Doping

Doping means the introduction of impurities into a semiconductor crystal to the

defined modification of conductivity. Boron (3 valence electrons= 3-valent) and
phosphorus (5 valence electrons= 5-valent) are two of the most critical materials that
can be doped with silicone. Other materials are aluminum, indium (3-valent) and
arsenic, antimony (5-valent).

The dopant is introduced into the lattice structure of the semiconductor crystal,
determining the doping form by the number of external electrons. For p-type doping,
elements with 3 valence electrons are used for n-doping, 5-valued elements. A factor
of 106 will increase the conductivity of an intentionally contaminated silicon crystal.
n-doping
The 5-valent dopant has more of an outer electron than the atoms of silicon. Four
outer electrons combine with one silicon atom at a time, while the fifth electron
travels freely and acts as a carrier of charge. This free electron needs much less
energy than the electrons that cause the intrinsic conductivity of silicon to be lifted
from the valence band into the conduction band. The electron-emitting dopant is
known as an electron donor (donare, lat. = to give).
The dopants are positively charged by the loss of negative charge carriers and only the
negative electrons can pass within the lattice. The n-type or n-doped are doped
semimetals whose conductivity is dependent on free negative electrons. These are also
classified as majority charge carriers because of the larger number of free electrons,
whereas free mobile holes are referred to as minority charge carriers.

Figure1: n-doping with phosphorus

the phosphorus atom donates its fifth valence electron. it acts as free charge carrier.
Arsenic is used as a phosphorus substitute since its coefficient of diffusion is lower.
This means that during subsequent operations, the dopant diffusion is less than that of
phosphorus and hence the arsenic stays at the place where it was initially inserted into
the lattice.
p-doping

The 3-valent dopant effect is just the opposite, unlike the free electron due to doping
with phosphorus. An extra outer electron can be trapped by the 3-valent dopants,
thereby leaving a hole in the valence band of silicon atoms. Therefore, the electrons
become mobile in the band of valence. The holes move in the opposite direction to the
movement of the electrons. The necessary energy to lift an electron into the energy
level of indium as a dopant, is only 1 % of the energy which is needed to raise a
valence electron of silicon into the conduction band.

The dopant is negatively charged with the inclusion of an electron, and these dopants
are called acceptors (acceptor, lat. = add). Again, in the crystal lattice, the dopant is
set and only the positive charges can pass. These semiconductors are called p-
conductive or p-doped due to positive holes. The holes are the main charge carriers,
analogous to n-doped semiconductors, and the minority charge carriers are free
electrons.

Figure2: p-doping with boron

the free place on the boron atom is filled with an electron. therefore, a new hole
(defect electron) is generated. these holes move in the opposite direction to the
electron.

Doped semiconductors are electrically neutral. Doped terms n- and p-type only apply
to the majority of charge carriers. A fixed negative or positive charged dopant belongs
to each positive or negative charge carrier.
In relation to the current flow, N- and p-doped semiconductors behave approximately
similarly. The number of charge carriers in the semiconductor crystal increases with
the increasing number of dopants. Only a very limited number of dopants are needed
here. Weakly doped silicon crystals contain just 1 impurity per 1,000,000,000 atoms
of silicon; heavily doped semiconductors contain, for example 1 foreign atom per
1,000 atoms of silicon.
Electronic band structure in doped semiconductors
In n-doped semiconductors, there is an electron in the crystal that is not bound by the
insertion of a dopant with five outer electrons and can therefore be transferred into the
conduction band with relatively little energy. So, the donor energy level is near to the
conduction band edge in n-doped semiconductors, the band distance to be resolved is
very small.
Analog, a hole is possible by the insertion of a 3-valent dopant in a semiconductor
that may already be filled by an electron from the silicon valence band at low energy.
The acceptor energy level for p-doped semiconductors is near the valence band.

Band model of doped semiconductors

Figure3: Energy VS. n,p-semicondctor.

To achieve high conductivity, conductive polymers have been doped using various
methods. As insulators, un-doped polymers have been documented, but their
conductivity can change from insulating to metallic upon doping. However, the
doping process for conductive polymers is entirely different from that of their
inorganic counterparts due to their special chemical structures. With the subsequent
creation of charge carriers, dopants in the polymer undergo redox processes in which
charges are transferred. The function of the dopant is not only to remove electrons
from the conductive polymers, but also to add electrons to the backbone of the
conductive polymers. A simple description of the effect of doping is that electrons are
extracted from the highest occupied molecular orbital (HOMO) of the valence
band(oxidation) or transferred to the lowest unoccupied molecular orbital (LUMO) of
the conduction band (reduction). In the form of polarons (radical ions), bipolarons
(dications or dianions), or solitons in the polymer, this oxidation/reduction phase
produces charge carriers. Based on their bond structures in the ground state,
conductive polymers can be classified into degenerate and non-degenerate systems.
Degenerate polymers in the ground state have two similar geometric structures, while
non-degenerate polymers in the ground state show two different structures with
different energies (e.g., benzenoid and quinoid structures, where the energy of the
benzenoid is lower than that of the quinoid). Solitons are the carriers of charge in
degeneration These structures as polyacetylene. Polarons and bipolarons, on the other
hand, act as the charge carriers in Systems like polypyrrole and polythiophene are
both degenerate and non-degenerate. The circulation of these Conductivity is created
by charging carriers along polymer chains. Conductivity is created by the movement
of these charge carriers along polymer chains. The oxidation and reduction processes
lead to p-type and n-type doping, respectively, in solid-state physics terminology. P-
type in the electron travels directly from the HOMO of the polymer to the species of
dopant and produces a hole in the backbone of the polymer. In n-type doping,
however, electrons from the dopant species pass to the polymer's LUMO, which
results in increased electron density. The density and mobility of charge carriers can
therefore be modified by doping.

As shown in figure 4, CPs can undergo both p-type doping and n-type doping. The
doping mechanism produces polarons/bipolarons that are positive or negative. Such
charge carriers are delocalized over the polymer chains, making electronic
conductivity simpler. In n-doping, the negatively charged carriers are generally not as
stable as positively charged forms, making p-doping more common both in academic
research and for practical applications. Representatively, the conductivity is a
consequence of p-type doping in PPy. With four separate electronic band structures,
the PPy chain exhibits four different electronic band structures Different degrees of
doping. PPy is an insulator with a wide band gap of approximately 3.16 eV in the
undoped state (Figure 5a). A π-electron is separated from the neutral PPy chain after
oxidation, and a local deformation occurs from the benzenoid structure to a quinoid
one to form a polaron. This gives rise within the band gap to two localized electronic
levels while the unpaired electron occupies the bonding state (Figure 5b). A second
electron is withdrawn from the PPy chain upon further oxidation, resulting in the
creation of a doubly charged bipolaron (Figure 5c). In the bipolaron, the benzenoid-
to-quinoid deformation is greater than in the polaron. When the polymer is oxidised
further, there is an overlap between bipolarons, leading to the development of two
small bipolar bands (Figure 5d) and a decrease in the 3.16 to 1.4 eV energy
difference.
Figure 4. The electronic band and chemical structures of polythiophene (PT) with (a)
p-type doping and (b) n-type doping.

Figure 5. Electronic bands and chemical structures illustrating (a) undoped; (b)
polaron; (c) bipolaron; and (d) fully doped states of polypyrrole (PPy).

A standard CP with a degenerated ground state is trans-polyacetylene. The single and

double bonds will exchange electrons when the chain contains an odd number of
carbons, resulting in two geometric structures (phases A and B) with the same energy
(Figure 6a). An unpaired π electron contains a radical form produced between the two
structures (Figure 6d). The defect was called a soliton (neutral). The soliton possesses
a certain mobility along the polymer backbone that makes its delocalization. They can
be destroyed by forming a double bond as the neutral solitons pass down the chain
and meet each other. They become more stable if the solitons have charge, since they
can be delocalized through the polymer chain. To form a positive or negative soliton,
a neutral soliton may be oxidized or reduced by a dopant. With no unpaired spin (S),
positive and negative solitons have positive and negative charges (Figure 6c, e). The π
electron travels over a long distance inside the polymer backbone and the regions of
individual charged solitons will overlap. A band-like mechanism called the soliton
band contributes to the interaction between charged solitons. The soliton band is in
the center of the polymer's HUMO and LUMO and can become larger with a rise in
the amount of doping (Figure 6b). In trans-polyacetylene, both solitons and polarons
serve as charge carriers that promote electronic conductivity. There are significant
extrinsic environmental factors, such as temperature, that affect the conductivity of
CPs, as well as intrinsic ones, such as the degree of doping.

Figure 6. (a) Schematic illustration of the geometric structure of a neutral soliton on a

trans-polyacetylene chain; (b) A soliton band with light doping (left) and heavy
doping (right); The band structure of transpolyacetylene containing (c) a positively
charged soliton; (d) a neutral soliton; and (e) a negatively charged soliton.
What are the factors that effects conductivity?
As insulating materials, polymers have long been recognized and are mostly used to
insulate cables and electrical devices. There are also a variety of electrically
conductive polymers, however. The electrical conductivity of these polymers is
dependent on the presence, along the polymer backbone, of conjugated double bonds.
Conjugation means that it consists of alternating single and double bonds in the
polymer backbone. The so-called localized σ bonds are the strong chemical bonds
between the carbon atoms, while the double bonds provide weaker and less tightly
localized π bonds. The conductivity of these polymers is however very low. Only
when an electron is removed by oxidation (p-doping) from the valence band or
applied by reduction (n-doping) to the conducting band does the polymer become
highly conductive. Charging defects (polaron, bipolaron and soliton) are created
through such a doping process that can pass through the polymer's backbone or to be
more precise, through the conduction band.

Figure7: movement of polaron

The radical cations/anions that form during doping, also called polarons, are partly
localized primarily because of Coulomb's attraction to its counterion, which typically
has a much lower mobility. Thus, the cell charge carriers are not the counter-ion, such
as I3- or Na+, but the charges on the polymer backbone. A relative high dopant
concentration (approximately 10 percent) is needed due to the strong interaction with
the counterion to allow the polarons to move in the field of surrounding counterions.

The conductivity of a material depends on both the density of charge carriers (number
of charges per unit volume) and how fast they can move in the material, to be more
specific, on their mobility μ.
A simple relationship between mobility of the charge carriers and the electrical
conductivity σ exist. If μe and μp are the mobilities of negative charges (electrons)
and positive charges (these are missing electrons called holes) then each of these
charge carriers will move with the velocity vector μeE and μpE in the electric field E.
The total current density is then

σ =e (ne μe+ np μp)

where e is the elementary charge, and ne and np are the number density (concentration)

of negative charges (electrons) and positive charges (holes).

Conductivity depends strongly on the temperature. It decreases with rising

temperatures for metals, whereas it increases for semi-conductors such as conducting
polymers.

Figure 8: Conductivity VS. temperature

The conductivity of conductive polymers decreases with falling temperature in
contrast to the conductivities of typical metals, e.g. silver, which increase with falling
temperature.