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Crystalline Silicon Solar Cells

Adolf Goetzberger
Joachim Knobloch
Bernhard Vo13
Fraunhofer Institute for Solar Energy Systems, Freiburg,
Germany

Translated by
Rache1 Waddington
Swadlincote, UK

John Wiley & Sons


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@ B.G. Teubner Stuttgart 1994:GoetzbergerNoS/Knobloch.
Sonnenenergie: Photovoltaik. Translation arranged with the approval of the publisher B.G. Teubner
Stuttgart, from the original German edition into English.

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Library of Congress Cataloging-in-Publication Data

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

British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library

ISBN 0 47I 97144 8

Produced from camera-ready copy supplied by the translator


About the Authors

Prof. Dr, rer. nat. Adolf Goetzberger


Born 1928 in Munich. Studied Physics at the University of Munich, 1955
Doctorate. 1955-5 8 Semiconductor development SIEMENS, Munich. 195 8-
63 colleague of W. Schockley (Nobel Prize Winner and co-inventor of the
transistor) in Palo Alto, Ca. USA. 1963 Bell Telephone Labs in Murray
Hill, N.J., USA. 1968-81 Director of the Fraunhofer Institute for Applied
Solid State Physics in Freiburg. From 1971, honorary Professor at the
University of Freiburg. From 1981 to retirement in 1993, Director of the
Fraunhofer Institute for Solar Energy Systems (ISE) in Freiburg. 1995
Farringten Daniels Award of the Int. Solar Energy Society, Dr. h.c. Uppsala
University, Sweden. 1997 Karl W. Boer Medal and EU Bequerel Prize.
Currently Director of TNC Consulting GmbH, Freiburg and President of the
German Solar Energy Society.

Dipl. Phys. Bernard Vol3


Born 1926 in Miinster, studied Physics at the University of Munster,
Diploma 1956. 1956-61 Semiconductor development, VALVO, Hamburg;
196 1-65 Development Director for Power Semiconductor Devices,
Semikron, Niirnberg; 1965-80 BBC, Mannheim, of which 11 years
Development Director for Power Semiconductor Components; From 198 1
to retirement in 1991, Director of “Crystalline Si Solar Cells” Department
at ISE, Freiberg; Main emphasis high efficiency (clean room technology).

Dr. rer. nat. Joachim Knobloch


Born I934 in LiegnitdSchlesien. Studied Physics at Munich Technical
University, Diploma 1959, Doctorate 1962. 1963-65 Scientific Assistant
“Radiation and Solid State Laboratory” at the University of New York,
N.Y., USA. 1966-68 Department of Development E. Leitz, Wetzlar; 1969-
82 Department of Development for Power Semiconductor Devices, BBC,
Mannheim. From 1982 Deputy Departmental Manager in the Department
mi Crystalline Silicon Solar Cells

of "Crystalline Si Solar Cells" at ISE, Freiburg. Responsible for analysis


and technology for crystalline silicon solar cells of very high efficiency.
The department has achieved several international records and is amongst
the world leaders in this specialist field.
Preface

Increased environmental awareness and the knowledge that all current


energy sources are limited, make it appear ever more imperative that solar
energy be made usable for the creation of electrical power. The principle
of converting sunlight into electrical power is very simple indeed. It is
converted directly into electrical power - the most valuable form of energy
- using solar cells. The advantages and elegance of this photovoltaic energy
transfer are obvious:
there are no inoving parts, unlike conventional energy generation; this
automatically reduces the need for maintenance; and
no fuel is necessary, this eliininates aln~ostall environinental impact.
Furthennore, the technical and technological procedures for the in anufacture
of solar cells and solar plants are basically understood, and long plant.
lifetinie can be expected.
Despite these positive arguments, the set-up costs for photovoltaic arrays,
which are many times higher than those for conventional power stations,
have prevented a widespread breakthrough of this new technology up until
now. Photovoltaics have, however, conquered the field of power generation
for satellites, as the question of cost does not play such a decisive role for
this application. The advantages of long lifetime, maintenance-free operation
and the lack of normal fuels as well as weight considerations are of decisive
importance in this field.
Crystalline silicon dominates the field of space technology, as well as
terrestrial applications, as a starting material for solar cells. The consumer
market, on the other hand, e.g. clocks and pocket calculators, is dominated
by solar cells niade of amorphous silicon, because in these cells the serial
connection necessary for current multiplication can be created
simultaneously with the production of the cells.
This book, which is concerned with the photovoltaic conversion of
sunlight into energy, therefore concentrates on the physical basics and
xii Crystalline Silicon Solar Cells

technological realisation options for solar cells made of crystalline silicon.


All relevant analysis and measuring techniques are dealt with.
The book is aimed at students of science and technology, as well as
engineers and technicians working in the development and production of
solar cells. It contains practical and theoretical results and experience gained
from many years’ work in research and development in the field of
crystalline silicon solar cells in the Fraunhofer Institute for Solar Energy
Systems (ISE Freiburg). The substance is presented in such a way that it
can easily be built upon at a later date.
The solar cell itself is a semiconductor component, specifically a large
area diode. The manufacture of solar cells therefore requires, as we will
discover, a large amount of knowledge and experience in the fields of the
physics and technology of semiconductor components. We will therefore
describe the basics of semiconductor physics in the first chapters, and then
concentrate on the physics of solar cells made of crystalline silicon. Apart
from a basic knowledge of physics and mathematics there are no specific
prerequisites to understanding this book.
Particular attention is paid to the physical and technical prerequisites for
attaining high efficiency. The high efficiency of solar cells can contribute
significantly to reducing the costs of a solar array.
The content and structure of this book follow the pattern below.
After a brief introduction to the history and significance of photovoltaics,
the first chapters are concerned with basic semiconductor physics.
The next chapter is concerned with the physics and technology of
crystalline silicon solar cells, and specifically the achievement of the highest
efficiencies.
The first section of Chapter 8 deals with different designs of solar cell
made of crystalline silicon. The subject of thin film solar cells made of
crystalline silicon is dealt with in some detail. This has been at the centre
of work in all relevant research institutions for some years. The cost
situation is expected to improve in the future. In the second section of
Chapter 8, some selected types of solar cells made of other materials are
described to complete the picture.
The final chapter deals in detail with all important measuring and
analysis procedures for the deterniination of physical semiconductor and
solar cell parameters.
We wish to thank everyone who, whether in a professional or personal
field, showed patience, understanding and helpfulness during the intensive
phase of creation of this book.
Preface xiii

We would like to thank Dr Glunz for writing some subsections in the


final chapter.
We also thank Prof. Luther for allowing us to use the infrastructure of
the ISE.

A. Goetzberger, B. VoB, J. Knobloch

Freiburg, Summer 1997


Contents

Preface .................................... xi

About the Authors ............................ xv

1 Photovoltaics ................................
1.1 The Principles of Photovoltaics . . . . . . . . . . . . . . . . . . .
1.2 The History of Photovoltaics . . . . . . . . . . . . . . . . . . . . .
1.3 The Importance of Photovoltaics . . . . . . . . . . . . . . . . . .

2 Solar Power ................................. 5


2.1 The Sun as a Source of Radiation . . . . . . . . . . . . . . . . . . 5
2.2 Standard Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3 The Principles of Photovoltaics .................. 9


3.1 Crystalline Structure and the Energy Band Diagram
for Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.1 The Energy Band Diagram for Tetrahedronal
Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.1.2 Electrons and Holes in a Semiconductor . . . . . . . . 14
3.1.3 Energy Levels: the Fermi Level . . . . . . . . . . . . . . . 14
3.1.4 Density of States for Electrons and Holes . . . . . . . 16
3.1.5 Thermal Equilibrium . . . . . . . . . . . . . . . . . . . . . . 19
3.2 The Conduction Mechanism in Semiconductors . . . . . . . . 20
3.2.1 Intrinsic Conduction, Field Current and Mobility . . 20
3.2.2 Impurity Conduction . . . . . . . . . . . . . . . . . . . . . . 24
3.2.3 Diffusion Current and Diffusion Constant . . . . . . . 27
3.3 The, Generation of Charge Carriers by the Absorption of
Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3.1 Absorption in Semiconductors . . . . . . . . . . . . . . . . 30
3.3.1.1 Absorption in Direct Semiconductors . . . . 30
vi Crystalline Silicon Solar Cells

3.3.1.2 Absorption in Indirect Semiconductors . . . 32


3.4 Recombination. Carrier Lifetime . . . . . . . . . . . . . . . . . . . . 34
3.4.1 Radiative Recombination . . . . . . . . . . . . . . . . . . . 35
3.4.2 Auger Recombination . . . . . . . . . . . . . . . . . . . . . . 36
3.4.3 Recombination via Defect Levels . . . . . . . . . . . . . 37
3.4.4 Recombination by Doping . . . . . . . . . . . . . . . . . . 42
3.5 Basic Equations of Semiconductor Device Physics . . . . . . 44
3.5.1 The Current Density Equations . . . . . . . . . . . . . . . 44
3.5.2 Poisson's Equation . . . . . . . . . . . . . . . . . . . . . . . . 45
3.5.3 The Continuity Equations . . . . . . . . . . . . . . . . . . . 45
4 Thep-n Junction ............................. 49
4.1 Basic Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2 Space Charge Region . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.2.1 Potential Difference . . . . . . . . . . . . . . . . . . . . . . . 51
4.2.2 Electric Field and Electric Potential . . . . . . . . . . . . 54
4.2.3 Space Charge Region Width and Capacitance . . . . . 57
4.3 The Biased p-n Junction . . . . . . . . . . . . . . . . . . . . . . . . 59
4.3.1 The p-n Junction with Low Recombination and
Weak Injection . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.3.2 Forward Current Characteristic and Saturation
Current . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

5 The Physics of Solar Cells ...................... 67


5.1 The Illuminated Infinite p-n Junction . . . . . . . . . . . . . . 67
5.1.1 The Current-Voltage Characteristic of an Infinite
Solarcell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.1.1.1 Short Circuit Current . . . . . . . . . . . . . . . 69
5.1.1.2 Open Circuit Voltage . . . . . . . . . . . . . . . 70
5.1.1.3 Fill Factor . . . . . . . . . . . . . . . . . . . . . . . 71
5.1.1.4 Efficiency . . . . . . . . . . . . . . . . . . . . . . . 71
5.2 Real Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5.2.1 Photocurrents in a Real Solar Cell . . . . . . . . . . . . . 73
5.2.1.1 Photocurrent from the Base . . . . . . . . . . 73
5.2.1.2 Photocurrent from the Emitter . . . . . . . . . 75
5.2.1.3 Photocurrent from the Space Charge
Region . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.2.2 Saturation Currents in a Real Solar Cell . . . . . . . . . 76
5.2.2.1 Saturation Current from the Base . . . . . . . 76
5.2.2.2 Saturation Current from the Emitter . . . . . 78
5.2.3 Ohmic Resistance in Real Solar Cells . . . . . . . . . . 79
5.2.3.1 Shunt Resistance (R,) . . . . . . . . . . . . . . . 79
Contents vii

5.2.3.2 Series Resistance (R, ) ............... 79


5.2.4 The Two Diode Model . . . . . ................ 79
5.2.4.1 Equivalent Circuit of a Real Solar Cell . . 81
5.2.4.2 The Influence of Ohmic Resistances . . . . . 83

6 High Efficiency Solar Cells ..................... 87


6.1 The Significance of High Efficiency . . . . . . . . . . . . . . . . 87
6.2 Electrical Losses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
6.2.1 Recombination Losses . . . . . . . . . . . . . . . . . . . . . 90
6.2.1.1 Recombination Losses in the Base . . . . . . 90
6.2.1.2 Photocurrent and Saturation Current from
theEmitter . . . . . . . . . . . . . . . . . . . . . . . 95
6.2.1.3 The Influence of Base Doping . . . . . . . . . 98
6.2.1.4 Recombination in the Space Charge
Region . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.2.2 Ohmic Resistance Losses . . . . . . . . . . . . . . . . . . . 102
6.2.2.1 Contact Resistance Metal-Semiconductor . 103
6.2.2.2 Ohmic Losses in the Semiconductors . . . I 110
6.2.2.3 Ohmic Losses in the Metal Contacts . . . . 113
6.3 Optical Losses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
6.3.1 Antireflection Processes . . . . . . . . . . . . . . . . . . . . 114
6.3.1.1 Antireflection Using a Thin Coating . . . . 115
6.3.1.2 Textured Surfaces . . . . . . . . . . . . . . . . . . 118
6.3.2 Losses due to Non-Absorbed Light . . . . . . . . . . . . 120
6.3.3 Shadowing Losses by Contact Fingers . . . . . . . . . . 121
6.4 The Structure of a High Efficiency Solar Cell . . . . . . . . . 122
6.5 Manufacturing Process for High Efficiency Silicon Solar
Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6.5.1 Process Sequence for the Highest Efficiency . . . . . 124
6.5.2 The Simplified Manufacturing Process . . . . . . . . . . 128
7 Si Solar Cell Technology ....................... 133
7.1 Techology for the Manufacture of Silicon . . . . . . . . . . . . 133
7.1.1 Basic Material . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
7.1.2 Refractioning Processes . . . . . . . . . . . . . . . . . . . . 135
7.1.3 The Manufacture of Polycrystalline Si Material . . . 135
7.1.4 Crystal Pulling Process . . . . . . . . . . . . . . . . . . . . . 136
7.1.4.1 The Czochralski (CZ) Process . . . . . . . . . 136
7.1.4.2 Float Zone Pulling . . . . . . . . . . . . . . . . . 138
7.1.5 The Manufacture of Silicon Wafers . . . . . . . . . . . . 139
7.1.6 Polycrystalline Silicon Material . . . . . . . . . . . . . . . 139
7.1.7 Sheet Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 141
7.1.7.1 The EFG Process . . . . . . . . . . . . . . . . . . 142
viii Crystalline Silicon Solar Cells

7.1.7.2 The SSP Process . . . . . . . . . . . . . . . . . . 143


7.2 Si Solar Cell Technology . . . . . . . . . . . . . . . . . . . . . . . . 143
7.2.1 Technologies for the p-n Junction . . . . . . . . . . . . . 144
7.2.1.1 Diffusion Technologies and the Theory of
Diffusion . . . . . . . . . . . . . . . . . . . . . . . . 144
7.2.1.2 Diffusion Technologies . . . . . . . . . . . . . . 148
7.2.2 Oxidation Technologies . . . . . . . . . . . . . . . . . . . . 152
7.2.3 Auxiliary Technologies . . . . . . . . . . . . . . . . . . . . . 155
7.2.3.1 Etching and Cleaning Techniques . . . . . . . 155
7.2.3.2 Photolithography . . . . . . . . . . . . . . . . . . 156
7.2.4 The Metallising of Solar Cells . . . . . . . . . . . . . . . . 156
7.2.4.1 The Structuring of the Finger Grid . . . . . . 156
7.2.4.2 High Vacuum Evaporation Technologies . . 157
7.2.4.3 Thick Film Technology . . . . . . . . . . . . . . 158
7.2.5 Antireflection Technologies . . . . . . . . . . . . . . . . . . 159
7.2.5.1 Applying an Antireflection Coating . . . . . 159
7.2.5.2 The Manufacture of Textured Silicon
Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . 160

8 Selected Solar Cell Types ....................... 163


8.1 Crystalline Silicon Solar Cells . . . . . . . . . . . . . . . . . . . . 163
8.1.1 Crystalline Silicon Concentrator Cells . . . . . . . . . . 163
8.1.2 Bifacial Solar Cells . . . . . . . . . . . . . . . . . . . . . . . 166
8.1.3 Buried Contact Solar Cells . . . . . . . . . . . . . . . . . . 166
8.1.4 MIS Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 168
8.1.5 Polycrystalline Silicon Solar Cells . . . . . . . . . . . . . 169
8.1.6 Crystalline Silicon Thin Film Cells . . . . . . . . . . . . 171
8.1.6.1 Advantages and Requirements . . . . . . . . . 171
8.1.6.2 The Relationship between Electrical and
Cell Parameters . . . . . . . . . . . . . . . . . . . 173
8.1.6.3 Manufacturing Technology for Si Thin
Film Solar Cells . . . . . . . . . . . . . . . . . . . 176
8.1.7 Multilayer Silicon Solar Cells . . . . . . . . . . . . . . . . 178
8.2 Thin Film Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 181
8.2.1 Amorphous Silicon Solar Cells . . . . . . . . . . . . . . . 181
8.2.2 Gallium-Arsenide Solar Cells . . . . . . . . . . . . . . . . 185
8.2.3 Cadmium-Telluride Solar Cells . . . . . . . . . . . . . . . 189
8.2.4 Copper-Indium-Diselenide Solar Cells . . . . . . . . . 190
8.3 Tandem Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
8.4 Dye-Sensitised Solar Cells . . . . . . . . . . . . . . . . . . . . . . . 193
Contents ix

9 Analysis and Measuring Techniques ............... 201


9.1 The Current-Voltage Characteristics . . . . . . . . . . . . . . . . 201
9.1.1 Measuring the I-V Curve Under Illumination . . . . . 202
9.1.2 Measuring the Dark Current Characteristic . . . . . . . 203
9.1.2.1 Dependence of Efficiency on Radiation . . 205
9.1.2.2 Dependence of Efficiency on Temperature 206
9.2 Solar Cell Spectral Response . . . . . . . . . . . . . . . . . . . . . 208
9.2.1 Spectral Response of a Front Illuminated Solar Cell 208
9.2.2 Spectral Response of a Back Surface Illuminated
SolarCell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.3 The PCVD Measurement Techniques . . . . . . . . . . . . . . . 212
9.4 The PCD Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
9.4.1 Determining the Emitter Saturation Current . . . . . . 215
9.4.2 Determination of the Surface Recombination
Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
9.5 Microwave Detected Photocurrent Decay . . . . . . . . . . . . 217
9.6 Modulated Charge Carrier Absorption . . . . . . . . . . . . . . . 220
9.7 Short Circuit Current Topography (LBIC) . . . . . . . . . . . . 225
9.8 The DLTS Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

Appendix A: List of Symbols .......................... 231

Appendix B: Physical Constants. Selected Si Parameters


at300K ............................... 233
Index ............................................ 235
Photovoltaics

1.1 THE PRINCIPLES OF PHOTOVOLTAICS

As the name suggests, the absorption of light - photons - in a


semiconductor can, under certain conditions, create an electric current. The
transformation principle is based upon the fact that in a semiconductor
fixed electrons can be converted into freely moving conduction electrons.
This simultaneously creates a positively charged ‘hole’ and thus a second
charge carrier with an opposing charge.
If a potential difference exists in the semiconductor material, whether
due to a p-n junction or an appropriate surface charge, then this charge
carrier can be forced to travel in an external circuit, i.e. an electrical
current c m be produced. In many cases, in particular in the case of
crystalline silicon, the charge carriers that have been created can only reach
this potential barrier because of thermal vibrations. No other force drives
them in this direction. This means that the charged particles will have to
exist until they reach the potential barrier. This lifetime or diffusion length
(the average distance travelled) is one of the key factors for the efficiency
of photovoltaic energy generation. Of course, a multitude of other physical
characteristics, such as cell design, help to determine functionality and
efficiency.

1.2 THE HISTORY OF PHOTOVOLTAICS


The physical effect which underlies photovoltaics was first observed by
Becquerel [l] in 1839, when he produced a current by exposing silver
electrodes to radiation in an electrolyte. The effect was described in more
detail by Adams and Day [2] in 1877. They observed that the exposure of
selenium electrodes to radiation produced an electric voltage, thus allowing
2 Crystalline Silicon Solar Cells

them to produce electric current.


The effect was then put on hold until the discovery of transistors and
the explanation of the physics of the p-n junction by Shockley [3] and
Bardeen and Brattain [4] in 1949, the year that marked the beginning of the
semiconductor era. Then, in 1954 Chapin et a1 [5] at the Bell Laboratories
in the USA developed the first solar cell based on crystalline silicon, which
had an efficiency of 6% - considerable at the time. This efficiency was
increased to 10% within a few years. The first viable use for solar cells
was in satellite power supplies. Photovoltaics proved their worth
convincingly in this application. The initial problem of high degradation of
efficiency by cosmic radiation has now for the most part been solved.
The main driving force behind the widespread use of photovoltaics for
terrestrial power supplies came in 1973 with the notorious oil shock. From
this point onwards numerous research and development institutions were set
up around the world, the majority of which were publicly financed. New
institutes were founded. All the available options for cost reduction were
examined, as it was already recognised that the excessive costs of
photovoltaic plants posed the largest obstacle for the widespread use of
photovoltaics.
The wide range of work on the reduction of the cost of silicon serves as
an example of these efforts. These are:
The development of a polycrystalline silicon material which could be
produced significantly cheaper than monocrystalline material by using
casting instead of the familiar pulling process. (See Chapter 7, Section
7.1.6 for further details.)
The development of methods for the production of sheet material to
eliminate the costs associated with the pulling of rods and the sawing of
wafers and to eliminate the wastage associated with cutting.
The development of low cost technological processes for the
manufacture of cells, e.g. silk screening processes instead of high
vacuum evaporation processes.
Apart from silicon, which is now used almost exclusively in the
generation of photovoltaic power, investigations were undertaken in
numerous institutions into other semiconductor materials. These were
successful in the development of amorphous silicon (a-Si) - a silicon
hydrogen compound [6]. This material has conquered the consumer market
(e.g. clocks, pocket calculators). The critical factor is not so much high
energy generation as electrical voltage at currents in the milli- and
microamp range. a-Si solar cells achieve the required voltage multiplication
- a solar cell only produces approximately 0.5 V - very easily by
monolithic integration during the manufacture of cells. Of all the other
materials made of III-V or II-VI semiconductors or heterocompounds, until
Photovoltaics 3

now copper-indium-diselenide (CIS)has been at the forefront [7].One


obvious advantage of this material is the adequate long-term stability of
solar cell parameters and the achievement of a relatively high level of
efficiency. So-called tandem cells represent a further sphere of work, in
which solar cells with differing absorption ranges are optically connected
in series in order to better utilise the solar spectrum.
At the beginning of the 1980s it was recognised that high efficiency in
solar cells was of great importance for the reduction of the costs of the
complete system. From this point onwards research and development has
mainly concentrated on achieving high levels of efficiency.

1.3 THE IMPORTANCE OF PHOTOVOLTAICS


The volume of solar cells currently produced world wide is approximately
100 Mega ‘peak watts’ (peak watts are the capacity of a solar power plant
at maximum sunshine). This order of magnitude is of course completely
unimportant with regard to energy generation. However, there are numerous
applications for which solar power brings great advantages. Thus, for
example, many signal stations are driven by solar power. Another field
which will grow significantly in the near future is photovoltaic power
supplies for isolated houses, for which connection to the grid is very
expensive. In the small appliance sector, e.g. power supplies for
independent mobile equipment (meters, electrical tools, etc.), solar cells are
becoming more popular.
Usage in the Third World will increase. Electrical lighting and the
operation of fridges, etc. alone represent a large improvement in the
standard of living in these countries. The operation of water pumps using
photovoltaics is another viable application in this area, which is certain to
become more and more common.
In the more distant future environmental concerns and the finite supply
of fossil fuels make it certain that the sun, as the only inexhaustible energy
source, will also be used for large scale power supplies. Just a fraction of
the solar energy that falls upon the earth would cover our entire current
energy demand. Thus, no restrictions are presented by the original energy
supply.

References

111 Becquerel A. E., Compt. Rendus de L’ Acadernie des Sciences 9, 1839,


p.561
[2] Adams W. and Day R., Proc. Roy. SOC.A 25, 1877, p. 113
4 Crystalline Silicon Solar Cells

[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

2.1 THE SUN AS A SOURCE OF RADIATION

The sun as a source of radiation is dealt with in detail in several well


known books such as [ 11. We will therefore only concern ourselves with the
most important points here.
According to current knowledge, the energy of the sun is created by the
nuclear fusion reaction of hydrogen and helium which occurs inside the sun
at several million degrees. The mass difference that occurs in this process
is converted into energy, As the sun is in radiation equilibrium with the
cold universe, it is principally its surface temperature which is determined
by this. This is 5900 K. Most fixed stars have surface temperatures of the
same magnitude owing to radiation equilibrium. Because all elements are
ionised to some degree at this temperature, and their spectral lines are
strongly broadened, the radiation consists of a multitude of spectral lines,
so that the gaseous surface of the sun radiates like a black body. The solar
energy that reaches the surface of the earth is determined by the ratio of the
diameters of the sun and earth and their distance apart. If we disregard the
deviations arising from the rotation of the earth around the sun, the most
recent measurement of the radiation power outside the atomosphere is Do
= 1.353 kW/mz. The value Dois known as the solar constant [2].
This radiation is then partially absorbed and scattered by its journey
through the atmosphere, thus being weakened. In the infrared region this
weakening is caused by the water and carbon dioxide in the air, while the
absorption in the visible range is caused mainly by the oxygen, and in the
ultraviolet range it is mainly caused by the ozone content. As well as a
reduction in radiation there is also a spectral shift. Rayleigh scattering, for
example, scatters the short wavelength light much more than the long
wavelength light. Figure 2.1 shows the spectral distribution of solar energy.
6 Crystalline Silicon Solar Cells

2.2 STANDARD RADIATION


The terms AM0 and AM1.5 used in Figure 2.1 are definitions for specific
radiation conditions. AM (‘air mass’) gives information about the amount
of air mass the radiation passes through in the individual case. The terms
are :
AM0 the extraterrestrial radiation, e.g. applicable to satellites in
space;
AM1 the vertical incidence of sunlight at the equator at sea level;
AM13 sunlight radiating through an air mass 1.5 times greater than
the vertical case.

x-
Figure 2.1 Spectral distribution of radiation intensity

It can be easily calculated that the radiation condition AM 1.5 is fulfilled


if the sun is at an angle of 41.8” above the horizon.
Both weather and location conditions have a great influence on the
composition of radiation. Diffuse light contains a large proportion of blue
radiation. Certain standards have been agreed for the determination of
efficiency. For terrestrial photovoltaics the standard is AM 1.5 global. The
term ‘global’ stands for the sum of direct and indirect radiation.
In the laboratory and in the production of solar cells, sun simulators very
closely approximate this spectrum using the light from a xenon ultra high
pressure lamp through various filters. All the following information about
Solar Power 7

efficiency and other results of solar cells are based on this standard
spdctrum.

References

[ 11 Duffie J. and Beckmann W., Solar Engineering of Thermal Processes,


2nd Edition, J Wiley & Sons
[2] Thekeara M.P., Solar Energy 18, 1970, p. 309
The Principles of Photovoltaics

3.1 CRYSTALLINE STRUCTURE AND THE ENERGY


BAND DIAGRAM FOR SEMICONDUCTORS

The direct transformation of light into electrical energy always requires a


semiconducting material. Semiconductors are solids and, like metals, their
electrical conductivity is based upon movable electrons. Ionic conductors
are not considered here. The primary consideration here is the level of
conductivity. Materials are known as
conductors at a conductivity of Q > lo4 (SZcm)-’;
semiconductors at a conductivity of lo4 > a > 10” (ncm)’;
non-conductors (insulators) at a conductivity of Q < lo-’ (ncm)-’.
This simple categorisation is, however, hardly an adequate criterion for
a definition and it is predominantly other characteristics, in particuiar the
thermal behaviour of conductivity, that form the basis for classification.
This is where metals and semiconductors behave in an opposing manner.
Whereas the conductivity of metals decreases with increasing temperature,
in semiconductors it increases greatly. Madelung [l] defined
semiconductors as follows:
Semiconductors are crystalline solids, which in their pure state insulate at
temperatures approaching absolute zero, but at higher temperatures either
possess a clearly demonstrable electronic conductivity, become conductive
due to the disruption of the ideal lattice structure, or in which the external
effect of conductivity can at least be induced.
So what is a crystalline solid? At this point we wish to differentiate
between two separate categories. On the one hand there are the so-called
amorphous substances. In these, the structure of individual atoms and
molecules displays almost no periodicity or regularity. Crystalline solids, on
the other hand, are distinguished by a perfect (or near perfect) periodicity
I0 Crystalline Silicon Solar Cells

of atomic structure. These materials naturally make it much easier to


understand the physical characteristics of solids. Therefore, the explanation
of semiconductor characteristics and the physical principles of photovoltaics
should be based upon crystalline semiconductors, and in particular
crystalline silicon.

3.1.1 The Energy Band Diagram for Tetrahedronal


Semiconductors

The bonding or arrangement of atoms in nature can occur in numerous


different ways. The deciding factor is the characteristics of the electrons in
the outer shell of the atom, the so-called valence electrons. Depending
upon symmetry and energy conditions, the arrangement of atoms can give
rise to different crystalline structures.

Figure 3.1 The diamond lattice [2]

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

This is demonstrated by other physical characteristics, such as the hardness


of these materials.
Figure 3.1 [2] shows the structure of a diamond lattice. We do not wish
to go into further details about this structure at this point. Please refer to
the specialist literature [3].
For electrical conductivity to occur in this type of crystal, some of these
bonds must be broken. Clearly, this can only occur if energy is expended.
At a temperature of T = 0 K no bonds are broken, i.e. no free electrons are
present. At T = 0 K the semiconductor is an insulator.
So what is the energy level structure in this type of crystal? We know
that according to Bohr's theory of the atom, electrons in an isolated atom
can only occupy well-defined energy levels. If we bring two atoms close
together in an imaginary experiment, then an interactive effect will occur,
splitting the energy levels of these two bonded atoms. This splitting
principle can be briefly described in terms of a mechanical theory of
coupled vibrations (Figure 3.2).

Figure 3.2 The principle of coupling mechanical oscillators


I2 Crystalline Silicon Solar Cells

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

If we transfer this analogy to the interactive effect in a crystal lattice,


then the splitting of energy levels can be represented as follows.
The vertical axis of Figure 3.3 represents electron energy, and the
horizontal axis represents the distance of atoms from one another. As the
distance decreases, the energy levels of the atoms split up more and more.
Similar to the mechanical analogy, the energy bands become increasingly
broad. At a specified distance between atoms (4,it is clear that there is an
energy gap between the two upper bands, the valence band and the
conduction band, in which there can be no electrons. The energy gap is
called the band gap, Eg, of a semiconductor. It further applies that when T
= 0 K, because no bonds are broken, none of the energy levels in the outer
The Principles of Photovoltaics 13

conduction band will be occupied. In the valence band, however, all


available energy levels are occupied. This means that no energy can be
absorbed from a connected external electrical field, i.e. electric current
cannot flow. The semiconductor is then an insulator. Only at higher
temperatures does it show conductivity, because then some electrons
occupy the energy levels in the conduction band.
This band structure, with an energy gap between the two outer energy
bands, also occurs in insulators. Semiconductors and insulators differ only
in the size of the band gap. In a semiconductor, even at ‘normal
temperatures’ (e.g. at room temperature) some electrons can jump the band
gap thus giving rise to electrical conductivity. In insulators the band
distance is so large that at normal temperatures no electrons can jump the
gap. Normal values for the energy of this band gap for semiconductors lie
within the range of a few tenths of electron-volts to approximately 2 eV,
whereas for insulators these energies are significantly higher.

4 I

Interatomic distance
Figure 3.4 The splitting of energy levels in an electrical conductor

Metals, on the other hand, behave in a totally different manner. They


seldom possess the strict periodicity of the crystal lattice. Electrons are
therefore not so closely linked as in a diamond lattice. The energy gap
diagram shows the case where the outer conduction band is partly occupied
by electrons. Thus, if an electrical potential is connected, then electricity
I4 Crystalline Silicon Solar Cells

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.

3.1.2 Electrons and Holes in a Semiconductor

In this section we work out the number of free electrons in a


semiconductor in relation to temperature.
First, however, some explanations concerning the phenomenon of
conduction itself. As we will demonstrate in more detail later, in the broad
temperature range of ‘normal’ temperatures the conduction band is ‘almost
empty’ and the valence band ‘almost full’ of electrons. ‘Almost empty’ in
the conduction band means that only a few electrons are in the permitted
energy states. Although, as the calculations given later will demonstrate, all
these states lie near the edge of the band, there still are numerous
unoccupied states close to the occupied levels, so these electrons are
capable of reaching a higher level by an almost continuous process. This
means that when connected to an electric field, energy can be continuously
taken up. It is then possible to treat the conduction electrons as the
electrons in metals are treated in classical physics. Owing to the level of
dilution they influence each other very little, but they are in a state of
continuous close interaction with the lattice of the crystal. This interaction
is highly complex and can only be considered statistically. However, these
interaction forces are extremely significant for the conduction process. To
take these into account, instead of the elemental electron mass m, an
effective mass mi is introduced.
Analogous to this is the behaviour in the ‘almost full’ valence band.
Some energy levels in this band are not occupied by electrons and these
energy levels also lie close to the edge of the valence band. As in the
conduction band, these empty states are surrounded by numerous occupied
states. This means that one such empty state can wander around within the
valence band. This empty state is known as a hole or defect electron. It has
proved sensible to treat this hole as an individual, i.e. as a charge carrier.
It is evident that this charge carrier has a positive charge and, like
electrons, is assigned an effective mass mi due to interaction with the
lattice. The defect electron or hole, like the electron, is a second type of
charge carrier. This is an extremely useful formalism for dealing with the
phenomenon of conductivity in semiconductors.

3.1.3 Energy Levels: The Fermi Level

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’).

Figure 3.5 Fermi-Dirac distribution function

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.

3.1.4 Density of States for Electrons and Holes

We begin with the distribution of electrons in the conduction band. How


large is the number N(E) of permitted energy levels for electrons per
volume unit in the conduction band in an energy range dE? We will spare
the complex calculations at this point. According to the rules of statistics
and quantum mechanics this number is found to be

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

For the solution in closed form we make two simplifications. Since at


normal temperatures E - E, N kT (at 25°C kT z 0.026 eV), we may
approximate
The Principles of Photovoltaics 17

Figure 3.6 Number of permitted states in an intrinsic semiconductor

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

After some manipulation this is found to be

=’[
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

n = N , exp( E F -EC ) (3.1.7)


kT
We see that in a semiconductor, in addition to the energy of the Fermi
level, the number of free electrons in the conduction band - and therefore
its conductivity - depends decisively upon temperature!
The number of holes in the valence band can be calculated in the same
way. This is found to be

='[
2zmp*kT
h2 ] 1
exp(
EV -EF
kT )
(3.1.8)

or

P v" exp(
EV -EF
kT ) (3.1.9)

Nv is thus by definition the effective density of holes in the valence band.


Figure 3.7 gives another overview of the energy levels scheme of an
intrinsic semiconductor at a finite temperature. It is apparent from Figure
3 . 7 ~that the density distribution depends upon the two variables in Figure
3.7a and Figure 3.7b. The shaded areas can in Figure 3.7a be assigned the
densities N , and N,, and in Figure 3 . 7 the
~ intrinsic carrier concentration.
For the ideal non-defective semiconductor in thermal equilibrium the
number of electrons in the conduction band must be equal to the number
of holes in the valence band. Therefore n = p, i.e.

N , exp( EF
kT
-EC ) = N , eXp("' -EF)
kT
(3.1.10)

We thus find the energy of the Fermi level to be

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

If we define np=nf, where ni is designated as the intrinsic carrier


densitv. then for Si at 300 K we obtain the following
I , " values r41: L 1

N, = 2.86 x 1019 cm" N , = 3.10 x 10'' cm1.3 E,, = 1.124 eV


ni = 1.08 x 10" cm"
The important point is that this value for ni deviates significantly from
the values given in the literature (e.g. ni is approximately equal to 1.4 x
10" ~ m - ~ The
) . new value, published in 1990, is fundamentally in
agreement with the values that were published in 1977 [ 5 ] and by our
institute in 1985 [6].

3.1.5 Thermal Equilibrium

The thermal equilibrium in the intrinsic case (i.e. an undoped


semiconductor crystal) will now be examined in more detail. The
concentrations of electrons and holes at a set temperature are the result of
dynamic equilibrium between the formation of electron-hole pairs
20 Crystalline Silicon Solar Cells

(generation) and the destruction of pairs (recombination) when electrons


from the conduction band fall back into the valence band. The generation
of charge carriers is certainly independent of the number of electron-hole
pairs that have already been formed, as the number of currently bound
electrons is incomparably higher than the concentration of free electrons.
As soon as charge carriers are formed, however, recombination is set in
action. This depends upon the concentration of charge carriers, and is,
according to the mass-action law, directly proportional to their number. If
we call R the recombination rate per volume unit and time unit, then

R =rpn (3.1.13)

where r is the recombination probability.


In thermal equilibrium the generation rate G is equal to the
recombination rate R. Therefore

G =R =rnp or where n p = n ,2 (3.1.14)

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).

3.2 THE CONDUCTION MECHANISM IN


SEMICONDUCTORS

3.2.1 Intrinsic Conduction, Field Current and Mobility

We wish to demonstrate that, in general, Ohm's law applies in a


homogeneous semiconductor.
As already mentioned, in a semiconductor free electrons and holes carry
the current. Electrons move in an electric field under the influence of a
force
The Principles of Photovoltaics 21

K = - q E =mb (3.2.1)

where E is the electric field, q is the elementary charge and b is the


acceleration.
In a vacuum with a constant electric field, an electron will very quickly
reach a high velocity due to constant acceleration. This is dependent only
upon the distance ‘starting point to end point’ and the magnitude of the
electric field, The situation is very different in a solid, i.e. also in a
homogeneous semiconductor. Although the same forces are in effect (where
we must replace m, with m: ), after a ‘short’ distance the electrons collide
with a lattice atom or an impurity atom, or occasionally with another
electron. This scattering process causes the electron to lose the energy
taken from the electric field, which is transfered to the lattice_in the form
of heat. Therefore after travelling an average free path length 1 and after an
average relaxation time f, a ‘collision’ occurs.

Figure 3.8 The path of a free electron in a crystal lattice: (a) without an
electric field; (b) with an electric field

Figure 3.8 gives a graphic picture of the situation. Whereas by purely


thermal movement the electron on average covers no distance, when an
electric field is connected it gains an additional velocity component Vdnnin
the opposite direction to the field, where
22 Crystalline Silicon Solar Cells

The average of all velocities gives half of this value, thus

-
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

I,, = n q VdriA (3.2.4)

and thus

In = n q -1- -g i E (3.2.5)
2 m,'

If we define

(3.2.6)

as the electron mobility, then

I, = n 4 P n E (3.2.7)

or

In = Q E (3.2.8)

where the electrical conductivity Q is

= =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

The total conductivity of a semiconductor is thus

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

lo 0 100 200 300 lo 0 100 200 300


T[OCI T I"C1
Figure 3.9 Mobility of electrons and holes as a function of temperature and
dopant concentration [7]

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

3.2.2 Impurity Conduction

In Section 3.1.4 we calculated the number of available charge carriers in


relation to temperature in a ‘pure’ semiconductor. The resistivity p of
intrinsic silicon at T = 300 K is found to be approximately 300,000 a m .
This varies very significantly with temperature according to the formulae
(3.1.7) and (3.1.9).
There is, however, in addition to increasing the temperature another
highly effective method of altering the concentration of charge carriers in
a semiconductor and thus its conductivity, namely by the purposeful
introduction of certain impurity atoms into the crystal.
If we replace a silicon atom in the crystal structure with an element
from the fifth group of the periodic table for example (e.g. phosphorus),
this atom ‘brings’ five valence electrons with it. Only four of these
electrons are required to bond to the crystal structure. It is therefore
plausible that the fifth electron is relatively loosely bound and can therefore
be ‘ionised’ even at low temperatures. We call these elements from the
fifth group of the periodic table ‘donors’, as they can easily ‘donate’
electrons. Their number per volume unit is designated by ND . In addition
to phosphorus, the elements arsenic and antimony are also used as donors
in semiconductor technology.
How high is the bonding energy of the fifth electron of these
substances? Bohr’s atomic theory helps us to determine this. Owing to the

..... . . . . . . . . Silicon atom

........ . . . . . . . . .
e m

... . .. . . . . . .+*G
Phosphorus atom

........
....... ...
.............
Figure 3.10 Electron orbits of a donor atom in a semiconductor
The Principles of Photovoltaics 25

relatively weak bond, this electron is located on an equivalent, relatively


large Bohr’s atomic radius - it is better to talk of the applicable wave
function here - which encompasses many silicon atoms (Figure 3.10).
To determine the bonding energy we can proceed as if calculating the
ionisation energy Ei of hydrogen in a vacuum. This works out as

(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‘

Considering the energy band diagram, this corresponds to an energy


level only slightly (approximately 10% of the energy of the band gap)
below the edge of the conduction band. It is therefore plausible that even
at very low temperatures (< 70 K) all these electrons will be ionised and
located within the conduction band. We can therefore expect an additional
10l6 cm” conduction electrons for a doping of, for example, ND = 10l6~ m - ~ .
This figure exceeds the number of electrons attributable to intrinsic
conductivity at room temperature of approximately 10” cm-3by six orders
of magnitude. Conductivity increases to the same degree. This further
means that in a wide temperature range conductivity is no longer dependent
upon temperature (or, to be precise, only slightly due to the dependency of
mobility on temperature), but rather on the number of dopant atoms.
Because conductivity is mainly determined by the negative conduction
electrons, a semiconductor that is doped in this manner is known as an n-
type conductor and the electrons are known as majority charge carriers,
whereas the holes - which are present in much lower numbers - are known
as minority charge carriers.
So how high is the number of holes in this example? We still have
neutrality of charge. The laws of the recombination and generation
26 Crystalline Silicon Solar Cells

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

p =ni’lN; = lo4 cm -3 (3.2.14)

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)

We then find for E, - E, in silicon at room temperature where


ND = 10l6 cm” and Nc = 10’’ cm-3 a value of approximately 0.18 eV, i.e.
the Fermi level lies approximately 0.18 eV below the edge of the
conduction band. This situation is shown in Figure 3.11 [8]. It also
demonstrates visually that the number of holes is significantly lower than
the number of electrons. This difference of several orders of magnitude
cannot be shown graphically.
We can also use elements from the third group of the periodic table as
dopants. The elements boron, aluminium, gallium and indium are used in
semiconductor technology. The missing bonding electron of a trivalent
dopant atom leads to the creation of a hole and thus an increase in the
positive conductivity of the semiconductor. This is therefore called a p-type
conductor and these types of dopant are known as acceptors; their quantity
per unit volume is designated NA.The holes are now dominant, i.e. the
majority charge carriers, and the electrons are the minority charge carriers.
The same regularity applies as in the case of doping with pentavalent
atoms, i.e. even at low temperatures all holes are active. It is therefore clear
that the Fermi level must be located close to the edge of the valence band.
Similarly to (3.2.16) the gap is

E, - E , =kTln(N,lN,) (3.2.17)
The Principles of Photovoltaics 27

E E E
4

ND

0
a) b) C)

Figure 3.11 N-type semiconductor: (a) Energy level of the donors;


(b) Fermi-Dirac distribution; (c) electron density in the bands [8]

5.2.3 uirrusion Lurrent ana uirrusion Lonstant

As well as the field current considered in Section 3.2.1, there is a second


tvDe of current transDort. namelv the movement of carriers due to
U l L l G l G l l G G b I l l GUIIGGILLI illlU11.
Since, as we have seen, electrons and holes move within semiconductors
according to statistical rules, we can apply the rules of diffusion to them.
If, for example, a concentration difference of electrons exists, then these
will be ‘driven’ from the higher to the lower concentration, i.e. they move
in the direction of the negative gradient and the flow dnldt in the direction
x (we only wish to consider the one-dimensional aspect here as this is often
adequate for semiconductor devices) is proportional to this concentration
gradient. Thus

(3.2.18)

where D, is defined as the diffusion coefficient of the electron.


28 Crystalline Silicon Solar Cells

Figure 3.12 Diffusion current dnldt as a function of the concentration gradient

The corresponding electric current density is

(3.2.19)

The diffusion current density of holes for a given concentration gradient


is found in the same way. Taking the sign into account, with Dp being the
diffusion coeficient of holes, this is found to be

(3.2.20)

We can sum up the four possible components of current density in a


semiconductor. For electrons

(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 THE GENERATION OF CHARGE CARRIERS BY


THE ABSORPTION OF LIGHT
Unlike opaque metals, semiconductors display what is for them
characteristic absorption behaviour. The most important characteristic is the
existence of the so-called absorption edge. For wavelengths, at which the
photon energy (E=hc/h) (c=speed of light in a vacuum) is greater than the
energy of the forbidden band, light is, depending upon the thickness of the
material, almost completely absorbed. In the case of long wavelength light
almost no absorption takes place due to its low energy. In this spectral
region the semiconductor is transparent. In the case of silicon the band
edge lies within infrared at 1-1.11 pm. Therefore silicon is excellently
suited as a base material for infrared optics.
The intensity of the light entering the crystal is weakened during its
passage through the crystal by absorption. The absorption rate is thus - as
in many other cases of physical behaviour - proportional to the intensity
that is still present. This leads familiarly to an exponential reduction in
intensity and can be described mathematically as follows:

(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%).

3.3.1 Absorption in Semiconductors

Absorption in semiconductors is a so-called basic lattice absorption, in


which one electron is excited out of the valence band into the conduction
band, leaving a hole in the valence band. Certain peculiarities of this
process should be taken into account. A photon possesses a comparatively
large amount of energy, but according to the De Broglie relationship
p = hu/c = h A has a negligibly small momentum. The conservation
principles of energy and momentum demand that during the absorption
process the crystal energy rises, but the crystal momentum remains almost
unchanged. This leads to certain selection rules.
In addition, we consider the relationship between energy and
momentum. For an electron in free space the following relationship applies:

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.

3.3.I . I Absorption in Direct Semiconductors

The absorption process is best demonstrated in direct semiconductors. As


we see from Figure 3.13 the minimum energy of the conduction band in
relation to the crystal momentum p lies directly above the maximum of the
valence band. When a photon is absorbed the energy E=hv is the energy
difference between the initial and final condition of the energy of the
crystal
The Principles of PhotovoItaics 31

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)

and the energy of the hole in the valence band is

(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)

The value for the constant C is approximately 2 x lo4 for a direct


semiconductor, if the absorption coefficient a is given in cm-' [lo].
In the case of direct GaAs semiconductor where Eg=1.42 eV and for
light with a photon energy of 1.52 eV (correspond to 3L=0.8 pm) the
32 Crystalline Silicon Solar Cells

I hv

Crystal momentum, p
Figure 3.13 Energy of the conduction band as a function of crystal momentum
(direct semiconductor)

absorption coefficient is found to be the value Q = 6.3 x 10’ cm-’ giving an


absorption length of x,, = 1.6 pm.
Light with a shorter wavelength is absorbed even better. It is
characteristic of a direct semiconductor that even in very thin layers of a
few pm the photovoltaically useful sunlight is almost completely absorbed.

3.3.I .2 Absorption in Indirect Semiconductors

The situation is different in an indirect semiconductor. In this case the


minimum of the conduction band and the maximum of the valence band lie
at different crystal momentums. The absorption behaviour is demonstrated
using Figure 3.14. The direct transition from the valence band to the
conduction band requires a higher energy level than hv = E,.
It is, however, possible to excite to the conduction band minimum if the
necessary change in momentum can be induced by thermal vibrations in
the lattice, i.e. a phonon. A phonon itself, although it only has a low
energy level in comparison to a photon, has a very high momentum. The
important point here is the fact that the probability of absorption is much
The Principles of Photovoltaics 33

---___

!+ Phonon absorption

b
Crystal momentum, p

Figure 3.14 Conduction band energy in relation to crystal momentum (indirect


semiconductor)

lower than for a direct semiconductor due to the involvement of two


different particles.
Different experimental measurements exist for crystalline silicon
[11],[12]. New results have been published in 1995 [13]. Figure 3.15 shows
this relationship between absorption coefficient, absorption length and
wavelength. In silicon, the absorption length for light with a wavelength of
1 pm is 140 pm where a = 72 cm-I. Therefore, for a high level of
absorption in silicon a crystal thickness of approximately 200 pm is
required, unless the light is locked into the crystal using reflection method
(optical confinement).
It should be mentioned that, as well as this type of absorption, which is
connected with the generation of charge carriers, there are also other
absorption mechanisms. For example, a photon can also give up its energy
by raising up an electron in the conduction band to a higher energy level.
From there the electron gives up its energy to the lattice in stages, thus
34 Crystalline Silicon Solar Cells

1 0 4 I,-. .-
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Wavelength (pm)

Figure 3.15 Absorption coefficient ct and absorption length of silicon in


relation to wavelength X , [ 131

increasing the energy of the lattice vibrations, i.e. the temperature in the
semiconductor. This absorption occurs at high electron concentrations.

3.4 RECOMBINATION, CARRIER LIFETIME


If ‘excess’ charge carriers are created in a semiconductor, either by the
absorption of light or by other means, i.e. the thermal equilibrium is
disturbed, then these excess charge carriers must be annihilated after the
source has been ‘switched o f f , As already mentioned, this process is called
recombination.
Three different mechanisms for recombination will be considered here.
The Principles of Photovoltaics 35

3.4.1 Radiative Recombination

Radiative recombination is when electrons ‘fall back’ from the conduction


band into the valence band, thus annihilating the same number of holes.
The process is the exact inverse to absorption, and it is clear that this
recombination energy must correspond to the energy E, of the band gap.
Therefore for this energy

E =Eg = h v =hclh (3.4.1)

or

h =hclEg (3.4.2)

In silicon this recombination is just as unlikely as absorption, which


means that indirect semiconductors should have long charge carrier
lifetimes. Figure 3.16 demonstrates this recombination process in direct and
indirect semiconductors.

I hV- Epi j hv+E p


!I

Crystal momentum, p Crystal momentum, p


(a) (b)
Figure 3.16 Radiative recombination: (a) in direct semiconductors; (b) in
indirect semiconductors

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

and that it is other mechanisms that primarily influence the lifetime of


charge carriers.
Before we examine the most important recombination process based on
impurities and defects in the material, we first consider the so-called Auger
recombination.

3.4.2 Auger Recombination

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

The Auger process is assigned a lifetime. It is clear that this


recombination is more probable, the higher the concentration of charge
carriers. Landsberg and others conducted theoretical deliberations on this
subject [15],[16]. For a simple reaction mechanism we can expect that for
The Principles of Photovoltaics 37

this three-particle process, e.g. for the electron-hole-hole process the


reaction mechanism will be proportional to p2n and for an electron-
electron-hole process, it will be proportional to n’p. This means that the
recombination rate R, for electrons, for example, is

R, = B n 2 p (3.4.3)

or thus the Auger lifetime rAug

,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.

3.4.3 Recombination via Defect Levels

It is a known fact that the lifetime in semiconductors is determined


fundamentally by the presence of impurities and crystal defects. It is
plausible that the inclusion of atoms that do not have the electron structure
of a pentavalent or trivalent dopant will give rise to defect levels, with
energy levels that need not lie near the edge of the band. They may lie
deeper in the forbidden band, and are thus called deep defects.
Figure 3.18 shows a large number of these energy levels for different
substances in silicon.
These impurity levels, also called ‘trap levels’ because they are traps for
charge carriers, determine the recombination of charge carriers to a high
degree.
The theory of this mechanism was developed by Shockley and Read
[20], and Hall [21]. It was further developed and completed at a later date
[22],[23]. This theory can be explained with reference to Figure 3.19.
For an energy level in the forbidden band four fundamental processes
are possible:
an electron is captured by an unoccupied energy level (1);
an electron is emitted from an occupied level into the conduction band
(2);
a hole is captured by an occupied energy level (3);
a hole is emitted into an unoccupied state in the valence band (4).
38 Crystalline Silicon Solar Cells

Li Sb P As Bi Ni S Mn. A9 Pi H9
r

B At Ca In Tt Co Zn Cu Au Fe 0

Figure 3.18 Defect levels of some elements in silicon

Figure 3.19 Recombination by defect levels

If we calculate the corresponding probabilities for these processes and


make the, in many cases permissible, assumptions that
there is no transition between levels;
the state of the energy level is not dependent upon its state of charge;
the duration of emission and capture is low compared with the average
time elapsed between capture and emission; and
the number of energy levels N,is small compared to doping,
The Principles of Photovoltaics 39

then we find the following relationship for the recombination rate R


(s-’ cm”) of excess charge carriers:

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

we find from the equation (3.4.5)

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

7 = t,, + tp0 (3.4.1 1)

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)

i.e. the minority carrier lifetimes are, refemng to (3.4.8), inversely


proportional to the number of impurities.
To show the dependency of carrier lifetime on the energy state of the
impurity level and the dopant concentration under the conditions of low
injection, we make the simplifying assumption that in equation (3.4.5) oP
= Q,. We furthermore assume a constant value for N,and set the value for
carrier lifetime, which is created by an impurity level in the mid-band,
equal to 1. After some manipulation, we find that for a p-material with
doping NA (cm-’) the following relationship applies for the relative lifetime
of electrons:

’ Shockley and Read [ 141 demonstrated that where Nt is small compared


with doping, An of electrons can be equated to Ap of holes.
The Principles of Photovoltaics 41

(3.4.14)

Figure 3.20 shows this relationship. It is clear from the representation


that the energy level is most effective in the mid-gap area and that lifetime
is independent of doping in this region.

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

For an energy level where E, = 0.2 eV, however, there is a strong


dependency. We will explain this using the examples of gold (Ep0.54 eV)
and titanium (EpO.2 eV). The capture cross-section is of equal magnitude
in both these cases, being

on x opx 1 . 0 ~ 1 0 + ~cm (3.4.15)

and N, is 1.0 x lOI3 ~ r n . ~We


. use the expression for diffusion length L.
This describes the average distance which a charge carrier covers in its
lifetime. This works out as L=(Dx.r)O.'. D is the diffusion coefficient. Then
42 Crystalline Silicon Solar Cells

Specific resistance (Qcm)


100 50 20 10 5 3 15 1 OX 0.2
h

s
-g
C
300
.-0
u)

3 200

100

Figure 3.21 Relationship between diffusion length and background doping at


fixed concentrations of gold and titanium

the diffusion length as a function of doping yields the values shown in


Figure 3.21.
It is clear that with gold as the impurity level the diffusion length is
almost independent of doping. However, with titanium as the impurity level
with an energy state below the band-edge, there is a marked dependency on
the basic doping of the material.
We can deduce the following: because many impurity levels and defects
in crystal lie between + 0.2 and 0.2 eV, then for a basic doping greater
than 10l6 ~ m -the~ ,normal level for solar cells, these have just as decisive
an effect as gold.

3.4.4 Recombination by Doping

The lifetime, calculated according to the above three recombination


processes, is thus
The Principles of Photovoltaics 43

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

We again see that


for doping less than 10" cm" (normal for almost all Si devices)
radiative recombination plays virtually no role, and carrier lifetime is
determined by the impurity level; and
only at doping levels greater than lo'* ~ m does
' ~ Auger recombination
become dominant.
In the range 10l6 to 10l8 cm" there is a marked discrepancy between
theoretical considerations and experimental results. This has already been
investigated by numerous authors [25]-[3 13. The relationship obtained
44 Crystalline Silicon Solar Cells

empirically by Kendall [quoted in [lS]], is frequently used at the moment,


according to which the lifetime in this range is calculated as

'50
T =
(3.4.17)
ND
1 +-
7 x 10l5

In this equation the carrier lifetime T~ in pure, undoped silicon was


previously assumed to be 400 ps.

3.5 BASIC EQUATIONS OF SEMICONDUCTOR


DEVICE PHYSICS
To calculate current and voltage relationships in semiconductor devices we
need, in addition to the current density equations developed in the above
section, the relationship between the electric charge in the crystal and the
field strength, as well as an equation governing continuity in the
semiconductor. Once again we limit ourselves here to the one-dimensional
point of view (positional coordinate x).

3.5.1 The Current Density Equations

According to the equations which we developed in the previous section,


both field and diffusion currents can occur in a semiconductor device. We
repeat these formulae here to provide a better overview.
For the electrons

(3.5.1)
dx
and likewise for the holes

(3.5.2)

The signs correspond to the conventional current direction.


The Principles of Photovoltaics 45

3.5.2 Poisson's Equation

If we assume that excess electric charges exist within a semiconductor, i.e.


that not all charges are completely neutralised, then there is obviously an
electric field. The relationship between the electric charge present and the
electric field arising from it is governed by Poisson's equation, which
follows from the general Maxwell equation. For the coordinates in the x
direction this can be written in the form:

--
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.

3.5.3 The Continuity Equations

So what is the relationship between absorption, recombination and electric


current? If we consider an infinitesimally small volume dV (Figure 3.23)
where

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

Therefore the difference in particle flows in this unit volume is equal to


the difference between the generation and recombination of these particles.
This means

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)

and similarly for holes


The Principles of Photovoltaics 47

-
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:

Madelung O., Handbuch der Physik, Bd. XX Halbleiter, Springer -Verlag,


1957
Salow et al., Der Transistor, Springer-Verlag, 1963
McKelvey S. P., Solid State and Semiconductor Physics, Harper and ROW,
New York, 1966
Green M. A,, J . Appl. Phys. 6 7 , 1990, p. 2944
Wasserrab T., Zeitschrgt fur Naturforschung 32a, 1977, p. 746
Ruckteschler R., Dissertation, Univ. Freiburg, 1987
Wolf H. F., Silicon Semiconductor Data, Pergarnon Press, 1969
Frank F. and Snejdar V., Physik and Technik der Halbleiterwerkstofle, Band
1, Akademie Verlag, Berlin, 1964
McKelvey J. P., Solid State and Semiconductor Physics, Harper and Row,
New York, 1966, p. 79
Pankove J. I., Optical Processes in Semiconductors, Prentice-Hall,
Englewood Cliffs, New Jersey, 197 1
Runyan W. R., NASA Report S.M.U-83-13, University of Dallas, 1967
Jellisson G. E. Jr. and Modine S.A., Report ORNL ITM-8002, 1982
Green M. A. and Keevers M. J., Progress in Photovoltaics 3 , 1995, p. 189
van Roosbroek W. and Shockley W., Phys. Rev. 94, 1954, p. 1558
Landsberg P. T., Solid State Electron. 30, 1987, p. 1107
Landsberg P. T., Appl. Phys. Lett. 50, 1987, p. 745
Beck S. D. and Conradt, Solid State Comun. 13, 1973, p. 93
Rohatgi A., IEEE - TED 31, 1984, p. 597
Hangleiter A. and Hacker R., Phys. Rev. Lett. 65, 1990, p. 215
48 Crystalline Silicon Solar Cells

Shockley W. and Read W. T., Phys. Rev. 87, 1952, p. 835


Hall R. N., Phys. Rev. 83, 1951, p. 228
Sah C. T. and Shockley W., Phys. Rev. 109, 1957, p. 109
Sah C. T., et al, Solid State Electron. 13, 1970, p. 759
Shockley W. and Read W. T., Phys. Rev. 94, 1954, p. 1558
Landsberg P. T. and Kousik G. S., J . Appl. Phys. 56, 1983, p. 1696
Hu C. and Oldham W. G., Appl. Phys. Lett. 35, 1979, p. 636
Bennett H. S., Solid State Electron. 27., 1984, p. 893
Tyagi M. S., J . Appl. Phys. 54, 1983, p. 2857
Fossum J. G., Mertens R. P., Lee D. S. and Nijs J. F., Solid State Electron.
26, 1983, p. 569
Tyagi M. S. and v. Overstraeten R., Solid State Electron. 26, 1983, p. 577
Mertens R. P., v. Meerbergen J. L., Nijs J. F. and v. Overstraeten R., ZEEE -
TED. 27, 1980, p. 949
The p-n Junction

4.1 BASIC EQUATIONS

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

4.2 SPACE CHARGE REGION


To understand the function of semiconductor devices and thus of solar
cells, a precise understanding of the processes within a p-n junction is
crucial. The base unit of many semiconductor devices is a semiconductor
body, in which two different dopants directly adjoin one another. This is
called a p-n junction if a p-doped area merges into an n-doped area within
the same lattice.
In a simple example we assume that - in silicon - both dopants are of
the same magnitude and merge together abruptly. Figure 4.1 may clarify
this behaviour.

Figure 4.1 Doping and concentration distribution of a symmetrical p-n


junction in thermal equilibrium

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

If we consider the behaviour of a p-n junction at room temperature, we


know almost all of the donors and acceptors are ionised. We can
approximate N; w N A = p p and A$ = ND = n, where
p , is the hole concentration in the p-neutral area, and
n, is the electron concentration in the n-neutral area.
Thermally generated charge carriers can be ignored in this context.
Owing to the thermal equilibrium between pair creation and
recombination, np = nf. Therefore, the concentration of electrons in the p-
neutral region is np = lo4 and in the n-neutral region the number of
holes is p , =lo4 ~ m - ~ .
The freely moving charge carriers will not follow the abrupt change in
concentration from N A to ND. Rather, the carriers will diffuse due to the
difference in concentration, i.e. the holes from the p region will move into
the n region, and the electrons from the n area will move into the p region.
Diffusion currents will arise. The ionised acceptors and donors, which are
no longer electrically compensated, remain behind as fixed space charges
(Figure 4.1 above). Negative space charges will arise on the left-hand side
in the p region and positive space charges arise on the right-hand side in
the n region. Correspondingly - as occurs in a plate capacitor - an electric
field is created at the p-n junction, which is directed so that it drives the
diffusing charge carriers in the opposite direction to the diffusion. This
process continues until an equilibrium is created, or in other words until the
diffusion flow is compensated by a field current of equal magnitude. An
(extremely large) internal electric field exists - even if both sides of the
semiconductor are grounded.
Three questions remain to be answered:
1. How large is this electric field?
2. What is the distribution of the electric voltage and of the electric field?
3. What is the capacity of this p-n junction?

4.2.1 Potential Difference

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

-d -q --- D-n dn 1 (4.2.3)


dx p, n dx

Simplifying, using Einstein's formula (3.2.23), we find that

*
dx
kTdn 1
=---
q n d x
(4.2.4)

This equation can be integrated straight away. The potential difference is


found to be

(4.2.5)

where UD is the diffusion voltage. U, is defined as U, = kT/q (thermal


voltage), approximately 25.9 mV at 300 K.
If we also introduce np = nf/NAand n, N,, we find that

U, = U, ln(NDNA/ni2) (4.2.6)

In our case where ND and NA = 10l6 cm-3 diffusion potential is


approximately 0.72 V for silicon at 300 K .
We have used classical methods for this calculation. We now
demonstrate the much more elegant method for determining the influences
of potential using Figure 4.2. In a p-n junction in thermal equilibrium the
Fermi level must be of the same magnitude in both regions. If this were
not the case, then we would have a perpetual motion engine.
It is thus clear that q x U, is equal to the energy of the band gap minus
the two respective distances of the Fermi level from the corresponding
band edges, i.e.

qUD = E g - E , -E2 (4.2.7)

and where
The p n Junction 53

Figure 4.2 The position of the Fermi level in a p-n junction

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)

and since niz = NaVexp(-E,/kT), it follows that

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

4.2.2 Electric Field and Electr,ic Potential


We now know the functional relationship between the concentration of
charge caniers and voltage levels. The local distribution of voltage and
field can be determined using Poisson’s equation.
To obtain the density of space charge, we again put in space charges

-
dE = - * - Q (4.2.11)
dx du* EE,

and thus

(4.2.12)

The analytical solution of this equation is not possible in general form.


We therefore use an approximation, which was suggested by Schottky as
early as 1942 [l].According to this, in the case of the abrupt p-n junction
observed here, and under the given concentrations, we can disregard at
room temperature the concentrations of n and p compared to the fixed
charges. We further introduce sharp limits to the ‘fluid’ limits of the space
charge region and divide the zone into the familiar two sections (Figure
4.1). In the region x, x < 0, the p region, the density of volume charge is
solely determined by the acceptors NA- and similarly in the n region,
0 < x < x, the density of volume charge is determined by the concentration
of donors ND+. In the other regions x < x, and x > x, the concentrations of
the respective charge carriers are constant. We find that for the space
charge region on the p side

dE = - -
- Ni (4.2.13)
dx EO

and for the n side

d E -- L N ; (4.2.14)
dx EE,
Outside these zones dEldx = 0.
The p n Junction 55

By integration - and taking into account the boundary conditions


Ex=,= 0 and Ex, = 0 - we obtain the following paths for the electricfield
In the p region of the space charge region

9 N*- (4.2.15)
E ( x ) = - -( x - X I )
€0

and in the n region of the space charge region

(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

NA-x, = Nix, (4.2.17)

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

I We note that x, is negative.


56 Crystalline Silicon Solar Cells

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

The distribution of the field strength and voltage are represented in


Figure 4.3.

Figure 4.3 Field and potential distribution in a p-n junction

Outside the space charge region the potential is as follows:


The p-n Junction 57

qNA- 2
vx-= - - xI p region
CEO
(4.2.21)
- qND+ 2
vx+- + - x, n region
Eo

4.2.3 Space Charge Region Width and Capacitance

To determine the width of the space charge region we introduce a potential


difference between x, and x, and find that

U,,= -
4 (N,,x: -NAx,') (4.2.22)
2EEo

we first substitute x, in accordance with formula (4.2.17) with

(4.2.23)

and considering the sign we find that

(4.2.24)

For later consideration of the dependency of the p-n junction on an


externally applied voltage UAwe replace U, with U, minus UA and thus
find that for x,

we also calculate
58 Crystalline Silicon Solar Cells

(4.2.26)

and it holds for the space charge region width W = xr + x, that

(4.2.27 )

The peak electric field is found to be

-1
UD-UA (4.2.28)
Empx W

The peak field strength is proportional to the voltage which is applied


and inversely proportional to the width of the space charge region.
The p-n junction can, as described above, be viewed as a plate
capacitor. Two different fixed space charges exist, which must be of equal
magnitude on both sides. Thus the charge is

If we put in these values for x, and x, as in equations (4.2.25) and


( 4 . 2 . 2 6 ) we find that

(4.2.30 )
Q

and thus for the capacitance C = dQ/dU

(4.2.31)

Solving equation for UD- UAwe find that


The p n Junction 59

(4.2.32)

Because in practice the doping of a p-n junction is markedly


unsymmetrical in both semiconductor devices and solar cells, it is clear that
by measuring the space charge capacitance in relation to U, - the external
voltage - the dopant concentration (i.e. the specific resistance) of the
weakly doped side can be determined.

Figure 4.4 Dopant profile and concentration distribution in a symmetrical p-n


junction in the conducting state

4.3 THE BIASED p-n JUNCTION

If we now connect an electric voltage UAwith the positive terminal to the


p-doped side and the negative terminal to the n-doped side, we thus reduce
60 Crystalline Silicon Solar Cells

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.

4.3.1 The p-n Junction with Low Recombination and Weak


Injection

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

4.3.2 Forward Current Characteristic and Saturation


Cu rrent
To determine the current we first find the increase in concentration of
charge carriers at the space charge limits x, and x,. Under the above
assumptions of low recombination and low injection, the concentration
gradient within the space charge region hardly changes. However, the
concentration of charge carriers within the space charge region in our case
(Figure 4.1) must fall by 12 orders of magnitude so that the weak
additional concentration hardly alters the total gradient. This means that the
potential distribution behaves in the same way as in an ‘unbiased p-n
junction’. The concentration distribution and potential are connected by an
exponential function here. Therefore this is still true in the case of a biased
p-n junction, but now the potential difference is reduced by UA. This
means that the concentrations of minority carriers at the points x, and x,
increase by the factor exp(U,lU,). Therefore

(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)

and the designation - dcp I dx = E


62 Crystalline Silicon Solar Cells

(4.3.5)

If we now integrate from x, to x, and consider that the voltage at the


boundaries is 0 and (U,,
minus UA), we find where UT= kT/q

Pn, =Ppexp - <qJq (4.3.7)

we find the concentration of holes in the biased state at point x, is again

, ,P,
P ~ ( ~= ) ,~ X (PUA 1 UT 1 (4.3.8)

So whst is the diffusion current density of the injected charge carriers?


For holes it is true that

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

As it is also true that


The p-n Junction 63

-
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

we can write the differential equation as

(4.52)

The general solution for this differential equation is

A p = A exp(xlLp) + B exp( - x l L p ) 4.53)

Since we take as a basis an infinitely elongated area n and p, it holds that


Ap(.o) = 0. This yields A = 0.
The constant B can be determined by the boundary conditions

Pn(x,,) = PnO exp ('A' T') (4.3.17)

After some manipulation we find that

P,@> =pn0+pno(exp(U,/U,) - 1 ) exp(-X/Lp) (4.3.18)


For the diffusion flow density of holes

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

Similarly, for the electron current density we find that

qDn ' n o
In = -(exp(UA/UT)- 1 ) exp(-x/Ln) (4.3.21)
Ln

We have determined this current density at the limits of the space


charge region. To find the total current density we must determine the
current at the point x = 0. We assume for this purpose that within the space
charge region the injected currents are constant at the first approximation,
and there is no change in the current. We can then equate the current
densities at the edges of the space charge region to the current density at
the point x = 0 and thus find the total current density as the sum of the
two.

'total = p' +In


(4.3.22)

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

p,, =ni'lND resp. npo = n i2 INA (4.3.24)

we find that for I,

(4.3.25)

The current density at a p-n junction - in a diode - is thus found to be

I = I , (expUA/UT - 1 ) (4.3.26)
The p-n Junction 65

References

[l] Schottky W., Zeitschriyt fur Physik 118, 1942, p. 23


[2] Shockley W., Bell Syst. Techn. 28, 1949, p. 435
5
The Physics of Solar Cells

5.1 THE ILLUMINATED INFINITE p-n JUNCTION

For a simple theoretical treatment, we once again consider a crystal with a


p-n junction, in which the two doped regions are infinitely extended. (In
practice a crystal thickness which is very large compared to the diffusion
length of the charge carrier is sufficient).
We once again start from Figure 4.1. We now illuminate the entire
crystal equally, in such a way that there is a homogeneous generation of
charge carrier pairs in the crystal. This can be achieved in practice if the
silicon crystal is exposed to infrared light near to the band edge. Then the
absorption coefficient of the light is very small, or in other words the
absorption is weak and thus almost equal throughout the crystal.
Using the continuity equation under these assumptions, we find a similar
differential equation to (4.3.12). However, in this case we must also take
generation into account.
For holes as the minority carriers on the n-side, it holds that

(5.1.1)

and also

(5.1.2)
68 Crystalline Silicon Solar Cells

Since generation is assumed to be constant and L, is also a constant, a


similar solution applies here as for (4.3.12), i.e.

A p = G T +~ A exp(x/Lp) + B exp(-xILp) (5.1.3)

With the boundary conditions of an infinite p-n junction we find that


for the hole current density

Zp = -(exp(U/U,)-
Dp P n o 1 ) exp( - x/Lp) -qGLpexp( -xILp) (5.1.4)
LP

and similarly for the electron current density in the p region

I, = -(exp(U/U,)
q’n npo - l)exp( - x/L,) -qGLnexp( -xILn) (5.1.5)
Ln

If we again disregard recombination in the space charge region and add


the two above current densities (at the point where x = 0) to the current
density from the space charge region, where

IR = q G W (5.1.6)

then the current density in the solar cell is

I =Z,(exp[U/U,] - 1) -qG(Ln +Lp + W ) (5.1.7)

If we designate q x G x (Ln+Lp+W) with ZL (the current density


generated by the light), we find that

I =Zo(exp[U/U,] -I)-IL (5.1.8)

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

Figure 5.1 Charge carrier distribution in an illuminated infinite solar cell

5.1.1 The Current-Voltage Characteristic of an Infinite Solar


Cell

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.

5. I.1.I Short Circuit Current

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

Figure 5.2 Voltage-current characteristic of an infinite solar cell

magnitude of the current, disregarding all losses in the cell, with AM1.5
radiation, can reach a peak of 44 mA/cmZ.

5. I . I .2 Open Circuit Voltage

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

V,, = U, In (1,/Io + 1 ) (5.1.9)

Since even at very low current densities we can disregard the value 1
compared with ZL/Ioand IL= I,, , we find that for V,,

Voc = UT In ( L110) (5.1.10)

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

open circuit voltage and thus efficiency is basically a question of reducing


the saturation current. From equation (4.3.25), following (5.2.13) we find
that for small dark current values the following three conditions must be
fulfilled:
diffusion length of minority charge carriers as high as possible,
doping concentration NA,No high, and
crystal volume as low as possible (thin wafer).
The first two parameters are linked to each other to some degree.
Considerations about optimal parameter combinations are dealt with in
Chapter 6.

5.1.1.3 Fill Factor

As always in electrical engineering, optimal power output requires a


suitable load resistor I?,, which corresponds to the ratio V,/I, (Figure 5.2).
V, and I, are, by definition, the voltage and current at the optimal
operating point and P , is the maximum achievable power output. We now
form the ratio of peak output (V, I,) to the variable (VocIsc) and call this
ratio the fill factor FF of a solar cell:

FF = V , I , I VocIsc (5.1.1 1)

The fill factor is so named because when graphically represented it


indicates how much area underneath the I-V characteristic is filled by the
rectangle V , I, in relation to the rectangle VocIsc. The fill factor normally
lies in the range 0.75 to 0.85.

5.1.1.4 Efficiency

The efficiency of a solar cell is defined as the ratio of the photovoltaically


generated electric output of the cell to the luminous power falling on it:

(5.1.12)

The current record for efficiency is held by a solar cell made of


monocrystalline silicon using very complex technology at approximately
23-24% (area 2x2 cm', radiation AM1 3.Commercially produced cells
currently have an efficiency of between 14% and 16%. In individual
special cases large area cells (and modules) have been produced with 17%
72 Crystalline Silicon Solar Cells

-19%. The significance of high efficiency for reducing the cost of a


complete solar array will be described in Chapter 6.
In general, the efficiency of photovoltaic energy conversion is very
limited for physical reasons. Around 24% of solar radiation has such a long
wavelength that it is not absorbed. A further 33% is lost as heat, as the
excess photon energy (in the short wavelength region) is converted into
heat. Further losses of approximately 15-20% occur because the cell
voltage only reaches around 70% of the value which corresponds to the
energy gap.

5.2 REAL SOLAR CELLS

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

Figure 5.3 Cross-section of a real silicon solar cell


The Physics of Solar Cells 73

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 Photocurrents in a Real Solar Cell

To calculate photocurrents we assume that the light enters on the emitter


side. The calculation is first made for monochromatic light. In the case of
the illumination by a spectrum we must integrate over all wavelength
regions of this spectrum. The integration limits for this are kin, the
smallest occurring wavelength, and ,,A the wavelength corresponding to
the energy of the semiconductor band gap, as longer wavelengths are not
absorbed. For sunlight h,, is around 0.3 pm, as at shorter wavelengths
there is almost no radiation, and in the case of silicon h,, z 1.11 pm.
We now need to calculate the current densities in the three regions,
emitter [El,space charge region [SCR],and base [B], so that

(5.2.1)

and the total current density is

(5.2.2)

5.2.I . I Photocurrent from the Base

Because in general the base is homogeneously doped, and a low level of


injection is present with normal solar radiation, a precise solution can be
found for the photocurrent in the base (in the short circuit case). The
applicable differential equation for the electrons is thus

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

In the case of monochromatic radiation this generation of charge carrier


pairs at distance x is

G(x) = a F ( l - R r ) e x p ( - a x ) (5.2.5)

where a is known to be the absorption coefficient of light in the


semiconductor, R , is the reflection coefficient and F is the photon flux (the
radiation power) supplied to the surface of the solar cell. These three
variables are all dependent upon wavelength. We thus find for equation
(5.2.3)

7
Dn d ’(An) + a F ( l - R , ) e x p ( - a x ) - -An = O (5.2.6)
‘n

The general solution for this is

a F ( l -R,)rn
An(x) =Acosh(x/L,) + Bsinh(x/L,) (5.2.7)
a’L,2 - 1

where

(5.2.8)

To determine the constants we apply the following two boundary


conditions, i.e. we take into account that recombination takes place at the
surface. The surface recombination velocity, measured in cm/s, is
designated S,.
SnAn = -Dn- d(An) at x=H
dx (5.2.9)
An = O at x qj+W
The Physics of Solar Cells 75

After some manipulation we find that

+ aLn exp(- aH‘)


X aLn - / \ / \

Lsinh
DnLn
-
[ y,]
+cosh -
(5.2.10)

The bracketed expression is called the geometry factor (see also [l]).

5.2.1.2 Photocurrent from the Emitter

If the emitter is homogeneously doped, then the solution for the


photoelectric current from the emitter is found to be the same as for the
base:

-
sPLP
+ a L p -exp(-axj)
X DP

However, homogeneous doping hardly ever occurs in practice. For a


diffused emitter, high dopant effects such as band gap narrowing and the
76 Crystalline Silicon Solar Cells

dead layer’ must be taken into account.


The dopant profile also has the consequence that lifetime and the
diffusion constant depend upon doping. This is described in further detail
in Chapter 6.

5.2.1.3 Photocurrent from the Space Charge Region

This photocurrent is very easily determined, since the charge carriers


generated in this region are drawn out of this area very quickly due to the
electric field. They virtually cannot recombine and therefore contribute
entirely to the current. This is found to be

I,,,(k) = q F ( l - R f ) e x p ( - a x , ) ( 1 - e x p ( - a W ) ) (5.2.12)

5.2.2 Saturation Currents in a Real Solar Cell

To calculate the saturation current density of a real cell we must once again
take into account the recombination effect at the surface.

5.2.2.1 Saturation Current from the Base

From a similar calculation to that for the photocurrent we find the


following relationship:

(5.2.13)

where G, is a geometry factor which reads

cosh(H’lL,) + (SJS,) sinh(H’lL,) (5.2.14)


G, =
(S,/S,) cosh(H’lL,) + sinh(H’/L,)

where S, = D,/Ln, the recombination velocity in the crystal.

’ 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.

10’2 10-1 100


HlLn
Figure 5.4 Geometry factor as a function of the base thicknessldiffusion
length relationship

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

thus efficiency in thin solar cells made of silicon [3],[4].

5.2.2.2 Saturation Current from the Emitter

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

A solution to this problem is given in the literature [ 5 ] using multiple


integration.
We can demonstrate the influence of surface concentration and the
The Physics of Solar Cells 79

surface recombination rate on the saturation current of the emitter by


looking at Figure 5 . 5 . The n’-doped emitter has a Gaussian type dopant
profile, its penetration depth is 1 pm.
We find from this, that for low saturation current - and thus high open
circuit voltages - two requirements must be fulfilled:
a surface recombination velocity less than lo3 cm/s, and
a surface concentration less than 2 ~ 1 0cm”.
’~
At high recombination rates (1 0’-l O6 cm/s) the surface concentration
should be approximately lozo ~ m - Detailed
~. investigations are made in
Chapter 6.

5.2.3 Ohmic Resistance in Real Solar Cells

Ohmic resistances also influence the efficiency of solar cells. We divide


these resistances into shunt resistance and series resistance.

5.2.3.1 Shunt Resistance (RJ

The magnitude of this resistance is determined by leaking currents along


the edges of the solar cell. Point defects in the p-n junction can also lead
to low parallel resistance. Such defects can be interruptions of the p-n
junction, which originate during the diffusion of the n emitter, impurity
particles have hindered diffusion at certain points. The base material can
also be in electrical contact with the finger system at some points, thus
creating a short circuit (if only a small one).

5.2.3.2 Series Resistance (R&

This resistance has the following components:


a contact resistance metal-semiconductor,
ohmic resistance in the metal contacts,
ohmic resistance in the semiconductor material.
Further considerations follow in Chapter 6.

5.2.4 The Two Diode Model


The simple exponential relationship between voltage and current density as
given by (4.3.26) is almost never observed at low voltages in the forward
direction [0.1-0.5 V] in real solar cell p-n junctions. For conventional
80 Crystalline Silicon Solar Cells

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)

We make the simplifying assumption that the following apply:


The impurity level lies exactly at the intrinsic Fermi level, i.e. roughly
in the mid-band region and it is distributed completely uniformly in the
space charge region.
At both sides of the p-n junction dopant level, lifetime and mobility are
of equal magnitude.
Then n , and p , are equal to n, [equations (3.4.6) and (3.4.7)]. If we first
consider the case where we apply a reverse voltage, then it becomes clear
that both types of charge carrier are very quickly ‘washed out’ due to the
high electric field in the space charge region, so that their densities become
small compared with n,. The equation (5.2.15) is then reduced to a
generation rate of

- R =ni/2r, (5.2.16)

where we also define T~,= T~,= T,.


However, if a voltage is applied in the forward direction, then the
recombination is slightly different. In the middle of the space charge region
the concentration of n and p must be equal. Since

n p = niz exp(U,/U,) (5.2.17)

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

and the recombination rate decreases - without giving further explanation


- (more detail in [ 6 ] ) exponentially on either side of the space charge
barrier, with a characteristic length of

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)

Precise calculations show that a multiplication by xl2 is required, giving

(5.2.22)

The factor before the exp function is designated IOz and now the diode
equation can be expanded to

I = I,, exp U,lU, + Io2 exp UA/2U , (5.2.23)

5.2.4.1 Equivalent Circuit of a R e d Solar Cell

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)

The corresponding equivalent circuit diagram is shown in Figure 5 . 6 .


Theoretically, we should find that n , = l and n2=2. In practice, however,
considerable deviations have been determined.
82 Crystalline Silicon Solar Cells

Figure 5.6 Equivalent circuit diagram for the two diode model of a real solar
cell

After some manipulation [6],[7], we can expand formula (5.2.22) to the


very complex equation

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

Figure 5.7 f(b) as a function of voltage, parameter T,,,, / T , ~[7]

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.

5.2.4.2 The Influence of Ohmic Resistances

The influence of ohmic resistances on solar cell parameters are shown in


Figure 5.9 and Figure 5.10.
Figure 5.9 shows the influence of shunt or parallel resistance. With
decreasing resistance the fill factor FF decreases in the first approximation
and only at very small values (below 100 ncm2 ) does the open circuit
voltage also decrease. Short circuit current is not influenced by parallel
84 Crystalline Silicon Solar Cells

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

resistance. As the shunt resistance in monocrystalline cells is greater than


1000 SZcm', we barely need to consider its influence. In polycrystalline
cells, on the other hand, due to internal shunt resistance at the grain
boundaries we should expect the parallel resistance to have an effect.
Figure 5.10 shows the influence of series resistance. Here too it is
primarily the fill factor that is influenced by increasing resistance. Only at
high (normally not possible) values does the short circuit current fall off.
To obtain the highest efficiency possible it is imperative that series
resistance is kept as low as possible (I 0.5 Clcm*).
The Physics of Solar Cells 85

0.1 0.2 0.4


-u
0.5
[Volt]
0.6 0.7

- -20 -

Figure 5.9 The influence of shunt resistance on solar cell parameters

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

Figure 5.10 The influence of series resistance on solar cell parameters


86 Crystalline Silicon Solar Cells

References

Sze S. M. Physics of Semiconductor Devices, 2nd Edn, 1981, p. 802


Aberle A,, Thesis, Univ. Freiburg, 1991
Knobloch J., Von B. and Goetzberger A., Proc. of th 6th PVSEC, London,
1985, p. 285
Goetzberger A,, Knobloch J. and Von B., Proc. of the 1st PVSEC,
Kobe, Japan, 1984, p. 517
Park S. S, Neugroschel A. and Lindholm F. A,, IEEE-TED 33, 1986, p 240
Sah Ch. T., Noyce R. N. and Shockley W., Proc. of the IRE 45, 1957, 1228
Chawla B. R. and Gummel H. K., ZEEE - TED 18, 1971, p. 178
Choo S. C., Solid State Electron. 11, 1968, p. 1069
Sah Ch.T., Noyce R. N. and Shockley W., Proc. of the IRE 45, 1957,
p. 1228
Baier J., Thesis, Univ. Freiburg, 1992
Beier J. and Von B., Proc. of the 23th IEEE-PVSC, Louisville, Kentucky,
1993, p. 321
Robinson S. J., Wenham S. R. et al., J. Appl. Phys. 78, 1995, p. 4746
High Efficiency Solar Cells

6.1 THE SIGNIFICANCE OF HIGH EFFICIENCY

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.

Figure 6.1 The cost breakdown of a solar array

The manufacturing costs of a solar array - power related costs such as


inverters and accumulators are not considered here - made up of crystalline
solar cells can be divided into four main categories. These are costs for
silicon wafers,
process technology,
module manufacturing, and
88 Crystalline Silicon Solar Cells

land, land preparation, electrical connections, etc.


The percentage cost breakdown shown in Figure 6.1 applies
approximately for large solar arrays.
All costs in the first approximation are proportional to area, and thus for
a solar array roughly inversely proportional to efficiency. Many writers
have dealt with this subject in detail [1]-[5]. High efficiency solar cells
require high grade silicon and costly technology. Cost estimates show,
however, that despite the increased cell cost, an increase in efficiency of
approximately 40% (relative) will reduce the cost of a large area solar array
by approximately 20% [6]-[8].
Looking at the matter from another point of view, we can calculate the
permissible module costs at different efficiencies for the desired cost of
electricity (planning target). This relationship is shown in Figure 6.2 [9].

150 I

Module efficiency 1
-
N

E 100 -
-tit
L

8
8
Q)
-
3
I
50

0 1

Figure 6.2 Permissible module costs as a function of given electricity costs,


calculated for different efficiencies [ 91

According to this, given a desired cost of 6 centskWh, an increase of


efficiency from 10% to 15% makes a module three times as expensive
permissible.
Since the 1980s, therefore, the majority of all research and development
work in the photovoltaic sector has concentrated on driving the efficiency
level as high as possible.
High Eflciency Solar Cells 89

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

Figure 6.3 Loss mechanisms in a solar cell

Optical losses reduce the level of solar radiation by reflection and


shadowing of the light as well as inadequate absorption of long wavelength
radiation, whereas electrical losses have a detrimental effect on both the
current and, above all, the voltage of a solar cell.
90 Crystalline Silicon Solar Cells

The final type of loss is based on semiconductor physics and


technology. Minimising this is therefore at the centre of work into
achieving high efficiency solar cells.
We begin by investigating electrical losses, and specifically the
influences related to semiconductor physics, i.e. losses by recombination,
and we investigate ohmic losses in the second section. We conclude by
considering optical losses and procedures for their reduction.

6.2 ELECTRICAL LOSSES

6.2.1 Recombination Losses

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.

6.2.1.1 Recombination Losses in the Base

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 - -

For very high photocurrents the surface recombination rate S, must be


less than 100 cm/s.
If the diffusion length L , falls below the value of the crystal thickness,
then the photocurrent will drop sharply.
If, however, the diffusion length L , is less than half the crystal
thickness, then the short circuit current I,,, although reduced, will be
almost independent of the surface recombination velocity S, .
Figure 6.5 shows the dependency of open circuit voltage V,, on
diffusion length L,, again with S, being a parameter. This representation
yields the following information:
For high values of S,, (10’-106 cm/s) diffusion lengths higher than the
crystal thickness are of no advantage, V,, achieves a saturation value.
For high open circuit voltages, S, must be <lo2 cm/s.’
Unlike a short circuit current, open circuit voltage does not approach
saturation as S, becomes smaller, but rises continuously.

’ We note that even at small values S, is still strongly dependent upon


carrier concentration, i.e. on the level of sunlight [lo].
92 Crystalline Silicon Solar Cells

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.

6.2.1.1.1 The Back Surface Field


The reduction of reverse side recombination is, however, hindered by
various constraints.
Since the back of a normal solar cell is completely metal coated, it goes
without saying that there is a high surface recombination velocity (Ohmic
metal-semiconductor contacts require high recombination velocities).
One familiar technical measure to improve this situation is the creation
of a highly doped p'-zone on the back surface of the solar cell base. This
p+-p junction (high-low-junction) is also known as a 'back surface field'
(BSF). Owing to the electric field which is created, less of the minority
High Efficiency Solar Cells 93

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

660 - Gauss profile S, = 1xlO6 cmls


d

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

junction to the back surface. Their calculations showed that in comparison


with a homogeneously doped base, it was possible to reduce the saturation
current by a factor of 20. Technological realisation is however extremely
costly, and to our knowledge has never occurred.
Recently, other ways have been found to reduce S,. The solution is to
coat a significant section of the back surface with a thermally generated
SiO, film, thus electrically passivating it. For the bonding of the cell, this
layer contains a number of holes of fixed distance and diameter, whose
total area is only approximately 1%-4% of the total area.
Metal
Si02
2
1 1 ' n+ emitter
Base

Si 02

Metal
Figure 6.7 Schematic structure of a high efficiency solar cell with a local
B SF

Figure 6.7shows schematically the cross-section of this type of cell. For


a good ohmic contact we also require high doping p+ under the contact
point, which also functions as a local BSF. We now have an effective
surface recombination rate which is composed of the recombination of
charge carriers at the Si-SiO, barrier and the - small percentage -
contribution of the metal area.
SiO, layers are of course also used for the passivation of the emitter.
Therefore, we now therefore examine some of their main characteristics.

6.2.1.1.2 SiO, Layer


The SiO, layer has played a decisive role in almost all silicon
semiconductor devices right from the start. Its relatively simple
manufacturing process by high temperature treatment under oxygen, but
predominantly the masking behaviour of the SiO, toward dopants and its
passivating effect, contributed decisively to making silicon the basic
material for most semiconductor devices. There are countless investigations,
mostly for use in IC or MOS structures. A comprehensive overview is
High Efficiency Solar Cells 95

provided by Nicollian and Brews [13]. Fundamental work on this theme


has also been carried out by Goetzberger [14],[15].
The effect of the SiO, layer can be described as follows. The abrupt
ending of the crystal at the surface leads to a density of defects of
approximately 10’’ cm-’, which are traps in the forbidden band, thus giving
rise to a high recombination rate. These traps are largely saturated by the
SiO, layer and thus become ineffective. By additional annealing, e.g. in
forming gas, the trap density can be reduced to values between 10’’ and
10” ern-', thus achieving surface recombination rates of 10-100 cm/s.
There are currently, for solar cell production, no better alternatives to
this passivating method. For further information, see Sze [16].

6.2.1.2 Photocurrent and Saturation Current from the Emitter

We can make the following statements about the photocurrent in the


emitter of a high efficiency solar cell, As the emitter is very thin, with a
penetration depth of a few tenths pm, and as the surface concentration of
the dopant concentration in high effrciency cells is only some 10’’ cm”, the
diffusion length of the minority carriers (holes) created here is several
times greater than the thickness of the emitter. They do not recombine in
the emitter, either recombining at the surface or travelling to the p-n
junction as photocurrent. This combined effect is enhanced at the p-n
junction by the electric field, which is caused by the doping concentration
gradient. This type of emitter is called transparenf. When considering the
photocurrent we can therefore restrict ourselves to the influence of the
surface recombination rate Spat the emitter surface.’
For an emitter with a surface concentration of 1x 10’’ cm-3- required for
low saturation current, as shown in Figure 5 . 5 - and a penetration depth of
x=OS pm, Figure 6.8 shows the influence of Sp on photocurrent. To
ihustrate this effect we have selected the term ‘Spectral Response’ (see
Chapter 9). The photocurrent is determined for radiation with light of
different wavelengths. Since the short wavelength light is predominantly
absorbed in the emitter, the current that is created in this region can show
very clearly the influence of Sp.This shows that a value Sp of around
lo3 cm/s is sufficiently low for an optimal photocurrent.
The saturation current density of an emitter depends on many
p armeters :

An emitter with the above penetration depth absorbs approximately 10%


of AM1.5 radiation.
96 Crystalline Silicon Solar Cells

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)

the dopant profile,


the surface doping concentration,
the penetration depth of the emitter, and
the surface recombination velocity.
The calculations for this were carried out by Aberle [lo] and
Ruckteschler [ 171, based upon the model of serial development of multiple
integrals suggested by Park [18]. The calculation has been carried out for
a Gaussian doping profile, since current diffusion technology gives high
efficiency solar cells this profile (see Chapter 7). This calculation takes into
account the band gap narrowing (reduction of the band gap at high doping)
and the dopant dependent mobility of charge carriers. For a real solar cell
we must also take into account the recombination under the metal coated
finger.
Figure 6.9 shows this relation~hip.~ From this representation we see that:
For all values where Sp>103cm/s the dark current density is at a
minimum.

Figure 6.9 is identical to Figure 5.5 as we wish to explain this in more


detail here.
High Eflciency Solar Cells 97

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

For all values where Sp>103cm/s the dark current density is at a


minimum.
S, values <lo3 cm/s are sufficient (as for the photocurrent) to achieve an
optimally low dark current density.
The lowest values for the dark current density are achieved only by the
combination N, 12x 10’’ ~ r n and
- ~ Sp<lo3 cm/s.
If we now consider the role of emitter thickness, Figure 6.10 shows that
in the case of a surface passivated with SiO, the emitter depth must be as
small as possible. On the other hand, at the desired surface concentration
of < 2x10” cm” the emitter transverse resistance between the contact
fingers is very high, thus giving rise to considerable ohmic resistance
losses. A workable compromise is a penetration depth of 0.3 pm.As shown
in Figure 6.11, a penetration depth of 2 pm is required under the metal
coated surface of the contact fingers, whereby the surface concentration
should be approximately 1x1OZo~ m - ~ .
98 Crystalline Silicon Solar Cells

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)

Emitter penetration depth xj [pm]


Figure 6.10 Saturation current density in a passivated emitter as a function of
emitter depth xj, where the surface concentration is the parameter

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

6.2.1.3 The Influence of Base Doping


According to formula (5.2.13), saturation current density in the base is
inversely proportional to the doping concentration. This should therefore be
as high as possible. However, the lifetime of minority charge carriers
decreases with higher doping (formula (3.4.17)). In this formula T~ is
assumed to be 400 ps. Recent results show that this value can also be
much higher. However, as this is usually not achieved due to material
quality and subsequent technological processes, we have based the
following discussion on a value of 200 ps.

' 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.

Finger LDD emitter


SiO,

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

Furthermore, for the purposes of clarity we have assumed no ohmic


resistance losses.
Other selected parameters for this calculation are:
emitter penetration depth 550.2 pm,
back surface S,, = 1000 cmh, and
2% shadowing by the finger grid.
Figure 6.13 shows the relationship between cell thickness, dopant
concentration and efficiency.
From this we find that for a 200 pm thick solar cell the optimal base
doping is approximately 4x 10l6cm” resistivity 0.4 ncm. However, if we
consider that at higher basic doping the carrier lifetime is also reduced by
impurity levels that lie outside the middle of the forbidden band (equation
(3.4.14) and Figure 3.20), it is advisable to select a lower basic doping
level. This also goes a long way towards compensating for the influence of
material manufacturing tolerances for resistivities of *15 ‘30.
The results of Section 6.2.1 for recombination losses are as follows:

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

Cell thickness = 100,200,400 pm


2350 - Sn = IOOO cm/s -
2275 -

Dopant concentration (cm-3)

Figure 6.13 Efficiency of a n’p-Si solar cell as a function of doping N , of the


base, with cell thickness as a parameter
High Efficiency Solar Cells IOI

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.

6.2.I . 4 Recombination in the Space Charge Region

In Chapter 5 we showed the dependence of the recombination current in


the space charge region under simplifying assumptions.
According to this

I IL=40mA/cm* j

10-10 10-9 10-8 10-7 10-6 105 104


[A/C+l
Figure 6.14 Dependency of the fill factor on the saturation currents I,, and I,,
102 Crystalline Silicon Solar Cells

(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.

6.2.2 Ohmic Resistance Losses

Figure 6.15 shows the ohmic series resistances of a solar cell.

Figure 6.15 Series resistance in a solar cell

The individual resistances are:


R, the metal-semiconductor-contact on total back surface,
R2 the semiconductor material (base),
R3 the emitter between two grid fingers,
R4 the metal-semiconductor-contact on the grid finger,
High Efficiency Solar Cells

R5 the grid finger, and


R6 the collection bus.

6.2.2.1 Contact Resistance Metal-Semiconductor

To determine the contact resistances R , and R, we shall examine the


metal-semiconductor contact in more detail. The theory explaining its
physical behaviour was worked out by Schottky [19] as early as 1939 (the
quick switching metal-semiconductor contact diode was named the
‘Schottky diode’ in his honour). With the discovery of the transistor [20]
contact technology become a very important branch of semiconductor
technology. In many cases, particularly for high performance components,
these contacts must also fulfil additional conditions. Owing to the very high
current load they must have an extremely low contact resistance, and also
tolerate extreme thermal shock stress.
In this section, we deal with the behaviour of an ‘ohmic’ contact, i.e.
the functional relationship between the current and voltage drop in a
metal-semiconductor contact should be linear, or at least quasi-linear and
the contact resistance should be low enough that the lost energy is small in
comparison with other losses in a semiconductor device. Thermal fatigue
plays only a minor role here.

6.2.2.1.1 Schottky Contact


If a metal is brought into contact with a pure semiconductor surface, a
potential banier similar to that in a p-n junction in a semiconductor is
created, fulfilling the requirement for thermal equilibrium between different
electron concentrations. Figure 6.16 clarifies this state.
It is true (further explanation in [21]) for a metal-n-semiconductor
contact

Figure 6.16 Potential barrier between metal and semiconductor


104 Crystalline Silicon Solar Cells

=qPm 4.1 (6.2.2)

and for a metal-p-semiconductor contact

(6.2.3)

is the barrier height of the metal-semiconductor contact,


is the work function of the metal, i.e. the energy
difference between Fermi level and vacuum level, and
qxs is the work function of the semiconductor; energy
difference between the edge of the conduction band and
the vacuum.
According to formulae (6.2.2) and (6.2.3) the barrier height should be
directly proportional to the work function of the metal. In reality we find
a very much lower dependency. In Figure 6.17 the experimentally
determined barrier heights applied to n-silicon are plotted as a function of
the work function of the metal [21].

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]

For the barrier height metal-n-silicon we find the approximation line

a,, z 0 . 2 q - 0.1 (6.2.4)


High Efjiciency Solar Cells 105

6.2.2.1.2 Ohmic Metal-Semiconductor Contact


How can we make a naturally rectifying contact show ohmic behaviour?
The basic principle rests upon a tunnelling process [21]. If a metal is
deposited directly onto a highly doped semiconductor, then a narrow space
charge region is created which electrons can ‘tunnel through’. Figure 6.18
demonstrates this effect.

Low barrier height

High doping
Figure 6.18 Charge transfer with ohmic contact: (a) tunnel effect,
(b) themionic effect

A further possibility for the transfer of electrons at low doping is


provided by the fact that charge transport takes place by the so-called
‘thermionic’ effect. A low barrier height and thus a metal with a low work
function [Om] is a prerequisite for this.
The specific contact resistance [Clcm2]for an n-semiconductor is found
to be as follows according to the theory [22],[23].
~. ~

For the tunnel effect:

k 4 x & 7
P, =-
qTA * h

where A* is an effective Richardson’s contact in which A * = A (m*/m,).


For the thermionic effect:

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

materials. However, for a surface concentration of approximately 1OI9 cm”


the barrier height must be < 0.5 eV. The selection of a suitable metal is
very restricted in this case however, as we saw from Figure 6.17.

6.2.2.1.3 Contact Resistance [R J of a Grid Finger

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

This behaviour can, as seen in Figure 6.21, be explained using a


resistance network. Voltage [Ul at the metallic grid finger is kept at zero,
grounded. As the metal film is some pm thick in practice, the voltage
I08 Crystalline Silicon Solar Cells

Figure 6.21 Distributed resistance network for the contact resistance


me tal-semiconduc tor

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)

where R , = FIX, is designated as the sheet resistance [measured in U O ,


ohmslsquare) (dimension Ohms). The contact resistance is then found to be

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)

Figure 6.22 represents this voltage distribution.

Contact -
X

U(X) = u0 e LT

\& \\

-X --
0
LT

Figure 6.22 Voltage distribution under the grid finger


\

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:

R, = I coth [L * IF] (6.2.10)

or where L , = (p, I Rd0.’ we find that

R, = -pc coth (6.2.11)


l*L,

Two approximate solutions are of particular interest:


110 Crystalline Silicon Solar Cells

1 . If L, 2 2L, then the value of coth nears 1 and the resistance R, is

(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.

6.2.2.2 Ohmic Losses in the Semiconductors

6.2.2.2.I Base Resistance


R, is the resistance of the solar cell base material, which in simple form is
found to be

R, = ps, D.A (6.2.14)

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.

6.2.2.2.2 Resistance in the Emitter


Figure 6.23 shows the current distribution in the emitter and the grid
fingers. The current flowing vertically from the base is diverted
horizontally within the emitter into the grid fingers.
High Eflciency Solar Cells 111

Figure 6.23 Current path in the emitter: left: side view; right: aspect

To calculate the resistance R , we proceed by calculating power loss P,


in the emitter between two fingers and dividing this power by P (since
P, = ZE2 R 3 ) , where Z, is the lateral current in the emitter. We further
assume that the current in the base of the solar cell flows homogeneously.
It is then clear that precisely half way between the fingers ( x = 0) no lateral
current will flow. We can therefore limit ourselves to Calculating one-half
of the intermediate area between two fingers. The current (Z,,,=),which
reaches the contact finger from the side, is now equal to the photocurrent
density j , multiplied by the area, from which the current is collected, i.e.

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

is equal to the sheet resistivity in W O , dR is found to be

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

It follows from this that

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.

6.2.2.3 Ohmic Losses in the Metal Contacts

6.2.2.3.1 Contact Finger Resistance


We proceed in a similar manner as for the calculation of R,. Again, 1 is the
length, L the width and u the thickness of the finger. pmctis the resistivity
of the metal. The result for R , is as before, equal to one-third of the series
resistance for the entire contact finger, i.e.

(6.25)

6.2.2.3.2 Busbar Resistance

The calculation of the resistance R, is also identical to the procedure in the


two previous sections. We must ensure that the current connection is in the
middle of the busbar (Figure 6.24). In this case, where a is thickness, L ,
the width and I, the total length of the busbar, the resistance of half the
busbar is

(6.2.26)

As we can easily calculate, if we collect the current at the end of the


busbar, the resistance R, will be four times greater than for a contact in the
middle.
The total serial resistance is found by linking the individual resistance
values R , to R, together in a suitable resistance network. If we once again
calculate all six resistances with regard to their contribution to serial
resistance R,:
Resistance R, (the resistance of the metal-semiconductor-contact on the
entire back surface) and R, (resistance of the semiconductor material
(base)) can be disregarded in all practical cases. If the contact material and
the finger width are correctly selected, then R, (the resistance of the
metal-semiconductor contact under a grid finger) also makes no significant
114 Crystalline Silicon Solar Cells

Figure 6.24 Structure of the contact grid

contribution. The resistances R, (resistance in the emitter between two grid


fingers), R, (resistance of a grid finger) and primarily R, (resistance of the
bus bar) primarily determine R,. For R, and R, a very careful compromise
must be sought between ohmic losses and shadowing losses (see
Figure 6.3 1).

6.3 OPTICAL LOSSES


Three factors are responsible for optical losses in solar cells:
The Si surface reflects 35%-50% of the light, depending upon
wavelength.
The grid structure shadows 3%-12% of the light, depending upon
design.
Absorption in silicon-indirect semiconductor-is very low in the long
wavelength sunlight range, i.e. near to the band edge. This light is
absorbed in the back surface contact without any photovoltaic effect.
Various technological measures are implemented to prevent or reduce
these losses.

6.3.1 Antireflection Processes

An antireflection effect can be achieved in two different ways. On the one


hand by a thin film of ‘antireflection coating’, and on the other hand by the
High Efficiency Solar Cells 115

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.

6.3.I . 1 Antireflection Using a Thin Coating

A reduction in reflection can be achieved by the 'optical quarter wave


length' principle. As shown in Figure 6.25, the penetrating light beam is
reflected at the barrier layer between the antireflection medium and the
silicon.

"0 Air or glass

"1 d1 Antireflection layer

"2 Silicon

Figure 6.25 Antireflection behaviour of a thin film.

Owing to continuity conditions and conservation of energy, an


electromagnetic wave undergoes a phase shift of x/2 upon entry into an
optically denser medium. If the thickness of the antireflection layer is
chosen so that the optical path, i.e. the product of refractive index and layer
thickness is equal to a quarter of the wavelength, then light of this
wavelength falling vertically is completely extinguished (destructive
interference). Written as a formula this condition reads:

n . d = -h (6.3.1)
4

According to Fresnel's formula the reflection factor is


116 Crystalline Silicon Solar Cells

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.

Reflection is at its minimum where nldl = W4.

(6.3.6)

R,, is equal to zero when

n ,2 =nOnz (6.3.7)

i.e. when
High ESficiency Solar Cells 117

-
Silicon
-

I . 1 . 1 . I . I I I " ' I ' '

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1


Wavelength (pm)
Figure 6.26 Refractive index of silicon in relation to wavelength and photon
energy

(6.3.8)

To calculate total reflection at thickness d, in relation to the wavelength,


we must consider that the refractive index of silicon changes according to
wavelength. Figure 6.26 shows this relationship.
Based on this relationship and with a reflection layer thickness such that
minimum reflection occurs where h = 0.6 pm: Figure 6.27 shows the
distribution of reflection in relation to the wavelength.

' The lowest total reflection under AM1.5is when the minimum is at
1=0.6pm.
118 Crystalline Silicon Solar Cells

-..-..-..-. Bare silicon


TiOz 70 nm
'. - - - I - - TiOz 70 nm + MgF2 110 nm
.-..-
..-..-....._.,-.._
..I.._..-.. _,
,
... ........_ --..-..-..-..-..-....._.._.._....,_._...
~

20 - *.
s
8
,
10 - 8

0 I

0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1


Wavelength (pm)
Figure 6.27 Reflection on pure silicon with one and two antireflection films, in
relation to wavelength

Total reflection, e.g. at AM13 sunlight, is easily obtained by


superimposing the radiation intensity and the reflection curves.
A further improvement can be achieved by using two antireflection
layers - naturally of different refraction indices and of different
thicknesses. The upper antireflection layer must have a lower refractive
index than the antireflection layer on the silicon. Figure 6.27shows that the
double antireflection layer gives two reflection minima. Correct selection
of parameters can reduce total reflection to 3%4%.

6.3.1.2 Textured Surfaces

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

Figure 6.28 Radiation paths for a textured silicon surface

Figure 6.29 Inverted pyramid structure after anisotropic etching. Dimension of


the pyramid is 20 x 20 pmZ

An additional antireflection coating allows a further reduction to


approximately 3%. In practice the best success has been achieved with so-
called inverted pyramids. Figure 6.29 shows an electron microscopic
picture of such a structure.
I20 Crystalline Silicon Solar Cells

6.3.2 Losses due to Non-Absorbed Light

The percentage of non-absorbed sunlight (AM 1.5) in a 200 pm thick solar


cell made of silicon is approximately 10%. To increase absorption, the light
is reflected by a reflecting metal on the back, thus doubling the absorption
path. Better techniques provide multiple reflection. The light is locked in
the crystal (light confinement).
An effective method is to fit the back surface of the solar cell with a so-
called random surface structure (Lambert's reflection), as shown in Figure
6.30.

Figure 6.30 Reflection behaviour with random Lambert's surface structure

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.

6.3.3 Shadowing Losses by Contact Fingers

Shadowing losses are in proportion to the number of fingers. The losses in


the emitter, on the other hand, are proportional to the cube of the distance
between the fingers, equation (6.2.23). Figure 6.3 1 shows this relationship.

-8
Y
40- -.----
50 vm
......-.,-.. 100 pm
30:
-
-
-0
([I
20-

10 -

0 . .

The width of the contact finger at a given sheet resistance of 100 W O


varies between 30-100 pm. Minimum loss exists with 10-15 fingers. After
this minimum the loss climbs relatively slowly, but as it nears a low
number of fingers it rises sharply. Calculations show that the dependency
in the emitter sheet resistance is relatively low.
From this discussion we find that the number of fingers should be
slightly higher than the calculated minimum, in order to compensate for
certain tolerances in manufacture.
122 Crystalline Silicon Solar Cells

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.

6.4 THE STRUCTURE OF A HIGH EFFICIENCY


SOLAR CELL
If we put all the knowledge and experience from this section into practice,
we get a solar cell structure as shown in Figure 6.32. To sum up the
parameters for a high efficiency solar cell:

Figure 6.32 The structure of a high efficiency solar cell made of


monocrystalline silicon

The base material is monocrystalline, float zone pulled and p-doped


(approximately 1 . 5 10l6
~ ~ m - ~with
) , a resistivity of approximately 1a m .
The base thickness is approximately 200 pm, primarily due to
technological manufacturing and handling processes.
The front surface facing the light is textured, preferably with inverted
pyramids.
High Eflciency Solar Cells 123

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'.

6.5. MANUFACTURING PROCESS FOR HIGH


EFFICIENCY SILICON SOLAR CELLS
In order to fulfil the requirements for these types of solar cells described in
the previous section, highly complex technologies are necessary which call
for a large number of technological steps. However, in the sequence of
these many steps of high temperature, photolithography and chemical
processes, the crucial point is the compatibility of the process steps that
follow one another. These must be selected and coordinated, so that they
124 Crystalline Silicon Solar Cells

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.

6.5.1 Process Sequence for the Highest Efficiency

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

n++Diffusion: Another oxidation process follows with an oxide thickness of


200 nm. Windows are opened along long ridges on the front (again using
photoresist and etching processes). An n++diffusion takes place in a high
temperature process using phosphorus (see Chapter 7, Section 7.2.1.2). The
remaining oxide is again removed and is followed by n+ diffusion.
n+ Drfusion: This stage begins with a further protective oxidation with an
oxide thickness of 200 nm. In this high temperature process the
phosphorus, which was previously only diffused into the surface, is
diffused to a depth of approximately 1-2 pm. When the oxide film on the
front is opened, an n+ diffusion takes place.6
Oxide Passivation: In a further high temperature process a 105 nm thick
SiO, film is created which, as mentioned, firstly serves as a single layer
antireflection coating on the front surface, and secondly, it also provides
the required surface passivation on both sides, keeping the surface
recombination velocity of charge carriers as low as possible. This
completes the semiconductor specific processes.
Metalising (back): of the cell. Again using photoresist, holes are opened in
the SiO, on the back of the cell for contact points, exactly at the points
where boron has been diffused. On top of this a continuous aluminium
layer with a thickness of 2 pm is vacuum evaporated. This aluminium also
serves as a mirror for the photons that have not yet been absorbed.
Metalising front): of the solar cell. Oxide windows are also opened on the
ridges and on the busbar, and using the ‘Lift Off Technique’ (see Chapter
7, Section 7.2.4.1) a sequence of layers of Ti-Pd-Ag is vacuum evaporated
with a total thickness of approximately 0.1 pm.
Contact Reinforcement, Annealing: Because the galvanic resistance in the
grid contact is a critical variable for total serial resistance, the metal of the
fingers and the busbar is reinforced by electroplating to approximately
10 pm. Since the fingers should if possible not be wider than they are high,
great efforts are required to achieve narrow, but high fingers. This galvanic
film, to improve contact with the evaporated silver, then undergoes
tempering at approximately 400°C in forming gas (6% hydrogen), This also
has the advantage of significantly improving the quality of the oxide. The
multitude of processes can be seen in Table 1. The highest level of
efficiency achieved using this method is over 23% (cell area 4 cm2)
[3 61,[371.

n+ means high surface concentration.


High Efficiency Solar Cells 127

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

6.5.2 The Simplified Manufacturing Process

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.’

LBSF Process RP-PERC Process


5 High temperature oxidations 2 High temperature oxidations
3 Dopant diffusions 1 Dopant diffusion
6 Photolithography processes 3 Photolithography processes

Texturizing: The surface of the Si-wafer (the same starting material as


described in Section 6.5.1), is etched in a hot alkali-alcohol mixture after
an oxidation process and the uncovering of what will become the front
side. This creates statistically distributed vertical pyramids (‘random
texture’). Then, without any intermediate step (only rinsing and cleaning),
n+ diffusion takes place.
n+ Diffusion: Diffusion of phosphorus onto the texturised side, creating a
phosphorus glass layer on both sides (see Section 7.2.1.2.1).
Oxide Passivation: After the etching of this phosphorus glass film, the 105
nm thick passivating and antireflection SiO, film is created in a second
high temperature process.
Metallising (Jront contact): Using photoresist processes and the ‘Lift-off
technique, contact points on the front and back are opened and the
Ti-Pd-Ag contact system is vacuum evaporated onto the front.
Metallising (back surface): Contact windows are opened on the back
surface and aluminium is vacuum evaporated over the entire area. Finally,
the galvanic reinforcement of the contact grid takes place and it is annealed
under the forming gas.

’ Random Pyramids - Passivated Emitter Rear Cell


High Eflciency Solar Cells 129

Material Fz-Si Fz-Si Cz-Si


Cell area [cm’] 4 21 4
n (in YO) 21.6 20.9 19.7

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

7.1 TECHNOLOGY FOR THE MANUFACTURE OF


SILICON

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.

7.1.1 Basic 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

SiO, + 2C -+ Si + 2CO (7.1.1)

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

Figure 7.1 A smelting furnace for the production of metallurgic silicon [ 11

As the energy consumed by this process is very high at 14 kWhkg,


production takes place in areas of the world where excess hydroelectric
power is available (e.g. Noway, Canada).
However, for silicon to be used in the semiconductor industry, the
impurities must be removed almost completely by further processes. The
remaining impurities in electronic grade silicon may only be some lo-''%.
For such a high purity grade, multistage processes must be implemented.
Si Solar Cell Technology I35

7.1.2 Refractioning Processes

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%.

7.1.3 The Manufacture of Polycrystalline Si Material

The manufacture of high purity silicon takes place according to the


principle demonstrated in Figure 7.2 [2].
Polycrystalline silicon is deposited in a reactor vessel following the
CVD principle (Chemical Vapor Deposition). The process is as follows: a
thin silicon rod (in this case u-shaped) is electrically heated to a
temperature of approximately 1350°C. A mixture of hydrogen (which must
also be high-purity) and trichlorosilane is introduced into the reactor vessel.
Trichlorosilane is reduced to silicon on the hot surface of the silicon, which
deposits itself on the rod surface. The process takes place according to the
following formula:

4 SiHC1, + 2 H, +3 Si + SiC1, + 8 HCI (7.1.2)

Thus, high-purity polycrystalline silicon is produced in a continuous


process to rod diameters up to 30 cm and rod lengths up to approximately
2 m.
More recently another process has been developed, based upon similar
chemical principles. In a type of fluidized-bed reactor, silicon is deposited
on the surface of fine silicon balls using silane created in situ. The silicon
powder manufactured in this manner with a particle size of some tenths of
a millimetre can be used either in the CZ pulling process described below
(Section 7.1.4.1) or for the direct manufacture of silicon foil (Sections
7.1.7.1 and 7.1.7.2).
I36 Crystalline Silicon Solar Cells

Figure 7.2 Equipment for the industrial precipitation of polysilicon [2]

7.1.4 Crystal Pulling Process

For the manufacture of semiconductor devices, as well as having high


purity levels, the silicon should be in single crystal form and free of
defects. Two processes have become established, the crucible pulling
process, also known as the Czochralski Process [3], and the float zone
pulling process.

7. I. 4. I The Czochralsh (CZ) Process

Figure 7.3 [4] shows the principle of the CZ process. Polycrystalline


material in the form of fragments obtained from polysilicon as described in
Section 7.1.3, is placed in a quartz crucible, which is itself located in a
graphite crucible, and melted by induction heating under inert gases. The
pulling process begins with the immersion of the single crystal silicon seed.
The vertical pulling movement and the rotary movement silicon to grow in
monocrystalline form on the seed crystal. Extremely precise balancing and
Si Solar Cell Technology 137

control of both movements, and precise control of the temperature of the


silicon melt allows the diameter of the crystal to be precisely adjusted.
Adding highly doped silicon fragments permits the simultaneous adjustment
of the desired doping, dependent upon level and type of conductivity.

Figure 7.3 Single crystal pulling by the Czochralski process [3]

It is unavoidable that a certain amount of oxygen, originating from the


quartz crucible, is incorporated in the crystal during this process. For most
semiconductor applications this is of minor importance, and in some cases
is even used to good effect to achieve gettering. For high efficiency solar
cells, however, it is a disadvantage as oxygen forms precipitates, which act
as recombination centres to reduce the lifetime of charge carriers. Our
institute, however, has managed to achieve an efficiency of 22% using this
material and suitable technologies.
I38 Crystalline Silicon Solar Cells

7.1.4.2 Float Zone Pulling

In float zone pulling the starting point is a polycrystalline rod, produced by


the CV‘D process described in Section 7.1.3 (but a straight rod of the
desired diameter). The principle is explained in more detail based on Figure
7.4 [ 5 ] .

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

upwards by the vertical movement of the induction coil whilst being


rotated.
When the silicon cools, it solidifies in single crystal form. The desired
doping is achieved by the addition of a suitable dopant in gaseous form
(e.g. phosphine PH, or diborane B,H,) to the inert gas. One advantage of
this process is the additional cleaning of the crystal. Impurities (in
particular metallic impurities) possess a very low segregation coefficient
to ), i.e. their solubility in liquid silicon is some orders of
magnitude higher than in solids. Thus these substances are largely carried
with the fluid zone and transported to the upper end of the crystal. This
process makes it possible - particularly with repeated pulling - to achieve
very perfect crystals of high purity and thus - if desired - high resistivity.

7.1.5 The Manufacture of Silicon Wafers

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.

7.1.6 Polycrystalline Silicon Material

As the cost of silicon is a significant proportion of the cost of a


photovoltaic array [Chapter 61, great efforts have been made to reduce
these costs since the beginning of worldwide photovoltaic activities in
1973. One principle which has emerged from these efforts is so-called
block casting, which does not involve the costly crystal pulling process.
This is shown in Figure 7.6 [7]. Silicon melted in a quartz crucible 1 is
poured into a square graphite crucible 8. Controlled cooling produces a
polycrystalline silicon block with a large grain structure. Precise control of
the cooling mechanism ensures that the grain boundaries are columnar, i.e.
aligned vertically to the surface. The grain size is some mm to cm. The
I40 Crystalline Silicon Solar Cells

U
Figure 7.5 Sawing Si slices by the "wire cutting technique" [6]

silicon blocks, with dimensions of up to 30 x 30 cm2 are initially sawn into


blocks with surfaces of 20 x 20 cm' or 10 x 10 cm'. Then, the above
sawing processes are used to produce square Si wafers of 10 x 10 cm2 and
0.3-0.4 mm thickness (very recently dimensions of 15 x 15 cm2 have also
been produced). Thus this starting material for solar cells is called
polycrystalline silicon.
This material is widely used and currently covers about 30% of all
silicon requirements for terrestrial energy photovoltaics. New research and
development work has made great progress both in relation to
homogeneous crystal growth and, more importantly, in reducing the number
of crystal defects in the individual grains [8]. We will go into more details
about solar cells made of this material in Chapter 8. One important point
is that unlike CZ material, this material contains non-critical quantities of
oxygen as it is crystallised in a graphite crucible, but on the other hand
does contain residual impurities from the crucible walls. Improvements
have been achieved here too by appropriate surface coating of the crucible.
Si Solar Cell Technology 141

%Y
Figure 7.6 Cross-section of a block casting equipment [7]

7.1.7 Sheet Materials

To avoid sawing processes in the manufacture of silicon wafers, activities


have for years been concentrated on the production of so-called sheet
material. In past decades a multitude of processes have been developed and
tested worldwide. With a few exceptions almost none of these got past the
laboratory testing stage. There are two reasons for this. For one thing in
many cases the required level of purity could not be achieved, as too many
impurities were introduced by the apparatus used at the high process
temperatures. Secondly, many defects and faults are created in the crystal
during the recrystallisation process, due to the high cooling speed which is
sometimes required. We will restrict ourselves to the reproduction of two
selected processes here.
I42 Crystalline Silicon Solar Cells

7. I. 7. I The EFG Process

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

Figure 7.7 The principle of an EFG plant [9]

The separation of individual wafers - dimensions lOOx 100 mm2 - is by


laser cutting. The material itself is polycrystalline, as in block cast silicon.
Solar cells in pilot production have achieved efficiencies of 13% to 15%.
This corresponds to the efficiency of solar cells made of polycrystalline
block cast Si material as well as monocrystalline CZ material in industrial
production.
Si Solar Cell Technology 143

7. I . 7.2 The SSP Process

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%.

Figure 7.8 Silicon foil production by the SSP process [ 101

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.

7.2 Si SOLAR CELL TECHNOLOGY


In this section we want to demonstrate the technologies for producing solar
cells from crystalline silicon. We can divide this field into four areas, i.e.
Technologies for the production of p-n junctions.
Technologies for the growing of SiO, layers.
Technologies for the production of electrical contacts.
Technologies for the reduction of reflection on the silicon surface,
I44 Crystalline Silicon Solar Cells

We also briefly describe the necessary auxiliary technologies such as


etching and cleaning techniques and photolithography.

7.2.1 Technologies for the p-n Junction

In semiconductor technology two basic procedures are known for the


production of p n junctions. These are diffusion and ion implantation
techniques. The latter however only plays a minor role in the production of
solar cells due to the high costs associated with it. It is only used in the
manufacture of specialised solar cells for satellite technology. The third
process, the alloying technique, was the dominant technology in early
semiconductors at the beginning of the 1950s. However, it is rarely used
today due to the wide dispersion of electrical parameters and high costs.
We will therefore only describe diffusion technologies.

7.2.I . I Difflusion Technologies and the Theory of D ffusion

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.I.1.1 The Complementary Error Function Distribution


The dopant source is inexhaustible. The concentration on the surface (N,)
is thus constant throughout the entire diffusion process. The concentration
within the silicon is only dependent upon diffusion time and diffusion
temperature (Figure 7.9).
The boundary conditions for the mathematical solution are:
N , = constant where 0 < t < 00 and N(x) = 0 where t = 0 and 0 < x < 00
where N , is the surface concentration.
Si Solar Cell Technology I45

Figure 7.9 Concentration distribution of dopant for an inexhaustible dopant


source

The solution for the differential equation (7.2.1) is thus


X

(7.2.2)

The expression in parentheses is called the complementary error function


distribution, and is represented by the letters erfc, thus

X
N ( x , t ) = N, erfc - (7.2.3)
2 fi7

Figure 7.10 shows the relationship between the ratio of concentrations


(NJN,) and the argument x i (Dt)"'.
To calculate the penetration depth xj of a p-n junction, we first find the
ratio of background concentration in the base silicon to surface
146 Crystalline Silicon Solar Cells

Figure 7.10 Concentration distribution according to the complementary error


function distribution

concentration. If this value is for example, we find from Figure 7.10,


that

X
- = 5.4 (7.2.4)
$7
and thus

x. = 5.4
I
$7 (7.2.5)

choosing diffusion constant, temperature and time leads to the penetration


depth.
Si Solar Cell Technology 147

7.2. I. I.2 Gaussian Distribution


In this diffusion process there is an exhaustible dopant source on the
surface with a concentration Q (cm-*). The solution of the partial
differential equation (7.2.1) for this reads:

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

7.2.1.1.3 Diffusion CoeSficient


The diffusion process takes place in semiconductors according to two main
principles. The diffusing substances can move across interstitials or diffuse
via vacancies. The speed of migration is very variable, but in both cases is
strongly dependent upon temperature. The quantative relationship is given
by the formula (7.2.8):

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.

7.2.1.2 Diffusion Technologies

In the diffusion process and the subsequent oxidation process, an


electrically heated tube furnace with a quartz tube is usually used. In solar
cell technology diffusion temperatures vary between 800°C and 1200°C.
The silicon slices to be treated are put into the constant temperature zone
of the furnace in quartz trays. Temperature consistency across the zone
length and over the diffusion times is better than 1"C, achieved using
modem diffusion equipment. Figure 7.13 shows the principle of the
standard diffusion process.
Both gaseous and liquid diffusion sources are used. Nitrogen, argon and
oxygen are used as carrier gases in the so-called open tube process. The
quantity and mix ratios must be adjusted according to the application, but
require very precise control.
Si Solar Cell Technology I49

l/T -
Figure 7.12 Temperature dependency of the diffusion coefficients of different
elements in silicon (according to Landolt-Barnstein)

The diffusion process requires, in addition to precise control of time and


temperature, certain heating and cooling phases. Slow cooling can be used
to produce a getter effect [13]-[14]. In this case impurities, mainly metals,
wander to the surface due to the drastic reduction of their solubility in
silicon with the sinking temperature, and their still high diffusion rate at
low tempzratures. They are absorbed there and are therefore harmless as
recombination centres.
The diffusion processes used in solar cell manufacture are described in
detail below.
150 Crystalline Silicon Solar Cells

Wafers on carrier Wafers on carrier

# bh -Valvesand
flow meter
I!@, IflrkDopant liquid

Figure 7.13 Principle of the diffusion process (open tube process)

7.2.1.2.1 Emitter Diffusion Processes


Since the starting wafers for solar cells are almost always doped with boron
and are thus p-conductive (concentrations from 10” to l O ” ~ m - ~an ) , n-
doped emitter is created using phosphorus.
Gas diffusion processes are used almost exclusively, whereby
phosphorus is introduced into the diffusion furnace either in the form of
phosphine (PH) or gaseous phosphorus oxychloride (POCI,). The latter is
introduced using nitrogen as a carrier gas. At the high temperatures of
approximately 800°C the dopant gases react with the surface of the silicon
when oxygen is added. In accordance with Si + 0, => SiO, silicon dioxide
is produced on the surface and secondly, phosphine is converted according
to

2 P H + 3 0 , -+P,O, +H,O (7.2.9)

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

Figure 7.14 Phosphorus profiles at diffusion temperatures of 950°C in relation


to diffusion time [ 161

This anomalous behaviour has been explained by various authors


[ 161-[ 191, by the fact that the diffusion coefficient rises sharply with high
concentrations and only at a certain low concentration does it behave
according to the familiar diffusion coefficients. This effect has the
disadvantage for solar cells that a dead layer is created, as already
mentioned. A dead layer of, for example, 0.3 pm depth will reduce
efficiency to approximately 10% (relatively).
A dead layer can be impeded using the following diffusion process for
reducing the surface concentration of the emitter. In a double diffusion
process [20],[21] the first diffusion step is a predisposition coat - a low
level diffusion of phosphorus at a temperature of approximately 800°C.
Then the phosphorus-silicate glass layer is removed by chemical means. In
a second diffusion step - this time at a temperature of 1000-1 100 "C - the
desired penetration depth of the phosphorus is achieved. A diffusion profile
152 Crystalline Silicon Solar Cells

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.

7.2.1.2.2 The Diffusion Process for the Back Surface Field


As we have already mentioned, a so-called back surface field (BSF) is
necessary for high efficiency solar cells.
The required pi doping is achieved by the diffusion of boron. BBr, can
serve as the boron source for this purpose, which can be handled in a very
similar manner to POCI,.
In industrial practice, aluminium is used for the creation of a BSF. The
technological doping process is that aluminium is introduced onto the
surface using vacuum evaporation or in the form of an ink by screen
printing, and alloyed at approximately 800°C (eutectic point 577°C). At
this temperature the aluminium partially diffuses and creates a p+ doping.
The recrystallised layers also act as good getter sinks.

1.2.2 Oxidation Technologies

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

2Si +O, + 2 H , O +2SiO, +2H, (7.2.11)

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

the (100) surfaces.


The addition of chlorine ions during the oxidation process is also
beneficial [23],[24]. As well as the removal of traces of metal by volatile
metal chloride, alkali atoms such as sodium are also removed and the
passivating characteristics of the SiO, layer thus improved. Chlorine can be
added to the process, e.g. by the addition of trichloroethane (TCA);
(formula C,H,CI,). The reaction for this oxidation process is

C,H,Cl, + 2 0 , +3HC1 + 2 C O , (7.2.12)

and

4HC1 + O , +2H,O +2C1, (7.2.13)

When TCA is added the supply of oxygen must be ensured, as


otherwise the highly poisonous phosgene may be formed because TCA is
154 Crystalline Silicon Solar Cells

now replaced by trans-LCD (also contains chlorine) for environmental


protection. The results are very similar.
New research - including that in our institute - into the use of SiO, as
a passivation layer in solar cells has yielded the following sumniarised
results:
Dry oxidation under high oxidation temperatures yields the lowest
values for the interface trap density and thus very low surface
recombination rates.
The density can be reduced even further by an annealing process at
approximately 45OOC (preferably in forming gas).
The lowest densities are achieved with (100) surfaces.
The masking effect of an SiO, layer in the diffusion process relies upon
the fact that the rate of diffusion of many diffusants in silicon dioxide is
lower by orders of magnitude than in silicon itself. The required SiO, layer
thickness for different diffusion temperatures and times is shown in Figure
7.16 for the two diffusants boron and phosphorus [25]-[26]. It is evident
that boron is masked by significantly thinner SiO, layers than is
phosphorus.
Fkherniore, SiO? is used for masking in alkaline etching processes as
well as for surface texturing. We will return to this subject in Section
7.2.5.2.

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

7.2.3 Auxiliary Technologies

Before examining in inore detail the technologies of solar cell surface


treatments, such as metal coating, antireflection coating and texturing, we
wish to comment upon the auxiliary teclinologies such as etching, cleaning
and photolithography.

7.2.3.I Etching and Cleaning Techniques

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].

This cleaning process is named after the company RCA.


156 Crystalline Silicon Solar Cells

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

Photolithography is used to structure the silicon dioxide used in the various


masking processes as described above. A thin film of photoresist is spun in
a yellow area - due to the light sensitivity of the photosensitive resist - on
the silicon wafer. Depending upon viscosity and revolution speed (some
thousands of revolutions per minute) a homogeneous film is created with
a thickness of 0.5-2 pm. After the film has been dried, it is passed through
suitable masks and illuminated with short wavelength light (approximately
0.4 pm). This process occurs in mask aligners, which permit structural
precision of about 1pm.
In the case of a positive resist, the long molecule chains are cracked at
the illuminated points and thus prepared for dissolving in alkaline solutions.
After successful etching of the SiO, layer the remaining resist is removed
using acetone.
In the case of a negative resist the illuminated points remain. It is used
if silicon is to be etched locally (positive resist is not resistant to this). The
resist is dissolved in hot chemicals.

1.2.4 The Metallising of Solar Cells

Of the many contact technologies which are used for semiconductors, we


only wish to describe those which are used in solar cell technology. We
first examine the structuring of the finger grid.

7.2.4.1 The Structuring of the Finger Grid

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+
/-

Mask illumination Evaporation of after dissolution


Photoresist c.g. of photoresist
development Ti, Pd, Ag
Figure 7.17 The principle of the ‘lift-off process

As shown in Figure 7.17, the required sequence of layers is vacuum


evaporated as a complete layer upon a structured photoresist. The crucial
point is that the photoresist layer has to be thicker than the vacuum
evaporated metal layer, so that the edges can be accessed during the
dissolution of the photoresist. The simultaneous use of ultrasound is helpful
during dissolving. In this way it is possible to produce structures which are
only some pm wide.
The third method, screen printing, in which metal paste is used,
dominates in a wide range of production techniques as it is particularly cost
effective, but the maximum finger width is about 100 pm.

7.2,4.2 High Vacuum Evaporation Technologies

The most up to date method for contacting is the vacuum evaporation of


metal layers, in many cases in several layers [2S]. The contact material to
the semiconductor is selected from the point of view of the required banier
height. Since, as described in Chapter 6 , the surface concentration of
dopant must be low ( -10”9 crns3)in a high efficiency solar cell to reduce
the surface recombination velocity, almost only titanium, with a barrier
height of approximately 0.5 eV can be considered. Owing to its low vapour
pressure and the necessary high temperature almost exclusively electron
beam evaporation is used.
Experiments involving theniial evaporation from a tungsten boat have
been carried out to determine how high the negative influence of the
electron beam evaporation is on the SiO, passivating layer. The sharp
I58 Crystalline Silicon Solar Cells

increase in the surface recombination velocity which occurs can, however,


be completely eliminated by subsequent annealing under forming gas [29].
As well as its low barrier height, titanium also has the advantage that it
belongs to the easily oxidizable metals and thus can reduce thin SiO, layers
whilst retaining good adhesion to the silicon. The normal layer thickness is
30 to 50 nm.
Titanium must, however, be protected from external oxidation by
another metal. Metals can be considered which themselves barely corrode
and which are compatible with the contact material, i.e. do not diffuse too
highly with the bonding agent and the subsequent covering material. Nickel
and palladium are suitable partners, these are deposited in approximately
the same thickness as titanium (m50 nm).
For the external contacting a third metal layer with good conductivity
and very low corrosion must be evaporated. Silver is preferred in many
cases. The silver layer is evaporated with a thickness of approximately
0.1 pm. The subsequent sintering at a temperature of approximately 400°C
under forming gas ensures a good adhesion between the contact layers. For
the necessary reduction of the electrical resistance of the contact finger it
is reinforced by the electroplating of Ag. Approximately 8 pm Ag is grown
onto the approximately 15 pm wide fingers of high efficiency solar cells.
In the case of a high emitter surface concentration (approximately
lozo~ m ' ~Cr-Ni
) contacts also give very good results. The back surface
contact on high efficiency cells consists of vacuum evaporated aluminium,
which produces a very good ohmic contact to the p-base material due to its
p-doping effect. In the case of solar cells with a local BSF, the silicon
dioxide on 98% of the surface is coated with aluminium. This functions as
a very effective optical reflector.

7.2.4.3 Thick Film Technology

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

recrystallised Si layer is created as with normal alloying, which contains a


high proportion of Ag and thus creates a good ohmic contact. This process
only gives sufficiently low contact resistances at surface concentrations on
the n+ emitter of approximately 10'' cm-3 .
Only aluminium (in the form of a paste) is used for the manufacture of
back surface contacts. Aluminium has two advantages. It forms alloys at
577°C (eutectic point) and has a relatively good solubility with
concentrations of approximately 10'' cm" in silicon. Thus in the
recrystallised layer formed upon cooling a p+ doping is achieved and thus
a BSF created. Normally sintering takes place at temperatures around
800°C since the best results are achieved thus. The significant increase in
open circuit voltage observed in practice at high sintering temperatures can
be explained by the above mentioned gettering effect. Since A1 is not
directly solderable, a silver-palladium paste is also sintered onto this layer
[331.

1.2.5 Antireflection Technologies

7.2.5.1 Applying an Antireflection Coating

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

7.2.5.2 The Manufacture of Textured Silicon Surfaces

To produce such structures the chemical-physical effect is used, that the


etching rate of silicon in an alkaline solution is dependent upon the crystal
direction [34],[35].For example, the dissolution rate of silicon in the (111)
crystal orientation is one or two orders of magnitude smaller than in the
(100) direction. The reason for this is that in the (111) plane for the cubic
face centred diamond lattice of silicon there is only one free valence to the
surface per atom, whereas for the (100) direction two valences are
available. It is therefore plausible that a considerably higher energy
expenditure is required to dissolve an atom from the ( 111) direction as for
the (100) direction. Therefore in high efficiency solar cells the (100) crystal
orientation, vertically to the surface, is selected.
The etching process takes place in an alkaline solution at approximately
70°C.Weak solutions of KOH or NAOH with a concentration of 10%-30%

Figure 7.18 Electron microscopic picture of silicon wafers with random


pyramids
Si Solar Cell Technology 161

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

Tsai S. C., Proc. IEEE, 57, 1969, p. 1499


Fair R. B. and Tsai S. C., J . Electrochem. Soc., 127, 1977, p. 1107
Jeppson K. 0. and Anderson D. J., J . Electrochem. SOC.,136, 1986, p. 397
Hu S.M. et al., J. Appl. Phys., 54, 1983, p. 6912
Knobloch J., Aberle A. and Vofl B., Proc. 9th EC PV Solar Energy C o n j ,
Freiburg, Germany, 1989, p. 777
Blakers A. W., et al., Proc. 9th EC PV Solar Energy C o n j , Freiburg,
Germany, 1989, p. 328
Wolf H. F., Silicon Semiconductor Data, Pergamon Press, 1976
Convell E. M., Proc. IRE, 46, 1958, p . 1281
Cosway R. G. and Wu C. F., J . Electrochem. Soc., 132, 1985, p. 15 1
Sah C. T. et al., J. Phys. Chem. Solids, 11, 1959, p. 288
Morinche S. and Yamaguchi S., Jpn. Appl. Phys., 1, 1962, p. 3 14
Kern W. and Puotinen D. A,, RCA-Review, 1970, p. 187
Bogenschutz A. L., Atzpraxis f i r Halbleiter, Hanser Verlag, 1967
Kopp J., Knobloch J. and Wettling W., Proc. 11th EC PV Solar Energy
ConJ:, Montreux, 1992, p. 49

1301 Cheek C., et al., IEEE TED, 31, 1984, p. 602


[3 11 Mertens R., et. al., Pmc. 14th EC PVSolar Energy C o n j , San Diego, 1980,
p. 1347
[32] Dubey G. C., Solar Cells, 15, 1985, p. 1
[33] Ralph E. L., Proc. 11th IEEE PVSpec. C o n j , 1975, p. 315
[34] Heuberger A., Mikromechanik, Springer-Verlag, 1989
[35] Price J. B., Semiconductor Silicon, Princeton, NJ, 1983, p. 339
Selected Solar Cell Types

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.

8.1 CRYSTALLINE SILICON SOLAR CELLS

8.1.1 Crystalline Silicon Concentrator 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.

Figure 8.1 The structure of an IBIC cell for concentrated light [ 5 ]

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

structure suggested by Lammert et al. [6] in 1974, the IBC [Interdigitated


Back Contact]. As the name suggests, both n+ and p+ diffusion structures
(Figure 8.1) and therefore also both connection contacts lie on the back of
the cell. This structure has the following advantages:
There is no shadowing of light by the finger structure.
The metal contacts can be broad and take up almost the entire back
surface. They are therefore of very low impedance, thus achieving a
very low series resistance.
The penetration depth of n+- and p+- layers are non-critical. There are no
losses due to a dead layer.
A disadvantage is that the diffusion length in the base of the cell must
be very high (if possible five times greater than the cell thickness), and the
surface recombination on the side facing the light must be extremely low.
Short wavelength light also increased the surface recombination velocity on
the front surface and caused degradation in the first cells. The problem was
solved, however, [7] by applying a very thin (a few tenths pm thick) p+
zone with a surface concentration in the region of approximately 10" cm-3
to the side facing the light. A disadvantage of this cell is that the nt- and
p'-connections must be insulated from each other at the points of contact
in a module.
Efficiencies of approximately 27% are achieved with this type of solar
cell at 100 suns. For lower concentrations around 50 suns, a cell has
recently been developed in which the p+ layer is again applied to the side
facing the light. Efficiencies of 26% have been achieved with these cells
PI.
The application of concentrator cells is limited to use in sun rich areas.
The problems of cost effective light concentration and sun tracking must be
solved.
This cell, in a slightly modified form, has proved that it can be used
under normal sunlight conditions. In the World Solar Challenge, the race
for solar powered automobiles over 3000 km in Australia from Darwin to
Adelaide in 1993, the company Sun Power Corporation, California, in
cooperation with Honda, Japan, manufactured 7000 solar cells of this type
[9]. The cells had dimensions of 7.3 x 2.4 cmz. They were manufactured
from Fz-Si with a resistivity of approximately 50 Rcm to achieve a very
high carrier lifetime of up to 2 ms. The cell thickness was 160 pm, reduced
using etching techniques. The contact layout was altered from the original
design. It consisted of many interlinked contact fingers with two
longitudinal collecting contacts. For the electrical insulation of the contacts,
as in many power semiconductors, the plastic polyimide is used.
In the manufacture of the 7000 cells a yield of ~ 9 0 %was achieved
referred to a cell efficiency of >20%. The average cell efficiency was
166 Crystalline Silicon Solar Cells

21.1%. This is an exceptionally good result. The solar powered car fitted
with with these cells won the race.

8.1.2 Biracial Solar Cells

If, instead of the very wide interdigitated fingers, an interdigitated finger


grid is deposited with a similar layout, but narrow like the high efficiency
solar cells, as shown in Figure 8.1, then this cell can be illuminated from
both sides. Various laboratories have worked on this type of cell [lo]-[13].
Such a cell, for example, is capable of collecting diffused light from the
back surface, thus increasing total efficiency. One variant of this cell
consists of a cell with an n+ layer on its back surface. This gives a structure
similar to a transistor. Cells built in our Institute according to this principle
have achieved efficiencies of 21.4% when illuminated on the non-
metallised side (under AM13 global) and 20.2% when illuminated on the
grid side (somewhat lower due to shadowing). This is the first bifacial solar
cell with efficiency on both sides >20%. These high, and very consistent,
values show both that the two sided surface passivation is very effective,
and that the carrier lifetime in the base material must be very high. Both
indicate a high standard of technology.

8.1.3 Buried Contact Solar Cells

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

Figure 8.2 Cross-section through a buried contact solar cell

technique does not require photomask processes or high vacuum


evaporation technologies, and is thus significantly more economic, it is
predestined for use in serial production. The double stage emitter is used
for the emitter structure, whereby the highly doped n++film is restricted to
the groovss. The p+ back surface field permits higher efficiencies.
Owing to the low process costs, several solar cell manufacturers have
bought a licence. It was shown that the manufacturing process was
somewhat more economic that the widely used screen printing technique
[161,[171.
A further advantage of this cell is the textured back surface, which
increases the confinement of light and thus the total efficiency. With this
type of cell (large area), average efficiencies of 18% have been achieved in
production [ 161. With specific techniques, such as an improved
antireflection coating and a local back surface field, efficiencies of up to
2 1% have been achieved in the laboratory [ 181. This beneficial structure is
still undergoing further development. In this case, too, attempts are being
made to reduce the number of process stages, in particular the high
temperature processes, thus achieving more economical solar cells [ 181.
I68 Crystalline Silicon Solar Cells

8.1.4 MIS Solar Cells


The fundamental difference between the MIS solar cell developed by Hezel
and his colleagues and the conventional Si solar cell is the fact that it does
not contain a p-n junction (Figure 8.3). The side of the cell facing the light
is coated by a very thin (approximately 2-4 nm) thermally grown silicon
dioxide film [19]. The finger grid is vacuum evaporated onto this and
finally, the entire surface is coated with a silicon nitride film, which may
be relatively thick due to its good transparency (some pm). This coating -
a dielectric - has four tasks:
Protects against environmental influences.
Functions as an antireflection layer.
Reduces surface recombination velocity.
Creates an n conducting inversion layer in the p semiconductor.
A decisive step towards increasing efficiency was achieved by the use
of caesium in this dielectric [20].Caesium's property of creating stable
charges was reported by Sixt and Goetzberger in the early 1970s [21].

Figure 8.3 Cross-section through an MIS solar cell [ 191

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

a high vacuum evaporation procedure. Furthermore, to prevent degradation


the cells must be bedded under glass which has been coated to allow the
absorption of ultraviolet light. After further improvements [22] 10 x 10 cm2
solar cells have been produced which achieve 15% efficiency.

8.1.5 Polycrystalline Silicon Solar Cells

Figure 8.4 shows a cross-section through a solar cell made of


polycrystalline silicon, We described the manufacture of the starting
material in the preceding section. The grain boundaries should be as
columnar as possible, i.e. they should run vertically to the surface of the
silicon wafer. It is clear that parallel grain boundaries severely detract from
the formation of a good p-n junction (leakage current, high saturation
current).

Figure 8.4 Cross-section through a polycrystalline silicon solar cell

Many publications have appeared on the theory of polycrystalline Si


solar cells since 1977 [23]-[27]. Ref. [28] contains a model of the crystal
boundaries in polycrystalline solar cells. More recent research has been
more concerned with the defects in individual grains, as it has been
established that these reduce efficiency [29] much more than do the grain
boundaries themselves, if their average distance apart is greater than the
average diffusion length by a factor of between five and ten, Such defects
can be, for example, the precipitation of impurities and crystal defects such
as vacancies and dislocations. One theory of the influence of the variables
I70 Crystalline Silicon Solar Cells

is that of de Pauw [30]. Three processes have been established to minimise


the recombination and efficiency reduction caused by defects and grain
boundaries. These are:
Passivation using hydrogen ions
Gettering using phosphorus
Gettering using aluminium.
In the first process, hydrogen ions created in an ion source and
accelerated to 1000 eV are implanted into the - finished - solar cell. The
precise mechanism of passivation has not yet been completely explained.
However, it has been proved [31],[32], that the free valences, the so-called
dangling bonds, are saturated by the stable silicon-hydrogen compounds
SiH, SiOH created [33],[34]. This type of hydrogen passivation primarly
increases the photocurrent [35],[36].
The second method, the gettering of impurities by phosphorus has
already been described in Chapter 6. According to this, the
phosphorus-silicate-glass film traps many impurities during diffusion.
When the silicon wafer is cooled from its diffusion temperature
(approximately 1100°C) these migrate to the surface due to their dramatic
reduction in solubility with decreasing temperatures, thus becoming
harmless with regard to recombination. The diffusion rate for these
impurities, even in the average temperature range (400-800°C) is known to
be considerable (see also Chapter 6). In [37] successful phosphorus
gettering in polycrystalline material is described in detail.
Various writers have described in detail the gettering of impurities by
aluminium [38]-[40]. According to these, two effects are responsible for
gettering. Firstly, the traps at the grain boundaries are saturated and
secondly, a p-p+-BSF structure can form on the boundary, because the
diffusion rate of aluminium along the grain boundaries is higher by orders
of magnitude than in the crystalline material [41]. Recently, some authors
have shown [42],[43], that a simultaneous gettering of phosphorus and
aluminium provide the best results. A comprehensive overview of defects
and their gettering is given by Schindler [44].
The efficiency of polycrystalline silicon solar cells has been continually
improved in recent years. With the option of high efficiency technologies,
efficiencies of approximately 16% are now being achieved [45]. On a
laboratory scale, over 18% efficiency has been achieved [46], although on
an area of 1 cm’. Efficiency on this type of small area cannot simply be
transferred to larger cells, as in this case the distribution of crystal
boundaries and defects plays a significant role.
Selected Solar Cell Types I71

8.1.6 Crystalline Silicon Thin Film Cells

8.1.6.I Advantages and Requirements

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

8.1.6.2 The Relationship between Electrical and Cell Parameters

In the following illustration, we show the efficiency in relation to the


various cell parameters. These are:
Solar cell thickness.
Diffusion length of minority charge carriers in the base.
Recombination velocity on the back and front surface.
Optical confinement, i.e. the reflection characteristics of the inner
surfaces.

8.I . 6.2.I Solar Cell Thickness

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.

8.1.6.2.2 Back Surface Recombination


Figure 8.6 shows the influence of back surface recombination on efficiency
for different base diffusion lengths. High efficiency levels are only
achievable if the diffusion length in the base is at least 3-10 times the cell
thickness, and the back surface recombination velocity is less than 100
cm/s. Such values can only be realised using high efficiency technologies.

8.1.6.2.3 Recombination at the Emitter


Figure 8.7 shows that the emitter recombination must only amount to
around 103-104 cm/s for high efficiency. Owing to the low penetration
174 Crystalline Silicon Solar Cells

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

depth, only a small part of the total photocurrent is generated in the


emitter. Lower recombination values could not be realised in any case, due
to the high doping in the emitter. The illustration demonstrates very clearly
the importance of good electrical confinement. Recombination at both
surfaces must be suppressed as far as possible.

8.1.6.2.4 Optical Confjnement


In Chapter 6 , Section 6.3.2 we considered this problem in detail. We once
again refer you to references [28]-[30] in Chapter 6. Further details are
also provided in reference [49] for this section. Figure 8.8 shows the high
influence of inner surface reflection characteristics on efficiency. Efficiency
increases from around 17% without inner reflection to almost 20% with
very good reflection characteristics. The question of how high back surface
reflection can be achieved in thin film solar cells has still not been
answered.
The above analyses have also been carried out for thin film solar cells
with a thickness of 5 pm. The relationships which were found were
naturally similar. A diffusion length of 50 pm is adequate for good
Selected Solar Cell Types 175

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

efficiency, instead of the 300 pm required for 30 pm cell thickness.


The results of the analyses are summed up here for the two dominant
influences; Shack - recombination, and Rback- back surface reflection .
Cell thickness
30 pm 5 Irm
A.
Shack 2 lo6 cm/s (no BSF) q = 13% 10%
Shack = lo4 cm/s average passivation q = 16% 14%
Shack = 10' LBSF structure q = 20% 16%
B.
-
RbackIOW 0.4 q = 17% 12%
Rbackvery good - 0.9 Tl = 20% 16%
These considerations of the efficiencies of thin film silicon solar cells
have been confirmed experimentally. With a 50 pm thick layer of
monocrystalline silicon, grown epitaxially onto a insulating substrate, solar
cells have been created in our institute with an efficiency of 19.2% [51].
As shown in Figure 8.9 an insulating SiO, layer is implanted onto a
silicon substrate. On top of this a layer of approximately 45 pm thick
monocrystalline silicon is epitaxially grown. Due to the insulating
176 Crystalline Silicon Solar Cells

20.0

19.5 0.9..

-
0'

19.0
$
v
#'

18.5 Reflection coefficient on the /'

.-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 Manufacturing Technology for Si Thin Film Solar Cells

All concepts have in common that


on a suitable substrate a
thin silicon film must be deposited, which is almost always subject to an
additional
recrystallisation step. In addition, suitable technologies should be
developed, facilitating a high optical confinement and low surface
recombination velocities.

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 8.9 Cross-section through a thin film solar cell on an insulating


substrate. All contact grids are on the front surface

economically be used directly as a sheet material in addition to


conventional techniques (rods, blocks, sawing).
A further interesting substrate material is ceramic, as it can be
manufactured to a high quality and can tolerate the high temperature
processes, which are necessary for recry stallising and cell processes. Even
the first silicon thin film cells by Barnett [52], in the late 1970s used a
ceramic substrate material. To name further materials under investigation:
graphite, steel, aluminium, glass and quartz. All these materials - except
for silicon - are afflicted by the problem of thermal-mechanical
mismatching. Before the active Si film can be deposited, the substrate must
be provided with an intermediate layer, a buffer. This intermediate layer
should first and foremost prevent the diffusion of impurities from the
substrate into the active Si layer, while also acting as an optical reflector
and serving as passivation for the back surface. Silicon dioxide, silicon
nitrite and silicon carbide come under consideration as materials.
Aluminium can be used as an optical reflector.

8.1.6.3.2 Techniques for Depositing the Active Si Layer


Two possible concepts are followed: depositing from the liquid and from
the vapour phase. Depositing from the liquid phase takes place using the
so-called LPE technology (liquid phase epitaxy). For depositing from the
vapour phase, PECVD technology (plasma enhanced chemical vapour
deposition) has proved to be the best option.
I78 Crystalline Silicon Solar Cells

In the vast majority of cases the particle size of the crystallites


immediately after depositing does not correspond with the requirements for
high efficiency. The layer must be recrystallised, remelted. The float zone
pulling process is suitable. The necessary melting heat can be created by
laser or lamp techniques.

8.1.6.3.3 Cell Technology


The manufacturing process for the p-n junction and for contacting differ
only slightly from the technologies described in Chapter 7, Section 7.2.
However, for a non-electrically conducting substrate, a front side contact of
the base material must be made, doubling the shadowing losses. Figure
8.10 shows the two concepts.

Figure 8.10 Concepts for thin film silicon solar cells [53]

The intention behind Section 8.1.6 was to make a significant step


forward in the economics of photovoltaics. Significant practical difficulties
still stand in the way of realising an economical silicon cell [53]. For more
detailed information on this field, the following entries in the reference list
give a comprehensive overview [54]-[56].

8.1.7 Multilayer Silicon Solar Cells

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

moderate surface concentration (n'). Both layers are extremely thin, at


0.1 vm. The total thickness of this cell has been selected as 10-20 pm.

Figure 8.1 1 Multilayer crystalline silicon cell [ 581 schematic and manufacturing
diagram

During the manufacturing process,' the starting point is a substrate


made, for example, of glass with a non-conducting coating. Then alternate
layers of p and n are deposited with a concentration of approximately 10"

' 1. Glass substrate, 2. Layer separation, 3. Groove for first polarity, 4.


Groove for second polarity, 5. Metallising.
iao Crystalline Silicon Solar Cells

atoms/cm3 (e.g. using CVD), approximately 2 orders of magnitude higher


than for conventional solar cells. The upper layer is covered by an
insulator, e.g. of SIN or SiO,.
Normal recrystallisation is only necessary to obtain grains on average >
3 pm. Then grooves are cut using a laser, as in the buried contact solar
cell. It has recently been possible to cut these grooves with a minimum of
slack [58]. Afterwards, diffusion of a dopant is used to give the grooves
polarity. A second laser process is used to remove the doping which has
just been applied on one side of the groove. Now the opposite polarity is
diffused in. Finally, as in the case of the buried contact, electroless
metallising takes place in the grooves.
This multilayer cell gives the following advantages.
As the individual layers are only a few pm thick, high efficiency can be
achieved with low diffusion length or low charge carrier lifetime. At a
permitted carrier lifetime of up to 0.1 pm, the doping of this layer may
be up to 10l8atoms/cm3 and the grain boundaries can have dimensions
less than 3 pm. Both permit depositing under less severe cleanliness
requirements. The high doping leads to a low dark current, thus giving
a higher open circuit voltage.
A further advantage of this cell lies in its relative insensitivity to surface
recombination. Most of the light is absorbed in layers away from the
surface and the charge carriers created thus do not often come into
contact with the surface.
One very interesting aspect of the multilayer structure is the capacity to
minimise lateral resistance losses by injection of the charge carriers
between the layers due to lateral differences in voltage [59]. A two-
dimensional simulation of this effect shows that in cases where the
diffusion lengths are greater than the thickness of the layer, the charge
carriers are injected into the other layers, thus injection takes place [60].
Therefore a distance from the contact finger of up to 1 cm is permitted,
with the result that shadowing is kept very low and the contribution to
dark current by the metal-silicon interface is very low too.
The optimal number of layers and thus the total thickness depends
primarily o n the two factors optical confinement and surface recombination.
We can see from [61] that with very good confinement of the light
(Lambert's Reflection), two layers give the highest efficiency. If, however,
specular reflection is only present on the back surface, then the optimal
number of layers is approximately 7-8, only slightly dependent on the
charge carrier lifetime.
An the efficiency value of 17.6% has been reported [62]. This 32 pm
thick cell consisted of five layers of high-grade silicon. The substrate was
made of highly doped silicon, the surface of which was coated with an
Selected Solar Cell Types 181

insulating layer. It is hoped that with a 50 pm thick cell, efficiencies up to


20% will be achieved.
Many technological hurdles must still be overcome to turn the
theoretical possibilities into practical concepts [61].

8.2 THIN FILM SOLAR CELLS


Great efforts have been made in research and development in the field of
thin film solar cells made of other materials, with cell thicknesses of a few
pm. Thin film solar cells can be expected to provide cost reduction and
energy savings in cell manufacture. All known semiconductor compounds
[III-V or II-IV materials] are direct semiconductors, so the absorption of
sunlight occurs within a crystal thickness of a few pm. For applications in
terrestrial solar technology, however, these cells must have an efficiency of
the same magnitude as those of crystalline silicon as well as high stability.
Of the large variety of solar cell types investigated, we have selected the
few which are at the forefront of current work due to the above criteria.
We thus consider four types of cell in this section, these are cells made of
amorphous silicon [a-Si],
gallium arsenide [GaAs],
cadmium telluride [CdTe], and
copper-indium-diselenide [CuInSe,].

8.2.1 Amorphous Silicon Solar Cells

Amorphous materials - glass is a typical example - differ from crystalline


structures primarily because the strict periodicity of the lattice is not
present. As a consequence, the normal selection rules for crystal do not
apply. In particular, the absorption of light occurs directly. Amorphous
silicon [a-Si] - a compound of silicon and hydrogen - has this
characteristic. The atomic structure is as shown in Figure 8.12.
The band gap of this semiconductor is approximately 1.7 eV, but varies
between certain limits due to the hydrogen content.
We will consider these solar cells in more detail due to their broad
application in the consumer market. In 1969 the physical characteristics of
amorphous silicon were described for the first time [63]. In 1977 the first
solar cells were produced in the RCA laboratory by Carlson [64],[65]. They
still had a very low efficiency of 2%. The rapid development which
followed has led to efficiencies of approximately 13% today.
The field of these solar cells is summarised in the references [66]-[68].
Hamakawa and Stafford provide very good detailed overviews [69],[70].
182 Crystalline Silicon Solar Cells

Figure 8.12 The atomic structure of amorphous silicon

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 *

Figure 8.14 The structure of an a-Si p-i-n solar cell [65]

An important discovery on the road to higher efficiency was that the


diffusion length of the charge carriers was very strongly influenced by
doping and was so extremely small that only a small part of charge carriers
could be collected. The solution to this problem was an intrinsic layer
(Figure 8.14), with a very thin (approximately 50 nm) p+- and n*- coating
on either side. This requires the highest degree of cleanliness for process
equipment and procedures. A wide space charge region is created in which
such high fields exist that almost all of the charge carriers created here can
reach the p-n junction. As the absorption in this cell structure takes place
almost exclusively in the intrinsic film, the efficiency could be raised to
more than 5% [71] for the first time.
A further improvement was achieved by depositing a silicon-carbon
compound (silicon carbide) onto the p+ side facing the light (by the
addition of methane CH, during the production process). This compound
(also a semiconductor with a band gap of over 2 eV) is transparent to light,
I84 Crystalline Silicon Solar Cells

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

This semiconductor with a high band gap is transparent to sunlight and


functions like surface passivation
Selected Solar Cell Types I85

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.).

Glass substrate TLO a-Si:H Metal


(Pin)
Figure 8.16 Integrated serial connection of a-Si solar cells

Currently, solar cells made of amorphous silicon make up some 20% of


current annual production (measured in peak watts). Their use in high
performance applications is still strictly limited due to the importance of
efficiency (see Chapter 6), unless they are used more for architectonic
reasons, e.g. in faGades.

8.2.2 Gallium-Arsenide Solar Cells

The semiconductor material GaAs has won widespread approval in


electronics. As early as the beginning of the 1950s GaAs was used in some
research laboratories as a substrate for future semiconductor devices.
Current applications are mainly in the field of optoelectronics, such as
diodes and laser. In the foreseeable future increased miniaturisation and
faster data processing are predicted. The physical and technological aspects
of this material have have been thoroughly investigated during more than
40 years.

’ Transparent Conductive Oxide


186 Crystalline Silicon Solar Cells

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

GaAs is also a very interesting material for photovoltaics. The energy


gap of this semiconductor is 1.42 eV and, as we can see from Figure 8.17,
it promises an almost optimal adaptation to solar radiation. Further
advantages are:
GaAs is also a direct semiconductor and therefore up to 90% of the
sunlight is absorbed in a film thickness of 2 pm.
The temperature dependency of efficiency in a GaAs solar cell is only
one-third of that of silicon due to the higher energy gap.
Furthermore, this binary semiconductor can be easily transformed into
a ternary semiconductor by the addition of elements from the third or fifth
group of the periodic table. This means that semiconductors with larger
Selected Solar Cell Types 187

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

In the first process (Figure 8.18) a molten mass of Ga is almost


completely saturated with As in a graphite crucible at a temperature of
approximately 850°C and dopants such as zinc and aluminium are added.
For processing, this is placed with the crucible open at the bottom over an
n-doped GaAs substrate. Firstly, a very small quantity of the n-GaAs is
dissolved from the surface and secondly, during contact with the molten
mass, zinc diffuses into the GaAs substrate thus doping a small part of the
substrate surface to a p-material (creation of a p-n junction) and thirdly,
within the dissolved layer near the surface some 85% of Ga is exchanged
for A1 (Alo,85Gao,~5As), thus creating a semiconductor with a band gap of
approximately 1.9 eV. Using this elegant method - in which all necessary
layers are created in a single step - an efficiency of >22% can now be
achieved (AM1.5) [76]. The process itself was described by Woodall and
Hovel as early as 1977 [77].
188 Crystalline Silicon Solar Cells

Figure 8.19 The structure of a high efficiency GaAs solar cell [78]

To improve efficiency still further n'-GaAs is required on the back


surface. Both epitaxy processes mentioned permit the creation of any
chosen layer sequence and dopant level. The structure of one such cell by
the MOVPE process is shown in Figure 8.19. This technique has been used
to produce the highest efficiency yet of 25% under AM1.5 conditions, or
with the same cell, 29% at 100 suns [78].
The use of a GaAs substrate is a large cost disadvantage. Great efforts
have therefore been made to deposit GaAs on another substrate. One option
is germanium, which has a thermal expansion mismatch of only 0.27% and
therefore permits a relatively fault free precipitation of GaAs [79]. Cells
produced in this manner are already used in satellite technology and
possess an average efficiency of approximately 18% (AMO) and could have
a big future in this field.
Silicon would be very desirable as a substrate material for reasons of
cost and better heat conductivity, but has an expansion mismatch of
approximately 4%. High stress would occur in the epitaxy layer and thus
high dislocation densities. A range of technologies is currently being tested
to circumvent this problem using a buffer layer. The individual layers are
heated several times and thus made stress free. A state is reached where the
Selected Solar Cell Types 189

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).

8.2.3 Cadmium-Telluride Solar Cells

Of the binary semiconductors it only remains to describe solar cells made


of CdTe. This material, with a band gap of 1.45 eV, is, like GaAs
described above, an almost optimal semiconductor for the conversion of
sunlight.
I90 Crystalline Silicon Solar Cells

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.

8.2.4 Copper-Indium-Diselenide Solar Cells

Of the different semiconductor compounds which are suitable for solar


cells, e.g. the so-called chalcopyrite semiconductor, the copper-indium-
diselenide cell has been the most highly acclaimed. This was described as
early as 1978 [87]. A good overview of this is provided by Schock [88]
and Mitchell [89]. The fact that high efficiencies were being achieved for
these thin film cells with no degradation being observed was partially
responsible for the increase in research activity in this field. Figure 8.21
shows the structure of a cell of this type. A layer of approximately 1 pm
thick molybdenum is deposited onto a glass substrate. Then the active layer
of Cu-In-Se, is deposited with a thickness of 1-3 pm in a high vacuum
using a multi layer evaporation process. As with all thin film cells a
window film of ZnO (band gap approximately 3.2 eV) is then deposited
onto a thin buffer layer of CdS with a thickness of 0.3 pm.
The CuInSe, layer itself is polycrystalline, so the influences of grain
boundaries and electronic states which exist in them strongly influence the
characteristics of photocurrent and open circuit voltage. In addition, low
defect densities are decisive for the very high efficiency of > 15% and
these can only be achieved using high vacuum evaporation techniques. The
Selected Solar Cell Types I91

- Al grid

n+ window film

n- buffer
p-absorber
p+-absorbe r
Back contact

Figure 8.21 Schematic layout of a CIS solar cell

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.

8.3 TANDEM SOLAR CELLS


For reasons of high utilisation of solar radiation it is desirable to connect
several solar cells with different band gaps together in series. For this
I92 Crystalline Silicon 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.

Transparent el. contact


llI
Glass
-- !‘I -a-Si-solar cell
+- / -Optical coupler
C
,S
I solar cell
Metal
Glass
Figure 8.22 Schematic structure of a four terminal tandem cell

However, the disadvantage of a serial connection of solar cells once


again appears. The weakest current from both cells determines the total
current and thus efficiency. By a suitable choice of band gaps it is possible
to roughly equalize the individual currents for radiation at AM1.5, but if
the intensity and spectrum of solar radiation changes a considerable
reduction in efficiency must be expected. Therefore, instead of a two
terminal contact each cell can be contacted individually. This involves an
additional cost. A conductive, transparent intermediate layer must also be
added. Furthermore, the electrical energy must now be managed by two
electrical charge regulators instead of one. We see that tandem cells are
connected with high costs and particularly complex technologies. Figure
8.22 shows the structure of a four terminal solar cell.
Two of this type of tandem cells currently at the research and
development stage are described here:
A GaAs tandem cell connected in series with a GaSb cell. A
concentration of 200 suns produces an efficiency of approximately
35%[93].
A combination comprising a cell made of a-Si on a CIS cell,
whereby the efficiency at one sun is 10%.
Selected Solar Cell Types 193

A multitude of different combinations is conceivable because it is


possible to alter the band gap of many thin film cells. Kriihler gives a
comprehensive overview of the entire field [94].

8.4 DYE-SENSITISED SOLAR CELLS


A semiconductor-electrolyte-contact cell can also be used to convert light
energy into electrical energy. The photovoltaic effect of this type of layout
was first observed by Becquerel in 1839.

Figure 8.23 The structure of a dye sensitised solar cell

A concept was developed by Gratzel in the late 1980s, which we will


explain using the schematic drawing in Figure 8.23 [95]. Nanoporous TiO,
is sintered at 500°C onto a glass plate, which is coated with a transparent
conductive oxide (TCO). A tin oxide doped with fluorine, which has a
sheet resistance of approximately 10 W O is used here as the conductive
film. The significantly more conductive IT04 cannot, unfortunately, be used
as it would not survive the sintering process. The semiconductor TiO, is
not an option for photovoltaics due to its band gap of approximately 3 eV.
It is transparent to sunlight; almost no absorption is possible. Therefore the
porous TiO, structure is coated with a dye based on ruthenium, such that
a monomolecular layer is created. The dye bonds chemically with the TiO,
surface. Visible light can be absorbed in this dye.

Indium Tin Oxide.


194 Crystalline Silicon Solar Cells

Sunlight is almost completely absorbed by the surface of the TiO,


colloids, which is now increased 1000-fold compared with a plain surface,
despite the extremely low absorption in the dye layer.

semiconductof aye ekcuolyte metal


counrer.elecrro5e

Figure 8.24 Schematic representation of a regenerative dye sensitised cell to


demonstrate cell voltage

The Ti0,-dye combination is placed in an electrolyte containing iodide


and triiodide. This cell is sealed by a further layer of TCO coated glass,
which is also platinum coated (using its catalytic effect). This is a very flat
cell, which is not clear from Figure 8.23. The dye coated TiO, layer is only
a few pm thick.
The functionality of this cell is based on the fact that light is absorbed
in the dye and thereb electrons are elevated to a higher energy level
(Figure 8.24, process (6). This level is above the conduction band edge of
titanium dioxide. Electrons are injected into the conduction band of the
TiO, (a) from this state. This charge injection, however, is in competition
with deactivation processes such as radiating and non-radiating
recombination. To get a good yield from the injection, the junction from
dye to TiO, must be such that the rate constant of charge injection is at
least 100 times greater than the rate of deactivation in the dye. With newly
developed dyes, charge injection of 90% is currently being achieved [96].
Unlike other solar cells, the electrons in TiO, are majority charge carriers,
which are thus not dependent on diffusion length.
The flow of electrons comes about because the electron loss from the
dye is quickly replaced by the iodide in the electrolyte, because it becomes
charged by giving up electrons, thus becoming triiodide ions (a).
These
Selected Solar Cell Types I95

electrons are neutralised at the backplate electrodes (0). The missing


electrons come through the outer circuit of TiO, (a).The flow of current
is thus ensured. These individually very complex processes can be found in
publications [97]-[ 1001.
Efficiencies of over 10% are currently being achieved. Despite the
simple structure of the cell - it requires no high temperature processes, no
expensive vacuum evaporation processes and no clean room technologies
- there are still a number of questions which require answers. One
significant problem is still long-term stability. A further question is the
acceptability of liquid solar cells. Attempts have been underway for years
to replace liquid electrolytes by a solid electrolyte. Conductive polymers
are a starting point in the search for a solid electrolyte. However, up until
now, no usable results have been achieved. Module manufacture is
naturally an important question - parallel and serial connection - with the
familiar problem of achieving as narrow a distribution of cell parameters as
possible. This cell concept is still at the research stage.

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Selected Solar Cell Types 197

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I98 Crystalline Silicon Solar Cells

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Selected Solar Cell Types I99

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200 Crystalline Silicon Solar Cells

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Analytic and Measuring Techniques

Measuring individual parameters and determining their complex


relationships is a fundamental prerequisite for the development and
advancement of solar cells. The more precisely these relationships and
dependencies can be determined, the more precisely can concepts for the
improvement of parameters be implemented. Because of the familiar cost
situation, two guiding principles must be followed. On the one hand, it is
necessary to make the solar cell efficiency as high as possible; on the other
hand, more cost effective technologies must be developed. An optimal
compromise between cost reduction and efficiency must be achieved. It is
for this reason that analysis is of such great importance.

9.1 CURRENT-VOLTAGE CHARACTERISTICS


As already mentioned, there is an international agreement that the
efficiency of solar cells should be measured under the AM13 spectrum. In
the laboratory, this radiation is approximated by a sun simulator. Figure 9.1
shows the block diagram for one such measuring set-up.
The light source is a xenon ultra high pressure lamp, which gives an
almost white spectrum, as the individual xenon spectral lines undergo a
high level of pressure broadening. The high intensities which still occur in
some spectral ranges are reduced by special filters to the extent that a good
approximation of the AM1.5 spectrum is achieved. The intensity is
calibrated using a specially calibrated solar cell, which must conform to
certain requirements. Its short circuit current must be in strict proportion to
radiation output. This means, for example, that diffusion length and surface
recombination of the calibration cell in its field of application must be
independent of the radiation.
To increase measuring precision, the intensity variations of the light
source are reduced by feedback of the measured intensity to the power
202 Crystalline Silicon Solar Cells

Sun simulator
AM1.S

Figure 9.1 Block diagram of a sun simulator

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.

9.1.1 Measuring the I-V Curve under Illumination

The current-voltage characteristic is measured by monitoring the current


from the solar cell point by point from zero to the short circuit current
using an electrical load regulator. From the current and voltage data
measured the computer calculates:
the open circuit voltage V,,,
the short circuit current I,,,
the current I, and voltage V, at the maximum power point,
the fill factor FF, and
the efficiency q.
All cell parameters are thus available, which are required for an
assessment of the quality of the cell and which the user needs, e.g. for the
construction of modules.
The actual analysis begins with the determination of the physical
variables that are responsible for the solar cell parameters.
Based on the discussion in the previous chapters, these are dependent
upon
Analysis and Measuring Techniques 203

the dark currents or saturation currents in the emitter and base,


the diffusion lengths of the charge carriers,
the surface recombination velocities on the front and back surface, and
the serial and parallel resistances.
In addition, shadowing by contacts, surface reflection and long
wavelength radiation, which is not absorbed, must also be determined.

9.1.2 Measuring the Dark Current Characteristic

The dark current characteristic, which determines the current-voltage


characteristic line for the solar cell as a normal diode, can be found using
the measuring system described above. The typical form of such a
characteristic is shown in Figure 9.2. The individual ranges of the
characteristic can be assigned different variables in the two diode model.
The diode equation ( 5 . 2 . 2 4 ) is repeated here.

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

must be overcome. The series resistance can be determined from the


difference between the two voltages:

(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)

Determining the dark current characteristic offers another advantage. It


can also serve to calculate the behaviour of solar cells - and therefore solar
modules - in advance for different climatic conditions, such as radiation
and temperature [ 1],[2]. Normally these dependencies can only be
determined by measurements of the I-V curve under illumination. However
by transferring the ratings from the dark current measurement to the
measurement under light (superimposition principle), these relationships can
be determined based on the much simpler temperature and intensity
relationships of the dark current characteristic. Good predictions can thus
be obtained about the energy yield of the solar plant.
Since it is of great importance to know how the efficiency of solar cells
depends upon temperature and radiation, we will include the calculation for
temperature and intensity dependencies at this point .

9.I . 2.1 Dependence of Efficiency on Radiation

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)

Thus the formula for efficiency reads

(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)

With the value for silicon of

kT
-
(9.1.8)
-4 x 0.04
voc

we find as a rule of thumb

A -r [YO] x 4xlnn (9.1.9)


rl
The efficiency of a silicon solar cell thus decreases, for example to
approximately 3% (relative) at half the radiation intensity.

9.1.2.2 Dependence of Efficiency on Temperature

We here assume radiation and therefore short circuit voltage to be constant.


The fill factor can also be assumed to be constant here. The relative change
in efficiency is then equal to the relative change in open circuit voltage. So

(9.1.10)

where
Analysis a n d Measuring Techniques 20 7

(9.1.11)
L p NrJ

We further assume that in the first approximation the temperature


dependency of the diffusion length and the diffusion coefficients can be
disregarded. I, then changes with the temperature only due to changes in n,.
Then where

ni2 = const. exp ( EgI kT) (9.1.12)

we can write for the dark current density

Z, = B exp (-E, I k7') (9.1.13)

where B contains several constant factors.


Then where V,,%(kTlq)x ln(ZJ1,)

Voc = - [ g]
k T ln-
4
+-
Eg

4
(9.1.14)

If we differentiate this equation for temperature - disregarding the small


change in band gap with temperature - we find that by replacing B with an
expression for V,,

(9.1.15)

As a rule of thumb we find that for silicon

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.

9.2 SOLAR CELL SPECTRAL RESPONSE

9.2.1 Spectral Response of a Front Illuminated Solar Cell

Spectral response is defined as the dependence of the collected charge


carriers (solar current) on the radiated photons of different wavelength
ranges. In the case of so-called external spectral response the total number
of radiated photons is counted, whereas in the internal case only those
entering the crystal are counted.
To determine this value the solar cell is illuminated with light from
different spectral regions. The layout of this measuring instrument is shown
in the block diagram Figure 9.3. The xenon high pressure lamp is again
used as the light source. Its light is guided through different colour filters
by a UV transparent fibre optic. The filter wheel is typically fitted with 19
filters, covering a wavelength range of 350-1019 nm (350 nm is the limit
for short wavelength light, where sunlight is still present; 1019 nm is the
approximate band edge of silicon; Ga-As cells can naturally also be
measured because their band edge lies below the value for silicon). The
band width of the individual filters is 8-10 nm.’
The light is first ‘chopped’, e.g. using a frequency a little above 100 Hz
(integral multiples of the mains frequency must be avoided due to coupling
mechanisms). After travelling through the filter the light is guided by a
beam splitter onto the test cell (half of the light) and the reference cell
(second half of the light).
Here, too, specific requirements are made of the reference cell. In the
intensity range from roughly 1/100 to 1/1000 sun the short circuit current
must be proportional to the intensity of the radiated light. It may not be a

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

0.9 1.0 1.1 1.2


Wavelength (nm)
Figure 9.4 Internal spectral response of a high efficiency cell with a transparent
emitter

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.

9.2.2 Spectral Response of a Back Surface Illuminated Solar Cell

In order to determine smaller surface recombination velocities as well,


Lillington and Garlick [ 5 ] suggested a method which is described in what
follows.
Analysis and Measuring Techniques 21 I

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

80 - S,, = 100 cm/s

60 -
1000

- -
E 40
v5:
20 -
'01

I I
0
300 500 700 900 1100
Wavelength (nm)

Figure 9.6 Calculated internal spectral behaviour of a back surface illuminated


solar cell

9.3 THE PCVD MEASUREMENT TECHNIQUE

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

Figure 9.7 Block diagram for a PCVD apparatus

The cell under investigation is excited, preferably by laser pulses. To be


precise this measuring apparatus is operated by an Nd-YAg laser which
emits light with a wavelength of 1064 nm. We thus obtain a consistently
high level of charge carrier creation in the entire base (due to the very low
absorption coefficient for this wavelength). A diode laser can also be
implemented, which emits light at a wavelength of 904 nm.
The decay of V,, and I,, is measured. From the different states and
distributions of the charge carriers produced, the following variables can be
determined:
the effective surface recombination velocity of the emitter,
the emitter saturation current (with good passivation),
the diffusion length in the base, and
the effective surface recombination velocity on the back surface.
However, it is also true that only those recombination parameters that
are dominant in the test cell can be relatively precisely determined.
214 Crystalline Silicon Solar Cells

However, it is still possible to determine the individual influencing


variables in a high efficiency solar cell with good surface passivation.
The test cell is first measured with the passivating surface. Then the
silicon dioxide on the back surface is removed. A In-Ga friction contact is
then deposited on the back surface, thus obtaining a surface recombination
speed greater than lo6 cm/s. The cell is measured once again and the
individual influencing variables can now be separated [8],[9].

9.4 TKE PCD METHOD

The measuring techniques described up to now all have in common that


ohmic contacts must be attached to take measurements. Therefore a
complete separation of recombination values, based upon the volume or
originating from the surface, cannot be achieved. With the PCD method
(Photo-Current-Decay) this is possible, since it does not require ohmic
contacts [ 101.
As shown in Figure 9.8 the silicon wafer under investigation is placed
in a high frequency resonant circuit, operated at a frequency of 13.56 MHz

I Nd YAg laser: 1064 nm, pulse

HF generator HF bridge Low pass filter

Figure 9.8 Block diagram of a PCD measuring apparatus


Analysis and Measuring Techniques 215

(the frequency permitted for research and industry) at about 1 mm distance.


Its electrical conductivity results in the damping of the resonant circuit. The
high frequency bridge is adjusted before measuring, such that the
differential current in the bridge is close to zero.
For the measurement, charge carrier pairs are created in the silicon
wafer using a flash bulb or a laser. The conductivity of the silicon wafer is
thus greatly increased, and the resulting detuning of the resonant circuit
causes a bridge current. After the light source is switched off the
conductivity of the silicon wafer returns to its original state, and the bridge
current decays. The decay of this current is measured (the filter serves to
suppress the upper harmonics). The data are picked up by a storage
oscillograph and processed by a PC. This measuring process allows us to
determine two parameters: (a) the emitter saturation current, and (b) the
surface recombination velocity.

9.4.1 Determining the Emitter Saturation Current

This saturation current is becoming ever more important because the


dominance of saturation current from the base decreases with the increasing
diffusion length of the charge carriers and lowered surface recombination
on the back surface. For very high efficiency the saturation current from
the emitter region must therefore be reduced.
To determine the emitter saturation current an n+ emitter is diffused
from both sides into high resistivity p-Si (> 100 S2cm). The important point
is that the cell is illuminated with such a high level intensity that high level
injection occurs in the base, whereas the emitter remains in low injection
due to its high dopant concentration. It follows from this that after the light
source has been switched off, the recombination of charge carriers in the
base is directly proportional to the carrier density, whereas the
recombination rate in the emitter is proportional to the square of the carrier
density. It is therefore possible to separate these two recombination effects.
The carrier density at different times during the decay is found from the
conductivity at the time, which is closely linked to the carrier density by
mobility. Based on this data, the computer reports the decay transient for
the carrier density. The result is given here, without going into the
theory [ 101.
216 Crystalline Silicon Solar Cells

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

If we plot the reciprocal momentary decay time T,,,,~ against the


corresponding average carrier density n, we find the following relationship:’

(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.

’ We have intentionally used the same designations as used in the above


mentioned literature of Kane and Swanson [ 101.
Analysis and Measuring Techniques 21 7

From the gradient of the straight line we can find the saturation current in
the emitter. This gradient is

(9.4.2)

The value can


thli be determined from the intercept of the axis.

9.4.2 Determination of the Surface Recombination Velocity

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.

9.5 MICROWAVE DETECTED PHOTOCURRENT DECAY

An improved method for determining the recombination parameters of a


silicon sample is microwave detected photocurrent decay (MW-PCD)
[12]-[15]. This differs from the inductive coupled PCD described in the
preceding section in the detection method of changes in conductivity.
The sample is located on a microwave antenna (see Figure 9.10) and is
illuminated by pulses from a Nd-YAg laser (wavelength = 1064). The
charge camers created in this manner An alter the conductivity Q of the
sample by Ao:

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.

Microwave Circulator Detector


source
Figure 9.10 Principle layout of MW-PCD (from [ 151)

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,

The variable y must therefore be defined with an eigen value equation,


which is dependent only upon the surface. For the case where S , = S, an
approximation can be found which can be directly solved [18],[19]:
Analysis and Measuring Techniques 219

- 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)

MW-PCD can be applied for very varied reasons. One important


application, for example, is the determination of the bulk lifetime for
different materials, since this variable, as shown in the previous chapters,
is decisive for solar cell efficiency. For this, the influence of the surface
recombination speeds must be reduced as far as is possible, so that the
measured variable corresponds with T~ as well as possible. One method
for minimizing S is the deposition of the wafer in an iodine/ethanol
solution during the measurement [ 2 0 ] .After a dip in hydrofluoric acid the
wafer is briefly rinsed and placed in a 1% iodine/ethanol solution and
measured. Using this method recombination velocities of 1 cm/s can be
achieved, i.e. the surface influence can be disregarded during the
measurement and T~ is measured direct. In this manner it is not only
possible to measure unprocessed starting material, but also the change in
220 Crystalline Silicon Solar Cells

bulk lifetime in silicon after various processing stages, since MW-PCD


works without contact and is non-destructive.
MW-PCD can also be used to determine surface recombination
velocities. To determine the value of S for an SiO, film, for example, the
effective lifetime of a SiO, wafer, passivated on both sides, is measured.
The highest level of precision for the value of S is achieved for silicon with
a high lifetime, since then T~~ is determined primarily by recombination on
the surface. The passivating film is then removed from both sides and the
wafer is measured in the iodine/ethanol solution (see above), so that tb can
be measured. This value of T~ allows us, with the help of the equation
(9.5.2), to determine the surface recombination velocity of the SiO, layer
or other passivating mediums with a high degree of precision.

9.6 MODULATED CHARGE CARRIER ABSORPTION

The modulated free charge carrier absorption, MFCA [21], represents


analternative method of determining minority charge carrier lifetime. An IR
laser beam transmitted by the sample (hv > E,) is used to determine the
charge carrier density [22],[23]. Owing to the free charge carrier
absorption, the absorption of the IR laser beam at a not too high charge
carrier density is directly proportional to the integral charge carrier density
N

(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

where An is the time and position dependent excess charge carrier


concentration, D is the diffusion constant, x is the depth coordinate, Tb is
the bulk lifetime and G(x,r) is the generation function. The boundary
conditions of this differential equation are given by the surface
recombination velocities S , and S,, and the surface recombination rates U s ,
and Us2:

(9.6.3)

where W is the sample thickness. After a long calculation using a Fourier


transformation we find the following complex function for the integral
charge carrier density, in relation to the modulation frequency a:

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.

, . I . .....I . . . ....., . . , .....I . . . . .... 2


11)

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)

Figure 9.12 Amplitude and phase curves for different recombination


parameters (from [ 151)

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

HeNe laser 3390 nm

!’

Laser diode

Signal Reference signal

-
- 0

Figure 9.13 Layout of MFCA (from [ 151)

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

Figure 9.14 Lifetime topography of a multicrystalline Si probe

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

Figure 9.15 Short circuit current topography of the same multicrystalline Si


probe as in Figure 9.14

9.7 SHORT CIRCUIT CURRENT TOPOGRAPHY (LBIC)

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

Figure 9.17 LBIC picture of a multicrystalline Si solar cell

roughly the amount of the cell thickness [27].

9.8 THE DLTS PROCESS

We should briefly mention the DLTS process, developed by Lang [28]. We


cannot and do not want to go into this any further and refer to the
specialist literature [29],[30]. Using this method it is possible to determine
an extremely low impurity concentration in a semiconductor according to
type and quantity. It permits the determination of concentrations that lie up
to five orders of magnitude below the dopant concentration.
Furthermore, the process permits the determination of the energetic level
and density of the states in a surface passivated with SO, [31],[32]. These
investigations show that the surface recombination velocity depends upon
the carrier density and thus the strength of the solar radiation.
228 Crystalline Silicon Solar Cells

References

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Raicu A,, Thesis, Univ. Freiburg, 1991
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Lillington P. R. and Garlick G. F. J., Proc. 18th IEEE PV Spec. C o n f ,
Las Vegas, 1985, p. 1677
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Rose B. M. and Weaver H. T., J . Appl. Phys. 54, 1983, p. 238
Bergmann R., Dissertation, Univ. Freiburg, 1988
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Kopp J., Knobloch J. and Wettling W., Proc. Zlth EC PV Solar Energy
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Analysis and Measuring Techniques 229

Schroder D. K., Semiconductor A4aterial and Device Characterization, John


Wiley&Sons, New York
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Appendix A

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

i Electric current P Electrical power


density prn Maximum power
k Boltzmann constant Pn Number of holes in the n
Ln Electron diffusion region
length PP Number of holes in the p
Hole diffusion length region
Transport length Elementary charge
Effective mass of Total electric charge
electron Recombination rate
Effective mass of hole Various serial resistances
Doping concentration Reflection coefficient
Refraction index of Parallel resistance
the antireflection R, Serial resistance
layers s n Surface recombination velocity
Acceptor of electrons
concentration Surface recombination velocity
Effective density in of holes
the conduction band Temperature
ND Donor concentration Applied voltage
"i Intrinsic carrier Diffusion voltage
dcnsity Temperature voltage
"n Number of electrons Voltage at maximum power
in the n-region point
"0 Refraction index in air VLX Open circuit voltage
"P Number of electrons "th Thermal velocity
in the p-region W Width of space charge
Surface concentration region
Effective density of Penetration depth
states in the valence
band
Appendix B

PHYSICAL CONSTANTS

4 Elementary charge = 1.602x 10 -I9 C


h Planck’s constant = 6 . 6 2 5 ~ JS
m, Electron rest mass = 1.1096~10”’ kg
k Boltzmann’s constant = 1.381 x IO”’ J/K
c Speed of light in vacuum = 2 . 9 9 8 ~
lo8 m / s
kT/q Thermal voltage = 0.02586 V (500 K)
€0 Permittivity in vacuum = 8 . 8 5 4 ~
10‘” F/m

SELECTED SI PARAMETERS AT 300 K

E, Energy gap = 1.124 eV


N, Effective density of states in the conduction band = 2 . 8 6 loL9
~ cm”
N, Effective density of states in the valence band = 3 . 1 0 ~ 1 0cm”
’~
“i Intrinsic carrier concentration = 1 . 0 8 10”
~ cm.’
P” Mobility of electrons (lO%rn” 300K) = 1110 crn2/Vs
,up Mobility of holes (1016cm”300K) = 410 cmZNs
Y Density = 2.33 g / 6311.’
eSi/ e, Dielectric constant 11.9
INDEX

Index Terms Links

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

Back surface field 92


Band gap 12
Band gap narrowing 96
Band structure 13
Barrier height 104
Bond, homopolar 10
Buffer layer 177
Busbar 113

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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
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Dark current characteristic 84 203


Dead layer 151
Defect level 27
Degradation 165
Diamond lattice 10
Diffusion
coefficients 148
constant 27
current 27
length 41
technology 148
Diode equation 64
DLTS process 226
Donor 24
Doping 24 25
base 98
influence of 42
Double diffusion process 151
Drift 22

Efficiency 71 87
EFG process 142
Einstein formula 29
Electrical conductivity 11

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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

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Gaussian distribution 141


Generation 20
Gettering 137 170
Glow discharge reactor 181
Grain boundary 139

Hole 14

Impurity conduction 24
Injection
high 40
low 40
weak 60
Intrinsic conduction 20

Kendall equation 44

Lambert's reflection 120


Lattice absorption 30
Lift off technique 157

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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

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Phosphor profile 150


Photocurrent 90
Photolithography 156
Photon energy 30
Poisson's equation 45
Potential difference 51
Potential, electric 51
Pulling speed 142
Pyramids, inverted 119

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

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Resistance (Cont.)
shunt 79 85

Segregation coefficient 139


Semiconductor 9
direct 30
indirect 32
Separation process 142
Shottky contact 103
Silicon
columnar 139 169
metallurgic 133
polycrystalline 135
powder 143
Solar array 87
Solar cell physics 67
Solar cell
amorphous 181
bifacial 166 210
buried contact 166
cadmium telluride 189
CIS 190
dye sensitised 193
gallium arsenide 185
IBIC 164
MIS 168

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Solar cell (Cont.)


real 72
tandem 191
thin film 170
Solar constant 5
Solid 9
Space charge 51
Space charge region 50
capacitance 57
width 57
Spectral response 210
SSP process 143
Sun simulator 201
Surface concentration 90
Surface recombination velocity 74

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

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Vacuum evaporation technology 157


Valence band 12
Voltage
built-in 82
diffusion 52
open circuit 70 91
thermal 52

Window layer 184

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