Module 4

Molecular Electronics
Molecular Electronics
 Molecular electronics is a field of research and technology that focuses on utilizing individual molecules
or molecular assemblies as functional electronic components
 It includes the study of electrical and thermal transport characteristics of circuits that use molecules.
 Molecular electronics is also known as molecular-scale electronics, moletronics or molectronics.
 It is a multidisciplinary field where fundamental electrical components including wires, transistors,
memory cells, and logic elements are made of molecules.
 Because single molecules constitute the smallest stable structures possible, this miniaturization is the
ultimate goal for shrinking electrical circuits.
 All modern fabrication of integrated circuits and electronic devices is possible due to advancements in
molecular electronics.
 The most successful commercial products in this field are organic devices, including organic
photovoltaic (PV) devices, organic light emitting displays, liquid crystal displays (LCD), organic
transistors, infrared imaging, and bio-sensors.

Goals of Molecular Electronics

 To miniaturize electronic devices  To reduce energy consumption
 To increase speed and efficiency  To create novel electronic devices
Some of the key materials used or studied in molecular electronics include:
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 behaviour 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.

By Prof. Shaludheen. S
6. Single-Molecule Junctions: The use of individual molecules as active components in electronic junctions
is a fundamental concept in molecular electronics.

Conducting Polymers: Introduction

 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 behaviour.
 A polymer which can conduct electricity is called conducting polymer
 Conductivity can be further increased by doping. Conductivities as high as 105 S/cm have been
observed for doped polymers
 Poly acetylene is the first conducting polymer synthesized. Poly aniline, Polypyrrole, Polythiophene
are examples of conducting polymers

Applications of Conducting Polymers

 Used in super capacitor, nano coating, biomedical etc
 Used as catalyst and biosensors

Classification of Conducting Polymers

By Prof. Shaludheen. S
Conjugated π-electron conducting polymers
 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 polymers

 Polymers with conjugated π-electrons in their back bone can be easily oxidized or reduced
resulting in the increase in their conductivity.
 Doping increases the conductivity by many orders of magnitude.
 Doped polymers have high electrical conductivities and are called as synthetic metals.
 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.
 The process of doping can be carried out by two methods: Negative and Positive doping.

Negative doping (n-doping) Positive doping (P-doping)

Negative doping is carried out by partial Positive doping is carried out by partial
reduction with electron donors. oxidation with electron acceptors.
In this process, the conducting polymer is In this process, the conducting polymer is
treated with a Lewis base (n-dopant) such as treated with a Lewis acid (p-dopant) such as
sodium naphthalide. I , Br , AlCl , AsF , etc.
2 2 3 5
This process reduces the polymers creating This process oxidises the polymers creating
negatively charged sites on polymer positively charged sites on polymer
backbone. backbone.

Polarons, Bipolarons and Solitons

As a result of the doping process, charged defects, such as polarons, bipolarons and solitons, are
introduced into the polymer structure. These defects then play the role of charge carriers.
By Prof. Shaludheen. S
  At first, the addition/removal of electrons facilitates the creation of a radical anion/cation (i.e.
polaron).
 Further addition/removal of another electron results in the formation of a dianion/dication (i.e.
bipolaron).
 Solitons are formed when bipolarons further lower their energy state.

Extrinsically conducting polymers

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 like carbon black,
metallic fibires, metal oxides etc. 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 processable 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.

Applications of conducting polymers

Conducting polymers are widely used:
 In rechargeable batteries.
 In making analytical sensors for pH, O2, SO2 , NH3 , glucose, etc.
 In the preparation of ion exchangers.
 In controlled release of drugs.
 In optical filters.
 In photo voltaic devices.
 In telecommunication systems.
 In micro-electronic devices.

By Prof. Shaludheen. S
  In bio-medical applications
ORGANIC LIGHT EMITTING DIODE (OLED)
 OLED is an advanced form of LED lighting, made from conducting polymers and are thin, light
weight and flexible
 It is a solid state device composed of thin films of organic
molecules
 OLED can provide very bright display with power
consumption lesser than the conventional LED.
Construction
o Substrate
o Anode
o A hole transport layer (HTL)/Conductive layer
o An electron transport layer (ETL)/Emissive layer
o A metallic cathode

 Substrate (clear plastic, glass, foil): The substrate supports the OLED

 Anode (should be transparent): The anode removes electrons from the conductive layer (adds
electron holes) when a current flows through the device. Usually indium tin oxide is used as anode

 Conductive layers: These layers are made up of organic molecules (polymer) that transport "holes”
from the anode. One conducting polymer used in OLEDs is polyaniline.

 Emissive layer: This layer is made of organic molecules (different polymer from the conducting
layer) that transport electrons from the cathode; this is where light is made on combining electrons
and holes. One polymer used in the emissive layer is polyfluorene

 Cathode (may or may not be transparent depending on the type of OLED): The cathode injects
electrons when a current flows through the device. Usually metals like calcium and aluminium are
used

Working
OLEDs emit light in a similar manner to LEDs through a process called electrophosphorescence
The process is as follows:
 Potential difference is applied to the two electrodes.
 The cathode supplies electrons to the emissive layer, while the anode creates electron holes in the
conductive layer.
 At the boundary between these layers, electrons combine with the holes.
 When this recombination occurs, energy is released as light (photons).
 The colour of light depends on the type of organic molecules in the emissive layer.
 The brightness of light depends on the amount of electric current applied. More current produces
brighter light

Advantages
 The OLEDs are flexible and hence it is very easy to manufacture OLED displays or other OLED
devices such as mobile phones, cameras, wearable devices etc.
By Prof. Shaludheen. S
  OLED consumes less power and are suitable for devices requiring less power consumption such as
android phones, portable gaming consoles, media players, digital cameras etc.
 It provides remarkable colour reliability, high efficiency and operational stability.
 They are very thin and small in size and hence are light in weight.
 OLEDs have large fields of view, about 170 degrees.
 OLEDs are easier to produce and can be made to larger sizes. Because OLEDs are essentially
plastics, they can be made into large, thin sheets.
Disadvantages
 Lifetime - While red and green OLED films have longer lifetimes (46,000 to 230,000 hours), blue
organics currently have much shorter lifetimes (up to around 14,000 hours)
 Manufacturing - Manufacturing processes are expensive right now.
 Water - Water can easily damage OLEDs.
 OLED screens are even worse compare to LCD when subjected to direct sunlight

PHOTORESISTS
Photoresists are light-sensitive materials used in the photolithography process to transfer circuit
patterns, such as those for semiconductors, on a silicon wafer. The photoresist material undergoes changes
in its chemical and physical properties when exposed to light, allowing for the creation of intricate patterns
on the surface of the substrate.
Conductive polymers, like PEDOT:PSS or polyaniline (PANI), are being explored as photoresists
for applications like 3D printing of conductive microstructures or creating patterned conductive layers

Composition:
Photoresist consists of:
1. Photoactive (light sensitive) compound
(PAC) : This is the material that reacts to
light, typically ultraviolet (UV) light
2. Alkaline-soluble resin: This provides the
main structure of the photoresist and helps
in forming patterns during processing.
3. Solvents: These control the viscosity and
other properties, allowing the photoresist to
be applied evenly on surfaces.

There are two main types of photoresists: positive and negative

Positive Photoresist Negative Photoresist
When exposed to UV light through a mask, When exposed to UV light through a mask,
the exposed areas of the positive photoresist the unexposed areas of the negative
become soluble, while the unexposed areas photoresist become soluble, while the
remain insoluble. exposed areas remain insoluble.
The soluble areas are then removed during The soluble areas are then removed during
the development process, leaving behind the the development process, leaving behind the
desired pattern on the substrate. desired pattern on the substrate.
The parts of the positive photoresists become The parts of the negative photoresists
soluble in a developer solution when exposed become insoluble in a developer solution
to light. when exposed to light.
Composed of a photosensitive compound, a Composed of a photosensitive compound, a
resin, and a solvent resin, and a solvent

By Prof. Shaludheen. S
 The choice between positive and negative photoresists depends on the specific requirements of the
semiconductor fabrication process. Positive photoresists are more commonly used.

Introduction to molecular devices based on conducting polymers

1. Biosensor based on conduction polymers

Biosensors (Biological sensor) are devices used to detect the presence or

concentration of a biological analyte, such as a biomolecule, a biological structure,
chemicals or a microorganism.
Conducting polymers have been widely applied to fabricate electrochemical
biosensors, because of their interesting and tunable chemical, electrical, and structural properties.
Common conducting polymers used in biosensors include polypyrrole (PPy), polythiophene (PTh),
and polyaniline (PANI).
Bioreceptor

Biosensors consist of three parts:

(i) Biorecognition element (Bioreceptor):

 A component that recognizes the analyte.
 Enzymes, Antibodies, nucleic acids, microorganisms can be recognition component
(bioreceptor).
 It differentiates the target molecules in the presence of various chemicals.
 It is in intimate contact with a transducer
(ii) A signal transducer: The biological interaction between the analyte and the bioreceptor is then
converted into a measurable signal by the transducer.
(iii) A reader device: A signal processing system that converts the signal into a readable form
By Prof. Shaludheen. S
Working
 In a conducting polymer based electrochemical biosensor, the recognition element is immobilized on
the conducting polymer electrode.
 This immobilization can be achieved through physical adsorption, covalent bonding, or other
techniques.
 When the biosensor comes into contact with the target analyte, the biological recognition element
selectively interacts with the analyte molecules.
 This interaction induces a change in the electrical properties of the conducting polymer.
 The change in the electrical properties of the conducting polymer is transduced into an electrical signal
through an electrochemical process.
 This can involve changes in conductivity, impedance, or redox reactions.
 The electrical signal is measured using appropriate instrumentation, such as a potentiostat, and the
signal is correlated with the concentration of the target analyte.

Advantages of conduction polymer based electrochemical biosensors

1. Biocompatibility: Conducting polymers are often biocompatible, making them suitable for interfacing
with biological molecules
2. Conductivity: the inherent conductivity of conducting polymers facilitates the direct transduction of
signals without the need for additional mediators
3. Ease of modification: Conducting polymers can be easily modified allowing for the immobilization of
various biological recognition elements.
4. Sensitivity and selectivity: The combination of the conducting polymer with specific biological
recognition element enables high sensitivity and selectivity for the target analytes.

Applications
 For detecting diseases like diabetes, infections, and cancer etc.
 To detect pollutants or toxins in water, air, or soil.
 For detecting contaminants like pathogens or allergens in food products.
 Monitoring biochemical processes in production or quality control.

2. Field-effect transistor based on conducting polymers

A Field-Effect Transistor, commonly known as FET, is a three-terminal semiconductor device that
utilizes an electric field to control the flow of current within the circuit

FETs have three terminals: the source (S), the drain (D) and the gate (G). It operates based on the modulation of the
conductivity between its source and drain terminals, induced by an electric field applied to the gate terminal. Common
conducting polymers used in FET include polythiophene, polypyrrole, and poly(3-hexylthiophene) (P3HT).

Uses: They do essential jobs like making signals louder, turning things on and off, and controlling voltage.
The path through which the electric current flows in the semiconductor can be either P-type or N-type.
This distinction leads to two categories of FETs: P-Channel and N-Channel FETs.

By Prof. Shaludheen. S
Working of field-effect transistor based on conducting polymers
 When we apply a voltage to the gate, it creates an electric field that either attracts or repels the charge carriers
(electrons or holes) in the conducting polymer channel region. This controls the flow of current between the
source and drain terminals.
 Depending on the type of conducting polymer, the applied gate voltage can either enhance or deplete the
charge carriers in the semiconductor channel.
 For example, in p-type conducting polymers, a positive gate voltage can deplete holes, while in n-type
conducting polymers; a negative gate voltage can deplete electrons.

 The modulation of charge carriers in the channel affects the current flow between the source and drain
electrodes.

Applications
 Flexible Electronics: Conducting polymer-based FETs are attractive for flexible and stretchable electronic
applications due to the inherent flexibility of the polymer materials.
 Low-Cost Electronics: The solution-processability of conducting polymers allows for cost-effective
manufacturing processes, potentially enabling the production of low-cost electronic devices.
Challenges
 Performance: Compared to traditional semiconductors conductive polymers have lower electronic
performance (mobility, on/off ratio).
 Stability: Stability issues, including degradation over time due to environmental factors, which reduces their
lifespan.

By Prof. Shaludheen. S
SYNTHESIS OF CONDUCTING POLYMER
Conducting polymers were synthesized using various methods, including
 Chemical oxidation
 Electrochemical polymerization
 Vapor phase synthesis
 Hydrothermal
 Solvothermal
 Template-assisted
 Electrospinning
 Photochemical methods
 Plasma polymerization.

“Chemical oxidation and electrochemical polymerization methods are mostly used”

Chemical method
 Conducting polymers have been chemically synthesized through the oxidation of monomers and
polymerization of corresponding monomers.
 One of its advantages is the chance of mass production at a reasonable price.

Electrochemical method
 Electrochemical synthesis is simple, cost-effective, can be performed in a single section glass cell,
reproducible and the fabricated films have required thickness and uniformity.
 The most widespread electrochemical technique is anodic oxidation of appropriate electroactive
functional monomers.

By Prof. Shaludheen. S