Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

Chapter 1
1.1.Introduction
Nanomaterials have attained excellent prominence during the 21st century for outstanding high-
quality applications in the field of electronics, biology, energy technology, quantum mechanics,
potential transport applications, battery technology, polymer chemistry and so on. Nanoparticles are
classified based on their size, shape, composition and origin. Immense physical, chemical, electrical
and photo-induced properties made nanomaterials one of the most wanted materials for optimal
economic and eco-friendly applications. Hundreds of novel nanomaterials have been well established
for various applications and some of them being commercialized for needy purposes.

Nanomaterial in simple can be defined as “Any synthetic or natural material that possesses at
least one external dimension in the order of 10-9 meter”. Specifically, terms like nanoparticles,
nanocomposite, nanofiber, 0-D, 1-D, 2-D, 3-D structures should be clearly distinguished for a better
understanding. A nanoparticle is the one whose three external dimensions i.e., length, breadth, depth
or diameter are in the nanoscale strictly. When a material contains any of the two external dimensions
in the nano range then it is termed as nanofiber. A nanocomposite has a multiphase composition with
at least any one phase containing the nanoscale distribution in size. Ceramic nanocomposites are the
widely used nanocomposite in present material science technology. The table shows composites of
size-dependent activity exhibited:

Table 1.1 Size distribution and applications of nanocomposites

Size (nm) Application

<5 Catalytic activities
<20 Magnetic materials
<50 Refractive index change
<100 Polymer applications

It is very clear from our day to day activities that almost all the scientific aspects are being
inspired by nature [1]. We are also surrounded by a variety of nanostructures. One of the best examples
of a nanostructure in the human body is DNA. Every part of our body is built from millions of
nanostructures which cannot be seen through the naked eye. A lotus leaf possesses excellent
nanostructures on its surface which acts as water repellant [1] and self-cleaning surface for notable
application. This structure is mimicked [3] and manufactured by several aircraft industries for the self-

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

cleaning application so that the maintenance of planes become more economical. Different animals
exhibit a variety of colors from their body because of different surface structures. Colors are exhibited
due to (a) Pigments and (b) Structural which is often referred to as physical and chemical colors [4].
Nearly 79% of the color is due to structural variation. Butterfly wings [2] possess needle-like periodic
sub microstructures when seen under a Scanning Electron Microscope (SEM) which was replicated
using Atomic Layer Deposition technique.

Figure 1: SEM image of the lotus leaf (left), FESEM image of the lotus leaf(right)
Butterfly wings are considered to be one of the most important templates for photonic applications
due to the different periodic structures exhibited.

1.2. Classification of Nano-Structured Materials

Enormous efforts had been put on the study of nanostructured materials to classify them
independently and as time progresses hundreds of novel structures have been developed for a wide
range of applications. At an early stage, Glitter [5] in 1995 classified these structured materials but
were not considered as allotropes of carbon were not taken into account. Later, Pokropivny and
Skorokhod [6] gave a modified classification.

1.2.1. 0-D NSMs: The material where all the dimensions lie within the nanoscale i.e., 1-100 nm come
under the 0-D NSM category. Essentially these are nanoparticles. Heterogeneous particle arrays, Core-
shell quantum dots, nano-lenses, nano-shells, nano-rings, etc. are 0-D NSMs. These are extensively
utilized in single-electron transistors, solar cells, light-emitting diodes and laser applications.

1.2.2. 1-D NSMs: A structured material that possesses one dimension out of the nanoscale is called
1-D NSM. The dimensional dependency of these nanostructured materials allows experts to fabricate

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

optoelectronic devices [7] and EEDs [8] with nanoscale dimensions. Nano-tubes, nano-wires, nano-
rods, nano-ribbons, hierarchical nanostructures fall under this category.

Figure 2: Different kinds of dimensions (left) and Different shapes of materials(right)

1.2.3. 2-D NSMs: A 2-D structured material has two dimensions out of nanoscale. These possess a
few similar and dissimilar properties from bulk. These are considered to be the fundamental building
blocks for nanodevices. Branched structures, nano-prisms, nano-plates, nano-sheets, nano-walls,
nano-disks, nano-junction are good examples of these structures. The novel applications include
sensors [9], photocatalysts, nanoreactors and templates [10].

1.2.4. 3-D NSMs: Here all three dimensions lie out of nanoscale. In simple words, they are bulk
materials. They have an ultimate performance in magnetic properties, electrode, and battery material,
absorption applications etc., Dendric structures, nanoballs, nano-coils, nano-pillars, nano-cones and
nano-flowers [11,12,13] are 3-D NSMs.

Figure 3: SEM Images of dendrites (left) and assembled spheres (right)

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

1.3. Different synthesis techniques.

Several synthesis routes have been practiced for the synthesis of nanostructured materials. In a
broad sense, the techniques are classified as Physical and Chemical methods as shown in the tree
below. NSMs can be divided into 0D, 1D, 2D and 3D NSMs, which generate a series of novel physical
and chemical properties that differ much from bulk materials. Many techniques have been developed
to synthesize and fabricate 0D, 1D, 2D and 3D NSMs with controlled shape, structure, size and
dimensionality.

Nano-strucutred material synthesis

Physical methods Chemical methods

Lithography Sputtering Lytropic Electrochemical Electroless

Evaporation template depostion depostion

Spay Inert gas

Hot & Pyrolysis Condensation Solvo - Chemical
Sol - gel
Cold thermal Vapor
method
plasma technique deposition
Sonochemical
reduction
Laser Solution
Pulsed laser Pyrolysis Combustion
ablation

Figure 4: Classification of physical and chemical methods for the synthesis of NSM

Among all the physical methods, Sputtering and Lithography techniques are used for
surface patterning and nanofabrication. The evaporation technique is widely used for thin-film
depositions. Hot and cold plasma method is used for alloy nanowires and laser ablation for mixed metal
oxide materials. Solution combustion synthesis is the cheapest among all but energy-intensive is
followed by hydrothermal technique.

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

1.4. Template assisted synthesis

Template assisted synthesis uses a template as a base material or casts a given material into
necessary morphology by controlling crystal growth and nucleation. The template method of synthesis
is divided into three types i.e., hard templates such as Anodizing Aluminum Oxide (AAO), soft
template and dual template. In soft template synthesis, three major steps are involved. The first step is
the preparation of a template; the second step is to use a synthetic route like hydrothermal approach or
solgel to achieve a target material. The last step is the removal of the template by chemical or physical
methods such as etching, sintering or dissolution so that the properties of the product are not affected.

The soft template utilizes chemical bonding, hydrogen bonding and other intermolecular forces
to deposit the target inorganic species through its interior or on the surface by the aid of synthetic
methods. Best soft templates include surfactants and polymers because of good reproducibility and
cost-effectiveness. Sodium Do-Decyl sulfate (SDS or Sodium Lauryl Sulphate), ethoxylated
polypropylene glycol, ligno-sulfates are examples of surfactant materials; Poly Ethylene Glycol (PEG),
Poly Vinyl Propylene (PVP), Polyvinyl Butyryl (PVB) include in high polymers. A high polymer is
one of the best choices to synthesize mesoporous materials because of their diverse molecular structure,
chemical stability and high molecular weight. This method focuses on the action of micelle that is
capable of forming an organic-inorganic phase for target material production. This makes self-
assembled arrangement in the solution as shown. The detailed mechanism of the process is explained
in the later stages of the report.

Figure 5: Soft template synthesis mechanism

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

1.5. Basics of Semiconductor Engineering materials

Solid materials are broadly classified into three categories based on their bandgap. The bandgap
is the difference between the energies of the valence and conduction band. They are conductors,
insulators and semiconductors. Conductors are those materials where the valence band and conduction
band overlap enabling immediate charge transport. Insulators have a very large gap between their
valence and conduction band. Hence a huge amount of energy is required to make a transition. In
contrast, semiconductor materials have a fairly calculative bandgap. Inorganic metal oxides are good
examples of semiconductors.

Again semiconductors are classified into intrinsic and extrinsic semiconductors. To facilitate
many real-time applications, bandgaps are purposefully tuned by adding pentavalent and trivalent
impurities. This is called doping. Another way to achieve this is composite making. The bandgap of
materials helps us in a thorough understanding of electrical and thermal properties for electronic device
applications. Any semiconductor material possesses two kinds of bandgap transitions – Direct and
Indirect.

The band structure is dependent on the propagation constant k which is equal to the momentum
required for the electron to jump from one band to the other. In direct bandgap semiconductors, when
an electron moves from conduction band to valence band it releases energy hν. Hence direct
recombination takes place by releasing energy equal to the difference in energy levels between
conduction and valence band concerning the momentum. The probability of the recombination is high
and radiative (release of light), so they were chosen for optical device studies.

Figure 6: Band structure of Direct and Indirect bandgap semiconductors

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

In an Indirect bandgap semiconductor there is a slight misalignment of both the bands with
respect to momentum. So, the electron has to lose some momentum to align itself. This situation is
highly unlikely to happen unless we have an external source to do so. The electron can lose momentum
if it interacts with phonon i.e., the vibration of atom in the crystal lattice. To achieve this, we should
introduce an intermediate energy state which is occurred due to the dislocations and defects in the
crystal lattice. This process is nonradiative (results in the evolution of heat). Iron oxide is an example
of indirect bandgap semiconductor metal oxide.

1.6. Photocatalysis
Industrial pollutants include toxic organic chemicals like insecticides, detergents, pesticides,
dyes, plastics, and heavy metals. Classical industrial methods for water purification faced many
limitations like slow kinetics, need for high temperature and strict pH control. To overcome these
problems researchers started initiating advanced oxidation processes, popularly known as AOP. This
includes photocatalysis, artificial photosynthesis, dye-sensitized solar cell, wastewater treatment and
water splitting for hydrogen generation.

Metal oxide materials serve as one of the best catalysts for the oxidation process. Photocatalysis
infers to the process of catalyzing a given reaction in the presence of light. Normally this process occurs
in semiconductors which is capable of producing electrons and holes for oxidation and reduction
mechanism. An ideal photocatalyst should be chemically and biologically inert, show high catalytic
kinetics, resistant to photo corrosion, cheap, non-toxic and capable of absorbing most of visible or near
UV spectrum. A complementary process for catalysis is a dye-sensitized solar cell and water splitting
as shown below.

Figure 7: Water splitting process (left) and Dye-sensitized solar cell (right)

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Controlled synthesis of α - Fe2O3 and its composites for Photo-Induced application

1.7. Photocurrent
The generation of electric current using a photosensitive material on the exposure of radiative
power is called photocurrent generation. The basic requirement for a material to act as photoanode is
high carrier mobility, fast interfacial charge transfer, high chemical stability, and low production cost.
When a target metal is strike with a light source it emits free charge carriers or electron known as photo-
electrons. The basic concept of harvesting solar energy has emerged from photocurrent. Solar cells
were designed using this concept where pentavalent and trivalent impurities are added on silicon to
enhance photocurrent. Each such plate is capable of generating 0.55-0.6 volt of energy upon harnessing
15-20% of solar energy.

The following setup shows an arrangement of photocurrent measurements. It consists of two

electrodes in an evacuated tube. The light rays strike the photo-sensitive metal oxide surface which is
called the cathode. An anode is placed opposite to it which acts as a collector.

Figure 8: Photocurrent measurement

When a potential is applied to the collector A all the photoelectrons are attracted to the other
end. The maximum current recorded in the ammeter gives us an idea of the number of photoelectrons
ejected from the metal oxide surface. Keeping the frequency of the incident radiation constant, with the
collector plate at positive terminal, the intensity of incident radiation versus photocurrent measurement
is noted. Usually, the plot of photoelectric current versus intensity of incident radiation yields a straight
line because the number of photoelectrons is directly proportional to the intensity of incident radiation.
If the negative potential is applied, the electrons which have attained threshold energy will reach the
collector. The photoemission process is instantaneous takes place within a Picosecond. Photocurrent
measurement is demonstrated in this project using ITO substrate.

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