO modified electrode was more stable as compared to
Au/ZnO and bare ZnO showing higher value of current with steady state current loss of
1.5% after 300 s (Figure 11d). This work demonstrated that noble metal-integrated ZnO
nanostructures provided a new platform for applications in designing enzymeless
biosensors. By decorating ZnO nanostructures with optimized alloy clusters, the
electrochemical activity can be further improved [79].
Due to the mild condition of solution phase synthesis, ZnO nanostructures can be directly
grown on a wide range of flexible and conductive substrates, making it possible to
fabricate free-standing and flexible electrochemical sensors. For example, ZnO nanorods
were uniformly anchored on the surface of carbon cloth by a simple hydrothermal method
[80]. The product was directly used as an electrode for the simultaneous determination of
dihydroxybenzene isomers. The electrodes showed good electrochemical stability, high
sensitivity, and high selectivity. The linear ranges of concentration for hydroquinone,
catechol, and resorcinol were 2–30, 2–45, and 2–385 µM, respectively, and the
corresponding limits of detection (S/N = 3) were 0.57, 0.81, and 7.2 µM.

Lithium Ion Batteries

With a growing world population and increasing industrialization, energy and environment
become the two main factors that restrict the society sustainability. It is thus of urgent need
to develop renewable energy conversion and storage techniques. Lithium ion batteries are
one of the most important energy storage devices, which dominate the market of portable
electronic devices, and also show potential in hybrid/electric vehicles. A typical lithium
ion batteries system mainly includes anode, cathode, electrolyte, and separator, of which
active materials used in both electrodes play pivotal roles in determining the overall
performance of batteries. For example, the specific capacity of graphite anode in current
commercial lithium ion batteries is as low as 372 mA·h·g−1, which is insufficient for
many applications. Searching for high-performance electrode materials remains one of the
most important focuses in the battery community. Among many potential electrode
candidates, ZnO nanostructures have attracted much attention due to the abundance of raw
materials, environmental benignity as well as facile synthesis [82–86]. In principle, the
reaction between lithium and ZnO anodes occurs through the so-called mechanism of
“conversion reaction”. During lithiation, the ZnO anode undergoes a conversion reaction
to form Li2O embedded with nanosized metallic zinc clusters. This step is followed by an
alloying reaction between lithium and the formed Zn NPs. The reaction processes are
described as the following equations:
ZnO + 2Li+ + 2e− ↔ Zn + Li2O (conversion step),
Zn + Li+ + e− ↔ LiZn (alloying step),
which yields a higher theoretical capacity (987 mA·h·g−1) than that of graphite [87–89].
However, the practical use of ZnO based anodes mainly suffer from low Columbic
efficiency (especially in the first cycle), severe capacity fading, and poor electrochemical
kinetics [90,91]. Firstly, the conversion step in the lithiation reaction represents the largely
irreversible reduction process of ZnO to metallic Zn. This irreversible chemical
transformation is partly responsible for the large initial irreversible capacity loss.
Secondly, the alloying step is accompanied by a large volume change (~228%) upon
cycling, which results in material pulverization, electrode failure, and thus rapid capacity
fading. The volume change of the anodes also results in the formation of an unstable solid-
electrolyte interphase (SEI) layer, which continuously traps Li ions, leading to capacity
loss. Thirdly, the low intrinsic electronic conductivity of ZnO materials causes a moderate
lithium ion diffusion coefficient and limits the high-rate applications. To enhance the
lithium storage properties of ZnO anodes, the construction of 3D ZnO hierarchical
nanostructures with proper morphology, composition, and assembly has been proven to be
an effective approach to overcome the above limitations.
(1) Capacity—Compared to the corresponding nanobuilding blocks, hierarchical
structures possess larger surface area, which increases the contact area between electrode
and electrolyte and thus the number of active sites for electrode reactions with lithium
ions. In addition, the hierarchical electrodes can lead to new lithium storage mechanisms,
such as surface, interface, and nanopore storage, which lead to excess capacity.
(2) Stability—The low-dimensional ZnO nanobuilding blocks have high mechanical
strength, more resistance to mechanical damage, and can be engineered to allow volume
change, and the assembled hierarchical structures can also prevent the possible
agglomeration during the continuous cycling. Both are essential to ensure the structural
integrity of the electrodes and long-term stability.
(3) Rate performance—The rate of battery operation is related to the solid-state diffusion
of lithium ions in the electrodes, which can be reduced in the nanoscale electrodes.
The assembly of ZnO hierarchical nanostructures shows great influence on the battery
performance. Zhang et al. [92] synthesized ZnO nanostructures with different morphology
by a facile hydrothermal and subsequent annealing treatment. The ZnO particles anode
delivers the largest initial discharge capacity of 1815.8 mA·h·g−1, and a reversible charge
capacity of 870.0 mA·h·g−1 at the current density of 50 mA·g−1, while cabbage-like ZnO
nanosheets’ electrodes displays better cycling stability. In other work, ZnO nanorod arrays
with dandelion-like morphology were grown on copper substrates by a hydrothermal
synthesis method [81]. The samples can be directly used as electrodes without any
additives or binders. Cycling performance was performed at a current density of 0.1 mA
cm−2. The charge capacity of the dandelion-like ZnO electrode decreases to 596, 481 and
419 mA·h·g−1 in the second, third and fifth cycles, respectively. The ZnO arrays keep a
capacity larger than 310 mA·h·g−1 even after 40 cycles, which is about four times higher
than the stabilized capacity of the bulk ZnO electrode. The unique dandelion-like binary-
structure played an important role in the electrochemical performance of the array
electrodes.
Besides the architecture design, the electrochemical properties of ZnO anodes can further
be improved by composting with electronically conductive agents (such as carbon
nanofibers, carbon nanotubes, graphene, metals, metal compounds and so on) [93–96].
Those additives can not only enhance the conductivity of the electrodes but also modify
the chemistry at the electrode/electrolyte interface. Therefore, 3D ZnO hierarchical
nanostructures with suitable surface or interface composition modification show unique
advantageous as improved lithium storage properties. In our previous studies, we
synthesized hierarchical flower-like ZnO nanostructure by a facile solution phase
approach. Au nanoparticles were functionalized on the surface of ZnO by subsequent
electrochemical deposition reatment. The diameter of the pristine ZnO microflower is
about 6–10 µm, and the length of an individual nanoneedle varies by 2–3 µm (Figure 12a).
After electrodeposition, Au nanoparticles with an average diameter of 4–6 nm are
decorated on the surface of each ZnO nanoneedle (Figure 12b,c). Comparing to the bare
ZnO material, the Au-ZnO hybrid hierarchical structures possess large specific surface
area, abundant void spaces, stable structure and strong electronic interaction between Au
nanoparticles and ZnO. Those structural characters are beneficial for lithium storage
enhancement. The initial discharge and charge capacity of Au-ZnO electrode are 1280 and
660 mA·h·g−1, respectively, yielding a Coulombic efficiency of 79% (Figure 12d). In
comparison, the initial discharge and charge capacity of pure ZnO electrode are 958 and
590 mA·h·g−1, respectively (Figure 12e). The initial Coulombic efficiency of ZnO
electrode is 52%, which is 27% lower than that of the Au–ZnO hybrids electrode. The
stability test results show that the charge capacity of the Au–ZnO electrode decreases to
519 and 485 mA·h·g−1 after the second and third cycle, and stabilizes at 392 mA·h·g−1
after 50 cycles (Figure 12f). In contrast, the capacity of the ZnO electrode decays rapidly
to 252 mA·h·g−1 (Figure 11f). The better lithium storage properties, including improved
capacity and cycle life of the Au–ZnO electrode, can be attributed to the Au nanoparticles,
which act as good electronic conductors and serve as a good catalyst during the
lithiation/delithiation process. Due to the strong electronic interaction between Au
nanoparticles and ZnO, electrons can easily reach all the positions where lithium ions’
intercalation takes place. This feature is very important when the battery is cycled at high
current density.
Anchoring ZnO nanostructures on various carbon materials, such as graphite, mesoporous
carbon, mesoporous carbon bubble, hierarchical porous carbon, vertically aligned
graphene, and graphene aerogels, also facilitates the electron and lithium ion transport
during charge/discharge cycles [97–99]. Those composite anodes show improved lithium
storage properties, especially high rate capacity, which are highly dependent on the strong
interaction between ZnO and carbon nanostructures. To strengthen this adhesion, one
strategy is in situ formation carbon modification and ZnO nanostructures from metal
organic compounds containing carbon and zinc elements. For example, Zhang and co-
workers designed a facile and scalable strategy to synthesize integrated, binder-free, and
lightweight ZnO nanoarray-based electrode as shown in Figure 13a [100]. Firstly, aligned
and ordered ZnO nanorods were grown on carbon cloth via a low temperature solution
deposition method. The ZnO nanorods were then served as the template as well as the Zn
source to induce the formation of zeolitic imidazolate frameworks-8 (ZIF-8), a typical
metal-organic framework, on the surface of ZnO nanorods (Figure 13b). Finally, unique
ZnO@ZnO QDs/C core–shell nanorod arrays were obtained by thermal treatment in N2.
Structure studies show that the shell of each nanorod is constituted by amorphous carbon
framework and ultrafine ZnO quantum dots (Figure 13c), resulting in a stronger adhesive
 force between carbon and the active ZnO materials, which is important in order to
accelerate the charge transfer in the electrode. Benefitting from this structure design, the
resultant ZnO@ZnO QDs/C anode not only exhibits remarkable cycling performance
(Figure 13d), but also provides a remarkable rate capability,
i.e., a reversible capability of 1055, 913, 762, 591, and 530 mA·h·g−1 at the current
density of 100, 200, 400, 800, and 1000 mA·g−1 (Figure 13e). t is worth mentioning that
the ZnO nanostructures can also be used as anodes for sodium ion batteries [101,102],
which are important complementarities of current lithium ion batteries. Due to the fact that
sodium chemistry is similar to the case of lithium, the established electrode-design
strategies for ZnO materials in lithium ion batteries system can be transferred to and
expedite the sodium ion battery studies.

4. Conclusions

In recent years, there have been explosive research and development efforts on ZnO
materials, ranging from facile synthesis to advanced characterizations and device
applications. 3D ZnO hierarchical nanomaterials possess a high surface area with porous
structures, and facilitate multiple physical and chemical processes. In addition, the
hierarchical materials not only inherit the excellent properties of an individual
nanostructure but also generate new properties due to the interactions between the nano
building blocks. Therefore, 3D ZnO hierarchical nanostructures provide a wide range of
applications. This review article summarized the main progress in the synthesis of 3D ZnO
hierarchical nanostructures via different solution phase methods, such as precipitation,
microemulsions, hydrothermal/solvothermal, sol-gel, electrochemical deposition, and
chemical bath deposition. In each method, the synthesis principle, factors that affect the
final structure and morphology, and typical examples are briefly discussed. Then, the
applications of the 3D hierarchical architectures in the fields of photocatalysis, field
emission, electrochemical sensors, and lithium ion batteries are analyzed, especially the
effect of hierarchical morphology on the performance are evaluated.

Despite these impressive advances, several challenges still remain.

(1)Although great success has been made on the controllable synthesis of 3D ZnO
hierarchical architectures, there is still room for improvement in terms of quality and scale
of the products. Moreover, new synthesis methods also provide opportunities to explore
novel morphology and understand the formation mechanism of the nanostructures.
(2)Besides the hierarchical architectures, the device performance is also related to the size,
composition and defects of ZnO nanostructures. Coupling the 3D nanostructures with the
ability of fine control over geometry and chemistry can further optimize the chemical and
physical properties.
(3)Direct study of the dynamic morphological and chemical evolution of ZnO
nanostructures during the practical applications is of significance to study the performance
degradation and develop strategies to improve the stability.

11.1.3. Methods of fabrication and real products

Hydrothermal Synthesis of ZnO Nanorods in the Diameter Regime of 50 nm
Bin Liu andHua Chun Zeng*
Abstract
Abstract Image
We report a novel wet-chemical approach at 180 °C for the synthesis of monodispersed ZnO
nanorods with high single-crystallinity. The method has successfully brought the ZnO nanorod
diameter from a reported 150 nm down to the 50 nm regime in this work. The aspect ratio of the
synthesized nanorods achieved is exceptionally high (in the range of 30−40). This simple low-cost
approach should promise us a future large-scale synthesis of ZnO nanostructures for many
important applications in nanotechnology in a controlled manner.

11.1.3. Methods of fabrication and real products

Journal of Physics D: Applied Physics
Hydrothermal synthesis of ZnO nanorod arrays for photocatalytic inactivation of bacteria
O Akhavan1, M Mehrabian2, K Mirabbaszadeh2 and R Azimirad3,4
Abstract
Arrays of ZnO nanorods were synthesized on ZnO seed layer/glass substrates by a hydrothermal
method at a low temperature of 70 °C. The effect of pH > 7 of the hydrated zinc nitrate–NaOH
precursor on the morphology and topography (e.g. size, surface area and roughness), the optical
characteristics (e.g. optical transmission and band-gap energy), hydrophilicity and antibacterial
activity of the grown ZnO nanostructure and nanorod coatings were investigated. For pH = 11.33
of the precursor (NaOH concentration of 0.10M), a fast growth of ZnO nanorods on the seed layer
(length of ~1 µm in 1.5 h) was observed. The fast growth of the ZnO nanorods resulted in a
significant reduction in the optical band-gap energy of the nanorod coating, which was attributed
to the formation of more defects in the nanorods during their fast growth. The surface of the ZnO
nanorod arrays was relatively hydrophilic (with a water contact angle of 16°) even after the
subtraction of their surface roughness effect (with a contact angle of ca 27°). This hydrophilicity
of the ZnO nanorods was assigned to the observed surface OH bonds. These characteristics
caused the ZnO nanorod arrays to show an excellent UV-induced photocatalytic degradation of
Escherichia coli bacteria. Furthermore, the synthesized ZnO nanorods were found to be strong
photo-induced antibacterial material, even without considering their high surface area ratio.

11.2. Biomedical applications

Sol-gel synthesis of thorn-like ZnO nanoparticles endorsing mechanical stirring effect and
their antimicrobial activities: Potential role as nano-antibiotics
Mohd Farhan Khan1,2, Akhter H.Ansari1, M. Hameedullah1, EjazAhmad3,
Fohad Mabood Husain4,5, Qamar Zia6,7, Umair Baig8, Mohd RehanZaheer2,
Mohammad MezbaulAlam9, Abu Mustafa Khan10, ZeidA.AlOthman9, IqbalAhmad4,
Ghulam MdAshraf11 & GjumrakchAliev12,13,14 nu pot copia din FOXIT!!!!!!

The effect of mechanical stirring on sol-gel synthesis of thorn-like ZnO nanoparticles (ZnO-NPs)
and antimicrobial activities is successfully reported in this study. The in-house synthesized
nanoparticles were characterized by XRD, SEM, TEM, FTIR, TGA, DSC and UV-visible
spectroscopy.
The X-Ray
Diffraction analysis revealed the wurtzite crystal lattice for ZnO-NPs with no impurities present.
The diametric measurements of the synthesized thorn-like ZnO-NPs (morphology assessed by
SEM) were well accounted to be less than 50 nm with the help of TEM. Relative decrease in
aspect ratio was observed on increasing the agitation speed. The UV-visible spectroscopy showed
the absorption peaks of the ZnO-NPs existed in both UVA and UVB region. A hypsochromic shift
in λmax was observed when stirring pace was increased from 500 rpm to 2000 rpm. The FTIR
spectroscopy showed the absorption bands of the stretching modes of Zn-O between 500 cm−1 to
525 cm−1. The Thermal analysis studies revealed better stability for ZnO-NPs prepared at 2000
rpm (ZnO-2000 rpm). TGA revealed the weight loss between two main temperatures ranges viz.
around (90°C–120°C) and (240°C–280°C).
Finally, the effect of ZnO-NPs prepared at different stirring conditions on the growth of Gram-
positive (Bacillus subtilis), Gram-negative (Escherichia coli) bacteria and a fungi (Candida
albicans) were examined; which showed good antibacterial as well as antifungal properties. These
findings introduce a simple, inexpensive process to synthesize ZnO-NPs using conventional
methods without the use of sophisticated equipments and its application as a potent nano-
antibiotic.

In the past decade, several research groups have developed metal oxide nanoparticles using savvy
routes1,2.
Among them, a significant category of zinc oxide nanoparticles (ZnO-NPs) have gained
importance since few years. Food and Drug Administration (FDA, USA) has categorized zinc
oxide (ZnO) as “generally recognized as safe” (GRAS) (21CFR182.8991). ZnO generates blue-
green luminescence while absorbing in the ultraviolet (UV) region. This property is exploited for
its use in sunscreens3, textile industries4, catalysts5, sensors6 and photodetectors7.
The presence of vacant and uncoordinated atoms at edges as well as large surface area to volume
ratio arising due to nanoparticulate organization augments the action of ZnO. Several reports have
associated the effective antimicrobial activity of ZnO with its chemical and physical properties8.
ZnO-NPs exhibit activity against broad spectrum of microorganisms9–12, and have been widely
used as active constituent for topical lotions, ointments and creams13,14. ZnO-NPs aqueous
suspension displayed better antibacterial efficacy than its TiO2 counterpart15.
A plethora of techniques including sol-gel method16, chemical vapor deposition17, pulsed laser
deposition18, sputtering19, hydrothermal synthesis20, and oxidation of metallic zinc powder21
have been exploited to prepare ZnO in diverse appearances and sizes for various applications.
A simple, well-controlled conventional synthesis process at near-room temperature can be utilized
for cost-effective production of ZnO-NPs and its use in functions of biological relevance. In this
study, the fabrication of thorn-like ZnO-NPs was done by sol-gel method while varying the
stirring conditions (viz. 500 rpm, 1000 rpm, 1500 rpm and 2000 rpm). The starting reagents used
for this synthesis were Zinc acetate dihydrate (ZAD), and NaOH while cetyltrimethyammonium
bromide (CTAB) was used as a capping agent. The in-house prepared nanoparticles were
characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM),
transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR),
thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning
calorimetric (DSC) and UV-visible spectroscopy. Furthermore, the antimicrobial activity of the
thorn-like ZnO-NPs, was assessed against both Gram-positive & Gram-negative bacteria
(Bacillus subtilis and Escherichia coli respectively) and fungi (Candida albicans).
Materials and Methods Materials. Zinc acetate dihydrate [Zn(CH3COO)2·2H2O] and sodium
hydroxide (NaOH) were purchased from Merck (India), cetyltrimethylammonium bromide
(CTAB) was from Loba (India) while nutrient agar (NA), nutrient broth (NB), peptone yeast
extract agar, sabouraud dextrose agar (SDA) and agar was from HiMedia (India). The chemicals
were of analytical grade and were utilized without additional purification. The glasswares were
properly washed, sanitized and autoclaved.
Synthesis of thorn-like ZnO nanoparticles. To prepare thorn-like ZnO-NPs, 0.2 g of CTAB was
added to 100 mL of bi-distilled (BD) water, in a flat-bottomed flask. To this, 10 mL of 1%
Zn(CH3COO)2·2H2O solution was added. The whole apparatus was kept on mechanical stirrer
under different stirring conditions viz. 500 rpm, 1000 rpm, 1500 rpm and 2000 rpm.
Subsequently, the NaOH solution was added drop-wise to the cocktail. Within few minutes of
agitation, the colloidal solution turned milky. The setup was retained as such for half an hour. The
system was then cooled, centrifuged, dried at room temperature in a desiccator, and washed with
BD water and methanol. No complex treatment (for example, high temperature and high pressure,
use of inert gas) was utilized for the synthesis. Finally, the samples of ZnO-NPs were stored in
amber colour container until further use.
X-Ray Diffraction Studies. The structural characterization of the ZnO-NPs was performed by X-
ray diffraction (XRD) and recorded as a function of 2θ angle. All the diffraction patterns were
prepared as step-scans.
XRD was performed in the 2θ range of 30°–70° with a step size of 0.01° and a scanning rate of
0.02 steps/second.
Thermal behavior of ZnO nanoparticles. Thermogravimetric analysis (TGA) and differential
thermal analysis (DTA). The degradation process and the thermal stability of ZnO-NPs were
investigated by TGA and DTA using thermogravimetric analyzer (SDT Q-600 TA Instruments,
Artisan Technology Group, IL, USA).
Initial sample weight was set as 5–8 mg for each operation. The sample was heated from ~24 °C
to ~900 °C at the rate of 10 °C/min in the nitrogen atmosphere at the flow rate of 200 ml/min.
Differential scanning calorimetric (DSC) analysis. DSC measurements of ZnO-NPs were
recorded on a scanning calorimeter Q-100 (TA instruments, DE, USA). The energy changes
associated with transitions were recorded at the temperature range of 20 to 600 °C. Samples of
known weight encapsulated in standard aluminium pans were placed in the sample holder and
analyzed24.
Antimicrobial activity of thorn-like ZnO nanoparticles. The thorn-like ZnO-NPs synthesized at
different stirring conditions (viz. 500 rpm, 1000 rpm, 1500 rpm and 2000 rpm) were tested for
bactericidal and fungicidal activity by disc-diffusion method25 as well as growth inhibition
studies against both Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli)
bacteria as well as fungi (Candida albicans) as standardized in our lab16.
In paper disc diffusion, diluted bacterial culture (0.1 mL) was plated uniformly with the help of a
spreader on nutrient agar (NA) plates. Sterile 8 mm discs (HiMedia Laboratories Pvt Ltd,
Mumbai, India) infused with the ZnO-NPs were placed on the plates, which were then incubated
at 37 °C for 24 hours. For antifungal activity of ZnO-NPs, the fungal culture were spread on
sabouraud dextrose agar (SDA) plates and incubated for 18–48 hours. An antibiotic disc (0.03
mg/disc; HiMedia Laboratories Pvt Ltd), doxycycline (for bacteria), and nystatin (for fungi) were
used as standard. The diameters of the resulting inhibition zones (in mm) of microbial
growth were measured for the determination of antibacterial and antifungal activities.
For growth inhibition kinetics, the bacteria were first grown on solid nutrient agar medium. Then,
fresh colonies were picked from the agar plates and inoculated into 100 ml of nutrient broth (NB)
medium. Growth was monitored at every 2 h under UV-visible spectrophotometer (Electronics
Corporation of India Limited, UV-2550) till 26 h. Similarly, antifungal tests were performed by
measuring the growth curve of C. albicans incubated in Yeast, peptone, dextrose (YPD) medium
containing different ZnO-NPs and growth was read every 2 h.
The experiments were repeated thrice and results are expressed as mean ± SD.
CLSI (formerly NCCLS) broth dilution method26,27 was utilized for determining the MIC values
against Candida and bacterial pathogens. MIC was defined as the minimum concentration of
ZnO-NPs at which there was no visible growth of the test pathogens28. Details of these
procedures have been provided in the supplementary section.
Statistical analysis. All the results are reported as Mean ± standard deviation (SD) of at least three
replicates.
Data were subjected to one-way analysis of variance (ANOVA) and the least significant
difference (LSD).
Results and Discussion
ZnO nanoparticles (ZnO-NPs) have been synthesized in various forms and structures such as
nanoflowers, nanorods, nanowhiskers, nanobelts, nanotubes, nanorings, nanocolumns, etc29–34.
They have been prepared employing diverse techniques including sol-gel method16, solution
precipitation method35, spray pyrolysis36, hydrothermal method37, microwave assisted
technique38 and many more. The processes generally used for ZnO-NPs preparation employ
change in various reaction parameters, such as change in temperatures ranging from low to
~1,500 °C, change in pressures from 1 atm to a few mTorr and so on; with majority of them
requiring complicated and expensive setups for carrying out the reaction. Incidentally, several
reports on production of flower-like ZnO nanorods hydrothermally at < 120 °C and a pH of
13.539; sodium dodecyl sulfate derived synthesis of chrysanthemum-like ZnO nanorods at 120 °C
for 24 hours40 and 10 hours41, and the creation of flower-like ZnO particles via sonochemical
method for42, are neither realistic nor cost-effective and present a few cases of complicated
syntheses process. Therefore, there is a paramount need for a cheaper and more user-friendly
synthesis system operable at low temperature, while considering the size and morphology of the
crystal, and pH of the solution, in order to avoid pricey and complex preparatory routes.
We have previously reported the synthesis of ZnO-NPs at low temperatures, while avoiding
sophisticated equipments16. The low temperature solution synthesis has been used by researchers
to produce flower-shaped ZnO nanostructures using the zinc acetate dihydrate and NaOH43.
Aqueous precipitation methodology at low temperatures proves to be versatile, economical route
and bestows a high yield44; resulting in the surface of nanoparticles being coated with high
concentration of zinc hydroxide44–46. Lately, our group has also developed flower-shaped ZnO
nanoparticles at different temperatures (at 25 °C, 35 °C, 55 °C, and 75 °C) utilizing simple sol–
gel synthesis process. It was found that nanoparticles synthesized at near-room temperatures
exhibited greater activity against microbes16. Several studies have employed the use of stirring
during preparation of ZnO-NPs47–49.
However, the method of producing ZnO-NPs exploiting stirring effect as the prime parameter has
not been reported till now. Herein, the effect of different stirring conditions on the size,
morphology, thermal stability and antimicrobial activity of ZnO-NPs has been evaluated.
X-ray diffraction analysis. A detailed investigation was performed to characterize the ZnO-NPs
synthesized at varying stirring conditions (viz. 500 rpm, 1000 rpm, 1500 rpm and 2000 rpm). The
phase and crystal parameters of the synthesized sample were explored by X-ray diffraction
patterns (Fig. 1). A most intense peak at 2θ = 36.2° is obtained along (101) orientation. The
sharpness and strong intensity of ZnO diffraction peaks indicate that the synthesized ZnO sample
is well crystallized. The peaks obtained for ZnO-NPs at 2θ = 31.9°. 34.7°,36.2°, 47.6°, 56.6°,
63.1°, 67.9° and 69.0° matches up with the lattice planes (100), (002), (101), (102), (110), (103),
(112) and (201) respectively. This is in accordance with several previous reports50,51. By
applying the Debye–Scherrer equation22, the average particle size were found to be ~25 nm, ~20
nm, ~7 nm and ~3 nm, respectively at 500, 1000, 1500 and 2000 rpm from the FWHM of
dominant peak (101). Therefore, the peak widths are inversely related to the crystal sizes52.
The (hkl) values agreed well with the standard card of ZnO powder sample (The International
Centre for Diffraction Data, PA, USA; ICDD card No: 080-0075); with the reflections assigned to
the powder pattern for the pure hexagonal wurtzite having lattice constant (c/a) of 1.60.
Additionally, the peaks obtained at planes (100),(002), and (101) are also suggestive of pure
wurtzite structure of ZnO52,53. No additional peaks related to impurities were noticed, validating
the pure form of the ZnO-NPs. The study also revealed the broadening of peaks on moving from
sample ZnO-500 rpm towards sample ZnO-2000 rpm; hence signifying a drop in the thickness of
sample structures with the concurrent increase in sharpness of thorn like morphology of ZnO-
NPs.
ZnO exists in three crystal lattice structures i.e. wurtzite (B4), zinc-blende (B3) and rock-salt
(B1)54,55. The ZnO zinc blende form can only be made stable by growing ZnO on cubic lattice
structure; the rock salt or Rochelle salt (NaCl) structure is metastable phase obtained only at high-
pressure. The wurtzite structure has a hexagonal unit cell with two lattice parameters ‘a’ and ‘c’ in
the ratio of c/a = √ 8/3 (1:633, an ideal value for wurtzite hexagonal structure) and belongs to the
space group C4 6v in the Schoenflies notation and P63mc in the Hermann–Mauguin notation.
Each tetrahedral Zn atom is surrounded by four oxygen atoms and vice versa56.
This structure is thermodynamically stable in an ambient environment55, and is represented as a
number of alternating planes of Zn and O ions stacked alongside the c-axis.
Electron microscopy. SEM characterization results showed the appearance of thorn like
morphology for ZnO-NPs and the desired structures appeared to be smaller and sharper for the
sample prepared at higher stirring rpm (Fig. 2A). Here, the SEM patterns agree well with the
XRD results. The TEM images (embedded with particle size distribution curves in inset)
identified the diametric evidences between 3–50 nm for the various samples prepared under
different stirring conditions (Fig. 2B). The thickness of the samples was found to be inversely
proportional to the speed of stirring (Table 1). The average aspect ratios (L/D; length by diameter)
were ~8.6 nm, ~9 nm, ~13 nm and ~18 nm, for ZnO-NPs prepared at 500, 1000, 1500 and 2000
rpm respectively. An increase in the aspect ratio was observed with the increase in speed of
agitation; showing an inverse relationship with the crystallite size (Table 1). High stirring
condition facilitates proper mixing and better dispersion with the surfactant, leading to the growth
along the length (c-axis) while decreasing the diameter. This could explain the concomitant
enhancement in aspect ratio on increasing the stirring rate while decreasing the nano-diameters of
the particles.
Spectroscopic studies of ZnO nanoparticles. UV-Vis absorption spectrum of ZnO-NPs was taken
after few minutes of sample preparation (Fig. 3A). The spectra recorded under different agitation
conditions presented noticeable differences in absorbance intensity as well as in wavelength
maxima (λ max). The main absorption peaks were found to be located around 315–340 nm; peaks
of sample ZnO-500 rpm & ZnO-1000 rpm existed in the UV-B region i.e. 320–400 nm and that of
sample ZnO-1500 rpm & ZnO-2000 rpm were found in UV-A region i.e. 290–320 nm. A shift in
the absorption peaks from UV-B to UV-A region was observed, when one goes from low stirring
conditions to high stirring speeds. Moreover, the intensity of absorption peaks was found to be
much elevated at 2000 rpm that that at 500 rpm.
At stirring speed of 500 rpm, the ZnO-NPs formed are more agglomerated and thickened with
less aspect ratio (L/D fractions), hence absorb at higher wavelength. However, on increasing the
stirring speed, the thorn shaped ZnO-NPs are formed more readily (as confirmed by the electron
microscopy), with lower agglomeration of particles. This increases the aspect ratios with the
proportionate decrease in the diameter; resulting in the shift of λ max from 328 nm to 316 nm,
with concomitant increase in the absorbance. The blue shift denotes the decrease in size of
particle (as indicated by TEM) and increase in band gap energy57. Our findings are in accordance
with those from previously reported studies indicating that shifts in the peak is dependent on the
size of the crystal, the solvent used, the reaction temperature, the technique of synthesis, and the
maturation time of samples58,59.
Moreover, the spectrum of the ZnO-NPs prepared at 500 rpm absorb poorly, while samples
synthesized at 2000 rpm exhibited maximum absorption.
The FTIR results were taken at room temperature within the range of 400 cm−1 to 4000 cm−1 for
thorn-like ZnO samples (Fig. 3B) with different stirring specifications. Metal oxides generally
exhibit absorption bands in fingerprint region (i.e. below 1000 cm−1), which arise from inter-
atomic vibrations. It was found that the peculiar Zinc oxide absorption band with stretching mode
of Zn-O was between 500 cm−1 to 590 cm−1, which corresponds to E2 form of hexagonal ZnO
wurtzite crystal (lattice) structure60. Peak near 1521.67 and 1470.21 observed in sample
corresponds to the asymmetric and symmetric stretching vibrations of C= O group, which may be
due to zinc acetate used in reaction61. The fundamental mode of vibration near 3492.95 cm−1
corresponds to the asymmetric and symmetric stretching H-O-H vibration. In literature, two
different OH group interactions have been reported on the surface of ZnO particles45: (i) the
1610–1630 cm−1 band is due to bending H-O-H vibration bands of chemisorbed water62, (ii) the
3000–3650 cm−1 band is due to the reversible dissociative absorption of hydrogen on Zn as well
as O site. The peak at 758 cm−1 can be attributed to the C-O bond stretching. These results prove
that the ZnO-NPs retained their structures even after being subjected to various stirring
conditions.

Thermal analysis of ZnO nanoparticles. The thermal properties of ZnO-NPs were determined by
differential thermal analysis (DTA)and thermogravimetric analysis (TGA). Sample was heated in
an aluminium pan upto 900 °C at the rate of 10 °C/min. The thermo-gravimetric analysis (TGA)
curves (Fig. 4A) revealed the weight loss in two main temperatures ranges, (90 °C–120 °C) and
(240 °C–280 °C). The weight loss around the temperature range (90 °C–120 °C) was ~ 17.08%,
which is ascribed to the loss of hydroxyl group. In continuation, the weight loss around
temperature range (240 °C–260 °C) was ~ 38.77%, which is accredited to the loss of acetate
groups. It is seen that the residual weights of ZnO-500 rpm, ZnO-1000 rpm, ZnO-1500 rpm and
ZnO-2000 rpm at 450 °C are 48.14, 48.30, 51.34 and 55.55%, respectively (Table 2). Thus, it can
be said that the sample ZnO- 2000 rpm is more thermally stable than the other samples.
DTA curves of ZnO-NPs were found to exhibit three exothermic peaks at 100 °C, 250 °C and 450
°C (Fig. 4B).
The exothermic peaks at 100 °C correspond to decomposition stage between 90 °C and 120 °C
while the exothermic peak at 250 °C corresponds to second decomposition stage (240 °C to 260
°C) in TGA (Fig. 4B). However, the exothermic peak at 450 oC corresponds to third
decomposition stage (420 °C to 470 °C) in TGA (Table 3). DSC analysis of ZnO-NPs prepared at
different rpm was studied as a function of rate of weight loss (w/g) versus temperature
(Supplementary Fig. 1). In case of ZnO-500 rpm, ZnO-1000 rpm and ZnO-1500 rpm
decomposition at 100 °C and 250 °C was found with − 13.95, − 16.43 and − 6.20 w/g weight loss
respectively. However, in the case of ZnO-2000 rpm the decomposition was observed only at 100
°C with − 3.624 w/g weight loss63.
Growth mechanism of ZnO nano-thorns. The growth of ZnO nano-thorns follows similar pattern
as that of ZnO nano-needles reported earlier16.
In a typical reaction, freshly synthesized Zn(CH3COO)2·2H2O solution was gradually added to
previously prepared CTAB solution under different stirring conditions; this mixing produces zinc
cation which further reacts with hydroxyl ion to form Zn(OH)2

16. Under basic conditions, Zn(OH)2 is sparingly soluble and exists mainly
in the form of a complex [Zn(OH)4]2− and leads to the development of some active reaction
pockets. In alkaline pH, the nucleation (formation of small growth units) step directs bidirectional
growth64 on the positive < 0 0 0 I> and negative < 0 0 0 Ī> faces of the crystal due to dipole
interaction, generally as a function of the growth rate (G), as follows:G<0 0 0 > = G<0 0 0 > >
G<0 0>
The formation of (Zn[OH]4)2− intermediates thus directs the development of elongated (rod-
shaped) ZnO-NPs arrays, bounded mainly by hexagonal prism < 0 I Ī 0> .
The surfactant CTAB not only hastens the formation of the growth units, but also directs their
two-sided growth65. Moreover, it also reduces the solution’s surface tension, which in turn
decrease the energy needed for the formation of a new phase. The diverse types of developed
complexes of (Zn[OH]4)2− and CTAB get adsorbed on the ZnO surfaces due to electrostatic
attractions, thus resulting in the elongation of c-axis (Fig. 5). This in turn actively extends
primarily towards the < 0 0 0 I> facet, thus leading to an increase in the number of spiny particles
(possessing good aspect ratio)39,66–68. This anisotropic growth leads to the development of
sharp thorn-like particles.
Variation in synthesis conditions like Zn2+ concentration and pH of the solution have been
reported to influence the stability and relative growth rates of different crystal planes, thus
affecting the morphology of ZnO nanoparticles69. In our experiment, the solutions were
deliberately stirred at varying speeds in order to determine its effect on the growth of ZnO
nanothorns. Mechanical stirring leads to the shear and better dispersion of nanoparticles. Higher
agitation speed may disturb the metal ion nucleation more extensively which minimizes the
particle agglomeration70, thus decreasing the size. It has been shown that change in stirring speed
results in variable cluster size of nanoparticles71. Hence, high agitation rate may well disperse the
particles being reduced, thus facilitating the interaction of individual particles with the surfactant,
thereby reducing the particle diameter.
Some of the benefits of this technique include the simple and economical synthesis methodology,
the moderate reaction temperature, use of conventional mechanical stirring conditions and the
lack of need for inert atmosphere72. It also does not involve high temperature and high pressure
for the initiation of the reaction.
Moreover, the utilization of certain toxic substances (that are essential ingredients for some
reaction processes) is not required.
Potential role of ZnO-NPs as nano-antibiotics. The studies where ZnO-NPs have demonstrated its
anti-pathogenic behavior are plentiful16,38,63,73–78. Its activity has been tested against a
plethora of disease causing pathogens, like Salmonella enteritidis, C. albicans, Listeria
monocytogenes, and Pseudomonas aeruginosa.
Similarly, the ZnO nanoparticles have also presented good results in the protection of food and
agriculture products against B. subtilis, E. coli, Botrytis cinerea and Penicillium expansum.
Keeping this fact in mind, our in-house prepared ZnO-NPs were further evaluated for their anti-
bacterial as well as anti-fungal efficacy using model microorganisms.
The antimicrobial activity was evaluated in terms of the zone of inhibition on NA plates. A
significant reduction in the growth of microbial stains (B. subtilis, E. coli, and C. albicans) was
observed at highest concentration (0.50 mg/mL) (Table 4). A maximum zone of inhibition (23
mm) was recorded for B. subtilis by ZnO-2000 rpm.
Our preliminary data also suggests that the antimicrobial activity of ZnO-NPs depends upon the
morphology and size of ZnO-NPs, which in turn depends on the stirring rate. ZnO-2000 rpm
being smaller in size readily diffuses into the growth medium, allowing greater interaction
between the NPs and the pathogen, hence exhibits
better microbicidal property. Similar biological activity has been reported for ZnO-NPs
synthesized from different approaches53. It can be also concluded that the Gram–positive stains
are more susceptible than Gram-negative strain, which can be attributed to the presence of special
cell wall structure containing different charged components.
It has been suggested that some nanoparticles might interact with the thiol groups of crucial
enzymatic machineries, hence leading to the loss of activity53. Even though this might happen, it
would be hard to predict the exact location where these NPs strike the microbial cells.
The relative potency of the ZnO-NPs against microbes was also assessed by its MIC value
(Supplementary Table 1), which was found to be 8 μ g/ml in all the cases. Furthermore, noticeable
difference in growth rate has been observed for all the microbes after 4 h of incubation with 0.5
mg/ml of ZnO-NPs (Fig. 6). The logarithmic growth phase of all the pathogens were found to be
prolonged starting from 5 h to more than 20 h of incubation (Fig. 6). ZnO-NPs exhibited broad
spectrum antibacterial activity against Gram-positive (B. subtilis) as well as
Gram-negative (E. coli) strains. These findings are indicative of the fact that the inhibitory
efficacy of ZnO-NPs is directly proportional to the stirring rate during the synthesis. Earlier
studies have similarly demonstrated the role of size and morphology of ZnO-NPs on its
antimicrobial activity16. Though B. subtilis is not as detrimental as other pathogenic bacteria, it
serves as a model for performing the pre-clinical anti-bacterial efficacy studies,as the mechanism
of action on the Gram positive bacteria remains the same. Similarly, the effect of ZnO-NPs
on the viability of C. albicans was also tested. It can be seen that for ZnO-NPs prepared at 2000
rpm, the growth reduction was highest followed by ZnO-NPs synthesized at 1500 rpm, 1000 rpm
and 500 rpm (Fig. 6). The results suggest that ZnO-NPs have a marked activity against C.
albicans, with cytotoxic effect being dependent on the stirring rate. These findings indicate that
ZnO-NPs can be applied superficially as a topical formulation against the pathogens.
In most of the dangerous microbes, the cell surface components such as proteins, polysaccharides
and teichoic acids, offer protection against host defenses and environmental conditions79.
Apparently, recent studies has revealed that certain long-chain polycations coated onto the
surfaces can efficiently eradicate Gram-positive as
well as Gram-negative bacteria on contact80,81. Researchers have proposed a number of modes
of interaction between microorganisms and NPs. The antimicrobial mechanism of ZnO-NPs is
primarily based on formation of reactive oxygen species like hydroxyl radicals, hydrogen
peroxide, and superoxide anions, which can damage cell membrane and result in cell leakage and
enhanced permeability82–84. Electrostatic binding of ZnO particles to bacterial surface kills the
pathogens by disrupting the bacterial outer membrane11. Several studies have specified
that ZnO-NP’s cell surface interactions affect permeability as well as morphology of cell
membrane63,76,85. As a result, the introduction of ZnO-NPs inside pathogens provokes oxidative
stress, ensuing in cell growth inhibition and, ultimately, cell death. However, the exact mechanism
of the toxicity has yet to be ascertained.

Conclusion
The present study encompasses the synthesis of thorn-like ZnO-NPs, prepared at different stirring
conditions (viz. 500 rpm, 1000 rpm, 1500 rpm and 2000 rpm) and the effect of mechanical
stirring on the fabrication of ZnO-NPs. Results show that the speed of agitation in the synthesis
protocol is a critical value in determining the size of the particles. It can be concluded that the
rotation speed has a consistent impact on the aspect ratio of ZnO-NPs. The anisotropic growth of
ZnO-NPs is promoted by stirring, possibly through the induction of internal shear force. Thus, the
morphology and size of ZnO-NPs can be tuned by simply adjusting the stirring speed. The in-
house synthesized nanoparticles displayed thorn like morphology with wurtzite crystal structure
and displayed high thermal stability. Significant antimicrobial activity reveals that the ZnO nano-
antibiotics may be used safely in anti-fungal and anti-bacterial therapeutic ointments, creams, etc.
However, the efficacy of these nanostructures is needed to be evaluated under in-vivo conditions
in experimental animal models before introducing them into clinical settings.

11.2. Biomedical applications

11.2.1. Biosensors
Biomedical Applications of Functionalized ZnO Nanomaterials: from Biosensors to
Bioimaging Ping Zhu , Zhengyang Weng , Xia Li , Xiangmei
Liu , Shuilin Wu ,* K. W. K. Yeung , Xianbao Wang ,
Zhenduo Cui , Xianjin Yang , and Paul. K. Chu P. Zhu,
Z. Y. Weng, X. Li, Dr. X. M. Liu, Prof. S. L. Wu, Prof. X. B. Wang Hubei Collaborative
Innovation Center for Advanced Organic Chemical Materials Ministry-of-Education Key
Laboratory for the Green Preparation and Application of Functional Materials Hubei Province
Key Laboratory of Industrial Biotechnology School of Materials Science and Engineering Hubei
University Wuhan 430062 , China E-mail: shuilin.wu@hubu.edu.cn ;
sxwsl1976@163.com Prof. K. W. K. Yeung Division of Spine Surgery Department of
Orthopedics and Traumatology Li Ka Shing Faculty of Medicine The University of Hong Kong
Pokfulam, Hong Kong 518053 , China Prof. K. W. K. Yeung Shenzhen Key Laboratory
for Innovative Technology in Orthopedic Trauma The University of Hong Kong Shenzhen
Hospital 1 Haiyuan 1 st Road , Futian Distract, Shenzhen 518053 , China Prof. Z.
D. Cui, Prof. X. J. Yang School of Materials Science and Engineering Tianjin University
Tianjin 300072 , China Prof. P. K. Chu Department of Physics and Materials Science
City University of Hong Kong Tat Chee Avenue , Kowloon, Hong Kong , China DOI:
10.1002/admi.201500494 1.
In view of their great potential for use in photoelectric devices and bio-medicine, one-dimensional
ZnO nanostructures have been extensively investigated since a nanobelt composed of semi-
conducting oxides was discovered in 2001. [ 4 ] To our knowledge, to date, the ZnO
nanostructure family is one of such families that is rich in structural variation, the typical
morphologies of which are shown in Figure 1 , [ 5 ] including highly ordered nanowire
arrays, nanorods, nanobelts, tower-like structures, nanorings, nanocombs, and even nanosprings.
Numerous methods, such as microemulsion techniques, [ 6 ] capping-agent/surfactant-assisted
synthesis, [ 7 ] electrochemical deposition, [ 8 ] hydrothermal/solvothermal processes, [ 9 ]
vapor deposition, [ 10 ] and pulsed laser deposition, [ 11 ] have been developed for the pro-
duction of these nanostructures. It is accepted that the performance of ZnO-based devices
depends upon the microstructure of the ZnO nanostructures. Hence, the size, orientation,
morphology, aspect ratio and den-sity of the crystals are critical factors in determining the poten-
tial applications of nanostructured ZnO materials in photoemit-ters, transducers, sensors and
catalysts. Therefore, strategies for controlling these factors has been a focus of research on ZnO-
based materials. For example, oriented ZnO nanorods, tubes The richness of the structures and
properties of members of the ZnO-based nanostructure family endows these materials with
diverse functionalities. In the last decade, the great potential of ZnO-based nanostructures for
biomedical applications due to their unique electronic, optical, catalytical, and antimicrobial
properties, as well as their excellent biocompatibility, has been recognized. The ever-deteriorating
environment and the rapidly aging population have given rise to an increase in diseases,
healthcare concerns and medical costs, particularly in developing countries, which has led to a
high demand for better and lower-cost biomedical devices with novel bio-functionalities. Here,
we review the recent advances in research on nano-structured ZnO-based biomaterials that have
been developed for biomedical applications, such as in biosensorsing, tissue regeneration,
bioimaging and drug delivery. Adv. Mater. Interfaces 2016, 3, 1500494www.MaterialsViews.com
www.advmatinterfaces.de

11.1.3. Methods of fabrication and real products

Surface Engineering of Nanostructured ZnO Surfaces
Marco Laurenti, Stefano Stassi, Giancarlo Canavese, and Valentina Cauda
Despite showing promising perspectives, the performances of ZnO nanomaterials are affected by
several drawbacks, including a poor chemical stability against reaction solutions and intrinsic
defects that are still preventing their integration into product applications. To overcome some of
these limitations, different functionaliza-tion strategies have been introduced to engineer the ZnO
surface properties. The synthetic methods used for surface functionalization are here discussed
and analyzed with respect to the morphology of the agent to be anchored and to the
functionalization approach. Several research efforts have been invested in studying various
preparation procedures for ZnO micro and nano-materials. Wet chemical approaches, like sol-gel,
hydro-thermal growths, electrodeposition and template-assisted routes,[40,41] as well as vapor-
phase methods, for example chem-ical vapour deposition (CVD), physical vapour deposition
(PVD) including sputtering and evaporation approaches,[42–44] and epi-taxial growth
methods[45] are among the most used ones. The great advantages of the wet chemical approaches
are the high synthesis versatility, low temperature employed and low costs.[9] From the other
side, dry methods take advantage of the high quality and excellent control over the level of
crystallinity of the synthesized ZnO structures, as well as the absence of contami-nation and high
purity of the final material.[46]. The combination of different properties with the ease and high
versatile synthesis of ZnO material in different micro and nanostructures offers a huge possibility
of potential applica-tions.

Applications
For example, ZnO is already used as an efficient catalyst in the selective oxidation of involving
oxygenates (i.e., alcohols, aldehydes, and carboxylic acids) and in methanol synthesis catalysts. It
is also largely applied as protective, anti-corrosion layer in galvanized steel products,[49–51] as
well as in paints and sunscreens as an UV absorber. Its biocompatibility makes this material
suitable, in the form of microparticles, for paste for-mulations in cosmetic applications.The
combination of the piezoelectric with the semicon-ducting properties of ZnO is found to result
into new exciting physical properties, [52–54] and it has recently opened the research field to
energy harvesting application. ZnO nanomaterials can be thus used as nanogenerators, able to
convert the mechanical deformation from the surrounding environment into electrical Zinc Oxide
(ZnO) nanostructures represent promising substrate materials for numerous applications, ranging
from new generation solar cells, to bio- and chemical sensors.

Properties
ZnO gathers a large number of interesting physical and chemical properties. It is also a very
versatile material in terms of possible preparation routes, morphologies, sizes and scales ranging
from micro to nano-level.[4]. More in details, ZnO is a metal oxide semiconductor of group II–
VI, with large band gap (3.37 eV) and large exciton-binding energy (60 meV) at ambient
temperature.[5,6] It shows absorption of UV light in the range 200–350 nm and emission in the
near UV and visible range from 500 to 600 nm. ZnO can crystallize in three different structures,
namely called rock salt, zinc blende and wurtzite.[4] However, at ambient pressure and
temperature the most thermodynamically stable, and thus the most common one, is the wurtzite
crystalline structure, constituted by tetrahedral units having the zinc atom at the center and the
oxygen atoms at the four corners.

11.2. Biomedical applications

Prof. Ji-Lie Kong,
Prof. Huan-Ming Xiong
Luminescent ZnO@polymer core–shell nanoparticles were synthesized and loaded with
doxorubicin (DOX) for the treatment of human brain cancer cells. ZnO@polymer–DOX
nanocomposites were decomposed at lysosomes to release DOX molecules, which penetrated into
the nucleus and finally killed the cells.

11.2.2. Drug delivery and nanomedicine

G.J. Owens et al. / Progress in Materials Science 77 (2016) 1–79
Sol–gel routes are regarded as the optimal method for modifying ZnO quantum dots (QDs),
because the synthetic reactions proceed near room temperature and do not harm the structure of
the nanoma-terial [141]. Previously reported ZnO NPs with various capping groups, including
polyvinylpyrrolidone [142], oleic acid together with diethanolamine [143], polyethylene glycol
methyl ether [144], and polymethylmethacrylate [145] among others. For example, the core–shell
model based on ZnO NPs enables drug loading, although further modification of the shell itself
can also be achieved via the sol–gel route [146]. Thus, the specific design of the NP system can be
tailored to localize agents to a given site and deliver payloads with far greater efficacy with
reduced systemic effects [148]. Beyond targeting cell surface receptors, these materials may also
be engineered to enter cells through intercellular endocytotic pathways and release drugs to
specific intracellular target sites [149].
An alternative strategy was also employed by Muhammad et al. [535]. These authors made use of
acid-decomposable ZnO QDs to seal the nanopores of MSNs and inhibit premature drug (DOX)
release. ZnO QDs behave as a dual-purpose entity that not only serves as a lid but also imposes a
synergistic anti-tumor effect on cancer cells. Another modification of pH-responsive MSNs, able
to overcome drug resistance, was published by He et al. [536]. Their composite NPs consisted of
MSN carriers still containing the porogen, CTAB, and DOX, where the surfactant served as a
chemosensitizer, thus enhancing drug efficacies whilst also acting secondary offensive against
multi-drug resistant cancers.

11.2.1. Biosensors
Sensing and Bio-Sensing Research
journal homepage: www.elsevier.com/locate/sbsr
Nanostructured ZnO-based biosensor: DNA immobilization and
hybridization
Ahmed Mishaal Mohammedb
, Ibraheem Jaleel Ibraheemb
, A.S. Obaida,⁎
, M. Bououdinac
An electrochemical DNA biosensor was successfully fabricated by using (3-aminopropyl)
triethoxysilane (APTES) with zinc oxide (ZnO) nanorods synthesized using microwave-assisted
chemical bath deposition method on thermally oxidized SiO2 thin films.
The current study focuses on biosensor technology based on multifunctional ZnO nanorods for
biological, biochemical and chemical applications. The nanostructures were fabricated using
chemical bath deposition (CBD). Before probe DNA immobilization and target DNA
hybridization detection, the surface of SiO2 thin films was modified with ZnO because of its
chemical composition, superior conductivity, and substantial attachment surfaces [33]. A novel,
label-free, and sensitive DNA sensor was developed using an interdigitated electrode (IDE) with
ZnO-modified SiO2 thin films. The current study explains the preparation of ZnO nanorods using
microwave-assisted CBD to produce nano-biosensors generate new compounds with high
sensitivity.
The results indicate that the fabricated sensor can be applied in low-cost biodiagnostics, forensic
testing, food analysis, and environmental monitoring. DNA immobilization and hybridization was
detected in ZnO-modified SiO2 thin films by controlling the surface chemistry with a K3Fe(CN)6
solution.
11.2. Biomedical applications
Sol–gel based materials for biomedical applications
Vezi full text
Metal oxide NPs, including ZnO, are versatile platforms for biomedical applications and
therapeutic intervention, especially in the treatment and imaging of cancers. There is an urgent
need to develop new classes of anticancer agents, and recent studies demonstrate that ZnO NPs
hold considerable promise. The concentration of various chemical groups (–ZnOH2+, –ZnOH, –
ZnO ) on the surface of ZnO NPs is pH dependent [133] and the availability of these reactive
groups lends ZnO NPs to antibody/ protein functionalisation via N-hydroxysuccinimide/1-ethyl-
3-(3-dimethyl-aminopropyl) carbodi-imide (NHS/EDC) coupling chemistry [134], as well as
other standard coupling approaches which can further improve cancer cell targeting.
ZnO NPs have also been shown to exhibit strong protein adsorption properties, which can be
exploited to modulate their cytotoxicity, metabolism or other cellular responses [135]. The sol–gel
method proposed by Spanhel and Anderson [136] in 1991 is commonly used to obtain ZnO
nanometer-sized particles to prepare nanoparticulate films with strong visible luminescent
properties, which are useful for optical and imaging methods [137]. Otherwise, the choice of acid
or basic catalysis and the temperature was pointed out to play a key role in the rates of the
hydrolysis– condensation reaction and in the equilibrium concentration of dissolved Zn2+
species, leading to changes in the size and shape of ZnO-based NPs [138].

11.2. Biomedical applications

Biomedical Applications of Zinc Oxide Nanomaterials
Yin Zhang1, Tapas R. Nayak2, Hao Hong2, and Weibo Cai1,2,3,*
We summarized the current status of the use of ZnO nanomaterials for biomedical
applications, such as biomedical imaging (which includes fluorescence, magnetic resonance,
positron emission tomography, as well as dual-modality imaging), drug delivery, gene delivery,
and biosensing of a wide array of molecules of interest. Research in biomedical applications of
ZnO nanomaterials will continue to flourish over the next decade, and much research effort

BIOIMAGING WITH ZNO NANOMATERIALS

Being inexpensive and convenient, fluorescence imaging has been widely used in preclinical
research [23-26]. Since ZnO nanomaterials exhibit efficient excitonic blue and near-UV emission,
which can also have green luminescence related to oxygen vacancies [27, 28], many reports exist
in the literature on the use of ZnO nanomaterials for cellular imaging.
Taking advantage of their intrinsic fluorescence, the penetration of ZnO nanoparticles in human
skin was imaged in vitro and in vivo [29]. The micelle encapsulated ZnO NCs were stable in
aqueous solutions and FA-conjugated ZnO NCs were found to accumulate intracellularly
throughout the cytoplasm, without inducing cytotoxicity in live KB cells which express high
levels of the folate receptor. Recently, transferrin-conjugated green fluorescent ZnO NCs were
also reported for cancer cell imaging with minimum cytotoxicity [31].
The optical properties of ZnO nanomaterials can be tuned by doping with appropriate elements
[32].
Heterostructural ZnO/Au nanocomposites, where Au NCs grow at the tip of ZnO nanorods or
along the nanorod surfaces, were synthesized and investigated for their optical properties and
biocompatibility [34].
In addition, these nanoparticles showed selective cytotoxicity to bacteria, as well as preferential
killing of leukemic T cells while sparing normal immune cells, because of the dissolution of
surface ZnO layer.
In one report, ZnO@polymer core-shell nanoparticles with emission in the green and yellow
range and high stability in aqueous solutions were reported [39]. When applied for in vitro cell
imaging, the ZnO QDs were found to be located in the cytoplasm, exhibiting stable luminescence
under UV light without significant cytotoxicity.
When compared with small molecules, nanomaterials are more suitable for multimodality
imaging because of the large surface area which provides more sites for functionalization, as well
as the possibility to engineer them for multimodal detection.
We recently synthesized green fluorescent ZnO nanowires (NWs), which could overcome the
abovementioned hurdles, and demonstrated that the ZnO NWs can be employed for targeted
imaging of cancer cells [44, 45].
For example, the size of ZnO NWs can be reduced to improve the tumor targeting efficiency; ZnO
NWs with fluorescence emission in the red or near-infrared (NIR) region are preferred which will
have better tissue penetration of the optical signal; the in vitro/in vivo stability of the ZnO NWs
needs to be evaluated and the long term toxicity should be studied.
To date, the use of radiolabeled, molecularly targeted ZnO nanomaterials has not been reported
yet. Combination of the high sensitivity of PET and intrinsic fluorescence of ZnO nanomaterials
through the use of radiolabeled ZnO nanomaterials can provide synergistic advantages and greatly
facilitate the development of ZnO nanomaterial-based anti-cancer agents and their future clinical
translation. PET, which detects the radiolabel rather than ZnO itself, is sensitive, quantitative, and
clinically relevant.

DRUG DELIVERY WITH ZNO NANOMATERIALS

ZnO nanomaterials are versatile nanoplatforms for not only bioimaging but also drug delivery
applications, due to their large surface area, versatile surface chemistry, phototoxic effect, among
others. In vitro studies have shown that ZnO nanoparticles can be highly toxic to cancer cells [65]
or bacteria and leukemic T cells [35]. Therefore, not only have ZnO nanomaterials been
investigated as drug/gene delivery vehicles, they have also been studied for cancer therapy.
ZnO QDs with intrinsic blue fluorescence were coated with folate-conjugated chitosan via
electrostatic interaction, [66]. It was suggested that DOX was entrapped through interaction with
the surface of ZnO QDs and/or folate via hydrogen bonding, whereas the external chitosan layer
enhanced aqueous stability of the ZnO QDs due to the charges and hydrophilicity.
Recently, Fe3O4-ZnO core-shell nanoparticles with an average diameter of 16 nm were prepared
to deliver carcinoembryonic antigen into DCs, which could also serve as
imaging contrast agents [68].
The cytotoxicity of aminopolysiloxane capped ZnO nanoparticles of different sizes (20, 60, and
100 nm, respectively) was evaluated in leukemia K562 and adriamycin-resistant K562/ A02 cells
[69].
The synergistic cytotoxic effect of the three ZnO nanoparticles and daunorubicin (DNR; which
can cause DNA damage and induce apoptosis in cells) against leukemia cells was also explored,
and the presence of ZnO nanoparticles were shown to enhance cellular uptake of DNR and inhibit
proliferation of the two cell lines.
Upon uptake of photosensitizers into cancer cells, irradiation with light of suitable wavelength
and dosage can generate reactive oxygen species (ROS) which can induce cell death and/or
necrosis [72]. ZnO nanoparticles can induce ROS such as hydroxyl radical, hydrogen peroxide,
and superoxide in aqueous solutions upon absorption
of UV illumination, making them good candidates for PDT [73]. For cancer therapy, combination
of different regimens can often lead to better efficacy, reduce side effects, and decrease the
likelihood of drug resistance.

GENE DELIVERY WITH ZNO NANOMATERIALS

A wide variety of nanomaterials have been investigated for gene delivery and gene therapy
applications, including ZnO nanomaterials which have shown promise in various literature
reports.
In a series of studies, three-dimensional tetrapod-like ZnO nanostructures were investigated as
gene vectors to deliver pEGFPN1 DNA (which contains the gene for green fluorescent protein) to
A375 human melanoma cells [75, 76].
Surface-coating of nanomaterials plays a critical role in efficient gene delivery. In one report, ZnO
QDs coated with positively charged poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)
polymers were used to condense pDNA for gene delivery [77].

BIOSENSORS BASED ON ZNO NANOMATERIALS

Biosensors (e.g. photometric, calorimetric, electrochemical, piezoelectric, among others when
categorized based on the detection principles) are widely used in healthcare, chemical/ biological
analysis, environmental monitoring, and food industry [78].
ZnO nanomaterials also exhibit various desirable traits for biosensing such as high catalytic
efficiency, strong adsorption capability, and high isoelectric point (IEP; ~9.5) which are suitable
for adsorption of certain proteins (e.g. enzymes and antibodies with low IEPs) by electrostatic
interaction [79]. Furthermore, high surface area, good biocompatibility/stability, low toxicity, and
high electron transfer capability also make them promising nanomaterials for biosensors [80]. The
majority of reported ZnO-based biosensors are for the detection of various small molecule
analytes such as glucose, phenol, H2O2, cholesterol, urea, etc. (Table 1). In addition, there are
also various biosensors for other molecules of interest and certain chemical/physical properties
such as pH [81, 82]. Interested readers are referred to several excellent review articles on this
topic for more detailed discussion [17, 78, 83]. Herein we will give a brief overview of this area
and only discuss selected literature reports.
Glucose Biosensors
Early stage ZnO-based biosensors were fabricated by loading GOx onto single crystal ZnO
nanocombs [79], NWs [84], or NW arrays [85] by physical adsorption, which exhibited high
sensitivity because of the strong affinity of GOx to glucose.
Phenol Biosensors
Phenolic compounds are highly toxic to animal and plants. Since they commonly exist in
industrial waste, it is important to detect and measure them for environmental monitoring. Many
of these biosensors have been fabricated on a platform of ZnO nanoparticles, because of the
inherent electrostatic attraction between electropositive ZnO nanostructures and tyrosinase, which
has a low IEP of 4.6 [97].
Tyrosinase has been adsorbed onto different ZnO nanomaterials such as ZnO sol-gel matrix
[98], ZnO nanoparticles [99], and ZnO nanorods [100] through electrostatic interaction, which
were further immobilized on a GCE.
To improve biosensor performance, ZnO nanostructures were fabricated on gold wires to facilitate
the nucleation for growth, which resulted in a response time of <5s [102]. Recently, a biosensor
based on ZnO nanorod microarrays on boron-doped nanocrystalline diamond substrates was
reported [103]. In another biosensor design, tyrosinase was encapsulated by CNT-ZnO-nafion
composite film on GCE, which exhibited excellent sensitivity and a very fast response time of 2s
[104].

H2O2 Biosensors
Recently, detection of H2O2 has become a vibrant research area as it plays an important role in
the food industry, environmental monitoring, and clinical diagnosis [105]. In one report, ZnO in
the form of nanosized flowers, dispersed in chitosan solution to form ZnO/chitosan composite
matrix which was further immobilized with HRP, were used to generate a biosensor with good
reproducibility and stability [106]. Another H2O2 biosensor was constituted by co-immobilizing
waxberry-like ZnO microstructure onto the surface of a GCE [107].

Cholesterol Biosensors
Cholesterol is an important molecule for humans and serum cholesterol level is an indicator for
various diseases such as hypertension, myocardial infarction, and arteriosclerosis [109, 110].
These biosensors were constructed by immobilizing cholesterol oxidase, through either physical
absorption or electrostatic interaction, onto various ZnO nanomaterials such as ZnO nanoporous
thin films grown on gold surface [112], well-crystallized flower-shaped ZnO structures [113],
electrodeposited ZnO nanospheres incorporated with Pt onto a GCE [114], gold/platinum hybrid
functionalized ZnO nanorods constructed on multiwalled CNT modified GCE [115], hexagon-
shaped ZnO nanorods grown on silver wire [116], or ZnO nanowalls chemically fashioned on
aluminium wires [117].

Urea Biosensors
Measurement of urea in the blood and serum is important for the diagnosis of renal and liver
diseases.
The first urea biosensor based on ZnO nanomaterials was reported in 2008, in which urease was
immobilized onto ZnO-chitosan nanobiocomposite film on indium-tin-oxide coated glass by
physical adsorption [119]. Subsequently, a similar biosensor was fabricated using the same design
but without chitosan, which gave significantly lower detection sensitivity [120]. Another
biosensor based on amperometric detection of urea was constructed by electrostatically
immobilizing urease to ZnO nanorods grown onto indium-tin-oxide coated glass, which had a
response time of 3s and a detection limit of 0.13 mM urea [121]. Recently, ZnO NW arrays
fabricated on gold coated plastics were also utilized in a urea biosensor, where urease was
immobilized by physical adsorption [122].

11.2.1. Biosensors
Review
SPECIAL ISSUE: Nano-Biomedical Optoelectronic Materials and Devices
Nanostructured ZnO for biosensing applications
XU ChunXiang1*, YANG Chi1
, GU BaoXiang2 & FANG ShengJiang1
Based on the unique properties, nanostructured ZnO could provide a stable immobilization for
biomolecules retaining their biological activity. It has been recently developed as a good
candidate for the construction of biosensors with enhanced analytical performance.
. We also described several important considerations
when working with nanostructured ZnO mainly centered on the fabrications of ZnO and
appropriate strategies for biosensor construction (e.g. modified electrodes and multilayered
immobilization).
PROPERTIES
Zinc oxide has attracted much attention particularly due to its widely applications in optics,
optoelectronics, sensors, and actuators [2,3]. The biocompatibility, low toxicity, high electron
mobility and easy fabrication of ZnO are favorable for biosensing [4–7]. Moreover, it has a high
iso-electric point (IEP) of about 9.5, which makes it suitable for adsorption of proteins with low
IEPs via electrostatic interactions [7]. Meanwhile, ZnO has probably the richest variety of
different nanostructures which is benefit for biosensor design. So far, ZnO combs, nanotubes and
nanorods have been employed to enzyme biosensor, immunosensor and other type sensor [8–12].
Especially, ZnO quantum dots (QDs) which have similar size as the biomolecules provide a good
interactive environment for the biomarker [13,14]. The scope of this article is focused on our
recent research progress on interaction/integration of ZnO QDs and ZnO one-dimensional (1-D)
nanostructure with biomolecules for sensor applications.

ZnO quantum dots biosensor

ZnO QDs as high aspect nanoparticles with high IEP have been promised as probes for
ultrasensitive detection of cancer biomarkers [13,14]. Their fluorescent properties have enabled
ZnO QDs to be used as labels for in vitro assays to quantify biomarkers, for example, the
conjugates of ZnO QDs with antibodies, aptamers, oligonucleotides, or peptides can act as the
target cancer markers.
ZnO QDs as electrochemical and fluorescent labels, a sandwich-type sensitive immunoassay
was developed based on immunoreactions between the an
tibody and antigen to detect the antigen CA19-9.
The results show that ZnO QD-based
immunosensor has a good specificity for CA 19-9 detection.
ZnO QDs were also employed in the lectin biosensor. A direct electrochemical biosensor for the
detection of allergy chicken ovomucoid (CHOM) based on bioconjugates of ZnO QDs binding
CHOM [18] has been reported.

1-D nano-ZnO biosensor

1-D ZnO nanomaterials were used as carriers with large surface to increase the loading
amount of enzymes. 1-D nanostructured ZnO is favor to immobilization of various
enzymes and is facilitate to the electron transfer between the redox centers of enzymes and
the electrochemical electrode [22,23].
A ZnO/Cu nanocomposite in situ-directed growth on electrode was prepared and applied
in biosesnor [30]. SEM images demonstrate that the morphology
of ZnO/Cu nanocomposite has a large specific surface area,
which is favorable to immobilize the biomolecules and re
alize the direct electron transfer between the electrode sur
face and the redox protein (Figure 3). As a model, this
ZnO/Cu nanocomposite is employed for immobilization of
GOx and the construction of the glucose biosensor.
Such ZnO/Cu nanocomposite pro
vides a good matrix for direct electrochemistry of enzymes
and mediator-free enzymatic biosensors.