MOLECULAR ELECTRONICS
• Molecular electronics involves the use of molecular building blocks for the fabrication
of electronic component for passive elements such as wire and for active elements
such as transistors
• Molecular electronics will change the size and scale of todays electronic devices,
which are of the order of micrometer to that tens of nanometers.
• Conventional electronic devices are traditionally made from bulk materials .Bulk
materials have inherent limits and growing increasingly demanding and costly.
•
Thus the idea was born that the components could be instead be built up atom by
atom in a chemistry lab.
• Concept of using molecule as a traditional electronic component was first presented
by AVIRAM and RATNER in 1974 proposed a theoretical molecular rectifier composed
of donor and an acceptor unit separated by a σ bonded tunneling bridge could
behave as a rectifier.
The study of the electrical and thermal transport characteristics
of circuits that use individual molecules or assemblies of them as
fundamental building blocks is known as molecular electronics.
Molecular electronics is also known as molecular-scale
electronics, moletronics or molectronics.
Molecular electronics is often considered as subdivision of nano
technology and nanoelectronics that is responsible for
electronics devolopment and design using nano building block.
• Most successful commercial product in the field are OLED, LCD,
Organic transistor, biosensor
• Materials used in molecular electronics are
1. Organic Molecules: Among organic molecules, conducting or
conjugated polymers which are polymers with conjugated double
bonds, such as polyacetylene, polythiophene, and polyaniline can
exhibit high charge carrier mobility, making them suitable for certain
electronic applications.
2. Metal Complexes: Transition metal complexes, including those based
on metals like ruthenium or iron can be designed to have specific
electronic and redox characteristics.
3. Carbon Nanotubes: Carbon nanotubes are cylindrical structures made
of carbon atoms. They can exhibit semiconducting or metallic behavior
depending on their structure.
•
4. Graphene: Graphene is a single layer of carbon atoms arranged in a hexagonal
lattice. It has exceptional electronic properties, including high electron mobility.
5. Self-Assembled Monolayers (SAMs): SAMs consist of organic molecules that
spontaneously organize and form a monolayer on a surface. SAMs can be used as
the foundation for molecular-scale electronic devices, providing a controlled
interface between the molecule and the substrate.
6. Single-Molecule Junctions: The use of individual molecules as active components
in electronic junctions is a fundamental concept in molecular electronics.
• Most organic polymers are insulators by nature due to the unavailability of free
electrons to create the conductivity
• But certain class of polymers which are conjugated (those that possess an
extended π-conjugation along the polymer backbone), exhibit conducting
behavior
• A polymer which can conduct electricity is called conducting polymer
• Poly acetylene is the first conducting polymer synthesized. Poly aniline,
Polypyrrole, Polythiophene are examples of conducting polymers
• The chemistry Nobel prize in 2000 was awarded for the discovery and study of
conducting polymers.
The Nobel Prize in Chemistry 2000 was awarded jointly to Alan J. Heeger, Alan G.
MacDiarmid and Hideki Shirakawa "for the discovery and development of
conductive polymers"
Alan J. Heeger Alan G. MacDiarmid Hideki Shirakawa
Poly acetylene is the first conducting polymer synthesized
Conducting Polymers
Intrinsically Extrinsically Co-ordination or Inorganic
Conducting Polymers Conducting Polymers Conducting Polymers
Conductive element Blended conducting
filled polymer polymer
Conducting Polymers Doped
having conjugated pi Conducting Polymers
electrons in
backbone
p-doping n-doping
Intrinsically conducting polymers
Intrinsically conducting polymers: These types of polymers have a solid backbone
made up of extensive conjugated system, which is responsible for conductance.
They are of two types
1. Conducting polymers having conjugated π-electrons in the backbone
2. Doped conducting polymers
Conducting polymer having conjugated ∏
electron in the back bone
• Conjugated polymers are organic molecules that are characterized by a
backbone chain of alternating double and single bonds.
• They possess conjugated π-electrons that can be easily delocalized rather
than being part of one valence bond.
• Currently, conjugated polymers are the most important class of organic
semiconductors used to fabricate OLEDs and optoelectronic devices due
to their unique optical, electrical, and mechanical properties
• Polyacetylene and Polyaniline are examples
Doped conducting polymer
• In pure form (undoped or pristine state), conducting polymers have
low electrical conductivity.
• To achieve high conductivity doping is necessary, doping increases the
conductivity by many orders of magnitude.
• Doping can be achieved by either partial oxidation with electron
acceptors (i.e. anions) or partial reduction with electron donors (i.e.
cations).
• Both partial oxidation and reduction are referred to as p-doping and
n-doping, respectively.
• Charged defects, such as polarons, bipolarons and solitons, are
introduced into the polymer structure as a result of the doping process.
• These defects then play the role of charge carriers.
• Once doping has occurred, the electrons in the π-bonds are able to
“jump” around the polymer chain and, while electrons are moving along
the molecule, an electrical current flow.
• Doped polymers have high electrical conductivities and are called as
synthetic metals
Positive doping (Oxidation)
• It is done by oxidation process. This typically removes some electrons
from π bonds of the conjugated double bonds and holes so created
can move along the [Link] polymer become conductive.
• The radical cation produced is called polaron. The polarons are
mobile and can move along the polymer chain by rearrangement of
double bonds and single bonds and hence the polymer become
electrically conducting.
• Oxidation process is of generally brought about by Lewis acids such
as FeCl3 , AlCl3 , BF3 etc.
[Link] of electron from the top of the valence band makes the valence band
patially filled hence facilitate the formation of cation ( polarons)
2. Further removal of electron results in the formation of dication( bipolaron)
Negative doping (Reduction)
• In this type, some electrons are introduced (reduction) into the
polymer having conjugate double bonds.
• The process of negative doping is brought about by adding Lewis bases
like Br2 , I2 AsF5, etc.
• The reduction of polyacetylene leads to the formation of a polaron and
bipolaron in two steps
• 1. Addition of electron to the bottom of the conduction band makes the
conduction band partially filled and hece facilitate the creation of radical
anion ( polaron)
• 2. Further addition of another electron results in the formation of
dianion (bipolaron)
Soliton
• They are special type of charged defect that are unique to conducting
polymer with a degenerate ground state and are not present in
conducting polymer like polyaniline polythiophene and poly pyrole
• On electronic rearrangement the two cations or two anions are far
away not in the adjacent carbon atom to generate soliton
Extrinsically conducting polymer
Those conducting polymers which owe their conductivity due to the presence of
externally added ingredients in them are called extrinsically conducting polymers.
They are of two types,
1. Conductive element filled polymers
• In this type, polymer acts as a binder to hold the conducting elements together in
solid entity
• The minimum concentration of the conductive filler, which is added to let the
polymer start conducting is called the percolation threshold.
• Important characteristics of these polymers are good bulk conductivity, cheaper,
light in weight, mechanically durable and strong, easily process able in different
forms, shapes and sizes.
2. Blended conducting polymers
• These types of polymers are obtained by blending a conventional polymer with a
conducting polymer either physically or chemically.
• Such polymers can be easily processed and possess better physical, chemical and
mechanical properties
Coordination or inorganic conducting polymer
. These polymer contain charge transfer complexes and are obtained
by combining metal atom with polydentate ligands
• Conducting polymers are widely used
1. In rechargeable batteries.
2. In making analytical sensors for pH, O2 , SO2 , NH3 , glucose, etc.
3. In the preparation of ion exchangers.
4. In controlled release of drugs.
5. In optical filters.
6. In photo voltaic devices.
7. In telecommunication systems.
8. In micro-electronic devices.