Documente Academic
Documente Profesional
Documente Cultură
Adolf Goetzberger
Joachim Knobloch
Bernhard Vo13
Fraunhofer Institute for Solar Energy Systems, Freiburg,
Germany
Translated by
Rache1 Waddington
Swadlincote, UK
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording,
scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or
under the terms of a licence issued by the Copyright Licensing Agency, 90 Tottenham Court Road,
London, UK W I P 9HE. without the permission in writing of John Wiley and Sons Ltd., Baffins
Lane, Chichester, West Sussex, UK PO19 IUD.
Weinheim.Brisbane*Singapore.Toronto
Goetzberger, Adolf.
[Sonnenenergie. English]
Crystalline silicon solar cells / Adolf
Goetzberger, Joachim Knobloch, Bernard VoB ; translated by Rachel
Waddington.
p. cm.
Includes bibliographical references and index.
ISBN 0-471-97144-8 (alk. paper)
1. Solar cells. 2. Silicon crystals. 3. Photovoltaic power
generation. I. Knobloch, Joachim, 1934- . 11. VoB, Bernhard,
1926- . 111. Title.
TK2960.G64 1998
621.31 ‘244-dc21 97-42008
CIP
A catalogue record for this book is available from the British Library
Preface .................................... xi
1 Photovoltaics ................................
1.1 The Principles of Photovoltaics . . . . . . . . . . . . . . . . . . .
1.2 The History of Photovoltaics . . . . . . . . . . . . . . . . . . . . .
1.3 The Importance of Photovoltaics . . . . . . . . . . . . . . . . . .
References
[3] Shockley W., Bell Syst. Tech. Journ. 28, 1949, p. 435
[4] Bardeen J. and Brattain W.H., Phys. Rev. 74, 1948, p. 230
[5] Chapin D. M., Fuller C. S. and Pearson G. L., J A p p f . Phys. 25, 1954,
p. 676
[6] Carlson D. E. and Wronski C.R., Appl. Phys. Lett. 28, 1976, p. 671
[7] Mitchell K. W., Eberspacher C . et a\., Trans Elec. Dev. 37, 1990, p. 469
2
Solar Power
x-
Figure 2.1 Spectral distribution of radiation intensity
efficiency and other results of solar cells are based on this standard
spdctrum.
References
In common with all elements of the fourth group of the periodic table,
silicon has four valence electrons. These atoms are arranged in relation to
each other, such that each atom is an equal distance from four other atoms
and that each electron forms a stable bond with two neighbouring atoms.
This type of lattice is known as the diamond lattice, because diamond -
comprising of tetrahedronal carbon - has this lattice structure. The bond is
known as a homopolar (or covalent) bond, and is also present in the
hydrogen molecule, for example. These bonds are extremely pronounced.
The Principles of Photovoltaics I1
Each of the two individual systems shown are tuned to one and the
same oscillation frequency. If they are not connected, then both have only
one oscillation frequency. However, if these systems are coupled together
(by a fictitious mass-free spring), then several oscillatory states with
differing frequencies occur due to the interactive effect. The number of
frequencies increases with the number of oscillators coupled. The stronger
the bond, the farther apart are the oscillation frequencies generated from
the original frequency.
AL
2.
\
F
5
I
I
I
d
-2
interatomic distance
Figure 3.3 The splitting of energy levels in a semiconductor
4 I
Interatomic distance
Figure 3.4 The splitting of energy levels in an electrical conductor
can flow. In some metals, the other variant occurs and the energy bands
overlap. This leads to the same physical behaviour as the first case.
Figure 3.4 shows an example of the band structure of a metal.
Which of the permitted energy levels in the conduction band are occupied
depends upon the probability of one electron achieving a specific energy
The Principles of Photovoltaics 1.5
level due to the temperature. This probability underlies the Pauli Principle,
which states that each available state can be occupied by a maximum of
two electrons (with different ‘spin’).
The result of statistical behaviour based on this selection principle gives the
Fermi-Dirac distribution, which we have reproduced here without giving in
further details. According to this, the probability f(E) of an energy level
being occupied is
(3.1.1)
where
E, is the so-called Fermi energy, which will be described in more detail
later,
k is the Boltnnann constant, and
T is the absolute temperature.
16 Crystalline Silicon Solar Cells
Figure 3.5 shows the probability for three different temperatures. When
T = 0 the probability of occupation for all energy levels where E > E, is 0
and when E < E, it is 1. At a finite temperature, the variables are
dependent upon temperature. If at this finite temperature E = E,, then -
where eo = 1 in the formula (3.1.1) - the occupation probability is 0.5. The
Fermi energy is defined such that the probability of occupation of this
energy level is 0.5.
To determine which energy levels are actually occupied, the distribution
of permitted energy levels must be determined.
N ( E ) dE = (3.1.2)
h3
where
h is Planck's constant.
rn; is the effective mass of the electrons, and
E, is the band-edge energy of the conduction band.
The number of permitted states is proportional to the square root of the
difference between the energy of the current state and the band-edge
energy of the conduction band. We also find from (3.1.2), that the number
of permitted states immediately at the conduction band edge is zero. Figure
3.6 shows the relation graphically. The upper curve is for electrons, and the
lower curve is for holes.
Now we can use equations (3.1.1) and (3.1.2) to calculate the number n
of electrons per volume unit in the conduction band. This is found to be
n = ff(E)N(E)dE (3.1.3)
Bc
1 E, - E
E -E, (3.1.4)
and because almost no states are occupied above Em,, we can select an
infinite integration limit instead of Ern,. Therefore
n = -m
8fi-
*”’ exp(E,lkT) ( ( E - EC)”’exp(-ElkT)dE (3.1.5)
h3 0
=’[
2xm,*kT 7
h2 ] EF - E C
exp( kT
(3.1.6)
18 Crystalline Silicon Solar Cells
The expression before the exp function is called the effective density of
states, N,, of electrons in the conduction band. Therefore
='[
2zmp*kT
h2 ] 1
exp(
EV -EF
kT )
(3.1.8)
or
P v" exp(
EV -EF
kT ) (3.1.9)
N , exp( EF
kT
-EC ) = N , eXp("' -EF)
kT
(3.1.10)
EF = E, + E v +-
kT
ln(N,IN,) (3.1.1 1)
2 2
For silicon with an effective mass of rn~=1.09rn0and rni=1.15rn0 [4] the
Fermi level is approximately 0.023 eV above the middle of the forbidden
band. If we take the product of n and p, we find
The Principles of Photovoltaics I9
E E E
4
t
0 N(E)- 0
1 -
f(E1 1 0 [ l - f ( E l I . N I E l '
(a) (b) (a
Figure 3.7 Term scheme of an intrinsic semiconductor
E
k T (3.1.12)
n p = N c N , expiEV - E c ) = N , N , exp(- 2)
kT
R =rpn (3.1.13)
It holds that
G l r =nI2 (3.1.15)
i.e. the intrinsic carrier density is determined by the ratio of the generation
rate and recombination probability. As the latter is a constant, ni is only
dependent upon G and thus temperature. It is very important to note that
this relationship applies not only for intrinsic semiconductors, but also for
all extinsic semiconductors in which the number of electrons and holes has
been altered by the addition of a dopant (which is normally the case for
semiconductor devices).
K = - q E =mb (3.2.1)
Figure 3.8 The path of a free electron in a crystal lattice: (a) without an
electric field; (b) with an electric field
-
Vdrin = -!-
QEt (3.2.3)
2 mn*
This drift is very small compared with the thermal velocity (with the
exception of very high fields, where a carrier multiplication also occurs).
The movement of charge carriers in an electric field results in an
electric current, which we will call the field current. The current density is
found to be
and thus
In = n q -1- -g i E (3.2.5)
2 m,'
If we define
(3.2.6)
I, = n 4 P n E (3.2.7)
or
In = Q E (3.2.8)
= =n4Pn (3.2.9)
The same applies for the holes and thus for the hole mobility
The Principles of Photovoltaics 23
p = -1 - t4 - (3.2.10)
P
2 mpf
cr = 4 ( w , +PIUP) (3.2.1 1)
i.e. conductivity is dependent upon the number and mobility of both types
of charge canier.
Mobility is itself dependent upon temperature, as well as the number of
dopant atoms (Section 3.2.2). Figure 3.9 shows this relationship for
electrons and holes [7].
104
103
[el
Pn
102
If we look at the situation for metals, on the other hand, the number of
free electrons is very high and independent of temperature. This high
number has the result that even with a low level of drift velocity, high
currents can be achieved, i.e. only a low field strength occurs during
current flow.
24 Crystalline Silicon Solar Cells
........ . . . . . . . . .
e m
... . .. . . . . . .+*G
Phosphorus atom
........
....... ...
.............
Figure 3.10 Electron orbits of a donor atom in a semiconductor
The Principles of Photovoltaics 25
(3.2.12)
where:
E,is the permittivity in vacuum;
E is the relative permittivity of the material; and
h is Planck’s constant.
This ionisation energy works out as E, % 13.6 eV (E = 1 in a vacuum).
To estimate the separation energy for the fifth electron of a donor
replace E with the value of relative permittivity for silicon, E , ~= 11.9 and
replace m, with m:. We can then estimate by comparison that the bonding
energy of the ‘fifth phosphorus electron’ is
m,*/mn
E, = E i H-= 0.105 eV (3.2.13)
‘Si‘
processes also still apply, i.e. the product np must equal nf. Because at an
impurity level of 10l6 ~ r n n- is
~ almost equal to the number of donors, p is
found to be
i.e. the number of holes is dramatically lower than the number of electrons.
We now consider the position of the Fermi level. It is plausible that in
this case the Fermi level must be much closer to the edge of the conduction
band.
Where n = ND
4
ND =NC exp(
-Ec
kT ) (3.2.15)
or
E, - E c = k T l n (NJN,) (3.2.16)
E, - E , =kTln(N,lN,) (3.2.17)
The Principles of Photovoltaics 27
E E E
4
ND
0
a) b) C)
(3.2.18)
(3.2.19)
(3.2.20)
(3.2.21)
"dx
and similarly for holes
The Principles of Photovoltaics 29
(3.2.22)
p d x
We now consider that the diffusion and field currents are not
independent of each other. Both come about due to statistical movements
and collisions. This connection between the diffusion coefficient and
mobility gives the so-called Einstein formula. This reads
kT (3.2.23)
D =-p
4
and is often used in semiconductor physics.
Unlike in a metallic conductor, where there is almost no diffusion
current due to the lack of concentration differences, in a semiconductor an
electric current is not automatically associated with an electric field,
because the diffusion current and the field current can oppose each other
and cancel each other out. As we will see later, it is precisely this fact that
is so important for the physical behaviour of a p-n junction.
(3.3.1)
30 Crystalline Silicon Solar Cells
where
F, is the number of photons at point x ;
F,,o is the number of photons on the surface x = 0; and
a, is the absorption coefficient.
The latter is itself dependent upon the wavelength, and determines the
penetration depth of the light and therefore the thickness of crystal
necessary to absorb most of the penetrating light. The absorption length xL
is also often introduced, corresponding to the value xL = l/u.At this
absorption length the intensity F, is reduced to l / e x F,,o (approximately
37%).
E = -P 2 (3.3.2)
2m
Results from quantum mechanics [9] show that with some modifications
the physical conditions of electrons in free space can be transferred to
electrons in a semiconductor. We want to exploit this with regard to
absorption.
E, -E, = h v (3.3.3)
If we now write the energy for the charge carrier according to equation
(3.3.2), we find the energy of the electron in the conduction band is
(3.3.4)
(3.3.5)
If we add the equations (3.3.4) and (3.3.5) taking (3.3.2) and (3.3.3) into
account, we find
(3.3.6)
We see from this that the crystal momentum increases with the rising
energy of the photon.
The probability of this absorption process naturally depends upon the
density of electrons and holes. As this nears zero at the edge of the band
and increases significantly farther away, it is clear that at higher photon
energies the absorption probability increases significantly, because the
photon energy is then sufficient for absorption to take place even when the
crystal moment lies outside the min/max situation. From theoretical
deliberations, which we do not wish to reconstruct here, we find the
following expression for the absorption coefficient:
(;
a, = C h - -Eg
1'" = C ( h v -Eg)," (3.3.7)
I hv
Crystal momentum, p
Figure 3.13 Energy of the conduction band as a function of crystal momentum
(direct semiconductor)
---___
!+ Phonon absorption
b
Crystal momentum, p
1 0 4 I,-. .-
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Wavelength (pm)
increasing the energy of the lattice vibrations, i.e. the temperature in the
semiconductor. This absorption occurs at high electron concentrations.
or
h =hclEg (3.4.2)
The lifetime of charge carriers with this recombination process was first
calculated by van Roosbroek and Shockley [14]. They obtained values of
approximately 0.75 s for silicon, independent of the concentration of donors
and acceptors. This result sharply contradicted all observations. Firstly, a
very small carrier lifetime had been measured and secondly a relationship
with dopant concentration had definitely been measured. It was therefore
obvious that this radiative recombination must play a very secondary role
36 Crystalline Silicon Solar Cells
In the Auger effect one electron gives up its extra energy to a second
electron in the conduction or valance band during recombination thus
moving it to a higher energy level. The excited electron then gives up this
additional energy in a series of collisions with the lattice, thus returning to
its original energy state. Figure 3.17 illustrates these two processes.
Figure 3.17 Auger recombination: (a) in the conduction band; (b) in the
valence band
R, = B n 2 p (3.4.3)
,P - 1
TAug -- -- (3.4.4)
R, Bn2
The value of the Auger coefficient B for silicon works out as 4 x
1OS3’ cm6 s-’ [ 17],[ 181. We can estimate that the Auger recombination first
becomes noticeable at dopant concentrations higher than 10” cm-’. In most
semiconductor devices it is therefore of lesser significance.
More recent measurements [19], however, in the dopant range
10’6-10’8 cmS3yield a twenty times higher value for the constant B.
Li Sb P As Bi Ni S Mn. A9 Pi H9
r
B At Ca In Tt Co Zn Cu Au Fe 0
where
Vth is thermal velocity,
n is electron concentration in equilibrium,
p is hole concentration in equilibrium,
N, is the number of the trap levels,
Q, is the capture cross section for the electrons, and
op is the capture cross section for the holes.
The variables n, and p l mean
Et - E,
n, =ni exp( kT ) (3.4.6)
and
Ei - E,
PI =n;exp( kT ) (3.4.7)
where E, is the energy of the defect level. Typical values for Q, and oPare
lo-’’ cm’. Vthis approximately lo7 cm/s at 300 K.
The driving force behind the recombination process is the term (np -
n:) if the charge carrier concentration deviates from the thermal equilibrium
condition.
By introducing the definition for charge carrier lifetime
1 1
- = NtOnVth and - = N‘ QP tVh (3.4.8)
‘no tPO
and
An
T =- (3.4.9)
R
40 Crystalline Silicon Solar Cells
Po + P , + A n no i n , An
i
7 = tn0 =Po
(3.4.10)
no +Po +An no + p o + An
if we equate An = np nf .-
We consider two cases:
1. For high level injection An >> no,n , , p o ,p , . We then find from equation
(3.4.10) the camer lifetime t is
The result can also be explained in that, in the case of high injection in
both energy bands, enough carriers are present, and lifetime is only
dependent upon the capture probability of electrons and holes and not on
their concentration [24].’
2. For low level injection no >> p o An n , , p , (i.e. for n doping) then for the
holes as minority charge carriers
tp = T (3.4.12)
PO
and for p doping where p >> no An n,, p , . For the electrons as minority
charge carriers
(3.4.13)
(3.4.14)
1 I
1 " " 1 " " 1 " " ~ " " ~ ~ '
0 0.2 0.4 0.6 0.8 1.o
EC Energy (eV) EV
Figure 3.20 Dependency of relative carrier lifetime on basic doping and
impurity energy level
s
-g
C
300
.-0
u)
3 200
100
1 --- + - +1-
- 1 1 (3.4.16)
'total 'radiation '~ugsr 'trap
All three depend to some degree upon dopant concentration. Figure 3.22
shows a summary of these dependencies.
Doping N, [cm-'1
Figure 3.22 Dependency of the different charge carrier lifetime processes on
doping
'50
T =
(3.4.17)
ND
1 +-
7 x 10l5
(3.5.1)
dx
and likewise for the holes
(3.5.2)
--
d2<p = -dE
- -- Q (3.5.3)
dxz dx EEO
where Q is the total electric charge in the crystal, E and E~ are the relative
permittivities in the material and in a vacuum, and cp is the potential.
To determine the total charge, we must remember, that the donors ND
are positively charged after they have given up an electron, whereas the
acceptors NA have a negative charge after creating a hole. Poisson's
equation for this case reads
(3.5.4)
Or, in words: the gradient of the field strength is equal to the total charge
divided by the relative permittivity of the material.
dV = d x dy dz (3 S . 5 )
a particle flow F,(x) may flow across the area dyxdz = A into this volume.
And at the same time a particle flow F,(x) emerges from this volume, after
the distance dx at the point x + dx. It is clear that F2(x)and F,(x) are the
same size if additional carriers are neither created nor destroyed in the
volume.
Now, however, we want to consider the situation in which changes
occur within this volume. We can then determine the particle flow F2(x) in
terms of F,(x) if we develop F2(x)to F,(x) in a Taylor series. With a small
46 Crystalline Silicon Solar Cells
enough value of 6 x we can restrict ourselves to the first term of this series.
We can write
F*(x) = F , ( x ) + -
W X ) 6x (3.5.6)
dx
Now if F,(x) is greater than F,(x), i.e. if the additive term on the right-
hand side of the formula is positive, then more particles will flow out of
the volume than into it. This means that in the volume more charge carriers
must be created per unit of time than simultaneously recombine.
X x+dx
Figure 3.23 Particle flow in a small volume
AF =- dF(x) 6 x dy dz = ( G - R ) 6 x dy dz (3.5.7)
dx
We convert these particle flows to electrons and holes and find the
following equation for the current density, taking the sign into account:
(3.5.8)
-
1-q,(x) = G - R (3.5.9)
4 d x
These equations are called the continuity equations. They govern the
relationship between current density and the size of generation and
recombination. We have now covered the most important equations for the
calculation of semiconductor devices.
References:
At the beginning of this chapter, the basic equations are summed up once
again as follows:
1. Current equations
"1
I,, = q ( p n n E +Dn-
dx (4.1.1)
(4.1.2)
2. Poisson's equation
(4.1.3)
3. Continuity equations
(4.1.4)
(4.1.5)
50 Crystalline Silicon Solar Cells
The left-hand side x<O would, for example, be doped with boron atoms
with a concentration of N A = 10l6atoms per ~ m -making
~, it p-conductive.
The right-hand side x>O, on the other hand, could be doped with
phosphorus atoms, at N, = 10l6~ m -making
~, it n-conductive.
The p-n Junction 51
This calculation utililises the fact mentioned above that in equilibrium the
field current must equal the diffusion flow in the opposite direction. We
first consider the case for electrons. In this case
dn
qnpnE = - ( I D , - (4.2.1)
dx
and where
52 Crystalline Silicon Solar Cells
E = - - dcQ (4.2.2)
dx
we find
*
dx
kTdn 1
=---
q n d x
(4.2.4)
(4.2.5)
U, = U, ln(NDNA/ni2) (4.2.6)
and where
The p n Junction 53
E, = kTln(Nv/NA)
(4.2.8)
E, = kTln(N,/N,)
we quickly obtain
q U , = Eg - kTln(N,N,/N,N,) (4.2.9)
U , = -ln(N,N,/n:)
kT
(4.2.1 0)
4
We previously showed the classical method, as we believe that this
introduction can be very helpful for a deeper understanding of the physics
of a p-n junction.
54 Crystalline Silicon Solar Cells
-
dE = - * - Q (4.2.11)
dx du* EE,
and thus
(4.2.12)
dE = - -
- Ni (4.2.13)
dx EO
d E -- L N ; (4.2.14)
dx EE,
Outside these zones dEldx = 0.
The p n Junction 55
9 N*- (4.2.15)
E ( x ) = - -( x - X I )
€0
(4.2.16)
The field path is thus linear with the positional coordinates and always
negative.’ Where x = 0 the field strength is at its maximum and both values
must be of equal magnitude. It then holds that
This means that the distances x, and x, - the distances in the space
charge region - are inversely proportional to the corresponding dopant
concentration and that the number of positive and negative space charges
are of equal magnitude on both sides.
We now determine the potential distribution in the space charge region
by integrating equations (4.2.15) and (4.2.16) with the following boundary
condition:
-
dv =0 for x = x , and x = x I (4.2.18)
dx
We find that
9% 1
cp(x)= - -(x, - x)’ +D n region of the depletion layer
&Eo 2
(4.2.19)
4% 1
cp(x)= -- -(xr - x)’ +C p region of the depletion layer
EEo 2
The point of origin for voltage is selected, so that cpx.o = 0. This allows us
to determine the constants C and D.We find that potential in the space
charge region is
cpx+
-- + -
9 ND+
[x: - (x, + x)’] n region
E=o
qNA- 2
vx-= - - xI p region
CEO
(4.2.21)
- qND+ 2
vx+- + - x, n region
Eo
U,,= -
4 (N,,x: -NAx,') (4.2.22)
2EEo
(4.2.23)
(4.2.24)
we also calculate
58 Crystalline Silicon Solar Cells
(4.2.26)
(4.2.27 )
-1
UD-UA (4.2.28)
Empx W
(4.2.30 )
Q
(4.2.31)
(4.2.32)
the diffusion current from that in the uncharged state. This is connected
with an increase in the concentration of free charge carriers. The product
np is now greater than nf. This means that the recombination rate R = r p
increases accordingly in the space charge region. A new stationary state
thus occurs in which excess recombinations are immediately compensated
by flows into the junction region. This means that compensating amounts
of carriers are driven into the space charge region from the high carrier
densities in the n and p regions. The zone becomes narrower and its
resistance is reduced. The current that now flows is known as the forward
bias current.
It is plausible that with a reversal of polarity the free carriers will be
drawn away from the space charge region. If the voltage is increased, then
the region will become wider and thus have a higher resistance. This
polarity is known as the reverse bias direction. The diode blocks the
current. In theory this reverse leakage current takes on a constant value
even at low reverse voltages. This is known as the saturation current of the
diode. The reverse direction is not relevant to solar cells, therefore we do
not explain this further. The saturation current, on the other hand, plays a
very important role in the physics of solar cells, and we now examine this.
Shockley [2] showed that given low recombination rates, the p-n junction
has specific characteristics. Low recombination rates mean a high carrier
lifetime, which is connected with a diffusion length that is large compared
with the width of the space charge region.
Because the respective minority charge carriers in the space charge zone
hardly ever recombine, they are driven far into the opposite region. They
are injected into this region and only recombine here. For the following
discussion, we also assume that this injected charge carrier concentration is
small compared with the concentration of majority charge carriers.
If we disregard the (very low) level of recombination in the space
charge region completely, then at point x, for example, the injected flow of
electrons must be compensated by the high number of available holes. We
can imagine that the high number of holes are driven there by a very weak
electric field, whereas the electrons conduct the current by diffusion due to
the concentration gradient. The field current of the electrons, on the other
hand, is negligible due to the very weak field, i.e. forward current has only
diffusion characteristics.
The p-n Junction 61
(4.3.1)
(4.3.2)
where npo and pnoare the respective concentrations in the unbiased case
[U,= 01.
For the sake of clarity, we wish to establish the relationship by another
means. We have assumed that the very high opposing field and diffusion
currents within the space charge region remain almost unchanged by the
application of voltage. If we equate these currents to holes we find that
(4.40)
or
kT
Dp = Pp 7 (4.41)
(4.3.5)
, ,P,
P ~ ( ~= ) ,~ X (PUA 1 UT 1 (4.3.8)
dP
f =-qD - (4.3.9)
pdx
and
(4.3.10)
9 dx.
as there is no generation here. For R
R = -A P (4.3.11)
‘‘P
-
where AF = (Pn(x,r) P n o 1.
If we combine this with the previous three formulae, we find that
d y Z --- AP
D p d2pn (4.3.12)
TP
-
d 'PnO = o (4.3.13)
dx2
(there is by definition no longer a gradient for pnoat point xr), taking into
account
(4.3.14)
LP = rl*PTP
(4.52)
Ip = - q o -
dP (4.3.19)
pdx
we need the first differentiation. If we substitute this, we find that
64 Crystalline Silicon Solar Cells
qDn ' n o
In = -(exp(UA/UT)- 1 ) exp(-x/Ln) (4.3.21)
Ln
and thus
This equation is known as the diode equation, and the first expression
in parentheses is the saturation current density I,. If we now introduce for
P n o and n p o
(4.3.25)
I = I , (expUA/UT - 1 ) (4.3.26)
The p-n Junction 65
References
(5.1.1)
and also
(5.1.2)
68 Crystalline Silicon Solar Cells
Zp = -(exp(U/U,)-
Dp P n o 1 ) exp( - x/Lp) -qGLpexp( -xILp) (5.1.4)
LP
I, = -(exp(U/U,)
q’n npo - l)exp( - x/L,) -qGLnexp( -xILn) (5.1.5)
Ln
IR = q G W (5.1.6)
We note that only those charge carriers generated either in the space
charge region or at a distance of one diffusion length from the p-n junction
contribute to current. Only this region of a solar cell is ‘active’.
The corresponding charge carrier distribution is shown in Figure 5.1 and
the current-voltage characteristic is shown in Figure 5.2.
The Physics ofsolar Cells 69
*I xr X
We see that the I-V characteristic of an illuminated solar cell lies in the
fourth quadrant (electro-technical standardisation).
For the purpose of comparison with this I-V characteristic, the
current-voltage characteristic of an unilluminated solar cell is also drawn
in Figure 5.2. The voltages are the same in both cases, whereas the current
in the illuminated solar cell is negative, i.e. the solar current flows against
the conventional direction of a forward biased diode.
We now describe the most important parameters of a solar cell.
As its name suggests, this current is obtained if the solar cell is short
circuited, i.e. there is no voltage at the cell. This current is designated Z,,
(from short circuit current).
From equation (5.1.8) we find that ZBc=-ZL, i.e. the short circuit current
is equal to the absolute light-current amount. We note here that the
70 Crystalline Silicon Solar Cells
magnitude of the current, disregarding all losses in the cell, with AM1.5
radiation, can reach a peak of 44 mA/cmZ.
The open circuit voltage V , is obtained when no current is drawn from the
solar cell. From (5.1.8) this is found to be
Since even at very low current densities we can disregard the value 1
compared with ZL/Ioand IL= I,, , we find that for V,,
i.e. the open circuit voltage is proportional to the logarithm of the ratio of
short circuit current to dark current. Since in good solar cells the short
circuit current very quickly nears a saturation value, the increase in the
The Physics of Solar Cells 71
FF = V , I , I VocIsc (5.1.1 1)
5.1.1.4 Efficiency
(5.1.12)
The following investigations are based upon the structure of a modem solar
cell. The cross-section of such a cell is shown in Figure 5.3.
The base, the starting material for a solar cell, is almost always p-doped.
Emitter SC
-,a
regionL.1
Base
r 7 - 7
x=o x: x;+w
J J
H'
I4 b
*
N
The n-doped region is called the emitter, a designation which has been
adopted from transistor physics. It is more highly doped than the base by
some orders of magnitude. The p-n junction is therefore unsymmetrically
doped. The space charge region, with width W therefore extends mainly
into the p region. The point xj marks the penetration depth of the p-n
junction. In practice it amounts to only a few tenth pm, so that for a crystal
thickness H of approximately 200 pm, the thickness of the base H’ is
roughly equal to H.
(5.2.1)
(5.2.2)
d 2(An)
+R (5.2.3)
Dn-T-
=-G
After some manipulation this yields
74 Crystalline Silicon Solar Cells
-dZ(An)
=- An - -
G
(5.2.4)
dxz ~,2 Dn
G(x) = a F ( l - R r ) e x p ( - a x ) (5.2.5)
7
Dn d ’(An) + a F ( l - R , ) e x p ( - a x ) - -An = O (5.2.6)
‘n
a F ( l -R,)rn
An(x) =Acosh(x/L,) + Bsinh(x/L,) (5.2.7)
a’L,2 - 1
where
(5.2.8)
Lsinh
DnLn
-
[ y,]
+cosh -
(5.2.10)
The bracketed expression is called the geometry factor (see also [l]).
-
sPLP
+ a L p -exp(-axj)
X DP
I,,,(k) = q F ( l - R f ) e x p ( - a x , ) ( 1 - e x p ( - a W ) ) (5.2.12)
To calculate the saturation current density of a real cell we must once again
take into account the recombination effect at the surface.
(5.2.13)
’ A dead layer is a highly doped region near the surface with such a short
lifetime that photons absorbed in it cannot contribute to the photoelectric
current.
The Physics of Solar Cells 77
The geometry factor is determined by the two variables S,/S,, and H’IL,
i.e. by the ratio of inner to outer recombination and the ratio of base
thickness H’ to diffusion length L .
Figure 5.4 [ 2 ] shows this relationship. If the diffusion length is around
half the cell thickness, then the surface recombination no longer has any
effect on the dark current. The geometry factor is 1.
If, however, the diffusion length is greater than cell thickness, then we
can differentiate between three cases:
where S,, > S, then G, > 1. In this case the dark current increases, thus
decreasing the efficiency of the solar cell.
where S,, = S, then G, = 1. The cell behaves like an ‘infinite’ cell.
where S, < S, then G, < 1. The dark current decreases with the
decreasing value of S,,. The dark current decreases, circuit voltage
increases and the efficiency of the solar cell is improved. This
behaviour opens the potential for increasing open circuit voltage and
78 Crystalline Silicon Solar Cells
The saturation current from the emitter is much more complex to determine
than that from the base. Since in reality the emitter always has a doping
profile, it follows that:
internal fields are present,
the diffusion length and the mobility of charge carriers are not constants
due to their dependence upon dopant concentration,
band gap narrowing takes place due to the high level of doping.
10.5
9.o
7.5
6 .O
4.5
3.0
1.5
1.0 L
1018 1019 1020
NS Icm -31
Figure 5.5 Saturation current of an emitter as a function of surface
concentration, with S, being parameter
diodes this is of very little significance, but for solar cells the functional
dependency in this voltage range is very important. As we will discover
later, the fill factor and thus efficiency are considerably influenced by this.
Therefore, we want to investigate this in detail. For this purpose, we need
to investigate recombination in the space charge region more closely.
The SRH recombination formula (3.4.5) after some manipulation, reads
(5.2.15)
- R =ni/2r, (5.2.16)
we find that
n = p = n , exp(UA/2UT) (5.2.18)
The recombination rate at the limits of the space charge region is therefore
The Physics of Solar Cells 81
n.
R = IexpUA/2U, (5.2.19)
2=0
kT
(5.2.20)
9Ema.x
where Em, is the electric field at the p-n junction. We then find that for
the recombination current
I* =
2kTqni
4 =,Emax
exp [../ y] (5.2.21)
(5.2.22)
The factor before the exp function is designated IOz and now the diode
equation can be expanded to
If we also take into account the resistances in the following equation for
the current-voltage characteristic line, then we find that
[
V -IRS
1[
V -IRs
I( V ) i , , exp --1 +Io2 exp --1 +- ' - I R ~
nlvT n2VT ] Rp
(5.2.24)
Figure 5.6 Equivalent circuit diagram for the two diode model of a real solar
cell
where
y.', is the built-in voltage,
0,and mP is the potential of the quasi Fermi level,
W is the space charge region width.
As well as precise knowledge of the dependency of the space charge
region W on the applied voltage and the applicable corrected built-in
voltage [7], it is mainly the factor f(b) that is decisive for the current
distribution in this starting region. The most decisive factors inf(b) are the
and T,,,, but above all their ratio to one another. Choo [S]
2
expande on the theory of Sah et a1 [9]. He found that the dependency of
the valueffi) at room temperature is dependent upon the applied voltage
as shown in Figure 5.7, where E,-E,, is a measure for the energetic distance
of the recombination centre from the intrinsic energy level Ei and the ratio
TpO/rnO is a parameter.
The bend of the curve is larger, the greater is the difference between T,,
and T,,. Consequently, the increase in initial current is no longer
The Physics of Solar Cells 83
I I I 1 I
0.0 0.1 OL 03 OW4 05 0'6
proportional to exp(V/2VT), but increases less sharply, which itself has the
consequence that the diode characteristic has a negative curvature in the
starting region. The typical shape of a characteristic is shown in Figure 5 . 8 .
This can have consequences for efficiency, mainly if the charge carrier
generation rate is low [sun < AM1.51, [10],[11]. Particularly solar cells
with a p-n junction lying very close to the surface may have severe space
charge defects, i.e. significantly differing values for T~~ and T~~ may occur.
Such cells are therefore bound to have a curved characteristic. Other new
investigations show that different conditions of surface recombination lead
to similar characteristics [ 121.
ooo
omo
oooo
0
0
0
0 0
1
10-9
0.0
O I
0.1
I
0.2
I
0.3
I
0.4
I
0.5
I
0.6
I
0.7 .a
lJ PI
Figure 5.8 The dark current characteristic of a Si solar cell
- -20 -
0.0 0,3
-
0,s
u [Volt]
0,6 0,7
-5-
n -10 -
N
E
U -15 -
h
E -20 -
-
-35 -
-40 L
References
At this point we wish to briefly explain the degree to which the total costs
of a photovoltaic array can be reduced by high efficiency solar cells.
150 I
Module efficiency 1
-
N
E 100 -
-tit
L
8
8
Q)
-
3
I
50
0 1
The basis for achieving high efficiency is the reduction of the total
amount of loss. We investigate this area intensively in this chapter. The
following considerations and calculations are based exclusively on solar
cells made of crystalline silicon. Many results will however - at least
partially - be applicable to other solar cell configurations. Figure 6.3 gives
an overview and classification of the different mechanisms for loss. These
can be divided principally into two areas.
I
electrical
ohmic
1 recombination
- Emitter region
SC material
Emitter Surface
- Contact material - Base region
Finger SC material
Collection bus Surface
Junction - Space charge region
For this analysis we use the formulae for photocurrents and saturation
currents in real solar cells, and investigate the influences of
diffusion length of the charge carrier,
dopant concentration and dopant profile, and
surface recombination velocity.
These sensitivity analyses are based on the most common solar cell
structure - emitter n+- and p-doped [10’6cm”] base. The penetration depth
of the emitter varies within the range 0.2-1 pm. The emitter surface
concentration varies within the range 5x10” to 1x1OZo~ m ’ ~ We. have
selected a crystal thickness of 200 pm, if not otherwise specified.
The photocurrent and saturation current from the base area are described by
the formulae (5.2.10) and (5.2.13).
In order to better demonstrate the function of the base area we assume
that
the emitter has no influence (ideal emitter), and
there are no shadowing and reflection or unabsorbed radiation.
Figure 6.4 shows short circuit current I C as a function of diffusion
length L , in the base with Surface Recombination Velocity [SRV] S, on the
back surface of the solar cell being a parameter.
This representation yields the following results:
If the diffusion length L , of the charge carrier is more than twice the
crystal thickness, then the short circuit current will reach a saturation
value.
High Efficiency Solar Cells 91
LL 1 I I I I I I
1,lO
42 - 100 -
LO - 1000 -
- -
104
“E 38
\
u 105,106
4
IE 36 - Sn=cmls
-
-8 34 - -
32 - -
740
720
700
680
c
> 660
E
u 640
>O
620
600
580
0 200 Loo 600 800 loo0 1200 1400 1600
Ln [ p m l
Figure 6.5 V, of a base dominated n'p solar cell as a function of diffusion
length in the base with recombination velocity at the reverse side
being the parameter
The result of this calculation is that for very high efficiencies the
diffusion length in the base represents a cardinal parameter. At diffusion
lengths greater than the crystal thickness, the reduction of surface
recombination on the back surface is decisive for the achievement of high
levels of efficiency.
charge camers created in the base can recombine on the back surface. The
BSF functions like an electrical mirror, 'throwing back' the charge carriers
into the inside of the cell. Its behaviour depends upon several parameters:
the surface concentration of p+ doping as well as its concentration
profile and penetration depth,
recombination in the p'-layer itself, and
charge carrier density at the junction, i.e. the relationship between
diffusion length and crystal thickness.
There is a whole range of methods for calculating this behaviour
precisely. We now give the results from [lo], which were calculated with
the help of the PC-ID programme Ell].
720 I I I I I I I I I I I
710
700
c 690
>
-E
680
>8
670
I I I I I I 1 I I
Figure 6.6 shows the influence of the BSF layer penetration depth and
surface concentration on V,, where S,, is lo6 cm/s (full metal coating). A
more technologically practicable value for penetration depth of
approximately 1 pm still does not yield a sufficient reduction in the
effective recombination rate to achieve very high efficiency.
An improvement on this structure was suggested by van Overstraaten
and Nijs in 1969 [12]. Like a graded base transistor, this was based on a
graduated p-doping throughout the entire base, increasing from the p-n
94 Crystalline Silicon Solar Cells
Si 02
Metal
Figure 6.7 Schematic structure of a high efficiency solar cell with a local
B SF
110 1 1 ’ 1 I I I I 1
100
100,1000 1
h
$?
90
v
8 80
- 50
+i 30
C
- 20
NS = 1 x1019 ~ r n - x~ ,= 0,Spm
10
0
300 400 500 600 700 800 900 1000 1100 1200
Wavelength (nm)
Figure 6.8 Internal spectral response of a solar cell (emitter with a Gaussian
profile, N,=10’9cmS3,xj=0.5 pm)
12.0 I I I I I Ilrlr
x j =lpm
I I I I I1111
NS
Figure 6.9 Saturation current of an emitter as a function of surface
concentration N , where Spis a parameter
so
25
n
N
E
s 20
::
0 5
rl=J
r_.
n
v)
0
n lo
aj
0
5
n
"
0 2 4 6 8 x)
We see from this that to achieve high efficiency a so-called 'two step
emitter', as shown in Figure 6.12, must be used.4
' The manufacture of a two step emitter using the double diffusion process
is described in Chapter 7 .
High Eflciency Solar Cells 99
I I I I 1
0 2 4 6 B 10
Emitter penetration depth xj [pm]
Figure 6.11 Saturation current density of an emitter with a high SRV as a
function of emitter depth xj where N , is the parameter.
I ++
P.
P+
SiO
Al contact BS F
Figure 6.12 Schematic structure of a solar cell with a 'two step emitter and
BSF'
100 Crystalline Silicon Solar Cells
2425 I 1 1 1 1 1 1 1 ( I I 1 1 1 1 1 1 ~ I I I 1 1 1 1 1 ~ I I l l l l l l
The dopant level in the base N A lies between 1.5 and 4 x 10l6 cm-’ (in
general the lower value is more favourable in practise).
The surface concentration N , of emitter doping is approximately
2 x loi9 cm-’.
For high efficiency a two stage emitter is required.
Both surfaces of the solar cell should be SO,-passivated, so that surface
recombination velocities of S,<lOO cm/s and S,< 1000 cm/s can be
achieved.
The diffusion length must be extremely high to achieve high eficiency,
but should be at least two to three times greater than the cell thickness.
I IL=40mA/cm* j
(6.2.1)
We see that the fill factor in particular is dependent upon the magnitude
of the current Zo2. If at voltage V, this reaches noticeable values in
comparison with Zol,the saturation current from the base and emitter, then
the fill factor will fall. Figure 6.14 shows the dependency of the fill factor
on the two saturation currents in the two diode model. (For the sake of
clarity we have assumed ohmic resistance losses to be zero.) We can see
from this that for high fill factors (FF > 0.80),Zolvalues of lo‘* A/cm2
must not be exceeded and Zo2 values have to be less than lo-” A/cm2.
(6.2.3)
EC
-
-2 0.6
rnc 0.L -
* 0.2
I I I I
-
0 3.5 4 4.5 5 5.5
EV
@,, (eV)
Figure 6.17 Barrier height in relation to the work function of the metal [21]
High doping
Figure 6.18 Charge transfer with ohmic contact: (a) tunnel effect,
(b) themionic effect
k 4 x & 7
P, =-
qTA * h
P, =- k
qTA *
exp [>] (6.2.6)
106 Crystalline Silicon Solar Cells
107
-
300 K
Theory
105 x PtSi-Si
o Al - Si
103
-
N
101
E
u 1
- 10'1
u
a
10-3
10-5
I 11 I
5 10 " 30
( 10-1oC,3/* I
Figure 6.19 Theoretical relationship between the contact resistance and doping
level, as well as barrier height [24]
We find from the formulae that in the first case the contact resistance
decreases with increasing doping, whereas in the second case it is
dependent only on the barrier height. This dependency is shown in Figure
6.19 (including some experimental results) [24],[25].
The left-hand side shows tunnel behaviour according to formula (6.2.5)
and the right-hand side shows thermionic behaviour according to formula
(6.2.6). As we will see later, for a necessary contact resistance of
Rcm', for example, a surface doping concentration of approximately
1OZo cmS3is required in order to permit the use of many metals as contact
High Efficiency Solar Cells 107
If we consider the current path under the grid finger as shown in Figure
6.20, it immediately appears plausible that the width of the current path -
the distribution of current density - is directly dependent upon the level of
specific contact resistance pc [see Section 6.2.2.1.21.For very small values
of pc the current travels mainly along the edge of the grid finger.
Conversely, high transition resistance leads to an expansion of the current
path.
Figure 6.20 Current path under the grid finger: 1 = length of grid finger, L =
width of grid finger, I = electric current
along the entire grid finger is also virtually zero. We are also justified in
making the assumption that the current path in the emitter is homogeneous,
i.e. that at right angles to the grid finger in the longitudinal direction the
same current density applies everywhere. Then in the layer dx the two
longitudinal and contact resistances dR, and dR, are determined as follows:
(6.2.7)
dR, = - pc (6.2.8)
ldx
where pc in [Ckm2] is the specific contact resistance.
Further mathematical analysis requires the solution of differential
equations, which we wish to avoid here. Please refer to the literature
[26]-[28].
The voltage distribution under the grid finger (at right angles to it) thus
works out as:
High Eficiency Solar Cells 109
(6.2.9)
Contact -
X
U(X) = u0 e LT
\& \\
-X --
0
LT
If we designate (p, / Rd0.’ as the transport length L,, the voltage drops
to l / e after the distance L,, and the current under the grid finger reduces
accordingly. The transport length is therefore a characteristic variable for
the current path.
The above mathematical analysis yields the following value for contact
resistance:
(6.2.12)
2 . If L , I2L, then coth nears the value of the factor in front of L . We thus
find the contact resistance to be
R, = - PC (6.2.13)
I*L
Result: If L , IO S L , then the resistance is independent of the width of
the contact finger.
If L , 2 2L, then the width of the finger alone determines the
contact resistance.
As an example of a high efficiency solar cell we wish to clarify the high
influence of the specific contact resistance pc and thus the transport length
LT.
For a desired grid finger width of 10 pm, L, 5 pm, i.e. where L , =
(pc/R,Jo.’ with a normal R, of approximately 100 CUD we find the required
~ a m 2 . As demonstrated in Figure 6.17 and Figure 6.19, for
pc of 2 . 5 lo-’
a surface dopant concentration ND of approximately lOI9 cm” this can only
be achieved using titanium as the contact material.
where A is the cell area for an Si wafer with a resistivity of p=l Rcm and
a thickness D of 200 pm yields R, = 0.020 SZ, and is negligible in most
cases.
Figure 6.23 Current path in the emitter: left: side view; right: aspect
Imax-- j l -d (6.2.15)
2
The current after distance x is then I(x) = jlx due to its homogeneity. We
now need to find the resistance dR in the infinitesimally thin layer dx. This
works out, as we can easily verify, to
-
P
dR =-dx (6.2.16)
x, 1
112 Crystalline Silicon Solar Cells
where p is the average resistivity of the emitter and xj its penetration depth.
Since
-
P =R, (6.2.17)
X.
J
R,
dR =-dx (6.2.18)
1
The power loss dP in the sheet dx is then calculated to be
dP = I ' M (6.2.19)
R , dx
dP = ( j l x ) ' - (6.2.20)
1
and by integration we find the total loss, i.e.
dlZ
P =j21R, f x z d x (6.2.21)
0
d' (6.2.22)
P =jZlR,--
24
This means that the power loss in the emitter increases by the cube of the
distance between the contact fingers. To find the value of R , we manipulate
the equation (6.2.23) to obtain P = I,,,, Re, = I,, R,. We then find that
(6.2.23)
R , is thus found to be
High EfJciency Solar Cells 113
R , = -R~ d (6.24)
16
R, is therefore equal to one-third of the electrical resistance of the emitter
layer between x = 0 and d/2.
(6.25)
(6.2.26)
texturising of the cell surface. In the latter, the surface is structured so that
multiple reflections allow most of the light to be absorbed in the cell.
"2 Silicon
n . d = -h (6.3.1)
4
R =
rf +ri +2r,r2cos28
(6.3.2)
2 2
1 + r l rz + 2 r , r 2 c o s 2 9
with
no - n ,
r, = - (6.3.3)
no + n ,
(6.3.4)
(6.3.5)
where
no is the refractive index of the uppermost layer (air or glass),
n, is the refractive index of the antireflection layer, and
n, is the refractive index of the silicon.
(6.3.6)
n ,2 =nOnz (6.3.7)
i.e. when
High ESficiency Solar Cells 117
-
Silicon
-
(6.3.8)
' The lowest total reflection under AM1.5is when the minimum is at
1=0.6pm.
118 Crystalline Silicon Solar Cells
20 - *.
s
8
,
10 - 8
0 I
In Figure 6.28 the silicon has a pyramidic surface. These structures can be
produced by anisotropic etching, with the angle at the peak being 70.5' (on
~ 1 0 0 surfaces).
) A vertical beam meets the silicon surface at an angle of
35.25".
Reflection is at the same angle. The reflected part meets the opposite
surface, so that again part of this light penetrates the crystal. The
calculation for total reflection shows, that for (AMl.5) sunlight instead of
approximately 35%, only 10% of the light is reflected.
High Eficiency Solar Cells 119
As can be seen from this illustration, the radiation can only exit via a
narrow leakage cone due to the high refraction index of Si.
The angle a, of this leakage cone is calculated as
1
sin2@, = - (6.3.9)
nz
For a value n,, = 3.5 we find that OC= 17".
If we calculate the radiation loss for light reflected into this cone, it
amounts to approximately 8.5% of the total light 1291. Further
improvements can be made by additional structuring to the front surface of
the cell. For further information we refer you to the literature [30]-[32].
We note here that the principle of confinement is more important the
thinner the silicon wafer. The thinner the wafer, the more often the light
must travel backwards and forwards within the crystal. For an efficient
High Efjciency Solar Cells 121
crystalline Si thin film cell (sheet thickness 30-50 pm) good confinement
is the most important prerequisite.
To sum up: Shadowing, reflection and lack of absorption reduce
photoelectric current. If this loss can be reduced in the best case to 6%, the
photoelectric current - which can be achieved with AM 1.5 solar radiation
- is approximately 41 mA/cmZ.(The theoretical maximum is 44 mA/cm2.)
Electrical losses, however lead to a further reduction in the above current.
-8
Y
40- -.----
50 vm
......-.,-.. 100 pm
30:
-
-
-0
([I
20-
10 -
0 . .
We find the minimum for these losses when the shadow loss is around
the same size as the ohmic loss in the emitter. Shadowing can be reduced
by another one-third by tapering the fingers and bus. Tapering of the
fingers occurs from the busbar.
The front surface, apart from the grid structure, is coated with a
thermally grown layer of silicon dioxide for passivation.
The emitter is two stage and has a surface doping concentration of
approximately 1 x lOI9 cmS3and a penetration depth of 0.5-1 pm under the
SiO, layer, the surface concentration is approximately 1x 10' cm" and the
penetration depth approximately 2-3 pm under the metal of the grid
structure.
The back surface of the cell is coated with a thermally grown SiO, layer
for passivation except for the point contacts (approximately 1%-2% of the
total area).
The local p'-doped BSF has a surface concentration of >lozo cm-' and
a penetration depth of 2-3 pm.
The SiO, passivation has a thickness of approximately 100 nm to
achieve a high antireflection effect on the emitter side (light entry).
The back surface contact has reflective characteristics and consists, for
example, of vapour-deposited aluminium.
For a cell of dimensions 2x2 cmz the gridJingers have a width of
approximately 15 pm and a thickness of around 8 pm (tapering away from
the busbar).
The busbar has a width of approximately 150 pm, and the contact
connection is located in the middle of the busbar.
As well as these constructive measures it must be ensured
technologically that the diffusion length in the base remains high
throughout all the process stages (see Chapter 7).
By implementing these measures it is possible to increase the efficiency
of monocrystalline solar cells in the laboratory under AM 1.5 to 23%-24%,
very close to the theoretical efficiency [33]-[35].
A further increase in efficiency can be achieved in crystalline silicon by
using thinner cells of approximately 10-30 pm. However, this requires
excellent passivation of the crystal surface and very good 'optical
confinement'.
do not interfere with each other. The design of such process chains is one
of the most important developmental tasks for all semiconductor devices.
We now describe two process sequences for high efficiency Si solar
cells, which have been developed in our institute. They naturally rely on
many known technologies. The first manufacturing process achieves an
efficiency of 23%. This is naturally also the more complex procedure.
However, since its high cost overcompensates for the cost reducing
potential brought by high efficiency, a simpler, more economical process
has been developed, whereby attention is focused on keeping the sacrifice
of efficiency as low as possible.
All the process stages described in the following section are described
and explained in more detail in Chapter 7. References are made at certain
points.
In Figure 6.33 the entire process sequence is divided into eight process
blocks, with each individual block containing several individual steps. The
process is explained based on this illustration. The starting point is - as
already mentioned - Fz-Si (float zone pulled Si material, see Chapter 7,
Section 7.15) with a resistivity between 0.5 and 1.5 R, a wafer thickness of
approximately 250 pm and a crystal orientation of (100) at right angles to
the surface of the Si wafer. The surfaces are etched or polished on both
sides. The wafer diameter is 3 in. or 4 in.
Texturizing: The silicon wafer is given an approximately 80 nm thick film
of SiO, by means of a high temperature process (see Chapter 7, Section
7.2.2.). A window structure is then created on one side of the Si wafer (to
be the front side, the side turned towards the light) using photolithography
and an etching process in buffered hydrofluoric acid, creating a multitude
of oxide-free square windows with dimensions 20 x 20 pm'. Deep etching
then takes place in these windows in a hot alkaline solution. Inverted
pyramids are created by this anisotropic etching with (1 11) orientation (see
Chapter 7, Section 7.2.5.2). The remaining SiO, ridgetops, not affected by
the alkaline solution, are then removed in an HF solution.
Boron-BSF Dvfision: By a further oxidation process, an SiO, film is
created with a thickness of 200 nm. On the other side - to be the back of
the cell - some windows are opened using a photoresist processes. Boron
is diffused into these windows in a high temperature process to create a
local pt back surface field. The remainding oxide is later removed by
etching.
High EfJiciency Solar Cells I25
Figure 6.33 Process sequence for the manufacture of a LBSF (Local Back
Surface Field procedure) solar cell with very high efficiency
I26 Crystalline Silicon Solar Cells
Figure 6.34 Reduced process sequence for the LBSF (Local Back Surface
Field) procedure for the manufacture of a high efficiency Si solar
cell
128 Crystalline Silicon Solar Cells
The aim was to reduce the processing cost compared with the process
described above. The process described below uses significantly fewer
process stages (see Figure 6.34 and Table 1 right). The resulting solar cell
structure is called a RP-PERC structure.’
The efficiency levels achieved are shown in Table 2. With Fz-Si and an
area of 4 cmz an efficiency of 21.6% can be achieved instead of > 23%
with the more complicated procedure. It is worth noting that even with Cz-
Si (Czochralski material, crucible pulled) a very economic Si material, with
efficiencies of almost 20 %, can be achieved.
Altering the process, as an experiment, an additional p+ back surface
field is added by the diffusion of boron. Efficiency increases, due to the
lower level of recombination on the back surface, so that for example, with
Fz-Si and an area of 4 cm’, 22.6% efficiency is achieved. It is thus
documented that even with greatly simplified processes, very high
efficiencies can be achieved.
Table 1 shows the number of process stages for the LBSF process and
for the RP-PERC process. Table 2 shows the efficiencies achieved by the
RP-PERC process.
References
Wolf M., Proc. 3rd EC PV Solar Energy ConJ, Cannes, France, 1980,
p. 204
Goldmann H., Proc. 14th IEEE PVSpec. Conf San Diego, California, 1980,
p. 923
Redfield S., Proc. 13th IEEE P V S p e c . ConJ, Washington, DC, USA, 1978,
p. 911
Ross jr. R. G., Proc 13th IEEE PV Spec. C o n f , Washington, DC, USA,
1 9 7 8 , ~ 1067
.
Grenon L. A. and Coleman M. G., Proc. 13th IEEE PV Spec. Conf.,
Washington, DC, USA, 1978, p. 246
Vofl B., Statusreport Photovoltaik, 1987, p. 73
Knobloch J., Aberle A. and Vofl B., Proc. 9th EC PV Solar Energy ConJ,
Freiburg, Germany, 1989, p. 777
Von B. and Knobloch J., Internationales Sonnenforum, 1988, p. 468
130 Crystalline Silicon Solar Cells
[91 DOE-Studie zitiert von Fan J.C.C. in Proc. 5th PVSEC, Kyoto, Japan, 1990,
p. 607
Aberle A., Thesis Univ. Freiburg, 1992
Basore P. A. Proc. 22nd IEEE PV Spec. Con$, Las Vegas, Nevada, USA,
1991, p. 299
van Overstraaten R. and Nijs J. JEEE TED 16, 1969, p. 632
Nicollian E. H. and Brews J. R., MOS Physics and Technology, Wiley &
Sons, New York, 1982
Goetzberger A., Bell Syst. Techn. 45, 1966, p. 1097
Goetzberger A. et al., Appl. Phys. Lett. 12, 1968, p. 95
Sze S. M., Physics Of Semiconductor Devices, 2nd Edn, Wiley & Sons, New
York, 1981
Ruckteschler R., Thesis, Univ. Freiburg, Germany, 1986
Park J. S., Neugroschel A. and Lindholm F. A., IEEE TED 33, 1986, p. 240
Schottky W., ZeitschriftJ Physik 113, 1939, p. 367
Shockley W., Bell System Techn. 28, 1949, p. 435
Schroder D.K. and Meier D.L., IEEE TED 31, 1984, p. 637
Chang C. Y. and Sze S. M., Solid State Electron. 13, 1970, p. 727
Padovani F. A. and Stratton R., Solid State Electron. 9 , 1966, p. 695
Yu A. Y. C., Solid State Electron. 13, 1970, p. 239
Chang C. Y. et al., Solid State Electron. 14, 1971, p. 541
Meier D. L. and Schroder D. K., IEEE TED 31, 1984, p. 647
Hower P. L., Hooper W. W., et al. in Semiconductors and Semimetals,
Willsrdson R. K. and Beer A. C., eds. Academic Press, New York, 1971,
pp. 178-183
Murman H. and Widmann D., IEEE TED, ED 16, 1969, p. 1022
Goetzberger A,, Proc. JSth IEEE PVSpec. Con$, Kissimmee, Florida, USA,
1981, p. 867
Campbell P., Wenham S. R. and Green M. A., IEEE TED. 37,1990, p. 331
Campbell P., Wenham S. R. and Green M. A., IEEE TED 35, 1988, p. 713
Uematsu T., Ida M., Hane K.,Kokunai S. and Saitoh T., IEEE TED 37,
1990, p. 344
High Eflciency Solar Cells 131
[33] Green M. A,, Proc. 10th EC PV Solar Energy Con$, Lissabon, Portugal,
1991, p. 250
[34] Sterck S., Knobloch J. and Wettling W., Progress in Photovoltaics, 2, 1994,
p. 19
[35] Knobloch, J., GlUnz S. W., Biro D., Warta W., Schaffer E. and Wettling W.,
Proc. 25th IEEE P V S p e c . ConJ, Washington, DC, USA, 1996, p. 405
[ 3 6 ] Zhao J., Wang A., Altermatt P. P., Wenham S. R. and Green M. A,, First
World Conference on Photovoltaic Energy Conversion, Hawaii, USA, 1994,
p. 1477
[37] Glum S. W., Knobloch J., Biro D. and Wettling W., Proc. 24rh EC PV
Solar Energy Con/, Barcelona, Spain, 1997, in press
7
Si Solar Cell Technology
In this chapter we first of all wish to describe in detail the process for the
production of highly pure crystalline silicon. We then want to explain the
technological processes which are applied to the manufacture of solar cells
from this material.
Apart from oxygen, silicon is the most commonly occurring element on the
earth. It mainly occurs as silicon dioxide (SiO,) in quartz and sand. Its
synthesis has been familiar for many decades. It is extracted from (mainly)
quartzite reduction with carbon in an arc furnace process. Figure 7.1 gives
an overview of the manufacturing process [l].'
The pulverised quartz and carbon are put in a graphite crucible. An arc
causes them to melt at approximately 1800°C. Then the reduction process
takes place according to the formula
The liquid silicon collected at the bottom of the crucible (melting point
1415°C)can then be drawn off. Its purity is approximately 98%. This is
called metallurgic-grade silicon (MG-Si) and a large quantity is used in the
iron and aluminium industries. More than 500,000 tonnes are manufactured
per year worldwide .
' The first six illustrations are direct copies of the originals, as listed in [ 11
and [2]
I34 Crystalline Silicon Solar Cells
The processes described here and in the following Section 7.1.3 are based
on developments by Siemens in the 1950s. They are now the standard
processes for the production of electronic grade silicon.
In the first stage pulverised metallurgic silicon is exposed to
hydrochloric gas in a fluidized-bed reactor. Trichlorosilane and hydrogen
are produced by the chemical reaction Si + 3 HCl + SiHCI, + H,
(exothermic reaction). Since trichlorosilane is a liquid at temperatures
below 30°C it can easily be separated from hydrogen.
The chlorides of the impurities from the process must now be separated
from the trichlorosilane. In a second stage the trichlorosilane is freed from
these impurities in fractional distillation columns. The other silicon
chlorides are also removed. Trichlorosilane distilled in this way fulfils the
requirements for electronic grade silicon. The impurity level is less than
1O-'O%.
Figure 7.4 Single crystal pulling by the float zone pulling method [ 5 ]
The puller is located within an enclosure flushed with inert gas. At the
lower end a single crystal seed is again melted onto the polycrystalline rod
by induction heating. After melting, a region of liquid silicon is propelled
Si Solar Cell Technology 139
Most semiconductor devices, including solar cells, require thin wafers with
a thickness of approximately 0.2 to 0.5 mm. The standard process for
wafers used the so-called inner diameter saw (ID), where diamond particles
are imbedded around a hole in the saw blade. The process is very cost
intensive and has the disadvantage that up to 50% of the material is
wasted. A new process has been established in the form of the so-called
multiwire saw, in which a wire of several kilometres in length is moved
across the crystal rod in several coils within an abrasive suspension, whilst
being wound from one coil to another (Figure 7.5) [ 6 ] .
The advantage of this is that thinner wafers can be produced and the
sawing losses are reduced by approximately 30% in comparison with the
ID saw process. Also crystal defects on the surface of the silicon slice are
significantly lower, reducing the manufacturing cost and increasing the
efficiency of the solar cells.
U
Figure 7.5 Sawing Si slices by the "wire cutting technique" [6]
%Y
Figure 7.6 Cross-section of a block casting equipment [7]
The EFG process (Edge defined Film Growth), based on the principle
shown in Figure 7.7 [9], consists of an octagonal tube being drawn from a
silicon melt using suitable graphite templates. The edge length of the
octagonal segments is a little above 100 mm, giving a total tube diameter
of approximately 30 cm. The thickness of the tube wall and thus the
thickness of the slices produced of a few tenths mm is set by the shape of
the graphite capillary as well as the prevailing temperature and pulling
speed (some cm/min). Tubes with a length of 4-5 m can be pulled using
this technique.
Crystal Growth of Silicon Ribbons
LI
level in crucible
The SSP process (silicon sheet from powder) as shown in Figure 7.8 [lo]
consists of silicon powder being placed in a quartz form (e.g. the above
mentioned spherical silicon powder can be used). In the first stage the
powder is sintered together. In the second stage the now self-supporting
foil undergoes a zone melting process. A polycrystalline material with very
large grains (millimetres to centimetres) is created. The melting process is
brought about by focused, incoherent light. Silicon sheets with a thickness
of approximately 400 pm can be produced in this manner. Solar cells have
been produced on a laboratory scale with an efficiency of approximately
13%.
To conclude Section 7.1 we should mention the work which was aimed
at replacing expensive gas phase refractioning processes for the
manufacture of high-purity starting silicon by metallurgic preparation
methods (leaching, gas blowing, etc.). Despite great efforts, the necessary
purity has never been achieved using these methods. The efficiencies of
solar cells made of this material are too low. This work was stopped a few
years ago.
The diffusion of solid substances in the Si solid obeys Fick's second law,
which in one-dimensional form reads:
(7.2.1)
where
N(x, t) is the concentration of diffusing substances at point x and
time t ;
D is the diffusion coefficient specific to each material, which
depends very strongly on temperature.
We will consider two solutions to this partial differential equation here.
(7.2.2)
X
N ( x , t ) = N, erfc - (7.2.3)
2 fi7
X
- = 5.4 (7.2.4)
$7
and thus
x. = 5.4
I
$7 (7.2.5)
N(x,t) = -
Q exp -( x / ~ J D ; ) Z (7.2.6)
&Dt
where the surface concentration N s is found to be
N s =- Q (7.2.7)
S,Ei
and is thus dependent upon the diffusion parameters. Figure 7.11 shows
this relationship. As is clear, the desired surface concentration (high or low)
can be adjusted - as discussed in Chapter 6.
1 f
T
x-------+
Figure 7.1 1 Concentration profiles of dopants with an inexhaustible diffusion
source
148 Crystalline Silicon Solar Cells
D = D o exp(-AlkT) (7.2.8)
where for a given substance Do and A are constant over wide temperature
and concentration ranges. The variable A is also called the activation
energy.
The functional dependency of coefficients on temperature can be
represented in the form of a so-called Arrhenius curve (log D + l/T).
Figure 7.12 shows the diffusion coefficients for many elements in relation
to temperature [ll]. Most of these values were determined in the early
1950s [12].
We see from Figure 7.12 that metals (e.g. Ti, Ag, Au) have higher
diffusion coefficients than dopants (e.g. Ph, B, As) by several orders of
magnitude, and therefore diffuse significantly quicker in silicon (substances
such as Cu and Fe not shown in this representation diffuse even quicker).
Therefore semiconductor technology requires extreme cleaness of
laboratory and process equipment. We also see that due to the exponential
temperature dependency of diffusion coefficients, the process temperature
must be very strictly adhered to.
Diffusion time, on the other hand, is much less critical, because the
penetration depth according to the formula (7.2.5) is proportional to dt.
l/T -
Figure 7.12 Temperature dependency of the diffusion coefficients of different
elements in silicon (according to Landolt-Barnstein)
# bh -Valvesand
flow meter
I!@, IflrkDopant liquid
to phosphorus pentoxide.
The P,O, created combines with the silicon dioxide growing on the
silicon surface to form liquid phosphorus silicate glass. This glass then
becomes the diffusion source.
The process using POC1, is similar. P,O, is also created in this process.
In addition, chlorine is released. Its significance for the cleaning of silicon
surfaces is well known in semiconductor technology as chlorine creates
volatile metal compounds [15].
In practice, however, phosphorus diffusion shows deviating behaviour
from the simple theory for the case of low penetration depth. In the case of
an inexhaustible source, the diffusion profiles obtained do not match the
above diffusion theory. Concentration profiles are obtained which are more
like those shown in Figure 7.14.
Si Solar Cell Technology
is obtained which follows the Gauss distribution. Both diffusion steps are
coordinated with each other in temperature and time, such that instead of
the saturation concentration of approximately 10” cm”, surface
concentrations of approximately 10’’ cm-, can be produced.
The thermal oxidation process (dry, i.e. without the addition of water
vapour) is, as mentioned above, according to the following formula:
Si + 0, +SiO, (7.2.10)
Oxygen diffuses through the SiO, layer which is forming. With this
process there is therefore no saturation thickness although the rate of
growth slows with the increasing thickness. At the outset the layer
thickness grows in proportion to time, at greater layer thicknesses (>1 pin)
approximately in proportion to the square root of time. An SiO, layer
requires a silicon layer of approximately 45% of its own thickness.
Wet oxidation (with water vapour) takes place according to the formula
The rate of growth in this case is significantly higher than for dry
oxidation, since the reaction process is clearly stimulated by the hydrogen.
Figure 7.15 shows the influence on the SiO, layer thickness of dry or wet
oxidation as a function of the reaction time and the oxidation temperature
P21.
Other influences can also alter the growth rate of SiO,. The oxidation of
highly doped silicon (>lozocm-’) is around 20% faster. Likewise the oxide
grows approximately 30% faster on the (111) orientated surfaces than on
Si Solar Cell Technology 153
t i hl
1 10
10
xO
[PI
10-1
10-2
10 102 103
t I min 1
Figure 7.15 The oside layer thickness with dry and wet oxidation
and
xO
[ pml
10-1
10 -2
Figure 7.16 Necessary oxide layer thickness for complete masking against
boron and phosphorus [ 251,[ 261
Si Solar Cell Technology 155
Various different etching and cleaning techniques are necessary for the
manufacture of semiconductor devices.
The surfaces of the silicon wafers must be free of contaminants as far
as is possible. These contaminants may be of molecular, ionic, or atomic
nature. Residues of the lapping, polishing and photoresist processes are, for
example, of molecular nature. Contamination by ions usually occurs by the
absorption of ions from the etching solution, whilst heavy metals such as
silver, copper and gold have an atomic character.
The most widely used procedure for surface cleaning is currently the so-
called RCA cleaning 1271.' This process is based upon the use of hydrogen
peroxide (H202)firstly as an addition to a weak solution of ammonium
hydroxide (NH,OH), and secondly hydrochloric acid (HCI). The cleaning
process is as follows: After preliminary cleaning in hot dilute nitric acid
(HNO,) and etching in buffered hydrofluoric acid (HF) the silicon wafers
are exposed to the peroxide solution at 80°C. Due to the severe oxidising
effect the organic residues are oxidised and simultaneously a large part of
the metallic traces complexed. In the subsequent cleaning stages - in the
hydrochloric acid again at 80°C - the remaining traces of metals are
converted into volatile metal chlorides and thus removed.
Etching the silicon dioxide layers occurs mainly in a weak solution of
hydrofluoric acid. Depending upon the desired etching rate the HF-solution
can be buffered with ammonium fluoride (NH,F).
Isotropic ,etching of silicon occurs in a solution of nitric acid and
hydrofluoric acid. The nitric acid oxidises the silicon to SiO,, which is then
dissolved by the hydrofluoric acid. The mix ratio determines the etching
rate and the surface structure created. To obtain, for example, a very
smooth, almost mirror finished surface, or a very low dissolve rate, the
etching mixture can be buffered with acetic acid (CH,COOH) and
phosphoric acid (H,PO,). Comprehensive information can be found in [28].
Following all cleaning processes rinsing with deionised water must take
place as the final stage. The current state of the art is a specific resistance
of 17-1 8 MRcm (near the theoretical value due to natural dissociation).
A separate branch of the chemical industry developed decades ago
concerned with the preparation of the necessary chemicals in extremely
pure form. As well as pure chemicals a multitude of compounds with
different mix ratios are available. All processes are performed in ‘clean
room s * .
7.2.3.2 Photolithography
Three methods are used for the structuring of the contact finger. In the first
a vacuum evaporation template with a perforated strip pattern is used,
which has the disadvantage that the smallest finger width is approximately
100 pm - or at best 50 pm. If narrower contact fingers are required to
reduce shadowing, the photoresist technique must be used.
Si Solar Cell Technology I57
Photoresist Solvent
Metal
I
P
- -. I
!-----
P+
/-
The advantage of thick film metal coating using the screen printing
process, which is, as mentioned, widespread in industrial solar cell
manufacturing [30]-[32], lies on the one hand in the low investment cost
and on the other hand in the scope for automating the process. The metallic
pastes used have, in addition to an organic binder which determines
viscosity, a flux, also known as sintered glass. Typically, such pastes
contain, in addition to 70% Ag in the form of platelets a few pm thick and
approximately 5 to 15 pm wide for the front contact, approximately 2%
sintered glass. The sintered glass is composed of lead oxide,
lead-boron-silicate or zinc-boron-silicate, the rest is binder. After
depositing, the layer is sintered at temperatures of approximately 600°C.
The sintered glass components melt and dissolve a small layer of silicon.
At the same time, this melt is enriched by silver. Upon cooling a
Si Solar Cell Technology 1.59
High vacuum evaporation technologies and thick film techniques are also
used for the manufacture of antireflection coatings. For a single layer
antireflection coating, titanium dioxide (TiO,) is used almost exclusively.
Its refraction index can be adjusted within a specific range during the
evaporation process by the selection of evaporation rate and the addition of
small quantities of oxygen. We thus obtain values of n=1.9 to n=2.3 with
very good transparency. The latter is a very important prerequisite for high
efficiency.
Thick film technologies are also used in mass production for costs
reasons. A paste containing titanium dioxide compounds is deposited onto
the surface of the silicon, either by spinning on or by the screen printing
technique. Finally, sintering takes place at temperatures of 600-800°C.
These antireflection processes can be linked to the above metal coating
by screen printing. The TiO, paste previously dried at temperatures around
200°C has silver paste added to it for the grid structure. Both are then
simultaneously sintered. As the thickness variance of the antireflection
layer only influences total reflection behaviour slightly (AM 13), then this
gives good antireflection characteristics.
160 Crystalline Silicon Solar Cells
are normal. To achieve the desired pyramid structures, the silicon surface
must be first fitted with a corresponding SiO, stripe structure, which, as
mentioned, will not be attacked by the alkaline solution. As the etch depth
and of course also the undercut is dependent upon the distance between the
individual SiO, strips and their width, these parameters must be carefully
matched to each other. Etching continues until the two neighbouring sides
underneath make contact. Inverted pyramid structures have become
dominant.
As mentioned, a reduction in reflection is achieved if the deposited SiO,
passivating layer has a thickness of 100 nm, so that with a refraction index
n=l.46 the h/4 condition is fulfilled.
References
[ 11 Diet1 J., Helmreich D. and Sirtal E., Crystals: Growth, Properties and Appli-
cations, Vol. 5 , Springer-Verlag, 1981, p.57
[2] Zulehner W. and Huber D., Crystals: Growth, Properties and Applications,
Vol. 8, Springer-Verlag, 1982, p. 92
[3] Czochralski J., Z. Phys. Chernie 92, 1977, p. 219
[41 see P I , p.4
PI see P I , P. 6
[6] see [l], p. 73
[7] see [l], p. 67
[8] Schtitzel P., Zollner Th., Schindler R. and Eyer A., Proc 23rd IEEE PV
Spec. Con$, Louisville, Kentucky, 1993, p. 78
[9] Wald F. V., Crystals: Growth, Properties and Applications, Vol. 5 ,
Springer-Verlag, 198 1, p. 157
[ 10) Eyer A., Schillinger N., Reis I. and Rtiuber A., Cryst. Growth, 104, 1990, p.
119
[ 111 Landolt-Bornstein Vol. 17 Part C Springer-Verlag, 1984, p. 494
[ 121 Fuller C. S. and Ditzenberger J. A., J. Appl. Phys., 27, 1956, p. 544
[13] Goetzberger A. and Schockley W.,J. Appl. Phys., 31, 1960, p. 1821
[ 141 Clays C. L., Proc. 2nd Brazillian Workshop on Microelectronics, Sao Paulo,
1980
[ 151 Rouen R. S. and Robinson P. H., J . Electrochem. Soc., 119, 1972, p. 747
162 Crystalline Silicon Solar Cells
In the first part of this Chapter we will describe four specific solar cell
configurations made of crystalline silicon. These are:
Cells for concentrator applications.
Cells manufactured according to MIS technology [Metal Insulator
Semiconductor].
Cells made of polycrystalline silicon.
Cells with thin base layers [20-50 pm].
In the second part of this Chapter we will concentrate on some thin film
solar cells made of other semiconductor materials, i.e.
Cells made of amorphous silicon (a-Si).
Cells made of semiconducting compounds e.g. gallium-arsenide (GaAs).
and cadmium-telluride (Cd-Te).
Cells made of copper-indium-diselenide, known by the abbreviation
CIS.
We will conclude with some consideration of tandem cells and dye
sensitized solar cells.
The concentration of sunlight brings two advantages for solar cells. Firstly,
the required area can be reduced according to concentration, so the cell can
be based on good monocrystalline silicon and use costly technologies. As
concentration rises, cell cost becomes less of a factor for the solar array.
Furthermore, open circuit voltage increases with the higher short circuit
current of the cell, which in the first approximation is proportional to
164 Crystalline Silicon Solar Cells
radiation power. This effect is intensified because due to the high injection
of charge carriers, their diffusion lengths are greater than in the case of low
injection (one sun). Thus the saturation current is reduced and therefore
open circuit voltage increased. At 100-fold concentration an increase in
efficiency of 20% (relatively) is achieved. For even higher radiation,
however, the influence of Auger recombination becomes so noticeable due
to the high carrier density that the increase in efficiency flattens out
considerably. Sinton et al. [ l ] redefined the Auger coefficient from the
dependence of open circuit voltage as a function of radiation, obtaining a
value approximately four times larger than was previously realised.
First generation concentrator cells were a development of conventional
solar cells with a finger structure on the surface facing the light. The main
problem was the minimising of serial resistance, which is primarily
determined by the layer resistance of the emitter and the resistance of the
contact finger. The distance between fingers therefore had to be very low
and to minimise shadowing, the fingers had to be very narrow.
A word on the history of the solar cell. In 1977 Burgess et al. [2]
introduced a cell with what was at the time a high efficiency of 15% at 50-
fold solar radiation. In 1980 Khemthong et al. [3] increased this value to
over 20% (at 40 suns). A decisive improvement was achieved by Sinton et
al. [4] and Swanson et al. [ 5 ] when they implemented and improved the
Selected Solar Cell Types I65
21.1%. This is an exceptionally good result. The solar powered car fitted
with with these cells won the race.
Another type of high efficiency solar cell is the Buried Contact Si solar cell
shown in Figure 8.2.
This structure was first suggested in 1985 [14], and is patented in many
countries. The significant difference in this cell is the buried contact. Using
laser technology, grooves of approximately 20 pm wide and up to 100 pm
deep are cut in Si wafers texturised according to the principle of random
pyramids to hold the grid fingers. The etching process which follows
removes the silicon destroyed by this process. These grooves provide two
advantages. Firstly, shadowing is reduced significantly when compared with
the normal grid structure of commercial solar cells. Values of only 3%
surface shadowing are obtained. Secondly, the grooves can be filled with
contact material. Thus, approximately the height of the grooves and thus
the metallisation can be five times its width [15]. In conventional cells,
even vacuum evaporated contacts and contacts reinforced by
electrodepositing, the ratio is 1:1, i.e. the metal contact height is equal to
its width. The five-fold height means a reduction in the resistance of the
contact finger by a factor of 5 , resulting in a significantly better fill factor.
The technology of metallising consists of an electroless deposited nickel
contact, which is reinforced after sintering with copper. Since this
Selected Solar Cell Types 167
One advantage of this solar cell lies in its manufacturing, which does
not require any high temperature procedures. The thin SiO, layer is
produced at a temperature of approximately 500°C.The number of process
stages is low. A disadvantage is that the n-inversion layer has a sheet
resistance which is between five and ten times higher than in conventional
silicon solar cells. This necessitates a finger structure with very small
distance between fingers, which means that the fingers must be very thin
due to shadowing. Electrical contacting can therefore only take place using
Selected Solar Cell Types I69
The cost of the solar cell still contributes more than 50% to the cost of the
commercial solar module (see Figure 6.1). Of the 50% approximately two-
thirds can be attributed to the silicon material itself. Therefore an important
target of research and development is to reduce these material costs. In
numerous industrial and public institute laboratories, work on thin film
solar cells made of crystalline silicon is at the centre of research and
development. The thickness of this type of thin film solar cell should total
around 10-50 vm. This is much larger than solar cells made of
semiconducting compounds, which are described in a later section. In these,
thicknesses are in the region of a few pm. Since silicon, unlike the
semiconducting compounds described below, is an indirect semiconductor,
its suitability for this type of thin film solar cell is limited, due to the low
absorption of photovoltaically useful sunlight. There are, however, strong
arguments in favour of silicon.
Silicon will never present any resource problems [see Chapter 7, Section
7.1.11.
The material is non-toxic both in the operation of solar cells and for
disposal purposes.
Solar cells made of crystalline silicon do not show any degradation of
efficiency.
The manufacturing technologies are closely related and linked with the
technologies for the manufacture of semiconductor devices, both
integrslted circuits and large area high performance semiconductor
devices. Therefore the technologies for the production of solar cells
from crystalline silicon can participate in the large pool of experience
relating to the manufacture of extremely pure starting material and
process technologies.
In addition to the advantage of low material usage, calculations show
that the efficiency of such a thin film solar cell can be increased.
A thin film solar cell made of crystalline silicon, however, places
additional demands on manufacturing technologies:
Owing to low absorption in the crystal, the light penetrating into the
solar cell must be reflected several times at the inner boundaries and
pass backwards and forwards in the Si crystal material, so that sufficient
absorption takes place. The light must be locked in (optical
confinement).
I72 Crystalline Silicon Solar Cells
The boundaries (front and back surface) of the solar cell must be very
well passivated, to keep the recombination of charge carriers - in
particular at the back surface (the side turned away from the light) - as
low as possible [electrical confinement]. Unlike in a thick solar cell,
significantly more charge carriers are created near to the back surface,
where there is a much greater danger of undesired recombination on the
surface.
Since such a solar cell is not self supporting, the selection of a suitable
substrate is one of the most important tasks, after depositing
technologies.
Many years ago Loferski [47] and Wolf [48] pointed out the theoretical
high efficiency of thin film solar cells made of crystalline silicon. The
authors of this book reported the most important requirements of this type
of cell in 1984 [49]. The reader is referred to Figure 5.4 in this book,
which demonstrates very clearly the potential of a thin film solar cell. A
recent review is given in [50].
21
n
20
8
W
>r '9
Y
L
.a, 18
0
E
W 17
16
Diffusion length I-,, (pm)
15 in the base
14 1 1 1 I 1 I
0 50 100 150 200 250 300
Solar cell thickness (pm)
Figure 8.5 Efficiency in relation to cell thickness, with diffusion length in the
base being a parameter
Selected Solar Cell Types I73
Figure 8.5 shows the path of efficiency in relation to cell thickness. The
parameters used in the calculation are:
Resistivity of the base 1 Rcm.
Surface concentration of the emitter 10” cm-3.
Emitter penetration depth 1 pm.
Shadowing and reflection losses on the emitter surface 8%.
Reflection on the inner emitter surface 90%.
Reflection on the inner back surface 95%.
Surface recombination velocity at the emitter 1000 cm/s.
Surface recombination velocity at the back surface 100 cm/s.
All assumed parameters have been realised in high efficiency solar cells.
In the investigations which follow, the above values are used, if not
stated otherwise.
We see from Figure 8.5, that very high efficiency values (for different
diffusion lengths) can be achieved with cell thicknesses of 20-50 pm.
In the calculations which follow, we have concentrated on one cell
thickness of 30 pm, which can also be realised.
21
, ( ,,
20 -
.*I @ I I ,
' ( 4
( I ,
'',' *, ,300
-
19
........==..
,
18 - 106' '*,
'.
b.
* '
* .
17 - *'. ... Diffusion length 45
* *.,
' \'* in the base urn)
16 - 8'
i.
r'.
30 8..
15 :
14 -
13 -
10' 102 103 104 105 106
Back surface recombination Sb& (cm/s)
Figure 8.6 The influence of back surface recombination for cell thickness 30
pm with diffusion length in the base being a parameter
20
c
25
t
2!*0 16
E
W
14 c I
12
10
10' 102 103 104 I05 106
(cm/s)
Emitter recombination Sfront
Figure 8.7 The influence of recombination on front and back surface (electrical
confinement) on efficiency
20.0
19.5 0.9..
-
0'
19.0
$
v
#'
.-a, /
inside of the front surface
0
E
17.5
17.0
16.5 I I 1 I I
0.0 0.2 0.4 0.6 0.8 1.o
Reflection coefficient on the inside of the back surface
Figure 8.8 Influence of optical confinement (inner surface reflection) on
efficiency
intermediate layer the contacts for n++and p+ are both on the front. High
efficiency technology was put to use in cell manufacture.
8.1.6.3.1 Substrate
Many alternatives are currently under investigation. These are: MG silicon
(see Chapter 7, Section 7.1,1), or MG silicon with significantly reduced
impurities by various gettering or float zone pulling processes. This
material is called UMG silicon (upgraded metallurgical silicon). It can
Selected Solar Cell Types 177
Figure 8.10 Concepts for thin film silicon solar cells [53]
A few years ago an interesting new concept was suggested for crystalline
silicon thin film solar cells [56]. The principle and the manufacturing
technologies are explained based on Figure 8.11. The schematic cross-
section shows a multilayer structure of alternate n-and p-doped layers. The
boundaries are highly doped (n") on the substrate side, whereas on the
front surface, the side turned towards the light, the n-layer contains a
Selected Solar Cell Types 179
Figure 8.1 1 Multilayer crystalline silicon cell [ 581 schematic and manufacturing
diagram
VP
Figure 8.13 Production process of a-Si solar cells using glow discharge [ 6 5 ] . S:
substrate; C, A: electrodes; VP: vacuum pump; RF: transmitter
Selected Solar Cell Types 183
The current production method for a-Si solar cells involves depositing
the individual layers in a high frequency glow discharge reactor as shown
schematically in Figure 8.13. Silane (SiH,) in a mixture with hydrogen is
split into hydrogen and silicon. The a-Si can then be deposited onto glass
or metal. The required p and n doping for the manufacture of solar cells is
achieved by the addition of diborane (B,H,) or phosphine (PH,).In the case
of evaporation onto glass the electrical contact is made using a conductive
oxide film (TCO).Indium-Tin-Oxide (ITO)is often used for this purpose.
Light
20 nma(pc)-Si (Ge) : H :
--n
f
-------
Metal, TLO c *
and functions as a so-called window layer.2This overcame for the first time
the 8% hurdle [72]. Then Hamakava [73] went one step further by creating
two solar cells directly above one another by deposition (Figure 8.15).
Owing to the intrinsic film, which was now only half as thick, together
with better deposition techniques (low defect density) and with the use of
antireflection films, efficiencies of 13% are currently achieved.
n-
I Aluminium I/
Figure 8.15 The structure of a a-Si solar cell with two intrinsic layers [40]
The critical problem of a-Si solar cells is their stability. The efficiency
drops, is degraded. The degradation acts primarily on the fill factor and the
short circuit current, whereas open circuit voltage remains almost constant.
Degradation can be reversed, but only by exposing the cells to a
temperature of approximately 160°C. This degradation was first researched
by Staebler and Wronski [74]. This effect was named the Staebler-Wronski
effect after them. Even today it has not been fully explained. The most
probable explanation is that the recombination of light generated charge
carriers causes weak silicon-hydrogen bonds to be broken in the
amorphous material, thus creating additional defects, which lower the
collective efficiency and increase serial resistance. Much research work is
underway to explain the cause of this effect, so that it can at least be
reduced by the use of technical measures [75].
One decisive advantage of the a-Si cell is that the necessary serial
connection of cells can take place simultaneously during manufacture. As
shown in Figure 8.16 an entire layer of TC03 is first deposited onto a glass
substrate, and then a stripe pattern created, for example by a laser beam.
Then the a-Si solar cell structure is deposited in a reactor. Then the cells
are structured, again using a laser, so that the subsequent evaporated metal
has contact to the TCO on the back of the glass substrate. Finally, the
evaporated metal coating must be separated at a suitable offset. It is thus
clear that in this case five cells are connected in series. This effect is
decisive in making a-Si solar cells dominate almost exclusively the small
output market (clocks, pocket calculators, etc.).
AM 1.5
Si 300K
iAs
Cd Ta
USb
A
Eg (aV)
2
L 3
Figure 8.17 Maximum solar cell efficiency for radiation of 1 sud1000 suns
(300 K) versus energy gap
band gaps can be produced, which can then act as a window layer, or with
smaller band gaps for tandem solar cells.
In addition GaAs solar cells have a much lower sensitivity to cosmic
radiation than do Si solar cells.
The GaAs solar cell is a cell with a p-n junction. There are currently
three manufacturing processes in use. These are:
Liquid phase epitaxy (LPE).
Metal organic vapour phase epitaxy (MOVPE).
Molecular beam epitaxy (MBE),carried out in an ultra high vacuum,
therefore used almost exclusively in research and development
laboratories.
Sliding rod
Graphite crucible Thermojunction
Furnace
Temperature
HZ
Figure 8.18 Principal arrangement for liquid phase epitaxy of GaAs solar cells
Figure 8.19 The structure of a high efficiency GaAs solar cell [78]
efficiency at 100 suns is approximately 24% [80]. Figure 8.20 shows the
layer structure of a GaAs/Si solar cell produced using MBE or LPE [81].
Figure 8.20 The structure of a GaAs solar cell on a silicon substrate [53]
Two problems stand in the way of increased use. One is the very high
price of the GaAs cell, if it has to be built on a GaAs substrate. The use of
another material for the substrate offers the best potential for development
here. The second is a problem with acceptability since Ga and As are toxic
substances.
However, perhaps the GaAs cell is one which could be used in the
concentrator application, where the cell price, even for a moderate
concentration of > 30 fold, as previously mentioned, is of less importance.
A further possibility for the use of GaAs may be in tandem solar cells (see
Section 8.3 below).
The first work dates back to the 1960s and early 1970s, when an
efficiency of 6% was achieved [82],[83]. Then work was put on hold until
the 1980s, when it was taken up again by numerous laboratories around the
world with different technologies. As well as the classical CVD technique,
and high vacuum evaporation technique, other techniques were successfully
developed such as electrolytic deposition and chemical spraying as well as
screen printing. A good overview is provided by Bonnet [84].
Like G A S , CdTe is a direct semiconductor and therefore sunlight is
totally absorbed in a layer of a few pm thickness. This also means,
however, that recombination on the surface must be prevented. In CdTe
solar cells n-CdS has proved successful as a window film. This
heterojunction (two semiconductor materials with different band gaps) has
the problem, however, that sunlight with a wavelength of -c 520 pm is
absorbed in the window film. Therefore, other substances are currently
being investigated. According to all tests to date, solar cells made of this
material possess high stability. The best laboratory cells have achieved
efficiencies of 10-14% [85],[86]. The advantage of this technology is that
with different, relatively cost effective technologies, efficiencies of 10%
can be achieved. However, the question of acceptability is just as critical as
for GaAs, since cadmium is poisonous and its hazardous nature both in
production and in accidents must be carefully considered.
- Al grid
n+ window film
n- buffer
p-absorber
p+-absorbe r
Back contact
cheaper screen printing technique has also been tested for the purposes of
cost reduction.
With a band gap of approximately 1 eV, CuInSe, is somewhat
unfavourable. The optimal utilisation of solar radiation, however, is
achieved by the addition of Ga into the In layer. This creates a quaternary
semiconductor, the band gap of which increases continuously with
increasing Ga concentrations. If the In is completely replaced, i.e. the
structure is CuGaSe, the band gap achieved is approximately 1.7 eV. It is
thus possible to achieve the optimal band gap of 1.4 eV.
In addition the surface layers have recently been improved, both in the
quality of the CdS buffer layer and the window film. Using this process
several laboratories have been able to achieve an efficiency of up to 17%
[901,[911.
Of the numerous research works in the field of CIS cells, we want to
mention those which attempt to replace selenium by sulphur [92]. Many
encouraging results have already been achieved in this field. CIS is one of
the main directions of attack for research in the field of thin film solar
cells.
purpose the band gap of the solar cell material must reduce from the side
turned to the sunlight to the back surface. For two cells, the optimum
absorption of sunlight is achieved if the uppermost cell is made of a
semiconductor with a band gap of 1.9 eV and the semiconductor material
of the lower cell has a band gap of 1.2 eV. The upper cell then absorbs
short wavelength light while the long wavelength light is allowed to pass
through and create charge carriers in the lower cell. The total efficiency is
approximated by taking the sum of the efficiencies of the individual cells.
References
Tsuo Y. S. and Milstein J. B., Appl. Phys. Lett. 45, 1984, p. 971
Schrtiter W. and Kiihnapfel R., Appl. Phys. Lett. 56, 1990, p. 2207
Verhoef L. A. et al., Appl. Phys. Lett. 57, 1990, p. 2704
Rohatgi A . et al., Proc. 23rd IEEE-PV Spec. ConJ, Louisville, Kentucky,
USA, 1 9 9 3 , ~ 111
.
Bruton T. M., Knobloch J., Mitchel A. and Teale R. S . , Proc. 10th EC PV
Solar Energy Conf.,Lisbon, Portugal, 1991, p. 667
Sandaresan R. et al., Appl. Phys. Lett. 55, 1984, p. 1162
Verhoef L. A. et a]., Appl. Phys. Lett. 57, 1990, p. 2704
Hartiti B., Mullert J. C., Siffert P. and Sarti D., Springer Proceedings in
Physics, Vol. 54, Polycrystalline Semiconductors II, p. 230
Schindler R., Solid State Phenomena, Vols. 37-38 (1194), pp. 343-354
Schindler R. et al., Statusreport Photovoltaik, BEO, Julich, 1996, Section 15
Narasirnha S., Kamra S., Rohatgi A., Khattak C. P. and Ruby D., Proc. 25th
IEEE PV Spec. Con$, Washington, DC, USA, 1995, p. 449
Spitzer M., Shewchun J., Vera E. S. and Loferski J. J., Proc. 14th IEEE PV
Spec. Con$, San Diego, California, USA, 1980, p. 375
Wolf M., Proc. 14th IEEE PV Spec. Conf., San Diego, California, USA,
1980, p. 647
Goetzberger A,, Knobloch J. and VoR B., Technical Digest PVSEC-I, Kobe,
Japan, 1984, p. 517
Goetzberger A., Proc. of the 26th IEEE PV Spec. Conf.
Hebling C., Glunz S. W., Schetter C. and Knobloch J., Proc. 14th EC PV
Solar Energy Con$, Barcelona, Spain, 1997, in print
Barnett, A. M. and Rothwarf, A,, IEEE-TED, 27 (4), 1980, p. 615.
Stocks, M. J., Cuevas, A. and Blakers, A. W., Progress in Photovoltaics, 4,
1996, p. 35
Statusreport Photovoltaik, BMBF, Projektrager BEO, Jiilich, 1996, Chapters
17 to 24
Wagner, B. F., Dissertation, Darmstadt, 1995.
Werner H. J., Bergmann R. and Brendel R., Festkorperprobleme, Vol. 34,
R. Helbig, p. 115
I98 Crystalline Silicon Solar Cells
Woodall J. M. and Hovel H. S., Appl. Phys. Lett. 30, 1977, p. 492
Tobin S. P. et al., Proc. of 21st IEEE PV Spec. Con$, Kissimmee, Florida,
USA, 1990, p. 158
Chu C. and Iles P. A,, Proc. of the 22nd IEEE PV Spec. Con$, Las Vegas,
Nevada, USA, 199 1, p. 15 12
Vernon S. M. et al., Proc. of the 22nd IEEE PV Spec. Con$, Las Vegas,
Nevada, USA, 1991, p. 3 5 3
Wettling W., in Solurzellen, Meissner, D., ed. Vieweg, 1993, p. 176
Cusano D. A,, Solid State Electronics 6, 1963, p. 217
Bonnet D. and Rabenhorst H., Proc. of the 9th IEEE PV Spec. Con$, Silver
Spring, Maryland, USA, 1972, p. 129
Bonnet D., in Solurzellen, Hrsg. Meissner D., ed. Vieweg, 1993, p. 119
Mitchel K. W. et a\., Solar Cells 23, 1988, p. 49
Skorp J. et al., IEEE-TED 37, 1990, p. 434
Loferski J. et al., Proc. 13th IEEE PV Spec. Con$, Washington, DC, USA,
1978, p. 190
Schock H. W., in Solurzellen, Meissner D., ed. Vieweg, 1993, p. 44
Mitchell K. et al., Proc. 20th IEEE PV Spec. Con$, Las Vegas, Nevada,
1988, p. 889
Hedstrdm J. et al., Proc. 23rd IEEE PV Spec. Con$, Louisville, Kentucky,
USA, 1993, p. 364
Zweibel K. et al., in Photovoltaic Insider's Report, Vol. XII, September,
1993
Tarrant R. and Ermer J., Proc. 23rd IEEE PV Spec. Con$, Louisville,
Kentucky, USA, 1993, p. 372
Fraas L. M. et al., Proc. 21sf IEEE PV Spec. Con$, Kissimmee, Florida,
USA, 1990, p. 190
Krtlhler W., in Solurzellen, Meissner D., ed. Vieweg, 1993, p. 109
Desilvestro J., Grtitzel M., et al., J. Am. Chem. SOC.107, 1985, p. 2988
0 Regan B., Moser J., Anderson M. and Grlitzel M., J . Phys. Chem. SOC.
94, 1990, p. 8720
Grtitzel M., Proc. Indian Acad. Sci., Vol. 107, No 6, 1995, p. 607
200 Crystalline Silicon Solar Cells
[98] Ferber J., Stangl R. and Luther J., Solar Energy, Materials and Solar Cells,
in print
[99] Hagfeldt A. and Gratzel M., Chem. Rev. 95, 1995, p. 49
[loo] Sadergreen S., Hagfeld, A,, et al., J . Phys. Chem. 98, 1994, p. 5552
Analytic and Measuring Techniques
Sun simulator
AM1.S
supply. Even higher precision is achieved if the data from the test cell and
the calibration cell, and thus the radiation intensity, are measured
simultaneously.
V -IR, V -IRs
In the starting region from 0 to approximately 0.15 V the two first terms
in equation (9.1.1) are negligible and the dark current is thus mainly
determined by the shunt resistance R p (in the logarithmically linear
representation the linear proportionality is represented as a curved line).
In the adjoining area (from 0.2 to 0.4 V) the dark current can be
assigned to the second term of the two diode model. As already
mentioned, in practice there is rarely a relationship with n,=2.
In the range 0.4 to 0.6 V the dependency on the first term of the
expression is dominant. If the dependency is according to n=1, then the
saturation current lo,, which is responsible for open circuit voltage, can
be determined from it.
In the region around 0.6 V serial resistance has a considerable influence
on the characteristic.
Based on this assignment of the different parameters to the various
regions of the dark current characteristic, the individual solar cell
parameters can be determined using a fit programme for the measured dark
current characteristic.
Series resistance R, can be determined more precisely by using
measurements under illumination as well as those in the dark. For the dark
current measurement a higher voltage (V,) is required than the open circuit
voltage ( V , J to obtain a current which has the same value as the short
circuit current, because the additional voltage drop at the series resistance
204 Crystalline Silicon Solar Cells
Voltage (V)
Figure 9.2 The typical shape of a dark current characteristic line
(9.1.2)
and thus ’
’ In most cases - but in particular in the case of high efficiency solar cells
with a back surface point contact (LBSF) - this resistance is not identical
with R, in illuminated conditions, because the flow of current differs
substantially in the ‘light’ and ‘dark’ cases.
Analysis and Measuring Techniques 205
(9.1.3)
We assume that the short circuit voltage I,, (in the first approximation) is
proportional to the level of radiation. We also replace Yo,in the formula for
efficiency by
(9.1.4)
(9.1.5)
where Plightis the light input. The temperature dependency of the fill factor
can be disregarded here. After some manipulation we find that for the
relative change in efficiency
206 Crystalline Silicon Solar Cells
(9.1.6)
where n is the air mass factor of light radiation [n = 1: one sun; n = 0.5:
half a sun].
Introducing Vocwe find for the relative efficiency change
(9.1.7)
kT
-
(9.1.8)
-4 x 0.04
voc
(9.1.10)
where
Analysis a n d Measuring Techniques 20 7
(9.1.11)
L p NrJ
Voc = - [ g]
k T ln-
4
+-
Eg
4
(9.1.14)
(9.1.15)
d(V,,) - -1
- (9.1.16)
dT T (Voc - 1.1)
and, with V,, being, for example, approximately 0.6 V, we find that at room
temperature
208 Crystalline Silicon Solar Cells
(9.17)
The relative change in the open circuit voltage and thus efficiency is
approximately 0.3% per degree.
2
In more recent measuring systems the colour filter is replaced by a double
monochromator. This permits a continuous ‘scanning’ of the total frequency
range.
Analysis and Measuring Techniques 209
UV fibre
Reference cell
Oscilloscope
*lLz
compensation
Figure 9.3
I
=
Block diagram of a measuring system for determining the spectral
response of a solar cell
cell with a local back surface field, as the recombination velocity in these
is dependent upon the number of charge camers generated, and strict
linearity of the short circuit current is therefore no longer preserved.
The short circuit current in both cells is measured by the ‘lock-in’
technique. The advantage of the ‘lock-in’ technique is that firstly a very
small current (< lo-’ A) can be determined. Secondly, it is possible to
irradiate the test cell with constant light - of very high intensity compared
with spectral light - without influencing the measurement results. The
dependencies of the solar cell parameters, e.g. surface recombination
velocity and charge carrier lifetime, on radiation intensity can now be
investigated. The measured values from the test and reference cells are fed
into a PC and processed.
To determine the internal spectral response it is also necessary to know
the precise reflection conditions on the surface in relation to the
wavelength. They must either be measured, or the measurement takes place
with a polished surface, because then the theoretical reflection values can
be included in the analysis [3],[4]. Figure 9.4 shows the internal spectral
response of a high efficiency cell with a transparent emitter. The
210 Crystalline Silicon Solar Cells
100
90
3
v
80
93
8 70
60
2 50
- 1 . 1
illustration further shows the response of the emitter, the space charge
region and the base in relation to the wavelength of the radiated light.
Two predictions can be made from this 'fit'. The diffusion length in the
base and the effective surface recombination on the back surface are
responsible for the spectral response in the long wavelength region. In high
efficiency cells the effect of these two variables cannot, however, be
separated. Only if the diffusion length is less than the thickness of the cell
can the spectral response in the long wavelength region give the effective
recombination velocity.
Secondly, the response in the short wavelength region permits
predictions to be made about the surface recombination velocity of the
emitter. As shown in Chapter 5 , this can only be determined for values
greater than lo3 cm/s.
Metal
SiO,
n+
p-base
Local BSF
SiO,
Figure 9.5 Structure of a solar cell for illumination from the rear side
In this case the test cell is not, as normal, illuminated on the emitter
side, but on the opposite side. Figure 9.5 shows the cross-section of a cell
produced especially for this purpose. This cell, which can be illuminated
from both sides, is called a bifacial cell (see Chapter 8, Section 8.1.2).
The back surface of this cell also has a finger grid in which the distance
between fingers must be ten times greater than the diffusion length of the
charge carriers in the base. This prevents the influence of high
recombination under the contact fingers. In addition, it is also advantageous
to apply a BSF under the metal coating to reduce recombination still
further. The calculated internal spectral response of such a cell is shown in
Figure 9.6.
As the short wavelength light is absorbed near the surface and thus
charge carriers are created some distance from the p-n junction, the surface
recombination velocity S,, has a strong influence on spectral behaviour. We
see from the illustration that values of S,, less than 10’ cm/s can still be
detennined. The prerequisite for this, however, is that the diffusion length
of minority charge carriers in the base is almost double the crystal
thickness.
21 2 Crystalline Silicon Solar Cells
100 I I 1
1
60 -
1000
- -
E 40
v5:
20 -
'01
I I
0
300 500 700 900 1100
Wavelength (nm)
We know from the above discussion that the diffusion lengths in high
efficiency solar cells with values greater than the thickness are very
difficult to determine. The process described in what follows offers an
improvement. The measuring layout is shown in Figure 9.7.
The process follows the principle of measuring the decay of short circuit
current and open circuit voltage after prior illumination (Photo-Current-
Vo 1t age-Decay) [61,[71.
This dynamic measuring principle has the advantage over the above
static process in that
no absolute measurement of the light intensity is necessary and thus
no knowledge of surface reflection must be available and
the precise absorption coefficient need not to be known.
Analysis and Measuring Techniques 213
generator
Pre-amplifier
SO0 I I
JK23.181
I oc = 3 . 3 ~ l O -A/crn2
~
-rHi = 3 . 6 ~ 6 ~s ’
loo0
5
v
&
n
G=
b 500
I I
0
1 6 11 16
Average carrier density (cm-3) *lo“
Figure 9.9 Decay transient for a test cell with face and back emitter [ 111
(9.4.1)
where
T,,,,~ is the momentary decay time,
thli is the high injection carrier lifetime,
s is the surface recombination velocity,
w is the thickness of the base, and
q is the unit charge.
From the gradient of the straight line we can find the saturation current in
the emitter. This gradient is
(9.4.2)
A test wafer is coated on both sides with the SiO, under investigation.
Because there is no emitter, we determine 1hhli+ s/w direct.
The SiO, film is then removed and the Si wafer submerged in a special
container (teflon case with a transparent plastic sheet window) filled with
hydrofluoric acid. The fact that the surface recombination velocity nears
zero when a silicon surface is covered with pure hydrofluoric acid is used
here.4 The measurement is now taken once again. The charge camer
lifetime is determined directly and therefore so is the surface recombination
speed.
In this manner it is possible to determine firstly extremely low surface
recombination speeds and secondly diffusion lengths that are significantly
higher than crystal thickness [ 113.
In Section 9.5 the modem, safe technique is described. In this method the
hydrofluoric acid is replaced by an iodinelethanol solution.
218 Crystalline Silicon Solar Cells
=401,+Pp)An (9.5.1)
where /, and pp are the mobility of electrons and holes. The 2.8 GHz
signal created by a microwave oscillator is guided via a circulator to the
sample of thickness W and reflected from there. For a fairly small change
in charge carrier concentration, the change in reflectivity is proportional to
the change in charge carrier concentration. The reflected microwave signal
is then guided via the circulator to a microwave detector, so that it is
possible to observe the exponential charge carrier decay using the
connected oscilloscope. If we now plot the measured transient in semi-
logarithmic scale, the decay constant can be determined by a fit from
the mono-exponential part.
This effective decay constant depends upon the volume lifetime ‘b and
the recombination speeds on both surfaces S, and S, from [16],[17):
1 = -1+ D y ’
- with tan(y W ) =
Y(S, +q (9.5.2)
‘cff ‘b (Dy - s,s,
- a _ +
1
'eff b' [?.s
-+--
A[$ (9.5.3)
The term W/2S describes the surface influence at small values of S, and
the term 1/D(W/n)*describes the surface influence at very large values of
S.
Time us)
Figure 9.11 Typical MW-PCD decay transient (from [ 151)
(9.6.1)
where AZ is the change in laser intensity, I is the original laser intensity and
K is the absorption constant for the free charge carrier absorption. This
absorption constant increases quadratically with the laser wavelength used
~41.
The free charge carriers are not generated by pulses as is the case for
most other methods of measuring lifetime, but sinusoidally. Since a phase
displacement occurs between generation light and charge carrier dynamics,
due to the lifetime of the charge carriers, the recombination parameters can
be determined from this. The time dependent continuity equation serves as
a basic equation for the derivation of the relationship between phase
displacement Y and the recombination parameters:
Analysis and Measuring Techniques 221
- -- D- 8 A n - -
An
+ G(x,t) (9.6.2)
at ax2 ‘b
(9.6.3)
where
L(0) = (9.6.5)
The phase shift Y(o) is calculated from the quotients of the imaginary
and real parts of the above expression, and the frequency dependent
amplitude A(o) of charge carrier modulation from the amount:
222 Crystalline Silicon Solar Cells
ImAN(w)
v(w) = -tan-' A(w) = IAN1 (9.6.6)
Rem(o)
In the case of a negligible surface recombination velocity this
expression can be greatly simplified to:
'b
"(0) = - arctan(or,) Ah) (9.6.7)
Figure 9.12 shows the calculated phase and amplitude distribution for
different recombination parameters.
83 O8
-0c 08
.
5 -.-.-.
-7-
.I 1ops.s -0-
-
loo )If. s 0 cmk
P O.4
n
k 02
m
5
OD
I . . . , .... I , ., .,...I . ., .....I . , ..
1 1M) lo00 loo00 1OOOOO 1OOOOOO
Frequency (Hz)
Thus the higher the volume lifetime or the lower the surface
recombination velocity, the earlier the increase in phase or the reduction in
amplitude begins.
Figure 9.13 shows the experimental realisation of the methods described
above at ISE.
Analysis and Measuring Techniques 223
!’
Laser diode
-
- 0
The IR beam ( h = 3.4 pm) emitted from a HeNe laser penetrates the
sample and is detected by an InSb IR detector (A). At the same point of
the sample, free charge carriers are generated by a GaAlAs laser diode ( h
= 780 nm), the intensity of which is sinusoidally modulated. As the free
charge carriers follow this modulation with a certain phase shift, the
intensity of the transmitted IR laser beam also changes sinusoidally due to
the absorption of IR light by the free charge carriers. The signal of the IR
detector (A) is passed on by a current-voltage converter to the signal input
of a ‘lock-in’ amplifier. The sinusoidal signal from the function generator,
which also serves as a modulation source for the driver of the laser diode,
is used as a reference for the ‘lock-in’ amplifier. To improve the signal to
noise ratio, half of the IR beam is guided to a second similarly constructed
IR detector (B) by a beam splitter and its signal is subtracted from the
signal of the signal detector (A) so that in the ideal case the noise
background of the HeNe laser is negligible. The phase shift between signal
224 Crystalline Silicon Solar Cells
and reference input of the ‘lock-in’ amplifier or the signal amplitude can
now be measured for different frequencies using a computer and evaluated.
As the sample is installed in an X-Y table and the IR detection beam
focused at approximately 100 pm, it is possible to plot lifetime topography.
Figure 9.14 shows the lifetime topography of an unprocessed
multicrystalline silicon sample. The crystal structure is clearly recognisable
in the measured lifetime. Although the lifetime is significantly reduced at
the grain boundaries and in micro-crystalline regions, within the grains
much better values are obtained.
The degree to which this local lifetime fluctuation is reflected in the
solar cell characteristics is of course of great interest. For this reason a
solar cell is processed from the sample shown in Figure 9.14 and the short
circuit current measured locally, Figure 9.15. The LBIC (Light Beam
Induced Current) method used will be described in detail in the next
section. A very good correspondence between the short circuit current and
lifetime topography can be clearly recognised. This shows once again the
increasing significance of lifetime for solar cell efficiency, but also the
opportunity to use the MFCA method to determine the material quality in
an unprocessed starting material.
Analysis and Measuring Techniques 225
The LBIC method (Light Beam Induced Current) allows us to show the
local distribution of the short circuit current in a solar cell. It is particularly
important to know this distribution in the case of polycrystalline solar cells.
Figure 9.16 shows the block diagram for the measuring apparatus
developed and constructed in our institute [25]. A tungsten halogen lamp
is used as a light source, the light from which is chopped with a frequency
of 2 kHz and transferred to the test cell via a fibre optic cable. The
illuminated surface of the solar cell has a diameter of approximately 0.1
mm. The X-Y table has a minimum step size of 10 pm and permits tracing
at 100 points per second also using a computer programme developed in
our institute [26]. For a test cell with dimensions of 2 x 2 cm with a
density of 200 x 200 points the measurement procedure is completed in
approximately 7 min. The apparatus also allows the additional illumination
of the test cell with constant light. A coloured filter wheel further permits
the selection of the wavelength of the measuring light.
226 Crystalline Silicon Solar Cells
Filter
Reference
Fibre optic
Reflection light guide
Y
I Lock-in
Computer
AID
,converter *
+*
IEEE488 *-
Figure 9.16 Block diagram of an LBIC mapping measuring instrument
The short circuit current of the test cell is measured for each point
illuminated. The level of current is then stored and converted for display on
a screen or output to a colour printer in different colours. From the
assignment of colours to currents we very clearly see the effective and less
efficient regions of the solar cell.
Figure 9.17 shows in black and white contrast the local distribution of
the short circuit current in a solar cell made of polycrystalline Si material.
In monocrystalline high efficiency solar cells with a local BSF structure,
this apparatus can be used to clarify the influence range of the back surface
point contacts. A wavelength is used which lies close to the band edge for
silicon, in order to create as many charge carriers as possible on the back
surface BSF structure. It can be demonstrated in this manner that the region
of influence is greater than the diameter of a point contact. It extends by
Analysis and Measuring Techniques 22 7
References
LIST OF SYMBOLS
Absorption coefficient Energy at the bottom of the
Relative permittivity conduction band
Efficiency Fermi energy
Wavelength Energy at the top of the
Electron mobility valence band
Hole mobility Photon quantity
Electrical conductivity Fill factor
Lifetime Generation rate
Barrier height Geometry factor
Resistivity Planck's constant
Electric potential Solar cell thickness
Activation energy Width of base
Effective Richardson Saturation current
constant Saturation current in the 2
Air mass diode model
Speed of light in Current from base
vacuum Current from emitter
Capacity Current generated by light
Diffusion constant Current at maximum power
Electron diffusion point
coefficient Electron current
Solar constant Hole current
Hole diffusion Current from the space
coefficient charge region
Energy Short circuit current
Electric field strength
232 Crystalline Silicon Solar Cells
PHYSICAL CONSTANTS
Absorption 29
coefficient 30
Acceptance problems 189
Acceptor 26
Activation energy 148
Antireflection coating 115 159
Antireflection process 114 159
Arrhenius curve 148
Auger coefficient 37
Capture cross-section 39
Charge carrier
concentration 60
intrinsic density 19
lifetime 34
majority 25
minority 25
Cleaning techniques 155
Concentrator cell 163
Conduction band 12
Confinement, optical 33
Contact finger 97
Contact resistance 107
Contaminants 155
Continuity equation 45
Crystal momentum 30
Crystal pulling 136
Crystal structure 30
Current
forward bias 60
reverse bias 60
saturation 76 95
short circuit 69 90
Current-voltage characteristic 69 201
CVD principle 135
Czochralski process 136
This page has been reformatted by Knovel to provide easier
navigation.
Index Terms Links
Efficiency 71 87
EFG process 142
Einstein formula 29
Electrical conductivity 11
Electron 14
Emission 37
Emitter 73
penetration depth 90
two step 98
Energy gap 12
Energy level 12
Equivalent circuit 81
Error function distribution 144
Etching 155
anisotropic 118
isotropic 155
Fermi-Dirac distribution 27
Fermi level 26 53
Field current 20 22
Field strength 58
peak 58
Field, electric 54
Fill factor 71
Float zone pulling 136
Foil material 143
Fresnel's formula 115
Hole 14
Impurity conduction 24
Injection
high 40
low 40
weak 60
Intrinsic conduction 20
Kendall equation 44
Light, monochromatic 73
Liquid phase epitaxy 187
Loss 90
due to non-absorbed light 120
optical 114
recombination 90
shadowing 121
Manufacturing costs 87
Masking 154
Mobility 20
Molecular beam epitaxy 187
MOVPE 187
Occupation, probability 14
Oxidation process 152
p–n junction 50
infinite 67
p and n neutral region 51
Passivation 94
PCVD method 211
Phonon 32
Rayleigh scattering 5
Recombination 20
Auger 36
by doping 42
radiative 35
SRH 80
via defect levels 37
Reflection factor 115
Refractioning procedure 135
Refractive index 116
Relative permittivity 25
Resistance
base 102
parallel 83
series 79 85 113
sheet 108
Resistance (Cont.)
shunt 79 85
Texturising 118
Thermionic effect 109
Thick film technology 158
Total charge 45
Transport length 109
Trap level 37
Tunnel effect 105
Two diode model 79