Synthesis of Oxide Nano

particles
Report submitted by:
Asma Ashfaq
In partial fulfillment for the award of degree of
MASTER OF SCIENCS
IN
PHYSICS & NANO-TECHNOLOGY
UNDER THE ESTEEMATED GUIDENCE OF
Dr.Naeem Ahmad(HEC Approved Supervisor)
DEPARTMENT OF PHYSICS
1
INTERNATIONAL ISLAMIC UNIVERSITY, ISLAMABAD
PAKISTAN
List of contents
Synthesis-Nanostructures
Nanoscale synthesis
Nanoparticles Synthesis
Synthesis-Different methods
Oxides Nanoparitcles
Introduction-ZnO Nanoparticles
Why ZnO?
How ZnO Nano-particles can be synthesised?
Characterization
Doping in ZnO
PROPERTIES OF NANOPARTICULATED OXIDES
Magnetic properties
Applications
Motivation
2
ACKNOWLEDGMENT
Apart from the efforts of me, the success of any project depends largely on the
encouragement and guidelines of many others. I take this opportunity to express
my gratitude to the people who have been instrumental in the successful
completion of this project.
I would like to show my greatest appreciation to Dr. NAEEM AHMAD. I cant say
thank you enough for his tremendous support and help. I feel motivated and
encouraged every time. Without his encouragement and guidance this project
would not have materialized.
The guidance and support received from all the members who contributed and
who are contributing to this project, was vital for the success of the project. I am
grateful for their constant support and help.
3
INTRODUCTION:
Nanostructures (1nm = 10
-9
m)

Zero-Dimension: Confined in all three spatial direction
Examples: Quantum dots, Nanoparticles
One-Dimension: Confined in two spatial directions
Examples: Nanorods, Nanowires, Nanotubes, DNA, Nanorings,
Nanobelts
Two-Dimension: Confined in one direction
Examples: Thinfilms, Interfaces, Membranes, Multi-layers,
Quantum- well
NANOSCALE SYNTHESIS
Nanoscale synthesis of metal oxides.
Two Broad categories.
TOP DOWN
4
BOTTOM UP
Top-down methods
begin with a pattern generated on a larger
scale, then reduced to nanoscale.
By nature, arent cheap and quick to
manufacture
- Slow and not suitable for large scale
production.
Bottom-up methods
start with atoms or molecules and build up to
nanostructures
Fabrication is much less expensive.
NANOPARTICLES SYNTHESIS
Gaseous phase methods
Liquid phase methods
GASEOUS PHASE TECHNIQUE
Principal: Gas phase precursors interact
with a liquid or solid- phase material
Gas state condensation
Chemical vapor deposition
LIQUID PHASE TECHNIQUE
Molecular self-assembly
Sol-gel processes
Electrodeposition / electroplating
Anodizing
Here we use for the synthesis of oxide nanoparticles THE SOLGEL METHOD.
SOL GEL METHOD
5
Sol-gel process consists in the chemical
transformation of a liquid (the sol) into
a gel state and with subsequent post-
treatment and transition into solid
oxide material.
WHAT ARE OXIDE NANO-
PARTICLES?
THE WORLD OF OXIDE NANOMATERIALS
Metal oxides play a very important role in many areas of chemistry, physics and
materials science. The metal elements are able to form a large diversity of oxide
compounds. These can adopt a vast number of structural geometries with an
electronic structure that can exhibit metallic, semiconductor or insulator
character. In technological applications, oxides are used in the fabrication of
microelectronic circuits, sensors, piezoelectric devices, fuel cells, coatings for the
passivation of surfaces against corrosion, and as catalysts. In the emerging field
of nanotechnology, a goal is to make nanostructures or nanoarrays with special
properties with respect to those of bulk or single particle species. Oxide
nanoparticles can exhibit unique physical and chemical properties due to their
limited size and a high density of corner or edge surface sites.
Particle size is expected to influence three important groups of basic properties:
a:Structural characteristics.
b:Electronic Properties.
c:Size In Simple characteristics.
Bulk oxides are usually robust and stable systems with well-defined
crystallographic structures. However, the growing importance of surface free
energy and stress with decreasing particle size must be considered: changes in
thermodynamic stability associate with size can induce modification of cell
parameters
and/or structural transformations and in extreme cases the nanoparticle can
disappear due to interactions with its surrounding environment and a high
surface free
energy. In order to display mechanical or structural stability, a nanoparticle must
have a
6
low surface free energy. As a consequence of this requirement, phases that
have a low
stability in bulk materials can become very stable in nanostructures. This
structural
phenomenon has been detected in
e.g; TiO2, VOx, Al2O3 or MoOx oxides.
We choose ZnO for synthesis.
WHY ZnO?
REASONS
Wide-Bandgap semiconductor.
Large exiton binding energy.
Radiation hard material
Enviornment friendly
Electronic material
Piezoelectric material
INTRODUCTION
Zinc oxide is an inorganic compound with the formula ZnO. It usually appears as
a white powder, nearly insoluble in water. The powder is widely used as an
7
additive into numerous materials and products including plastics, ceramics,
glass, cement, rubber (e.g. car tyres), lubricants, paints, ointments, adhesives,
sealants, pigments, foods (source of Zn nutrient), batteries, ferrites, fire
retardants, etc. ZnO is present in the Earth crust as a mineral zincite; however,
most ZnO used commercially is produced synthetically. In materials science,
ZnO is often called a II-VI semiconductor because zinc and oxygen belong to the
2nd and 6th groups of the periodic table, respectively. This semiconductor has
several favorable properties: good transparency, high electron mobility, wide
bandgap, strong room- temperature luminescence, etc. Those properties are
already used in emerging applications for transparent electrodes in liquid crystal
displays and in energy-saving or heat-protecting windows, and electronic
applications of ZnO as thin-film transistor and light-emitting diode are
forthcoming as of 2009.
CRYSTAL STRUCTURES
Zinc oxide crystallizes in three forms:
hexagonal wurtzite,
cubic zincblende,
and the rarelyobserved cubic rocksalt.
The wurtzite structure is most stable and thus most common at ambient
conditions. The zincblende form can be stabilized by growing ZnO on substrates
with cubic
lattice structure. In both cases, the zinc and oxide are tetrahedral. The rocksalt
NaCl-type
structure is only observed at relatively high pressures - ~10 GPa.
3
The hexagonal and zincblende ZnO lattices have no inversion symmetry
(reflection of a crystal
relatively any given point does not transform it into itself). This and other lattice
symmetry
properties result in piezoelectricity of the hexagonal and zinc blende ZnO, and in
pyro-electricity
of hexagonal ZnO.
The hexagonal structure has a point group 6 mm (Hermann-Mauguin notation) or
C6v
(Schoenflies notation), and the space group is P63mc or C6v. The lattice
constants are a = 3.25
and c = 5.2 ; their ratio c/a ~ 1.60 is close to the ideal value for hexagonal cell
c/a = 1.633. As
in most II-VI materials, the bonding in ZnO is largely ionic, which explains its
strong
8
piezoelectricity. Due to this ionicity, zinc and oxygen planes bear electric charge
(positive and
negative, respectively). Therefore, to maintain electrical neutrality, those planes
reconstruct at
atomic level in most relative materials, but not in ZnO - its surfaces are
atomically flat, stable
and exhibit no reconstruction. This anomaly of ZnO is not fully explained yet.

Wurtzite structure
9


Zinc blende structure
Synthesis of Zinc Oxide Nano
Particles:
Zinc oxide quantum dot nano particles absorb UV light but are
optically transparent making them useful as the active ingredient of sunscreens.
The absorption wavelength is a function of particle size when the particles are
small. This synthesis involves particle growth at 65C; samples removed at
longer times give larger particles. The cut-off wavelength from the absorption
spectra can be used to estimate the particle size. Nanoparticles
Equipment:
10

1L beakers for hot water bath and ice bath
thermometer to measure 65C
Stirbars and stirring hotplate
50 and 250 mL Erlenmeyer flasks
25 mL graduated cylinder
0.01 g balance
UV spectrometer
Chemical Required
Zn(CH
3
CO
2
)
2
.
H
2
O (0.10g per batch)
(CH
3
)
2
CHOH (165mL per batch). Isopropanol vapors irritate the
respiratory tract and eyes. Wear eye protection and use in a fume hood.
Avoid skin contact.
Ice
Stock NaOH Solution for 6 batches:
11

Procedure:
ssDissolve 0.20 g NaOH in 100 mL isopropanol with heating. (Quickly
weight out about 2 pellets of the hygroscopic NaOH and immediately
transfer to the waiting solvent.)
Begin heating a large beaker of water to 65C.
.
Meanwhile, dissolve 0.10 g Zn(CH
3
CO
2
)
2
.
H
2
O in 25 mL isopropanol with heating
in a fume hood
12
Meanwhile, prepare an ice bath by adding water to ice. Place 125 mL
isopropanol in a flask and chill the flask in the ice bath.
When the zinc acetate solid has all dissolved, add that solution to the 125 mL of
chilled isopropanol.
Also obtain 15 mL of 0.050 M NaOH in isopropanol and chill the solution. (A
stock solution may already be chilled.)
13
Slowly transfer the chilled NaOH solution to the chilled and rapidly stirring zinc
acetate solution using a pasteur pipet.
Place the flask with the mixed solution in the 65C water bath and start taking
samples .
14
Calculations:
E
g
= hc /
h =6.626x10
-34
Js
c =2.998x10
8
m/s
e =1.602x10
-19
C

0
=8.854x10
-12
C
2
/N/m
2
m
0
= 9.110x10
-31
kg
e.g;
For ZnO:

bulk
=365nm
=8.66
m
e
*=0.24
m
h
* = 0.59
The x-intercept of the linear portion of the absorbance as a function of
wavelength graph is a measure of E
g
.
15
The effectivemassmodel suggests
where r is the radius of the nanoparticle. The second term is the particle-in-a-box
confinement energy for an electron-hole pair in a spherical quantum dot and the
third term is the Coulomb attraction between an electron and hole modified by
the screening of charges by the crystal.
After multiplying by r
2
, rearranging, and using the quadratic formula,
Precautions:
Isopropanol vapors irritate the respiratory tract and eyes.
Wear eye protection and use in a fume hood. Avoid skin contact.

16
Doping:


In semiconductor production, doping intentionally introduces impurities
into an extremely pure (also referred to as intrinsic) semiconductor for the
purpose of modulating its electrical properties. The impurities are dependent
upon the type of semiconductor. Lightly and moderately doped semiconductors
are referred to as extrinsic. A semiconductor doped to such high levels that it
acts more like aconductor than a semiconductor is referred to as degenerate.
N-type Doping or Donor:
In semiconductor physics, a donor is a dopant atom that, when added to
a semiconductor, can form a n-type region.
For example, when silicon (Si), having four valence electrons, needs to be doped
as an n-type semiconductor, elements from group V like phosphorus (P) or
arsenic (As) can be used because they have five valence electrons. A dopant
with five valence electrons is also called a pentavalent impurity. Other
pentavalent dopants are antimony (Sb) and bismuth (Bi).
When substituting a Si atom in the crystal lattice, four of the valence electrons of
phosphorus form covalent bonds with the neighbouring Si atoms but the fifth one
remains weakly bonded. At room temperature, all the fifth electrons are liberated,
can move around the Si crystal and can carry a current and thus act as charge
carriers. The initially neutral donor becomes positively charged (ionized).
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P-type Doping or Acceptor:
A p-type semiconductor (p for Positive) is obtained by carrying out a process
of doping by adding a certain type of atoms (acceptors) to the semiconductor in
order to increase the number of freecharge carriers (in this case positive holes).
When the doping material is added, it takes away (accepts) weakly bound
outer electrons from the semiconductor atoms. This type of doping agent is also
known as an acceptor material and the vacancy left behind by the electron is
known as a hole.
The purpose of p-type doping is to create an abundance of holes. In the case
of silicon, a trivalent atom (typically from Group 13 of the periodic table, such
as boron or aluminium) is substituted into the crystal lattice. The result is that one
electron is missing from one of the four covalent bonds normal for the silicon
lattice. Thus the dopant atom can accept an electron from a neighboring atom's
covalent bond to complete the fourth bond. This is why such dopants are
called acceptors. The dopant atom accepts an electron, causing the loss of half
of one bond from the neighboring atom and resulting in the formation of a "hole".
Each hole is associated with a nearby negatively charged dopant ion, and the
semiconductor remains electrically neutral as a whole. However, once each hole
has wandered away into the lattice, one proton in the atom at the hole's location
will be "exposed" and no longer cancelled by an electron. This atom will have 3
electrons and 1 hole surrounding a particular nucleus with 4 protons. For this
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reason a hole behaves as a positive charge. When a sufficiently large number
of acceptor atoms are added, the holes greatly outnumber
thermal excited electrons. Thus, holes are the majority carriers, while electrons
become minority carriers in p-type materials.
Techniques of Doping and synthesis:
The synthesis of n-type semiconductors may involve the use of vapor-phase
epitaxy. In vapor-phase epitaxy, a gas containing the negative dopant is passed
over the substrate wafer. In the case of n-type Gas doping, hydrogen sulfide is
passed over the gallium arsenide, and sulfur is incorporated into the
structure This process is characterized by a constant concentration of sulfur on
the surface. In the case of semiconductors in general, only a very thin layer of
the wafer needs to be doped in order to obtain the desired electronic
properties The reaction conditions typically range from 600 to 800 C for the n-
doping with group VI elements and the time is typically 612 hours depending on
the temperature.
Process:
Some dopants are added as the (usually silicon) boule is grown, giving
each wafer an almost uniform initial doping To define circuit elements, selected
areas typically controlled byphotolithography
[8]
are further doped by such
processes as diffusion and ion implantation, the latter method being more
popular in large production runs because of increased controllability.
Small numbers of dopant atoms can change the ability of a semiconductor to
conduct electricity. When on the order of one dopant atom is added per 100
million atoms, the doping is said to be low orlight. When many more dopant
atoms are added, on the order of one per ten thousand atoms, the doping is
referred to as heavy or high. This is often shown as n+ for n-type doping
or p+ for p-typedoping.
Doping in ZnO:
Doping in ZnO play an important role to tailor the properties of nanostructures.
There are four types of doping elements. Doping is expected to induce some
changes in the morphology, optical, electrical, and magnetic properties of the
nanostructures
Doping with donor impurities to achieve high n-type conductivity, such as
Al, Sn, In, Pb etc.
Doping with acceptor impurities to achieve p-type conductivity, such as N,
As, P etc.
Doping with rare-earth elements such as Tb, Ce, Eu, and Dy to achieve
19
desired optical properties.
Doping with transition metals such as Mn. Co, and Ni etc. to achieve
desired magnetic properties.
Aligned In-ZnO
NWs
Curves using different techniques;

Room-
20
temperature PL spectra of different nanostructures: 1) Tetrapods, 2) needles, 3)
nanorods, 4) shells, 5) highly faceted rods, 6) ribbons/combs
PROPERTIES OF
NANOPARTICULATED OXIDES
CHEMICAL PROPERTIES
ZnO occurs as white powder commonly known as zinc white or as the mineral
zincite. The mineral usually contains a certain amount of manganese and other
elements and is of yellow to red color. Crystalline zinc oxide is thermo-chromic,
changing from white to yellow when heated and in air reverting to white on
cooling. This is caused by a very small loss of oxygen at high temperatures to
form the non-stoichiometric Zn1+xO, where at 800 C, x= 0.00007.
Zinc oxide is an amphoteric oxide. It is nearly insoluble in water and alcohol, but
it is soluble in (degraded by) most acids, such as hydrochloric acid:
ZnO + 2 HCl ZnCl2 + H2O
Bases also degrade the solid to give soluble zincates:
ZnO + 2NaOH + H2O Na2(Zn(OH)4)
ZnO reacts slowly with fatty acids in oils to produce the corresponding
carboxylates, such as oleate or stearate. ZnO forms cement-like products when
mixed with a strong aqueous solution of zinc chloride and these are best
described as zinc hydroxy chlorides. This cement was used in dentistry.
ZnO also forms cement-like products when reacted with phosphoric acid, and
this forms the basis of zinc phosphate cements used in dentistry. A major
component of zinc phosphate cement produced by this reaction is hopeite, Zn3
(PO4)24H2O.
ZnO decomposes into zinc vapor and oxygen only at around 1975 C, reflecting
its considerable stability. Heating with carbon converts the oxide into zinc vapor:
ZnO + C Zn + CO
Zinc oxide reacts violently with aluminum and magnesium powders, with
chlorinated rubber and linseed oil on heating causing fire and explosion hazard.
It reacts with hydrogen sulfide to give the sulfide: this reaction is used
commercially in removing H2S using ZnO powder (e.g., as deodorant).
ZnO + H2S ZnS + H2O
When ointments containing ZnO and water are melted and exposed to ultraviolet
light, hydrogen peroxide is produced. Metal oxides ar1e used for both their redox
and acid/base properties in the context of Absorption and Catalysis. The three
key features essential for their application as absorbents or catalysts are
the coordination environment of surface atoms,
the redox properties,
the oxidation state at surface layers. Both redox and
acid/base properties are interrelated and may attempts
can be found in the literature to establish correlations of
21
both properties.105,106 In a simple classification, oxides
having only s or p electrons in their valence orbitals tend
to be more effective for acid/base catalysis, while those
having d or f outer electrons find a wider range of uses.
The solid in a given reaction conditions that undergoes reduction and reoxidation
Simultaneously by giving out surface lattice oxyen anions and taking oxygen
from the gas phase is called a redox catalyst. This process necessarily demands
microscopy
reversibility and implies dynamic operation. The commonly accepted mechanism
was
developed by Mars van Krevelen and essentially implies that redox systems
require highelectronic conduction cations to manage electrons and high oxygen-
lattice mobility.
Based on modern isotopic exchange experiments, the redox mechanism of
chemical
reactions can be more specifically divided in
(i) extrafacial oxygen in which adsorbed (oxygen) species react (electrophilic
reaction),
(ii) interfacial oxygen where lattice oxygen vacancies are created (nucleophilic
reaction).
There are enormous evidence that nucleophilic oxygen is capable of carrying out
selective oxidations while it seems that electrophilic species seems to exclusively
work on non-selective ones. Latter, it was shown that hydrocarbon selective
oxidation starts with H-abstraction steps and that the filling of oxygen vacancies
require the cooperation of a significant number of cations.105 So, typically, an
oxidation reaction demands to optimize three important steps: the activation of
the C-H bond and molecular oxygen, and the desorption of products (to limit
over-oxidation). The effect of size on these key steps is unknown but can be
speculated to be related to the oxidation state of surface cations and their ability
to manage electrons and the influence of non-stoichiometry on the gas-phase
oxygen species handling and activation.
Many oxides also display acid/base properties. Oxide materials can contain
Bronsted and Lewis acid/base sites. Bronsted acid (A) and base (B) interactions
consist of an the exchange of protons as HA + B = A- + HB+. Lewis proposed a
different approach
to measure acid-base interaction as depicted by (B:) + A = d-B Bd+. Latter,
Petterson introduced the concepts of hard and soft acid and base but, usually,
acid/base properties of solid are rationalized in terms of Bronsted and Lewis
definitions. In any solid, two independent variables, the acid/base strength and
amount (density per surface unit) need to be addressed to give a complete
picture of its acid/base characteristics. Such characteristics are basically linked
to the nature (valence/cation size) of the element present in the oxide and
general views of the behavior of Bronsted/Lewis acidity as a function of solid
state variables have been published.106 Essentially, Lewis acidity is characeristic
of ionic oxides and practically absent (unless very aggressive outgassing
treatments) in covalent oxides. The strongest Lewis acid oxides are Al2O3 and
22
Ga2O3. As a general rule, the stronger the Lewis acid, the few available sites
(amount) due to the higher level of surface hydroxylation. As mentioned,
because Lewis acidity is mostly associated to oxides with ionic character, Lewis
basicity is mostly associated with them. This means that the stronger the Lewis
acid sites, the weaker the basic sites and vice versa. On the contrary, most of
the ionic metal oxides do not carry sufficiently strong Bronsted acidity to
protonate pyridine or ammonia at room temperature although the more acid of
them can do it at higher temperatures. In spite of this, the surface OH groups of
most ionic oxides have a basic more than acid character. Covalent low-valent
nonmetal oxides (SiO2, GeOx, BOx) also show quite weak Bronsted acid
properties. Finally, strong Bronsted acidity appears in oxides of elements with
formal valence five or higher (WO3, MoO3, N2O5, V2O5, and S-containing oxides).
Electronic Properties;
ZnO has a relatively large direct band gap of ~3.3 eV at room temperature;
therefore, pure ZnO is colorless and transparent. Advantages associated with a
large band gap include higher breakdown voltages, ability to sustain large
electric fields, lower electronic noise, and high temperature and high-power
operation. The bandgap of ZnO can further be tuned from ~34 eV by its alloying
with magnesium oxide or cadmium oxide.
Most ZnO has n-type character, even in the absence of intentional doping.
Native defects such as oxygen vacancies or zinc interstitials are often assumed
to be the origin of this, but the subject remains controversial. An alternative
explanation has been proposed, based on theoretical calculations, that
unintentional substitutional hydrogen impurities are responsible. Controllable n-
type doping is easily achieved by substituting Zn with group-III elements Al, Ga,
In or by substituting oxygen with group-VII elements chlorine or iodine. Reliable
p-type doping of ZnO remains difficult. This problem originates from low solubility
of p-type dopants and their compensation by abundant n-type impurities, and it is
pertinent not only to ZnO, but also to similar compounds GaN and ZnSe.
Measurement of p-type in "intrinsically" n-type material is also not easy because
inhomogeneity results in spurious signals.
Current absence of p-type ZnO does limit its electronic and optoelectronic
applications which usually require junctions of n-type and p-type material. Known
p-type dopants include group-I elements Li, Na, K; group-V elements N, P and
As; as well as copper and silver. However, many of these form deep acceptors
and do not produce significant p-type conduction at room temperature. Electron
mobility of ZnO strongly varies with temperature and has a maximum of ~2000
cm2/(Vs) at ~80 Kelvin.[21] Data on hole mobility are scarce with values in the
range 5-30 cm2/(Vs).
Optical properties.
The optical conductivity is one of the fundamental properties of metal oxides and
can be experimentally obtained from reflectivity and absorption measurements.
While reflectivity is clearly size-dependent as scattering can display drastic
23
changes when the oxide characteristic size (primary/secondary particle size) is
in/out the range of photon wavelength,62 absorption features typically command
main absorption behavior of solids. Due to quantum-size confinement,
absorption of light becomes both discrete-like and size-dependent. For nano-
crystalline semiconductors, both linear (one exciton per particle) and non-linear
optical (multiple excitons) properties arise as a result of transitions between
electron and hole discrete or quantized electronic levels. In the first case,
depending on the relationship between the radius of the Nanoparticle (R) and the
Bohr radius of the bulk exciton (RB = 2/e2; exciton reduced mass and
dielectric constant of the semiconductor), the quantum confinement effect can be
divided into three regimes; weak, intermediate and strong confinement regimes,
which correspond to R >> RB, R RB, and R << RB, respectively.63 The effective
mass theory (EMA) is the most elegant and general theory to explain the size
dependence of the optical properties of nano-meter semiconductors, although
other theories as the free exciton collision model (FECM)64 or those based in the
bond length strength correlation65 have been developed to account for several
deficiencies of the EMA theory.
For the onset of light absorption, e.g. the optical band gap, as well as for all other
electronic transitions present in the optical absorption spectrum, the EMA theory
predicts a r-2 dependence, with a main r-1 correction term in the strong
confinement regime, while FECM gives a exp(1/r) behavior. It can be thus
concluded that metal oxide semiconductors would present, as a first rough
approximation, an optical band gap energy with an inverse squared dependence
of the primary particle size if quantum confinement dominates the energy
behavior of the band gap. Shows that this happens to be the case for (direct
band gap) Fe2O3 or (indirect band gap) CdO but not for Cu2O, CeO2,, ZnO, and
TiO2. Limited deviations from the R-2 behavior, as observed for ZnO70 in or
SnO2,74 can be based in the known fact that the theory overestimates the blue
shift and can be justified with a proper calculation of electronic states by using
simple quantum mechanical methods, while marked deviations are usually based
in several chemical/physical phenomena not accounted for in the previous
discussion. In the case of Cu2O68 or CeO2 it appears to be directly related with
the presence of Cu2+ (remarkably for very low particle size) and Ce3+ ions at the
surface of the nano structured materials. At the moment it is not clear if the
presence of these oxidation states are intrinsic to the nanostructure or result
from the specific procedure of preparation. The case of WO3 share also some of
the difficulties pointed out above. Kubo et al. were able to show that the band
gap of this oxide decrease with size from ca. 3.0 to 2.8 eV as a function of R but
the presence of a variable number of oxygen defects, reduced W redox states
and mid-gap electronic states with size makes this an open question. TiO2 is the
other example included in having a band gap energy behavior with marked
differences from that expected r-2 behavior. While bulk TiO2 is an indirect
semiconductor, nano structured TiO2 materials are likely direct ones.72,78 This
may be a general result. As discussed in ref. 79, the confinement of charge
carriers in a limited space causes their wave functions to spread out in
momentum space, in turn increasing the like hood of radiative transitions for bulk
24
indirect semiconductors. This may also be the case of NiO. The indirect nature of
the absorption onset would complicate the analysis of the optical band gap
energy due to the above mentioned step structure of the absorption onset (which
includes phonon-related absorption/emission features). In spite of this, the
steady behavior shown in can not be accounted for by small variations in the
absorption onset and should be grounded in other physical phenomena. Other
optical excitations which showed quantum-size confinement effects concern the
excitation of optical phonons of oxides. The effects of size on the phonon
spectra of oxide materials have been well established by using Raman scattering
experiments on nano crystals, in combination with the theoretical phonon
confinement
Models essentially, the theoretical background for the study of nano crystalline
materials is provided by the phonon confinement model. This factor is the main
responsible for the changes observed in the Raman spectrum which are caused
by the size effect. Nevertheless, other factors have been described which can
contribute to Raman spectrum modification as the non-stoichiometry or the
internal stress/surface tension. The phonon confinement model links q vector
selection rule for the excitation of Raman active optical phonons with long-range
order and crystallite size In an amorphous material, owing to the lack of long-
range order, the q-vector selection rule breaks down
and the Raman spectrum resembles the phonon density of states. Nanocrystals
represent an intermediate behavior. For a nanocrystal of average diameter L, the
strict infinite crystal selection rule is replaced by a relaxed version, with the
result that a range of q vectors is accessible due to the uncertainty principle, The
q vector relaxation model can be used for the purpose of comparing
experimental data with theoretically predicted phonon confinement. According to
this model, for finite sized crystals, the Raman intensity can be expressed using
the equation 1:
The (L) represents the particle size distribution, q is expressed in units of a L
(being
aL the unit cell parameter), ( q ) is the phonon dispersion, and 0 is the
intrinsic linewidth of the bulk crystal. A spherically symmetric phonon dispersion
curve is assumed and approximated by a simple linear chain model.84 For a
given phonon mode, the slope of dispersion away from the BZ center determines
the nature of the modification in the Raman line shape as a function of crystallite
size: a negative slope, towards lower frequency, would produce a downshifted
(red-shifted) Raman peak, while
a positive slope would result in an up-shifted (blue-shifted) Raman peak, in
addition to an asymmetric peak broadening, as the crystallite size reduces.
Usually is chosen for this kind of analysis the most intense Raman mode for the
solid studied. Some examples of application of the confinement model for
qualitative interpretation of Raman results in series of nano structured oxides like
anatase ZnO, TiO2, CuO, Cr2O3, ZrTiO4, CeO2 or manganese oxides can be
found elsewhere. In all cases, optical absorption features of nano sized oxides
are additionally influenced by non-stoichiometry size-dependent defect effects.
25
Typical point defects in
nano structured oxides concern oxygen or cation vacancies and/or the presence
of aliens species, like Cu2+ and Ce3+. Vacancy defects introduce gap states in
proportion to the defect number; in fact, a random distribution of (equal) vacancy
defects introduce a
gaussian-like density of states which may produce mid-gap states and/or be
localized near the valence and conduction bands depending on the electronic
nature (donor/acceptor) of the defect and giving characteristic localized
features in the UV-visible spectrum. Such point defects mainly contribute to the
Raman spectra by producing a broadening of the peaks. Alien cations display
specific features, like the localized d-d or f-f transitions of Cu/Ce. Besides
electronic modifications, point defects but particularly alien ions, like Cu2+ and
Ce3+ above, induce strain effects and concomitant structural differences in
atomic positions with respect to bulk positions. The influence of strain in the
optical absorption spectrum has been nicely demonstrated in the work of Ong et
al. for ZnO, showing the splitting of the first exciton peak for large values of
compressive strain. Strain effects (including parameter variations measured in
optical phonons with the help of the Gruneisen parameter) are inherent to nano
structured materials and may be comprised in the general, ambiguous term of
surface effects usually claimed to account for significant deviations the
confinement theories. Surface effects and, particularly, non stoichiometry related
to the preparation method are critically important for very low particle size and
produce characteristic features in the UV-visible spectrum for certain oxides, as
SnO2 or ZrO2.
Transport properties.
Oxide materials can present ionic or mixedionic/electronic conductivity and it is
experimentally well established than both can be influenced by the nanostructure
of the solid. The number of electronic charge carriers in a metal oxide is a
function of the band gap energy according to the Boltzmann statistics. The
electronic conduction is referred to as n- or p-hopping-type depending on
whether the principal charge carrier are, respectively, electrons or holes. The
number of free electron/holes of an oxide can be enhanced by introducing non-
stoichiometry and, in such case, are balanced by the much less mobile
oxygen/cation vacancies. In an analogous manner to hoping-type conduction,
ionic conduction takes place when ions can hop from site to site within a crystal
lattice as a result of thermal activation, and is typically interpreted on the basis of
a modified Ficks second law. Four mechanism types have been observed for
ionic conduction: direct interstitial, interstitialcy, vacancy, and grotthus. As charge
species (defects; impurities) in polycrystalline oxides typically segregate to
particle boundaries to minimize strain and electrostatic potential contributions to
the total energy, there is a contribution to the conductivity parallel to the surface
which becomes important at the nanoscale regime. The charge carrier (defect)
distribution also suffers strong modification from bulk materials as there is
presence of charge carries through the whole material as a consequence of the
shielded electrostatic potential depletion at surface layers of nanosized
26
materials. As a result of these nanoscale derived effects, it is well known that
CeO2 exhibits an improved n-type conductivity which may be four order of
magnitude greater than the corresponding to bulk/micro-crystalline ceria, and is
ascribed to a significant enhancement of the electronic contribution. Alteration of
the transport properties is also observed in ZrO2 but the physical ground is still
far from being understood. The strong size-dependence observed for the
electrical conductance in the context of gas-sensing devices has been recently
reviewed for the SnO2, WO3, and In2O3 oxides. In proton conductors, like SrCe
Yb O3-d, enhanced conduction and faster kinetics under H-atmospheres are
observed in nanosized samples as these phenomena are largely determined by
boundary/interfacial effects. Interesting to stress here is that some of the most
dramatic effects of he nanostructure on ionic transport in oxides are observed in
the field of Li+-ion batteries. An outstanding enhancement of Li+-ion vacancy
conductivity have been achieved using Li-infiltrated nanoporous Al2O3.
Mechanical properties.
Main mechanical properties concerns low (yield stress and hardness) and high
(superpasticity) temperature observables. Information on oxide nanomaterials is
scarce and mainly devoted to analyze sinterability, ductibility, and superpasticity.
In particular, an important number of works have showed significant
improvement in sintering with up to 600 K lower temperatures with respect to
bluk counterparts. In conventional/bulk materials the yield stress () and harness
(H) follow the Hall-Petch (H-P) equation:
/ H / H k d-1/2 (2) = 0 0 + where the initial constants describe friction stress and
hardness, d is the primary particle/grain size and k the corresponding slope. The
H-P effect in bulk materials is attributed to the particle/grain boundaries acting as
efficient obstacles for slip transfer (stress) or dislocations (hardness). Typically
by decrease the particle/grain size down to the order of a few tens nanometers
the H-P slope, which is positive, gets smaller values. However, below such
critical point it appears that conventional dislocation mechamisn(s) cease(s) to
operate and a d-n (n> ) behavior or a reversal H-P mechanism would
become progressively dominant.101,102,103 On top of this, these mechanical
properties are also found to be strain-rate dependent; an enhanced strain rate
sensitivity at room temperature is observed for TiO2 and ZrO2 with decreasing
primary particle/grain size. In spite of such facts, it is clear that oxide materials
(like Al2O3, ZrO2, CeO2, and TiO2) sintered under vacuum or using the spark
plasma technique display enhanced yield strength and hardness with respect to
conventional/bulk ceramic materials and have the additional properties of being
transparent (films), being potential materials for the aerospatial industry.
Superplasticity refers to the capacity of oxide materials to undergo extensive
tensile deformation without necking or fracture. The phenomenological
relationship for superplasticity is defined as: where is the strain rate, D is the
adequate diffusion coefficient, G is the shear modulus, b is the Burgers vector,
is the applied yield strength, and p/n the particle size and yield strength
exponents. implies that reduction of the particle size leads to an increase of the
27
super plasticity strain rate at constant temperature, or to a reduction in the super
plasticity temperature as a constant strain rate, but very studies have been
reported having oxides as the subject of the work. Essentially, policrystalline
tetragonal ZrO2 appears as the most celebrated example of a superpacticity
ceramic, and together with TiO2 are the only nano-oxides subjected to studies. At
room temperature, nanocrystalline oxides may have a small amount of ductibility
beyond that exhibited by bulk materials but they are not superplastics. Al high
temperatures, they seem to exhibit significant compressive ductility and strain
rate sensitivities that are indicate of superplasticity.
Magnetic properties
It is possible to induce room-temperature ferromagnetic-like behavior in ZnO
nanoparticles without doping with
magnetic impurities but simply inducing an alteration of their electronic
configuration. Capping ZnO nanoparticles (_10 nm size) with different
organic molecules produces an alteration of their electronic configuration that
depends on the particular molecule, as evidenced by
photoluminescence and X-ray absorption spectroscopies and altering their
magnetic properties that varies from diamagnetic to ferromagneticlike
behavior
Magnetic properties can be induced by
Dopping
Capping
Dopping
Already described above.
Surface-capping of ZnO nanoparticles
A series of ormosils were prepared by varying the mole ratio of TEOS to DEDMS
and then used for surface-capping of ZnO nanoparticles. the abbreviations for
various surface-capped ZnO nanoparticle samples. As a typical example, 6.5 g
of ZnO was mixed with 50 ml of absolute ethanol and 150 ml of deionized water
by shearing at 4000 rpm for 5 min (BME100LX high-speed shearing machine,
Weiyu Machinery & Electronics Company Limited, Shanghai, China), followed by
ultrasonication (SK3200H, Shanghai Kudos Ultrasonic Instrument Company
Limited, China) for 20 min. The resulting ZnO suspension was then slowly
transferred to a 500-ml three-necked flask, followed by the addition of 0.5 ml of
ammonia solution as the catalyst, generating a mixed suspension. Into the mixed
suspension were added a proper amount of premixed TEOS and DEDMS and
25 ml of absolute ethanol. The resulting mixed reactants were vigorously stirred
at 60 C for 6 h, allowing the surface-capping of ZnO nanoparticles by ormosils.
Upon completion of the surface-capping process, the mixed products were
washed with ethanol and filtered, and the solid residue was collected as the as-
prepared surface-capped ZnO nanoparticles. As-prepared ZnO nanoparticles
28
were dried at 100 C in air for 12 h, generating the final samples for
characterization. The same process for preparing surface-capped sample ZT1D2
was also performed in the absence of ZnO nanoparticles generating sample
T1D2 as a control sample.
29
Scientific research;
The last years,following the proposal by
Ohno;
The research on these magnetic semiconductors has been mainly
focused on theso-called Diluted magnetic semiconductors (DMS):
semiconductors containing a small amount of magnetic impurities.The main
challenge for this kind of materials is to preserve their magnetic character at
room temperature (RT), that is,
Curie temperature (TC) above 300 K, in order to be useful for technological
applications.
Despite some initial promising results on Mn:ZnO, it is not clear if DMS
can exhibit this required high-temperature magnetism.
For most of the experimental results, doubts arose about the real origin of
magnetism. For some cases it was demonstrated that the
magnetism was due to segregation of metallic clusters
The most recent and outstanding works on this field showed that the
magnetic properties are not exclusively related to the presence of the magnetic
ions but strongly determined by the defects.
Kittisltved et al.
showed that Mn:ZnO nanoparticles and thin films
only show RT ferromagnetism when capped with molecules that introduce n-type
defects, while other capping that introduce p-type defects leads to no RT
ferromagnetism. On the contrary, for Co: ZnO films the n-type defects favor the
appearance of RT ferromagnetism while p-type defects yield to no RT
ferromagnetism.
Rubi et al
also found that magnetic properties of Co- and Mn-doped ZnO
powder samples are modified by thermal annealing in different atmospheres that
favor the presence of p- or n-type defects
Coey et al.
insulating HfO2 the effect appears even without doping.1
Experimental observation of Capping of ZnO
NPs
Capping ZnO NPs with a variety of organic molecules modifies its
electronic structure
ZnO NPs were prepared by sol-gel
30
Subsequently capped with 3 different organic molecules:
Tryoctylphosphine (TOPO),
Dodecylamine (AMINE), and
Dodecanethiol (THIOL)
Bond to the particle surface through an O, N, and S atom,respectively.


Amine
31
Figure 1. (a) X-ray diffraction patterns of the AMINE, THIOL, and TOPO samples. Diffraction
maxima of a ZnO wurtzite type unit cell.
(b) Low-magnification image of the AMINE sample, showing the size distribution.
(c) HREM image along
Conclusions
The magnetic properties strongly depend on the preparation method.
slight modifications in the preparation conditions and size of thiol-capped
Zn NPs lead to important variations in their magnetic properties.
Absorption of certain organic molecules onto ZnO nanoparticles modifies
its electronic structure and gives rise to a ferromagnetic-like behavior at
room temperature even in the absence of magnetic ions
32
Application
During the battle of human being fighting against bacteria and viruses, organic
medicine has become ever indispensable in daily life. Excessive usage of these
medicines, however, will transform bacteria into other forms which are much more
difficult to conquer. Moreover, as the entire human being is growing even more
conscious of the importance of healthy life and good living habits, people use
antibacterial products to create a hygienic environment to ensure the ultimate
protection of healthy life style.
Because of Nano ZnO's unique antibacterial characteristics and excellent physical
stability, it can serve as an effective antibacterial agent. Besides, Nano ZnO does not
discolor, nor does it require ultra-violet to get activated. These properties make Nano
ZnO a superior non-organic antibacterial agent versus other materials used nowadays,
such as photo-catalyst, which needs ultra-violet light to be activated, and Silver Ion,
which will discolor over the course of time.
Furthermore, ZnO is a multi-functional semi-conductive material. In the rapidly-growing
electronic industries, ZnO may be used as a functional material in plastics, pigments
and fibers in various kinds of products, offering immense benefits such as anti-static,
electromagnetic-shielding and UV-blocking. Therefore, Nano ZnO powder will be
further used in many different industries to deliver exceptional features and to enhance
product performance not reached by those made of traditional ZnO.
33
Medicine Application Nano ZnO Specification
ZnO is generally regarded as safe food additives under the
condition of superb manufacturing process and feeding process. Element Zinc is the
biggest micro metal that universally exists in live body, and is also the biggest micro
metal among human body. All creatures need zinc as it composes of cells as the
cofactor of fundamental enzyme system. Daily-recommended intake for adult is 15mg,
and 25mg for breast-feeding mother. ZnO features mild wound astringent, inflammation
reduction/relief, and anti-microbial functions, also serves as a remedy for dermatitis
and infection diseases, such as eczema, impetigo, ringworm, slack abscess, itch and
psoriasis. The diameter of a nano ZnO measures approximately 10 ~ 20nm. Most of
them are fiber structure observed under microscope, with the features of fine grains,
exceptional purity, and extraordinary whiteness.
Cosmetics,Sunscreen Application Nano Zno
Specification
1. Nano ZnO shows excellent ability in resisting UVA and UVB. It also displays
excellent grain subtlety, high purity, and extremely low harmful content. It is also
suitable for the use in sunscreen products to block the UV away from human body.
ZnO is both safe and mild to body, approved by Food and Drug Administration
(FDA) as one of two sunscreen ingredients of the first category skin-care products.
Physical sunscreen ingredients are neither being absorbed nor be reduced by
human body. It is proven that TiO2 has its flaws in blocking UVA (wave length
ranging between 340 ~ 400nm), and that only ZnO can completely screen both
UVA and UVB.
34
2. Traditional ZnO normally appears unnaturally white when applied on the skin.
Lifesavers, frequent users have a dislike for its white appearance. So the ordinary
ZnO is not widely used for UV blocking. However, nano ZnO improves the above
shortcoming and the test result was approved by CSIRO (Australian
commonwealth scientific & industrialresearch organization). They found that nano
ZnO block blocks double UV that ordinary ZnO does. Nano-infinity Nanotech Co.,
Ltd. produces high purity ZnO whose grain size is smaller than light wave yet the
color being pure white. When ZnO is used as ingredient of UV blocking cream or
lotion, it is silky and transparent and without color after applied onto humanskin.
Therefore, Nano ZnO is the best ingredient to make cosmetics.
Industrial Application Nano Zno Specification
1. Nano ZnO is not only fabulous in its performance but also tends to replace ordinary
ZnO. In many new fields, it shows unrivaled effects over ordinary ZnO. The
excellent performance of nano ZnO makes itself perfect replacement for traditional
micronized ZnO.
35
2.
Industrial Applications as Below:
Animal Feedstuffs and Drugs: The feedstuffs that
contain nano ZnO deliver much better effect than those with micronized ZnO do,
along with other benefits, such as higher absorption rate and less required dosage.
Rubber Industry: Nano ZnO is the most effective inorganic surfactant and
sulfurizing accelerator, featuring faster sulfurizing and wider temperature ranges,
which will lead to faster transformation into zinc sulfide and thus more efficient
production of anti-abrasion rubber.
Ceramics Industry: Ceramic industry is widely using ZnO as white dyestuff. With
nano ZnO, ceramic ware sintering temperature can lower to 400 ~ 600oC, yet
surface is burned as polishing as a mirror.
Textile Industry and Commodity Chemical Industry: Producing deodorant,
antibacterial, FIR and UV-blocking fiber.
Painting Industry: Nano ZnO is a new-type of anti-static agent. Putting semi-
conductive nano ZnO into resin can result in better static shielding.
e.g;
ZnO nanostructures based Nanodevices
36



37
Motivation
Major unresolved issues in ZnO material for its direct use in potential
applications:
P-type material
Band gap tailoring toward visible range
Establishment of ferromagnetism with high T
c
Definite picture regarding the actual mechanism of ferromagnetic ordering
Practical use of these prepared nanostructures
REFERENCES
A research paper on SYNTHESIS AND CHARACTERIZATION OF
ZnO
NANO-PARTICLES by Jayanta Kumar Behera
A research paper on Magnetic Properties of ZnO Nanoparticles by M.
A. Garcia,*,, J. M. Merino,, E. Fernande Pinel,,
38
A research paper on Metal Oxide Nanoparticles by Marcos
Fernnde Garci a,
Jos A. Rodriguez

Dr. Shumaila Sajjad assistant professor IIUI
Dr. Khasif Nadeem assistant professor IIUI
6. Dr. Javed Iqbal assistant professor IIUI
39