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Unit-4
Unit-4

Chemistry of materials for memory and display systems 08 hours.

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

electronic memory devices -organic/polymer electronic memory devices (organic
molecules, polymeric materials, organic-inorganic hybrid materials).
Display Systems: Liquid crystals (LC’s) - Introduction, classification, properties and
application in Liquid Crystal Displays (LCD’s). Jablonski Diagram. Photoactive and
electroactive materials, Light emitting electrochemical cells. Nanomaterials(QLED’s)
and organic materials (OLED’s) used in optoelectronic devices.

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Memory Devices
Introduction
Definition - A memory device is a piece of hardware used to store data. Most electronic
devices such as computers, mobile phones, tablets, etc all have a storage device that stores
data.

There are two basic types of memory:

i. Primary/main memory – Ex - Random Access Memory(RAM) & Read-Only
memory(ROM)
ii. External/secondary memory - Ex - CD-ROM, USB Flash Drive
A microchip also called a chip, a computer chip, an integrated circuit is a set of electronic
circuits on a small flat piece of silicon.
On the Silicon microchip wafer, miniature electrical switches are created of interconnected
shapes which can turn a current on or off called “transistors”. In order to achieve greater
density of data storage and faster access to information, more components are deliberately
packed onto a single Silicon microchip and hence the size of these transistors have decreased
enormously to 32 nm at present. Reduction in size of transistor below certain level increases
power consumption and results in unwanted heat generation. Therefore, the currently used
silicon-based semiconductor memory devices cannot fulfil the requirements of information
storage of the near future.

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Alternative memory device materials are

 Ferroelectric random access memory (FeRAM),

 Magneto resistive random access memory (MRAM),
 Phase change memory (PCM)
 Organic/polymer memory devices

BASIC CONCEPTS OF ELECTRONIC MEMORY

An electronic memory device is a form of semiconductor storage which is fast in response

and compact in size, and can be read and written when coupled with a central processing unit.

For a material to show memory effect, the main essential requirements are:

1)The individual memory cells, must possess at least two stable states.
2) These states must be stable for a period appropriate for the data storage.
3) The two states must be switched by an external stimulus. This is called as the writing
process.
4) The states must be distinguished by applying a further external signal. This called as the
reading process.

Example – 1- Silicon based electronic memory devices - In these devices data stored is
proportionate to the charge stored in the memory cells. Memory cells exhibit two stable
charged states which are coded as “0” and “1”.
Example – 2- New organic/polymeric devices - Exhibit two electrically stable states known
as electrical bistability (ON and OFF state state) when an external electric field is applied. In
these devices, information is stored and retrieved by encoding these two states. Therefore,
these chemical materials store information in the form of changed properties under applied
electric field.

CLASSIFICATION OF ELECTRONIC MEMORY MATERIALS

There are three classes of materials which exhibit bistable states and hence used in memory
devices. They are:
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1) Organic molecules,
2) Polymeric materials,
3) Organic- inorganic hybrid materials.

1) Organic molecules
(a) Acene derivatives: Acenes are polycyclic aromatic compounds consisting of linearly
fused benzene rings possessing high charge carrier mobility.
Examples - Pentacene, perfluoropentacene, naphthalene, anthracene.

(b) Charge transfer complexes: These molecules have two parts, electron donor and
electron acceptor. Donor is an organic molecule and Acceptor can be either metal or organic
molecule. 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 device.
Example – 1 - Copper and 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex (Cu- TCNQ)
Example – 2 - Zinc(II) phthalocyanine (CuPc) complex. In this zinc metal is acceptor and
organic molecule Pc is the donor
(c) Triple-layer structure sandwiched between two outer metal electrodes.
These molecules show two bistable conductivity states on applying voltage and is non-
volatile and rewritable, with higher ON/OFF ratio and more than one million write-read-erase
cycles.
Example: 2-amino-4,5-imidazoledicarbonitrile (AIDCN)/AI/AIDCN trilayer structure
interposed between an anode and a cathode.

2)Polymeric molecules
(a) Polyimides (PIs) : Most commonly used polymeric materials for organic electrical
memory applications having high thermal stability and mechanical strength and can
be easily processed in solution. They exhibit two stable charged states under applied
electric field due to Donor-Acceptor structure.

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Ex - Phthalimide acts as the electron acceptor & triphenylamine acts as an electron

donor

(b) Conjugated Polymers

Conjugated polymers are rich in pi electrons and they can be made to show charge states
by incorporating electron acceptor groups in their back bone. This induced charge
transfers channel and determines the volatility of the memory device.
Ex – poly (3-phenoxymethylthiophene used in D- RAM
Ex – poly (ethylene-2,6-naphthalate) in flash devices

(c) Polymers with fullerenes or graphene:

Carbon nanomaterials such as fullerenes, graphene and their derivatives have
good optoelectronic properties. Polymer with covalently attached fullerene, in
which the carbazole group of polymer serves as the electron donor and C60 serves
as the electron acceptor, has been synthesized.
Ex – ITO/Polymer-C60/Al device exhibited non-volatile rewritable memory
behaviour.

(d) Polymers Containing Metal Complexes

Transition-metal complexes exhibit reversible redox properties and hence when
introduced into polymer backbones, can improve the stability of conductive states.
Ex – Ferrocene (Fe) is the commonly used metal complex exhibiting non-volatile
memory when introduced in to polymer.

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3) Organic- inorganic hybrid materials.

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.
(a) Organic-Carbon Allotrope Hybrid Materials
Polymers containing electron donors, such as thiophene, fluorene, carbazole and
aniline derivatives can be combined with Fullerenes to obtain a charge transfer
hybrid material with donor-acceptor ability and electrical bistable states.
Ex – Fullerenes exhibiting high electron-withdrawing ability, and capturing six
electrons. They are used in WORM memory effect devices.

(b) Organic-Inorganic Nanocomposites

These are the hybrid electronic memory devices in which organic polmer with
appropriate functional group is clubbed with metal nanoparticles, quantum dots and
metal oxide nanoparticles.
Ex – 8-hydroxyquinoline containing polymer with gold nanoparticle sandwiched
between two metal electrodes. Bistable electronic transition states are observed
when an electric field is applied due to charge transfer between the Au
nanoparticles and 8-hydroxy- quinoline.

Display Systems
Liquid crystals
Introduction to Liquid Crystals

Matter can be classified as solids, liquid and gases. In solids, molecules are closely
packed in a regular fixed arrangement and hence have both positional and
orientational order. They are anisotropic.
Liquids on the other hand, lack intermolecular forces and hence the molecules or
atoms in them move randomly. They are isotropic in nature.
A distinct ordered liquid state of matter where the molecules have orientational
order but only have partial positional order are termed as “Liquid Crystals”. Hence
the extent of molecular ordering in this state is between highly ordered crystalline

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state (anisotropic), and completely disordered (isotropic) liquid state and is often
referred to as “mesogenic phase”.

The molecules in mesogenic phase though are in constant motion, orient in a

preferred direction and said to have “orientational order” which can be referred by a
“director” or vector denoted by Λn. However, they lack positional order.
NOTE: Isotropic—Equal physical properties along all axes. Ex– Glass, metals, ice
crystals.

Structural requirement for a liquid crystal

1) Molecules must be elongated and must have rigid central part.

2) Molecules must have functional groups that exert a force of attraction and holds the
molecule parallel to each other (imparts orientational order)
3) Molecules must have flexible ends which twists and wriggles (imparts positional
order)
4) Molecules must preferably have aromatic rings and conjugated double bonds
imparting rigidity

Classification of liquid crystals

1. Lyotropic liquid crystals— These liquid crystals are heterogeneous substances formed
when appropriate quantity of polymer is dissolved in a suitable solvent to obtain a
lyotropic liquid crystal. Generally, the solute is amphiphatic with a long chain

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hydrocarbon bearing a polar group at end and the solvent is water which is sandwiched
between the polymeric segments. (Ex. kevlar)
2. Thermotropic liquid crystals—These liquid crystals are homogeneous, chemically
identical and are formed by thermal processes where a suitable polymer is heated to
above its glass transition temperature to get a semi liquid melt of thermotropic liquid
crystal. (Ex. Vectran)
Thermotropic liquid crystals may be further classified as:
a) Nematic liquid crystals
b) Chiral Nematic liquid crystals
c) Smectic liquid crystals

(a) Normal Nematic liquid crystals - In this phase the molecules maintain a preferred
orientational direction but positional order is completely absent and they can
diffuse throughout the sample.
Ex - para-azoxyanisole (PAA)
(b) Cholesteric / Chiral Nematic phase - These are optically active molecules
arranged in layers with functional groups protruding out of the molecular plane. In
Cholesteric nematic phase, the orientation of each layer can be altered resulting in
a twist of one layer relative to other towards right or left about the axis
perpendicular to the preferred molecular direction. Thus the director of the liquid
crystal traces a helical path resulting in a spiral arrangement of molecules capable
of rotating the plane polarized light. The angle of twist is temperature dependent
and is referred to as “pitch” of the crystal which affects the wavelength of color
reflected.

(c) Smectic phase—Liquid crystal molecules whose side chain has 8 carbon atoms
and above exhibit this phase often characterized by well-defined planes with weak
interlayer forces. This permits the crystal to exist in various layered

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configurations differing in macroscopic textures. They are classified based on

molecular arrangement in layers.

ELECTRO-OPTIC EFFECTS IN LIQUID CRYSTALS

If a film of liquid crystal is placed between two plates and an electric field is applied across
them, the director points to a particular direction. The deformity begins at a threshold value
of the applied field and increases with increase in the strength of the field. This deformity
brings significant change in the optical characteristics of the liquid crystal.
Liquid crystal display systems make use of the property of molecular twist in liquid crystals.
Hence twisted Nematic liquid crystals are widely used. When a small voltage is applied,
liquid crystals reorient themselves as they have a permanent dipole moment. For non-polar
molecules an electric dipole is induced.
The liquid crystals are sandwiched between two polarizer film whose polarization axes are
held at 90˚ to each other. A ray of plane polarized light is irradiated on the first polarizer film.
The linearly polarized light passing through the first molecular layer of liquid crystal rotates
along the molecules and enters the second molecular layer. The twist of light is proportional
to liquid crystal molecular twist. When this occurs repeatedly, the light coming out from the
second end of polarizer film shows array of colors.
Each liquid crystal may constitute a segment of alpha numeric display system used in
watches, dash boards, biochemical meters and analytical instruments.

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Light-emitting electrochemical cell

Definition - 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) a heavily doped semiconductor
containing mobile ions.
The holes from p-type semiconductors recombine with electrons from n-type and based on
the semiconductor material used and the amount of doping, an LED will emit coloured light
at a particular spectral wavelength when forward biased
Harder materials with stronger molecular bonds generally have wider bandgaps.

Working of LED

LED Symbol

Quantum dot LEDs

Construction and working - Quantum dots are small semiconductor crystals with properties
that are vastly different from those of bulk semiconductors as a result of their nanoscale size.
A layer of quantum dots is sandwiched between electron and hole-transporting layers.
Therefore, electrons and holes are accumulated in the quantum dot layer by an applied
electric field and slowly will recombine emitting narrow spectrum of photons. Colour
emission can be adjusted by altering the particle size.

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Advantages of QLEDs over ordinary LEDs

 colour accuracy,
 higher colour saturation,
 higher contrast ratio
 higher peak brightness
 faster response time
Disadvantages of QLEDs
 limited viewing angles
 High price
 require stable polymer shell for support
 uneven degradation of pixels
 poor outdoor visibility
Applications of QLEDs in optoelectronic devices
An optoelectronic device is an electrical gadget that uses light or converting electrical energy
to light.
The major optoelectronic devices using QLEDs are -
1. Light Emitting diodes – used for display, lighting, communication, remote control, etc
2. Laser Diodes – used for data storage, telecommunication
3. Photodiodes – used for telecommunication
4. Solar cells – used for energy conversion
The use of QLEDs in optoelectronic devices leads to
a) high quantum yields,
b) high molar extinction coefficients,
c)large effective Stokes shifts,
d)broad excitation profiles,
e) narrow/symmetric emission spectra,

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f) high resistance to reactive oxygen-mediated photobleaching, and

g) high resistance to metabolic degradation.
QD-LEDs are the more reliable solutions for flat-panel TV screens, digital cameras, mobile
phones, and personal gaming equipments. QD-LEDs displays will be large, flexible and
would not deteriorate as easily as OLEDs

Organic materials (OLED’s) used in optoelectronic devices

The emission mechanism of the OLED is similar to inorganic light emitting diode, which is
usually called an "LED". Therefore, it is called as "organic light emitting diode (OLED)"
Construction and working - LED devices consists 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 exited organic material returns to its ground state, then emission occurs.

Properties
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:
1.OLED devices have solid and planar structure. Therefore, OLED display panels are very
thin, flat and lightweight.
2.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.
3.The response time of OLEDs is as fast as micro- or nanosecond order. Therefore, OLED
displays can produce sharp moving images.
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These features are extremely attractive, compared with LCD, which is currently the major
display technology. Since LCDs are non-emissive displays and utilize molecular orientation
change, the levels of contrast ratio, viewing angle, response time, etc. are limited by
fluctuation of molecular orientation and the restricted speed of molecular motion.
4.In OLEDS, the emission is from organic materials. Using variety of different organic
materials various colors can be generated. Therefore, full-color images can be created.
5.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.
6.Due to use of TFTs, high information content is possible with OLED displays. This means
that large size TV with large information content such as full- high-vision, 4K and high
resolution 500 ppi, are possible.
7.The efficiency of OLEDs is already very high and will be improved in the future.

In OLED lighting applications:

1.OLEDs have a solid and planar device structure. Therefore, the lighting units of OLEDs are
thin, planar and lightweight.
2.The planar shape avoids heat concentration. Hence, temperature elevation in OLEDs is very
low.
3.OLEDs are self-emission devices, emission of light from OLED lightings is non-
directional.
An important drawback of the OLED technology is the lack of trust and cheap patterning
methods for various colour pixels. Because OLEDs are composed of small molecule organics,
they are not consistent with the classical lithographical patterning techniques that necessitate
exposure to solvents which completely deteriorate the structures of OLED.

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