Organic Electronics

(ELEC324)

Material and Electronic properties of

Organic semiconductors
 Recap from last lecture
 Introduction to Organic Electronics/Photonics

 Motivations
 Low cost and ease of device fabrication
 Flexible and light-weight applications
 Large area and high volume market
 Good emitters of light including white

 Current challenges/bottlenecks
 Low charge carrier mobility
 Degradation and low lifetime
 Parameter spreads
 Low resolution of the printing processes (to be discussed in later lecture)

 Research work within the group and globally

 Current and potential future applications

ELEC324 - [2018]
 Overview on today’s lecture
 Material Properties
 Intermolecular interactions via Van der Waals force
 Atomic bonding of Carbon
 Bonding of carbon with adjacent atoms

 Electronics Properties i.e. formation of energy levels

 Equivalent Conduction and Valence bands i.e. HUMO and LUMO levels

 Density of States in disordered Organic semiconductors

 Gaussian distribution (or an exponential approximate)
 Laplace distribution

ELEC324 - [2018]
 Properties of Organic materials
 Organic materials consist of mainly carbon and hydrogen atoms. The key
feature that allows such materials to posses conductive properties is attributed
to the presences of alternating single and double bonds between adjacent
carbon atoms, and conjugation of the carbon atom with adjacent atoms

 Consider the chemical structure of Polyacetylene below:

double bond Monomer unit - C2H2

single bond

Chemical structure of Polyacetylene

 Organic materials consists of repeated monomer units. E.g. monomer unit in

polyacetylene is C2H2, which repeats n times depending on its conjugation length.
Each unit is linked with adjacent unit by weak Van der Waal force
ELEC324 - [2018]
 Material properties of organic materials
 Van der Waals forces are weak interactions caused by momentary changes in
electron density in a molecule. They are the only attractive forces present in non-
polar compounds, and amongst the weakest of interaction between molecules,
compared to the dipole-dipole interaction and hydrogen bonding

 The strength of Van der Waals interaction between molecules depends on the
surface area of the molecule i.e. larger area results in stronger interactions

 Such intermolecular forces defines the molecule's boiling point, melting point and
solubility i.e. low intermolecular force results in low boiling/melting points

 Note compounds dissolve in solvents having similar kinds of intermolecular forces

‘like dissolves like’. For example many organic solvents are either non-polar i.e.
hexane or weakly polar i.e. diethyl ether

 There has been huge demand for development of organic materials with high
solubility in order to adopt low-cost deposition techniques such as printing and
spin-coating processes (discussed in later lecture)

ELEC324 - [2018]
 Carbon (building block) in ground state
 In order to understand conjugation in organics, we first need to consider the
atomic orbital of Carbon, which has an atomic number 6

 Atomic number, also known as proton number, is the number of protons found
in the nucleus. And in an atom of neutral charge, the atomic number is also equal
to the number of electrons around the nucleus. How are such ‘Fermions’ i.e.
electrons, protons and neutrons located?

 In atomic physics and quantum chemistry, the

distribution of electrons of an atom or molecule
in atomic or molecular orbitals is described by
the so-called Electronic configuration
i.e. in s-orbital, p-orbital, d-orbital and f-orbitals
which may be occupied by a maximum of 2, 6,
10 and 14 electrons respectively

 Also, Pauli’s exclusion principle defines the distribution of such fermions. The
principle states that such particles cannot be in the same location with the same
energy state at the same time i.e. two electrons going around the nucleus can
not be in the exact same state at the same time
ELEC324 - [2018]
 Carbon (building block) in ground state
 Using Pauli’s exclusion principle, the electronic configuration of carbon in
ground state can be presented as shown on the left-hand side

No of electrons

Coordinate

E.g. Shape of the s- and p-orbitals

 Each orbital holds two electrons of opposite spin. For carbon, two electrons of
opposite spin occupy the 1s orbital, and the next two occupy the 2s orbital, and the
remaining two electrons are distributed in the p-orbitals i.e. one in px and another in
py leaving pz empty. The shapes of respective orbitals are as shown above

 As there are two electrons in the p-orbitals with single electron, this suggests that
carbon is divalent rather than tetravalent as it normally exists. Why?
ELEC324 - [2018]
 Carbon in excited state
 Carbon is tetravalent rather than divalent as it usually exist in the excited state
where its energy is lower. In excited state, an electron from 2s orbital is promoted
to the empty 2pz orbital

 Subsequently, hybridisation or mixing of orbitals takes place so as to form

new hybrids and stable orbitals which form stronger overlaps

ELEC324 - [2018]
 Hybridisation of Orbitals
There are three types of hybridisations:
i. sp1 – occurs when one s-orbital mixes with one p-orbital i.e. pz to form a new sp-
hybrid orbital as shown in example below. Such new hybrid orbitals are stable and
form stronger overlaps with other orbitals as described in next slide

s-orbital p-orbital sp-hybrid orbital

Example of the hybridisation of one s and one p orbitals i.e. sp1

ii. sp2 – occurs when one s-orbital mixes with the two p-orbitals i.e. py and pz to
form two new sp2 hybrid orbitals

iii. sp3 - occurs when one s-orbital mixes with all the three p-orbitals i.e. px, py and
pz, which results in formation of three new sp3 hybrid orbitals

ELEC324 - [2018]
 sp2 Hybridisation of orbitals
 For carbon, sp2 hybridsation commonly occurs where 2s orbital mixes with the
2px and 2py orbitals resulting in three sp2 hybrid orbitals. Note in this case, the
2pz orbital remains unhybridised (darker grey shading in diagram below)

Hybridised
orbitals

Unhybridised orbital

 New sp2 hybrid orbitals lie equidistant from each other at 120o in the x-direction
whilst the pz unhybrid orbital lie perpendicular in z-direction to the hybrid orbitals

 Subsequently, such orbitals can then overlap with orbitals of other atoms to form
either a strong sigma () or weak pi () bonds. Note hybrid orbtials form  whilst
unhybrid orbitals form  bonds
ELEC324 - [2018]
 Bonding of Carbon atoms
 Consider two atoms of carbon where adjacent unhybridised pz-orbitals overlap either
constructively or destructively to form  -bonds, resulting in discrete energy levels
compromising of the so-called Highest occupied molecular orbital (HOMO) and
Lowest unoccupied molecular orbital (LUMO) or the  - * respectively. Such overlap
of unhybridised pz orbitals between adjacent carbon atoms is known as Conjugation

Unhybrid p-orbitals No electrons * energy

overlap to form  -bond level

Two electrons of
C1 C2 opposite spin in 

Three hybrid orbitals lie at Adjacent sp2 hybrid orbitals

120o from each other overlap to form  -bond

C1 Bonding between C2
Source: http://www.orgworld.de/ two carbons

Energy structure of the two Carbon

ELEC324 - [2018]
 Bonding in Small molecules
 In single monomer unit, such as Benzene ring shown below, from a class of
aromatic hydrocarbon, the number of carbon atoms is small i.e. 6. Subsequently
there are 6 electrons in the pz orbitals which are delocalised

 Other atoms i.e. hydrogen, can bond

with the hybrid orbitals to form 
bonds, whilst the unhybrid pz orbitals
overlap to form respective LUMO and
HOMO energy levels

 Each of the monomer unit or benzene

ring can be attached to form small
molecule. E.g. Pentacene, comprises
of 6 benzene rings as shown below
Energy structure of benzene

ELEC324 - [2018]
 Bonding in Conjugated polymer
 Conjugated polymers, such as Poly(p-phenylene) (PPV) shown below, consists
of a rigid rod host polymer with much higher number of carbon atoms. In the
example below, the monomer unit consists of 8 electrons in the pz orbitals
however this is a multiple n depending on the number of repeated monomer unit

 Increase in number of carbon results

in more pz orbitals, which increases
the overlapping of such orbitals and
formation of equivalent bands such
as conduction and valence bands

 In organics, such bands are known as:

i. Highest Occupied Molecular Orbital
(HOMO) or -band
(similar to valence band in silicon)
i. Lowest Unoccupied Molecular
Orbital (LUMO) or *-band
Energy structure of conjugated
(similar to conduction bands in silicon) polymer PPV

ELEC324 - [2018]
 Energy Bands
 Below shows an example of another conjugated polymer, Polythiophene. As the
number of repeated monomer units increases, equivalent energy bands are formed

E.g. Chemical structure of

Polythiophene with ‘n’ number of
repeated units

 LUMO (*) and HOMO () are equivalent to conduction and valence band in
inorganic semiconductors but with much narrower widths

 Energy gap between LUMO and HOMO is considered the band gap (Eg) with
typical values ranging between 1.8 – 2 eV (note in silicon Eg = 1.166 eV)
ELEC324 - [2018]
 Density of States (DOS) Distributions
 In solid state, it is essential to determine the distribution of the carriers (i.e. holes
and/or electrons), with respect to energy within the different bands (i.e. LUMO
and HOMO)

 Quantum Mechanics allows the determination of the number of available states,

in cm3 per unit of energy, also known as the Density of States (DOS), within the
LUMO and HOMO levels

 In organics, the DOS function which describes the number of states per energy
interval at a given energy level, can be given by either of the following functions,
as discussed in the next slides:
i. Gaussian distribution (or exponential approximate)
ii. Laplace distribution

 Note for amorphous silicon, the DOS is also described by an exponential function
whilst for crystalline silicon, the DOS is described by a parabolic function

ELEC324 - [2018]
 i. Gaussian Distribution for DOS (intrinsic)
 Density of states N(E) in disordered organic
semiconductor consists of discrete levels,
commonly described by a Gaussian1-2 distribution
with respect to energy E, in both HOMO and LUMO
levels (as shown in the diagram)

 Gaussian distribution describing the DOS has a
simple form of:

No  E 2 
N E 
Eg intrinsic states
exp  2 
2   2 

height of the peak width of the ‘bell’

where No is the total DOS,  is the variance or the width

of the DOS and E is the energy interval

 Within the Gaussian, the DOS states increases

rapidly with energy to a peak value and thereafter
decreases
ELEC324 - [2018]
 i. Gaussian Distribution for DOS (extrinsic)
 Most organic semiconductors contain
‘residual dopants’ left behind after synthesis

 Such dopants introduce extrinsic states

electron energy
(either as donor or acceptor)

 Extrinsic states are assumed to be smaller

and lie at lower energy levels than the intrinsic states
intrinsic states. Carriers are able to move
extrinsic states
between the two states

 Mathematical solutions, particularly when

hole energy
determining the carrier concentration using
the Gaussian expression (as described later
involving integration) can be cumbersome

 Thus an exponential approximate at the

Gaussian tail is commonly adapted

ELEC324 - [2018]
 Exponential approximate at Gaussian tails
 Focusing on LUMO level only (note this applies to HOMO level too), the tail of the
Gaussian at low energies (where the conduction occurs) can be assumed to follow
an exponential3 function of the form:
not squared dependency on the energy

 E 
N '  E   N '  0  exp  
 C
kT

N‘(0) is effective rate of change of DOS at intrinsic level,

Tc characteristics temperature associated with width of the
distribution or slope of the exponential, and also gives
degree of disorder expressed in ‘Meyer-Neldel’ Energy4

 Here, Meyer-Neldel Energy given as kTC /q,

is a useful material and modelling parameter
for organics. The value of Tc varies depending
on nature of the disorder of the semiconductor

 It is essential to determine the energy ranges

at which exponential approximate is applicable
i.e. energy ranges where conduction occurs
ELEC324 - [2018]
 Exponential fits to the Gaussian
 Taking the logarithmic of the exponential function:

 E 
N '  E   N '  0  exp  
 C
kT

 Such that,
E
log e N '  E   log e N  0  
kTc

 In the above expression, a plot of logeN’(E) against E, has a slope of 1/kTc

 Assuming a typical value for TC we can fit these in the Gaussian function as in
the next slide

ELEC324 - [2018]
 Exponential fits to the Gaussian
 Exponential lines fit to the Gaussian function only at certain energies.
The slope of the fitted line corresponds to typical values of TC = 425k or MNE
(kTC /q) of 38 meV as observed in real devices. (Note for ordered silicon the
value of kT/q ~ 26 meV)

(Log scale)
Density of states, N(E)

Gaussian
distribution

exponential
fits

Energy, E
 As the fits are only applicable in smaller energy ranges, it is thus erroneous to
apply this approximation to devices that operate at high voltages such as diodes
ELEC324 - [2018]
 ii. Laplace Distribution for DOS
 Due to the limitation of fitting the exponential
over a wider energy range onto the Gaussian
distribution (L2), other distributions are thus
explored such as the Laplace (L1) distribution

 Laplace5 is a double exponential function which

has been used in a number of variants including
Maxwell-Boltzmann, Fermi-Dirac Statistics and
increasing in more recent developments of
physics, electronics and materials science intrinsic states

extrinsic states
 The Laplace distribution describing the DOS
can have a simple form:

N (0)  E 
N E
'
exp  
kTc  c
kT

ELEC324 - [2018]
 b. Laplace Distribution for DOS
 Better fits obtained to L1 rather than L2 for wider energy ranges, which
corresponds to applied voltages in devices
e.g. typical voltages in Schottky diodes is 5 V (in exponential region) and in TFTs is 1 V
(in sub-threshold). These regions correspond to exponential dependency of carrier
concentration with voltage

ELEC324 - [2018]
 Summary
 Conjugation or overlap of the unhybridised pz orbitals between carbon
atoms results in formation of equivalent energy bands i.e. HUMO and
LUMO

 Study of the DOS is crucial to understanding the conduction mechanisms in

disordered organic semiconductors

 TC is a key parameter related to the disordered nature of the materials and

also the width of the DOS functions

 TC is an important parameter in modeling of organic devices i.e. thin-film

transistors and Schottky diodes

ELEC324 - [2018]
 Revision Questions
1. Describe how organic materials can constitute to semiconducting properties

2. Describe what its meant by the density of states in organics

3. Describe the difference between the Gaussian and Laplace DOS

Next lecture
 Distribution functions i.e. how many states are filled with electrons

 Determination of the expression for the carrier (electron) concentration

 Transport mechanisms and Universal Mobility Law

ELEC324 - [2018]
 References
1. H. Bässler, Phys. Stat. Sol. (B), vol. 175, pp. 15, 1993
H. Bässler, Phil. Mag. B, vol. 50, pp. 347, 1984

2. Y. Roichman et. al., Physica Status Solidi A -Applied Research, vol. 201, pp. 1246, 2004

3. M. Vissenberg and M. Matters, Physical Review B, vol. 57, pp. 12964-12967, 1998

4. W. Meyer and H. Neldel, Z. Tech. Phys. (Leipzig), vol. 18, pp. 588, 1937

5. S. Kolt et. al., “The Laplace distribution & generalisations”, Birkhauser Bosont 2001.

ELEC324 - [2018]