Professional Documents
Culture Documents
Electric Properties
5.1 Conductivity of polymers
Polymers are very good insulators! Most plastic materials are not conducting
and used to insulate good conductors such as metals.
http://physicaplus.org.il
Application of conducting polymers in many different fields, for example:
• printed electronics
• OLEDs / displays, OFET
• photodiodes, photovoltaics (OPV)
r v
electrical conductivity σ defined via j = σE
r v
j
with current density and electrical field E
→ measure of ability of material to conduct electric current
Conductivity requires movability of electrons (along one chain and from chain
to chain), which is different in amorphous and crystalline state of polymer.
ides.com
Chapter05 1
Polyacetylene
Shows a small conductivity already at room temperature.
Polyacetylene is a conjugated polymer
(alternating single and double bonds).
Wikipedia.org
Single- and double bonds can exchange with no change in energy. A free radical
forms at the position at which the two ground states A and B meet. → This
defect is called a soliton.
→ Charge storage on the polymer chain leads to a structural relaxation (and vice
verse), which in turns localize the charge.
For simplicity, the chemical structure of the soliton is drawn as an abrupt change
from phase A to B; but as shown by experiments and calculations, the
structural relaxation in the vicinity of the domain boundary extends over
approx. 14 carbon atoms.
A charge can be freely moved along the polymer backbone like a soliton in a
channel. This results in a good conductivity along the polymer backbone.
Wave that propagates without dispersing are called solitary wave or soliton. In
hydrodynamics the energy dissipation process is compensated by contributions
from nonlinear processes.
∂u ∂u ∂ 3u
Basic example of soliton equation: +u + =0
∂t ∂x ∂x 3
∂ 2u 1 ∂ 2u
Differs from normal wave equation: − =0
∂x 2 c 2 ∂t 2
Chapter05 2
This topological defect (soliton) is mobile:
- calculated activation energy for motion ~ 2 meV
- soliton mass about 6me
photonicswiki.org
The π band is referred to as the valence band and the π* is called the conduction
band. This assumes a perfectly coplanar chain. The width of the valence band
and the conduction band is about 5 eV. The energy gap or band gap Eg is about
1.5 eV, this also known as the ionization potential. The bottom of the conduction
band is also known as the electron affinity.
Doubling the period will lead to a modulation of the electronic density, called
charge density wave (CDW), and thus to a superstructure. The doubling of the
Chapter05 3
unit cell will reduce the Brillouin zone to half; which leads to a gap 2Δ right at
the Fermi energy.
→ The system undergoes a metal-to-insulator transition.
The model shows that the soliton creates a localized electronic state, which is a
non-bonding state, at a energy lying in the middle of the π-π* band gap, between
the bonding-antibonding levels of the perfect, dimerized, chain. In other words it
is located at the Fermi level.
Chapter05 4
A single a) Neutral soliton (singly occupied state): the carbon atom at the boundary is
electron is
added to the neutral, and there is one spin unpaired
carbon atom
so that it’s
now neutral π*
and s=1/2
S0
neutral, ½ spin soliton:
Q=0 π
s = 1/2
b) Positive soliton (unoccupied state): carbon atom at the boundary is left with a
positive charge, and there are no unpaired spins
π*
+
S
positive, spinless soliton:
Q = +q π
s=0
c) Negative soliton (doubly occupied state): carbon atom at the boundary is left
with a negative charge, but there are no unpaired spins
π*
-
S-
negative, spinless soliton:
Q = -q π
s=0
abstraction of an electron I2
e-
iodine (I2) abstracts an electron from the top of the valence band, becoming an
I3- ion
polaron formation - note: counter
superposition of charged and neutral ion I3-
soliton
+
hole created in the polymer chain does not delocalized due to the structural-
impose localization and the coulombic binding to the iodine ion
The mobility of the polaron can be high, and then the charge is transported along
the polymer backbone. However, the mobility of the counter ion is low.
web.mit.edu
Chapter05 6
In a crystalline inorganic material, setting a charge onto a site does not change
the surroundings, as the crystal lattice is rigid. In contrast in many disordered
organic materials charge creates a distortion of its surrounding.
Quasi-particles:
• combinations of quasi-particles forming new quasi-particles (unlike
mathematical solitons that do not interact!)
• combination of charges and lattice distortions
π π*
P- P+
Q = -|q| Q = +|q|
π π s = 1/2
s = 1/2
positive polaron
negative
-
negative polaron in poly para-phenylene (PPP)
Chapter05 7
Poly-para-phenylene (PPP)
PPP has no degenerated ground state. The ground state is the benzenoid state A.
The first excited state is the quinoide state B with slightly higher energy.
Chapter05 8
A bipolaron is a bound state of two charged solitons of like charge (or two
polarons whose neutral solitons annihilate each other) with two corresponding
mid-gap levels.
- +
B B
Q = -2|q| Q = +2|q|
π* π*
s=0 s=0
BP- BP+
π π
Example:
- -
negative bipolaron in poly para-phenylene (PPP)
Chapter05 9
separation still sufficiently large that adjacent soliton overlapping is small and
conductivity is low.
At higher doping, the soliton wave functions overlap with the result that the
intergap soliton band merges with the HOMO. The soliton overlap is sufficient
for electrons (in the case of donor doping) to move freely along the chain.
→ quasi metallic transport
low high
π π
S S
π π
Chapter05 10
band gaps. This is largely because the carriers have very short lifetime (<1 ns)
due to rapid recombination and deep hole trapping.
Photoconductive polymers can be p-type (hole-transporting), n-type (electron-
transporting), or bipolar (capable of transporting both holes and electrons). Most
practical photoconductive charge-transporting polymers are p-type.
Example: polysilane
Polysilanes can be quasi-conjugated polymers, but their backbones are
composed of silicon atoms. The effective mobility can be high: μ = 1 cm²/Vs
Chapter05 11
Applications:
• anti-static coating for photo-films, mobile-phones
• radiation protection of electron-beam based monitor technology
• (auto)darkening windows to reduce passing light
Applications:
Photocopier working with xerography (standard for office copying)
Old: chalkogenide-glasses (Se), toxic – today: photoconducting polymers
Mechanism of photoconductivity:
exciton
Chapter05 12
An exciton is an excited quasi-particle in a solid, which is formed by a
Coulomb-bound electron-hole pair. Excitons may be treated in two limiting
cases, depending on the properties of the material:
Wikipedia.org
ifw-dresden.de
Chapter05 13
Singlet and triplet excitons can also be formed due to interaction following
charge injection; theoretically, this follows a one-to-three ratio, i.e., only a
quarter is of singlet type.
blog.disorderedmatter.eu
Applications:
organic photovoltaic (OPV) cell is a
photovoltaic cell that uses conductive
polymers or small organic molecules
spie.org
Chapter05 14
The basic operational mechanism for current generation in organic
photovoltaics cells can be split into 4 steps:
www2.warwick.ac.uk
v v v
Drift velocity v = μ ⋅ E with mobility μ in the electric field E
Chapter05 16
Further improvements in this model have been proposed where a spatially
correlated site-energy distribution was considered. This is known as the
correlated disordered model (CDM).
However, in polymers charge transport occurs via hopping of polarons instead
of the charge carriers itself. The transition rates have been modeled by Marcus,
and the field and temperature dependence of the mobility has been obtained.
Example: polysiloxane
Regime with constant slope in the log I - versus - log t presentation shows
the presence of different scaling laws.
Theoretical description:
Model of a one-dimensional dispersive transport: Transport in amorphous solid
is described by a broad distribution g(ε) of single-exponential hopping rates.
http://www.uni-muenster.de/Physik.AP/Denz/
← semi-transparent Al-electrode
← photo-conducting polymer
← semi-transparent Al-electrode
← polyester support
5.6 Electroluminescence
Since 1990 conjugated polymers are known which emit light in response to the
passage of an electric current or to a strong electric field. It is the result of
radiative recombination of electrons and holes in a material.
Chapter05 19
In an OLED, an electrical current causes electrons (-) to move from the cathode
to the emissive layer (EML), creating a negative charge in the emissive layer.
The positively charged anode attracts electrons from the conductive layer
(HTL), creating a positive charge in the conductive layer, which recombine with
holes (+) in the conductive layer attract electrons from the emissive layer, which
recombine with the electron holes, lowering the energy level of the electrons and
emitting light as a by-product.
auo.com
OLED Devices:
← negative electrode
← electroluminescent film
← positive electrode
← support
sigmaaldrich
Chapter05 20
Examples: poly-para-phenylenevinylene (PPV)
PPP Devices:
Al
PPP
ITO
glass
Special: PPP devices emit blue light → blue LED become possible!
Chapter05 21
Further application: All-polymer laser:
Chapter05 22
Future:
New or improved properties from the synthesis of new conjugated polymer
Conjugated polymers containing
electron-transporting, hole-
transporting, and blue light-
emitting units
Chapter05 23
5.8 Dielectric behavior of polymers
Most polymers are very good insulators.
wikipedia.org
Not all polymers behave the same when subjected to voltage and thus polymers
can be classified as ‘polar’ or ‘non-polar’ to describe their variations in
dielectric behavior.
Examples of polar polymers are PMMA, PVC, PA (Nylon), PC
Examples of non-polar polymers are PTFE (and many other fluoropolymers),
PE, PP and PS
For polar polymers the alternating current (AC) frequency is an important factor
because of the time taken to align the polar dipoles. At very low frequencies the
dipoles have sufficient time to align with the field before it changes direction
and the dielectric constant is high. At very high frequencies the dipoles do not
have time to align before the field changes direction and the dielectric constant
is lower. At intermediate frequencies the dipoles move but have not completed
Chapter05 24
their movement before the field changes direction and they must realign with the
changed field. Polar polymers at low frequencies (60 Hz) generally have
dielectric constants of between 3 and 9 and at high frequencies (106 Hz)
generally have dielectric constants of between 3 and 5.
For non-polar polymers the dielectric constant is independent of the alternating
current frequency because the electron polarization is effectively instantaneous.
Non-polar polymers always have dielectric constants of less than 3.
wikipedia.org
= 1 − iω ∫ φ (t )e dt
ε0 − ε∞ 0
ε ′′(ν ) ∞
= ω ∫ φ (t )cos ωtdt
ε0 − ε∞ 0
Chapter05 25
Simple assumption: function φ(t) ∝ e(-t/τ), =) one relaxation time τ
ε ′(ν ) − ε ∞ 1
=
ε0 − ε∞ 1 + ω 2τ 2
ε ′′(ν ) ωτ
= (Lorentz shape)
ε 0 − ε ∞ 1 + ω 2τ 2
Chapter05 26
Example: amorphous polymer
polyethylmethacrylate at 272 K at different pressures of p= 1(1), 340(2), 690(3)
and 1020(4) bar shows strong pressure dependence.
Chapter05 27
α and β relaxation are very different for different polymers
a) α- process
τα the relaxation time of the α- process follows the so-called
⎛ B ⎞
Vogel-Fulcher-Tammann (VFT)-law τ α = τ 0 exp⎜⎜ ⎟⎟
⎝ T − T0 ⎠
With the reference temperature T0 (typically 50°C below glass transition
tempearture). The VFT-law is equivalent to the Williams-Landel-Ferry (WLF)-
equation which is related to the temperature-time-superposition principle. Thus
the α- process obeys the temperature-time-superposition principle for the shift-
parameter aT:
τα C (T − T0 )
log(aT ) = log =− 1 and C1 = B / (T − T0 );C2 = T − T0
τ0 C2 + (T − T0 )
b) β- process
τβ is single activated (Arrhenius behavior) with a weak T-dependence
At high temperatures it leads to the α- process.
Commonly the relaxation strength is Δεα > Δεβ (with some exceptions).
Superposition principles:
For amorphous polymers above their Tgs, there is a convenient approximation
which makes experiments easier. It is known as time-temperature
superposition, and it relates time to temperature for viscoelastic materials. If
not temperature but pressure is varied in the experiment the so called pressure-
time-superposition principle is observed for polymers.
Chapter05 28
Example: normalized master-curve of ε' and ε" for polyethylacrylate •, ,
resembles data measured at 1, 340 and 690 bar
Chapter05 29