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PHYSICS OF SOLAR CELLS:

PART I

Solar Cells
Instructor: Dr. Alessia Polemi

OUTLINE:
Structure of semiconductors
Energy band structure and carrier concentration
pn junction (very short review)

INTRO
Semiconductor solar cells devices
1) Semiconductors absorb light and deliver a portion of the energy of
the absorbed photons to carriers: e- and h+.
2) A semiconductor diode separates and collects the carriers and
conducts the generated electrical current in a specific direction.
a solar cell is simply a
semiconductor diode designed
to absorb and convert light
energy from the sun into
electrical energy.

Conventional solar cell


Sunlight is incident from the
top
Metallic grid
Antireflective coating
n-type and p-type are
brought together to form a
junction.
The diodes other electrical
contact is formed by a
metallic layer on the back of
the solar cell.

STRUCTURE OF
SEMICONDUTORS

Properties of semiconductors
Solar cells can be fabricated from various semiconductor materials
most commonly silicon (Si) crystalline, polycrystalline, and
amorphous
GaAs
GaInP
Cu(InGa)Se2
CdTe

Properties of semiconductors
Solar cell materials are chosen on the basis of:
how well their absorption characteristics match the solar
spectrum
their cost of fabrication
Silicon is the most popular choice
its absorption characteristics are a fairly good match to the
solar spectrum
Silicon fabrication technology is well developed (electronics
industry) IC

Structure of Solids
The solids used in photovoltaics can be broadly classified as
crystalline, polycrystalline, or amorphous.
Crystalline single-crystal materials;
Polycrystalline materials with crystallites (crystals or equivalently grains)
separated by disordered regions (grain boundaries);
Amorphous materials that completely lack long-range order
Crystalline:
- long-range order represented by the lattice and a basic building block (the unit
cell)
- Fixed positions (there are only 14 crystal lattices possible in a three-dimensional
universe)

Structure of Solids
Polycrystalline:
- composed of many single-crystal regions = grains, that exhibit long-range order
- the transition regions between the grains are termed grain boundaries
- grain boundaries have a significant influence on physical properties (they can
getter dopants or other impurities, store charge in localized states arising from
bonding defects)
- grain boundaries are broadly classified as open or closed. An open boundary is
easily accessible to gas molecules; a closed boundary is not.
- Diffusion coefficients are generally an order of magnitude larger along such
boundaries than those observed in single-crystal material

Structure of Solids
Amorphous solids:
- disordered materials that contain large numbers of structural and bonding
defects
- no long-range structural order (there is no unit cell and lattice)
- composed of atoms or molecules that display only short-range order, at best
- there is no uniqueness in the amorphous phase, e.g. there are a myriad of
amorphous silicon-hydrogen (a-Si:H) materials that vary according to Si defect
density, hydrogen content, and hydrogen-bonding details.

Phonon spectra
Because of the interactions among its atoms, a solid has
vibrational modes. The quantum of vibrational energy is called
phonon.
Phonons can be involved in heat transfer, carrier generation
(thermal or in conjunction with light absorption), carrier
scattering, and carrier recombination processes.
They behave like particles, e.g. when an electron in a solid
interacts with a vibrational mode, the event is best viewed as an
interaction between two types of particles, electrons and phonons

Phonon spectra

Phonons have a dispersion relationship Epn(k) [k wave


vector of the vibrational mode]. Analogous to the dispersion
relationship for light (Ept=hc|k|/2)
Epn(k) is more complicated and gives what is called phonon
spectrum or phonon energy bands in a solid. In the case of
both phonons and photons, k has the interpretation of
particle momentum.

Phonon spectra
SINGLE-CRYSTAL, MULTICRYSTALLINE, AND
MICROCRYSTALLINE SOLIDS
Phonon spectrum for Si and GaAs
O refers to optical branches
(these modes can be strongly
involved in optical properties)
A refers to acoustic branches
(so called because frequencies
audible to the human ear)
T and L refer to the transverse
and longitudinal modes

Phonon bands in two crystalline solids: (a) silicon, and


(b) gallium arsenide

Phonon spectra
1) Of the order of 108 cm-1
2) Notice! Superimpose the plot for
all photon energies Ept<3eV (solar
spectrum) versus k onto phonon
spectrum
Si

the momentum of the photons constituting the majority of the solar


spectrum is very small compared to the momentum of phonons
phonon energies are of the order of 10-2eV,10-1eV. Photon energies,
at least those in the NIR, VIS, NUV range, are of the order of 1eV

Phonon spectra
NANOPARTICLES AND
NANOCRYSTALLINE SOLIDS

As particle or grain size becomes smaller, the surface-to-volume


ratio increases and surface-stress effects on bulk and surface
phonon modes become more important
AMORPHOUS SOLIDS

There is no Brillouin zone in reciprocal space because there is no


unit cell in real space (there is no crystal lattice)
It is difficult to distinguish between acoustic and optical phonons
Phonons play the same critical roles in electron transport, heat
conduction, etc., as they do in crystalline solids

ENERGY BAND STRUCTURE


AND
CARRIER CONCENTRATION

Energy Band Structure


We have already looked at how by solving SE for periodic crystalline
structures we obtain electronic properties

2 +
E

2m
E V ) = 0
2 (
!
Motion of the e- in the crystal is
like that of an e- in free space if its
mass, m, is replaced by an effective
mass m

Energy Band Structure


Frequently, the detailed E(k) plot is not needed.
In many applications:
BandGap EG,
CB edge EC,
VB edge EV,
and local vacuum level EVL (energy needed to escape the
material) or equivalently electron affinity = energy to promote
an e- from the bottom of the CB to the vacuum level

Single crystal
Software wxAMPS

Energy Band Structure


Even polycrystalline and amorphous materials exhibit a similar band
structure (over short distances, the atoms are arranged in a periodic
manner and an electron wavefunction can be defined).
However, there are a large number of localized energy states within
the mobility gap that complicate the analysis.

Localized states:
- acceptor-like
- donor-like
- amphoteric in nature

Software wxAMPS

Energy Band Structure


Acceptor states: neutral when empty and negative when occupied
by an electron (ionized)
Donor states: neutral when occupied by an electron and positive
when empty (ionized)
Amphoteric gap states:
can be occupied by none,
one, or two valence
electrons. Their charge
state depends on their
occupancy

Software wxAMPS

Energy Band Structure


Localized (gap) states can serve as sources of carriers for the
bands = doping
It is possible to have so many gap states present in a material that
they form a band within the energy gap. Such a band within the
energy gap is termed an intermediate band (IB).

Software wxAMPS

Energy Band Structure


Very resourceful equation!

2 +

2m
E V ) = 0
2 (
!

Possible solution Excitons: can be involved in the light absorption


process in solar cell materials
Excitons are multi-electron solutions that may be viewed as an
electron bound to a hole via Coulombic attraction

Energy Band Structure


1) Binding energy is dictated by the Coulombic attraction
materials that polarize more have lower binding energies (i.e., the binding
energy correlates inversely with the dielectric constant)

2) They can be created by photon absorption


3) They can be mobile in a solid. When they move, energy moves, but
not net charge. Since they are not charged, they can only move by diffusion.

4) If excitons are produced by light absorption in a solar cell


and are to be utilized, then some process must also be present to
convert the exciton into at least one free negativepositive
charge carrier pair

Energy Band Structure


Where are e- and h+ located in terms of energy bands?

Density of states

Carrier Concentration
Density of states in the CB gC ( E ) =

Density of states in the VB gV ( E ) =

mn* 2mn* ( E Ec )

2 !3
m*p 2m*p ( EV E )

2 !3

"#cm 3eV 1 $%

"#cm 3eV 1 $%

Carrier Concentration
@thermal equilibrium (i.e. at a uniform temperature with no external
injection or generation of carriers), probability of finding an e- (or h
+) is given by the Fermi function
1
f (E) =
" E EF %
1+ exp $
'
# k BT &

T=0
! 2 ! 3 2 N $
EF =
#
&
2m " V %

2/3

kB = Boltzmann constant

EF

for e-

Carrier Concentration

Carrier Concentration
n0 =

Ec +
Ec

gC (E) = 4 (2mn* )3/2 h 3 (E Ec )1/2


= A(E Ec )1/2
Density of states in the CB

gC (E) f (E)dE
E EF

f ( E ) exp
k BT

Fermi-Dirac function
Boltzmann function

Carrier Concentration
" (EC EF ) %
n0 = N C exp $
'
k BT &
#
n0 = Electron concentration in the CB
Nc = Effective density of states at the CB edge
Ec = Conduction band edge, EF = Fermi energy
kB = Boltzmann constant, T = Temperature (K)

Effective Density of States at CB Edge


3/2

! 2 mn*kBT $
NC = 2 #
&
2
h
"
%

Nc = Effective density of states at the CB edge, me* = Effective mass of the electron
in the CB, k = Boltzmann constant, T = Temperature, h = Plancks constant

Carrier Concentration

" (EF Ev ) %
p0 = NV exp $
'
k BT &
#
p0 = Hole concentration in the VB
Nv = Effective density of states at the VB edge
Ev = Valence band edge, EF = Fermi energy
kB = Boltzmann constant, , T = Temperature (K)

Effective Density of States at VB Edge


3/2

! 2 m k T $
NV = 2 #
&
h
"
%
*
h B
2

Nv = Effective density of states at the VB edge, mh* = Effective mass of a hole in


the VB, k = Boltzmann constant, T = Temperature, h = Plancks constant

Intrinsic semiconductors
Mass Action Law

"
%
E
2
n0 p0 = ni = N C NV exp $ G '
# k BT &
ni = intrinsic concentration

The np product is a constant, ni2, that depends on the material properties NC, NV,
Eg, and the temperature. If somehow n is increased (e.g. by doping), p must
decrease to keep np constant.

Mass action law applies


in thermal equilibrium
and
in the dark (no illumination)

Intrinsic semiconductors
In un-doped (intrinsic) semiconductor, n. of electrons in CB and n.
of holes in VB are equal
no = po = ni (ni =intrinsic carrier concentration)

" EG %
ni = N C NV exp $
'
# 2kBT &
The Fermi energy in intrinsic semiconductor

EV + EC kBT ! NV $ typically very close to the


Ei =
+
ln #
& middle of the bandgap
2
2
" NC %

Intrinsic semiconductors

# EG &
ni exp %
(
2k
T
$
B '

ni: very small compared with the densities of states and typical
doping densities (ni 1010 cm3 in Si) and intrinsic semiconductors
behave very much like insulators they are not good conductors
of electricity
Intrinsic concentration.swf

Extrinsic semiconductors
n. of e- and h+ in their respective bands, and hence the conductivity, can
be controlled through the introduction of specific impurities, or
dopants, called donors and acceptors

Extrinsic semiconductors
All impurities introduce additional localized electronic states
into the band structure, often within the bandgap.
- If the energy of the state ED introduced by a donor atom is
sufficiently close to the conduction band edge (within a few
kBT), there will be sufficient thermal energy to allow the extra eto occupy a state in the CB. The donor state will then be
positively charged (ionized).
- Similarly, an acceptor atom
will introduce a negatively
charged (ionized) state at
energy EA.

Extrinsic semiconductors
Usually donors and acceptors are assumed to be completely ionized so
that
noND in n-type material and
poNA in p-type material.
The Fermi energy:

ND
EF = Ei + kBT ln
,
ni

NA
EF = Ei kBT ln
ni

Extrinsic semiconductors
Bandgap narrowing
- Very large concentration of dopants the dopants can no longer
be thought of as a minor perturbation to the system, i.e. effect on
the band structure bandgap narrowing (BGN) and thus
increase of intrinsic carrier concentration
- BGN is detrimental to solar cell performance; solar cells are
typically designed to avoid this effect
- BGN may be a factor in the heavily doped regions near the solar
cell contacts

Extrinsic Semiconductors: n-Type

As has 5 electrons
(a) The four valence electrons of As allow it to bond just like Si but the fifth electron is
left orbiting the As site. The energy required to release to free fifth-electron into the CB
is very small. (b) Energy band diagram for an n-type Si doped with 1 ppm As. There are
donor energy levels just below Ec around As+ sites.

Extrinsic Semiconductors: n-Type


Nd >> ni, then at room temperature, the
electron concentration in the CB will
nearly be equal to Nd, i.e. n Nd
A small fraction of the large number of
electrons in the CB recombine with holes
in the VB so as to maintain np = ni2

np = ni2
n = Nd and p = ni2/Nd
ni2
= eN d e + e
N d

h eN d e

Extrinsic Semiconductors: p-Type

B has 3 electrons
(a) Boron doped Si crystal. B has only three valence electrons. When it substitutes for a
Si atom one of its bonds has an electron missing and therefore a hole. (b) Energy band
diagram for a p-type Si doped with 1 ppm B. There are acceptor energy levels just
above Ev around B- sites. These acceptor levels accept electrons from the VB and
therefore create holes in the VB.

Extrinsic Semiconductors: n-Type


Na >> ni, then at room temperature, the
hole concentration in the VB will nearly be
equal to Na, i.e. p Nd
A small fraction of the large number of
holes in the VB recombine with electrons
in the CB so as to maintain np = ni2

np = ni2
p = Na and n = ni2/Na
ni2
= eN a h + e e eN a h
N a

Semiconductor energy band diagrams

Energy band diagrams for (a) intrinsic (b) n-type and (c) p-type
semiconductors. In all cases, np = ni2. Note that donor and acceptor energy
levels are not shown. CB = Conduction band, VB = Valence band, Ec = CB
edge, Ev = VB edge, EFi = Fermi level in intrinsic semiconductor, EFn = Fermi
level in n-type semiconductor, EFp = Fermi level in p-type semiconductor. is
the electron affinity. , n and p are the work functions for the intrinsic, ntype and p-type semiconductors

Compensation Doping
Compensation doping describes the doping of a semiconductor with
both donors and acceptors to control the properties.
More donors than acceptors

N d N a >> ni

n = Nd Na

More acceptors than donors

ni2
ni2
p=
=
n Nd Na

N a N d >> ni
p = Na Nd

ni2
ni2
n=
=
p Na Nd

PN JUNCTION:
DARK CURRENT
(very short review)

Basic of pn junction
Remember: this is the simplest solar cell possible

pn Junc&on
Properties of the pn junction
(a) The p- and n- sides of the pn
junction before the contact.
(b) The pn junction after contact, in
equilibrium and in open circuit
(depletion region, SCL). Built-in
field E0 tries to drift holes back into
p and electrons into n.
(c) Carrier concentrations along the
whole device: at all points, npoppo =
nnopno = ni2

(d) Net space charge density net


across the pn junction. Charge
neutrality.
Acceptor concentration

Depletion Widths

Donor concentration

N aWp = N dWn

pn Junc&on
(e) The electric field across the pn
junction is found by integrating net
in (d).
Field (E) and net space charge density
Net space charge density

Field in depletion region

E ( x) =

W p

net ( x )dx

dE net ( x )
=
dx

eN dWno eN aWpo
Eo =
=

eN a N dWo
Emax =
( Na + Nd )

pn Junc&on
(f) The potential V(x) across the
device. Contact potentials are not
shown at the semiconductor-metal
contacts now shown.
dV

E =

dx

(g) Hole and electron potential


energy (PE) across the pn junction.
Potential energy is charge
potential = q V

V ( x) =

%
Vo
'
eN d
'
2
V

x
+
W
(
)
0
n
'
2
E ( x ) dx = &
' eN a x W 2
p )
' 2 (
'
0
'
(

x Wn
0 x Wn
Wp x 0
x Wp

Some algebra

eV0 EG
Na Nd
eV0 = kBT ln
ni2

pn Junc&on
By establishing continuity at the junction:
Depletion region width

2 (N a + N d )Vo
Wo =

eN
N
a
d

1/ 2

where Wo = Wn+ Wp is the total width of the depletion region under a zero applied
voltage

ENERGY BANDS

LEFT: Consider p- and n-type semiconductor (same material) before the formation of the
pn junction, separated from each and not interacting.

Open circuit pn-junction


1) Same EF
2) Away from M, in the n-type, Ec-EFn
is the same
3) Away from M, in the p-type, EFpEv is the same
4) The bandgap must be the same EcEv in the two materials
5) Ec and Ev must bend in the SCL
a) e- diffuse from n to p, they
deplete the n-side near the
junction Ec must move
away from Efn
b) h+ diffuse from p to n, they
deplete the p-side near the
junction Ev must move
away from Efn

P0 = eqVo /kBT

P =e

Energy band diagrams for a pn junction under


(a) open circuit and (b) forward bias

q(Vo V ) /kBT

Energy band diagrams for a pn junction under reverse bias


(Shockley model)

Bias.swf

Forward Biased pn Junction

-
+

Vo
V

+
-

Forward biased pn junction and the injection of minority carriers. The negative
polarity of the supply reduces the potential barrier V0 by V. Potential barrier
against diffusion is reduced to V0-Vmore injection of minority carriers

Forward Bias: Diffusion Current


Assuming Boltzmann statistics + some algebra

Hole diffusion current in n-side in the neutral region

J D,hole

2
h i

eD n
=
Lh N d

eV
exp
1
k BT

Einstein relation:
Dh = hkBT/e,
De = ekBT/e

Similar expression for JD,elec in the p-region.

Forward Bias: Total Current

The total current anywhere in the device is constant. Just outside the depletion region it is
due to the diffusion of minority carriers.

Forward Bias: Diffusion Current


Ideal diode (Shockley) equation

(
! eV $ +
J = J o *exp #
& 1" k BT % ,
)
Reverse saturation current

'! eD $ ! eD $* 2
h
e
J o = )#
+
& #
&, ni
(" Lh N d % " Le N a %+

Jo depends strongly on the


material (e.g. bandgap) and
temperature

Forward Bias: Diffusion Current


Diode (Shockley) equation

(
! eV $ +
J = J 0 *exp #
& 1" k BT % ,
)
= 1 2
Ideality factor

Ge, Si and GaAs Diodes: Typical Characteristics

I
Ge

Si

GaAs

1 mA

0.2

0.6

1.0

Schematic sketch of the I-V characteristics of Ge, Si, and GaAs pn junctions.

Forward Bias: Recombination Current

Some minority carries also recombine in the SCL supply provides also for the
electrons and holes lost in SCL Recombination Current

Typical I-V characteristics of Ge, Si and GaAs pn junctions

Typical I-V characteristics of Ge, Si and GaAs pn junctions as log(I) vs. V. The slope
indicates e/(kBT)