UNIT-4

Chemistry of Materials for Memory and Display Systems

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.

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.
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 1. Transistor Type Electronic Memory

In order to store data in a 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
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. Capacitor have two parallel plate electrodes and charges are
stored in these electrodes under an applied electric field. Bistable states of capacitors is
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.

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 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.

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 consist 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.

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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
1. Organic molecules
There are different category of organic molecules which exhibit bistable or
multistable states when external field is applies. 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].

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 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.

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).

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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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 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) that exhibit a phase of matter that has 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
a 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.
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. Here define a new term
mesogen, is rigid rod like or disc like molecules which are components of liquid crystalline
materials.

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
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shows translational symmetry. Most liquid crystal compounds exhibit where more than one
phase.
Structural requirement for a liquid crystal
 Molecules must be elongated and must have rigid central part.
 Molecules must have functional groups that exert a force of attraction and holds the
molecule parallel to each other (imparts orientational order).
 Molecules must have flexible ends which twists and wriggles (imparts positional order).
 Molecules must preferably have aromatic rings and conjugated double bonds imparting
rigidity.

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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 S 2, 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 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 T 1, 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: It is a type of photoluminescence and it is the ability of certain molecules

to re-emit the absorbed radiations immediately. Fluorescence stops emitting light after
the removal of the incident source. Example: Bioluminescence, rubies and gem stones
Phosphorescence: It is a type of photoluminescence and it is the ability of certain
molecules to re-emit absorbed radiations slowly (delay in re-emission). Phosphorescence
continues emitting light even after the removal of the incident source.

Example: glowing paints, glow signs