Introduction

EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
1
What semiconductor basics are important for solar cells?
carrier generation, loss, and transport
p-n junction
metal semiconductor contacts
2
Outline Semiconductor basics classes
Need to know how many carriers at what energy and where in the device
Properties of Semiconductors
Band gap & band diagrams
Density of states
Fermi-levels
Carrier Concentration: Intrinsic and doped
Recombination and Generation
Transport properties and mechanisms
PN junctions
Built-in electric field
Current flow mechanisms under voltage and light bias
Diode equation
Metal semiconductor contacts
Schottky
Ohmic
I
2
3
4
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Outline Basics part II
3
Recombination
-Types
- Lifetime
- Diffusion length
- Surface recombination
Generation
-Types
- Photons
Transport properties and mechanisms
- Diffusion
- Drift
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Motivation
Part I described how to calculate the carrier concentration in bulk
material in equilibrium
Part II discusses how carrier concentrations are altered from
equilibrium by two factors:
Generation and recombination of carriers
Transport of carriers from one region to another.
Need to determine processes for recombination and generation,
and their rates.
Need to determine the processes for transport, and how they
depend on the carrier concentrations.
We will consider drift and diffusion as the transport processes.
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Continuity equation
5
Powerful general equation widely used in many fields
S V
t
= +

The change in a quantity depends on the

generation or removal rate (S) and the vector
function describing the transport of V

Apply this to carriers in a semiconductor

R G J
q t
t z y x n
n
+ =

1 ) , , , (
For electrons. is the electron current
and G and R are the generation and
recombination rates, respectively
n
J

EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation & Recombination
Even with no external inputs, carriers are continuously
moving from band to band, but at equilibrium, the carrier
concentration does not change as a result of these
processes.
Generation refers to any process by which electrons
move from valence band to conduction band to
conduction band, leaving
behind a hole in valence band.
Recombination is any process
by which electrons from
conduction band move
back into the valence band,
thereby removing a hole
from the valence band.
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Recombination
7
There are three basic types of recombination in the bulk of a single-crystal
semiconductor:
Band to band recombination (radiative transition in direct bandgap
semiconductors)
Shockley-Read-Hall (SRH) recombination. Also called trap assisted
recombination
Auger recombination
E
E
t
Band to band SRH Auger
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Recombination Band to Band
8
Band-to-Band recombination usually emits a photon (radiative)
The emitted photon has an energy similar to the band gap
Dominates in direct bandgap semiconductor devices (e.g.,
LEDs and concentrator or space solar cells made from GaAs)
Can be neglected for silicon solar cells since Si is an indirect
bandgap semiconductor and radiative recombination is
extremely low
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Recombination - Shockley-Read-Hall
Recombination through a defect is called
Shockley-Read Hall Recombination (SRH
recombination)
The defects, either foreign atoms or structural
defects, may be unintentional or deliberate
Does not occur in perfectly pure, defect free
material.
The defect introduces an additional state into
the forbidden gap. Energy levels near mid-gap
are very
effective for recombination whereas defect
states close to either band edge are not as
effective
SRH recombination is a two-step process: An
electron (or hole) is captured in the defect state.
If a hole (or electron) moves to the same
energy state before the first carrier is thermally
re-emitted, then recombination occurs.
SRH recombination dominates in indirect
semiconductors
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Recombination - Auger
Involves three carriers
An electron and a hole recombine, but
rather than emitting the energy as heat
or as a photon, the energy is given to
a third carrier, an electron in the
conduction band.
Auger recombination is most important
in heavily doped or heavily excited
material
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Recombination lifetime
11
Recombination rate is proportional to the excess carrier density (ie, no net
recombination at thermal equilibrium)
Recombination rates for majority carriers equals that of minority carriers
Rate (R) is proportional to the product of n and p
Assuming low level injected material (where the number of minority carriers is less
than the doping) we define the minority carrier lifetime () which is related to the
recombination rate
) (
2
i
n np
dt
dp
dt
dn
R = =
o
n
n n n
n
R =

= ,

o
p
p p p
p
R =

= ,

in n-type material in p-type material

1 1 1 1

= + +
rad SRH aug
Think of the lifetime as the average time a carrier can spend in an excited state after electron-
hole generation before it recombines
Lifetimes are defined for each of the recombination mechanisms
The total recombination rate is given by:
aug SRH rad
and , ,
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Diffusion length
12
The " minority carrier diffusion length" is the average distance a carrier can
move from point of generation until it recombines.
The diffusion length is related to the carrier lifetime by the diffusivity
where L is the diffusion length (cm), D is the diffusivity (cm/s ) and t is the
lifetime (s)
Example calculation of L for silicon (assume p type, doping 5x10
16
/cm
-3
)
D
e
=23 cm/s ; assume a lifetime of 1 msec; L = 1500 microns
This is a large distance, considering a typical solar cell wafer is only 200 to
300 microns thick, and suggests we need to consider the effect of wafer
surfaces on lifetime
D L =
e e
q
kT
D =
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Surface Recombination
13
By definition, bonds are disrupted at the surface of a semiconductor
material and there is a high probability of dangling bonds and defects
unless special efforts are made to terminate and passivate that surface
Similarly to SRH recombination due to defects in the bulk, surface defects
can lead to very rapid recombination of minority carriers
Characterized by a surface recombination velocity (s) which depends on
the two dimensional density of traps at the surface (N
t
) and the
recombination cross section () which is on the order of 10
-15
cm
2

th
is the carrier thermal velocity (approx. 10
7
cm/sec)
Typical values:
-unpassivated silicon surface: 10
7
cm/sec
-carefully prepared thermally oxidized silicon: < 10 cm/sec
t th
N v s n s R = = ;
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation: Basic Processes
In order to move from one band to another, there are several requirements:
Carrier must gain enough energy to move from one band to another
There must be an electron in the valence band or at another low energy
level.
There must be an unoccupied space to which the electron can move.
Energy can come from thermal energy or from photons.
Unless there is a thermal gradient across the material, thermal energy
does not cause a net generation rate, as it is balanced by recombination.
Hence, will only consider generation due to photons.
Every recombination process has an inverse generation process, but not all
are practically observed.
In most photovoltaic devices, the number of light-generated carriers are of
orders of magnitude less than the number of majority carriers already present
due to doping. Thus, the number of majority carriers in an illuminated
semiconductor does not alter significantly. However, the number of photo-
generated minority carriers outweighs the number of minority carriers
existing in the solar cell in the dark, and therefore the number of minority
carriers in an illuminated solar cell can be approximated by the number of
light generated carriers.
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation: Photons
Photons are quantum mechanical particle that describes electromagnetic
radiation.
Properties of photons:
Photons have small momentum, but large energies.
Energy given by either energy (usually in eV) or by wavelength or
frequency.
Photon flux gives number of photons/sec.cm
Can convert between photon flux and power density (for a monochromatic
source) by:
=

= h
hc
E
in microns
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation: Photons
The energy of a photon has a major impact on how the
photon interacts with the semiconductor.
If the photon <E
G
, then ideally no generation
If photon >= E
G
, then photon can be absorbed.
Excess energy above E
G
generally given off
as heat
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation: Band to Band
Band-to-band generation can occur via either direct or indirect transitions
In indirect materials to get an absorption we must either absorb a phonon in
addition to the photon, or emit another phonon after the absorption of the
incoming photon.
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Absorption coefficient, , (units cm
-1
) is a measure of the probability of
absorbing a given photon.
intensity of light (I
o
)at any distance (x) into the material is
where I
o
is the light intensity at the top surface.
Absorption depends on the likelihood of the transition occurring lower for
processes near the band edge, increasing for higher photon energies.
For band-to-band transitions, the absorption
coefficient has the form
Temperature changes in a
material cause a change in
the band gap (E
G
as T ),
hence changing the
absorption edge in a material.
Generation: Absorption coefficient
2 1
) (
G
E
x
o
e I I

=
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation: Absorption coefficient
Direct band gap materials generally have a more rapid increase
in absorption and larger
Absorption depth, 1/, where intensity of light in semiconductor
falls to 1/e, also commonly used.
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
20
Generation Rate
Generation rate given by the number of photons
absorbed in a material, and usually assumed to alter
the number of carriers in the energy bands.
Number of photons at a given distance x into a material
given by:
Generation rate given by:
x
s ph
e N N

=
N
ph
is the number of photons in the material
N
s
is the number of photons at the surface
is the absorption coefficient and depends on
x is the distance into the material
x
s
ph
e N
dx
dN
G

= =
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Generation Rate
Generation rate depends on the wavelength of incident light
(different ) and also varies with position in the material.
Large means light absorbed close to surface, small means
light absorbed relatively uniformly in entire material.
If x << 1/, then generation
can be assume constant.
x
s
e N G

=
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Sample Calculation
Given 100 W/m
2
of monochromatic light (=1000nm) on a silicon substrate
200 microns thick, calculate the generation rate at the surface and at x=100
microns
N
s
=100w/m
2
(1/1.6x10
-19
)(1/1.24)J
-1
=5x10
16
cm
-2
sec
-1
From the plots, is approx. 100 cm
-1
, so 1/ = 100 microns G not
constant with depth
At the surface:
G=N
s
=100 cm
-1
(5x10
16
cm
-2
sec
-1
)= 5x10
18
cm
-3
sec
-1
At 100 microns deep into the silicon:
G=N
s
e
(-x
)=100 cm
-1
(5x10
16
cm
-2
sec
-1
)e
[(-100cm-1)(0.01cm)]
= 1.8x10
18
cm
-3
sec
-1
23
Transport
Electrons (holes) in the conduction (valence) band are free and can move
throughout the crystal. We will consider two transport mechanisms: Drift and
diffusion.
Both these transport mechanisms depend on constant, random motion of electrons.
Electron moves in a given direction until it scatters due to an interaction with the
crystal lattice.
Electrons have a distribution of velocities around an average thermal velocity V
th
determined by the temperature T
The net motion in the absence of an external influence is zero
Thermal velocities are fast (on the order of 10
7
cm/sec)
Drift transport: In the presence of an electric field, carrier movement due to the
presence of the E-field is superimposed on the random motion
Diffusion transport: In the presence of a concentration gradient, carrier movement
due to the presence of the gradient is superimposed on the random motion
kT v m
th e
2
3
2
1
2 *
=
k =Boltzmanns constant, m* is
the effective mass for conductivity
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
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Transport-Drift
An applied electric field E results in a net carrier
velocity called the drift velocity, Vd. The carriers are
accelerated during the time t between lattice
scattering events so we can write the following
expression:
Define the mobility of the carriers as
Current due to electric field
Note that usually only one of the components in this
equation for conductivity is significant because of the
large ratio between the two carrier densities
( )

= = +
1
q n p
n p
*
n
n
m
qt
=
E qn qnv J
n d n

= = E qp qpv J
p d p

= =
( ) E E p n q J J J
p n p n total

= + = + =
*
*
n
d
d n
m
qEt
v
v m qEt
=
=
and
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Transport-Drift Si resistivity / mobility data
Electron mobility vs. doping
Hole mobility vs. doping
Resistivity vs. doping density
26
Transport-Diffusive
Diffusive transport: the random thermal motion of charged particles in
a concentration gradient results in a net particle flow and thus a
current
J qD
dn
dx
n n
= + for electrons
J qD
dp
dx
p p
= for holes.
D
p
kT
q
p
=
for holes
D
n
kT
q
n
=
for electrons.
D
n
, D
p
are the diffusivities for
electrons and holes, respectively
and can be related to the mobility
values by the Einstein
relationship:
EEE 598: Fundamentals of Solar Cell Design and Fabrication Fall 2010 Honsberg
Transport-Drift + Diffusive
If both an electric field and a concentration gradient are present, the total current
density is the sum of both drift and diffusive components:
dx
dp
qD E qp J
dx
dn
qD E qn J
p x p px
n x n nx
=
+ =