UNIT – 4

MATERIALS FOR MEMORY AND DISPLAY SYSTEMS

Memory devices:

Conventional memory devices are implemented on semiconductor-based integrated

circuits, such as transistors and capacitors. With the advancement of technology, there is an
increase in the demand for high performance digital gadgets. To improve the performance of
gadget, capacity of data storage device needs to be improved. In order to achieve greater density
of data storage and faster access to information, more components are deliberately packed onto a
single chip. The size of transistors has decreased from 130 nm in the year 2000 to 32 nm at
present. Silicon- based semiconductor devices become less stable below 22 nm reducing their
reliability to store and read individual bits of information. Reduction in size of transistor below
certain level increases power consumption and results in unwanted heat generation.
A Semiconductor device having the primary function of electronically storing information is
called as a memory device.

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 (CPU, a processor).

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

1) The individual memory cells, must possess at least two stable states, which are coded
as “0” and “1”.
2) These states must be stable for a period appropriate for the data storage.
3) They can be switched between two states by an external stimulus. This is called as
the writing process.
4) The states can be distinguished by applying a further external signal. This called as
the reading process.
New organic/polymeric materials exhibit two electrical stable states known as electrical
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bistability. They shift from one state (ON state) to other state (OFF 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
change in their properties under applied electric field.

CLASSIFICATION OF ELECTRONIC MEMORIES

A computer system contains several kinds of storage. Each type of storage is used for
a different purpose.

The classification of Electronic memories is given below:

Electronic memory

Non- volatile Volatile

ROM Hybrid RAM

WORM EPRO Flash EEPR DRAM SRAM

O

According to the storage type of the device, electronic memory can be divided into two
primary categories:

1. 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.
Random access memory (RAM): It is a volatile memory. RAM requires the stored
information to be periodically read and re-written, or refreshed, otherwise the data will
be lost. It is further divided in to SRAM (Static random access memory) and
DRAM (Dynamic random access memory).
2. Non-volatile memory:
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This is further divided in to:
a. Read only memory (ROM): ROM is factory programmable only; data is physically
encoded in the circuit and cannot be programmed after fabrication. ROM is further
classified in to WORM ( write-once read-many- times memory)and EPROM(Erasable
programmable read only memory).

b. Hybrid memory: Hybrid memory allows data to be read and re-written at any
time. It is further classified in to flash and EEPROM memory.

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.
Under each category, lot of different types of molecules exhibiting memory effect are
available. Few of them are described here:

I. ORGANIC MOLECULES
There are different category 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 the OFF state to the ON state, or from the ON state to the OFF state.
All these materials can be used in organic electronic memory devices. Few of them are
mentioned here.

1. Acene derivatives: Acenes are the polycyclic aromatic compounds consisting of

linearly fused benzene rings. They are the very first discovered organic memory
devices because of their high charge carrier mobility.

Ex : pentacene, perfluoropentacene, naphthalene, anthracene, tetracene, etc.,

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Pentacene :

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 form. Both forms
exhibits a very good hole mobility and hence it behaves as a p-type semiconductor.

Perfluoropentacene :

When all the hydrogen atoms of pentacene are replaced by fluorine atoms the resulting molecules
is perfluoropentacene. Strongly electron withdrawing nature of fluorine atoms converts this
molecule in to n-type semiconductor.

Pentacene and Perfluoropentacene, both have similar structure and similar crystal
packing but former behaves as p-type semiconductor and latter behaves as an n-type

Semiconductor. Therefore, these molecules together exhibit charge-transfer processes

that are useful for memory applications.
2. Charge Transfer Complexes:
These molecules have 2 parts one is electron donor and second is electron acceptor. Donor is
an organic molecule. 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.

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 Ex: TCNQ (tetracyanoquinodimethane complex)

II. POLYMER MOLECULES

There are five classes of polymers which exhibit memory effect and are used in electronic
memory devices.

1. Functional polyimides (PIs):

Functional polyimides (PIs) are one of the most commonly used polymeric
materials for organic electrical 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 an
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 device.

2. 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 transfer channel determines volatility of the memory device. D-A type
conjugated polymers are used to fabricate different types of memory device, such as
volatile DRAM and SRAM devices, and non-volatile WORM and Flash devices.

Ex: Polyacetylene

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iii. 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).

1. 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. Fullerenes exhibit
high electron-withdrawing ability, and can capture up to six electrons. They are used in
WORM memory effect devices.

2. Organic-Inorganic Nanocomposites
These are the hybrid electronic memory devicesin which organic polmer 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 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.

The advantages of organic and polymer molecules based electronic memory devices are:
a) They can be processed easily.
b) Structure of the molecule used can be design through chemical synthesis.
c) Device structure is very simple.
d) Dimension of the device can be decreased (miniaturized).
e) Cost of production is less.
f) Power consumption during operation is low.

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DISPLAY SYSTEM
LIQUID CRYSTALS
Introduction Liquid crystals (LC)
 The general classification of mater are Solids , liquids and gases
 Solids have definite orientation and positional order , Liquid do not have both orientation
and positional order. Liquid crystal is a state of mesophase whose properties comes
between conventional solids and liquids. Due to this unique property of Liquid crystal
they play an important role in modern technology.

 Liquid crystal flow like a liquid and have orientation order as that of solids
 A liquid crystal is a thermodynamic stable phase characterized by anisotropy of properties
without the existence of a three-dimensional crystal lattice, generally lying in the
temperature range between the solid and isotropic liquid phase, hence the term mesophase.

 Liquid crystals find application in the areas of science and engineering,

particularly in display systems of modern electronic gadgets. Devices using
liquid crystal displays have the advantage of low power consumption and hence
are widely used in display devices of mobile communication appliances, aircraft
cockpit, laptops and related electronic equipments.
Relation between chemical structure and liquid crystal
Substance to behave as liquid crystal they should process following properties
 Molecule should be elongated
 Molecules should have both flexible and rigid structure
 Solubility rate is different in different part of the molecule
Example: n-alkanes and n-alkanoic acid do not exhibit liquid crystal properties but when double
bond is introduced within these structure the substance behave as liquid crystals

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Classification
Liquid crystals can be first organized into
1. Thermotropic (temperature dependent) - The class of compounds that exhibit liquid
crystalline behavior on variation of temperature alone are referred to as
thermotropic liquid crystals.
Example – Cholesteryl benzoate is solid but on heating it shos liquid crystal behaviour at

temperature 145.5 oC to 178.5 oC

Thermotropic liquid crystals may be further classified as:

a. Nematic liquid crystals - Nematic (Greek nematos = thread like) liquid crystals
are formed by compounds that are optically inactive. The molecules have elongated
shape and are approximately parallel to one another. In this phase the molecules
maintain a preferred orientational direction but positional order is completely absent
and they can diffuse throughout the sample. An example of a nematic liquid crystal
is para-azoxyanisole (PAA) which exhibits liquid crystalline behaviour in the

temperature range of 118 oC to 135 oC.

b. Chiral Nematic liquid crystals - Chiral nematic or twisted nematic liquid crystals
are formed from optically active compounds having chiral centres. Compared to
nematic phase where all the molecules are approximately parallel to one another,
in chiral nematic phase, the molecules arrange themselves so as to form a helical
structure.

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 c. Semectic liquid crystals - Substances that form semectic phases are soap-like. Infact,
the soft substance that is left at the bottom of a soap dish is a kind of semectic liquid
crystal phase. In semectic mesophase, there is a small amount of orientation order and
also a small amount of positional order. The molecules are arranged in regularly spaced
layers (positional order). Within the layer they tend to point along the director
(orientation order).

2. Lyotropic (concentration dependent) - Some compounds transform to a liquid

crystal phase when mixed with a solvent. They have both polar lyophilic and a non-
polar, lyophobic end. They are amphiphilic compounds. Such amphiphilic
molecules form ordered structures in both polar and non-polar solvents. They are
usually obtained by mixing the compound in a slovent and increasing the
concentration of compound till liquid crystal phase is observed. Such liquid
crystals are called lyotropic liquid crystals. The formation of lyotropic
mesophases is dependent on the concentration of either the component or the
solvent. Examples: (i) soap (soap - water mixture) molecules (ii) phospholipids
which are biologically important molecules where each cell membrane owes its
structure to the liquid crystalline nature of the phospholipid - water mixture.

Properties of Liquid crystals

 Liquid crystal show properties of both solids and liquids. Liquid crystal are anisotropic and
the physical properties of the system vary with the average alignment with the director. If
the alignment is large the material is very anisotropic. Similarly if the alignment is small
the material is almost isotropic.

 Liquid crystal show some properties of liquid like they have flow like liquid, they have
surface tension, and viscocity.

 Liquid crystal show some properties of solids such as orderly arrangement, optical and ,
electrical properties. Uses of Liquid crystals

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Application of Liquid Crystals:

1. In Display systems:
Due to less consumption of power as compared to other display they are used in
i. Automobile dash boards indicators, traffic signals, advertisement boards and petrol pump
indicators.
ii. Various analytical instruments like pH meter, conductometer, colorimeter, Potentiometer,
etc.,
iii. Various electronic gadgets including watches, TV, calculators, mobile phones, laptops,
desktops, etc.,
2. Thermography: Thermography measures surface temperatures by using infrared video
and still cameras. These tools see light that is in the heat spectrum. Images on the video or
film record the temperature variations of the skin, ranging from white for warm regions to
black for cooler areas.
i. In Medical Thermography:
Used in the early detection or diagnosis of tumour or breast cancer besides orthopedic
disorders such as arthritis and back pain etc. The basic principle is that heat changes
produced in the affected skin are different from the healthy skin.
ii. In Radiation & pressure sensors:
Cholesteric liquid crystals have been used in versatile and inexpensive radiation
sensors. These devices are based on the principle of conversion of radiation energy into
heat energy and the measurement of the heat energy using a thermal transducer.
iii. In electronic industry
iv. In detection of air pollutants :
Used to detect the impurities in the atmosphere. The colour of the liquid crystals
changes in the presence of impurities.
3. Point of potential failure in electric circuit - Liquid crystal are also sensitive to electric
field so they are used in detection of point of potential failure in electric circuit.

4. In Research work : Liquid crystals are employed as solvent in spectroscopic studies like
NMR, IR and UV. It is used in pH meter, conductometer, colorimeter, potentiometer and other
analytical instruments to detect the structure of various organic compound.
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 Other Applications of Liquid crystals:

 Cholesteric liquid crystal substances, when applied to the surface of the skin, have been
used to locate veins, arteries, infections, tumors and the fetal placenta which are warmer
than the surrounding tissues.
 Liquid crystals are widely used in cosmetic industry in manufacturing of liquid crystal
makeup removers, lipsticks and lip glasses containing cholesteric liquid crystals.
 Liquid crystals are using extensively in pharmaceutical industries.
 Liquid crystal polymers also gained much interest on industrial applications. polyester
liquid crystals were developed for fire resistant, and are used as coating for multifibre,
optical cables due to good surface roughness, low coefficient of friction. Polyesters are
used for moulding with improved elastic modulus.
Jablonski Diagram

Jablonski diagram is an energy diagram which describes about various emission pathways by the
molecules after the absorption of light. The various processes are as follows:
1. Absorption: In the first step, the absorption of radiation by the molecules takes place. After the
absorption of radiation, molecules get excited to higher electronic states like S1, S2, S3 or
T1,T2.T3 etc.
2. Non-radiative transitions:
 Internal Conversion (IC): The transition of molecules from higher excited states(S3,S2 or
T3,T2) to higher vibrational levels of S1 or T1 state is called internal conversion(IC) . It is
a non-radiative process.
 Inter System Crossing (ISC)- The transition of molecules from S2 toT2 or S1 toT1 is called
ISC. It is also a non-radiative process.
3. Radiative transitions:
 Fluorescence- It involves the transition of molecules from S1 to ground state (S0) through
a radiative process, called fluorescence. Fluorescence always occurs from S1 state .
 Phosphorescence- It involves the transition of molecules from T1 state to the ground state
S0 and is rather slow since it is a forbidden transition. This process has much longer
lifetime.

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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.

PHOTOACTIVE AND ELECTROACTIVE MATERIALS

Present day technological developments in the information – oriented society are mainly
attributed to discovery of electronic, optoelectronic, and photonic devices which use
inorganic semiconductors. 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. Devices using organic materials
have the following advantages over inorganic semiconductor-based devices:

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a. They are lightweight.
b. They are flexible.
c. They can be easily synthesized by chemical methods.
d. Cost of production is less.
e. They can be used in novel thin-film flexible devices.
f. 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 opto-electronic phenomena as:

a) Absorption and emission of light radiation in the wavelength region from

ultraviolet to near infrared.
b) Photogeneration of charge carriers.
c) Transport of charge carriers.
d) Injection of charge carriers from the electrode.
e) Exhibit excellent nonlinear optical properties.

Organic compounds with extensive conjugation and π-electron systems are capable of
exhibiting above mentioned set of properties. Those organic materials can be broadly
classified in to three categories:

a) Small molecules
b) Oligomers with well-defined structures.
c) Polymers
Small organic molecules are crystalline in nature. Few examples for this class of
molecules are, the metal and metal-free phthalocyanines, porphyrines, poly- condensed
aromatic hydrocarbons, like anthracene, pentacene, and fullerenes.

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Conjugated oligomers are a new family of organic π-electron systems, with well-defined
structures, whose properties and functions can be controlled by varying the π -
conjugation length. Few examples for this class are, pentacene, and oligothiophenes.

Polymers are bad conductors of electrons. But, conducting polymers with extensive
conjugation and π – electron system exhibit above mentioned electro-optical behaviour and
they are excellent functional materials. Examples of this class of polymers which find
extensive application as organic semiconducting materials are, polyacetylene poly(p-
phenylene), poly(p-phenylene vinylene), poly(9.9-
dialkylfluorene), polythiophenes, polypyrroles, and polyanilines.

Nanomaterials used in optoelectronic devices:

There is a demand for miniaturization of electronic devices and integrated

circuits. Even though the size silicon transistors have been reduced from 1000 nm three
decades ago to about a few tens nanometres today, there are limitations to further reduce
their size. Nanomaterials with electro-optical properties can help in size reduction of future
opto-electronic devices. Graphene, fullerenes, carbon nanotubes (CNTs), are carbon based
materials which show good electrical, electronic and optical properties. Quantum dots (QDs)
with typical diameters as low as 0.5 nm of a large diversity of materials, including silicon,
germanium, different III-V compound

semiconductors, such as GaAs, GaN, InN, GaP, InP, AlN, InAs, II-VI materials, such
as CdS, CdSe, ZnS, ZnSe, and semiconducting oxides such as In 2O 3, ZnO, TiO2, etc.
show interesting properties. These materials along with low-dimensional structures also
exhibit unique kind of light-matter interactions like surface plasmon resonance,
spintronics, plasmonics etc. They can be used in future photonic and electronic 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.
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Aside from the mobile ions, their structure is very similar to that of an organic light-emitting
diode (OLED).
LECs have most of the advantages of OLEDs, as well as additional ones:
 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.
 Recently developed materials such as graphene or a blend of carbon nanotubes and
polymers have been used as electrodes, eliminating the need for using indium tin oxide for a
transparent electrode.
 The thickness of the active electroluminescent layer is not critical for the device to operate.
This means that:
 LECs can be printed with relatively inexpensive printing processes (where control over film
thicknesses can be difficult).
 In a planar device configuration, internal device operation can be observed directly.

Quantum Light emitting diodes (QLED’s)

Over the past decade, organic light-emitting diodes (OLEDs) have been successfully launched in
the display industry, dominating the flat panel display (FPD) market owing to the advantages of
self-emissive devices including both performance and form factor metrics, such as high contrast
ratio (CR) and substrate flexibility. However, despite the successful industrialisation of OLEDs,
the demand for higher colour saturation and higher electrical stability has emerged for next-
generation displays.
 Quantum dots (QDs) are promising materials for the emissive component of self-emissive
light-emitting diodes (LEDs) due to their high colour saturation in a narrow wavelength
range, easy colour tunability by control of their size and prominent stability.

 Particularly, electroluminescence (EL)-based quantum dot light-emitting diodes (QD-LEDs)

driven by an electric field also have a flexible form factor and superior CR because they are
self-emissive devices such as OLEDs.

 Moreover, since EL-based QD-LEDs utilize the ultimate material properties of inorganic
QDs, a high colour gamut with high colour tunability and electrical stability are expected.
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 Therefore, QD-LED technology is getting increasingly attractive as new device technology
for next-generation smart displays.

Synthesis of QD materials
 A colloidal QD is composed of three parts, as shown in below Fig.
 : It consists (i) a core Nano crystal, (ii) a shell layer and (iii) a surface-binding ligand.
 The core nanocrystal generates light through the radiative recombination of an exciton,
which is an electron–hole pair (EHP), confined in the core region.
 The wavelength of the emissive light is determined by the optical band gap, which is directly
modified by the composition and the size of the core nanocrystals.
 To obtain the desired colour and high colour purity, control of the size and uniformity of the
core nanocrystal is the key factor during the synthesis of QDs.
 As core nanocrystal materials, cadmium selenide (CdSe), indium phosphide (InP) and zinc
telluride selenide (ZnTeSe) are commonly used.
 In contrast to the core nanocrystal, the shell layer gives a quantum confinement effect by
surrounding the core.
 The highest occupied molecular orbital (HOMO) of the shell is higher, and the lowest
unoccupied molecular orbital (LUMO) of the shell is lower than that of the core, forming a
quantum well to confine the exciton. within the core nanocrystal.

OLED – Organic Light Emitting Diode

 OLEDs work in a similar way to conventional diodes and LEDs, but instead of using layers of
n-type and p-type semiconductors, they use organic molecules to produce their electrons and
holes.
 A simple OLED is made up of six different layers. On the top and bottom there are layers of
protective glass or plastic.
 The top layer is called the seal and the bottom layer the substrate. In between those layers,
there's a negative terminal (sometimes called the cathode) and a positive terminal (called the
anode).

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 Finally, in between the anode and cathode are two layers made from organic molecules called
the emissive layer (where the light is produced, which is next to the cathode) and the
conductive layer (next to the anode).

Working principle 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.
Application of OLED :
 Broadly speaking, you can use OLED displays wherever you can use LCDs, in such things as
TV and computer screens and MP3 and cell phone displays.

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 Their thinness, greater brightness, and better colour reproduction suggests they'll find many
other exciting applications in future.
 Apple, originally dominant in the smartphone market, has lagged badly behind in OLED
technology until quite recently.
 In 2015, after months of rumors, the hotly anticipated Apple Watch was released with an
OLED display.
 Since it was bonded to high-strength glass, Apple was presumably less interested in the fact
that OLEDs are flexible than that they're thinner (allowing room for other components) and
consume less power than LCDs, offering significantly longer battery life.
 In 2017, the iPhone X became the first Apple smartphone with an OLED display.

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