Lecture 7

Thin Film Solar Cells (I)

References:
1. Physics of Solar Cells. Jenny Nelson. Imperial College Press, 2003.
2. Photovoltaic Materials, Series on Properties of Semiconductor
Materials, Vol.1, Richard H. Bube, Imperial College Press, 1998.
3. Handbook of Photovoltaic Science and Engineering. Antonio Luque,
Steven Hegedus. Wiley, 2003.
4. Photovoltaic Solar Energy Generation. Adolf Goetzberger, Volker U.
Hoffmann. Springer, 2005.
5. Wikipedia (http://en.wikipedia.org/wiki/Main_Page).

Why Thin Film Solar Cells

As minority carrier diffusion lengths exceeds absorption depths, p-n junctions
make efficient photoconverters. However, monocrystalline solar cells are
expensive to produce and are used in very limited areas.
Energy
emitter
n-type

EC

base
p-type

e-

h
300 m

EV

e-

EF
h+

0.3 m
Distance

For PV to provide the full level of C-free energy required for electricity and
fuel, solar power cost needs to be ~5 cents/kWh ($1.00 /Wp). Thin film solar
cells provide cheap alternatives.

Challenges of Thin Film Solar Cells

Polycrystalline and amorphous semiconductors contain intrinsic defects
increasing the density of traps and recombination centers. As a result,

Diffusion lengths are shorter, so the material needs to be a strong

optical absorber. Alternatively, multiple junctions must be used to make
the device optically thick. It may be necessary to use extended built-in
electric fields to aid carrier collection. e.g. p-i-n structures in amorphous
silicon cell.
Losses in the layer close to the front surface are greater. It is better to
replace the emitter with a wider band gap window material.
The presence of defect states in the band gap makes the material
difficult to dope, and limits the built-in bias available from a junction
through Fermi level pinning.
The presence of grain boundaries and other intrinsic defects increases
the resistivity of the films particularly at low doping densities.
The presence of defects makes the minority carrier lifetime and diffusion
rate are carrier density dependent.

Materials for Thin Film Solar Cells

Requirements:
They should be low cost, non-toxic, robust and stable.
They should absorb light more strongly than silicon. Higher absorption
reduces the cell thickness and so relaxes the requirement for long
minority carrier diffusion lengths, allowing less pure polycrystalline or
amorphous materials to be used.

Materials for Thin Film Solar Cells

Silicon is the only elemental semiconductor which has a suitable band

gap. Compound semiconductors greatly extend the range of available
materials and of these II-VI binary compounds and I-III-VI ternary
compounds have been used for thin film photovoltaics. Many of them
are direct band gap semiconductors with high optical absorption.
A number of materials have been identified of which the best developed
at present are amorphous silicon (a-Si), polycrystalline cadmium
telluride (CdTe), polycrystalline copper indium diselenide (CuInSe2
or CuInGaSe2), microcrystalline thin film silicon (-Si), and
molecular electronic materials.
Usually produced by physical or chemical deposition techniques
which can be applied to large areas and fast throughput.
Note that the term thin film refers more to solar cell technologies with
mass production possibilities rather than the film thickness.

Laboratory Thin Films Cell Efficiencies

Efficiency is the Best Metric to Gauge Progress

Amorphous Silicon
Amorphous silicon (a-Si) is the best developed thin
film material and has been in commercial production
since 1980. As a material for photovoltaics, it has the
advantages of relatively cheap, low temperature
(<300oC) deposition and possibility of growing on a
variety of substrates.
Defects in a-Si
The lattice of a-Si contains a range of bond lengths
and orientations, as well as unsaturated dangling
bonds. The long range order of the crystal is gone.
In a-Si, Si atoms are arranged in an approximated
tetrahedral lattice but with a variation of up to 10o in
the bond angle. The loss of order results that the
selection rules for photon absorption are relaxed,
and a-Si behaves like a direct gap material.

Amorphous Silicon
Defects in a-Si
The variation of Si-Si distance and
orientation gives rise to a spreading
in the electron energy levels, which
appears as a tail in the density of
states at the top of VB and the
bottom of CB, called Urbach tail.
Dangling bond states are due to
unsaturated Si atoms with one valance
orbital not involved in bonding. They
may be positively charged (D+), neutral
(D0) or negatively charged (D-). An
excess of D- gives rise to n type a-Si
while excess D+ gives rise to p type.
The defects can be created uniformly throughout the material by irradiating
the material by heating, sudden cooling, or by extrinsic doping. They are
deep in the band gap.

Amorphous Silicon
Absorption
The loss of crystal order renders the
absorption coefficient is about an order
of magnitude higher than in crystalline
silicon at visible wavelengths.
There is no well defined E-k relationship
and no requirement to conserve crystal
momentum. Absorption depends simply
on the availability of photons and the
density of states in VB and CB, much as
it does in direct gap crystal.
a-Si used for solar cells typically has a
band gap of 1.7eV, as a result of
passivation of a-Si with hydrogen.
The band gap is not optimum for solar energy conversion, while material
with lower concentration of hydrogen is unstable due to poor doping and
transport properties.

Amorphous Silicon
Doping
In unpassivated a-Si, the defect density is so high (>1016 cm-3) that the
material cannot normally be doped. The extra carriers which would be
introduced into the CB or VB by donor or acceptor impurities are captured
by dangling bond defects.
DOS

P 0 P + + e
e + D0 D

VB

CB
before passivation
after passivation
Energy

D- are recombination centers for holes, this decreases the minority

Since
carrier lifetime.

The background density of defect states may be reduced by saturating

the dangling bonds with atomic hydrogen. Hydrogen forms a bond with
the unpaired electron in a D0 defect and removes the capacity of that
defect to trap an electron or hole. Passivation with 5-10% hydrogen
reduces the density of dangling bonds to ~1015 cm-3, from which workable
p-n junctions can be made.

10

Amorphous Silicon
Doping
EC
donor level

EF

defect level

EC
defect level

acceptor level

n type

EV

p type

EF
EV

Transport
The defect states which remain after hydrogen passivation act both as
charge traps and recombination centers, and dominate charge transport in
a-Si.
The distribution of tail states below CB and above VB edges act as traps
for mobile carriers. Charge carriers in these states move by a sequence of
thermal activation and re-trapping events.
The distribution in energy leads to a distribution in the time constant for the
transport. So the usual transport parameters of mobility, lifetime, and
diffusion constant are density dependent.

11

Amorphous Silicon
Transport
The density of tail states in the CB is often
modeled as

E EC
Nt
g( E ) =
exp

k B T0
kB T0

DOS
VB

CB
before passivation
after passivation
Energy

Charge transport in such a defective medium is sometimes called

dispersive transport.

minority carrier lifetime in undoped hydrogenated amorphous silicon

The
(a-Si:H) is typically 10-20 s and the diffusion length around 0.1 m.
Electron mobility is rather better than hole mobility, probably due to an
asymmetric trap distribution.
With doping the defect density increases and diffusion lengths are much
reduced. So the carrier collection in a p-n junction would be extremely poor,
and consequently p-i-n structures are used.

12

Amorphous Silicon
Stability
Amorphous silicon suffers from light-induced degradation known as the
Staebler Wronski effect --- The defect density in a-Si:H increases with
light exposure, over a time scale of months, to cause an increase in the
recombination current and reduction in efficiency.

13

Amorphous Silicon Solar Cell Design

Amorphous Silicon p-i-n Structures
The basic a-Si solar cell is a p-i-n
junction. As the diffusion lengths are so
short in doped a-Si, the central intrinsic
(undoped) region is needed to extend
the thickness over which photons may
be effectively absorbed.

EVAC

qVbi

p
EC

n
EF

EV
p

n
Distance

The built-in bias is dropped across the width of the i-region, creating an
electric field which drives charge separation. In the p-i-n structure
photocarriers are collected primarily by drift rather than by diffusion.
The thickness of the i region should be optimized for maximum current
generation.
So the cell should be designed so that the depletion width is greater than
the thickness of the i region at operating bias. In practice , it is ~0.5 m.

14

Preparation of Amorphous Silicon

The a-Si is usually deposited by plasma deposition of silane or glow
discharge, but a number of other deposition methods such as sputtering
and hot wire CVD are being investigated.

Hot Wire CVD

A typical RF PECVD
chamber and related
parts. A siliconcontaining gas such as
a mixture of SiH4 and H2
flows into the chamber.

15

Amorphous Silicon Solar Cell Design

p-i-n Solar Cell Device Physics
Because the doping level in the p and n regions are so much higher than in
the intrinsic region, the depletion widths within the p and n regions are very
small and can be neglected. Provided that the background doping is low
enough, the space charge region thickness is equal to that of the i-region.
p type

i type

high background
doping or high bias

n type

low background
doping or low bias

If the charged background doping in the i region is too high, at biases

above some threshold the i region will not be completely depleted. The
remaining neutral part of the i layer is a dead layer and does not
contribute to the photocurrent.

16

Amorphous Silicon Solar Cell Design

p-i-n Solar Cell Device Physics

At high injection levels (e.g. high

illumination), the free carriers in the i
region becomes significant and will
arrange themselves to minimize the
electrostatic potential energy. In very
high injection conditions the field
vanishes throughout most of the i
region and np.
Dn Dp
Da =
Dn + Dp

n
near dark

EC
EF
EV

illuminated

EC
EFn

EFp
The current is now driven by diffusion
EV
rather than drift. The diffusion rate is given
by an ambipolar diffusion.

The electron and hole lifetimes are generally not constant. At low light
intensity charge carriers are likely to be trapped in tail states, extending
their lifetime. The dark current is therefore intensity dependent.

17

18

Fabrication of a-Si Solar Cells

Superstrate design
Layers of TCO, p-type, undoped and ntype a-Si are deposited in sequence on
glass substrate. ZnO is deposited onto the
n-layer followed by a metal (Al) for the rear
contact.
Substrate design
Layers of TCO, p-i-n structures are
deposited on a metal substrate (steel) for
the back contact. The p-layer can be very
thin and textured.

a Ag/ZnO textured back reflector

19

Strategies to Improve a-Si Cells Performance

Light Induced Degradation
The Staebler Wronski effect is the most important barrier to the widespread
use of a-Si solar cells. Light-induced degradation is stronger in materials
with a higher hydrogen content, yet a high hydrogen content is needed
for suitable doping and transport properties.
If a-Si could be produced with a lower original dangling bond density, less
hydrogen would be needed for passivation. One possibility is the hot wire
CVD technique which appears to produce good a-Si when saturated with
only 1% hydrogen.
Improvement of VOC
The VOC in a-Si solar cells is substantially less than the optical band gap
(0.89 V compared to 1.7 eV). It can be increased by the use of either (i) a
wider band gap emitter such as a-SiC:H or (ii) a polycrystalline Si emitter,
in which degenerate doping is possible.

20

Strategies to Improve a-Si Cells Performance

Improvement of JSC
Improve the blue light response in the p-layer. This could be achieved by
replacing the a-Si p-layer with a wider band gap a-SiC:H window, or by a
graded a-SiC:H-a-Si:H layer.
Improve the long wavelengths light response in the i-region. This could be
achieved with light trapping techniques to increase the optical path
length within the cell, or with the use of multilayer a-Si cells.
Date

Design

Efficiency

1977

Schottky diode

6%

1980

a-Si:H p-i-n

6%

1982

a-SiC:H/a-Si:H p-i-n heterojunction

8%

1982

textured substrates

10%

1987

grading of p-i interface

12%

1990s

multi-gap design

13%

21

Strategies to Improve a-Si Cells Performance

Improvement of Limiting Efficiency
Multi-gap cell designs are possible using aSiC:H as the material for a wider gap cell
and a-SiGe:H for a narrower gap cell.

Two terminal tandem design

Structure of triple-junction pi-n substrate-type solar cells

The limiting efficiency for three cell devices is calculated to be 33%. The
main problems have been the poorer quality of the alloy relative to a-Si
and incorporating large area tunnel junction.

22

Polycrystalline Thin Film Materials

A polycrystalline material is composed of microcrystallites or grains of the
semiconductor arranged at random orientations to each other.
The material is crystalline over the width of a grain,
being typically the order of one micron. As the grains
are large in quantum mechanical terms, the band
structure and therefore the absorption coefficient, is
virtually identical to that of the single crystal
material. However, the transport and recombination
properties are strongly affected by the presence of
the interface or grain boundary.
The different orientations of neighboring crystal grains give rise to
dislocations, misplaced atoms (interstitials), vacancies, distorted
bond angles and bond distances at the interfaces. In addition, extrinsic
impurity atoms are likely to concentrate at the grain boundaries.
The various types of defect introduce extra electronic states and act as
intra-band-gap states or trap states. Deep defect levels may act as
recombination centers.

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Polycrystalline Thin Film Materials

Band Profile in the Presence of Grain Boundary
We consider the case of a grain boundary in n type material. As the local
neutrality level of the defects 0<EF, the states will be acceptor-like and
trap electrons. This gives rise to a plane of fixed negative charge at the
interface, and a layer of positive space charge on either side where the n
type material had been depleted.
n-sc

interface

n-sc

EVAC

EVAC

EC

EC

EV

EF

0
EV

n-sc

interface

n-sc

EVAC
EC

EF

EF
EV

+ + -- -- ++

The electrostatic force sets up a potential barrier opposing further

majority carrier migration, while the minority carriers see a potential well
at the grain boundary and are pulled towards it and the probability of
recombining with a trapped majority carrier is high.

24

Grain Boundaries and Transport

The effect of grain boundaries on charge transport
depends on whether they lie normal to or parallel
to the direction of current flow.
When current is flowing across a grain boundary, the
potential barriers slow down the transport of majority
carriers, limiting its mobility, while the potential well
drive minority carriers towards recombination centers
at the grain boundary, reducing its diffusion length
and lifetime.
Increasing the trap density increases the space charge stored at the
grain boundary. So the barrier height , conductivity and recombination .
Increasing the doping first increases the barrier height, but at higher
doping levels the traps become saturated, the space charge region begins
to contract and the barrier is reduced.
Grain boundary lying parallel to the direction of current flow principally
affect minority carriers. Majority carriers traveling parallel to the grain
boundary are not affected. But minority carriers are still likely to be trapped.

25

Grain Boundaries and Transport

The resistivity of a polycrystalline material is high
at low doping levels, falling rapidly at some
intermediate doping levels until finally it compares
with crystalline values at high Nd.
However, high doping tends to increase the losses
of minority carriers via recombination at grain
boundaries. As with crystalline materials, the best
material is a compromise between high lifetime
and high conductivity.
Increasing the density of free carriers by illumination
reduces the net charge stored at the grain boundary
and hence the barrier height.
As EB is reduced under increasing illumination the
EB high light intensity
majority carrier mobility, and hence the conductivity
are increased.
Intensity dependent mobilities are commonly
EB low light intensity
observed in polycrystalline semiconductors.

26

Grain Boundaries and Recombination

To evaluate the overall effect on minority carrier transport characteristics,

1
1
1
1
1
=
+
+
+
eff SRH gb Auger rad
Grain boundary effects influence the I-V characteristics of polycrystalline
solar cells in several important ways:
The effect
of grain boundaries in reducing majority carrier mobility may
increase series resistance.
The enhancement of minority carrier recombination at grain boundaries
reduces lifetimes and increases dark current.
Because minority carrier lifetimes and diffusion lengths are carrier
density dependent, the photocurrent may be bias dependent, and not
well approximated by JSC, indicating simple diode equation descriptions
are not appropriate.

27

Thin Film Silicon Solar Cells

Thin film microcrystalline silicon (-Si) is characterized by grain sizes of
~1 m. It has the optical properties of crystalline silicon, while its electronic
properties are dominated by the grain boundaries.
Defect states at grain boundaries include dangling bonds typical of a-Si as
well as extrinsic impurities introduced during growth.
-Si can be prepared by the same techniques as multi-crystalline Si,
normally by casting of molten silicon into aggregates or sheets. A range of
other techniques have been investigated for thin film polycrystalline
material, including liquid phase epitaxy, chemical vapor deposition and
the crystallization of amorphous silicon.
The goal is to fabricate cells by depositing the -Si on cheap ceramic or foil
substrates, or on glass.

28

Thin Film Silicon Solar Cells

As in any polycrystalline material, the diffusion length in -Si is effectively
limited by the grain size, which limiting the cell thickness or effective
carrier collection of a few microns or tens of microns.
However, the low absorption coefficient means that a layer of -Si of a
few microns thick harvests less than half of the available photons.
Two basic approaches to improving performances:
Light trapping in thin film Si solar cells. Light trapping techniques
have to be used to increase the optical path length inside the cell.
Texturing front and back surfaces could increase the optical depth by a
factor of ~20. This relaxes the need for a long diffusion length, and
allows higher base doping increasing VOC.
Parallel multijunction thin film Si solar cells. The cell is composed of
consecutive micron-thick layers of p and n type -Si. Layers of similar
polarity are connected together to give a set of p-n junctions connected
in parallel.

29

Thin Film Silicon Solar Cells

Structure of parallel multijunction
thin film Si solar cells

Further reading:

30

Summary

31