Liquid Junction Solar Cells

1. Charge Carriers in Electrode Materials

Metal (Pt)
Electrons

Semiconductors (n
Si)
Electrons and holes

Solid Electrolytes
(LaF3)
Ions

Insulators
(SiO2)
No charge
carriers

2. Electrodes in solution
For current to pass through the interface Metal/Solution, an electrochemical reaction
must occur, for example a reduction on the cathode Working Electrode (WE): Fe 3+ +
e Fe2+. For a complete circuit, the cell also needs a Counter Electrode (CE) for the
reverse anodic reaction on the anode.

Metals

Semiconductors

Solid Electrolytes

Insulators

Without applied bias the

potential drop occurs
across the Helmholtz
(double) layer

Most of the potential

drop is in the
semiconductor
instead of in the
solution.

No electron
exchange
and no ion
exchange.

The potential on the WE is

determined by the redox
species with the largest
electron exchange current
density i0,e (the rate of
electrons going back and
forth between redox
species and electrode in
equilibrium i.e. at zero
current). e.g. Pt electrode
senses O2 in a river
because O2 has the higher
i0,e with Pt

Transport of charges to
and from solution is
limited to those redox
systems that have
states that overlap
with the
semiconductor bands

No electrons
exchange occurs at
the surface, just ions
exchange with the
solid often with very
high selectively.
The reaction with
fastest ion exchange
current, i0,i
determines the
potential. In the case
of LaF3, that is F-. In
the case of glass, that
is H+. It is an ionselective sensor

If it is an oxide
insulator it will
exhibit pH
sensitivity like
an oxide
semiconductor

Potential drop
occurs in the
insulator

Often there are different redox species involved in establishing the equilibrium
potential in which case we speak about a mixed potential zero external current
but no net reaction (e.g. corrosion)

3. Semiconductors Band Bending

When the semiconductor is in contact with the solution a band bending occurs as its
Fermi levels equilibrates with a redox couple.

The initial difference between the SC EF and the solution Fermi Level (i.e., its
electrochemical potential), determines the extent of band bending at the interface
SC/liquid junction when the interface reaches equilibrium. This difference is also the
maximum theoretically attainable photo-voltage. The photo-voltage can thus be
manipulated by varying the redox couple in the electrolyte.

A/ A
V =EF
The region of the Band Bending is referred as the Space Charge layer, which
usually has 0.1 -1 m
During band gap excitation, the space charge layer assists in charge separation as
the electrons are driven into the bulk semiconductor and holes to the electrolyte
interface (for p-type semiconductor, this situation is reversed!).
Under open circuit conditions, electrons accumulate within the conduction band,
resulting in the flattening of bands.

The flat-band potential (V FB) is that potential one needs to apply to make the bands
flat in the semiconductor all the way to the surface (it can be deduced from a
capacitance measurement of the interface)
For a semiconductor covered with an oxide (e.g. Si with SiO 2, TiO2) the flat band
potential is a function of pH (ionization of the surface OH groups changes with pH)
and is often independent of redox systems. The more the pH is increased, the
more the conduction band edge is shifted to more negative potentials.

4. Semiconductors: Quantization concept

Max Plank discrete energy quanta photons. The energy of each photon is
related to the wavelength of the radiation:
= frequency (Hz = s1)
'

hc
E=h= [ J ] ,[eV ]

34

h=Plan k s constant :6.63 10

Js

c=Speed of light (3 108 m/s)

= wavelength (m)

These energies are very small and hence are usually measured using a new energy
unit called electron-volts. One eV is the energy acquired by an electron when
accelerated by a 1.0 V potential difference. Energy acquired by the electron is qV.
Since q is 1.6 1019 C, the energy acquired is 1.6 1019 J. which is defined as 1 eV.

1 eV =1.6 1 019 J
4.1.

The Energy Band Model

Si has 4 electrons in its outermost shell, but there are 8 possible states. When
atoms come together to form a crystal, these shells overlap and form bands.

Metals

Either:
Valence Band is partially
Filled
Conduction and Valence
bands overlap

5. Atomic configurations of Si

Semiconductors

Eg = 1.1eV for Si

Insulators

Eg > 3 eV
Eg ~5 eV (Diamond)
Eg ~8 eV (SiO2)

Bohr model The energy of electrons in atomic systems is restricted to a limited

set of values.
In silicon: 10 of the 14 Si-atom electrons occupy very deep lying energy levels
and are tightly bound to the nucleus
The remaining 4 electrons, called valence electrons are not very strongly
bound and occupy 4 of the 8 allowed slots. Ge (Germanium) and C have the
exact same configuration, except that its cores have 28 and 12 electrons
respectively.

Covalent bonding each atom shares its electrons with its nearest neighbor.
At 0K: In Si, no electrons are
available for conduction in this
covalent structure, so the
material is and should be an
insulator.
Every valence site is
occupied by an electron,
thus, it does not contribute to
current.
No electrons allowed in band
gap
No electrons with enough
energy to populate the
conduction band
No Carriers

Above 0K: Enough thermal energy ~kT

(k=8.62E-5 eV/K) can break some bonds.
Thermal excitation
At 300K, some bonds are broken creating a free
electron, and at the same time, a hole (absent
electron) that can move on the valence band of
the crystal by accepting electrons from other
bonds thereby creating a hole.
@ 300K : Eg(Si) = 1.1 eV >> kT = 25.86 meV,

Electrons

Holes

6. Doping
Donor: creates extra electron
Phosphor (P) atom: 5 valence electrons
# P atoms = # free elect

Acceptor: creates available hole

Boron (P) atom: 3 valence electrons
#B atoms = #holes

Ionization energy of donor:

Ei = Ec-Ed ~ 40 meV
Since 40meV ~kT, all donors (P atoms)
are ionized at room temperature.
ND ~ n (electrons)
There is an electron freezeoutat low temperatures (low kT)

Ionization energy of acceptor:

EA - EV ~ 40 meV
Since 40meV ~kT, all acceptors (B
atoms) are ionized at room temperature.
NA ~ p (holes)
There is a hole freeze-out at low
temperatures

7. Intrinsic Fermi Level

The Fermi level is the total chemical potential for electrons (or electrochemical
potential for electrons) and is usually denoted by or EF. The Fermi level of a body

is a thermodynamic quantity, and its significance is the thermodynamic work

required to add one electron to the body (not counting the work required to remove
the electron from wherever it came from).

8. P-N Junction

9. Semiconductor-Liquid Junction