ENGINEERING MATERIALS

COURSE CODE : 16EM42B

UNIT-IV
Organic Electronic Materials:
• Conducting Polymers
• Semiconducting Organic Materials
• Organic Superconductors
• Organic Piezoelectric Materials.

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 Conducting Polymers - Advantages
Combination of properties

Metals Plastics
High conductivity Light-weight
Ease of processing (spin coating)
Low cost
Corrosion resistance
Flexibility, chemical inertness

Applications: Sensors, Battery Electrodes, Screening materials,

displays and solar cells
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 Conducting Organic Materials :
• Organic Materials that can conduct electricity with conductivity
range from 10-16 to 105 S/cm.
• Conducting Polymers can be largely classified in two categories
• Conducting polymeric composites
It comprises of :-
• Matrix - insulator material;
• Reinforcement - conducting materials ( in the form of particles,
fibers or whiskers) such as metallic powder, carbon black and
carbide.
• Intrinsically conducting polymers
• Chemical structure of this polymers are responsible for conducting
mechanism .
• Conductivity can be tuned from insulating state to superconducting
state by chemical modification or by changing the degree and
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nature of doping.
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 Two types of conducting organic materials

Conducting polymeric Intrinsically conducting

composites polymers

HOMO: Highest Occupied Molecular Orbital

- Similar to valance band of inorganic semiconductor
- It is the highest energy that could act as an electron donor in organic
semiconductors.

LUMO- Lowest Unoccupied Molecular Orbital

- Similar to conduction band of inorganic semiconductor
- It is the lowest energy that could act as an electron accepter in
organic semiconductors.

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How the conjugated organic polymer is
converted into a conducting polymer ?
A full orbital can not conduct electrons,
so to get a conjugated material to conduct, we must add or
remove charges (doping process)

Two options:
 Remove electrons from the HOMO (create holes)
 Add electrons to LUMO

- Chemically (oxidizing/reducing agents) or electrochemically

(applied potential)

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 Conducting mechanism of conjugated
polymers
• C.Polymers have -bonds and -bonds.

• -bonds are fixed and immobile due to covalent bonds

between the carbon atoms.

• -electrons are relatively localized and responsible for unusual

electronic properties.

• C.polymers have alternating single and double bonds along

the polymer chain.

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 Two conditions to become conductive
1. The first condition for this is that the polymer consists of
alternating single and double bonds, called conjugated double
bonds.

In conjugation, the bonds between the carbon atoms are alternately

single and double. Every bond contains a localised “sigma” (σ)
bond which forms a strong chemical bond. In addition, every
double bond also contains a less strongly localised “pi” (π) bond
which is weaker.

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2. The second condition is that the plastic has to be disturbed - either
by removing electrons from (oxidation) or inserting them into
(reduction), the material. The process is known as Doping.

1-oxidation (loss) with halogen (or p-doping).

CH n   I  CH n   I 3
3x
2

2- Reduction (Gain) with alkali metal (called n-doping).

CHn   xNa  CHn  x

 xNa 

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 Charge Carriers
• Negative/ positive Soliton/radical ion.
• Negative/ positive Polaron
• Negative/ positive Bipolaron

• Charge sustained on the unsatisfied bonds can be moved on the

molecule by an electric field.

• Doping process which might oxidizes or reduce one of the bonds

along the chain, creating electron donor or acceptor.

• Addition of charge creates new and unfilled electronic energy

states that lie within the original HOMO-LUMO energy gap.

• The charges can be transported via polarons, bipolarons or

excitons.
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• Polarons : A species comprises of both the electron or hole and the
structural deformation of the lattice around it.

• Excitons : where positively and negatively charged polarons attract

each other and form an electrically neutral energy carrier

• Bipolarons : A stable combination of two nearby polarons with a

lower energy state.

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• The halogen doping transforms polyacetylene to a good conductor.

• Oxidation with iodine causes the electrons to be jerked out of the

polymer, leaving "holes" in the form of positive charges that can
move along the chain.

• The iodine molecule attracts an electron from the polyacetylene

chain and becomes I3ֿ. The polyacetylene molecule, now positively
charged, is termed a radical cation, or polaron.
• The lonely electron of the double bond, from which an electron
was removed, can move easily. As a consequence, the double
bond successively moves along the molecule.

• The positive charge, on the other hand, is fixed by electrostatic

attraction to the iodide ion, which does not move so readily.
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 Factors that affect the conductivity
• Density of charge carriers
• Mobility
• Polaron length
• Conjugation length
• Overall chain length
• Charge transfer to adjacent molecules

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 Synthesis of Conducting polymers

Chemical Electrochemical
Chemical Method: Condensation Polymerization

Electrochemical synthesis:
- Used when the monomer can be oxidized in the presence of a
potential to form reactive radical ion intermediates for
polymerization.

- High quality Films.

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 Electrochemical polymerization
(1) Constant current or galvanostatic
(2) Constant potential or potentiostatic
(3) Potential scanning/ cycling methods in a standard three
electrode cell.

The most commonly used anodes are gold (Au), chromium

(Cr) , nickel (Ni), palladium (Pd), platinum (Pt), titanium
(Ti), and conducting (indium tin oxide coated) glass slides,
cadmium sulphide (CdS), and graphite.

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 Characterization of conducting polymers
1. Charge transfer mechanism
Cyclic voltammetry (CV) provides basic information on
- The oxidation potential of the monomers,
- Film growth the redox behavior of the polymer
- The surface concentration.
Cyclic voltammograms are very useful for
- analysis of charge transfer rate,
- charge transport process and
- for unveiling the complex interactions that occur within
polymer segments, at specific sites, and between ions and
solvent molecules.
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Chronoamperometry is commonly used to
- Determine the charge transport diffusion coefficient
- To study phase formation, phase transitions and relaxation.
- It can determine the total charge consumed.

Electrochemical impedance spectroscopy (EIS) represents

another powerful tool for investigating charge transfer rate and
charge transport process in films and membranes.

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 2. Chemical Species Analysis

• Spectroscopic techniques: UV-Vis, Fourier transform infrared

(FTIR) and Raman spectroscopy;
- With electrochemical methods to monitor the chemical changes
occurring in the surface film.

• Electron spin resonance spectroscopy (ESR):

- Used to investigate the nature of charged defects formed upon
doping of conducting polymers
- Characterizing radicals and radical cations produced by oxidation
or reduction during eletropolymerization.

3. Crystal structure
• X-ray diffraction (XRD), X-Ray absorption near edge structure
(XANES), and extended X-ray absorption fine structure (EXAFS)
techniques.
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4. Surface morphology

• SEM ( Scanning electron microscope ) - most frequently used

technique for acquisition of high resolution images of the surface
morphology of polymers.

• STM/AFM – 3-D, atomic scale images can be obtained.

STM can be applied even under wet conditions, i.e. both the probe tip
and the sample immersed in the electrolyte.

5. Composition
• Non-Destructive X-ray photoelectron spectroscopy (XPS) is
frequently used to obtain atomic information on the surface
composition of conducting polymers.

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 n- type organic Materials
• To carry electrons easily the conjugated carbon backbone needs to
be electron deficient, i.e. has a high electron affinity.

• Typical Examples :
NTCDA – Naphthalene tetracarboxylic dianhydride
PTCDA – Perylene tetracarboxylic dianhydrie
PTCDI - Perylene tetracarboxylic diimide

• These materials exhibits relatively low mobility.

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 n-type organic semiconductors Discussions
materials
3', 4' - dibutyl-5 High mobility - 0.2 cm2/V-s
5''-bis(dicyanomethylene) -5
5''- dihydro-2,2':5'
2''-terthiophene (DCMT)
Polyacetylene (PA) - n-doped via ion implantation of Li+ at
low levels ( 1017 /cm3)
Problem : Doping ions are mobile when
external electric field is applied, hence
not compatible with device operation.
F16CuPc Addition of strong electron withdrawing
Copper hexadecafluorophthalocyanine groups, -F, -CN, -Cl
Mobiliy- 0.03 - 0.2 cm2/V-s
C36F26 ( Perfluorocarbons) Efficient n-type organic polymers
C22F14 (Perfluoropentacene)
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 Difficulties in development of high performance
n-type organic Semiconductors

1. Under operating conditions they have low stability and high

sensitivity to oxygen and moisture due to the organic anions
and carbonions.

2. Their rapid degradation in mobility and on/off ratio,

although improved oxidative stability and mobility had been
reported.

On off ratio: ratio of currents in the on- and off- state

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 p- type organic Materials
• Pentacene
• Oligomers
• phthalocyanine

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 Pentacene
• Pentacene is a polycyclic aromatic compound with five condensed
benzene rings.

• High thin film transistor hole mobility ( > 1 cm2/V-s).

• Vapor deposited pentacene TFTs claimed exceptional mobilities

ranging from 2-5 cm2/V-s.

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Major problems during processing of Pentacene

• Instablility in air

• Low solubility in organic solvents

• Oxidation disrupts transport and crystallization in

devices.

• Pentacene can condense into two closely related but

not perfectly matched crystal phases, leading to
polymorphic crystal growth, mismatched grains
resulting in decreased device performance.
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 Development of Soluble pentacene precursors
• The precursor was cast into thin films from a solution of methylene
chloride or toulene.

• Well packed pentacene films on exposure to heat (approx. 140▫ C).

Result is ---- TFT mobility  0.1-0.2 cm2/V.s, lower than

through vapor deposition routes.

• Enhanced mobility could be achieved by

 Chemical modification of substrate
 By optimization of the processing and conversion conditions of
the precursor.

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 Method-2
• Development of functionalized pentacene.

• To synthesize heterocyclic analogs fused with thiophene

rings allow greater intra- and inter- molecular overlap
between the pi-conjugated units.
Results in  single crystal phase.

• Example - TIPS pentacene, which is light enough to be

purified and deposited using vaccum sublimation.

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 Oligomers
• Oligomers contains conjugated oligothiophene and polymers.
• Good solubility and can be easily purified.
• They form polycrstalline thin films.
• Several end group substitutions, such as long alkyl n-hexyl chains,
have been developed to improve the film self-organization
(ordering and stacking).
• A carrier mobility of 1.1 cm2/V.s had been reported for alkyl
substituted oligothiophene.
• Mobility can be improved by using high temperatures for film
deposition.

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 phthalocyanine
• Cu-phtalocyanine mobility 0.02 cm2/V.s in a p-channel FET.
• Fused aromatic compounds, such as
Dihydrodiazapentacene mobility 0.006 cm2/V.s
Bisdithienothiophene mobility 0.05 cm2/V.s
diphenylbenzo-dichalcogenophenes mobility 0.17 cm2/V.s
dibenzothienobisbenzodithiophene mobility 0.2 cm2/V.s

• Excellent thermal and chemical stability.

• Devices derived based on them are stable in air for months.
• They also show excellent photoelectric characteristics, therefore
have been widely used as solar cells, optical limiters and
photoconductors.
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 Ambipolar Organic Materials
• Organic semiconductors can be both p-type and n-type

• No particular properties favouring electrons or holes

• When incorporated in a transistor design, the charge

carrier type will be determined at the interface between
the semiconductor and the metal electrode injecting the
charge.

• For example, aluminium chlorophthalocyanine (AlPcCl)

is usually regarded as a p-type semiconductor ,

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• AlPcCl deposited on a gate insulator with thin gold electrodes was
subject to annealing at 150 oC.

• A layer of electric dipoles was formed at the interface between the

gold and A1PcC1. This changed the alignment of electronic states
so that the sample switched to n-type behaviour.

• Pristine pentacene could also have ambipolar behaviour.

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 Field Effect Transistor

 An organic semiconductor deposited onto a dielectric (e.g. SiO2)

 Gate electrode for conductivity control.
 This device operates in an enhancement mode, i.e., the conductivity
in increased by the applied bias in the device.

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• One of the performance parameter mobility.
• The charge carriers mobilities in these FETs are found to be lower
than that of the inorganic semiconductor devices.

• The primary reason for this is  the lack of well-organized

crystals.

• Consequently, carrier mobilities remain very low and limited by

inter-chain hopping rather than intra-chain transport.

• To achieve high carrier mobilities, highly organized molecular or

polymeric layers are necessary

• Higher levels of crystallinity assist such transfer.

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• Carrier mobilities in organic TFTs exceeding 2 cm2/V.s with
on/off current ratios in excess of 108 have been achieved.

• Semiconducting polymer-based FETs are much cheaper than

Si based devices.

• The possibility of making flexible and flat panels open a new

area of large-area cost-effective plastic electronics if the slow
response and limited lifetime can be significantly improved.

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 Organic Light Emitting Diode
• Electroluminescence (EL) in organic semiconductor was
discovered in 1990 in PPV (poly phenylenevinylene), which
has a bright yellow colour owing to the onset of absorption
around 517nm,
– corresponding to HOMO-LUMO energy gap of 2.5 eV.

• Electroluminescence has also been reported from poly

(pphenylene), polyfluorene(PFO, blue light: 380-420
nm) and P3AT.

• The emission wavelength of organic semiconductors

can be tuned in whole visible region (380-700 nm)
through chemical modification.

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• For example, copolymer engineering can be used to tune the
emission wavelength in PFO-related materials.

• Copolymerization with PPV-like unit  red emission

• Copolymerization with benzothiadiazole (BT) units green

emissions
Advantages
• Their low operating voltage
• low material cost
• high flexibility
• Easy processing
• possibility of fabricating large area display devices

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 Organic Light Emitting Diode

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 Efficiency of OLED

 =  x rst x q x coupling
•  - charge balance,
• rst - ratio of singlets to triplets
• q - photoluminescent quantum efficiency
• coupling - optical output coupling efficiency

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To improve the OLED efficiency
1. The number of electrons and holes injected into the device should
be balanced and their recombination probability optimized.

2. The triplet states in OLED devices are non-radiative. Development

of new phosphorescent materials has enabled the triplet lifetime to
be reduced significantly.

3. The photoluminescence quantum efficiency, the ratio between

radiative and non-radiative decay processes should be
maximized by controlling metal diffusions.

4. The output coupling should be increased by increasing the surface

roughness of the substrate-air interface; by optimizing geometry
of the surface to reduce the total internal reflection and to enhance
surface emission; by two-dimensional patterning and formation of
photonic crystals.
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 Organic Super Conductors
1-D super conductors

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 2- D super conductors
• Superconductivity exhibited in two dimensions was first realized
in charge transfer salts based on bis (ethylenedithio) tetrathiafulvalene
(BEDT-TTF), a quasi-two dimensional electron donor molecule.
• In this system, half of eight sulfur atoms are located at the periphery
of the donor molecule, leading to a better orbital overlap.
• This overlapping of molecular orbitals leads to the formation of broad
electron energy bands in the crystal.
•

Fig: Chemical Structure of BEDT-TTF

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• A variety of electron acceptors used in 2-D SC

linear, tetrahedral and polymeric anions, with remarkably

different compositions.
However, superconductivity only occurs when certain
anions have been employed, e.g., centrosymmetric anions.

• Other 2-D superconductors:

 BEDO-TTF[(bisethylenedioxy)]tetrathiafulvalene].
DODHT[(1,4-dioxane 2,diyldithio)dihydrotetrathiafulvalene].

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 Organic piezoelectric
materials
• Piezoelectric Material will generate
electric potential when subjected to
some kind of mechanical stress.

• If the piezoelectric material is

exposed to an electric field
(voltage) it consequently lengthens
or shortens proportional to the
voltage.

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• Polyvinylidene fluoride, polyvinylidene difluoride or simply PVDF
is a chemically stable synthesized by the polymerization of
vinylidene difluoride.

• As early as 1969 Kawai discovered the piezoelectric effect of

PVDF and first measured its g31 and d31 coefficients, which were
at least one order of magnitude greater than those of other
polymers.

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5-distinct crystalline phases: α, β, γ, δ and ε.
Different phases are related to different chain conformations:
TTT (all trans) planar zigzag for the β-phase,
TGTG’ (trans-gauche-trans-gauche) for the α and δ phases and
T3GT3G’ for γ and ε phases

The β-phase highest dipolar moment per unit cell

It is the one that gives the PVDF its piezoelectric properties.

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• The stretching mechanism is of particular interest.
• In this kind of β-phase formation, the applied stress results in the
alignment of polymer chains into the crystals so that an all-trans
planar zigzag (TTT) conformation is inducted.

 Such mechanism allows the dipoles to align normal to the direction

of the applied stress.

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 Piezoelectric co-efficients (pC/N) at T=75-80oC
• For uniaxially stretched PVDF
• d31 = 16
• d32 = 3
• d33 = -20 - -23
• For biaxially stretched PVDF
• d31 = 5
• d32 = 5
• d33 = -20 - -25

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 Other piezoelectric polymers
• Polyvinylidene cyanide and its co-polymers
• Aromatic and aliphatic polyureas
• PVC, PVF, Nylon 11
• Aromatic polyamides
• Polyvinyl acetate
• PVDF coploymers with triflouroethylene (P[VDF-TrFE),
P[VDF-TFE]and hexafluoropropylene (P[VDF-HFP).
• PVDF blends with polymethyl methacrylate (PMMA)

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Advantages of organic piezoelectric materials
• Smaller acoustical impedance
• Low young’s modulus
• Large mechanical deflection
• Flexibility
• Ease of thin film fabrication
• Nearly perfect match with water and other liquids and human
body.

Applications: Sensor, actuator, cable, stress guage,

transducer hydrophone and various equipment parts for
medical applications.

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