UNIT-IV

Chemistry of Materials for Memory and Display Systems 08 hours

Memory Devices: Introduction, concepts of electronic memory. Classification of electronic
memory materials -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.

Display Systems
Display Systems are used to share information in a digital format. A display consists
of three primary components: display assembly, controller, and backlight. The display
systems are made with different types of materials such as, cathode ray tubes (CRT),
Liquid Crystal Display (LCDs), Light Emitting Diodes (LEDs) etc.

Liquid Crystals
Liquid crystals (LC) are a phase of matter that have properties between those of a
conventional liquid, and those of a solid crystal.
A large number of organic molecules with long chain such as cholesteryl
acetate (CH3COOC27H45), cholesteryl benzoate (C6H5COOC27H45), etc show LC
behavior. A liquid crystal (LC) may flow like an ordinary liquid, but have the
molecules in the liquid arranged and /or oriented in a crystal-like way or they show
anisotropy like crystalline solids.
Example:

Both small molecules and polymers may exist in the liquid crystalline state, but
generally special spatial structures like rigid rod like or disc like molecules are
required. Mesogens are rigid rod like or disc like molecules which are components of
liquid crystalline materials.

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The liquid crystals have molecules in constant motion which orient in a preferred angle
called “director”.
Liquid substances are more or less entirely disordered and crystalline materials are
ordered in all three dimensions, the LCs lie in-between in properties. Liquid crystals
are ordered in one or two dimensions only. Liquid crystals all exhibit some degree of
fluidity.
Crystalline materials demonstrate long range periodic order in three dimensions. By
definition, an isotropic liquid has no orientational order.
Characterizing Liquid Crystals: The following parameters describe the liquid
crystalline structure:
[1] Orientational Order
[2] Positional Order.
Each of these parameters describes the extent to which the liquid crystal sample is
ordered.
Orientational order: Measure of the tendency of the molecules to align along the
director on a longrange basis.
Positional order: The extent to which the position of an average molecule or group of
molecules shows translational symmetry. Most liquid crystal compounds exhibit
where more than one phase.
Classsification of liquid crystals:
1. THERMOTROPIC LIQUID CRYSTALS: Liquid crystals are said to be
thermotropic if the liquid crystalline properties depend on temperature. They are
further classified into:
Nematic liquid crystals

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It is most common phases in which the molecules have no positional order, but they
have long-range orientational order. In Greek ‘nematic’ means thread hence, thread-
like structure of nematic crystals.
Nematics have fluidity similar to that of ordinary (isotropic) liquids but they can be
easily aligned by an external magnetic or electric field. An aligned nematic has the
optical properties of a uniaxial crystal and this makes them extremely useful in liquid
crystal displays (LCD).

Smectic liquid crystals

In the case of Smectic type LC, the molecules have both positional order and
orientational order. The smectic phases, which are found at lower temperatures than
the nematic, form well-defined layers can slide over one another like soap.
Based on the orientation of the director there are three types of smectic phases. If the
director is perpendicular to the planes it is called smectic A, if the director makes an
angle other than 90˚ is called smectic C and if the director is perpendicular to the
smectic plane with the molecules themselves into a network of hexagons within the
layer is called as smectic B.

Cholestric liquid crystals

The cholestric phase can be defined as a special type of nematic LC in which the thin
layers of parallel mesogens have their longitudinal axes rotated in adjacent layers at
certain angle.

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The molecules in cholesteric liquid crystals are in a twisted and chiral arrangement.

2. LYOTROPIC LIQUID CRYSTALS

Some compounds transform to a liquid crystal phase when mixed with a solvent. They
have both polar lyophilic and non polar lyophobic end. They are amphiphilic
compounds. Such amphiphilic molecules form oredered strucutres in both polar and
non polar solvents. They are usually obtained by mixing the compound in a solvent
and increasing the concentration of compound till liquid crystal phase is observed.
Such liquid crystals are called lyoptropic liquid crystals. The formation of lyotropic
mesophase is dependent on the concetration of either the component or the solvent.
Example: soap molecules (soap – water mixture)
They can arrange them themselves in: Discontinuous cubic phase (micellar cubic
phase), Hexagonal phase (hexagonal columnar phase) (middle phase), Lamellar
phase.

Applications of Liquid Crystals:

Liquid crystal technology had a major effect in many areas of science and engineering,
as well as device technology. Liquid crystals consume very little electrical power.
Hence, they find use in many electronic devices.

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1. Liquid Crystal Displays: Used in display devices (LCDs) such as Laptops, watches,
calculators, clocks, etc.
2. Liquid Crystal Thermometers: Chiral nematic (cholesteric) liquid crystals reflect
light and the color reflected also is dependent upon temperature.
3. Optical Imaging: An application of liquid crystals that is only now being explored
is optical imaging and recording.
4 Liquid Crystals are also used in medical applications.
5. Cholesteric liquid crystals are used in thermography in the testing of radiations in
those devices which convert radiation energy into heat energy (tumor detection).

Jablonski Diagram

A Jablonski diagram is basically an energy level diagram, arranged with energy on a

vertical axis, to study the mechanism of absorption and emission of light in
molecules/atoms. The Jablonski diagram is widely used in fluorescence spectroscopy
to illustrate the excited states of a molecule and the radiative and non-radiative
transitions that can occur between them.

In the Figure, S0 represent the singlet ground state and S1 and S2 represent the
first and second singlet excited state. T1 represent the triplet states of the fluorescent
material. When light is absorbed by the material, the electrons in the S 0 state are
excited to S1 or S2. From excited state S2, the electrons will be relax to S1 state. The
process is called as internal conversion and occurs within a time span of 10 -12 seconds.
The energy corresponding to this process is lower than the absorption energy. There

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are two possible routes for the emission from the energy state S1 to ground state S0. If
the emission is from S1 to S0 directly, then this type of emission is called as
Fluorescence. On the other hand, if the emission is mediated through the triplet state
T1, then it is termed as phosphorescence. Transition from the singlet state to triplet
state is called as intersystem crossing. The typical lifetime of fluorescence is <10-8s
and that of the phosphorescence ranges from seconds to several minutes.

Fluorescence: The process of emitting energy higher than the incident radiation
is called fluorescence. Fluorescence stops almost at once when the incident radiation
stops.

Example: Bioluminescence, rubies

The ability of certain molecules to absorb the higher energy radiations (ultra
violet) and emit lower energy radians (visible) of radiations. Fluorescence stops
almost at once when the incident radiation stops.

Phosphorescence: The process of emitting energy relatively slower than it is

absorbed in the form of light is known as Phosphorescence. Phosphorescence
continues emitting light even after the removal of the incident source.

Example: glowing paints, glow signs

Electro active and photo active materials

Present day technological developments in the information oriented society are

mainly attributed to discovery of electronic, optoelectronic, and photonic devices. In
recent years, new organic materials which exhibit electro-optical properties similar or
superior to classical inorganic materials have been discovered. Accordingly, new
fields of organic electronics, organic optoelectronics and organic photonics using
organic materials have emerged.

Optoelectronics: Optoelectronics is the communication between optics and

electronics which includes the study, design and manufacture of a hardware device
that converts electrical energy into light energy through semiconductors.

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Optoelectronic devices: A hardware device that converts electrical energy into light
and light into energy through semiconductors. Optoelectronic devices are primarily
transducers i.e. they can convert one energy form to another. They can also detect light
and transform light signals to electrical signals for processing by a computer.

Devices using organic materials have the following advantages over inorganic
semiconductor-based devices

• They are light weight

•They are flexible
• They can be easily synthesized by chemical method
• Cost of production is less
• They can be used in novel thin-film flexible devices
• 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 referred to as photo and

electroactive organic materials. They are also called as organic semiconductors. When
these materials are used in devices, they exhibit optoelectronic phenomena as:

• Absorption and emission of light radiation in the wavelength region from

Ultraviolet to near infrared.
• Photo generation of charge carriers.
• Transport of charge carriers.
• Injection of charge carriers from the electrode
• Exhibit excellent nonlinear optical properties.

Organic compounds with extensive conjugation and n-electrons systems are capable
of exhibiting above mentioned set of properties. These organic materials can be
broadly classified in to three categories.

• Small molecule
• Oligomers with well-defined structure
• Polymers Small organic molecules are crystalline in nature.

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Small molecule

Few examples for this class of molecules are, the metal and metal free
phthalocyanines, porphyrins, poly-condensed aromatic hydrocarbons like
anthracenes, pentacene and fullerenes.

Oligomers with well-defined structure

P-Conjugated oligomers are new family of organic Π-electron system with well
defined structures. Whose properties and functions can be control by varying the n-
conjugation length, Few example for this class are, pentacene and oligothiophenes.

Polymers Small organic molecules are crystalline in nature.

Polymers are bad conductors of electrons. But conducting polymers with extensive
conjugation and n-electron system exhibit above mentioned electro-optical behaviour
and they are excellent functional materials example of the class of polymers which
find extensive application as organic semiconducting materials are, polyacetylene,
poly (p-phenylene vinylene), poly (99-dialkylfluorene), polythiophenes, polypyroles
and polyanilines

Quantum Dots Light Emitting Diodes (QLEDS)

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. Compared with traditional LED display, QLED display
has advantages in flexible and robust application

Construction and working of QLEDs

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 A classical QD-LED is composed of three layers: one inner layer of QDs as an
emissive layer, one outer layer that transports electrons, and one outer layer that
transport holes. After applying an electric field on the outside layers, electrons and
holes shift in the layer of QD, where they are captured by QD and recombine, and
emitting photons.

A great effect of increased recombination efficiency is obtained by constructing an

emissive layer in a single layer of QDs, so that the electrons and holes may be moved
directly from the surfaces of electron-transport layer and hole-transport layer.

Applications of QLEDs
1. Quantum dot-LEDs are used in phototherapy
2. Quantum dot-LEDs are used display and lighting systems
3. Quantum dot-based light-emitting diodes for near-field scanning optical

microscopy
4. As lighting systems in digital cameras.

Organic Light Emitting Diodes (OLED)

OLED stands for Organic Light Emitting Diode, or Organic LED. It is a display
technology consisting of OLED panels that emit their own light when an electric
current is passed through them. As a result, OLEDs are super-light, have a true
contrast ratio, wide color range, deep color saturation and wide viewing angle.

Organic light emitting diode (OLED) has drawn tremendous attention in

optoelectronic industry over the last few years. Their properties such as low cost, light
weight, flexibility, and transparency have raised enormous interest for their potential
applications in displays and lightings.

STRUCTURE OF OLEDS

An OLED is a solid-state device consisting of a thin, carbon-based semiconductor

layer that emits light when electricity is applied by adjacent electrodes. In order for
light to escape from the device, at least one of the electrodes must be transparent. The
intensity of the light emitted is controlled by the amount of electric current applied by

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the electrodes, and the light's colour is determined by the type of emissive material
used. To create white light, most devices use red, green, and blue emitters that can be
arranged in several configurations.

Construction and working of OLED

1. To make an OLED light up, we simply attach a voltage (potential difference)

across the anode and cathode.
2. As the electricity starts to flow, the cathode receives electrons from the power
source and the anode loses them (or it "receives holes," if you prefer to look at
it that way).
3. Now we have a situation where the added electrons are making the emissive
layer negatively charged (similar to the n-type layer in a junction diode), while
the conductive layer is becoming positively charged (similar to p-type
material).
4. Positive holes are much more mobile than negative electrons so they jump
across the boundary from the conductive layer to the emissive layer. When a
hole (a lack of electron) meets an electron, the two things cancel out and release
a brief burst of energy in the form of a particle of light—a photon, in other
words. This process is called recombination, and because it's happening many
times a second the OLED produces continuous light for as long as the current
keeps flowing.

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Applications of OLED

1. OLEDS are widely used in display systems such as TV, Computer screens.
2. Smart phones and tablet displays.
3. Used to make super-thin pages for electronic books and magazines.

QLED vs. OLED

• OLED is a fundamentally different technology from LCD, the major type of
TV.

• QLED is a variation of LED LCD, adding a quantum dot film to the LCD
"sandwich."

• OLED is "emissive," meaning the pixels emit their own light.

• QLED, like LCD, is "transmissive" in its current form and relies on an LED
backlight.
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. Aside from the mobile ions, their structure is
very similar to that of an organic light emitting diode (OLED).
Example: Pd(II) hydrazine complexes, phenanthrene-imidazole based ionic
molecules.

Memory Devices

A memory is just like a human brain. It is used to store data and instruction.
Computer memory is the storage space in computer where data is to be processed and
instructions required for processing are stored.

The memory is divided into large number of small parts. Each part is called a cell.
Each location or cell has a unique address which varies from zero to memory size
minus one.

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Concepts of electronic memory:
➢ The basic goal of a memory device is to provide a means for storing and
accessing binary digital data sequences of “1’s” and “0’s”, as one of the core
functions (primary storage) of modern computers.

➢ 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 (CPU, a processor).

➢ In conventional silicon-based electronic memory, data are 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 memory devices:

According to the device structure, electronic memory devices can be divided

into four primary categories: transistor-type, capacitor-type, resistor-type and charge
transfer type.

1. Transistor Type Electronic Memory

In order to store data in memory devices, it must have minimum 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 (C). In this electronic circuit, “0” and “1” corresponds to the
discharge and charged states of the C, respectively.

In comparison to the semiconducting memory devices, an organic

resistor memory device stores data in a completely different fashion. While the current
memory devices store data based on the presence of charge, an organic memory
resistor memory device stores data based on two conductivity states. The low
conductivity state and high conductivity state are assigned the “0” and “1” or “ON”
and “OFF” respectively. Therefore, in this organic resistor memory device, the organic
material itself is the memory element. But a semiconducting memory device generally

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consists of a minute and complicated electronic circuit. Therefore, organic transistor
memory device structure can be simplified and the device can be fabricated in simple
steps.

2. Capacitor Type Electronic Memory

Organic and polymeric ferroelectric materials can be used in capacitor

type electronic memory device. Capacitors have two parallel plate electrodes and
charges are stored in these electrodes under an applied electric field. Bistable states of
capacitors are based on the amount of charge stored in the cell. Data can be stored

in these devices based on different charge stored in the cell. Charges stored in the cell
maintain electric polarization that can be switched between two stable by an external
electric field.

3. Resistor Type Electronic Memory

This type of memory device used switchable resistive materials to store data. It is
based on the charge of the electrical resistivity of materials in response to an applied
voltage (electric field). Electrical bistabilty arises in these materials due to different
electrical resistivity which are assigned ON and OFF states.

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 4. Charge transfer Type Electronic Memory

This type of electronic devices is based on the charge transfer effect of charge
transfer complex. A charge transfer (CT) complex consists of two parts, one electron
donor and other an electron acceptor. It is also called as donor –acceptor (D-A)
complex. The conductivity of a CT complex is dependent on the ionic binding between
the D-A components. In CT complex partial transfer of charges occurs from donor part
to the acceptor part. This results in difference in conductivity. CT complexes exhibit
bistable states due to difference in conductivity. This behaviour is used to design
molecular electronic devices. Many organic CT systems, including organometallic
complexes, carbon allotropes (fullerene, carbon nanotubes and graphene) based
polymer complexes, gold nanoparticle- polymer complexes and single polymers with
intra-molecular D-A structures are used for memory applications.

TYPES OF ORGANIC MEMORY MATERIALS

There are three classes of materials which can exhibit bistable states and are used in
organic memory devices. They are,

1. Organic molecules
2. Polymeric materials
3. Organic-Inorganic hybrid materials

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 1. Organic molecules
There are different categories of organic molecules which exhibit bistable or
multistable states when external field is apply. When a threshold voltage is
applied they undergo a transition from ON to OFF state or from OFF to ON
state. All these materials can be used in organic electronic memory devices. Few
of them are mentioned here,

Examples:

a. Pentacene and Perfluropentacene both have a similar structure and crystal packing,
but former behaves p-type semiconductor and latter behaves as an n-type
semiconductor. Therefore these molecules together exhibit charge-transfer process
that are useful for memory applications.

[Note: When all the hydrogen atoms of Pentacene are replaced by fluorine atoms the
resulting molecule is Perfluropentacene].

Pentacene Perfluropentacene

b. Zinc(II)phthalocyanine complex. In this zinc metal is acceptor and organic molecule

phthalocyanine is the donor.

2. Polymeric materials

Polymer memory refers to memory technologies based on the application of

organic polymers. Some of these technologies use variations in the resistance of
carrying polymers under reading/write command. Different architectures are based
on ferroelectric polymers. The characteristics of polymer memory are low-cost and
high-performance and have the potential for 3D stacking and mechanical adaptability.
Polymer memory is the best technology among others. It is mainly because of their
expansion ability in three-dimensional spaces.

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 Example:

➢ A polymer known as (PEDOT) is a vital plastic was used to store the digital
data as a gigabyte and be adequately modest to rival CDs and DVDs.
➢ Shape memory polymers (Ex: polyvinylchloride, polyurethanes) can react to
temperature, light, pH and moisture, there are several exciting possibilities for
these elements in fabrics. These include relaxation, aesthetics; wound
monitoring, security against environmental conditions, quick controlled drug
relief, and more.
3. 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).
A. Organic–Carbon allotrope hybrid materials

Polymers containing electron donors such as thiophene, fluorine, carbazole and

aniline derivatives can be combined with fullerenes to obtain a charge transfer hybrid
materials with donor-acceptor ability and electrical bistable states. Fullerenes exhibit
high electron-withdrawing ability and can capture up to six electrons. They are used
in warm memory effect devices.

B. Organic–Inorganic Nanocomposites

These are hybrid electronic memory devices in which organic polymer with
appropriate functional group is clubbed with metal nanoparticles, quantum dots and
metal oxide nanoparticles. An example is a composite of 8-hydroxyquinoline
containing polymer with gold nanoparticles sandwiched between two metal
electrodes. Bistable electronic transition states are observed when an electric field is
applied due to charge transfer between Au nanoparticles and 8-hydroxyquinoline.

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