MODULE 4: Nanomaterials and Display systems

Nanomaterials: Introduction, size dependent properties of nanomaterials (Surface

area, Catalytic, Conducting), preparation of nanomaterials by sol-gel and co-
precipitation method with example. Introduction, properties and applications-
nanofibers, nanophotonics, nanosensors

Display systems: Liquid crystals - Introduction, classification, properties and

application in Liquid Crystal Displays (LCD’s). Properties and application in
Organic light emitting diodes (OLED’s), Quantum Light emitting diodes (QLED’s).

Perovskite materials- Introduction, properties and applications in optoelectronic

devices

NANOMATERIALS
Introduction: Nanotechnology can be defined as the manipulation of atoms and
molecules (one billionth) scale (1-100 nm) to produce devices, structures or systems
having at least one novel or superior property. Materials having at least one
dimension in the nanoscale are called nanomaterials. Conceptualization of
nanotechnology was done by Richard Feynman in 1959. The impact of
nanotechnology is quite significant. When the bulk materials are reduced to
nanometer size, the properties exhibited by these nonmaterial’s are of tremendous
use.
For example,

1. Opaque materials become transparent (copper),

2. Insoluble substances become soluble (gold),
3. Stable materials become combustible (aluminium).

In fact, at normal scales, gold is chemically inert but at nanoscales, gold

nanoparticles can serve as potent chemical catalysts. The study of these
nanomaterials is known as nanoscience.
 Size dependent properties
1. Surface area: The material properties of nanostructures are different from the bulk
due to the high surface area over volume ratio and possible appearance of quantum
effects at the nanoscale. If a bulk material is sub divided into individual nano materials,
the total surface area greatly increased. This will make materials more chemically
reactive in some cases materials that are inert in bulk form are more reactive when
converted into nano scale and affect their properties like Catallytic activity, gas
adsorption chemical reactivity significantly.

Ex. Bulk gold is catalytically inactive. But Gold nano particles are catalytically very
active for selective redox reaction.

2. Catalytic properties: Nanomaterial-based catalysts are usually heterogeneous

catalysts broken up into metal nanoparticles in order to speed up the catalytic process.
Metal nanoparticles have a higher surface area so there is increased catalytic activity
because more catalytic reactions can occur at the same time. Nanoparticle catalysts can
also be easily separated and recycled with more retention of catalytic activity than their
bulk counterparts.

3. Conducting properties: The properties like conductivity or resistivity are come

under category of electrical properties. These properties are observed to change at
nanoscale level like optical properties. The examples of the change in electrical
properties in nanomaterials are like Conductivity of a bulk or large material does not
depend upon dimensions like diameter or area of cross section and twist in the
conducting wire etc. However it is found that in case of carbon nanotubes conductivity
changes with change in area of cross section. It is also observed that conductivity also
changes when some shear force (in simple terms twist) is given to nanotube.
Conductivity of a multiwalled carbon nanotube is different than that of single
nanotube of same dimensions. The carbon nanotubes can act as conductor or
semiconductor in behaviour but we all know that large carbon (graphite) is good
conductor of electricity.
 General methods of Synthesis

There are two approaches for the synthesis of nanomaterials and the fabrication of
nanostructures. Top down approach refers to slicing or successive cutting off a bulk
material to get nano-sized particle. Bottom-up approach refers to the build-up of a
material from the bottom: atom by atom, molecule by molecule or cluster by cluster.
Both approaches play very important role in modern industry and most likely in
nanotechnology as well. There are advantages and disadvantages to both
approaches
Preparation of Nanomaterials
1. Sol-gel process:

The sol-gel method of synthesizing nanomaterial is very popular amongst chemists

and is widely employed to prepare oxide materials.

The sol-gel process can be characterized by a series of distinct steps.

Step 1: Formation of different stable solutions of the alkoxide or solvated metal

precursor (the sol).

Step 2: Gelation resulting from the formation of an oxide- or alcohol- bridged

network (the gel) by a polycondensation or polyesterification reaction that results
in a dramatic increase in the viscosity of the solution.

MOR + H2O → MOH + ROH (hydrolysis)

MOH+ROM→M-O-M+ROH (condensation)
Step 3: Aging of the gel (Syneresis), during which the polycondensation reactions
continue until the gel transforms into a solid mass, accompanied by contraction of
the gel network and expulsion of solvent from gel pores. The aging process of gels
can exceed 7 days and is critical to the prevention of cracks in gels that have been
cast.

Step 4: Drying of the gel, when water and other volatile liquids are removed from
the gel network. This process is complicated due to fundamental changes in the
structure of the gel. The drying process has itself been broken into four distinct
steps: (i) the constant rate period, (ii) the critical point, (iii) the falling rate period,
(iv) the second falling rate period.

If isolated by thermal evaporation, the resulting monolith is termed a xerogel. If the

solvent (such as water) is extracted under supercritical or near supercritical
conditions, the product is an aerogel.

Step 5: Dehydration, during which surface- bound M-OH groups are removed,
thereby stabilizing the gel against rehydration. This is normally achieved by
calcining the monolith at temperatures up to 8000C.

Step 6: Densification and decomposition of the gels at high temperatures

(T>8000C). The pores of the gel network are collapsed, and remaining organic
species are volatilized. The typical steps that are involved in sol-gel processing are
shown in the schematic diagram below.

2. Co-Precipitation method
 In this technique, an inorganic metal such as acetate, chloride, nitrate is
dissolved in aqueous medium.

 Metal cations exist in the form of metal hydrate species such as [Al(H2O)6]3+
and [Fe(H2O)6]3+.

 When a precipitating agent such as NaOH or NH4OH is added, these species

get hydrolysed with the increase in pH, condensation of hydrolysed species
takes place.
 These concentration of the solution is is termed as supersaturation. At this
concentration only, formation of nucleation initiates. The particles get
precipitated into metal hydroxide.
 The above precipitate is filtered, washed with water and calcined at higher
temperature to remove the counter anions of the metal salt used such as acetate
or nitrate then finally grinding to get a fine powder.

Nanofibers
Nanofibers are fibers with diameters in the nanometer
range (typically, between 1 nm and 1 μm). Nanofibers
can be generated from different polymers and hence
have different physical properties and application
potentials.

Nanofibers are cylindrical structures with an outer

diameter below 1000nm and an aspect ratio (ratio of
length and width) is greater than 50.

Electrospinning method is widely used to synthesize

nano fibers.

Ex: Chitosan, polymers, nanocomposites etc.

Properties:

 High porosity
 High surface area
 High encapsulation efficiency
 High thermal and chemical stability
 Controllable morphology during synthesis

Applications:
 Used in medicinal fields like cancer diagnosis
 In textiles
 Tissue engineering
 In drug delivery systems
 In lithium ion batteries
 As materials in optical sensors, air filtration
 As electrode materials in redox flow batteries

Nanophotonics
It is a branch of optics, optical engineering, electrical engineering, and
nanotechnology. Nanophotonics is also called nano-optics which investigates the
behaviour of light on nanomater scale as well as interactions of nanometer sized
objects with light.

Ex: Photonic crystals, wave guides, nanoantennas etc.

Properties:
Shows dynamic optical properties like Absorption, transmission, reflection and light
emission and are different from bulk material
Applications:
 Used in solar cells for more light harvesting
 In sensing devices
 Luminescence applications
 In optical switching
 In media transmitting technologies
 In medical applications like controlled release of anticancer therapeutics.
 In optical storage devices
 Nanosensors
Nanosensors are nanoscale devices that measure physical quantities and convert these
into signals that can be detected and analyzed.

There are several ways proposed today to make nanosensors; these include top-down
lithography, bottom-up assembly, and molecular
self-assembly.

Nanosensors possess the capability to measure to

the point of single molecule level.

These are chemical or mechanical sensors that can

be used to detect the presence of chemical species
or nanoparticles or monitor physical parameters
such as temperature on the nanoscale.

Ex: CNT based fluorescent nanosensors

Quantum dots based nanosensors

Properties:
Nanosensors shows good

 electromagnetic,
 chemical,
 acoustic,
 thermoelectric, or optoelectronic properties.

Applications:

 Used to detect various chemicals in gases for pollution monitoring

 To monitor physical parameter such as temperature
 As accelometers in MEMS (Micro Electro Mechanical Systems) devices such as
airbag sensors
 To monitor plant signaling and metabolism to understand in plant biology
 Used in neurotransmitters in brain for understanding neurophysiology
 Display systems
LIQUID CRYSTALS
The liquid crystals are a unique state of matter between solid (crystalline) and liquid
(isotropic) phases.

Classification of liquid crystals

A. Thermotropic liquid crystals

B. Lyotropic liquid crystals

Thermotropic liquid crystals: A liquid crystal is said to be thermo tropic if molecules
orientation is dependent on the temperature.

By increasing the temperature, the increase in energy and thereby movement of constituent
molecules, will induce phase changes.

Thermotropic liquid crystals have been classified into the following types:

1. Nematic liquid crystals (thread-like liquid crystals): The molecules move either
sideways or up and down.

Since the molecules are oriented in one direction, they exhibit anisotropy and the
molecules are readily aligned in the same direction in the presence of electric and
magnetic fields.

Ex: p-azoxyphenetole

2. Smectic liquid crystals (soap-like liquid crystals): The molecules in smectic

crystals are oriented parallel to each other as in the nematic phase but in layers.
3. Cholesteric liquid crystals: This type of mesophase is formed by derivatives of
cholesterol such as cholesteryl esters.

Ex: Cholesteryl benzoate

Lyotropic liquid crystals
The orientational behaviour of lyotropic crystals is a function of concentration and
solvent.These molecules are amphiphilic – they have both hydrophilic and
hydrophobic ends in their molecules.

The hydrophilic end is attracted towards water, whereas the hydrophobic end is water
repellent and attracted towards non-polar solvents.

Properties of liquid crystals

1. They exhibit optical anisotropy.

2. The intermolecular forces are rather weak and can be perturbed by an applied
electric field.

3. Liquid Crystal can flow like a liquid, due to loss of positional order.

4. Liquid crystal is optically birefringent, due to its orientation order.

5. Liquid crystals, like all other kinds of matter, exhibits thermal expansion.

Applications of liquid crystals

Liquid crystals have a wide range of applications in various fields, including
electronics, optics, displays, sensors, and medicine.

Application in Liquid Crystal Displays (LCD’s)

1. Liquid Crystal Displays (LCDs): The liquid crystal layer in LCDs allows for the
display of images and text through the use of electrical currents that control the
orientation of the crystals.

2. Sensors: such as temperature sensing, humidity sensing, and chemical sensing.

3. Optical Devices: used in variable optical attenuators, phase shifters, and tunable
filters, optical communication systems, spectroscopy, and imaging.

4. Medicine: used in drug delivery systems, where the drug is encapsulated in the
liquid crystal matrix and delivered to specific target cells.
Organic Light Emitting Diodes (OLED’s)
“OLEDs are thin film devices consisting of a stack of organic layers sandwiched
between two electrodes. OLEDs operate by converting electrical current into light via
an organic emitter”.

Properties of OLED
1. Thinness and flexibility: OLEDs are very thin and flexible,
which makes them suitable for use in curved or flexible displays.

2. High contrast: OLEDs have a high contrast ratio,

which means that they can produce deep blacks and bright whites, resulting
in images with vivid and rich colours.

3. Fast response time: OLEDs have a fast response time, which means that they can
switch on and off quickly, resulting in smooth and seamless motion in video content.

4. Wide viewing angle: OLEDs have a wide viewing angle, which means that the
image quality is maintained even when viewed from different angles.

5. Energy efficiency: OLEDs are energy efficient, as they do not require a backlight
like traditional LCD displays, resulting in lower power consumption.

6. Self-emissive: OLEDs are self-emissive, which means that they do not require a
separate light source, resulting in a thinner display.

7. Long lifespan: OLEDs have a long lifespan, as they do not contain a backlight that
can degrade over time, resulting in a longer-lasting display.

Applications of OLED
1. Televisions and displays: OLED displays are used in televisions, monitors,
smartphones, and other electronic devices.

2. Lighting: OLEDs can also be used as a source of lighting in various

applications, including automotive lighting, street lighting, and architectural
lighting.

3. Wearable devices: The thin and flexible nature of OLEDs makes them suitable
for use in wearable devices, such as smart watches and fitness trackers.

4. Automotive: OLEDs can be used in automotive applications, such as

dashboard displays, interior lighting, and taillights.

5. Medical: In medical applications, such as in surgical lighting and medical

imaging, that can help improve medical procedures and diagnosis.
 Quantum Light Emitting Diodes (QLED’s)
Quantum dot light emitting diodes are a form of light emitting technology and consist
of nano-scale crystals that can provide an alternative for applications such as display
technology”.
Properties of QLED

 Accurate and vibrant colours: QLEDs are capable of producing highly accurate
and vibrant colours due to their use of quantum dots, which emit light of a
specific colour when they are excited by a light source or an electrical current.

 Energy-efficient: QLEDs are more energy-efficient than traditional LCD

displays because they do not require as much backlighting.

 High contrast: QLED displays have high contrast ratios, which means that the
difference between the darkest and brightest areas of the display is greater,
resulting in more detailed and lifelike images.

 Long lifespan: QLEDs have a longer lifespan than traditional LCD displays
because they do not suffer from the same issues of backlight burnout or color
fading over time.

 Fast response times: QLED displays have fast response times, which means
that they can display fast-moving images without motion blur or ghosting.

 Flexibility: QLEDs can be made on flexible substrates, which allows for the
creation of flexible displays that can be bent or curved.
Applications of QLED

 Televisions and displays: QLED displays are commonly used in televisions,

monitors, smartphones, and other electronic devices.

 Lighting: Including automotive lighting, street lighting, and architectural

lighting.

 Medical imaging: In medical imaging applications, such as in MRI machines,

to produce high-resolution and accurate images.

 Virtual and augmented reality: QLED displays are suitable for use in virtual
and augmented reality applications due to their ability to produce vibrant and
accurate colours, which can enhance the immersive experience.

 Advertising displays: Such as digital billboards and signage, to produce high-

quality and eye-catching visuals.
Perovskite materials
The name perovskite represented any compound
that has ABX3 formula where an octahedron of C
ions surrounded the B ion and the most abundant
Perovskite ones are MgSiO3 and FeSiO3.

Perovskite family includes several types of oxides

like transition metal oxides with the formula
ABO3. A perovskite is a material that has the same
crystal structure as the mineral calcium titanium
oxide (CaTiO3), the first-discovered perovskite
crystal.

Ti⁴⁺ is bonded to six O²⁻ atoms to form corner-

sharing TiO₆ octahedra.

Properties of Perovskite materials

Perovskite materials shows outstanding optical and electrical properties which
include

 High absorption coefficient

 High carrier mobility
 Long carrier lifetime
 Long carrier diffusion length, and
 High defect tolerance

Applications of Perovskite materials

 Photochromic devices
 Electro chromic devices
 Image storage materials
 Solar cells
 LEDs, and lasers
 Scintillation and Solar concentrators
 Photocatalysts