I / II SEMESTER (22CHES12/22)

DAYANANDA SAGAR COLLEGE OF ENGINEERING

Accredited by National Assessment & Accreditation Council (NAAC) with ’A’ Grade
(An Autonomous Institution affiliated to Visvesvaraya Technological University, Belagavi &
ISO 9001:2015 Certified)

DEPARTMENT OF CHEMISTRY
SHAVIGE MALLESWARA HILLS, KUMARASWAMY LAYOUT
BENGALURU-560111

2022-23
 Dayananda Sagar College of Engineering
Department of Chemistry

MODULE- 5
Materials for Memory and Display Systems

Introduction to Memory Devices:

Definition: 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).
Basic 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).
• Data storage technologies consists of ferroelectric random access memory (FeRAM),
magnetoresistive random access memory (MRAM), phase change memory (PCM), and
organic/polymer memory have appeared on the scene of the information technology industry.
• 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.
• The new technologies are based on electrical bistability of materials arising from changes in
certain intrinsic properties, such as magnetism, polarity, phase, conformation and conductivity,
in response to the applied electric field.
• Organic/polymer electronic memory is likely to be an alternative or at least a supplementary
technology to conventional semiconductor electronic memory.
• The advantages of organic and polymer electronic memory include good processability,
molecular design through chemical synthesis, simplicity of device structure, miniaturized
dimensions, good scalability, low-cost potential, low-power operation, multiple state properties,
3D stacking capability and large capacity for data storage.
Classification of Electronic memory device- Based on storage type

Fig. Classification of electronic memory devices based on storage type.

• According to the storage type of the device, electronic memory can be divided into two primary
categories: volatile and non-volatile memory.
• Volatile memory eventually loses the stored information unless it is provided with a constant

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power supply or refreshed periodically with a pulse. The most widely used form of primary
storage today is volatile memory
• Electronic memory can be further divided into sub-categories, as read only memory (ROM),
hybrid memory, and random access memory (RAM).
• 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. RAM requires the stored
information to be periodically read and re-written, or refreshed, otherwise the data will be lost.
• Among these types of electronic memory,
(a) write-once read-many-times (WORM) memory,
(b) erasable programmable read only memory (EPROM),
(c) electrically erasable programmable read only memory (EPROM)
(b) hybrid non-volatile and rewritable (flash) memory,
(c) static random access memory (SRAM) and
(d) Dynamic random access memory (DRAM) are the most widely reported polymer memory
devices.

Classification of electronic memory devices- Based on Device structure

According to the device structure, electronic memory devices can be divided into three primary
categories: transistors, capacitors and resistors. With their respective ability to amplify electronic signals,
to store charges, and to produce proportional electric currents, electronic memory devices can be
constructed from transistors, capacitors and resistors.
1. Transistor – type electronic memory device
• Inorganic transistors are widely used in conventional semiconductor memory.
• Organic (including polymer) transistors are also of great potential for memory applications Organic field-
effect transistor (OFET) type memory devices have attracted considerable research interest due to their
easily integrated structure and the non-destructive reading of a single transistor.
• In addition, the mechanical flexibility of organic materials makes them compatible with plastic substrates
for lightweight and flexible device design.
2. Capacitor - type electronic memory device
• Capacitors can store charges on two parallel plate electrodes under an applied electric field.
• Based on the amount of charge stored in the cell, the bit level (either “0” or “1”) can be encoded
accordingly.
• When the medium between the electrodes is merely a dielectric, the stored charge will be lost
eventually.
• Thus, (Dynamic random access memory) DRAM using a dielectric capacitor is volatile memory,
and the information stored in DRAM eventually fades unless the capacitor charge is refreshed
periodically.
3. Resistor - type electronic memory device
• Devices incorporating switchable resistive materials are generically classified as resistor-type
memory, or resistive random access memory (RRAM).
• Unlike transistor and capacitor memory devices, resistor-type memory does not require a specific
cell structure (e.g. FET) or to be integrated with the CMOS (complementary metal-oxide-
semiconductor) technology.

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• Resistor-type memory devices store data in an entirely different form, for instance, based on
different electrical conductivity states (ON and OFF states).
• Electrical bistability usually arises from changes in the intrinsic properties of materials, such as
charge transfer, phase change, conformation change and reduction–oxidation (redox) reaction,
in response to an applied voltage or electric field.

Types of Organic-Based Electrical Memory Devices

Organic Molecules:
• Organic electronic memory devices based on organic molecules were first reported in several
acene derivatives including naphthalene, anthracene, tetracene, pentacene, perylene kind of
molecules. Subsequently, the effect of different D–A structures on the electronic switching
properties of triphenylamine-based molecules is of great interest.

• Device consists of organic molecule embedded between ITO and Ag electrodes.

• The device exhibited reproducible negative differential resistance (NDR) and can be electrically
switched between the ON state and the OFF state.
• Organometallic and all-organic CT complexes have been explored for use in organic memory.

Polymeric Materials:
• Polymeric materials have advantage over the small organic molecules due its good solution
processability, high thermal stability and mechanical strength.
• The molecular structure of polymeric materials can be tailored using electron donors and
acceptors of different strengths, spacer moieties and functional group to induce different
switching behaviors for electronic memory applications.
• In D–A structured polymer of phthalimide as the electron acceptor, and triphenylamine as
electron donors can be used as electrical memory applications.
• 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.
• An electric field-induced CT state can be formed, which is the main mechanism responsible for
the memory behaviour. The Al/polymer/ITO device exhibits dynamic random access memory
(DRAM) behaviour with an ON/OFF current

Organic–Inorganic Hybrid Materials

• Generally, organic–inorganic hybrid materials are composed of organic layers containing
fullerenes, carbon nanotubes, graphene, metal nanoparticles, semiconductor nanoparticles or
inorganic quantum dots (QDs).

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• Organic–Carbon Allotrope Hybrid Materials: Fullerene and its derivatives possess high electron-
withdrawing ability, and are able to capture up to six electrons. For organic electronic memory
applications, they have been widely used as electron acceptors to form CT complexes with
polymer-containing electron donors, such as thiophene, fluorene, carbazole and aniline
derivatives. CNT, single-walled carbon nanotubes (SWNTs), Graphene oxide (GO) nanosheets
also used as acceptor materials.
• Organometallic and all-organic CT complexes have been explored for use in organic memory.
• All films of these organic CT complexes exhibited electrically bistable states at room temperature
and a short transition time from high to low resistance.

Display system
Definition: Display System means a system for the use of Display Materials. The display systems
consists of Photoactive and electroactive materials as the active materials which convert the electrical
energy into to light emission.
Photoactive material: materials that changes its properties when exposed to light, often in the
ultraviolet or visible region of the electromagnetic spectrum. Example: conducting polymers such as
polythiophene, polypyrole and nanomaterials such as TiO2, ZnS etc.
Electroactive materials: An electroactive material exhibits a change in size or shape when stimulated
by an electric field. Example: polyacetylene, Barium Titanate, Potassium Niobate etc.

Applications of Photoactive and electroactive materials: Photoactive and electroactive materials

belong to the huge field of photonics, where materials that actively interact with light are tuned and
optimized to achieve effects such as;
• Convert electrical signal to light- light emission (LEDs and lasers, just to name the most common
ones)
• Light detection, with related signal amplification (e.g., in photomultipliers) and processing
operations.
• Alternatively, they can be used to develop light-sensitive circuits and switches (such as with
photoresistors),
• Convert light into an electrical signal (photodiodes – PV Cells)
Nano-materials and organic materials used in optoelectronic devices
1. Organic materials as optoelectronic devices: Organic molecules used as optoelectronic
devices: Small molecules and conjugated polymers, the two main types of organic materials used
for optoelectronic and photonic devices, can be used in a number of applications including
organic light-emitting diodes, photovoltaic devices, etc. Organic molecules having alternative
conjugation with planar sp2 carbon in the backbone structure are basically used for optoelectronic
application. These conjugated materials hence, behave as semiconductor materials. Anthracene
is one such molecule known for almost a century (1910) possesses alternative conjugation and
planar structure.

Anthracene

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Organic semiconductor materials in general can be separated into two classes: conjugated
polymers and small molecules.
Polymers have high molecular weights that result good mechanical and thermal stability, and
hence, polymers are advantageous for large-area device fabrications. Example: polythiophene,
polycarbazole

Small molecules have advantages in good batch-to-batch repeatability, high crystallinity, and
excellent charge carrier mobilities due to strong intermolecular π-π stacking. Example:
pentacene, triphelylene

2. Nano materials as optoelectronic devices

• Optical properties such as absorption, transmission, reflection, and light emission are
exhibited by nanomaterial.
• Intrinsic characteristics of nanoparticles such as size, shape, and surface properties
determines its applications.
• At a specific wavelength (frequency) of light, the collective oscillation of electrons on the
metal nanoparticle surface causes a phenomenon called surface plasmon resonance, which
results in a strong extinction of light which makes nanomaterial as materials for optical and
optoelectronics applications.
• Metal oxides such as TiO2 and ZnO and quantum dots such as CdSeS and ZnS are used for
optoelectronic applications.
Jablonski diagram: Jablonski diagram is a diagram that illustrates the electronic states and often the
vibrational levels of a molecule, and also the transitions between them. Once a molecule has absorbed
energy in the form of electromagnetic radiation, there are a number of routes by which it can return to
ground state. The two main routes are: radiative process and nonradiative process

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Radiative process: It involves the emission of the absorbed energy as radiation or photon.
• Fluorescence: If the photon emission occurs between states of the same spin state (e.g. S1 → S0)
this is termed fluorescence. Since the transition is between similar state, it is allowed transition
and lifetimes of fluorescent states are very short (1 x 10-5 to 10-8 seconds).
• Phosphorescence: If the spin state of the initial and final energy levels are different (e.g. T1 →
S0), the emission (loss of energy) is called phosphorescence. This a forbidden transition and
hence, fluorescence is statistically much more likely than phosphorescence for most molecules.
Phosphorescence somewhat longer (1 x 10-4 seconds to minutes or even hours; think about glow-
in-the-dark flying disks).
Nonradiative process: Three nonradiative deactivation processes,
• Internal conversion (IC): Internal conversion is the radiationless transition between energy states
of the same spin state (compare with fluorescence-a radiative process).
• Intersystem crossing (ISC): Intersystem crossing is a radiationless transition between different
spin states (compare to phosphorescence).
• Vibrational relaxation: Vibrational relaxation, the most common of the three--for most
molecules, occurs very quickly (<1 x 10-12 seconds) and is enhanced by physical contact of an
excited molecule with other particles with which energy, in the form of vibrations and rotations,
can be transferred through collisions. This means that most excited state molecules never emit
any energy because in liquid samples the solvent or, in gas phase samples, other gas phase
molecules that are present "steal" the energy before other deactivation processes can occur.

Liquid crystals
Introduction
• LCs are a unique state of matter, between solid (crystalline) and liquid (isotropic) phases some
compounds form a distinct, different intermediate phase, sometimes referred to as the “fourth
state of matter” or “mesophase”.
• Possess properties characteristics of both crystalline solids and liquids.
• Also possess properties characteristics not found in either solids or liquids.
• May response to external perturbation and some changes colour with temperature

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Classification of LC’s

Nematic Liquid Crystals: The nematic phase has calamitic or rod-shaped organic molecules that have
no positional order. But these molecules tend to self-align in order to have long-range directional order
having long axes that are roughly parallel to each other. The molecules of the nematic phase show
fluidity that is similar to the fluidity in an ordinary isotropic liquid. However, we can easily align the
molecules in this phase through the application of an external magnetic or electric field. When these
molecules are aligned into an order, the nematic phase shows optical properties of uniaxial crystals, and
therefore, these phases are very useful in liquid crystal displays.
Smectic Liquid Crystals: Smectic liquid crystals are a type of liquid crystals that have well-defined
layers of molecules that are able to slide over one another. This behavior is similar to the sliding effects
given by soap. Moreover, smectic liquid crystals occur at temperatures lower than that of the nematic
liquid crystals. The term smectic originates from the Latin word “smectius” which means “cleaning”; in
other words, it means the presence of soap-like properties. Therefore, the smectic phase is positioned in
order along one direction.
Cholesteric Liquid Crystals: Cholesteric liquid crystals are a type of liquid crystals made only of chiral
molecules. This type of phase shows chirality. Often, we call this phase a chiral phase or a twisted
nematic phase due to its chirality. The term cholesteric comes from its first observation where this phase
of matter first appeared in cholesterol derivatives. We can observe this type of phase exhibiting a twisting
of the molecules, which are perpendicular to the director where the molecular axis is parallel to the
director.

Properties of LC’s:
• Liquid crystals can flow like a liquids, due to loss of positional order.
• Liquid crystals is optically birefringent, due to its orientational order
• Transition from crystalline solid to liquid crystals can be caused by change in temperature- gives
rise to thermotropic liquid crystals
• The properties of liquid crystals which 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. Example:

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thermotropic liquid crystals reacts to changes in temperature and change their phase and
orientation.

Fig: Types of liquid crystals

Applications of Liquid Crystals displays (LCDs.)
Liquid crystal technology has had a major effect many areas of science and engineering, as well as device
technology. Example: Liquid Crystal Displays, the most common application of liquid crystal
technology is liquid crystal displays (LCDs.)
Principle: The basic working principle of LCD is blocking of light. It does not produce light on its own.
So external light source is used.

Working:
• LCD uses background light (backlight) to display the image, and does not produces any
independent illumination.
• When the external light passes from one polarizer to the next polarizer, external supply is given
to the liquid crystal, the polarized light aligns itself so that the image is produced in the screen.
• When no external bias is applied the molecular arrangement is not disturbed. When the external
bias is applied the molecular arrangement is disturbed and it and that area looks dark and the
other area looks clear.
• A display is made up of millions of pixels. A pixel is made up of three subpixels; a red, blue and
green—commonly called RGB. When the subpixels in a pixel change colour combinations, a
different colour can be produced.
• With all the pixels on a display working together, the display can make millions of different
colours. When the pixels are rapidly switched on and off, a picture is created.
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Organic Light Emitting Diodes (OLED’s): OLED (organic light-emitting diode), also known as
organic LED is a light-emitting diode that emits light when an electric current is passed through its
emissive layer. OLEDs use organic materials to emit light, rather than traditional backlighting used in
LCD displays. Molecules commonly used in OLEDs include organometallic chelates, fluorescent and
phosphorescent dyes and conjugated dendrimers.
The OLED contains three basic layers: the cathode, anode and organic layer. The organic layer
consisted of an emissive layer and a conductive layer. When a current is passed through the material,
electrons are generated at the cathode, and “holes” are generated at the anode which eventually combine
to emit light through fluorescence or phosphorescence method.
Properties of OLED:
• OLED is a self-emissive display, and no extra backlight unit is needed.
• OLED fabrication is typically a low temperature process, which is suitable for flexible
optoelectronics applications.
• OLEDs are electronic devices that employ a series of thin, light-emitting films composed of
hydrocarbon chains, rather than semiconductors laden with heavy metals like gallium arsenide
phosphide as in existing LED technology.
• These organic arrays between two conductors with different work functions produce bright light
by utilizing less energy.
• Compared with existing liquid crystal display (LCD) technology, OLED exhibits the advantages
of self-emission, vivid colours, low power consumption, wide viewing angle, ultrathin thickness,
fast response time, simple structure, rollable, low driving voltage high brightness, and wide
viewing angle.
• OLEDs are prone to burn-in, are costly, and require the use of advanced techniques.
Consequently, the light source is often used for small-screen products such as smartphones.
Applications of OLED
• Digital Display in devices such as TV screens, computer monitors, portable systems, smart
phones, handheld games consoles.
Difference between LCD Vs. OLED:
LCD OLED
It uses background light to display the image It uses independent and separate illuminating
pixels
LCD screen offers cleaner white colour The OLED has lower brightness than LCD but
because it has a strong backlight has better viewing angles
LCD screen requires the same amount of OLED requires less power, their images did
constant power as the type of image they not display too much white colour
display
Not a flexible display system It is a flexible display system
No Burn-in observed OLEDs are prone to burn-in

Quantum Light emitting diodes (QLED’s): The structure of a QLED is similar to the basic design of
an OLED. The major difference is that the light emitting devices are quantum dots, such as cadmium
selenide (CdSe) nanocrystals.
In this technology, a layer of quantum dots is placed between electron and hole-transporting

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layers, like sandwiched structure. Electrons and holes are accumulated in the quantum dot layer by an
applied electric field. Then, they will recombine and emit narrow spectrum of photons.
Properties
• QLED is cost-effective, much more brightness and more efficient as well as more stable devices
made of environmentally sustainable materials such as Quantum dots (QDs). 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 or
QLEDs) driven by an electric field also have a flexible form factor and superior CR (contrast
ratio) 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. Therefore,
QD-LED technology is getting increasingly attractive as new device technology for next-
generation smart displays.
• Screens made with quantum dot technology stand out for the depth of colour produced by the
changing brightness. The advantages are the natural colours, the limitless life of the panel and
reduced energy use.
Application of QLED
• Flat panel TV screen
• Digital Cameras
• Mobile Phones
• Handheld game consoles
Light emitting electrochemical cells (LEC) - A light-emitting electrochemical cell (LEC) 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).
Properties
• 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.
• There are two distinct types of LECs, those based on inorganic transition metal complexes
(iTMC) or light emitting polymers. iTMC devices are often more efficient than their LEP based
counterparts due to the emission mechanism being phosphorescent rather than fluorescent.
• Compared with conventional organic light-emitting diodes (OLEDs), LECs contain simple
device architecture (generally only one light- emitting layer), and can use air-stable metals (e.g.
Al, Ag and Au) as the cathodes directly.

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• Compared to other iTMCs, ionic iridium complexes have been widely utilized in optoelectronics,
owing to their relevant luminescent properties, such as high emission quantum yields, stability
and easy tunability of the emission color.
Application of LEC
• Flat panel TV screen
• Digital Cameras
• Mobile Phones
• Handheld game consoles

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