Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Dr. N. Suresha.
M.Sc., Ph.D., M.Phil., B.Ed.
HOD
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Department of Chemistry
Bangalore Institute of Technology, B`lore
 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Module-II
Materials for Memory and Display Systems
Syllabus
[Memory Devices: Introduction, Basic concepts of electronic memory, History of organic/polymer
electronic memory devices, Classification of electronic memory devices, types of organic memory devices
(organic molecules, polymeric materials, organic- Inorganic hybrid materials).

Display Systems: Photo-active and electro-active materials, Nanomaterials and organic materials used
in optoelectronic devices. Liquid crystals (LC’s) - Introduction, classification, properties and application in
Liquid Crystal Displays (LCD’s). Properties and application of Organic Light Emitting Diodes (OLED’s)
and Quantum Light Emitting Diodes (QLED’s), Light emitting electro-chemical cells.]

Electronic Memory Devices:

An electronic memory device is a form of semiconductor storage which is fast in response and
compact in size. It is a piece of hardware used to store data. Most electronic devices such as
computers, mobile phones, tablets, etc., have a storage device that stores data and/or programs.

In order to achieve a greater density of data storage and faster access to information, more
components are deliberately packed onto a single chip. To improve the performance of electronic
gadget, capacity of data storage device needs to be improved. The feature size of memory device
has decreased from 130 nm in the year 2000 to 32 nm at present. Reduction in the size of memory
devices below certain level increases power consumption and leads to heat generation. Silicon-
based memory technologies cannot satisfy the requirements for information storage due their power
consumption, unwanted heat generation and less stability below 22 nm. Organic and polymer
electronic memory devices have appeared in new data storage technologies as they possess good
processability, low-power operation, more stability, no heat generation, miniaturized dimensions
and large capacity for data storage.

The advantages of organic and polymer electronic memory devices include;

i. They can be processed easily and their production cost is low.

ii. Their dimension can be miniaturized.
iii. They consume less power.
iv. They can be staked in 3D and store large amount of data.

Basic Concepts of Electronic Memory: Memory is needed in all electronic devices like
computers, laptops, mobiles, etc. Without memory, a computer is nothing but a simple device with
no brain. The computer memory is a temporary storage area. It holds the data and instructions that
the Central Processing Unit (CPU) needs

The basic concept of electronic memory devices is-

i. They must be capable to store and access binary digital data (charge states) which are
encoded as “0” and “1” that must be stable for appropriate period. The memory devices
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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

which exhibit electrical stable states (0 and 1 or ON and OFF) is known as electrical
bistability.
ii. They can be switched between two electrical states by an external field to read and write
processes.

The electronic memory can be classified as follows

Volatile memory: It loses the stored data eventually when the power is switched off. It needs to be
refreshed periodically. Ex. RAM, DRAM, SRAM, etc.
Non-volatile memory: It retains the data even in the event of power failure. Ex. ROM, WORM,
PROM, EPROM, etc.
Primary memory: It is the main internal memory of electronic gadget like computer, laptop, etc,
and can be directly accessed by the processor. It is integral part of the device and its storage
capacity is limited. There are two types of primary memory:
1. Random Access Memory(RAM)
2. Read-Only memory(ROM)

1. Random-access memory (RAM): It is a read/write memory used to store data which is directly
accessible by the CPU. It is volatile as the data stored in RAM is lost when the power is turned
off. There are two types of RAM:

i. Static RAM (SRAM): It is a type of volatile memory and needs to be periodically

refreshed. It is faster and more reliable than DRAM. It is a low density device and used as
cache memory in computer.
ii. Dynamic RAM (DRAM): It is also a type of volatile memory uses capacitors and
transistors to store the data. Due to the discharge of capacitors, they need to be periodically
refreshed otherwise data will lost. Due its high density and fast responding performance it is
being used as a main memory for most computers.

2. Read-only memory (ROM): It is the data or program stored by the manufacturer during
fabrication. It allows read-only operations and is non-volatile. Therefore the data stored on it is not
lost even when the power is switched off. Data stored on ROM cannot be altered or programmed
after fabrication. There are four types of ROM:
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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

i. WROM: It is write once read multiple memory. Once the data is written on it, it cannot be
altered. It is used store data for long period of time. Ex. CD-RS, XVD+RS.
ii. PROM - Programmable ROM: It can only be programmed once by the user. It is not
erasable.
iii. EPROM - Erasable programmable ROM: It is a memory device whose content can be
erased by exposing it to UV light. It allows users to write new data on it after erasing.
iv. EEPROM - Electrically Erasable and Programmable ROM: The content on EEPROM
can be programmed and erased electrically.

Secondary memory: It is the external memory and is not directly accessible by the processor. To
access the data from this device, it needs to be connected to the system. It is a non-volatile memory
so the data is retained even in the event of power failure. It can store large amount of data when
compared to main memory. Some common examples of secondary memory include:
i. Hard disk drives (HDD): It is a non-volatile magnetic storage device that uses mechanical
platters to store data and a moving read/write head to access data.
ii. Solid-state drive (SSD): It is a non-volatile storage device used to store data. It is better
than hard disks as it doesn’t contain any moving components. Thus they are faster, consume
less power and do not produce noise during operation.
iii. Optical disks: It is an electronic data storage medium that uses optical storage techniques
and technology to read and write data. The most commonly used forms of optical disk are:
i. CD-ROM - Compact Disc Read-Only Memory: It is an optical disk containing
audio, video or data added by a manufacturer. Computers can only read but not write
or alter the contents of a CD-ROM.
ii. CD-RW - Compact Disk Re-Writable: It is an erasable disc that can be reused. The
data on a CD-RW can be erased and recorded over again.
iv. USB flash drive: It is a data storage device that includes a flash memory and an integrated
Universal Serial Bus (USB) interface. Most USB flash drives are removable, rewritable and
smaller than optical disks. They store data depending on storage capacity like 2GB, 4GB,
8GB, 32GB, 64GB and 128 GB.
v. SD card: It is also known as Secure Digital Card. It is a small flash memory card designed
to provide high capacity memory in a small size.
vi. Magnetic tape: It is a medium for magnetic storage made up of a thin, magnetizable coating
on a long narrow strip of plastic film. It was widely used before CDs and DVDs were
introduced.
vii. Floppy disk: It is a storage medium made of a thin and flexible magnetic storage medium in
a square plastic enclosure lined with a fabric that removes dust particles from the spinning
disk.

Classification of memory devices:

Electronic memory devices can be classified into the following types based on device structure.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

1. Transistor-Type Electronic Memory

2. Capacitor-Type Electronic Memory
3. Resistor-Type Electronic Memory
4. Charge Transfer Effect type

1. Transistor-Type Electronic Memory:

A transitory type semiconducting electronic memory device contains a fine electronic circuit
including transistor and capacitor. They have become the nerve cells of the information system.

Inorganic transistors have been widely used in conventional semiconductor memory devices.
Organic transistors also have great potential for memory applications due to their integrated
structure, lightweight and flexible device design. It is composed of source, drain, gate electrodes, a
dielectric insulator layer and an active semiconductor layer. An electrical signal applied to the base
(gate) influences the semiconductor material’s ability to conduct electrical current, which flows
between the emitter (source) and collector (drain). The electrodes can be Au, Pt, Al, Cu, Cr or other
metals. Among the many possible memory devices, organic field-effect transistor (OFET) memory
is an emerging technology with the potential of light weight, low-cost, flexible charge storage
media. An OFET memory device consists of at least one polymeric material either in its dielectric
insulator layer or active semiconductor layer or both. Source and drain electrodes are fabricated on
a preformed semiconductor layer.

2. Capacitor-Type Electronic Memory:

Capacitors can store data between two parallel plate electrodes under an applied electric field.
Charge generation (polarization) between the electrodes by the applied electric field is responsible
for data storage. If the material used between the electrodes is ferroelectric in nature, a permanent
electric polarization can be maintained and longer retention time can be achieved i.e. data retains
for long period of time. Thus, memory based on ferroelectric capacitors (FeRAM) is non-volatile
memory.

Organic and polymeric ferroelectric materials can be used in DRAM and FeRAM applications.
FeRAM structures, including 1T1C (T – transistor, C – capacitor), 2T2C, 1T2C and others, have
been developed. The simplest DRAM and FeRAM cells have similar structures, both utilizing 1T1C
(Shown in fig a) as the building components. The upper electrode of the capacitor is made of Pt, Ir

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

or Ru, and the lower electrode is Pt/Ti. TiN is used to interconnect between the access transistor and
the storage node of the capacitor.

[Note: A Word Line provides the current to select which row of bits is to be read or written. The Bit
Line either reads the bit on that Word Line or it allows a current applied to the Bit Line to program
the bit]

3. Resistor-Type Electronic Memory:

Devices incorporating switchable resistive materials are generally classified as resistor-type

memory, or resistive random-access memory (RRAM). RRAM is a type of non-volatile random-
access (RAM) computer memory that works by changing the resistance across a dielectric solid-
state material, often referred to as a memristor. Unlike transistor and capacitor memory devices,
resistor-type memory does not require a specific cell structure. Resistor-type memory devices store
data in an entirely different form.

Resistor-type electronic memory has a simple structure with an organic/polymer thin film
sandwiched between two electrodes on a glass/silicon wafer/ plastic/ metal foil). The top and
bottom electrodes can be aluminum, gold, copper, p- or n-doped silicon, and ITO. The basic
configuration of resistor type memory device is shown in figure a - two-dimensional, fig b - 2D
memory array, fig c - three-dimensional (3D) data storage devices.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

4. Charge Transfer Effects type:

A charge transfer (CT) complex is defined as an electron donor–acceptor (D–A) complex,

characterized by an electronic transition to an excited state in which a partial charge transfer occurs
from the donor moiety to the acceptor moiety. The conductivity of a CT complex is dependent on
the ionic binding between the D–A components. As illustrated in below figure-

i. If the donor is characterized by small size and low ionization potential, a strongly ionic salt
forms and a complete transfer of charge (with the CT degree value, δ > 0.7) occurs from the
donor to the acceptor, making the ionic salt insulating.
ii. If the donor is very large and has a high ionization potential, a neutral molecular solid (δ <
0.4) forms, which is also insulating.
iii. If the donor has intermediate size and moderate ionization potential, it tends to form a
weakly ionic salt with the acceptor, which possess incomplete charge transfer (0.4 < δ < 0.7)
and is potentially conductive.

The formation of such a conductive CT complex is employed to design electronic memory devices.

Many organic CT systems, including organo-metallic complexes, carbon allotrope (fullerene,

carbon nanotubes and graphene)-based polymer complexes, gold nanoparticle–polymer complexes
etc., have been explored for memory applications.

History of Organic/Polymer Electronic Memory Devices:

Based on various natural phenomena, different forms of storage have been reported since the 1940s.

In 1968, Gregor reported bistable electrical switching device as an information storage device
containing Pb/polydivinylbenzene, tetracene and polystyrene polymers. But the performance was
not satisfactory for practical applications.

In 1969-70, devices with bistable electrical conductivity in thin polymer (tetracene, polystyrene,
etc.) films sandwiched between metal electrodes were discovered. They exhibit better performance,
but required high operating voltage of about 30 V.

In 1995, polymer ferroelectric random-access memory (FeRAM) devices which operate at 1 V were
fabricated as a promising memory technology.

In 2001, organic field-effect transistor (OFETs) memory devices were discovered.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

In 2003, WORM type memory devices consisting of a thin film p-i-n silicon diode and a mixture of
two conductive polymers poly (ethylene-dioxythiophene) and poly (styrene sulfonic acid) were
developed. During the same period, gold, carbon nano tube as electron acceptors and polyaniline,
poly-3-hexathiophene as electron donors were used in several polymer electronic memory devices
like WORM and DRAM.

In 2005, ultrathin organic materials with multilevel conductivity states in ITO/MEH-PPV/AI

devices consisting of MEH-PPV poly (2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene)
films were introduced.

In recent years, organic-based resistive memory materials and biodegradable memory devices have
been introducing. In order to achieve ultra-high density memory devices, organic materials with
multilevel stable states are highly desirable.

Types of organic memory devices:

With the rapid developments in the electronic industry in recent years, information technology
devices, such as personal computers, mobile phones, digital cameras and media players, have
become an essential part of our daily life. From both the technological and economic viewpoints,
the development of novel information storage materials and devices has become an emergent issue
facing the electronics industry. Due to the advantages of good scalability, flexibility, low cost, ease
of processing, 3D-stacking capability and high capacity for data storage, organic-based electronic
memory devices have been promising alternatives or supplementary devices to conventional
inorganic semiconductor-based memory technology.

1. Memory device Containing Pentacene (p-type) and Perfluoropentacene (n-type) organic

materials:

Organic thin-film transistors (OTFTs) containing organic semiconductors materials (both p- and n-
types) have attracted a great deal of interest for use in lightweight, low-cost, large-area and flexible
electronic products such as flat-panel displays, sensors, smart cards, etc. They are sandwiched
between two outer metal electrodes, anode and cathode.

Pentacene is a well-known p-type organic semiconductor in which holes are the majority carriers.
Perfluoropentacene is a well-known n-type organic semiconductor in which electrons are the
majority carriers.

Pentacene: Pentacene (C22H14) is a polycyclic aromatic hydrocarbon consisting of five linearly-

fused benzene rings. It is one of the most commonly studied conjugated organic molecules since its
hole mobility i.e., p-type semiconductor nature is similar to amorphous silicon.

When an electric field is applied, it generates excitons and exhibits high field-effect mobility. The
planar shape of pentacene facilitates easy crystal packing and the π-system extends over pentacene
molecules, enabling the intermolecular overlapping.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Perfluoropentacene: Perfluoropentacene is a well-known n-type organic semiconductor in which

electrons are the majority carriers. It can be obtained by the fluorination of pentacene. Introduction
of fluorine atoms enhances electron density on the structure and possess high electron field-effect
mobility.

The memory device constructed using p-type and an n-type semiconductor material is an ambipolar,
transistor type memory device like OTFT. To develop flexible, non-volatile ambipolar organic
memory devices, Pentacene as p-type semiconductor and perfluoropentacene as n-type
semiconductor are sandwiched between the electrodes, SiO2 insulator and Si substrate as shown
below. An ambipolar transistor can work as both an n- and p-channel transistor (duel gate). When
the gate is biased positively relative to the off region, an accumulation of layer of electrons is
formed at the perfluoropentacene/SiO2 interface and the device works as an n-channel OTFT. On
the other hand, when the gate is biased negatively relative to the off region, an accumulation layer
of holes is formed within the pentacene layer adjacent to the perfluoropentacene layer and the
device works as a p-channel OTFT.

These devices have shown good memory characteristics, a long retention time (of more than one
year) and outstanding flexibility. Flexible electronic devices have attracted great attention because
of their advantages of good portability, contact with non-flat surfaces and bio-friendly interfaces
compared to conventional silicon technology. These OTFTs containing perfluoropentacene and
pentacene exhibit a high electron and hole mobilities of 0.042 and 0.041 cm 2/V/s. Hence, they find
applications in flexible electronic products such as flat-panel displays, sensors, smart cards, light
emitting diodes (LEDs), logic gate, shift register, Flip-Flop and counter circuits.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

2. Memory device containing Triphenylamine (donor) and Phthalimide (acceptor) polymeric

materials:
Polymeric materials for use in memory devices have attracted significant scientific interest due to
their several advantages, such as low cost, solution processability, high mechanical strength and
possible development of three-dimensional stacking devices. Polymeric materials can be modified
using electron donors and acceptors with varying strengths, steric effects and electroactive pendant
groups to provide different switching behaviors.

Functional polyimides (PI) are the most attractive polymeric materials for organic electrical
memory applications due to their good solution processability, high thermal stability, flexibility and
mechanical strength. PIs exhibit various kinds of memory properties, including the volatile memory
properties (dynamic random access memory (DRAM), static random access memory (SRAM)) and
the non-volatile memory properties (FLASH), write once read many (WORM).

Triphenylamine acts as an electron donor and Phthalimide acts as an electron acceptor to form a
D–A structure in functional polyimide. The main mechanism for the memory behaviour is the
formation of an electric field-induced charge transfer (CT) complex.

F3 C CF 3
O O

N N N

O O
Triphenylamine Phthalimide n
(Donor) (Acceptor)

Molecular structure of functional PI (TPC6F-PI)

A charge transfer complex type memory device can be constructed by sandwiching a functional
polyimide containing donor and acceptor molecules in between cathode (Al) and anode (ITO)
electrodes as shown below. Triphenylamine is the donor cell and phthalimide is the acceptor cell of
TPC6F-PI structure. When electric field is applied through the electrodes, electron is easily excited
from triphenylamine to phthalimide. However, the excited state tends to relax to phthalimide by
internal conversion leading to the formation of CT complex which is beneficial to stable the ON
state. After the applied voltage is turned off, the CT complex is slowly return to the initial state.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

The Al/TPC6F-PI/ITO device exhibits excellent thermal stability and dynamic random-access
memory (DRAM) behaviour with an ON/OFF current ratio of up to 105. The switching behaviour is
likely to be dominated by triphenylamine to phthalimide field-induced charge transfer.

Display Systems:
In recent years, the display technology is more advanced. The organic materials exhibit both optical
and electrical properties similar or superior to inorganic semiconductor materials have been using in
display technology because of their easy processability, synthesis, structure modifications and low
cost. The display systems designed using organic semiconductor materials have several advantages
like light in weight, flexible, low cost, good quality image, wide viewing angle, etc., over the
systems constructed using inorganic semiconductor materials.

Photoactive materials:
Photoactive materials are the materials that have the ability to interact with the light radiations and
produce chemical transformations. Ex. elemental semiconductors like silicon, complex compounds
like CdTe or GaAs, metal oxides like TiO2 and ZnO, liquid crystals, etc, are well known
photoactive materials.

Principle: When the photoactive material is irradiated with light having energy equal or higher the
material band gap, it generates electrical current due to the jump of electrons from the valence band
to the conduction band. The photo-generated electrons and holes are exploited in a different way for
applications like acceleration of chemical reactions, degradation of pollutants in gas and liquid
phase, decomposition of contaminants, etc.

Applications:

 They can be used as fluorophores (re-emission of light) in organic light emitting diodes.
 Used in the making of solar cells.
 Used in the degradation of organic dyes like acid orange, methylene blue, phenol, etc.
 Used in the purification of air and water.

Electroactive materials:

Electroactive materials are the materials which exhibit a change in size or shape when stimulated
by an electric field. Ex. Ferroelectric polymers, liquid crystalline polymers, ionic polymer-metal
composite, etc. They possess unique properties such as high mechanical flexibility, low density,
structural simplicity and low cost. These materials change reversibly their volume, optical,
mechanical and other properties by very small alterations in the applied electric field.

Applications:

 They have been used in artificial muscles.

 They have been used display systems like, TV, computer, laptop, etc.
 They are used in switching windows, electromagnetic shutter.
 They can be used in actuator, sensors, robotics, etc.

Optoelectronic devices:
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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Optoelectronic devices are the special types of semiconductor devices that are able to convert
light energy to electrical energy or electrical energy to light energy. Solid crystalline minerals,
which are heavier than insulators but lighter than metals, are used to make these devices. Ex.
light-emitting diodes (LED), Solar cells, Photodiodes, optical fibers and laser diodes.

Properties:.

 They can be easily fabricated.

 They are cost-effective.
 They have the compact size.
 They consume less power.

Working principle: i. when the device converts light energy into electrical energy; Ex Solar
cell.

 When the light (photons) of energy greater than the band gap of the semiconductor is falls
on the solar cell, the energy of the photons gets transferred to the cell.

 Electron-hole pairs are generated near the depletion region of the p-n junction diode.

 These electrons and holes are separated from each other due to the electric field of the
depletion region and do not recombine.

 Electrons move toward the n-side and holes move toward the p-side of the
semiconductor.

 Due to this movement, an emf is observed.

 When an external load is connected to a solar cell, the flow of current can be observed in
the load.

Working principle: ii. When the device converts electrical energy into light energy; Ex
Light Emitting Diode (LED).

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

 LED consists of a heavily doped p-n junction diode and is used in forward bias.
 p-side is rich in holes and the n-side is rich in electrons.
 When current is applied in forward bias, the electrons from the n-side of the diode move
towards the p-side which has holes.
 The combination of 1 electron and 1 hole results in the release of a photon which is
emitted in form of light that we see in LED.

Applications:

1. LEDs are used in indication lights, computer components, medical devices, watches,
instrument panels, switches, fiber-optic communication, consumer electronics, household
appliances, traffic signals.

2. The solar cells are applicable in rural electrification, telecommunication systems, ocean
navigation aids, electric power generation in space and remote monitoring and control
systems.
3. Photodiodes are used in many types of circuits and different applications such as cameras,
medical instruments, safety equipments, communication devices and industrial equipments

4. Optical fibers are used in telecommunications, sensors, fiber lasers, bio-medicals and in
many other industries.

5. The laser diodes are used in fiber optic communication, optical memories, military
applications, CD players, surgical procedures and Local Area Networks.

Nanomaterials: Now days, everyone uses the term ‘nano’ for anything which is small. But in
chemistry, a nanomaterial refers to a material with at least one of its external dimension is in
nanoscale (1 – 100 nm).

A natural or manufactured material in which the size of particles is in the range of 1 – 100 nm
is called nanomaterial.

Nanomaterials are of interest because at nanoscale they show unique optical, magnetic, electrical,
and other properties. These emergent properties have the potential for great impacts in electronics,
medicine and other fields showing new applications.

Silicon Nanocrystals: Silicon nanocrystals (Si NCs) have attracted significant attention today
because of its use in optoelectronics. Tuning of energy gap for light emission from Si NCs is

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

achieved by engineering their size, surface, alloying and doping. This opened up a new door for the
development of Si NCs-based optoelectronic devices such as LEDs, non-volatile memories, photo-
detectors, solar cells, etc.

Following are the properties of Si NCs favorable for optoelectronic devices:

 They are low cost, nontoxic, practically unlimited availability and device fabrication.
 Doped Si NCs have high quantum yield of more than 60%.
 They have ability to absorb light over a wide range from ultraviolet to mid-infrared.
 They are compatible with silicon-based technology and exhibit room-temperature
photoluminescence.

Organic materials: i. Light absorbing materials: These are the materials that have the ability to
absorb light radiation such as wood, coal, organic matter, etc. Vantablack can absorb 99.9 percent
of ultraviolet (UV), visible and infrared (IR) light.

Poly (3-hexylthiophene) (P3HT): It is a poly-alkyl-thiophene based donor type semiconducting

polymer. It is used in organic electronics primarily because of its regular end-to-end arrangement of
side chain. It is hydrophobic at neutral state and has π-π conjugation in its backbone. It has a hole
mobility in the range of 10-3-10-1 cm2V-1s-1.

Following are the properties of P3HT favorable for optoelectronic devices:

 It has excellent electrical conductivity, electroluminescence and nonlinear optical properties.

 It has high environmental stability, high capacitance, low cost, high conductivity, excellent
mechanical stability, high thermal and chemical stability.
 It has an efficient inter chain p-stacking of the conjugated backbones allows for the optimum
transport of positive charge carriers (holes).
 It exhibits high field-effect mobility up to 0.012 cm2/V/s.

Applications: It is commonly used in the development of organic photovoltaics, perovskite solar

cell, organic transistor and electric sensor devices.

ii. Light emitting materials: These are the materials that have the ability to emit light when
voltage is applied. An organic light-emitting diode contains a thin-film semiconducting polymer
sandwiched between two electrodes (anode and cathode). When electrons and holes are injected
from the electrodes, the recombination of 1 electron and 1 hole results in the release of a photon
which is emitted in form of light.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Poly [9-vinylcarbazole] (PVK): It consists of linear chains of repeated molecular units (CH2-CH)n
with pendant 9H-carbazole side groups, is a well-known p-type thermoplastic π-conjugated
semiconducting polymer. It is an efficient hole transport material (HTM) and hence used as a main
basis in electronic and optical material devices like light emitting diodes. PVK can be used at
temperatures of up to 160 - 170 °C and is therefore a temperature-resistant thermoplastic polymer.
The electrical conductivity changes depending on the illumination. For this reason, PVK is
classified as a semiconductor or photoconductor. It is resistant to acids, alkalis, polar solvents and
aliphatic hydrocarbons.

Following are the properties of PVK favorable for optoelectronic devices:

 PVK film is hydrophobic, thermally stable with a relatively high glass transition temperature
(Tg = 200 °C) and can be easily deposited without any doping and post treatments.
 It has high hole mobility, suitable energy levels that match with the perovskite layer.
 It has long-term stability in air as well as good photochemical and thermal stability.
 It shows an emission spectrum that covers the entire blue region, owing to the properties of
pendent carbazole groups.
 Electrical conduction in PVK is ruled by both field assisted and temperature activated
hopping processes.

Applications: PVK is used in:

 Electrophotography ex- copiers and laser printers

 Fabrication of polymer photonic crystals.
 Organic light-emitting diodes.
 Photovoltaic devices.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Liquid Crystals:

Liquid crystal is a state of matter between highly ordered crystalline and disordered liquid states.
Their properties are between those of conventional liquids and solid crystals. That is, a liquid
crystal may flow like a liquid, but its molecules may be oriented in a crystal-like way.

In 1888, Friedrich Reinitzer, Austrian botanist, discovered the liquid crystal. He found that
cholesteryl benzoate on heating to 145.4 °C becomes a cloudy liquid, which on further heating to
178.5 °C turns into a transparent liquid. This phenomenon is reversible, i.e. on cooling, first it
becomes cloudy liquid and then solid at the same temperatures. Thus, cholesteryl benzoate has two
melting points and exists as a liquid crystal between 145.4 °C and 178.5 °C.

In crystalline state, not only do the molecules occupy specific positions but also tend to orient in a
preferred direction. Thus the molecules have both positional and orientational order.

In liquid state, the molecules neither occupy specific positions nor are oriented in any particular
direction. The molecules are free to move at random and collide with one another abruptly changing
their positions thus losing both positional and orientational order.

In liquid crystal state, the molecules are free to move but are oriented in a particular manner. Thus
the molecules have no positional order but retain some orientational order.

Liquid crystals exhibit optical anisotropy, i.e. they show different optical properties when light
incident in different directions. This makes the liquid crystals to find applications in the field of
electrical and electronics.

Classification of liquid crystals: Liquid crystals are classified as follows.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

1. Thermotropic liquid crystals: Compounds that have liquid crystal behaviour with the
variation of temperature alone are called thermotropic LCs. Ex. Cholesteryl benzoate (145.5 –
178.5 oC), p-Azoxyphenetole (137 – 167 oC), p-Azoxyanisole (116 – 135 oC), etc.

Thermotropic LCs can be further classified into four categories.

i. Nematic LCs: Nematic liquid crystals have elongated, rod-like shape and molecules are
arranged in parallel chains. They have orientational order but no positional order. In
Nematic LCs, the molecules are aligned in a single direction resulting in a non-layered
structure. Ex. p-Azoxyanisole.
ii. Cholesteric LCs: Cholesteric crystals have elongated shape and the molecules are
arranged in such a way that they form a helical structure. They are also called as twisted
nematic LCs. Ex. Cholesteryl benzoate.
iii. Smectic LCs: Smectic LCs are also have elongated, rod-like shape but the molecules are
arranged in layers. They have a small orientational order and also positional order. Ex.
Terephthalylidene-bis-4-n-butylamine.
iv. Discotic LCS: Discotic LCs have disc-like or plate-like structures. They have
orientational order but no positional order. In discotic LCs, most molecules tend to
position themselves in columns arranged in hexagonal lattice. The arrangement resembles
stacked coins. Ex. Benzene-hexa-n-alkanoate.

2. Lyotropic liquid crystal: Compounds that show liquid crystal behaviour with the variation of
concentration and temperature are called lyotropic LCs. They contain a lyophilic end and
lyophobic end, that is, they are amphiphilic in nature.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

They can be prepared by mixing a compound containing both lyophilic and lyophobic ends in a
solvent and increasing the concentration of compound till liquid crystal phase is observed. Ex.
Soap-water mixture, Phospholipid-water mixture, etc.

Opto-electric properties of liquid crystal:

Optical property: The molecules in liquid crystals are oriented in preferred direction. This is called
orientational order. Because of this preferred orientation, when a plane polarised light is passed
through the liquid crystal, the plane of polarised light rotates through certain angle (θ). The
molecule that has the ability to rotate the plane polarised light is called optically active molecule.
Nematic liquid crystals exhibit this property.

Liquid crystal is placed between two polarizers (1 & 2). Polarizer-2 is crossed (inclined) with
respect to polarizer-1 through an angle same as the angle of ration of PPL by liquid crystal. The
PPL obtained from polarizer-1 passes through the liquid crystal and gets rotated by an angle (θ) due
to the orientation of molecules in liquid crystal. The rotated PPL passes trough polarizer-2 and
emerges out. Hence, the display above polarizer-2 looks brighter.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Electrical Property: When electricity is applied trough the liquid crystal, the preferred orientation
of molecules in LC is lost and they try to orient themselves in the direction of applied field. As a
result, liquid crystal undergoes deformation.

When electric field is applied through the polarizers, the molecules in liquid crystal rearrange
themselves in the direction of applied electric field and the rotation of PPL is also get affected as
shown in below figure. The light passes from polarizer-1 cannot passes through polarizer-2. Hence,
the display above polarizer-2 looks darker.

Thus display appears brighter and darker in absence and presence of electric field respectively. This
type of optical and electrical property of a material is called optoelectronic property. Liquid crystals
exhibit this property and therefore are used in DISPLAY system.

Construction and working of LC display:

Construction: A simple numeric display as in calculators, watches, etc., consisting of seven

segments (pixels) which are filled with liquid crystal mixture is placed between bottom and top
glass plates. The electrode patterns are also drawn on glass plates to pass electricity. The distance
between top and bottom glass plats is cell thickness which is usually in the range of 4 to 8 μm. The
seven segments labelled as a, b, c, d, e, f and g are electrically interconnected and controlled
independently to display the ten digits is shown in the below figure.

Working: Case-i: When electricity is applied to only back light source by pressing the “ON”
button on calculator, light passes through polarizer-1 to give plane polarized light (PPL) which then
passes through the liquid crystal wherein, plane of the polarized light get rotates through certain
angle. Then the rotated PPL passes through polarizer-2. As a result, display appears brighter
without displaying any number (fig.-1).

Case-ii: Depending on the application of electric field to the segments a, b, c, d, e, f and g and also
to the back light source, corresponding digit can be seen on the display. For example, if electricity is

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

applied to the segments a, b, d, e and f, by pressing the button “2” on calculator, the liquid crystal
molecules in these segments align to the applied field and change the rotation angle of light and
prevent the passing of light through polarizer-2. Hence, the segments a, b, d, e and f looks darker
and digit “2” can be seen on display. Meanwhile, since the electricity is not applied to the segments
c and g, PPL gets rotate through certain angle by liquid crystal which then passes out of polarizer-2.
Hence, segments c and g looks brighter. Therefore, digit “2” can be seen on display (fig.-2).

Similarly, by applying electricity to the segments a, b, c, d, e, digit 3 can be seen on display. By

applying electricity to the segments b, c, digit 1 can be seen on display. If electricity is applied to
all the segments, number 8 will be shown.

Properties:

 Liquid crystals can flow like liquids due to the loss of positional order.
 Liquid crystals are optical anisotropic due to their orientational order.
 Liquid crystals do not emit light directly, instead, use a backlight or reflector to produce
images in colour or monochrome.
 LCDs can easily be made into different shapes using liquid crystals, have a lower response
time, infinite colour contrast and wide viewing angles, lower weight and potentially lower
power consumption.

Applications:

 LCs are used in a wide range of applications, including LCD televisions, computer
monitors, instrument panels, aircraft cockpit displays, etc.
 They are commonly used in LCD projectors and portable consumer devices such as digital
cameras, watches, calculators and mobile telephones.
 They are used in pH meters, conductometers, colorimeters, thermometers, traffic signals.
etc.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Organic light emitting diodes (OLEDs):

In recent years, the display industry has progressed rapidly. One of the most important
developments is the ability to build flexible, transparent and very thin displays for electronic
gadgets. This led the researchers to find OLEDs.

“Organic light emitting diodes (OLEDs) are monolithic devices consist of a series of organic thin
films sandwiched between two thin-film conductive electrodes that emits light under the influence
of an electrical field”.

Working of OLEDs:

 Substrate – Foundation of the OLED, can be plastic, glass or metal foil.

 Cathode - Negatively charged particles transfer from cathode to EML with the help of ETL.
 Electron Injection layer (EIL) - It receives electrons from the cathode and injects them
deeper into the device.
 Electron Transport Layer (ETL) – Supports the transport of electrons across it so that
they can reach the emissive layer.
 Anode – Positively charged particles transfer from anode to EML with the help of HTL.
 Hole Injection Layer (HIL) – It receives holes from the anode and injects them deeper into
the device.
 Hole Transport Layer (HTL) – This layer supports the transport of holes across it so that
they can reach the emissive layer.
 Emissive Layer (EML) – It converts electrical energy into light energy. It is the heart of the
device where electron and hole recombine to form excitons having high energy. These
excitons falls to lower energy by emitting light (electroluminescence).

Properties of OLEDs: OLEDs exhibits the properties of self-emission, great image quality, bright
colors, very high contrast, wide viewing angle, fast response time, simple structure and low power
consumption.

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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

Applications of OLEDs: The organic light-emitting diode (OLED) is one of the most promising
technologies for display and lighting applications compared with existing liquid crystal display
(LCD) technology.

OLEDs are used to create digital displays in devices such as television screens, computer monitors
and portable systems such as smart phones, tablets, light panels and handheld game consoles.

Quantum dot light emitting diodes (QLEDs):

QLEDs are a new form of light emitting technology based on nanoparticles and their structures are
similar to the OLED technology. In this technology, a layer of quantum dots is placed between
electron and hole-transporting layers to form a sandwiched structure. Electrons and holes are
accumulated in the quantum dot layer by an applied electric field. Then, they will recombine and
emit light. This technology is a novel innovation to help the display industry. They are recognized
as great alternatives to organic light-emitting diodes due to their enhanced performances.

“Quantum dot light emitting diodes (QLEDs) are devices consist of a nano-scale crystals
sandwiched between two thin-film conductive electrodes that emits light under the influence of an
electrical field”.

Working principle in QLEDs: The emission mechanism of QLED is similar to OLED. In QLED,
the emitter is a semiconductor nanoparticle, while in the OLED, the emitter is an organic material.

In QLED, a layer of cadmium-selenium quantum dots is sandwiched between inorganic electron-

transporting (ETL) and hole-transporting (HTL) layers. When electric field is applied, electrons are
injected from cathode and move to QDs (EML) through ETL. Holes are injected from anode and
move to QDs (EML) through HTL. Electrons and holes captured in the quantum dots are recombine
to form excitons having high energy. These excitons falls to lower energy by emitting light
(electroluminescence).
Note: In a typical QLED, ZnO nanoparticles with high electrical conductivity are used in the
electron transport layer and V2O5 nanoparticles are in the hole transport layer. Colloidal CdSe/ZnS
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 Applied Chemistry study material (CS-stream)– Module -2: Dr. N Suresha, M.Sc., Ph.D., M.Phil., B.Ed.

(quantum dots) have high quantum yield and high photo stability at room temperature, are used as
emitters.

Properties of QLEDs: They are cost-effective, more brightness, more efficient, high color purity
with low power consumption, high quantum yield, low weight, more stable and environmental
friendly.

Applications of QLEDs:

 used to create digital displays in devices such as television screens, computer monitors and
portable systems such as smart phones, tablets and light panels.
 used in phototherapy to treat the skin disorders (psoriasis, skin allergy, wound healing) and
various cancers including skin, head and neck, tongue and breast cancers.
 used in biomedical applications such as, bio-imaging and medical diagnosis.
 used in optoelectronic applications.
 used in the manufacturing of photovoltaic cells.
 used in photo detectors for detecting both infrared and visible light.

QUESTION BANK:

1. Write a short note on transistor type and capacitor type memory devices.
2. Write a short note on charge transfer type memory device.
3. Explain the type of organic memory device containing p-type and n-type semi
conducting materials.
4. Explain the type memory device containing donor type and acceptor type polymeric
materials.
5. Describe the working principle of photoactive materials. Mention any four properties
and four applications favorable for optoelectronic devices.
6. Describe the working principle of electroactive materials. Mention any four properties
and four applications favorable for optoelectronic devices.
7. What are light emitting materials? Explain any four properties and applications of poly
(9- Vinyl Carbazole) (PVK) suitable for opto-electronic devices.
8. What are light absorbing materials? Explain any four properties and applications of Poly
(3-hexylthiophene) (P3HT) suitable for opto-electronic devices.
9. What are liquid crystals? Discuss the working principle of liquid crystal display.
10. What are organic light emitting diodes? Discuss the working principle and mention its
properties and applications.
11. What are quantum dot light emitting diodes? Discuss the working principle and mention
its properties and applications.
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