Chapter 1

INTRODUCTION
Technological advancement is the need of the times. In the field of nanotechnology
implemented in electronics, the possible answer is printed electronics. Keeping in
mind, development in the future, it is important to research and implement new
methodologies to processing. This, if successful would bring about a great impact by
putting less stress on the environment, lower the cost of production and hence
bringing in a higher opportunity to touch lives.

In the last few decades, evolution in the field of electronics has been quite interesting
and rapid. Starting with the technology based on - wafers, hybrid and now printed. The
wafer technology is the traditional fabrication process in electronics making use of the
vacuum evaporation, lithography and other techniques adding up to high production
costs. The hybrid technology, used the traditional techniques with bar coating, inkjet
printing. And currently the fully printed fabrication processes are adopted. The main
advantages of low cost, usage on flexible substrates, enabling large surface area are
very attractive. Solution processable materials such as semi conductors, dielectric are
used; this brings in a possibility for faster and easier production. Hence, carbon
materials like carbon nanotubes, graphene having excellent properties of conductivity,
charge transport have attained great attention in this field. Carbon nanotubes, with its
advantage of solution processibility along with superior properties with respect to
mechanical strength, conductivity, band gap tunability.

With my work based on carbon nanotube field effect transistors, I put an effort to
fabricate and optimize carbon nanotube field effect transistors on plastics. A good
performance of the devices would lead to their application in display electronics and
sensing systems.

This section gives a detail look on carbon nanotubes, printed electronics and field
effect transistors. Types of Inkjet printing technologies are briefly described.

1.1 Carbon Nanotubes

The history of carbon nanotubes goes back farther than most people think.
In fact, a US patent was given to two British men in 1889, on the production of carbon
nanotubes utilizing marsh gas, otherwise known as methane. The method employed is
essentially the same as used today. The patent describes the production of “hair-like
carbon filaments” for electrical lighting. This patent also described about some of the
unique electrical and mechanical properties, “Carbon filament may be bent and twisted
into various shapes and will spring back to their original form on being released.”[1]

In 1960’s a group at National Carbon Company in Parma, Ohio and later

in the 1970’s at and the University of Canterbury in Christchurch, New Zealand,
helped
to characterize the carbon nanotubes.
Later in 1983, a company called Hyperion Catalysis perfected ways to produce
nanotubes and began incorporating them into fuel line for cars. The nanotube’s high
conductivity would dissipate any electrical charge that could potential build up and
spark. Today, 60 percent of the cars on the road use Hyperion’s nanotube incorporated
fuel lines. Hyperion’s nanotubes are also incorporated into plastic wing panels. This
allows the plastic on the wing to be grounded and then sprayed with paint droplets that
are charged up to 20,000 volts. The drops are attracted to the wing and stick, thus
reducing the wasted paint that would normally mist away in the air.

The real research and work with carbon nanotubes began in 1991, when Sumino
Limijima and his colleagues created some nanotubes at the research laboratory of the
electronics multinational NEC in Tsukulba, Japan[2]. Here they used, high-resolution
transmission electron microscopy to observe carbon nanotubes, that the field really
started to take off.

Researchers at the Institute of Chemical Physics in Moscow independently discovered

carbon nanotubes and nanotube bundles at about the same time, but these generally
had a much smaller length-to-diameter ratio. The shape of these nanotubes led the
Russian researchers to call them "barrelenes“.

1.1.1 Structure of Carbon Nanotubes

Carbon nanotubes are rolled up graphene layers, which are generally 0.2- 5 µm long
having diameters up to 1-2 nm. The honey comb sheets of carbon are rolled up into
cylinder. Multiwall carbon nanotubes and single wall nanotubes are the two different
types of nanotubes depending upon the rolling.

Figure 1.1: Types of Carbon nanotubes

The possible ways of rolling of the graphene layer gives different CNTs -Zig Zag,
chiral and arm chair. The characteristics of these CNTs are that they are metallic or
semi-conducting in nature depending upon their rolling up.

⃗⃗⃗⃗
𝐶h is a chiral vector which is related to the diameter of the tube.

A chiral vector ⃗⃗⃗⃗

𝐶h is defined as in terms of 𝑎1 and 𝑎2 , and is a linear combination.

⃗⃗⃗⃗
𝐶h = 𝑚1 𝑎1 + 𝑚2 𝑎2

𝑎1 and 𝑎2 are unit vectors which define the graphene lattice and θ is the angle
between one of the two unit vectors, either 𝑎1 or 𝑎2 and the chiral vector ⃗⃗⃗⃗
𝐶h .

Figure 1.2: Building of CNTs from graphene sheets, the primitive vectors and an
example of chiral vector and chiral angle.
Figure 1.3: Bravais Lattice graphene

Based on interpreted with the θ angle, which is the angle between the chiral vector,
carbon nanotubes can be classified into some specific structures.

Chiral : 0⁰<θ<30⁰

Zig-Zag : θ = 0⁰ or 60⁰

Arm chair : θ = 30⁰

Figure 1.4 : Different types of CNT: depending on the rolling.

From the study of band structure, we get to the conclusion that the zig-zag and the
chiral have 1/3rd metallic and 2/3rd semi conducting CNTs and for arm chair
confurigation all the CNTs are metallic in nature.

Hence in the device we can use only zig zag and chiral ones, as they can be used as
semi-conductors. Very high purity of semi-conducting carbon nanotubes must be used
for the active channel. This is important since, it affects the performance of carbon
nanotube transistors affecting the current ON/OFF ratio.

Sorting of carbon nanotubes is required. Many techniques are used in order to sort the
semi-conductor and the metallic tubes.

1.1.2 Synthesis and sorting of Carbon Nanotubes

By the different synthesis methods, the diameter of the SWNTs can be modulated;
consequently the band gaps and their conducting and metallic nature. HiPCo method,
High pressure carbon monoxide disproportionation process which uses of flowing CO
gas with Fe(CO)5 as catalyst produces SWNTs with diameter 0.7- 1.2 nm.

Another method the CoMoCAT method uses molybdenum and cobalt as catalysts
results into SWNTs with 0.8 nm, where as with the arc discharge method tubes of
diameter around 1.5 nm. This method uses high current to carbon rods. Another
technique called the laser ablation method too produces CNTs of diameter around 1.5
nm, using vaporization of carbon atoms from graphite target in an inert atmosphere by
a high power laser. It must be noted that just after their synthesis, SWCNTs have a
natural tendency to form bundles because of the Van der Waals’s forces between their
walls.

The methods that are used to separate metallic and semi conducting SWNTs are based
on the functionalization of the SWNTs walls. These processes can be divided into two
categories: covalent and non covalent functionalization.

Covalent functionalization is a technique which is used from 1998 and in order to

increase the solubility of SWNTs. This discrimination is based on the electronic
properties. This method affects the band gap converting the m-carbon nanotubes into
semi conducting ones. The disadvantage of this method is that it affects the charge
transport by introducing scattering sites for charge carriers.

The non covalent functionalization method which is widely used is using Sodium
dodecyl sulphate (SDS), sodium cholate, sodium dodecylbenzene sulphonate (SDBS),
and many other bile salts to disperse SWNTs in aqueous solution. The principle is
based on the hydrophobic group (tail) in contact with the nanotube and hydrophilic
group (head) in contact with the water. There is no efficient separation by these
surfactant-dispersed SWNTs, due to the interactive nature of the CNTs.

Density gradient ultracentrifugation (DGU) (see Figure 1.6a) is the first method which
showed the separation between semiconducting nanotubes and the metallic ones. [3]
This method used a mixture of two surfactants in different ratios. Next step was
ultracentrifugation in a density gradient medium, hence, the carbon nanotubes (CNTs)
were sorted based on the density difference and therefore by diameter and band gap . It
was quite interesting that this resulted in a multi-layer coloured solution, where
different colours corresponded to tubes of different band gaps. Repetition
centrifugation processes resulted in to SWNT fractions having a narrow distribution of
nanotube diameters. This is a very effective technique applied for commercial
purposes, separating both SWNTs produced Arc Discharge method with a high 99%
semiconducting and 98% metallic purity.

Gel chromatography is another method which is (Figure 1.6b) based on the specific
adsorption of SWNTs in an allyl dextran-based gel. The interaction of this gel media is
differently with s-SWNT and m-SWNT, such as van der Waals forces.[4] Different
interaction of the nanotubes with different curvature will have been given by different
surfactant coverage. Hence, by performing multicolumn gel chromatography, and

In different columns, by successively injecting SDS surfactant to the vertically stacked

column, SWNTs with different diameter and chiralities can be obtained . Using this
agarose gel technique, it is possible to obtain large-scale separation of SWNT, up to
the scale of liters.[8] This technique allows to obtain separation of SWNTs in large
scale up to litres.
Figure 1.5: (a) Density gradient ultracentrifugation (DGU),[40] (b) multicolumn gel
chromatography,[43] and (c)

Another technique obtained by Krupke et al. to discriminate metallic and

semiconducting SWNTs from a raw mixture using dielectrophoresis.[5] In this method,
an electric field gradient generated by a microelectrode array and placed on a SDS-
based SWNT dispersion. Hence, in this way the semiconducting SWNTs remain in a
stationary position, while the metallic tubes migrate towards the electrodes due to their
greater dipole moment and is collected [6]. For large scale separation of s-SWNTs,
agarose gel electrophoresis is used.

1.1.3 Polymer wrapping of Carbon Nanotubes

Polymer wrapping method uses molecules to wrap and select s-SWNTs. This method
was adopted from the interesting feature of DNAs is that their nucleobases have π
stacking interaction with the surface of the s-SWNTs, resulting in helical wrapping at
the surface of the tubes.
Figure 1.6: Showing the Carbon Nanotube wrapping with pits

The principle includes, that the conjugated back bone wraps up around the nanotube
wall, while the polymer chains which are hairy wraps the SWNTs wall with the Wan
der Waal’s interaction. Several simulations performed by Gao et al. give an indication
that the alkyl tails of neighbouring polymer chains zip and align around the nanotubes
due to the Wan der Waal’s interaction. Polyfluorene derivatives have an affinity
towards different chiralities and diameters of SWNTs. Literature shows that these
polymers in particular have selectivity towards CNTs produced by the HiPCo method
with larger diameter. Poly(9,9 didodecylfluorene-2,7-diyl-altanthracene-1,5-diyl)
(PF12-A) shows selectivity to nanotubes with larger diameter, and it is claimed that
this large diameter selectivity is due to the anthracene unit.[53] In contrast to other
fluorene copolymers, poly(9,9-dioctylfluorenyl-2,7-diyl and bipyridine) (PFO-BPy)
can extract almost single chirality small diameter nanotubes

(97% of (6,5)-SWNTs) using p-xylene as solvent.[54] This result opened the

opportunity

for extracting single chirality s-SWNTs using polymer wrapping.

Figure 1.7: wrapping orientation with different polymers

It has been reported by Bao et al demonstrating that poly thiopenes with long alkyl
chains have a good efficiency to disperse and separate carbon nanotubes. The best
polythiophene derivative they reported is regioregular poly(3-dodecylthiophene) (rr-
P3DDT).

Figure 1.8: Different polymers used for separation of semi conductivity CNTs from metallic
ones
1.1.4 Electronic properties of SWCNTs

Since, the SWNTs are rolled up graphene layers; hence their electronic properties of
SWNTs derive from the electronic configuration of graphene, in which the bonding π
orbitals form valence states and the anti-bonding π* orbitals form conduction states.

Figure 1.9: Graphene Band Structure

Figure 1.2a shows the band structure in the extended

first Brillouin zone of graphene. The unique electronic properties of SWNTs originate
from the quantum confinement of the electrons normal to the nanotube rolling axis.
The periodic boundary conditions around the nanotube circumference require that the
component of the momentum ( 𝑘 ⃗ ) along the circumference is quantized ( 𝐶 . ⃗⃗⃗⃗
𝑘⊥ = 2𝜋𝑗,
[11]
where j is a non-zero integer). This quantization leads to the formation of a set of
discrete sub-bands for each nanotube as described by the red parallel lines in Figure
1.2a. The crossing of these lines with the band structure of graphene determines the
electronic structure of the nanotube. If the lines pass through the Fermi point (K or
K’),
the nanotube is a metal (m-SWNT); otherwise the nanotube is a semiconductor
(s-SWNT).
The nature of the tube in terms of metallic or semiconducting behaviour is also
related to the values of the indices (n, m). When |n-m| = 3q (where q is an integer), the
nanotubes are metallic or semi-metallic. In any other case, they are semiconducting.
Theoretically, in an as-synthesized crude mixture of SWNTs there are approximately
one-third metallic/semi-metallic SWNTs and two-third semiconducting SWNTs
available.[12]
The transition energy (band-gap) of semiconducting nanotubes Eg can be described
by using a simple tight-binding model, given by the equation:

4ℏ𝜈𝑓
𝐸𝑔 = = 𝛾(2𝑅𝐶−𝐶 /𝑑𝐶𝑁𝑇 )
3𝑑𝐶𝑁𝑇

Where,
𝜈𝑓 is electron Fermi velocity
γ is the nearest neighbour interaction energy
𝑅𝐶−𝐶 is the nearest neighbour C-C distance and
𝑑𝐶𝑁𝑇 is the nanotube diameter.[13]

Their electronic states are organized in discrete bands, with a one-dimensional density
of
electronic (DOS) states known as van Hove singularities. Two examples of energy
diagram and DOS of m-SWNT and s-SWNT are presented in Figure 1.2b and c,
respectively. No real band gap is observed in the m-SWNT system.

1.1.5 Charge Transport in CNTs

Due to the confinement along the circumferential direction, SWCNTs are in the
class of the quantum mechanical systems. Thus the transport properties can be
described considering the model for 1D nanowires, with the lateral dimensions W,
[14] [15]
H much smaller than the length L (W, H « L). To understand the different
transport regimes, we define the important length scales that are involved in the
electron motion:
λF = 2π/KF , the Fermi wavelength, which is the wavelength of the electrons at
the Fermi level. It is related to the Fermi energy of the free electron gas

𝐸𝐹 = ℏ2 k F /2m

This coincides with the length for which the quantum effects are relevant, i.e.
the quantization of the bands in SWCNTs due to the lateral confinement.
  λcoh, the coherence length, which indicates the mean distance that the
electron can travel without losing its phase due to phonon-electron,
electron-electron or defects scattering.

 λel, the elastic mean free path which represents the travelling length of the
electron before it undergoes an elastic scattering event. The elastic
scattering leaves the electron phase unchanged, differently from the
inelastic scattering events, but changes the electron momentum.

 λloc, the localization length which indicates the average spatial extent of
the states in the system under study. In a infinite 3D pure crystal λloc =
∞ and the electron is completely delocalized. In the presence of a certain
degree of disorder, λloc ≲ 𝐿 and the electron can be weakly or strongly
localized.

In nanowires with lateral dimensions W, H <= λF and length L » λF , the quantum

lateral confinement produces the discrete one dimensional sub-bands.
Consequently the conduction is quantized and occurs though the 1D sub-bands that
are named conduction channels. In this situation the transport along the wire axis
depends on the characteristics length scales and could be diffusive, in which the L
» λel and the resistance grows linearly (incoherent transport) or exponentially
(coherent transport), or ballistic, in which no scattering events are present and the
resistance is determined by the number of conduction channel and it is
independent of the length. In this last regime, to estimate the conductance in a
single channel, we can use the Landauer theory considering the conductor
connected with two electrodes. The electron waves that approach the conductor
from the electrodes are partially transmitted and reflected through the electrodes.
For a given energy, several modes propagate inside the electrodes.
Thus we can define the Landauer conductance as:

G= GοT(E) with 𝐺𝑜 = 2𝑒 2 /ℎ

where T(E) is the sum of the transmission probability over all the modes, that at zero
temperature is limited to the mode at EF
Go is called conductance quantum

In a situation of transparent electrical contacts, in which no reflection occurs, and

highly order in the system (T = 1), the conductance formula becomes:

G = GoN with 𝐺𝑜 = 2𝑒 2 /ℎ

where N is the number of transmitted modes and Go represents the conductance of the
single mode. m-SWCNTs, i.e. armchair[10, 10], possesses two sub-bands which cross
the Fermi level, resulting in two conducting channels.

If the scattering length within the nanotube is much longer than the length of probed
nanotube and the contacts are transparent, the conductivity of the nanotube has the
ideal value G = 2Go.[16] However, in the real experiment, the environment (substrate),
the presence of centers of scattering such as defects, impurities and distortion on the
structure and the choice of the contacts material negatively affects the theoretical
conductance.

1.1.6 Transport in CNT Networks

To understand the transport in carbon nanotube networks and also the various factors
involved in the carbon nanotube charge transport various research works have been
done and theories established on various factors which may be affecting the transport
phenomena in the carbon nanotube networks. It is quite obvious to understand that the
carbon nanotubes’ transport processes would be different in the case charge transport
in single carbon nanotubes and when in networks. The proximity of the CNTs even
modifies the intra-nanotube transfer. This is affected through bending and distortion of
the lattice as well as Wan der Waal’s inter-nantube interaction. These two effects
results into energetic barrier that hinders the charge transport and consequently
decreases the conductivity.

The observed the side walls of nanotube are same as the graphene sheets in the
graphite is around 3.5⁰ A. When the simulations in the model with length higher than
3⁰A done, it was demonstrated that the interaction between the 𝜋 orbitals of the two
nanotubes decreases and the quantum conductance presents discrete resonant peaks.[17]
This makes the hopping phenomena responsible for the charge transport. Thus, charge
can hop from one tube to another tube through resonant tunneling and the conductivity
of the network depends on the intertube tunneling efficiency. With this principle, the
phenomena why the ordered networks have higher conductivity can be demonstrated.
This is because, in the ordered networks, the contact surface between the nanotubes, is
higher than the randomly distributed networks, hence increasing the probability of the
tunneling event and the conductivity overall.
In the device, practically, the other aspects like different deposition methods,
synthesis, presence of different chiralities and introduction of impurities or other
chemical species as in the case of functionalized nanotubes play a very important
role.[18]
The different methodologies used for synthesis of Carbon nanotubes lead to metallic
and semiconducting species, with wide range of chirality that are randomly interfaced
in a network.

According to the perturbation theory, the resonant tunneling events between two states
happen at the Fermi-point of two nanotubes only if the conservation of the momentum
and energy is generated. Different chiralities posses’ different Fermi momenta, hence,
poor tunneling, thus are lowering the values of conductivity.

Another important factor which affects the transport phenomena of the carbon
nanotubes is the density of the networks or the number of the carbon nanotubes
involved in the bulk film. Modeling the nanotubes, as conducting sticks and implying
the percolation theory, it predicts that
𝜎 ∝ (𝑁 − 𝑁𝑐 ) with 𝑙√𝜋𝑁𝑐 = 4.236

Where N − 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑛𝑔 𝑠𝑡𝑖𝑐𝑘𝑠

Nc − 𝑐𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑟 𝑡ℎ𝑒 𝑝𝑒𝑟𝑐𝑜𝑙𝑎𝑡𝑖𝑜𝑛 𝑡ℎ𝑟𝑒𝑠ℎ𝑜𝑙𝑑
𝑙 − 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑛𝑔 𝑠𝑡𝑖𝑐𝑘𝑠

1.1.7 Contacts to Nanotubes: Schottky Barriers

Two types of barriers can form at the metal/tube interface and increase the contact
resistance beyond the ideal h/4e2 value. The first is a barrier created by an imperfect
interface between the contact metal and the nanotube. Its resistance is a function of the
cleanliness of the interface and the overlap of the metal–nanotube electronic states. Au
and Pd have proven to make the best contacts to nanotubes, with near-perfect
transmission frequently obtained [19].

More fundamental is the Schottky barrier that can form at the interface of a metal and
a semiconducting nanotube. The properties of the Schottky barrier will depend on the
band alignment at the interface (Fig. 3a). In the absence of interface states believed to
be a good approximation for the metal/tube interface [20] , the heights of the Schottky
barriers for hole and electron injection are given by the work function of the metal
contacts, φM, the work function of the nanotube, φNT, and its energy gap, Eg.

When the Fermi level of the metal lies at the midgap of the nanotube (Fig. 3b) there
will be a Schottky barrier for both n and p carrier injection, whereas when it aligns
with the hole band (Fig. 3c) there would be no barrier to hole injection but a large
barrier to electron injection.
Figure 1.10: Energy diagram and Density of States(DOS) a)of m-SWNTs and b)s-SWNTs .
The shapes peaks are the van Hove singularities of SWNTs

From different experiments, it has been made clear that the contact properties very
sensitive to the ambient environment and device history. It was also noted [19] that a
high work function by itself is not sufficient to assure ohmic contacts. For example, Pt
has a larger work function than Pd but forms more resistive contacts, probably due to
additional tunneling barriers formed as a result of poor wetting of the tube by the
contact metal.

Since the energy gap grows with decreasing diameter (𝐸𝑔 ∼ 1/𝑑𝑡 ) it is clear from the
above equation that for every metal there exists a critical nanotube diameter below
which a Schottky barrier with finite height will form and the height of this barrier will
increase with decreasing diameter.

The assessments in the past have provided a consistent picture of contact properties of
semiconducting nanotubes, although a major challenge remains to make good ohmic
contacts to tubes with diameters 1.5 nm and smaller. Surprisingly, even small-
bandgap/metallic tubes show significant barriers in this range [21] . The origin of this
behaviour is still not completely understood.

1.2 Introduction to Printed Electronics

Printed electronics is a subject of electronics which deals with solution printing of thin
films on various substrates. Electrically functional electronic or optical inks are
deposited on the substrate creating active and passive components such as thin film
transistors, resistors, capacitors and coils. Here the inks can be composed of different
carbon based compounds and these can be deposited by solution based techniques.
The main feature of printed electronics is that, it gives us a possibility to print many
micro-structured layers one above another in a much simpler and cost effective
manner. This gives a wide opportunity to implement new and improved functionalities
to the device. The resolution of printing is very high (in µm or nm) with precision.
Printing technologies divide between sheet-based and roll-to-roll-based approaches.
Sheet-based inkjet and screen printing are best for low-volume, high-precision
work. Gravure, offset and flexographic printing are more common for high-volume
production, such as solar cells, reaching 10,000 square meters per hour
(m²/h).[18][19] While offset and flexographic printing are mainly used for
inorganic[20][21] and organic[22][23] conductors (the latter also for
[24]
dielectrics), gravure printing is especially suitable for quality-sensitive layers like
organic semiconductors and semiconductor/dielectric-interfaces in transistors, due to
high layer quality.[24] If high resolution is needed, gravure is also suitable for inorganic
[25]
and organic [26] conductors. Organic field-effect transistors and integrated
circuits can be prepared completely by means of mass-printing methods.[24]
Both organic and inorganic ink materials can be used for the printing methods
provided with proper control in their viscosity, surface tension and solid content.
Solubility, wetting, adhesion as well as post treatment conditions after deposition play
a very vital role, since they have the ability to change the morphology of the layers.
With respect to the conventional electronic methodologies, printed electronics
provides an opportunity to modify the mechanical flexibility and functionality by
chemical adjustment.

Obviously, the performance is not expected to be as great as that of the conventional

electronics, since they are solution processed and the charge carrier mobility is lower
than conventional method.

A brief summary between the conventional electronics and printed electronics is

shown here
Conductive polymers are the materials which can be used for solution processed
applications. Other alternative materials with high performance are also researched.

1.2.1 Organic Semi Conductors

Organic semiconductors are the carbon based conjugated systems having delocalized π
bonds. Carbon have an electron configuration of 1s2 2s2 2p2, in total of six electrons,
with four valence electrons available for pairing. Through the linear combination of
the 2s and 2p atomic orbitals, the atom can form hybridized sp, sp2 or sp3
orbitals, with its four valence electrons that can participate to the formation of up
to four bonds. While the electrons in the hybridized orbitals can form strong
covalent σ-bonds with other atoms, defining the organic compound backbone,
those of the 2p orbitals (not involved in the hybridization) form the weaker π-
bonds (fig.1.8). This type of bond allows the delocalization of the free electrons
over the carbon atomic plane, attributing semiconducting properties to the system.
Two or more atoms connected by σ-bond and π-bond constitute a conjugated
molecule.[27]

Figure 1.14: Sketch of the double bond between two sp2 hybridized carbon atom
The repetition of these conjugated sub-units (monomers) results into the polymers.
With the increase in the monomers the conjugation increases, facilitating the
electronic delocalization. Delocalization is eased by reduction in the energy gap
between the HOMO (highest occupied molecular orbitals) and LUMO (least
occupied molecular orbitals) levels.

To briefly, understand the charge transport in the organic semiconductors, it is

important to know the concept of polarons. Since, contrary to the metals, the
electrons are localized in the semi-conductor results into local deformation of the
molecule. This charge structure interaction can be described as a strong electron-
phonon coupling and therefore for charge transport this phonon and charge must
move coordinately. This quasiparticle couple is called polaron. By applying an
external field, the polaron can travel across the system carrying the local deformation
of the lattice. Thus, the polaron can be positive or negative with spin of (+,-) ½ and
can be considered as a defect due to the vacancy of an electron. Furthermore, in the
case of a second doping stage, if we remove a second electron, the formation of a
bipolaron occurs. This new spineless now particle, can be again positive or negative but
stable bipolarons are known to exist in a few materials, including polyacetylene and a
number of oxides. [28]

Figure 1.15: Band structure containing a positive polaron and a positive bi polaron

The charge transport within a molecular solid has two main components; an intra-
molecular, or rather the motion of the polaron along the chain and the inter-molecular
that regards the jump of the charges between the molecules composing the molecular
solid.

The first is a coherent event which takes place within extended molecular states. On
Figure 1.16: Charge transport; 1-2; a backbone charge transfer -intra-molecular. 2-3, inter-
chain transfer though hopping

the other hand, the inter-chain transfer is the most spread charge transport mechanism,
plays a crucial role in the charge transport [29] and is governed by the presence of weak
inter-chain reaction and by the degree of disorder in the organic system.

Some of the semi-conducting polymeric materials are N2200, PEDOT: PSS, P3HT,
P3DDT.

1.2.2 Carbon Nanotubes based organic semi conductors

Carbon nanotubes as discussed earlier in the section 1.1, provides an alternative to the
use conventional polymers as semiconductors. They having outstanding electrical and
mechanical properties, along with processibility in solution deposition methods makes
them suitable candidate as semi-conductors. Although it has to be mentioned that
various techniques such as gel chromatography, polymer wrapping etc. needs to be
employed in order to separate tthe semi-conducting carbon nanotubes from the
metallic ones with very high purity for better performances in the devices.

Carbon nanotube based polymer solution have been successfully used in coating
methods like spin coating[30,31], spray coating[32], self assembly coating[33], dip
coating[34], rod coating[35] to printing techniques such as screen printing[36] , inkjet
printing [37]aerosol printing [38–40] , transfer printing [41], and contact printing [42]
techniques have eliminated the need of using a high-vacuum environment and
multistage patterning process, thus paving the way for scalable manufacturing of
large-area, low-cost, and flexible electronics.
1.3 Brief History of Transistors
The history of transistors goes back to the year 1947, when John Bardeen (1908-
1991), William B. Shockley (1910-1989) and Walter H. Brattain (1902-1987) invented
the first transistor made up semi conductor material which was able to do both-
amplify an electrical signal and secondly, allow flow of current. This was developed in
the Bell labs when they were trying to find a replacement of the old and bulky vacuum
tubes. Before this, the vacuum tubes were used in the telephone technology,
amplifying current. Since they are not so reliable and excessive power was consumed.

Figure 1.17: John Bardeen(with spectacles), William Shockley (using the microscope) and
Walter Brattain (standing behind) at Bell Labs, 1948 [43].

After the invention of germanium transistor the three terminal device known as the
“point contact” device (in the middle of last century), inorganic semiconductors have
been started to utilize as a dominant materials in electronics.

Figure 1.18: History of transistors

In 1960, Kahng and Atalla [44] fabricated the first silicon-based metal-oxide-
semiconductor transistor. This was ground breaking and since then technology and
processing of transistors based on silicon has seen an upsurge.

In these recent years, increasing interest has been focused on Organic Electronics,
since there an ease of fabrication of these transistors, along with the cost effectiveness.
A research field focused on this has been working continuously to improve the
performance of the transistors. The current ON/OFF ratio, mobility, working at low
voltages hence lower power consumption are the main parameters which are mainly
optimized on. This would lead to a low cost, large area plastic electronics employing
transistors and diodes based on organic semiconductors. For the advances in the field
of electronics, realization of Moore’s law is necessary so miniaturization of transistors
play a very vital role.

The Moore’s law as observed in 1965, states that the number of transistors in a
dense integrated circuit doubles approximately every two years. The observation is
named after Gordon Moore, the co-founder of Fairchild Semiconductor and Intel,
whose 1965 paper described a doubling every year in the number of components per
integrated circuit,[45] and projected this rate of growth would continue for at least
another decade.[46]

Figure 1.19: Moore’s law

1.4 Field Effect Transistors

The first demonstration of field effect in a carbon based material was observed in an
organic molecule, phtalocyanine, in 1964[47], but only later, in the 1987, the first
organic polythiophene-based FET was realized by Koezuka[48]. This development
consequently buoyed up intense study of carbon based compounds, leading to the
synthesis of organic semiconductors with increasingly performance. However, over
the last twenty years, the discovery of new carbon allotropes, such as graphene and
carbon nanotubes, and their outstanding electrical properties gave a huge impetus to
the fabrication of FETs with the highest performance ever.

1.4.1 Brief History of SWNT-FETs

Figure 1.20: Showing first SWNT- FET device

The CNT FETs were first developed by Dekker’s group at Delft university and by
IBM for a convenient back-gate geometry [49,50]. While the device (Fig. 3a) is similar
to the Si-based FET as shown in Fig. 2a [50], the detailed device physics are very
different [51,52]. In Si or other conventional semiconductor based FETs, carriers are
generated by thermal excitation from dopant levels, and the polarity of the FET is
determined by the type of dopants, that is either donor (n-type) or acceptor (p-type) [53].

Figure 1.21: Device architecture of the first Si based FETs[64]

In a CNT FET, the situation is very different. This is because CNT is naturally
intrinsic onto which substitutional or stable doping is unlikely [54–56]. As a result,
controlled doping is very difficult for CNT, which prevented the CNT technology
from being developed into a high performance CMOS technology for a long time
[57,58]
. Indeed, doping in CNT is neither easy nor desirable. Since the high carrier
mobility in a CNT mainly results from the stable and perfect sp2 structure of the CNT,
and the introduction of dopants in CNT would distort the otherwise perfect structure
and compromise its electric prop-erties, leading to stronger scattering, lower carrier
mobility and thus lower performance [57].

In a high performance CNT FET fabricated via the doping-free process [59] , the
conduction CNT channel is intrinsic with perfect sp2 lattice in which carriers are
provided directly from the metal electrodes rather than by thermal excitation [60,61] ,
making the CNT FETs suitable for low temperature electronics applications [62]. In
addition, the properties of the contact also determine the polarity of the CNT FETs.
When a metal electrode is brought into contact with a semi-conductor, the Fermi levels
of the metal and the semiconductor are usually not identical. This misalignment in the
Fermi levels would lead to certain degree of charge transfer between the metal and the
semiconductor, and as a result a Schottky barrier (SB) forms between the metal and
semiconductor [63]. For high performance devices, this is highly undesirable since the
presence of a SB severely limits the injection of carriers from the metal electrode to
the semiconductor, or from the semiconductor to the metal.
Figure 1.22: the output characteristics of the first CNT FETs developed by Dekker’s group in
1998 [49].

The fabrication of the back-gated CNT FET is fairly straightforward. Pt electrodes

were used as the source and drain, which was pre-patterned on a SiO2 surface, and
CNT was transferred onto these metal electrodes to form channels. The doped Si
substrate beneath the SiO2 was used as the back-gate, which may effectively modulate
the carrier concentration in the channel and in the region near the metal/
semiconductor CNT interface. In particular, the SB may be significantly thinned at
large gate bias, allowing the carrier injection into the CNT to change from thermionic
emission to thermally assisted tunneling mode, leading to a large on and off state
current ratio. The transfer characteristic of the device (Fig. 3b, inset) reveals clearly
that the device is a p-type FET, whose conductance can be changed over six orders of
magnitude from on-state at negative gate voltage to off-state at large positive gate
voltage. It should be noted, however, that the device current is relatively small, of the
order of tens nA. This is because there exist a SB between Pt and CNT, limiting the
hole injection efficiency from Pt into the CNT channel. The low current level not only
leads to slow speed of the device, but also limits the driving ability of the device and
makes it unsuitable for high performance applications. Perfect ohmic contacts can be
made to the SWNTs either to the valence band using Pd [60] or to the conductance band
of the CNT using Sc [61], rendering both n-type and p-type high performance CNT
FETs operating close to the ballistic limit available.

1.4.2 Geometry of Field Effect Transistors

Field effect transistors, also known as thin film transistors, when their fabrication is
done by deposition of thin films, consists of three terminals- the source, drain and the
gate. In a top gate bottom contact, the contacts are printed first on the substrate, on top
of that the semiconductor layer and the gate is separated by a thin dielectric film. W is
the width of the channel, L the length or the channel while t is the thickness of the
dielectric.
The thickness of the semi conducting film and the dielectric plays a crucial role in the
performance of the transistor, which would be later discussed in the sections.

Figure 1.23: Shows different configuration of FETs[80].

Each of the four FETs or realized as TFT geometries shown in Fig. 22 has certain
advantages and disadvantages. For example, the presence of an energy barrier at the
interfaces between the source and drain contacts and the organic semiconductor layer
and is expected to impede the exchange of charge carriers between the contacts and
the semiconductor. Various experiments and simulations on such geometries have
shown that for the same energy barrier height, TFTs with a staggered structure (a, d)
have the advantage of being less affected by this energy barrier than TFTs with a
coplanar structure (b, c) [65–69]. It has been inferred however, that in case of the bottom-
gate coplanar structure (b), the effect of the energy barrier on the carrier exchange
efficiency can be substantially reduced by modifying the surface of the source and
drain contacts with a thin organic monolayer carrying an appropriate dipole moment
[70, 71,72,73,74,75]
or with a thin metal oxide[76–79].

In the bottom-gate coplanar structure (b) the gate dielectric layer and the source and
drain contacts are deposited before the organic semiconductor layer film. This is
advantageous for especially very high mobility organic semiconductors, especially
those that are vacuum-deposited small-molecule materials, but also many high-
mobility polymers, adopt a thin-film microstructure that is very sensitive to external
perturbations. Hence, with the bottom-gate coplanar structure (b), methods involving
thermal treatments and/or solvents can be safely employed to prepare the gate,
dielectric and the contacts first without harming the semiconductor layer.

Hence to conclude, depending upon the materials, the deposition techniques and
fabrication methods adopted the best possible suitable architecture for the film thin
transistor is opted keeping in mind the desired results from the devices. The source
drain channel lengths, L typically is in the range of 10-100µm and W, channel widths
between 100µm- 1000µm.
1.4.3 Working Principle of the FETs

The field effect transistor works as a voltage controlled current source. A voltage VG is
applied across the gate dielectric in order to modulate the current between the source
and the drain, when a given voltage VD is applied between the source and the drain.
The semiconductor film and the gate electrode are capacitively coupled, since there is
a dielectric layer between the two, such that application of a bias on the gate induces
charge in the semiconductor film. Much of this charge is mobile and moves in
response to the applied source drain voltage VD. Ideally, when no gate voltage is
applied, the conductance of the semiconductor film is extremely low because there are
no mobile charge carriers; i.e., the device is off. It is only when the gate voltage is
applied, mobile charges are induced, and the transistor is on, hence the name field
effect transistors.

Figure 1.24: showing the positions of HOMOs and LUMOs with respect to the Fermi levels of
the source and drain contacts and how they change on application of the bias gate voltage and
drain voltage.

The electronic energy level diagrams in Figure 2a shows the positions of the highest
occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals
(LUMOs) of the organic semiconductor with respect to the Fermi levels of the source
and drain contacts, when no gate voltage is applied. Even now, if a small gate bias
were applied, there would be no conduction because there are no mobile charges in the
semiconductor, as this is shown in the fig 2b . Although there is a shift in the position
of the HOMO and the LUMO levels on application of positive and negative gate bias.
Application of positive bias shifts the HOMO and LUMO levels down, hence lowering
the energy. Only sufficient amount of gate bias brings the LUMO level in resonance
with the Fermi level of the contacts, therefore allowing a possibility to have mobility
of the charges. At this point, mobility of charges take place only if the V D that is the
drain voltage is applied and hence there can be a current flow between the source and
the drain as in fig d. Similarly, whereas the application of negative bias across the
source and the drain shift the HOMO and LUMO levels up such that the HOMO level
is in resonance with the contact Fermi levels and electrons move out of the
semiconductor and into the contacts, leaving positively charged holes. These holes are
now the mobile charge carriers on application of the drain voltage as shown in fig e. It
must be noted in the fig. d and e that the source is always the charge injecting contact
regardless of the sign of the gate voltage.

The diagrams in the above figure are important as they make us visualize the
mechanism by which the organic thin film transistors are modulated by the gate bias.
The given description on the above paragraph is simplistic and for a real and
quantitative description of the process an account of the presence of the charge traps
and residual dopants must be taken. In additionally, the diagrams in Figure 1.24 might
lead one to believe that any organic semiconductor can be made to conduct holes or
electrons, depending on the sign of the gate voltage. This is not true; in general, since a
given organic semiconductor can be made more conductive with either a positive or a
negative gate voltage, but not both, with only a few recent exceptions like that of
carbon nanotubes which are ambipolar in nature . This leads to the conclusion that
organic semiconductors are classified according to whether they are hole (p-channel)
conductors or electron (n-channel) conductors.

Observing again at Figure 2b for the case of n-type conduction and VD = 0, and
assuming ohmic contacts and zero-threshold operation (these assumptions will be
qualified shortly), application of a positive VG induces positive charges at the
gate/insulator interface and an
equal number of negative charges near the organic/insulator interface (supplied by the
source and drain contacts). With no source-drain bias applied, this negative charge
density will be uniform across the channel. For a positive VD the areal density of
charge (C/cm2) induced at a given position x alongthe channel is proportional to the
voltage difference VG - V(x):

qind(x) = n(x) et = Cox(VG - V(x))

where Cox is the capacitance of the insulator per unit area, typically reported in
nF/cm2,
n(x) is the number density of charges in the channel (no./cm3)
e is the fundamental unit of charge, and
t is the thickness of the charged layer in the channel.
Figure 1.25: a) Carrier concentration profile of TFT in the linear regime b) pinch-off
occurs when VDVG- VT c) Carrier concentration profile of TFT in the saturation
regime.

It is observed that in all most occasions, it is never at VG= 0 that there is introduction
of charges into the active channel. This can be due to various reasons- like a mismatch
in the Fermi level of the metal contact and the LUMO, resulting into a charge transfer
between the metal and inorganic semiconductor, consequently causing a dipole and
band bending in the organic semiconductor, hence a VG has to be applied in order to
achieve the flat zone condition. Also in another situation of traps present in the film,
they need to be filled in order to make the channel conduct. On the contrary, if there is
a doping, this results into the channel to be conductive even at VG= 0. In order to
handle all these situations a threshold voltage VT is introduced. For example for an n
type channel, doping shifts VT negatively while traps shift it, VT positively, while
depending of the alignment of the mismatch of the Fermi level of the metal and the
LUMO, the VT may be either positive or negative.

Hence the equation changes to qind(x) = n(x) et = Cox(VG - VT - V(x))

Figure 4a shows that, when VD = 0, the channel charge density is uniform for a given
VG (since ideally VT is not a function of x, and when VD = 0, V(x) =0).

However, when VD is nonzero but less than VG, there is a linear gradient in the charge
concentration, Figure 4b. For a given small value of VD, the average value of qind is
Cox(VG - VT - VD/2), which is the induced areal charge density in the center of the
channel. To the left
of center, the charge density will be higher, and to the right, the charge density will be
lower.

Now using Ohm’s law and the definition of conductivity

𝐼𝐷 𝑉𝐷 𝑊
= 𝜎 = (𝑛𝑖𝑛𝑑,𝑎𝑣 𝑒𝑡) 𝜇𝑉𝐷
𝑡𝑊 𝐿 𝐿

where σ is the conductivity, μ is the carrier mobility (i.e.,velocity per unit electric
field), and nind, av is the average carrier concentration in the channel. Substituting eq
2 into eq 3, we obtain

𝑊 VD
𝐼𝐷𝑙𝑖𝑛 = 𝐶𝑜𝑥 µlin [(VG − VT ) − ] VD
𝐿 2

which is commonly rewritten as the linear regime.

𝑊 V2D
𝐼𝐷𝑙𝑖𝑛 = 𝐶𝑜𝑥 µlin [(VG − VT ) − ]
𝐿 2

In this Linear regime for |VG – VT | >> VD, the charge density is uniformly distributed
along the channel, and the device operates as a resistor. The drain current is linear with
applied drain voltage.

But as the VD is increased, as shown in the fig the carrier concentration becomes non-
uniform, decreasing from the source to the drain such that when V G-VT VD , the
channel becomes pinched as a result of no potential difference between the gate and
the part of the channel nearest to the drain. This is shown in fig b

Now on further increasing the VD, it would push the voltage always toward the source,
without any increase in the current due to the fact that the integrated resistance of the
channel from the source to the pinch point remains the same, and carriers are swept
across the narrow space charge region from the pinch point to the drain by the
(comparatively) high electric field in the depletion region. Hence on substituting VD=
VG-VT , we get the saturation regime, and the current in the saturation regime is given
by

𝑊
𝐼𝐷𝑠𝑎𝑡 = 𝐶 µ [(V − VT )2 ]
𝐿 𝑜𝑥 sat G
1.4.4 Electrical characterization of TFTs

The TFTs are typically characterized in one of two ways-

 Output curves - By holding VG constant and sweeping VD (commonly referred

to as ID-VD or output curves; see Figure 3a)

Figure 1.26: showing ID – VD curves for TFTs at different values of VG.

 Transfer curves- by holding VD constant and sweeping VG (commonly referred

to as ID-VD or transfer curves; see Figure 3b)

Figure 1.27 :showing ID –VG curves at a constant value of VD . Here VT is the threshold or
pinch off voltage.
Note: If contact effects and trapping are not too problematic, these traces can be
modelled quantitatively using I-V relationships derived from Ohm’s law.

 Field Effect Mobility- The mobilities in the different regimes give us a direct
indication of the performance of the field effect transistors.

Linear Mobility calculated in the linear regime for | VG- VT| > |VD|

𝐿 𝜕𝐼𝐷
µ𝑙𝑖𝑛 =
𝐶𝑜𝑥 𝑊𝑉𝐷 𝜕𝑉𝐺

and saturation mobility calculated in the saturation regime for |VD|>| VG-
VT|>0

2𝐿 𝜕√𝐼𝐷 2
µ𝑠𝑎𝑡 = ( )
𝐶𝑜𝑥 𝑊𝑉𝐷 𝜕𝑉𝐺

 ION/OFF- Current ON OFF ratio- It is relates to maximizing mobility. A higher

ION/OFF ratio is an indication of better performance. It is generally expressed as
10x.

 Sub threshold swing- S It is a measure of how rapidly the device switches from
the off state to the on state in the region of exponential current increase and is
typically reported in V decade-1or mV decade-1. Sn , sub threshold swing =
CoxS (VnF cm-2 decade-1), which yields the required number of gate-induced
carriers to effect a one-decade increase in the current near Vo (the exponential
increase in current shown on the adjacent axes ) and thus allows meaningful
comparison of films on different dielectrics. A large subthreshold swing
generally implies a large concentration of shallow traps, i.e., a diffuse turn-on
region. Both ION/IOFF and Sn are dependent on the device geometry, operating
conditions, and measurement apparatus and thus are only truly useful when
cited along with this information or when used to compare devices tested under
identical circumstances [81].

Since these are the features define the performance of the field effect transistors, it is
necessary to have a good semiconducting material, which is to an extent fulfilled by
carbon nanotubes.
1.5 Introduction to Inkjet Printing
Inkjet printing offers unique advantages over other methods of printing. It requires
absolutely no prefabrication of templates, allowing for a rapid printing process at low
cost. Additionally, due to its precise method of patterning, post-printing steps are not
necessary. Furthermore, multiple materials can be deposited simultaneously with the
use of multiple ink cartridges, and the amount of deposited material can be controlled
with great precision. Finally, due to the nature of inkjet printing technology, multiple
layers can be printed on top of one another with great ease.

1.5.1 Classification of Inkjet Printers

Inkjet printers can be classified based on its principle of printing technology into two
categories- Continuous and Drop on Demand.

1.5.1.1 Continuous

Continuous inkjet printing supplies a continuous stream of ink droplets. The principle
is that these droplets are charged upon leaving the nozzle and are then deflected by
voltage plates, where the applied voltage determines whether the droplet will be
deposited onto the substrate or recycled through the gutter. Therefore, even though
when the printer is not actually printing anything onto a substrate, a stream of droplets
is still being ejected from the nozzle and recycled through the gutter.

1.5.1.2 Drop on Demand

As the name suggests, a drop-on-demand inkjet printer ejects a droplet of ink only
when it is told to do so. Therefore, when the printer is not actually printing anything
onto a substrate, there are no droplets being ejected from the nozzle. Drop-on-demand
inkjet printers can be further split into two categories, namely thermal and
piezoelectric.

Thermal inkjet printers

Thermal inkjet printers, at times referred to bubble jet printers, contain a thin film
resistor in the nozzle. In order to eject a droplet, this thin film resistor is heated by
passing current through it. This causes the ink in the nozzle to vaporize, creating a
bubble and a large increase in pressure, which forces ink droplets out of the nozzle.
Hewlett-Packard, Canon, and Lexmark employ this type of drop-on-demand inkjet
printer.

Piezoelectric inkjet printers

They contain a piezoelectric transducer in the nozzle. When voltage is applied to the
piezoelectric transducer, it deforms and causes an increase in pressure, which forces
ink droplets out of the nozzle. In terms of consumer printers, Epson employs this type
of drop-on-demand inkjet printer. The Fujifilm Dimatix printer, which is specialized
commercial inkjet employ the piezoelectric drop-on-demand technology as well.
Dimatix printer 2830 is used in this work, because of control over drop volume and
spacing and therefore better resolution can be obtained.

Based on the usage, the printers be classified into consumer and commercial printers.

1.5.1.4 Consumer based printers

Consumer inkjet printers are quite cheap and offer familiarity, so there is no need to
learn new software or hardware. Nevertheless, these printers are made to print a
specific type of ink, so developing useable ink can be a bit more difficult. The new ink
must match the original ink in all aspects. Furthermore, in the instance where a new
ink clogs the nozzle, some consumer inkjet printers are easier to clean than others. In
general, each Hewlett-Packard printer cartridge has its own nozzle, allowing the user
to easily remove the cartridge and clean it. On the other hand, the nozzle for Epson
printer cartridges is built into the printer itself and cannot be easily removed for
cleaning. The most prominent disadvantage for consumer inkjet printers is their
overall lack of control. In particular, the drop volume and spacing cannot be adjusted,
and the resolution is relatively low.

1.5.1.5 Commercial based printers

Commercial printers are used since they have a great deal of control over drop volume
and spacing, and they provide better resolution. Though expensive, these printers, like
the Fujifilm Dimatix are specifically made for printing various types of materials.