An introduction to device physics and

(organic) photovoltaics
Piers Barnes

Lecture 1: Refresh key solid state concepts for inorganic semiconductors

Energy bands
density of states
Fermi distribution
Intrinsic vs doping
mobility
drift and diffusion

Background reading on semiconductor materials and devices:

Physics of semiconductor devices (Sze): available as from the library both as a hard
copy and in electronic form.
Physics of solar cells (Nelson): available from the library
Online book: http://ecee.colorado.edu/~bart/book/book/title.htm
Britney Spears Guide to Semiconductor Physics: http://britneyspears.ac/lasers.htm
 Electrons in solids

LUMO

HOMO

Filled energy levels

Lithium: 1s2 2s1

ELECTRON ENERGY
 Semiconductors and insulators

conduction
band edge

Eg band gap

valence band
edge Non-interacting orbitals

Diamond structure

Eg = 5.5 eV

Diamond structure lattice constant (size of unit cell)

 Band structure
• Delocalised electrons can be considered as plane waves with wave vector k
units: cm-1 (this often called the crystal momentum, pcrystal = ħk)
• Given the periodic potentials within the crystalline lattice, a band structure
can be calculated.
• This gives the energy of an electron for different momenta (k) within the first
Brillouin zone (primitive cell of the reciprocal lattice).
• The reciprocal lattices is the Fourier transform of the real-space crystal lattice
to give points of spatial frequency.

Eg band gap (indirect transition)

Brillouin zone of diamond

Using the band diagram below, estimate the maximum wavelength of a
photon needed to excite an electron across the band gap?

What wavelength photons would be needed for critical point 3 (CP3)?

 Density of electronic states
Describes a continuous distribution of allowed electronic energy states per unit
volume per unit energy, D(E). Sometimes also uses letters g, N or acronym DOS.

Units for 3D material: cm-3 eV-1

Integrating D(E) across an energy range thus gives the number of states per unit
volume.
 What kind of material is this?

What kind of material (in blue) is this?

Would you classify (intrinsic) anatase as a metal, semiconductor or insulator?

Courtesy University of Utah Physics Dept.
 workfunction
• Workfunction,  = minimum energy required to
remove an electron from surface of material

Vacuum energy
•  = energy difference between Fermi level, EF,
and vacuum energy
 empty levels
• low workfunction metals highly reactive EF
– e.g. Ca, Mg
filled
• high workfunction metals, relatively inert energy levels
– e.g. Au, ITO

• low workfunction materials typically used for

electron injecting electrode (cathode)

• high workfunction materials typically used for

hole injecting electrodes (anode)
 Energy scales
Electrochemical scale, 0 = NHE
(up is negative direction)
Vacuum scale, 0 = vacuum energy
Normal
(up is positive direction)
hydrogen
electrode
Saturated
calomel
electrode
Vacuum scale
• What’s the difference between work function,
ionisation potential and electron affinity in
solids?

• How could we measure them?

 Free electron gas model
• Combines Drude model with Fermi-Dirac statistics
• Assumes valence electrons in a crystal are
confined to the crystal but are otherwise free and
non-interacting.
• The electrons obey the Pauli exclusion principle
• Electron mass, me, modified to an effective
electron mass, me*, to maintain consistency
between observations and band structure
calculations
 Fermi energy and Fermi Level
T = 0K T > 0K

metal semiconductor

f(E) is the probability of finding an

electronic state of energy E
occupied. T is the temperature, and
k is Boltzmann’s constant. EF is the
http://archive.cnx.org/contents/97d8f4d5-6cb1-4b8f-a4f0-
06c627e81ec4@1/mobile-carriers-and-the-fermi-function
f(EF) = 1/2 Fermi level when T > 0.
Fermi-Dirac distribution

f(E) is the probability of finding an electronic

state of energy E occupied. T is the
temperature, and k is Boltzmann’s constant.
f(EF) = 1/2

Chemical potential, μ, and EF are often

used interchangeably (if no electrostatic
potential is present). μ = dG/dN where G
is the Gibbs free energy of the system and
N is the number of particles in the system.
The chemical potential at T = 0 K is the
Fermi Energy. The Fermi level, EF, includes
the effects of electrostatic potential and
can also be referred to as the
electrochemical potential, 𝜇ҧ (but also,
loosely, just as μ)
 Boltzmann approximation
1 𝐸𝐹 −𝐸
𝑓 𝐸 = 𝐸−𝐸𝐹 𝑓(𝐸) ≈ e 𝑘𝐵 𝑇
1+ e 𝑘𝐵 𝑇
Boltzmann approximation is
reasonable at energies more
than about 2kBT from the Fermi
level.
f(E), probability of occupancy

The approximation allows

easier estimates of charge
carrier densities to be made
more easily. By determining the
effective density of states at the
conduction (Nc [cm-3]) and
valence (Nv [cm-3]) band edges:
3/2
2𝜋𝑚𝑒∗ 𝑘𝑇
𝑁𝑐 = 2
ℎ2
3/2
2𝜋𝑚ℎ∗ 𝑘𝑇
𝑁𝑉 = 2
ℎ2
 Intrinsic semiconductors
n is the free electron concentration [cm-3]
p is the free hole concentration [cm-3]
n

The effective density of states (Nc and Nv [cm-3]) at the band edges correspond to
Intrinsic the concentration of electrons or holes that would be at the conduction or
𝐸𝐹 −𝐸𝑐 valence band edges if the Fermi level were also at that band edge. It is estimated
𝑛= 𝑁𝑐 e 𝑘𝑇 by the integrated product of the Boltzmann distribution (occupancy per unit
- energy) and the density of states in the band (states per unit energy – typically
Ec assumed to be parabolic).
ENERGY

3/2 3/2
EF 2𝜋𝑚𝑒∗ 𝑘𝑇 2𝜋𝑚ℎ∗ 𝑘𝑇
𝑁𝑐 = 2 𝑁𝑉 = 2
Ev ℎ2 ℎ2
𝐸𝑣 −𝐸𝐹 In an intrinsic semiconductor the difference between EF and the band energies is
+ 𝑝=𝑁 e 𝑘𝑇 Eg/2. This can be used to estimate the intrinsic concentration of carriers in the
𝑣
material, ni, using the Boltzmann distribution:
Law of mass action: n p = ni2 ~ 1010 cm-3
−𝐸𝑔
(very low concentration at T = 300 K, c.f
5 × 1022 atoms cm-3)
𝑛𝑖 = 𝑁𝑐 𝑁𝑉 e2𝑘𝑇
 Intrinsic vs doped semiconductors
Acceptor density = NA Donor density = ND

Intrinsic p type n type

n ≈ ND
n ≈ ni - n ≈ ni2/NA - - - - -
ENERGY

Ec conduction band
EF
Ev valence band
+ p ≈ ni + + + + +
Very low minority
p ≈ NA p ≈ ni2/ND
concentrations at room
temperature
Intrinsic vs doped semiconductors
Ionized dopants release or
accept electrons from the
conduction or valence band
respectively, increasing the
concentration of free carriers.
This concentration is less
strongly dependent on
temperature.

Doping shifts the Fermi-Dirac

distribution up or down
relative to an intrinsic
semiconductor resulting in a
majority population of
electrons (n-type) or holes
(p-type)

From Sze (Physics of

semiconductor devices)
 If the effective density of states at the conduction band edge in MAPbI3 is Nc =
1e21 cm-3 what is the free electron concentration in the semiconductor in the
dark at T = -196, 25, 100 deg C assuming the material is intrinsic semiconductor?

If an organic semiconductor with a band gap of 1.7 eV is doped with a

concentration of 10-18 cm-3 of electron acceptors what is the concentration of
free holes in the material?

If the effective density of states in the conduction and valence band is 1020 cm-3
what is the concentration of free electrons in the material at room temperature?
 Charge carrier effective mass
• Curvature of the band edge in k space (conduction or valence,
often approximated as a parabola) can be parameterised by
an electron (or hole) effective mass, m*e or m*h. Ignoring
band offset for indirect semiconductors:

ℏ
∗ 2
𝑚 = ൘ 2
𝑑 𝐸
𝑑𝐤 2
Effective mass can be positive (electron) or
negative (hole).

e.g. For silicon m*e/me = 0.26 and m*h/me =0.39

Rest mass of an electron me = 9.1 × 10-31 kg

Effective mass may also be modified due to

distortion of surrounding lattice (polaron)
 Charge carrier mobility
Drude model – free non interacting electrons, velocity → 0 after colliding with
immobile positive ions

At equilibrium, 0 = (electrostatic + magnetic – retarding) force

p is momentum (force = dp/dt), B is the magnetic field (ignore here), m* is effective

mass of electron, and τ is the time between collisions.

Solve for p and divide by m* to give the drift velocity vd.

 Charge carrier mobility
• Average charge carrier drift velocity (vd) proportional to electric field
strength (E)
• The proportionality factor is known as the mobility: 𝐯𝐝 = 𝜇𝐄 (units
cm2 s-1 V-1)
• Different mobilities for electrons and holes.
• The concept can be explained by considering a free electron gas
with the Drude model, where electrons accelerate until they are (on
average brought to rest by scattering from impurities and phonons
etc.:
𝑞
𝜇 = ∗ 𝜏ҧ 𝜏ҧ is the average scattering time
𝑚

1 1 1 1
= + + +⋯
𝜏 𝜏𝑖𝑚𝑝𝑢𝑟𝑖𝑡𝑖𝑒𝑠 𝜏𝑙𝑎𝑡𝑡𝑖𝑐𝑒 𝜏𝑑𝑒𝑓𝑒𝑐𝑡𝑠
 Drift current
Current - flow of electric charge in the form of charge carriers (e.g. electrons,
holes, ions, protons) [A]= [C s-1].

J = -q n vd (similar +ve contribution for holes)

Where J is the current density [A cm-2], n is the carrier density [cm-3], q is the
electronic charge the and vd is the drift velocity [cm s-1], and n is the
concentration of charge carriers.

Force on positive charge = q E

However scattering prevents continuous acceleration (Drude approximation)

*

vd = μ E (where μ is the mobility [cm2s-1V-1]

Displacement current (P is polarization):

- =-qμEn
*
 Voltage and resistance
From previous slide: d
J=-qμnE

Ohms law:

J=σE

Where σ is the conductivity [S cm-1] = 1/ρ (resistivity [Ω cm])

E = V/d (in one dimension, where d is distance between contacts)

Potential difference – free energy per unit charge. [J C-1]

J A = σ V/d (where A is area)

V=IR (where R = Aσ/d and conductance G = 1/R [S]

From Drude approximation, μ = q τ/me*, mobility influenced by

scattering time (e.g. defect density, lattice vibrations/phonons).
The resistance of thin film of material 500nm thick is measured to be 5k
Ohms between two parallel evaporated contacts 1 mm long, separated by 10
microns.

Estimate the conductivity of the material.

A Hall measurement is used to find the material is a semiconductor with a

carrier concentration of n = 4e17 cm3

Estimate the electron mobility.

 Diffusion
Fick’s first law (in 1 dimension, x, assuming n is positive charge concentration)

𝜕𝑛
𝐽 = −𝑞𝐷
𝜕𝑥

Fick’s second law

𝜕𝑛 1 𝜕𝐽
=−
𝜕𝑡 𝑞 𝜕𝑥

Where D is the diffusion coefficient [m2 s-1], related to mobility by the Einstein
relationship (or Einstein-Smoluchowski relation):

D = μ kB T/q

Concentration gradients can result in currents

 Summary
• Semiconductors density of conduction and valence band
states separated by a band gap, Eg.
• The average energy required to remove an electron from
the material is the work function, corresponding to the
Fermi Level.
• At thermal equilibrium the Fermi-Dirac distribution can be
used to define the average occupancy of an energy state by
an electron (even a molecular material). This can often be
approximated by the Boltzmann distribution.
• For a given temperature the mobility is proportional to the
diffusion coefficient.
• The product of mobility and carrier concentration are
proportional to the conductivity.