Materials Chemistry for Energy and Data Processing (24CHECS12)

Module - 1
Materials for Memory Devices
What is Memory?
A memory is just like a human brain. It is used to store the data and instructions.
Memory devices are electronic components used to store data and instructions temporarily
or permanently.
They are essential components in modern electronic devices such as computers,
smartphones, and digital cameras.
All the data that enters into the computer first get converted into the binary number
system. One digit in binary number system is called bit and combination of eight bits is
called byte. Bit is the smallest measuring unit of computer memory.

Bit = 0 or 1
1 Nibble = 4 bits
1 Byte (b) = 8 Bits
1 Kilobyte (KB) = 1024 Bits
1 Megabyte (MB) = 1024 KBytes
1 Gigabyte (GB) = 1024 MBytes
1 Terabytes (TB) = 1024 GBytes
1 Petabytes (PB) = 1024 TByte

Memory is primarily of two types

 Internal Memory − cache memory and primary/main memory
 External Memory – magnetic disk/optical disk etc.

Characteristics of Memory Hierarchy are following when we go from top to bottom.

 Capacity in terms of storage increases.
 Cost per bit of storage decreases.
 Frequency of access of the memory by the CPU decreases.
 Access time by the CPU increases.

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Introduction to Memory Devices

With the rapid development of electronics industry in recent years, information

technology devices such as personal computers, mobile phones, digital cameras and media
players have become an essential part of our daily life.
As the performance of digital gadgets advances, the complexity of data storage
devices increases correspondingly. Conventional memory devices are implemented on
semiconductor based integrated circuits such as transistors and capacitors. In order to achieve
greater density of data storage and faster access to data information, more components
(transistors and capacitors) need to be deliberately packed onto a single chip. As a result, the
size of the transistors has been decreased from 130 nm in the year 2000 to 32 nm at present.
however, the silicon-based semiconductor devices (transistors) become less stable below 22
nm, and the reliability to store and read individual bits of information will be substantially
reduced. Further, the power consumption and unwanted heat generation are also of increasing
concern. Therefore, the current state-of-the-art memory technologies are no longer capable of
fulfilling the requirements for information storage of the near future.

The new data storage technologies such as ferroelectric random access memory
(FeRAM), magnetoresistive random access memory (MRAM), phase change memory (PCM)
and organic/polymer memory have appeared as effective alternatives for future information
storage. Particularly, the advantages of organic and polymer electronic memory systems
including low cost, good processability, molecular design through chemical synthesis,
simplicity of device structure, miniaturized dimensions, good scalability, low-power
operation, and large capacity for data storage have made them promising alternatives to
conventional inorganic semiconductor- based memory technologies.

By using organic/polymeric materials as storage media, flexible and miniaturized

memory devices with simple structure can be fabricated with particular ease through solution
processing. Most importantly, the electronic properties of organic/polymeric materials, and
thus the device performance, can be tailored through molecular design cum chemical
synthesis.

Basic Concepts of Electronic Memory

Electronic memory is a type of storage technology that uses semiconductor materials

to store digital data.
 Electronic memory devices are known for their speed and compact size, which

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makes them ideal for use in electronic devices.

 Electronic memory devices can be both read from and written to, meaning that data
can be stored and retrieved as needed.
 Electronic memory devices store digital data using binary code, which is a system of
representing information using only two symbols 0 and 1.
 Memory cells are small units of semiconductor material that can store a single bit of
information. The most common types of memory cells are DRAM and SRAM cells.
 Multiple memory cells are organized into arrays, which consist of rows and columns
of memory cells. The organization of the memory array determines how data is
accessed and how quickly it can be accessed.
 In conventional silicon-based electronic memory, the data is 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 Memories

 According to the storage type of the device, electronic memory can be divided into
two primary categories: volatile & non-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.
 The non-volatile memory can be further divided into sub-categories, as ROM and
hybrid memory. ROM is factory programmable only; data is physically encoded in
the circuit and cannot be programmed after fabrication. Hybrid memory allows data

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to be read and re-written at any time.

 A WORM memory device can be used to store archival standards, databases and
other massive data where information has to be reliably preserved for a long period
of time. Conventional CD-Rs, DVD±Rs devices are examples of WORM memory.
 Flash memory is another type of non-volatile electronic memory. Different from
WORM memory, its stored state can be electrically reprogrammed, and it has the
ability to write, read, erase and retain the stored state. No power is needed to
maintain the information stored in flash memory.
 Further, RAM requires the stored information to be periodically read and re-written,
or refreshed, otherwise the data will be lost. The RAM can be divided into DRAM
and SRAM.
 DRAM is a type of volatile random access memory that stores each bit of data in a
separate capacitor within an integrated circuit. The stored data eventually fade
unless the device is refreshed periodically. The volatility, ultrafast data access time
and structural simplicity hold great promise for high density and fast responding
performance, making DRAM memory the main memory for most computers.
 SRAM is another type of volatile memory. The term “static” differentiates it from
“dynamic” RAM (DRAM) which must be periodically refreshed. SRAM exhibits
data remanence, but it is still volatile, and the stored data are eventually lost when
the memory remains in the power-off state. SRAM is faster and more reliable than
the more common DRAM. Due to its high cost, SRAM is often used only as a
memory cache.

History of Organic/Polymer Electronic Memory Devices

• Different forms of storage devices have been reported since 1940s. A computer system
usually contains several kinds of storage, each with an individual purpose.
• In 1960s, amorphous semiconductors received great interest in the memory device
applications owing to their unusual electrical properties.
• During 1960-70s, electrical bistability (a device exhibits two states of conductivities at
the same applied voltage) and resistivity phenomenon was observed in
Pb/polydivinylbenzene, tetracene and styrene polymer materials. All the materials have
showed bistable switching and memory switching effects. But the performance was not
satisfactory.
• In 1995, ferroelectric polymer films of 1 nm thickness were fabricated. These required

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just 1 V to switch between two states. Since then polymer ferroelectric RAM (FeRAM)
was developed as a promising memory technology.
• In 2003, a WORM type memory device was developed consisting of a thin film p-i-n
silicon diode and a mixture of two conductive polymers, poly(ethylenedioxythiophene)
and poly(styrene sulfonic acid).
• In 2004, ultrathin film organic materials were discovered with multilevel conductivity
states. In order to achieve ultrahigh density memory devices, organic materials with
multilevel stable states are highly desirable.
• In 2005, multilevel conductance switching films were discovered, which were
dramatically improved the amount of data stored per area or volume. Further progress
in the development of multilevel organic polymer has been made in recent years.
• The International Technology Roadmap for Semiconductors (ITRS) has identified
polymer memory as an emerging memory technology since the year 2005.

Classification of Electrical Memory Devices

According to the device structure, electronic memory devices can be divided into
four primary categories viz., Transistor type, capacitor type, resistor type and charge transfer
type.

1. Transistor type electronic memory

In order to store data in a memory device, 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. In this electronic circuit, “0” and “1” corresponds to the

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„discharged‟ and „charged‟ states of the capacitor respectively.

By arranging these transistors in a particular pattern, memory chips can store vast
amounts of data in the form of binary numbers. They are classified into two main
categories:

 Static Random Access Memory (SRAM) uses transistors as switches and can
retain data as long as power is supplied to the device.
 Dynamic Random Access Memory (DRAM) on the other hand, uses a capacitor
to store charges, and the charges must be refreshed regularly to retain data.

2. Capacitor type electronic memory device

Organic and polymeric ferroelectric

materials can be used in capacitor type
electronic memory devices. Capacitors have
two parallel plate electrodes and charges are
stored in these electrodes under an applied
electric field. Bistable states of capacitor are
based on the amount of charge stored in the
cell. Charge stored in the cell maintains
electric polarization that can be switched
between two stable states by an external
electric field.

3. Resistor type electronic memory device

Memory devices containing switchable resistive

materials are classified as resistor-type memory,
or resistive random access memory (RRAM).
Resistor-type electronic memory usually has a

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simple structure, having a metal- insulator-metal

structure generally referred to as MIM structure.

The structure comprises of an insulating layer (I)

sandwiched between the two metal (M) electrodes
and supported on a substrate (glass, silicon wafer,
plastic or metal foil). Initially, the device is under
high resistance state or “OFF” and logically “0”
state, when resistance changed or under external
applied field changes to low resistance state or
“ON” logical value “1”.

4. Charge transfer type electronic memory device

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. The conductivity of a CT
complex is dependent on the ionic binding between the D–A components.

If the donor has intermediate size and ionization potential, it tends to form a weakly ionic salt
with the acceptor, which possesses incomplete CT (0.4 < δ < 0.7) and thus is potentially
conductive.

Explain the types of organic memory devices by taking p- type and n-type
semiconducting materials.

Types of Organic Memory Materials/Devices

There are three classes of materials which can exhibit bistable states and are used in
organic memory devices. They are
1) Organic Molecules

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2) Polymer Molecules
3) Organic – Inorganic Hybrid Materials
Under each category, different types of molecules are exhibiting memory effects as
described below;
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 „OFF‟ state to „ON‟ state or vice versa. All these materials can be used in
organic electronic memory devices. Few of them are mentioned here.

i) Acene derivatives: Acenes are the polycyclic aromatic compounds consist of linearly
fused benzene rings. They are the very first discovered organic memory materials because
of their high charge carrier mobility.

Examples for acenes are pentacene, perfluoropentacene, naphthalene, anthracene, tetracene

etc.,

Structure of Pentacene

The most important member of acene family is pentacene. it is a linearly fused

aromatic compound with five benzene rings. it can be obtained in crystal and thin film
forms. both forms exhibit a very good hole mobility and hence it behaves as a p-type
semiconductor.

When all the hydrogen atoms of pentacene are replaced by fluorine atoms, the
resulting molecule is called perfluoropentacene. Strong electron withdrawing nature of
fluorine atoms convert this molecule into n-type semiconductor.

Structure of perfluoropentacene
Both pentacene and perfluoropentacene have similar structure and similar crystal
packing but pentacene behaves as p-type semiconductor and perfluoropentacene behaves as

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n-type semiconductor. therefore these molecules together exhibit charge-transfer processes

that are useful for memory applications.

i) Charge transfer complexes

These molecules have two parts, one is electron donor and the 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
devices.

Examples
a) Copper and 7,7,8,8-tetracyanoquinodimethane
(TCNQ) complex (Cu-TCNQ)
b) Zinc (II) pthalocyanine (ZnPc) complex. In this
zinc metal is acceptor and organic molecule Pc is
donor.
Structure of Cu-
TCNQ

a) CT complex with methanofullerene 6,6-phenyl C61-butyric acid methyl ester (PCBM)

as the organic electron acceptor, and tetrathiafulvalene (TTF) as the organic electron
donor.

ii) Small organic molecules containing both electron donor and acceptor in a single
molecule (D-A molecules)

They exhibit bistable conductivity states due to electron transfer from Highest Occupied
Molecular Orbital (HOMO) to Lowest Unoccupied Molecular Orbital (LUMO). They are
known as Donor- Acceptor molecules (D-A molecules)

Example: DRAM device based on SNACA electron acceptor naphthalimide (NA) and
electron donor carbazole (CA) were linked by a hydrazone bond.

Also some small organic D-A molecules proved to exhibit multilevel stable states and
hence they are used to increase device capacity by three times. This type of device is
called as ternary memory device.

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Discuss the use of Polyimide Polymeric material for Organic memory device?

II. Polymer Molecules

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

i) Functional polyimides (PIs)

Functional polyimides (PIs) are one of the most commonly used polymeric materials for
organic electronic 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 the triphenylamine acts as 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.

Triphenylamine Phthalimide

i) 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 induces 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.

ii) Polymers with fullerenes or graphene

Carbon nanomaterials such as fullerenes, graphene and their derivatives have good
optoelectronic properties. polymer with covalently attached fullerene, in which the
carbazole group of polymer serves as the electron donor and C60 serves as the electron
acceptor and acted as device for non- volatile rewritable memory behavior.

iii) Polymer containing metal complexes

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Transition metal complexes exhibit reversible redox properties. When these are introduced
into polymer backbones, they can improve the stability of conductive states. Ferrocene
(Fe) is the commonly used metal complex. which exhibits non-volatile memory when
introduced into polymer.

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)

i) 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 exhibits high electron
withdrawing ability and can capture up to six electrons. they are used in WORM memory
effect devices.

ii) Organic-Inorganic Nanocomposites

In these kind of memory devices, organic polymers with appropriate functional group is
clubbed with metal nanoparticles, quantum dots and metal oxide nanoparticles. For
example, 8- hydroxyquinoline containing polymer with gold nanoparticle sandwiched
between two metal electrodes showed bistable electronic states when an electric field is
applied due to charge transfer between the Au nanoparticles and 8-hydroxy-quinoline.

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