Department of Chemistry BCHECS12/22

BMS INSTITUTE OF TECHNOLOGY & MGMT.

MODULE - I
MATERIALS FOR MEMORY DEVICES

Memory devices: Introduction, Basic concepts of electronic memory. Classification of

electronic memory devices. Types of organic memory materials: Small organic molecules:
acene derivatives (Pentacene and perfluoropentacene), charge transfer complexes (Cu-
TCNQ). Polymeric materials: Functional polyimides, and polymer containing metal
complexes (Ferrocene polymer complex). Organic-inorganic hybrid materials: Au
nanoparticle with 8-hydroxy quinoline.
Self-study: Other Types of organic memory materials: naphthalene, anthracene, tetracene
and ZnPc: Zn(II) pthalocyanine complex.

MEMORY DEVICES
What is Memory?
A memory is just like a human brain. It is used to store data and instructions.
Memory devices are electronic components used to store data and instructions temporarily or
permanently.
They are essential components in modern electronic devices such as computers, smartphones, and
digital cameras.
All the data that enters the computer first get converted into the binary number system. One digit in
binary number system is called bit and combination of eight bits is called byte. Bit is the smallest
measuring unit of computer memory.
Bit = 0 or 1
1 Nibble = 4 bits
1 Byte (b) = 8 Bits
1 Kilobyte (KB) = 1024 Bits
1 Megabyte (MB) = 1024 KBytes
1 Gigabyte (GB) = 1024 MBytes
1 Terabytes (TB) = 1024 GBytes
1 Petabytes (PB) = 1024 TByte
Memory is primarily of two types
• Internal Memory − cache memory and
primary/main memory
• External Memory − magnetic disk / optical
disk etc.
Characteristics of Memory Hierarchy follow when we go from top to bottom.
• Capacity in terms of storage increases.
• Cost per bit of storage decreases.
• Frequency of access of the memory by the CPU decreases.
• Access time by the CPU increases.

Dr. A. Vijaya Bhaskar Reddy, Assistant Professor of Chemistry

 Department of Chemistry BCHECS12/22

BMS INSTITUTE OF TECHNOLOGY & MGMT.

Introduction to Memory Devices
With the rapid development of the electronics 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.
As the performance of digital gadgets advances, the complexity of data storage devices
increases correspondingly. Conventional memory devices are implemented on semiconductor
based integrated circuits such as transistors and capacitors. To achieve greater density of data
storage and faster access to data information, more components (transistors and capacitors) need to
be deliberately packed onto a single chip. As a result, the size of the transistors has decreased from
130 nm in the year 2000 to 32 nm at present. However, the silicon-based semiconductor devices
(transistors) become less stable below 22 nm, and the reliability to store and read individual bits of
information will be substantially reduced. Further, power consumption and unwanted heat
generation are also of increasing concern. Therefore, the current state-of-the-art memory
technologies are no longer capable of fulfilling the requirements for information storage of the near
future.
The new data storage technologies such as ferroelectric random-access memory (FeRAM),
magnetoresistive random access memory (MRAM), phase change memory (PCM) and
organic/polymer memory have appeared as effective alternatives for future information storage.
Particularly, the advantages of organic and polymer electronic memory systems including low
cost, good processability, molecular design through chemical synthesis, simplicity of device
structure, miniaturized dimensions, good scalability, low-power operation, and large capacity for
data storage have made them promising alternatives to conventional inorganic semiconductor-
based memory technologies.
By using organic/polymeric materials as storage media, flexible and miniaturized memory
devices with simple structure can be fabricated with ease through solution processing. Most
importantly, the electronic properties of organic/polymeric materials, and thus the device
performance, can be tailored through molecular design cum chemical synthesis.
Write a note on Basic Concepts of Electronic Memory ?
Electronic memory is a type of storage technology that uses semiconductor materials to store
digital data.
• Electronic memory devices are known for their speed and compact size, which makes them ideal
for use in electronic devices.
• Electronic memory devices can be both read from and written to, meaning that data can be stored
and retrieved as needed.
• Electronic memory devices store digital data using binary code, which is a system of representing
information using only two symbols 0 and 1.
• Memory cells are small units of semiconductor material that can store a single bit of information.
The most common types of memory cells are DRAM and SRAM cells.
• Multiple memory cells are organized into arrays, which consist of rows and columns of memory
cells. The organization of the memory array determines how data is accessed and how quickly it
can be accessed.

Dr. A. Vijaya Bhaskar Reddy, Assistant Professor of Chemistry

 Department of Chemistry BCHECS12/22

BMS INSTITUTE OF TECHNOLOGY & MGMT.

• In conventional silicon-based electronic memory, the data is stored based on the amount of
charge stored in the memory cells. Organic/polymer electronic memory stores data in an entirely
different way, for instance, based on different electrical conductivity states (ON and OFF states)
in response to an applied electric field.
• Organic/polymer electronic memory is likely to be an alternative or at least a supplementary
technology to conventional semiconductor electronic memory.
Classification of Electronic Memories

• According to the storage type of the device, electronic memory can be divided into two primary
categories: volatile & non-volatile memory. Volatile memory eventually loses the stored
information unless it is provided with a constant power supply or refreshed periodically with a
pulse. The most widely used form of primary storage today is volatile memory.
• The non-volatile memory can be further divided into sub-categories, as ROM and hybrid
memory. ROM is factory programmable only; data is physically encoded in the circuit and cannot
be programmed after fabrication. Hybrid memory allows data to be read and re-written at any
time.
• A WORM memory device can be used to store archival standards, databases and other massive
data where information has to be reliably preserved for a long period of time. Conventional CD-
Rs, DVD±Rs devices are examples of WORM memory.
• Flash memory is another type of non-volatile electronic memory. Different from WORM
memory, its stored state can be electrically reprogrammed, and it can write, read, erase and retain
the stored state. No power is needed to maintain the information stored in flash memory.
• Further, RAM requires the stored information to be periodically read and re-written, or refreshed,
otherwise the data will be lost. The RAM can be divided into DRAM and SRAM.
• DRAM is a type of volatile random-access memory that stores each bit of data in a separate
capacitor within an integrated circuit. The stored data eventually fades unless the device is
refreshed periodically. The volatility, ultrafast data access time and structural simplicity hold
great promise for high density and fast responding performance, making DRAM memory the
main memory for most computers.
• SRAM is another type of volatile memory. The term “static” differentiates it from “dynamic”
RAM (DRAM) which must be periodically refreshed. SRAM exhibits data remanence, but it is
still volatile, and the stored data is eventually lost when the memory remains in the power-off
state. SRAM is faster and more reliable than the more common DRAM. Due to its high cost,
SRAM is often used only as a memory cache.

Dr. A. Vijaya Bhaskar Reddy, Assistant Professor of Chemistry

 Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

Below content is only for understanding

Transistor is a device constructed by placing oppositely doped semiconductor material
between two similarly doped semiconductors.
• In production, transistors are printed on a silicon wafer through a complex process
called lithography. Overall, it’s a kind of device that can both conduct and insulate.
• Without any voltage applied to the base, the transistor acts as an insulator — outputting 0.
Applying a positive voltage to the base would turn the transistor into a conductor —
outputting 1.
• The transistor can only create binary information: a 1 if current passes through, or a 0 if
current doesn't pass through. From these 1s and 0s, called bits, a computer can create any
number as long as it has enough transistors grouped together to hold all the 1s and 0s.
• For instance, the word ‘Hello’ can be stored in the form of binary codes as shown below;

What does a transistor Do ?

A transistor is really simple and really complex, which can do two different jobs. It can work
as an amplifier and a switch.
• When it works as an amplifier, it takes in a tiny electric current at one end (input) and
produces a much bigger electric current (an output) at the other. it’s a kind of current
booster.
• When it works as switch, a tiny electric current flowing through one part of a transistor can
make a bigger current flow through another part of it.
• A field-effect transistor (FET) consists of a channel of N- or P-type semiconductor material
through which current flows, with a different material (laid across a section of the channel)
controlling the conductivity of the channel. One end of the channel is known as the source,
the other end of the channel is called the drain, and the control mechanism is called the gate.
By applying a voltage to the gate, you control the flow of current from the source to the
drain.
Source: It is a terminal through which
charge carriers enter the channel.
Drain: It is a terminal through which charge
carriers leave the channel.
Gate: This terminal controls the
conductivity between source and drain
terminals.

Dr. A. Vijaya Bhaskar Reddy, Assistant Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

Explain the construction and working mechanism of various Electrical Memory

Devices.
According to the device structure, electronic memory devices can be divided into four primary
categories viz., Transistor type, capacitor type, resistor type and charge transfer type.
1. Transistor type electronic memory
In order to store data in a memory device, it must have a minimum of two distinct electronic
states. These states are assigned as “0” and “1” or “ON” and “OFF” respectively. A transistor type
semiconducting electronic memory device contains a fine electronic circuit, including a
complementary metal oxide semiconductor (CMOS) transistor and capacitor. In this electronic
circuit, “0” and “1” correspond to the ‘discharged’ and ‘charged’ states of the capacitor
respectively.
By arranging these transistors in a particular pattern, memory chips can store vast amounts of data
in the form of binary numbers. They are classified into two main categories:
• Static Random Access Memory (SRAM) uses transistors as switches and can retain data if
power is supplied to the device.
• Dynamic Random Access Memory (DRAM) on the other hand, uses a capacitor to store
charges, and the charges must be refreshed regularly to retain data.

2. Capacitor type electronic memory device

Organic and polymeric ferroelectric materials
can be used in capacitor type electronic
memory devices. Capacitors have two parallel
plate electrodes and charges are stored in these
electrodes under an applied electric field.
Bistable states of capacitor are based on the
amount of charge stored in the cell. Charges
stored in the cell maintain electric polarization
that can be switched between two stable states
by an external electric field.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

3. Resistor type electronic memory device

Memory devices containing switchable resistive materials
are classified as resistor-type memory, or resistive
random-access memory (RRAM). Resistor-type electronic
memory usually has a simple structure, having a metal-
insulator-metal structure generally referred to as MIM
structure.
The structure comprises of an insulating layer (I)
sandwiched between the two metal (M) electrodes and
supported on a substrate (glass, silicon wafer, plastic or
metal foil). Initially, the device is under high resistance
state or “OFF” and logically “0” state, when resistance
changed or under external applied field changes to low
resistance state or “ON” logical value “1”.

4. Charge transfer type electronic memory device

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 transfer of charge
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.
If the donor has intermediate size and ionization potential, it tends to form a weakly ionic salt with
the acceptor, which possesses incomplete CT (0.4 < δ < 0.7) and thus is potentially conductive.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

Explain the types of organic memory devices by taking p- type and n-type
semiconducting materials.
Types of Organic Memory Materials/Devices
There are three classes of materials which can exhibit bistable states and are used in organic
memory devices.
They are 1) Organic Molecules
2) Polymer Molecules
3) Organic – Inorganic Hybrid Materials
Under each category, different types of molecules are exhibiting memory effects as described
below;
I. Organic Molecules
There are different categories of organic molecules which show bistable or multistable states when
external field is applied. When a threshold voltage is applied, they undergo a transition from ‘OFF’
state to ‘ON’ state or vice versa. All these materials can be used in organic electronic memory
devices. Few of them are mentioned here.
i) Acene derivatives: Acenes are polycyclic aromatic compounds consist of linearly fused
benzene rings. They are the very first discovered organic memory materials because of their high
charge carrier mobility.
Examples for acenes are pentacene, perfluoropentacene, naphthalene, anthracene, tetracene etc.,
The most important member of the acene family is pentacene. It is a linearly fused aromatic
compound with five benzene rings. it can be obtained in crystal and thin film forms. both forms
exhibit a very good hole mobility and hence it behaves as a p-type semiconductor.

Structure of Pentacene
When all the hydrogen atoms of pentacene are replaced by fluorine atoms, the resulting molecule
is called perfluoropentacene. Strong electron withdrawing nature of fluorine atoms convert this
molecule into n-type semiconductor.

Structure of perfluoropentacene
Both pentacene and perfluoropentacene have similar structure and similar crystal packing but
pentacene behaves as p-type semiconductor and perfluoropentacene behaves as n-type
semiconductor. Therefore, these molecules together exhibit charge-transfer processes that are
useful for memory applications.
Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry
Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

ii) Small organic molecules containing both electron donor and acceptor in a single molecule
(D-A molecules)
They exhibit bistable conductivity states due to electron transfer from Highest Occupied Molecular
Orbital (HOMO) to Lowest Unoccupied Molecular Orbital (LUMO). They are known as Donor-
Acceptor molecules (D-A molecules)
Example: DRAM device based on NACA electron acceptor naphthalimide (NA) and electron
donor carbazole (CA) were linked by a hydrazone bond.
Also, some small organic D-A molecules proved to exhibit multilevel stable states and hence they
are used to increase device capacity by three times. This type of device is called as ternary
memory device.

Naphthalimide Carbazole

Discuss the use of Polymeric material for Organic memory device ?

II. Polymer Molecules
There are different classes of polymers which exhibit memory effect and are used in electronic
memory devices.
i) Functional polyimides (PIs)
Functional polyimides (PIs) are one of the most used polymeric materials for organic electronic
memory applications. They have high thermal stability and mechanical strength and can be easily
processed from solution. In functional PIs, phthalimide acts as the electron acceptor, and
triphenylamine acts as electron donor to form a donor-acceptor structure. They exhibit two stable
charge states under applied electric field. These states arise due to transfer of electrons from donor
to acceptor. This bistability is used to store data in memory devices.

Triphenylamine Phthalimide
Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry
Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

ii) Conjugated Polymers

Conjugated polymers are rich in pi-electrons, and they can be made to show charge states by
incorporating electron acceptor groups (ex., metals) into their backbone. This induces charge
transfer channel determines volatility of the memory device. D-A type conjugated polymers are
used to fabricate different types of memory devices such as volatile DRAM and SRAM devices,
and non-volatile WORM and flash devices.

For instance, poly pyrrole is a conductive polymer that coordinates with metal ions like iron, nickel
and cobalt to form metal-polypyrrole complexes.
Thes metal-ppy complexes are used in memory devices for resistive switching applications.

The lone pair of electrons present on nitrogen atoms of polypyrrole rings coordinate with metal
atoms like Fe, Ni and Co to form coordinate covalent bonds.
Further, when polyaniline doped with metal ions like Au, Ag and Cu, it shows enhanced C-T
properties. Hence, it is widely used in WORM type memory applications.
iii) Polymer containing metal complexes
Metal polymer complexes play a significant role in memory devices due to their tunable electronic
properties and stability. Transition metal complexes exhibit reversible redox properties. When these
are introduced into polymer backbones, they can improve the stability of conductive states.
Ferrocene (Fe) is a commonly used metal complex. which exhibits non-volatile memory when
introduced into polymer.

Ferrocene based polymer complexes have gained significant attention for memory devices due to
their redox active nature, thermal stability and tunable electronic properties.
In Ferrocene, Fe is sandwiched between two cyclopentadienyl rings and the reversible oxidation-
reduction (Fe2+/Fe3+) making it ideal for charge storage and resistive switching behaviour.
Ex., Fe-PVP used in ReRAM applications due to its ability to switch b/w high resistance to low
resistance. (poly(ferrocenyl)Silane)) used in OFETs, Fe-polythiophene used in WORM devices.

Poly(ferrocenyl)silane

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

Discuss the use of organic-inorganic hybrid materials in memory devices

Organic-Inorganic Hybrid Materials
Generally, organic-inorganic hybrid materials are composed of organic layers containing inorganic
materials. Inorganic materials used are allotropes of carbon like fullerenes, carbon nanotubes,
graphene and metal nanoparticles, semiconductor nanoparticles and inorganic quantum dots (QDs)
i. Charge transfer complexes
These molecules have two parts, one is electron donor and the second is electron acceptor.
Cu-TCNQ complex is widely studied for its potential use in non-volatile memory devices due to
its bistable resistance-switching properties. These devices exhibit two stable charge states which
arise due to transfer of electrons from donor to acceptor under the influence of external field and
this principle is used in memory devices.
• TCNQ (Tetracyanoquinodimethane) is an electron acceptor molecule that forms charge-
transfer complexes with metals like copper.

• The Cu-TCNQ complex consists of copper atoms bound to the TCNQ molecules via
coordination or charge-transfer interactions, resulting in a semiconducting or partially
conductive material.
Other examples
a) Zinc (II) pthalocyanine (ZnPc) complex. In this zinc metal is
acceptor and organic molecule Pc is donor.

Structure of Cu-TCNQ
b) CT complex with methanofullerene 6,6-phenyl C61-butyric acid methyl ester (PCBM) as the
organic electron acceptor, and tetrathiafulvalene (TTF) as the organic electron donor.
ii. Organic-Inorganic Nanocomposites
In these kinds of memory devices, organic polymers with appropriate functional group is clubbed
with metal nanoparticles, quantum dots and metal oxide nanoparticles. For example, 8-
hydroxyquinoline containing polymer with gold nanoparticle sandwiched between two metal
electrodes showed bistable electronic states when an electric field is applied due to charge transfer
between the Au nanoparticles and 8-hydroxy-quinoline.
Au nanoparticles with 8-hydroxy quinoline: Gold nanoparticles (AuNPs) functionalized with 8-
hydroxyquinoline (8-HQ) are explored for use in memory devices due to their unique electronic
properties and the ability to form resistive switching devices.
Material Structure
• 8-Hydroxyquinoline (8-HQ): A small organic molecule with strong electron-donating and -
accepting properties, often used as a ligand in coordination chemistry. Its conjugated system
facilitates electron transport.
•

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

• Au Nanoparticles (AuNPs): Act as charge storage centres or conduction bridges due to their
high electrical conductivity and ability to interact with the 8-HQ ligand.
• In these devices, AuNPs are typically embedded in an organic 8-HQ matrix or functionalized
by 8-HQ to enhance electron transfer and charge trapping.

Charge Transport Mechanisms

The primary mechanisms for resistive switching in AuNP/8-HQ memory devices include:
• Charge Trapping and Detrapping: Electrons are trapped in AuNPs, altering the device’s
conductivity.
Applications
• Resistive Random Access Memory (ReRAM): AuNP/8-HQ composites are ideal for
resistive switching memory.
• Data Storage: The charge trapping properties of AuNPs make them suitable for non-volatile
memory applications.
• Flexible Electronics: Organic components (like 8-HQ) enable fabrication on flexible
substrates.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

MATERIALS FOR DISPLAY SYSTEMS

Display Systems: Introduction to Photoactive and electro active materials,
Nanomaterials and organic materials used in optoelectronic devices. Liquid
crystals (LCs): Introduction, classification, properties and application in
Liquid Crystal Displays (LCD s) Differences between liquid crystal and
solid/liquid. Properties and application of Organic Light Emitting Diodes
(OLED s) and Quantum Light Emitting Diodes (QLED, Light emitting
electrochemical cells.
Self-Study: Properties and functions of Silicon (Si), Germanium (Ge), copper
(Cu), Aluminium and Brominated flame retardants in computers.

Define photoactive and electroactive materials and write their working principle in display
system ?
Photoactive and electro active organic materials are the semiconductors composed of π-electron
systems which are used in electronic and optoelectronic devices.
Working Principle
Photoactive and electroactive material absorb and emit light in the UV to IR region. Display
system (OLED) consisting of photoactive and electroactive material absorb light and allows an
electron to jump from HOMO of a Donor to LUMO of an Acceptor. This phenomenon generates
and transport charge carriers.
When electrons move from cathode, anode allows
movement of holes towards light emitting layer
under an applied field. Electron-hole pairs are
created at the Light-Emitting-Layer and energy is
released due to recombination. This energy is
sufficient to excite an electron from HOMO to
LUMO in the light emitting layer made of
photoactive and electroactive materials. There is a
re-emission of light while electron is returning to HOMO level. This light is extracted by a
transparent substrate placed adjacent to either of the electrode.
Photoactive Materials
• Photoactive materials are materials that interact with the light
electromagnetic field and modify their own properties.
• Generally speaking, photoactive materials interact with the light and
produce the light emission (LEDs and lasers are the most common ones)
• Photoactive materials can be used to develop light-sensitive circuits and
switches (such as with photoresistors), or more generally, to convert light
into an electrical signal (i.e., to build photodiodes). All of these materials and devices found diverse
applications in our everyday life.
• There are various photoactive semiconductors ranging from simple silicon to more complex compounds
like CdTe (cadmium telluride) or GaAs (Gallium arsenide), to metal oxides like TiO2 and ZnO.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

Electroactive Materials
• Electroactive materials exhibit electrical activity or response to
electrical stimuli.
• Electroactive polymers are widely studied electro active materials.
• Electroactive polymers (EAPs) are smart materials that can
undergo size or shape structural deformations in the presence of an
electrical field.
• One of the most common applications for EAPs is in the field of
robotics in the development of artificial muscles; hence
electroactive polymer is often referred to as an artificial muscle.
• The wide range of applications of these materials include electrodes and membranes for electrochemical
energy conversion and storage, electroceramic devices and sensors, organic diodes, magnetic and optical
devices, and photoresists.
Nanomaterials and organic materials used in optoelectronic devices
i) Organic Materials used in Optoelectronic Devices
In recent years, new organic materials that exhibit electro-optical properties superior to classical
inorganic semiconductor materials have been discovered.
Devices using organic materials have the following advantages over inorganic semiconductor-based
devices.
a) They are lightweight., flexible and can be easily synthesized by chemical methods.
b) Cost of production is less.
c) Properties can be fine-tuned by structure modification.
Hence, they are being used in organic photovoltaic devices (OPVs), organic light emitting diodes
(OLEDs) and Organic field effect transistors (OFETs).
Organic materials used in optoelectronic devices are called as organic semiconductors, when these
materials are used in devices, they exhibit opto-electronic phenomena as;
a) Absorption & emission of light radiation in the wavelength region from UV to near-IR.
b) Photogeneration of charge carriers.
c) Transport of charge carriers.
d) Injection of charge carriers from the electrode.
e) Exhibit excellent non-linear optical properties.
Organic compounds with extensive conjugation and pi-electron system are capable of exhibiting above
mentioned set of properties. Example anthracene, pentacene, fullerenes, polyacetylene, polythiophenes
and polyanilines.
Polythiophenes are conjugated polymers, environmentally and thermally
stable material. Chemical structure of P3HT - Poly (3-hexylthiophene) is a
polymer with chemical formula (C10H14S)n.
It is a polythiophene with a short alkyl group on each repeat unit. Highly
ordered (P3HT) are composed of closely packed, p–p stacked (p–p distance of
0.33 nm).
The improved electronic properties of nanostructured P3HT are listed as follows:
1. P3HT is a semiconducting polymer with high stability and exhibits conductivity due to holes
therefore considered as p-type semiconductor.
2. Poly-3-hexylthiophene (P3HT) have great capability as light-absorbing materials in organic
electronic devices.
3. P3HT has a crystalline structure and good charge-transport properties required for Optoelectronics.
4. P3HT has a direct-allowed optical transition with a fundamental energy gap of 2.14 eV.
Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry
Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

5. Fundamental bandgap of P3HT is 490 nm visible region, corresponding to π→π* transition, giving
electron-hole pair.
Applications:
1. P3HT-ITO forms a p-n junction permit the charge carriers to move in opposite direction and hence,
used in Photovoltaic devices. 2. It can be used as a positive electrode in Lithium batteries.
3. Used in the construction of Organic Solar Cells. 4. Manufacture of smart windows.
5. Used in the fabrication new types of memory devices.

ii) Nanomaterials used in Optoelectronic Devices

Any substance in which at least one dimension is less than 100 nm is called nanomaterial.
They have revolutionized optoelectronic devices due to their unique electronic, optical, and
structural properties.
The properties of nanomaterials are different from bulk materials due to:
1. Quantum Confinement effect
2. Increased surface area to volume ratio

Quantum Dots (QDs) : CdSe, CdTe, PbS, PbSe, InP, ZnS

Applications: Light-emitting diodes (LEDs), lasers, photodetectors, solar cells
Advantages: Tunable bandgap, high quantum yield, size-dependent optical properties

Carbon-Based Nanomaterials: Graphene, CNTs and Fullerenes

Perovskite Nanocrystals

Metal Nanoparticles and Nanowires: Au, Ag, Cu nanoparticles/nanowires

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

Department of Chemistry BCHECS12/22
BMS INSTITUTE OF TECHNOLOGY & MGMT.

Liquid crystals (LC’s) - Introduction, classification, properties and application

in Liquid Crystal Displays (LCD’s)
• Liquid crystals are partly ordered materials, somewhere between their solid and liquid phases
and displays the properties of both solid and liquid.
• Their molecules are often shaped like rods or plates or some other forms that encourage them to
align collectively along a certain direction.
• Liquid crystals are anisotropic, which means their properties depends on the direction in which
they are viewed.
• In a liquid crystal, molecules tend to maintain their orientation, like the molecules in a solid, but
also change positions freely, like the molecules in a liquid. This means that liquid crystals are
neither a solid nor a liquid, but rather a state in between the two.
• Liquid crystals are sensitive to various stimuli, such as temperature, electric and magnetic
fields. The sensitivity combined with the self-assembling behaviour of liquid crystals make
them extremely interesting and fascinating.
• For instance, ordinary solids melt into ordinary liquids as the temperature increases—e.g., ice
melts into liquid water. Some solids actually melt twice or more as temperature rises. Between
the crystalline solid at low temperatures and the ordinary liquid state at high temperatures lies
an intermediate state, the liquid crystal.
Characteristics/properties
• Liquid Crystals generally have several common characteristics. Among these are a rod-like
molecular structure, rigidness of the long axis, and strong dipoles and/or easily polarizable
substituents.
• The characteristic of the liquid crystalline state is the tendency of the molecules (mesogens) to
point along a common axis, called the director. This is in contrast to molecules in the liquid
phase, which have no intrinsic order. In the solid state, molecules are highly ordered and have
little translational freedom.
• The characteristic orientational order of the liquid
crystal state is between the traditional solid and
liquid phases.
• Liquid crystal phases are generally cloudy in
appearance, which means that they scatter light in
much the same way as colloids such as milk.
• Liquid crystals, like all other kinds of matter are
subject to thermal expansion. As the temperature rises, the average spacing between the aligned
molecules of liquid crystal increases.
• Hence, if a suitable liquid crystal mixture is painted onto the surface of a patient's body, it can
often reveal the sites of infection or tumors, which cause increases or reductions in local blood
flow giving rise to temperature anomalies.
• Inexpensive thermometers can be made by printing a succession of suitably formulated LC
mixtures on a paper or plastic strip which is held in contact with the surface whose temperature
is to be measured.

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 Department of Chemistry BCHES102/202
ATRIA INSTITUTE OF TECHNOLOGY
Classification
There are many classes and sub-classes of liquid crystals, but for the purposes we will divide them
into two kinds as depicted below.
Nematic: In the nematic phase, the molecules are not layered but are pointed in the same direction.
As a result, the molecules are free to rotate or slide past one another.
Smectic: In smectic phase, the molecules maintain the general order of the nematic phase but are
also aligned in layers. Several variants of the smectic phase are known, depending on the angle
formed between the molecular axes and the planes of molecules. The simplest such structure is the
so- called smectic A phase, in which the molecules can rotate about their long axes within a given
plane, but they cannot readily slide past one another.
• Smectic liquid crystals have been found to have fast electro-optical
response time. Hence, smectic phase liquid crystals along with nematic
liquid crystals are used in producing liquid crystal display (LCD) screens.
Cholesteric liquid crystals (CLCs), also known as chiral nematic liquid crystals, exhibit unique
optical and structural properties due to the presence of chirality. The molecules are aligned like in a
nematic phase, but their orientation rotates helically around a fixed axis.
They are widely studied for applications in displays, sensors, optical devices, and lasers.

Application of LCDs
The important applications of liquid crystal materials in display systems are given below,
• The liquid crystal displays (LCDs) are used in aircraft cockpit displays.
• The television is main application of LCD.
• Mostly the computer monitor is made up of LCDs.
• The LCDs are commonly used in all the digital wrist watches for displaying time.
• The LCDs are used in mobile screens.
Application of Liquid Crystals in LCDs
• LCDs offer several advantages over other display technologies previously used. They are
thinner and lighter and draw much less power than cathode ray tubes (CRTs).
• 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.
• The properties of liquid crystals make them suitable for use in displays are; their ability to
affect the path of plane polarized light and their reaction to changes of temperature.
• The liquid crystal display screen works on the principle of blocking light rather than emitting

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 Department of Chemistry BCHES102/202
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light. LCDs require a backlight as they do not emit light them.
• An important property of LCs is that they are affected by electric current. A special kind of
nematic LC, called a twisted nematic (TN), is naturally twisted, as depicted on the left. When
a current is applied to this type of LC, it will untwist a certain amount depending on the
current's voltage. LCDs use these liquid crystals, since they react predictably to electric
current, and the degree of the twist can control how light passes through the material.
How LCDs work ? (Just for understanding)
A basic LCD diagram is shown to the right.
It has a mirror (A) in back, which makes it
reflective. A piece of glass (B) with a
polarizing film is placed on the bottom side,
and a common electrode plane (C) made of
indium-tin oxide is placed on top in order to
receive electricity. A common electrode
plane covers the entire area of the LCD to
pass electrical current along. Above that is
the layer of liquid crystal substance (D).
Then comes one more piece of glass (E) with
an electrode in the shape of the rectangle on
the bottom and, on top, another polarizing
film (F), at a right angle to the first one.

To power the LCD, the electrode is hooked up to a power supply, such as a battery. When there is
no current, light entering through the front of the LCD will pass through the LCs and polarized
glass to the mirror and bounce right back out. But when the battery supplies current to the
electrodes, the liquid crystals between the common-plane electrode and the electrode shaped like a
rectangle untwist and block the light in that region from passing through. This untwisting and
subsequent blockage of light makes the LCD show the rectangle as a black area.

How will you differentiate liquid crystals from pure liquids and crystalline solids?
Liquid crystals, pure liquids, and crystalline solids differ in their molecular arrangement and
properties. Here's how you can differentiate between them:
1. Molecular Arrangement
Liquid Crystals: Liquid crystals have an intermediate molecular order between that of liquids and
crystalline solids. The molecules in liquid crystals are more ordered than those in typical liquids but
less ordered than those in crystalline solids.
Pure Liquids: In pure liquids, the molecules are randomly arranged and have no long-range order.
They have relatively high mobility and flow freely.
Crystalline Solids: Crystalline solids have a highly ordered and repeating three-dimensional
arrangement of molecules or atoms. This arrangement extends throughout the entire solid, resulting in
a well-defined crystalline structure.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

 Department of Chemistry BCHES102/202
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2. Optical Properties
Liquid Crystals: Liquid crystals exhibit unique optical properties. They can change their optical
properties in response to changes in temperature, pressure, or electric fields.
Pure Liquids: Pure liquids are optically isotropic, meaning they have the same optical properties in
all directions.
Crystalline Solids: Crystalline solids may exhibit optical anisotropy depending on their crystal
structure. Some crystals have different optical properties along different crystallographic axes.
3. Flow Properties
Liquid Crystals: Liquid crystals can flow like liquids, but their flow properties may be anisotropic,
meaning they flow differently in different directions due to their molecular alignment.
Pure Liquids: Pure liquids flow freely and have isotropic flow properties, meaning they flow
uniformly in all directions.
Crystalline Solids: Crystalline solids do not flow like liquids. While some may exhibit plastic
deformation under stress, their flow is generally limited to specific crystallographic planes or
directions.
4. Response to External Stimuli
Liquid Crystals: Liquid crystals can respond to external stimuli such as changes in temperature,
pressure, or electric fields by altering their molecular orientation and optical properties.
Pure Liquids: Pure liquids do not typically exhibit significant responses to external stimuli. They
maintain their random molecular arrangement regardless of external conditions.
Crystalline Solids: Crystalline solids may respond to external stimuli through phenomena such as
piezoelectricity, ferroelectricity, or changes in conductivity, depending on their crystal structure and
composition.

Properties and application of Organic Light Emitting Diodes (OLED’s)

• Over the last few years, organic light-emitting diodes (OLEDs) have found promising
applications in flat-panel displays, replacing cathode ray tubes (CRTs) or LED displays.
• Organic Light Emitting Diode (OLED) is a carrier injection type electroluminescent device that
uses organic materials. The emission mechanism of the OLED is similar to inorganic light
emitting diode, which is usually called an ‘LED’. Therefore, it is called ‘Organic Light
Emitting Diode’ (OLED).
• OLEDs are thin-film organic semiconductor light-emitting devices consisting of two electrodes
an anode and a cathode and organic layers are placed between two electrodes. Multiple organic
layers are used, in which each layer plays an intrinsic role. When a voltage is applied to an
OLED device through anode and cathode, charge carriers are injected from the electrodes to the
organic layers. Anode injects holes (positive charges) and cathode injects electrons (negative
charges) to the system. The holes and electrons are transported to an emission site and
recombined. Organic materials in the emission site are excited by recombination of holes and
electrons. When the excited organic material returns to its ground state, then emission occurs.
• Anode is transparent and made of indium tin oxide & cathode is reflective and made of metal.

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 Department of Chemistry BCHES102/202
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An OLED consists of:

1. Substrate. Regarded as the base of an
OLED, it is made up of a thin translucent glass.
2. Anode. It is also called as emitter. Its
function is to emit electrons when a voltage is
applied across terminals.
3. Organic layer. The layer above anode is
called organic layer. It contains conductive
polymer made of hydrogen or carbon
molecules.
4. Conductive layer. This layer is made of organic plastic molecules and helps to move holes from
the anode.
5. Emissive layer. This layer is made of organic materials that are different from those used in the
conductive layer. It helps to transport electrons from cathode.
6. Cathode. Cathode is the topmost part of OLED displays. It injects electrons when a potential
difference is applied across terminals.

Properties and Applications of OLED

OLEDs are mainly used in display and lighting applications. They exhibit several unique features
which have made them so useful for these applications.
Important features of OLEDs for display and lighting applications are given below
In Display Applications
i) OLED devices have solid and planar structure. Therefore, OLED display panels are very thin,
flat and lightweight.
ii) OLED devices have self-emission property and hence their devices have high contrast ratios
and wide viewing angles, which are very significant factors for displays.
iii) The response time of OLEDs is fast as micro or nanosecond order. Therefore, OLED display
can produce sharp moving images.
iv) These features are extremely attractive, compared with LCDs, which is currently the major
display technology.
v) The driving voltage of OLED devices is low, just a few volts. Therefore, OLEDs can be
driven by thin film transistors (TFT). Hence, the power consumption of OLED displays is very
low.
vi) Overall, the current OLED technology provides remarkable colour fidelity, high efficiency and
operation stability. OLED displays are mainly used in digital devices such as high-end television
systems, computer monitors, pocket-size systems such as Android phones, media players, digital
cameras, portable gaming consoles and mini screens.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

 Department of Chemistry BCHES102/202
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Quantum Dot Light-Emitting Diode: Properties and Applications
• Quantum dot light-emitting diode (QLED) attracted much attention for the next generation of
display due to its advantages in high color saturation, tunable color emission, and high stability.
• QLED offers many benefits for the industry in comparison to existing technologies. One of
them is that it does not require the use of rare or expensive metals (for example, with coltan to
produce mobile phones).
• In addition, its manufacturing and recycling process is much less polluting than that of screens
using inorganic semiconductors.
• In QLEDs, a film of nanocrystals is placed before LED lights and since each nanocrystal
quantum dot makes its own light, the colors produced are brighter and more accurate.
• The structure of QLED is like the fundamental design of OLED, but the difference is that the
light emits from the QDs, such as cadmium selenide (CdSe) nanocrystals.
A QLED (QD-LED) device consists of two electrodes, an anode and a cathode and QD layer
placed between two layers. When a voltage is applied to an QLED device through anode and
cathode, charge carriers are injected from the electrodes to the QD layer. Anode injects the
holes (+ve charges) and cathode injects electrons (-ve charges) to the system. The holes and
electrons are transported to an emission site and recombined. QD material in the emission
site is exhited by recombination of holes and electrons. When the exited QD returns to its
ground state emits the energy in the form of photons.

Advantages of QLEDs
QLEDs are superior to other display technologies like liquid crystal displays (LCDs),
OLEDs and plasma displays due to their unique features like;
a) High brightness
b) High efficiency with long lifetime
c) More flexibility
d) High color rendering index and
e) Low processing cost.
Applications
QLEDs are more reliable solutions for flat panel TV screens, digital cameras, mobile phones and
personal gaming equipment. QLEDs displays will be large, flexible and would not deteriorate as
easily as OLEDs.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry

 Department of Chemistry BCHES102/202
ATRIA INSTITUTE OF TECHNOLOGY
Explain any four properties and applications of Light emitting materials - Poly[9-
vinylcarbazole] (PVK)] suitable for optoelectronic devices.
Light emitting electrochemical cells
• A light-emitting electrochemical cell (LEC or LEEC) is a solid-state device that generates light
from an electric current (electroluminescence). LECs are usually composed of two metal
electrodes connected by (e.g. sandwiching) an organic semiconductor containing mobile ions.
• The structure of LECs is very similar to that of organic light-emitting diode (OLED).
• LECs have most of the advantages of OLEDs, as well as additional ones as given below;
i) The device is less dependent on the difference in work function of the electrodes.
Consequently, the electrodes can be made of the same material (e.g. gold). Similarly, the
device can still be operated at low voltages.
ii) Recently, the use of graphene, carbon nanotubes and polymer based electrodes has been
reported eliminating the need of indium tin oxide for a transparent electrode.
iii) The thickness of the active electroluminescent layer is not critical for the process, which
means they can be printed using simple printing processes

Applications
LECs are the simplest and least expensive thin film lighting
devices available to date. They consist of a single active layer.
They are used as electroluminescent inks and stickers.
The prototypes of LECs are considered to be the first LEDs.

Poly (N-vinyl carbazole) (PVK)

Poly (N-vinyl carbazole) (PVK) is a polymer and an efficient
hole transport material to prepare highly efficient and stable planar
heterojunction perovskite solar cells.
Properties of PVK
1. It is a semiconducting polymer and an electron acceptor converts ultra-violet
(UV) light into electricity.
2. PVK has a band gap of 3.4 eV, optical absorption edge stating at 350 nm capable of absorbing
Ultra-Violet light.
3. The PVK film is hydrophobic, thermally stable with a relatively high glass transition
temperature (Tg) of 200 °C
4. The PVK solution also showed good wettability, and provide uniform thin films on glass/ITO
substrates.
Applications
1. PVK is used in OLEDs for light harvesting applications.
2. Used in the fabrication of light-emitting diodes and laser printers.
3. Used in the fabrication of organic solar cells when combined with ITO on glass substrate.
4. Used in the fabrication of solar cells when combined with Perovskite materials.

Dr. A. Vijaya Bhaskar Reddy, Associate Professor of Chemistry