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Physics of Thin-Film
Photovoltaics
Scrivener Publishing
100 Cummings Center, Suite 541J
Beverly, MA 01915-6106
Publishers at Scrivener
Martin Scrivener (martin@scrivenerpublishing.com)
Phillip Carmical (pcarmical@scrivenerpublishing.com)
Physics of Thin-Film
Photovoltaics
Victor Karpov
and
Diana Shvydka
This edition first published 2022 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA
© 2022 Scrivener Publishing LLC
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Library of Congress Cataloging-in-Publication Data
ISBN 9781119651000
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Cover design by Russell Richardson
Set in size of 11pt and Minion Pro by Manila Typesetting Company, Makati, Philippines
Printed in the USA
10 9 8 7 6 5 4 3 2 1
Dedication
To our parents
v
Contents
Preface xi
Part I General and Thin Film PV 1
I. Introduction to Thin Film PV 1
A. The Origin of PV. Junctions 1
B. Fundamental Material Requirements 3
C. Charge Transport. Definition of Thin Film PV 4
D. Distinctive Features of Thin Film PV 7
References 11
Part II One-Dimensional (1D) Diodes and PV 13
II. 1D Diode 13
A. Metal-Insulator-Metal Diode 13
B. Schottky, Reach-Through, and
Field-Compensation Diodes19
1. Schottky Diode 19
2. Reach Through Diodes 21
3. Field Compensation Diode 23
C. P-N Homo-Junctions 24
D. Heterojunctions 26
E. Other Relevant Types of Diodes 28
F. Field Reversal Diode: A Counterintuitive Case 29
G. Cat’s Whisker Diode 30
III. 1D Solar Cell 32
A. 1D Solar Cell Base Model 32
B. Numerical Modeling of 1D PV 38
1. Governing Equations 39
2. Device Model Parameters 40
3. Some Modeling Results 42
IV. Photovoltaic Parameters 43
A. Second-Level Parameters 44
B. Practical Solar Cells and Third-Level Metrics 46
vii
viii Contents
C. Indicative Facts 49
D. Phenomenological Interpretation. Ideal
Diode with Other Circuitry Elements 52
V. Case Study 54
A. Field Reversal PV 54
1. Analytical Approach 55
2. Numerical Modeling of the Field
Reversal Device Operations 60
B. Miraculous Back Contact 68
References 72
Part III Beyond 1D: Lateral Effects in Thin Film PV 79
VI. Examples of Multidimensional Numerical Modeling 79
VII. Introduction to Random Multidimensional
Phenomena81
VIII. Lateral Screening Length 84
A. Shunt Screening 84
B. Bias Screening 85
C. Quantitative Approach and Linear
Screening Regime 88
IX. Schottky Barrier Nonuniformities 91
X. Semi-Shunts 93
XI. Random Diodes 96
A. Weak Diodes 96
B. Random Diode Arrays in Solar Cells 99
C. Random Diode Arrays in PV Modules
and Fields 105
XII. Nonuniformity Observations 109
A. Cell Level Observations 109
B. Module Level Observations 118
XIII. Nonuniformity Treatment 121
References 125
Part IV Electronic Processes in Materials of Thin Film PV 131
XIV. Morphology, Fluctuations, and the Density of States 132
A. The Materials of Thin Film PV
are Fundamentally Different 132
B. Noncrystalline Morphology 134
C. Long Range Fluctuations of Potential Energy 136
D. Random Potential in Very Thin Structures 139
E. Numerical Estimates and Implications 142
XV. Electronic Transport 144
Contents ix
A. Band Transport in Random Potential 144

B. Hopping Transport Through Thin
Noncrystalline Films 147
1. Hopping Between Ideal Electrodes 149
2. Hopping Between Resistive Electrodes 151
3. Critical Area and Mesoscopic Fluctuations 153
XVI. Recombination in Quasi-Continuous Spectrum 155
XVII. Noncrystalline Junctions 161
XVIII. Piezo and Pyro-PV 164
A. The Nature of Piezo-PV 164
B. Piezo-PV Observations 169
C. The Significance of Piezo-PV 171
References 174
Part V Electro-Thermal Instabilities in Thin Film PV 181
XIX. The Two-Diode Model 182
A. Linear Stability Analysis 183
B. The Two-Diode Modeling: Numerical
Estimates and Scaling 184
XX. Distributed Diode Model 186
A. Introduction 186
B. Linear Stability Analysis 187
XXI. Simplistic Numerical Modeling 188
XXII. Spontaneous Hot Spots 190
A. Introduction 190
B. Observations 191
C. Numerical Modeling 195
1. Electrical Model 195
2. Thermal Model 199
D. Modeling Results 200
E. Approximate Analytical Model 205
XXIII. Related Work 207
XXIV. Conclusions on the Electro-Thermal
Instabilities in Thin Film PV 209
References 210
Part VI Degradation of Thin Film PV 213
XXV. Thin Film vs Crystalline PV Degradation
Processes213
XXVI. Observations 215
A. Cell Degradation 216
B. Module Degradation 222
x Contents
XXVII. Categories of Degradation 225

A. General Categories 225
B. Thin-Film PV Instabilities 227
1. Shunting Instability 227
2. Contact Delamination Instability 229
XXVIII. Accelerated Life Testing 231
A. Examples of Very Strong ALT: HALT 232
1. EBIC HALT 232
2. LBIC HALT 234
B. Actuarial Approach to ALT 235
C. Concluding Remarks on Degradation 236
References 237
Appendix. Some Methodological Aspects of Device Modeling 243
Appendix A: Model of Series Connection 243
Appendix B: The Diffusion Approximation 245
Appendix C: Long Range Potential 248
1. Point Changes 248
2. Columnar Charges 251
References 253
Index 255
Preface
There is no longer a need to argue about the importance of solar energy and
the necessity of furthering the photovoltaic (PV) industry. These issues have
been addressed by many sources in the media and publications. Excellent
books have been published covering the basics of photovoltaics including
both the underlying classical physics and material implementations.
Taking advantage of the above issues sufficiently presented, this book
will concentrate on several subjects left beyond the scope of the exiting
photovoltaic texts. These subjects are all related to thin film photovoltaics
(such as CdTe, CIGS, or a-Si:H based) whose properties and operations
turn out to be quite different from that of the classical PV presented mostly
by the crystalline Si structures. The obvious differences lie in the device
thinness (microns instead of millimeters) and its morphology (polycrys-
talline or amorphous instead of crystalline).
The thinness effect may be so significant that the photogenerated charge
carriers reach the electrodes without much recombination even in the
imperfect non-crystalline material, which deemphasizes the classical con-
cept of recombination limited PV performance. On the other hand, the
transversal resistance not self-averaging across thin disordered structures
leaves a possibility of significant lateral nonuniformities, some of which
can be quite detrimental. In addition, the non-crystalline morphology
leads to continuous energy spectra of localized states instead of discrete
levels in crystals, which results in new transport mechanisms (hopping)
and recombination features. Finally, an important part of thin film PV
possess piezo-electric properties, which leads to the concept of piezo-PV
unknown in the classical PV science.
Taken together, the latter subjects form the physics of thin film PV as a
distinctive field of its own. This book will for the first time provide a con-
sistent presentation of that field. In other words, this book will not describe
the material of classical PV science, which has been masterfully described
in other PV books, but will instead introduce material that has never been
presented in PV books before.
xi
xii Preface
To better explain our book title, we would like to emphasize the term
of physics as defining the filed that is not necessarily related to the object’s
materials, chemistry or engineering. The physics was always related to phe-
nomena per se, regardless of the material specificity. Think, for example,
of the Newton’s second law where the material structure does not matter,
think about the fact that the Planck’s constant and Boltzmann’s constant
do not depend on which material they describe, and how, in the physics of
disordered systems, it does not matter what is the chemical composition
of a system, etc. Similarly, in the photovoltaic science, the basics (built-in
field, junction, and so on) remain material unspecific. Along these lines,
our book concentrates on the aspects that are not sensitive to the material
structure or composition. That is not to denigrate the known great contri-
butions to photovoltaics from the materials sciences and chemistry, which
appear dominant from any query of recent publications, but rather to pref-
ace our book limitations.
In our experience, the concept of a distinctive field of thin film PV phys-
ics may not appear obvious to everybody: quite a few in the community
believe that thin film PV must be understood in the framework of classical
PV science developed earlier and proven for thick crystalline systems. Such
a resistance appears rather paradoxical given that thin film PV is made of
materials that seem unacceptable from the classical PV perspective, and
yet they often outperform classical PV. Our book solves that paradox by
switching to a new physics paradigm.
The book is naturally broken into six parts, each containing several
interrelated sections.
Part I, consisting of just section I, gives a general introduction to PV
including the concepts of junctions, material requirements, and distinctive
features of thin film PV.
Part II, encompassing sections II to V, concentrates on one-dimensional
concepts relevant to thin film PV. It presents a densely populated zoo of
various diodes, some quite different from p-n junctions, including the ones
that play a significant role in thin film PV operations. It then extends that
diode consideration on one-dimensional analysis of solar cells, including
some important case studies.
Part III, made up of sections VI to XIII, takes the consideration beyond
one-dimensional physics considering lateral effects, such as shunting, ran-
dom micro-diodes, weak diodes, etc., addressing both the related theory
and observations.
Part IV, including sections XIV to XVIII, concentrates on electronic pro-
cesses in disordered materials of thin film PV which addresses morphology,
fluctuations, transport properties, recombination in the quasi-continuous
Preface xiii
spectrum of localized states, operations of nonocrystalline junctions, and,

finally, piezo photovoltaics.
Part V, formed by sections XIX to XXIV, presents the subject of
electro-thermal instabilities in thin film PV starting from the exactly
solved two-diode model and current hogging to spontaneously formed hot
spots conducive of performance degradation.
Part VI includes sections XXV to XXVIII and discusses a sensitive issue of
device degradation for thin film PV, including both solar cells and PV modules.
It then discusses the problematic of accelerated life testing and risk analyses.
Finally, our book has an Appendix that comprise three parts of method-
ical value” the validity of in-series representation of complex band dia-
grams, the nature of saturation current in diode models, and accurate
estimates for the electron potential fluctuations.
We are grateful to many people who have helped us to learn the subjects
presented in this book. Our exposure to PV science and industry started
with First Solar LLC (Perrysburg, OH) before the year 2000, at which time
its research and production groups combined many enthusiastic contrib-
utors including H. McMaster, G. Dorer, G. Nelson, R. C. Powell, D. Rose,
U. Jayamaha, E. Bykov, T. Maxon, R. Harju, T. Colman, L. McFaul, N. Reiter,
T. Kahle, G. Khouri, G. Rich, M. Steel, and many others, to all of whom we
are grateful for their intelligent friendly support. We would like as well
to acknowledge our interactions with the PV group of the University of
Toledo including A.D. Compaan, X. Deng, A. Vijh, D. Giolando, A. Vasko,
Y. Roussillon, V. Parikh, L. Attigalle (Cooray), M. Mitra, M. Nardone, X. Li,
V. Plotnikov, K. Wieland, and J. Drayton. Finally, we would like to express
our gratitude to the members of CdTe PV National Team at NREL, starting
with their remarkable managers K. Zweibel, B. von Roedern, H. Ulllal, and
brilliant contributors B. McCandless, D. Albin, V. Kaydanov, T. Ohno, J.
Sites, T. Sampath, A. Fahrenbruch, and so many others.
This book is intended for three readership categories. One is that of
graduate and advanced undergraduate students with some understanding
of the general physics and familiarity with the basic concepts of condensed
matter. We hope that our book will bring to them a flavor of live physics in
an informal manner as used by practicing researchers. It may help to open
their eyes to a more general fact that the science of physics often evolves
in its own ways quite different from those implied by the standard curric-
ulum textbooks, and, for some, to become an evidence that physics can be
relevant for PV.
Our next category of readers belongs to those in academic teaching and
research revolving around semiconductors, device physics, and thin film
structures. For that category, we aim to provide a fresh look at a number
xiv Preface
of subjects so established that they appear “carved in stone” for ages as

dictated by the classical photovoltaic science developed during the times
when thin film technology PV did not exist. Our book will invite that cat-
egory of readers to pay more attention to the issues of variability and sta-
tistics apparent to those working for industry rather than for academia.
Finally, we hope that some of our book topics and approaches can become
a part of university curricula for PV/device physics or related disciplines.
We identify our third category of readers as the industrial R&D profes-
sionals of all levels. Their business responsibilities and hectic environment
do not often leave much time to follow the published research and appreci-
ate new concepts. We believe that our book will help the curious readers of
that category to broaden their horizons and open new approaches towards
technology goals. On top of that, adopting some concepts of our book
could create beneficial synergy between physics and solar technology.
Victor Karpov
Diana Shvydka
Sylvania, Ohio, USA
February 2021
Part I
General and Thin Film PV
I. Introduction to Thin Film PV

A number of brilliant texts are readily available describing the general
photovoltaic (PV) principles and their classical implementations [1–6], as
well as various specifics of thin film PV [7–11], and we are not going to
duplicate them in any form. This section will briefly overview main book
concepts especially addressing the underlying physics of PV functionality
different between the crystalline and thin film devices. Such a synthetic
view will help to inter-relate various sides of the physics of thin film PV as
a subject of its own.
A. The Origin of PV. Junctions

We recall that PV effect in general is presented by the light generated voltage.
The PV voltage when the system absorbed light creates electric asymmetry
in the form of spatially separated opposite electric charges, electrons and
holes, which can be extracted and utilized in the form of electric current.
For the charge separation to occur, there must be a built-in electric field
as illustrated in Fig. 1 presenting a basic design of PV devices made of
two semiconductor layers. The built-in field originates from the junction
formed by those layers. Historically, such junctions were between p- and
n-types of semiconductor layers; hence, the name of p-n junctions tradi-
tionally associated with PV devices. However, p-n junctions are neither
necessary nor sufficient elements of systems with built-in fields as dis-
cussed below. For example, semiconductor/metal junctions in Fig. 1 will
generate their own built-in fields that can be either beneficial or detrimen-
tal to PV device functionality.
In general, the built-in electric fields always emerge with junctions of
any two chemically different materials. The underlying physics is that one
of the materials will be energetically more favorable for the electrons than
the other. To minimize the system energy, the electrons will therefore
Victor Karpov and Diana Shvydka. Physics of Thin-Film Photovoltaics, (1–12) © 2022 Scrivener
Publishing LLC
1
2 Physics of Thin-Film Photovoltaics
light
front contact
Layer 2
Layer 1
back contact
Fig. 1 Conceptual design of a solar cell. Front and back contacts are metallic, and the
former one is transparent to light (shown in waving lines). The presented built-in electric
field E is caused by the dark positive and negative charges shown as + and –. R is a load
resistor. For specificity, the diagram presents a two semiconductor layer design, such as
p- and n- materials with the field E in their junction proximity. However, sufficient electric
fields can exist as well in the proximities of semiconductor-metal junctions.
move there leaving the one with unbalanced positive charge; hence, the
built-in field between the spatially separated opposite charges of electrons
and holes, qualitatively similar to that of electric capacitor. The number of
electrons moving across the junction is determined by the balance between
the above mentioned energy gain and the energy loss due to the necessity
of overcoming the Coulomb attraction to the positive charges left behind.
The built-in electric fields of that nature are omnipresent and are not lim-
ited to photovoltaics, or p-n junctions, or other artificial structures.
Another reading of the latter statement is that photovoltaics do not nec-
essarily have to be related to or understood in terms of p-n junctions. In
reality, any (not only p-n) junctions of different materials produce built-in
electric fields. Some of them, but not all, create photovoltaic effect.
For example, a junction of two metals produces the built-in field under-
lying the phenomenon of thermoelectricity, but not suitable for PV because
the light does not penetrate in a metal deep enough and because that field is
screened (by metal electrons) beyond a nanometer thin region, insufficient
for light absorption. However the built-in fields of metal/semiconductor
(rather than metal/metal) junctions can make good diodes and PV devices.
As another example, we point at a charge acquired by a solid particle
immersed in a liquid. Curiously, that example explains how wines and
many other liquid products consist of charged micro particles suspended
in a somewhat ionized water. We will return to that example later in the
book describing the so called “red wine effect” in PV.
Note that junction fields require electronic exchange between two mate-
rials while their direct physical contact is not necessary. As an illustration,
General and Thin Film PV 3
chemically different metal electrodes of a capacitor will spontaneously

acquire opposite charges proportional to the difference in their work
functions. That process often called the ‘dielectric absorption’ takes time
sufficient for the inter-plate electron transfer. Along the same lines, two
different metals separated by a dielectric or semiconductor layer will
exchange electrons forming the built-in electric field throughout that layer
as described more in detail next (Sec. II).
B. Fundamental Material Requirements

A well known feature of all PV devices is that at least some of their consti-
tuting materials must have a not-too-wide forbidden gap, say G ~ 1–2 eV.
The origin of that criterion is that larger band gaps exceeding the energies
of most of sun spectra photons would not allow efficient light absorption
necessary to produce enough electrons and holes. However, there is also
the opposite requirement of those gaps being not too small, so that effi-
ciently absorbing narrow band semiconductors are not good for PV either.
As a result, semiconductors with substantial but not-too-wide forbidden
gaps G ~ 1–2 eV, such as Si, Ge, CdTe, CIGS and some others are most
suitable for PV.
The not-too-narrow gap limitation is less intuitive and may be worth
explaining here. It is dictated by PV functionality as a power source. The
power is a product of electric current and voltage, P = IV where both I and
V components must be not too small. I is proportional to the light induced
charge generation rate favoring significant absorption coefficients in the
sun spectral region of ħω ~ 0.5–2 eV. Forbidden gaps G ~ 1–2 eV of many
semiconductors fall in that region. To the contrary, the typical dielectric
gaps G ≳ 4 eV are too wide for sufficient absorption (for example, window
glass that is practically transparent and does not absorb light).
The requirement that undermines the suitability of narrow gap semi-
conductors (despite their strong absorption coefficients) is related to the
voltage component: V ≤ G/q, where q is the electron charge. To explain the
latter inequality we note that V can be related to the difference in Fermi
energies in two metal electrodes as illustrated in Fig. 2. We recall that the
Fermi (quasi-Fermi) energy describes the energy change due to removing
one particle from the system. Therefore, ∆EF ≡ EF1 – EF2 gives the energy
change due to transferring one electron between the two metals, and so
does qV. On the other hand, the metal Fermi energies must not overlap
with the semiconductor conduction or valence bands because such an over-
lap would mean that the semiconductor has in reality metal conductivity
(no gap between the Fermi level and forbidden gap edges). As illustrated
metal semiconductor metal
EF1
G eV
EF2
Fig. 2 Band diagram of a metal/semiconductor/metal structure where EF1 and EF2

represent quasi-Fermi levels determined by voltage drop V across the semiconductor.
in Fig. 2, G presents the upper limit of the difference between the elec-
tron and hole Fermi levels allowing their steady state spatial separation.
Increasing V beyond G/q would shift the Fermi levels beyond the forbid-
den gap turning the semiconductor into metal thus shorting the built in
field and the circuit.
Another wording of the same is that electrons and holes recombine very
efficiently when the two Fermi levels are close thus suppressing their spatial
separation and the built-in field. Assuming point defect mediated recom-
bination, it can be shown more quantitatively [12] that the electron-hole
recombination rate strongly accelerates with decrease of the gap G. As a
result, there exists a range of gaps optimizing PV performance, G ≲ 2 eV.
It should be remembered however, that the latter optimum gap prediction
was derived under certain assumptions about the nature of (defect facili-
tated) recombination, lack of traps, insignificant leakage due to shunts, and
others clearly outlined in the original work [12].
C. Charge Transport. Definition of Thin Film PV

We now consider charge carriers transport in the junction region where
the built in field is significant; that region is often called the space charge
region, simply because the field and charge density are E = 4πρ (where
E and ρ are correspondingly the field and charge density, and we use
the Gaussian system of units). The built-in field extends through a lim-
ited thickness lE determined by the condition that the change of electron
energy through lE equals the difference in Fermi levels ∆EF of the materials
involved. In the order of magnitude, the latter condition yields q 2nlE2 /ε ~ ∆EF
where n is the charge concentration (cm–3) and ε is the dielectric permit-
tivity (for simplicity, we neglect possible differences in n and ε between
the junction components). Using the ballpark values, ∆EF ~ 1 eV, ε ~ 10,
16
n ~ 10 cm –3 yields lE ~ 1 μm. This estimate is consistent with the pub-
lished data for various junctions.
In the built-in field region, the charge carrier transport is dominated
by drift with velocity v = μF where μ is the mobility and F = qE = qV/lE is
the electric force. The diffusion with coefficient D = μkT (according to the
Einstein formula where k is the Boltzmann constant and T is the tempera-
ture) is insignificant contributing to the transport time a relatively small
fraction of kT/qV ≪ 1 assuming the typical V ~ 1 V and kT ~ 0.025 eV
(room temperature).
The drift transport approximation is sufficient if the light absorption
is limited to the space charge region, which applies to many thin-film
structures. That approximation is well justified when the light absorption
length is short enough, labs ≲ lE, limiting charge carrier generation to the
built-in field region, which takes place in CdTe, CIGS, and a variety of
other thin-film PV materials. However, some crystalline structures, such
as Si and Ge, possess the non-direct band structures with absorption
lengths in the hundred of microns range. In such materials, charge carriers
generation extends way beyond the built-in region, and the transport is
dominated by diffusion rather than drift. We recall that the characteristic
diffusion distance and time are related as LD  Dt where D is the diffu-
sion coefficient.
The above discussed drift and diffusion times,
τE = l/v = l2/(μqV) and τD = l2/D, (1)
describe how long it take for a charge carrier to travel distance l to the
device terminals. These times must be short enough to avoid significant
electron-hole recombination. If the characteristic recombination time is
τr, we must require that the relevant transport time to device terminals,
τe or τd be shorter than τr. The corresponding criteria are discussed in
Sec. XVI below. Here, it suffices to note that τr is extremely sensitive to
material parameters and device structure, which brings in multiple ele-
ments of materials science and PV technology. In particular, recombina-
tion processes are strongly facilitated by structural defects (imperfections,
impurities, surface states) that depend on details of material composition;
interfacial recombination can play a significant role for some junctions, etc.
At a qualitative level, we discriminate between thick and thin PV
structures. Typical of crystalline PV, the former are such that the elec-
trons and holes diffuse long distances to the device terminals and τd can
be longer than τr, i.e. interaction with defects becomes inevitable during
their long trips. To the contrary, the characteristic drift time τe is much
shorter than τr in thin PV where recombination becomes almost immate-

rial. As a result, defects and imperfections determine thick PV efficiency
quite significantly. That observation undisputable for thick PV, can become
confusing when uncritically extended over thin film PV where it is not
warranted. Furthermore, a century-long successful history of crystalline
(Si, in the first place) PV made the concept of defect facilitated recombi-
nation literary a commandment dominating all PV understanding across
the discipline. That paradigm has triggered various defect characterization
studies in thin film structures, and, while no correlations between defects
and thin film PV performances was established, that activity continues.
Of course, the difference between ‘thick’ and ‘thin’ devices is related to
the fact that the former have thickness l ≫ lE where lE is the linear dimen-
sion of the built-in field region, as presented in Fig. 3. To the contrary, l ≲ lE
or l is just slightly greater than lE for ‘thin’ devices. In the absence of field,
charge carriers have to travel by diffusion. Taking into account the Einstein
relation between the mobility and diffusion coefficient, the ratio of ‘thick’
over ‘thin’ device transport times is estimated as
thick Vq l 2
 1 (2)
thin kT lE2
where V is the voltage across the device, q is the electron charge. Given
the typical |Ve| ~ 1 eV, kT ~ 0.025 eV (room temperature), l on the order of
hundreds of micron and lE in microns, the ratio in Eq. (2) can be as large as
5 6
10 –10 . The latter inequality is consistent with the typical experimental
lE l
Fig. 3 Diffusion of the photogenerated electrons and holes to the electrodes in a ‘thick’
device. White circles represent defect recombination centers. The figure is aimed to show
that interactions with such centers may be likely when charge carriers exercise long-time
diffusion movements.
data: the diffusion times τd,thick ~ 10–100 μs (in crystalline Si PV) and td
~ 1–10 ns in thin film PV. With those numerical values, using the typical
recombination times τr in the range of micro- to milliseconds (as evaluated
for various semiconductors [3, 13–17]), one should expect τr ≫ τd for thin
film PV.
Based on the latter estimate, thin film PV can operate in the opposite
limit τ ≪ τr where the role of defect related recombination is on average
insignificant. Unfortunately, they have other vulnerabilities related to lat-
eral nonuniformity of their parameters. From a very general point of view,
such nonuniformity originates from the lack of transversal self-averaging
across too thin structures, which allows significant fluctuations between
different spots. Due to device thinness, some sparse spots represent para-
sitic conductive paths (ohmic or non-ohmic) between opposite electrodes.
These paths work as recombination highways degrading PV efficiency. We
emphasize that such a nonuniform recombination is qualitatively differ-
ent from that by point defects in thick PV and call for different mitigating
strategies.
Furthermore, having reached the electrodes their respected ter-
minals, electrons and holes undergo fast lateral transport inside the
contact metals taking them to the above mentioned recombination
channels, through which they disappear. We will see in what follows
that the recombination times τrc of such channels (presented in Fig. 4)
form an exponentially broad spectrum decaying towards shorter val-
ues. The channels with characteristic recombination times of the order
of charge carrier travel times τ dominate because the channels with τrc
≫ τ are inefficient, while those with τrc ≪ τ are too rare. This feature is
more quantitatively explained in Sec. XVI following Fig. 104 and subse-
quent chapters. At this point, we conclude that thin film PV can operate
through multidimensional processes where electric currents across and
along films are strongly coupled. From the practical perspective, surface
treatments that can block the recombination channels appear to be a
strategy improving thin film efficiency. That approach has been success-
ful as established on purely empirical grounds before it was theoretically
substantiated.
D. Distinctive Features of Thin Film PV

Another distinctive feature of thin film PV is that their forming layers are
noncrystalline, but rather polycrystalline (CdTe and CIGS types of PV)
or amorphous (a-Si:H based PV). That type of ’imperfect’ morphology is
lE ~ l
Fig. 4 In thin film devices, drift rather than diffusion can determine the kinetics of
photogenerated carriers. They readily arrive at the corresponding electrodes avoiding
interactions with recombination centers. Having reached the electrodes they can move
to the entrances of rare but highly efficient recombination channels shorting between the
electrodes and playing the role of recombination highways.
inevitable with inexpensive fast deposition techniques not giving enough

time for satisfactory crystallization. The polycrystalline films consist of
tightly packed individual grains, each having more or less perfect crys-
talline order inside. They are formed during deposition and subsequent
treatments where random atomic configurations are ordered within local
regions dictating grain sizes. In the course of such crystallization, material
pushes away all ’foreign’ atoms and structural units towards grain bound-
aries (GB). (Similar to apples in a freezer where water crystallization breaks
and pushes away organic tissues.) As a result, GB material is chemically
different from that of interior. These chemical differences entail built-in
electric fields that will spatially separate electrons and holes between the
grain interior and GB (see Fig. 5) creating local electric field and poten-
tial variations. One other general consequence of independently forming
grains is that having grown enough they compete for space and exert pres-
sure on each other upon physical contact. The resulted compressive stress
can translate into electric potential when the material structure is piezo-
active, such as with CdS, ZnO and some others, as explained more in detail
next (Sec. XVIII).
As illustrated in Fig. 5, spatial separation of charge carriers at GB can
significantly decrease the probability of their recombination compared
to crystalline materials where electrons and holes are distributed uni-
formly. That creates a possibility for polycrystalline thin film PV to poten-
tially outperform their crystalline counterparts. On the other hand, high
concentration of impurities and defects in the grain boundary interfaces
enhances the recombination processes, which can make grain boundar-
ies detrimental and polycrystalline material PV devices perform worse
e
EC
G
EF
EV
VB
h
Fig. 5 Role of grain boundaries in noncrystalline thin film PV. Left: Sketch of the
electron hole pair creation by a photon of energy exceeding the forbidden gap G. Ec and
Ev are conduction and valence band edges, EF is the Fermi energy. Short horizontal lines
represent defect states located at the grain boundary. Note that the positive (attractive
to electrons) GB charge is assumed arbitrarily. For the case of negative GB charge, the
potential well (barrier) for electrons (holes) will turn into a barrier (well). Right: the GB
barrier requires charge carrier activation [with probability proportional to exp(–VB/kT)]
which suppresses recombination (presented by vertical arrows).
than crystalline PV. The latter feature was evidenced in some polycrystal-
line Si structures. Furthermore, it will be shown below (Sec. XVI) that the
very nature of recombination processes in non-crystalline materials can
be significantly different from that dominating crystalline PV and affect-
ing both the GB and main junction processes. Overall, the role of grain
boundaries remains debatable and material/recipe specific with experi-
ments exhibiting either beneficial or detrimental GB effects. It is possible
that some of GBs in thin films form, with certain probability, much more
effective recombination channels than others. Those channels can play the
role of recombination highways depicted in Fig. 4.
A physically nontrivial and practically important property of thin film
PV (further discussed in Sec. V) is that, under certain conditions, they
exhibit thermal runaway instabilities favored by low heat transfer param-
eters as well as low sheet resistances along with significant currents and
voltages. These instabilities result in local (~ 1 mm) spots of elevated tem-
perature that can degrade PV performance and trigger nonuniform struc-
ture damage. We will discuss later their underlying physics and factors that
can be tweaked to mitigate the latter detrimental effects by proper device
engineering.
A more specific structure of the two major brands, CdTe and CIGS
based thin film PV is presented in Fig. 6. It is understood that in reality
the glass is facing up in CdTe cells. The CdTe and CIGS layers are absorb-
ers responsible for the light conversion into photogenerated electrons and
holes. The question of their doping has been debatable for decades, with
Grid
Glass
Buffer (ZnO)
TCO
CdS
CdS
CuIn(Ga)Se2
CdTe
Mo
Back metal Glass
(a) (b)
Fig. 6 A cross-sectional view of a superstrate (glass sheet up) CdTe based and substrate
(glass sheet down) CIGS based thin film solar cell (not to scale). The CdTe cell front
contact is formed by the transparent conductive oxide (TCO). The typical layer
thicknesses are 2-4 µm for CdTe and CIGS, 0.1-0.2 µm for CdS, 0.5 µm for TCO and
buffer layer, 0.1-0.2 µm for back metal (Mo for CIGS), 1-3 mm for glass. The drawing
does not show the polycrystalline structure of CdTe, CIGS, and CdS layers. Red arrows
represent incident sunlight.
extreme views ranging from that these materials cannot be effectively

doped to that of beneficial or detrimental role of certain impurities. Many
of such mutually exclusive points have found experimental confirmations
with particular device recipes.
Furthermore, the role of CdS layer often found with CdTe and CIGS
remained mysterious long after it was empirically found to be extremely
important and practically irreplaceable in spite of its lack of contribution
to photocurrent. We shall see in what follows (Sec. XVIII) that its piezo-
electric properties may be a key leading to piezo-photovoltaic coupling
beneficial for PV operations.
Finally, the back contact layer renders yet another set of puzzles. While
the Mo back contact is typical of CIGS PV, there are several successful rec-
ipes of back contact in CdTe based PV. It was found indeed that the back
contact has profoundly strong effect on device operations in spite of the
fact that it is not photoactive (light does not penetrate there). The so-called
back barrier due to the junction field between the semiconductor and back
metal turns out to be a culprit. More in detail, the physics of back contact
functionality will be discussed in Sec. VB. The front contact layer, such as
TCO in CdTe based PV or ZnO in CIGS, has its nontrivial properties as
well, as also discussed in the subsequent chapters.
Last but not the least is the issue of thin film PV degradation. Light,
elevated temperatures, and humidity can all play a detrimental role in
degradation processes. Some PV companies went under being unable to

solve these problems. It often happened that the most efficient PV devices
exhibited the highest degradation rates calling upon tradeoffs between
efficiency and stability. It should be understood that PV degradation is
inevitable with any PV in full compliance with the general Le Chatelier -
Brown principle stating that when a settled system is disturbed, it will
adjust to diminish the change that has been made to it, or, roughly stated,
any change in status quo prompts an opposing reaction in the responding
system [18]. With respect to PV, that principle predicts that PV structures
will evolve in such a way as to decrease the light induced electric currents;
hence, degradation. While all PVs degrade, the thin film ones are espe-
cially vulnerable due to their thinness allowing formation of conductive
transverse channels (shunts). In addition, thin film structures accumulate
extremely high electrostatic energy density (similar to narrow gap (~ 1
µm) electric capacitors) capable of discharging with huge power dissipa-
tion transforming material structure towards electric shorts that minimize
the electric energy. A more in detail discussion of these issues will be given
in Sec. XXVII B.
References
1. M. A. Green, Solar Cells: Operating Principles, Technology and System
Applications, Prentice Hall, Englewood Cliffs, N.J., 1982.
2. A. L. Fahrenbruch, R. H. Bube, Fundamentals of Solar Cells, Academic Press
(1983).
3. J. L. Gray, The physics of Solar Cells, in Handbook of Photovoltaic Science and
Engineering, p. 61, Edited by A. Lique and S. Heggedus, Wiley (2002).
4. J. Nelson, The Physics of Solar Cells, Imperial College Press (2003).
5. P. Wurfel, Physics of Solar Cells, Wiley (2005).
6. T. Dittrich, Material Aspects of Solar Cells, Imperial College Press (2015).
7. T. J. Coutts, J. S. Ward, D. L. Young, K. A. Emery, T. A. Gessert, and R. Noufi,
Critical Issues in the Design of Polycrystalline, Thin-film Tandem Solar
Cells, Prog. Photovolt: Res. Appl. 11, 359 (2003).
8. Thin Film Solar Cells Fabrication, Characterization, and Applications, Edited
by J. Poortmans and V. Arkhipov, Wiley (2007).
9. S. R. Kodigala, Cu(In1xGaxSe2 Based Thin Film Solar Cells Elsevier,
Amsterdam New York, (2010).
10. R. Scheer and H.-W. Schock, Chalcogenide Photovoltaics, Wiley (2011).
11. Advanced Characterization Techniques for Thin Film Solar Cells, Edited by
D. Abou-Ras, T. Kirchartz, and U. Rau, Wiley (2011).
12. W. Shockley and H. J. Queisser, Detailed Balance Limit of Efficiency of p-n

Junction Solar Cells, J. Appl. Phys., 32, 510 (1961).
13. A. G. Milns, Deep impurities in semiconductors, Wiley Interscience (1973).
14. D. K. Schroder, Carrier Lifetimes in Silicon, IEEE Trans. Electron Devices,
44, 160 (1997).
15. S. Parola, et al, Study of photoluminescence decay by time-correlated single
photon counting for the determination of the minority-carrier lifetime in sil-
icon, 4th International Conference on Silicon Photovoltaics, SiliconPV 2014,
Energy Procedia 55, 121 (2014).
16. S. Khatavkar et al, Measurement of Relaxation Time of Excess Carriers in
Siand CIGS Solar Cells by Modulated Electroluminescence, Technique,
Phys. Stat. Solidi. A, 215, 1700267 (2018).
17. V. N. Abakumov, V. I. Perel, I. N. Yassievich, Nonradiative Recombination in
Semiconductors (Modern Problems in Condensed Matter Sciences), North-
Holland (1991).
18. Wikipedia paper https://en.wikipedia.org/wiki/Le_Chatelier%27s_principle
Part II
One-Dimensional (1D) Diodes and PV
II. 1D Diode
The concept of diode underlies almost all the aspects of PV operations.
Diode means a two-terminal device allowing an electric current to pass
in one (forward) direction, while blocking it in the opposite (reverse)
direction. Its nonlinear current-voltage (IV) characteristic is omnipresent
in structures where the electron transport is affected by potential barriers.
In reality, those barriers are associated with junctions. Here we discuss the
simplest case of such a barrier to see how it leads to the diode type IV and
which barrier parameters are important. In this part of the book, we con-
sider only 1D structures and processes implying that there is no significant
lateral nonuniformities and currents.
It has become a standard in diode introduction literature to start with the
notion of p-n junction [1–11]. However important, the latter concept appears
somewhat oversold in applications to thin film PV at least. We would like to
emphasize that the rectifying diode characteristics can be caused by practi-
cally any kind of junctions. Therefore, we decided to start with an example
far away from the p-n situation to show how the diode IV becomes possible
otherwise. We will touch upon the p-n junction concept later referring in the
meantime to the ample high-quality literature presenting that concept.
A. Metal-Insulator-Metal Diode
We consider a barrier formed by a contact of chemically different mate-
rials, so that the electron energy changes at their interface. The material
where it is higher represents a potential barrier that the electron needs to
overcome in order to penetrate that material. A barrier between a metal
and vacuum represents the simplest case. By definition, its height equals
the metal work function, i.e. the minimum energy required to extract an
electron from the metal to the vacuum. In other words, it is the difference
between vacuum level of energy and the Fermi level in the metal.
Victor Karpov and Diana Shvydka. Physics of Thin-Film Photovoltaics, (13–78) © 2022 Scrivener
Publishing LLC
13
Fig. 7 represents the energy band diagram of a nonmetal layer sand-

wiched between two identical metal electrodes, the simplest junction sys-
tem allowing connections to the external power source. Since the Fermi
energies in the latter lie against the forbidden gap of the middle layer, the
lowest available energy states are above that layer conduction band edge.
The electrons in metals have to increase their energies, from the Fermi lev-
els up to that edge, in order to penetrate into the nonmetal layer. In other
words, they have to overcome the corresponding potential barriers W1 or
W2 in Fig. 7. Note that W1 = W2 for a particular case of similar metals in
Fig. 7. Note also that neither W1 nor W2 are the metal work functions. They
represent instead the differences between the metal work functions and
electron affinity of the non-metal layer. The affinity is defined as a mini-
mum work necessary to extract the electron from the edge of the conduc-
tion band to the vacuum level (which is assumed to lie above that edge).
Shown in Fig. 8, the current-voltage characteristic for a symmetric struc-
ture in Fig. 7 demonstrates saturation for strong enough voltages of both
signs. The underlying physics is that the current approaches a maximum
when the two barriers differ enough.
A comment is in order with regards to the diagrams in Figs. 7, 9 and
many others throughout the book: they all represent coordinate depen-
dencies for the electron energy. In some cases, it is customary to use the
terminology of the electric potential dividing the energy by the elemen-
tal charge q. It must be remembered however that the latter terminology
J1 J2
J1 J2
W1 W2 W1 W2+qV
EF1
EF1 EF2 qV
EF2
(a) (b)
Fig. 7 Energy band diagram of a symmetric potential barrier separating two metal
electrodes. The barrier heights W1, W2 measured from the corresponding Fermi levels of
the metals EF1, EF2 are the same when no voltage is applied, and the currents from these
metals balance each other. Applying voltage V shifts the Fermi levels by the energy qV
relative to each other, causing the corresponding difference in the current.
One-Dimensional (1D) Diodes and PV 15
J, arb. units
V, arb. units
kT/q
Fig. 8 Current-voltage characteristic of a system with symmetric barrier illustrated in Fig. 7.

The saturation current at both negative and positive biases is equal to J00 exp(−qW1/kT).
J1 J2
EF1
W2 EF1
qV
EF2 EF1 EF2 qV EF2 EF2
V=0
EF1 W1 -qV
(a) (b) (c) (d)
Fig. 9 Energy band diagram of an asymmetric potential barrier between two different
metal electrodes. (a) The current J2 ≫ J11 is the saturated current under negative (reverse)
bias. (b) The currents are equal, J1 = J2 under zero bias as limited by activation over the
barrier W2. (c) The forward current J1 exponentially grows with further increase in bias
and approaches saturation close to the flat band barrier condition where J2 ≪ J1.
(d) Further increase in forward bias exponentially suppresses the reverse current J2.
(often used in physics books) is not exactly consistent with the definition
for the electric potential as the energy per charge: it neglects the negativity
of the electron charge producing strictly speaking minus of the electric
potential instead of the potential itself. For example the energy of a positive
particle will increase in the direction where the electron energy decreases.
In most cases the above mentioned negligence does not result in any mis-
understanding. We encourage the reader to keep this comment in mind
while switching between the physics related diagrams and electric poten-
tial mappings such as presented in Figs. 116 and 117. We assume that the
barrier is surmounted by activation i.e. the necessary energy is provided by
thermal fluctuations. The probability of such fluctuations is proportional

to the Boltzmann exponential exp(−W1(2)/kT). It is typical that W1(2) >> kT.
For example, kT ≈ 0.026 eV at room temperature while W1(2) is on the
order of characteristic differences in band energies in solids, i.e. W1(2) ≲ 1
eV. With the above factor in mind, the current density (per area) from a
metal to nonmetal layer can be presented as
W1(2)
J1(2) J 00 exp .
kT
The preexponential factor J00 will coincide with the well-known preex-
ponential of the thermoelectronic emission [12],
4 πqmk 2 A
J 00 = A∗T 2 , with A∗ = 3 ≈ 120 2 2 (3)
h cm K
where A* is the Richardson constant. Its numerical value here is given for
the case of free electrons when the effective mass m equals the true electron
mass; h is the Planck’s constant. Eq. (3) is derived by counting the number
of electrons crossing unit area per time, nv 4 with v ⊥ = 8kT πm being
the average velocity component perpendicular to the area element, and
3/2
n the electron concentration. An additional power of temperature, T ,
appears due to the concentration of states available to the electrons in a
narrow energy band kT. That concentration is roughly estimated as 1/λ3
where h mkT is the de Broglie wavelength of the electrons.
In many cases, Eq. (3) can be modified to account for diffusion and the
details of band structure. It is important however, that in all such cases J00
remains a power function of temperature that is much weaker than the
exponential multiplier in the equation for current. In a good approxima-
tion, the preexponential can be treated as a constant and the numerical
value in Eq. (3) gives a ballpark of expected preexponential multipliers.
A word of caution may be in order here to stipulate that, for simplic-
ity, the non-metal layer is tacitly assumed to make negligibly small effect
on the electric current. In other words, its resistance is taken to be much
below that of the junction itself: it is much ‘easier’ for the electron to drift
through that layer than to get activated into it through the junction.
Consider next the ‘dark’ (i.e. no illumination) current-voltage charac-
teristics (neglecting photo-generated carriers). The energy difference W1(2)
between the barrier height at the interface and the Fermi level EF1(2) in the
adjacent metal remains constant under external field as fixed by the differ-
ence in parameters of the two materials.
When the electrodes are identical as shown in Fig. 7, electric bias V cre-
ates the difference qV between their Fermi levels. [We recall that the Fermi
level coincides with the chemical potential equal to the change in system
energy when the number of electrons changes by one. On the other hand
moving the electron across the electric potential difference results in the
energy change qV.]
While the energies W1 and W2 remain constant, the activation energy
for the electrons of one of the electrodes increases by qV in Fig. 7, since
they have to overcome the maximum barrier located at the opposite inter-
face. The difference qV in the left and right barriers makes the correspond-
ing currents different. For the case of positive voltages illustrated in Fig. 7,
their absolute values can be written as
J1 = J00 exp(−qW1/kT) and J2 = J1 exp (–qV/kT)
and the current voltage characteristics, J = J1 – J2 takes the form
qV
J J1 1 exp . (4)
kT
It saturates as illustrated in Fig. 8.

While the IV characteristic in Eq. (4) is non-ohmic, it does not yet rep-
resent a major diode property of exponentially strong asymmetry between
the currents of opposite senses. That property naturally appears with
asymmetric barrier illustrated in Fig. 9 where the two interfacial energy
steps W1 and W2 are substantially different. Physically, this system can be
a dielectric or semiconductor layer sandwiched between two different met-
als, for example, CdTe between Al and Au. In the asymmetric case, the
barrier shape exhibits a finite slope even under zero bias as shown in Fig.
9(b). According to Fig. 9, the barrier heights limiting the current are given
by the effective values
W1,eff = max{W1, W2 − qV}, (5)

W2,eff = max{W2, W1 + qV}.
The corresponding currents are given by,
W1(2),eff
J1(2) J 0 exp .
kT
They have exponentially different saturated values:
J max W2 W1
exp .
J min kT
In Fig. 10 these currents correspond to the regions (d) and (a) respectively.
The voltage region (c) of increasing forward current is by the factor
(W2 − W1)/kT ≫ 1 wider than the region (b) of increasing reverse current
corresponding to the diagrams (c) and (b) in Fig. 9.
The IV curve of Fig. 10 represents the typical diode characteristic. We
note that the saturation-like region under forward bias region is always
present in real diodes, although it is often omitted in semiconductor
textbooks as irrelevant. Furthermore that region per se is tantamount to
non-dissipative current neglecting the inevitable ohmic resistance in a
material. Taking the latter into account renders that region a finite slope as
depicted in Fig. 10 by dashed line.
Limiting ourselves to the regions (a) -(c), the current voltage character-
istic can be now presented as
qV W2
J J 0 exp 1 , J0 J 00 exp . (6)
kT kT
Ohmic
resistance
Joexp(-W1/kT) (d)
J, arb. units
(c)
(b) (W2-W2)/q
V, arb. units (a)
kT/q Joexp(-W2/kT)
Fig. 10 Current voltage characteristic of a system with asymmetric barrier illustrated in

Fig. 9. Regions (a) - (d) refer to the corresponding band diagrams in Fig. 9. The saturation
current in the reverse and forward bias regions are J1 and J2 ≫ J1 respectively.
The latter is the standard diode equation containing two important fac-
tors: strong asymmetry between reverse and forward regions and expo-
nentially low reverse saturation current. We would like to emphasize that
asymmetric potential barrier – not necessarily of rectangular or trapezoid
shape – is a single major factor leading to the IV characteristics of diode
type. Because such barriers are omnipresent (their absence would require
rather special circumstances), the diode IV are found everywhere in elec-
tronics, device physics, and even in biophysics where they exhibit them-
selves e.g. as current voltage characteristics of ion channels in biological
membranes [13].
We note finally that our analysis here tacitly neglected a number of pos-
sible complications, such as interfacial and metal induced gap states, possi-
ble screening, localized states and recombination in the intermediate layer,
which will affect the barrier heights and the saturation current J0, without
any impact on the functional form of the current voltage characteristic in
Eq. (6).
B. Schottky, Reach-Through, and Field-Compensation

Diodes
1. Schottky Diode
Schottky diode is in general due to a contact between a metal and a semicon-
ductor. Metal contacts are inevitable with all semiconductor applications.
Because the Fermi levels of metals and semiconductor components are dif-
ferent, the electrons move from one of them to another forming excessive
electric charges across the junction as illustrated in Fig. 11. For the ideal
case of perfectly clean uniform interface, the classic Mott-Schottky theory
predicts the interfacial barrier height W equal the absolute value of the
Fermi levels differential. The characteristic width of that barrier is given by
the electrostatic screening length, which is often described for electrons Lsn
and holes Ls(p) by the equation (in Gaussian units)
Wε
Lsn( p ) = (7)
2πN d (a )e 2
where ε is the dielectric permittivity, and Nd(a) stands for the concentration
of donors (acceptors) in respectively n-type or p-type materials. As a ball-
15 −3
park estimate, one can assume W ~ 1 eV and Nd(a) ~ 10 cm , and ε ~ 10,
which yields Lsn(P) ~ 1 μm.
Eq. (7) assumes discrete energy levels of donors or acceptors responsible

for the electric charge in the band bending region of Fig. 11. To the contrary,
when the material is non-crystalline and has a quasi-continuous spectrum
of energy levels with density g(EF) (cm−3erg−1) at the Fermi energy in the
forbidden gap, the screening length is described by the equation [14]
ε
Ls = 2 . (8)
4 πe g ( EF )
15
Using for a rough estimate the same ~ 10 cm−3 localized states more
or less uniformly distributed over the energies in the gap of ~ 1 eV yields
15 −1
g(EF) ~ 10 cm−3eV , and again Ls ~ 1 μm. The characteristic Schottky
barrier width in the micron range appears to be a rule of thumb estimate
for various materials.
While the Mott-Schottky theory remains a classical concept presented
in every semi-conductor textbook, more recent studies revealed a rather
complicated picture [15] with no general rules for the Schottky barrier
(a) (b)
Fermi level
energy
Fermi level Fermi level
Metal Semiconductor Metal Semiconductor
(c) (d)
Conduction band
Barrier
Semiconductor for holes
energy
Valence band
Fig. 11 Schottky barrier formation: (a) No electric contact; the Fermi level is arbitrarily
chosen to be higher in a metal. (b) When the Fermi energies of two materials put in
contact level out, the metal and semiconductor acquire opposite excessive charges. (c) The
positively charged metal repels holes and attracts electrons; (d) Tantamount to a barrier
for holes.
conduction band
forbidden gap
∆W
EF
ψ(x)
∆x
x
metal insulator
Fig. 12 Gap states due to electron tunneling from the metal to dielectric side create
electric dipoles with charges presented by ⊕ and ⊖ symbols. ψ(x) stands for the electron
wave function of the electron state in a metal facing forbidden gap in the tangent
dielectric.
height. The existing models accounting for surface and metal induced gap
states [16] along with experimental results [17, 18] are not consistent with
the Mott-Schottky concept of simple electron transfer (built-in field for-
mation) between the two materials at MS interfaces.
It is quite obvious that interfacial localized states on the metallurgical
junction can hold electric charges creating additional contribution to the
barrier hight and width. However, even with the ideal interfaces, the gap
state phenomenon illustrated in Fig. 12 predicts substantial deviations
from the Mott-Schottky theory. Its underlying physics is that the electron
states below the Fermi level EF on a metal side penetrate by tunneling
into the forbidden gap of an adjacent semiconductor under the barrier of
height ∆W. The characteristic penetration length Dx   mDW is on
the order of several angstrom for the typical parameters ∆W ~ 1 eV, and
−27
electron mass m ~ 10 g. Along with the left behind positive charges, these
electron tails create an electric dipole layer. Its corresponding energy dif-
ferential is estimated as q 2 εDx  DWq 4 (m  2 ε 2 )  0.1 − 1 eV . Because
the latter value is comparable to the original Schottky-Mott barrier of
|W1 — W2| we conclude that other factors (forbidden gap, electron effec-
tive mass, surface states) may have very significant effect on the barrier
height making it more an empirical parameter than a predicted value.
2. Reach Through Diodes

When the semiconductor thickness is large enough compared to the
screening length [of Eq. (7) or (8)], the two metal contacts on its opposite
surfaces can be considered independent of each other. Such a structure is
sketched in Fig. 13 where the two metals are different causing asymmetric
We2
We1 We2 We1 EF2
G
qV Wh2
EF1
Wh1 Wh2 Wh1

Ls2 Ls2
Ls1 Ls1
(a) (b)
Fig. 13 Reach-through structure of a semiconductor layer sandwiched between two

different metals when the layer thickness exceeds the screening length.
band bending. The parameters assumed (arbitrarily here) are such that the
energy barriers involved form the hierarchy Wh2 < Wh1 < We1 = We2 at zero
voltage in Fig. 13 (a). For small voltages V applied as shown in Fig. 13 (b),
the current is due to hole transport remains constant (electronic barriers
are too high and block the electrons). The current is then determined by
the barrier Wh2. However, from some voltage on, the electronic current
controlled by the barrier We2 starts contributing exponentially strong, i.e.
the total current sharply increases, which phenomenon is often referred to
as the ‘reach-through’. Various other band diagrams can lead to the reach-
through behavior [12]. The corresponding current voltage characteristics
are presented in Sec. VB below with PV applications.
The voltage Vrt upon which the double Schottky barrier structure turns
into the reach-through regime can be estimated from the condition that
the maximum energy point in the diagram of Fig. 13 (a) shifts all the way
through the system forming the configuration of Fig. 13 (b). Based on the
(possibly oversimplified) model of uniformly doped material [19],
2Wh1 Wh2
VRT 1 . (9)
q Wh1
Furthermore, using the available data and assuming that the electric
current through the barrier Wh2 is thermally activated, it was estimated
that Wh2 ~ 0.5 V. Because Wh1 ~ 1 eV, we finally get a rough estimate Vrt
~ 0.6 V.
The most sensitive approximation behind Eq. (9) is that it completely
neglects electron tunneling. The latter is more difficult to evaluate for it
depends on the barrier shape, generally unknown. Also, such tunneling
can be thermally and defect assisted, which makes it laterally nonuniform.
It will be discussed more in subsequent chapters.
The reach-through related issues will be further discussed in connection

with the back contact problems and related nonuniformities (Sec VB) and
Schottky barrier nonuniformities (Sec IX).
3. Field Compensation Diode

Field-compensation diodes possess the property that the semiconductor
charge carrier concentration decreases due to the metal contact related
built-in electric field. The underlying physics is somewhat similar to that of
self-compensation phenomenon (see e.g. Ref. [20] and references therein)
where a semiconductor spontaneously generates deep level defects that
trap the charge carriers thus decreasing the system energy when that
gain exceeds the energy cost of defect creation. A unique feature of the
field-compensation is that the energy decrease is achieved through its elec-
2
trostatic component ∫ dx(εE /8π) by suppressing the built-in field via com-
pensation as illustrated in Fig. 14. That effect originally analyzed for a more
complex PV structure [21], has similarity with that of the field-induced
doping [22].
We now use a simple approximation to establish the condition for that
effect. We consider both screening lengths in Fig. 14 the same and equal
Ls. We approximate the built-in fields as E1(2) = W1(2)/qLs and their related
2
energy as WE = ε( E1(2) / 8π )ALs where A is the contact area. Let wd denote
the energy spent to create a deep level defect responsible for compensation.
(Assuming, in the spirit of self-compensation mechanism, some energy
gain due to the charge carrier localization, wd would stand for the differ-
ence between the former energy loss and the latter gain. In case the so
defined Wd is negative, the compensation takes place regardless of the field
effect.) The energy loss for defect generation is estimated as Wd = NLAwd
where L is the thickness of the semiconductor layer and N is the defect con-
centration. Neglecting the final field energy in the compensated structure
We1 G
We2
L
L G
Wh2
Wh1 Ls2
Ls1
(a) (b)
Fig. 14 Metal-semiconductor-metal structure before field compensation (a) and after that
(b). Note the decrease in Fermi energy and increase in screening length making the field
almost uniform.
compared to WE and omitting all the numerical multipliers of the order of

unity, the field compensation criterion WE/Wd > 1 becomes,
W12(2)ε
> 1. (10)
8π wd q 2 NLL s
15 −3
For a rough numerical estimate we use W1(2) ~ wd ~ 1 eV, N ~ 10 cm ,
L ~ Ls ~ 3 μm, ε ~ 10, which yields the left-hand-side of Eq. (10) on the
order of one. We conclude that the field compensation effect is possible
provided favorable parameters in thin film structures. It seems to be unre-
alistic for semiconductor layers thicker than 10 μm and would favor flex-
ible structures, such as chalcogenide based CdS, CdTe, CIGS, where the
characteristic energies wd of defect creation can be relative low.
The field-compensation effect can result in the extension of the built-in
electric field through out the structure, which improves the carrier
collection. More important can be its caused communication between
the two layers tangent to the opposite semiconductor surfaces in Fig.
14 through the suppression of screening. That opens a avenue to govern
device operations by attaching a desired complementary layer across one
of the semiconductor components. Such can be e.g. a buffer layer on the
opposite side of CdS component of CdS/CdTe PV structures. There are
numerous experimental evidences in favor of such interpretation [21].
C. P-N Homo-Junctions
Fig. 15 presents the standard diagrams for p-n homojunctions commonly
adopted to describe the properties of crystalline PV. We note that in the
doped crystalline material the electrostatic screening lengths are pre-
sented by Eq. (7). The corresponding diffusion lengths LDn Dn n and
LDp D p p with Dn(p) and τn(p) being the electrons (holes) diffusion coef-
ficients and lifetimes, determine how far the charge carriers can diffuse
during their lifetimes. As usual, the quasi-Fermi levels EFn( p) in Fig. 15
are defined in such a way that the nonequilibrium charge carrier concen-
trations n(p) are proportional to exp(EFn( p) kT ) mimicking the relation
n0(p0) ∝ exp(EFn(p)/kT) between the Fermi energy EFn(p) and equilibrium
charge carrier concentration n0(p0).
One feature misrepresented in Fig. 15 is a possible strong asymme-
try between the n- and p-parts of a diode. For illustrative purposes, we
20 −3 15 −3
mention here3, Nd ~ 10 cm vs. Na ~ 10 cm , Lsn ~ 0.35 μm vs. Lsp ~
Real space
p-type n-type
Lsn
LDp Lsp LDn
Energy space
–
quazi-Fermi level
Fermi level
Fermi level
quazi-Fermi level
Fig. 15 The real space and energy space diagrams for the classical p-n homojunction
under light. Lsn and Lsp are the electrostatic screening lengths in n and p regions, so
that Ls = Lsn + Lsp is the depletion width. The red arrows represent light and its e – h
generation process. The depicted relations between device linear sizes, screening lengths,
and diffusion lengths are not to scale and rather arbitrary in the drawing.
300 μm, and LDn ~ 12 μm vs. LDp ~ 1100 μm corresponding to τn ~ 350

μs and τn ~ 1 μs.
In connection with the latter numerical parameters, we would like
to note that the highly doped n-type material becomes rather imper-
fect containing significant concentrations of various defects facilitating
recombination. It is natural then that the lifetime in n-material is so much
shorter than that in p-type. Also, we observe that the lifetimes in good
(p-type) and defective (n-type) materials vary in the range of roughly 1
μs to 1 ms, a ballpark for Si and many other semiconductors [23–27, 30].
An important feature of the classical p-n model (not presented in Fig.
15) is that it can include surface recombination implying that because of
the relatively high degree of structural disorder in the interfaces, they can
serve as efficient recombination facilitators. The surface facilitated recom-
bination can be described by the corresponding lifetime τs that contrib-
utes to the charge carrier decay by adding its reciprocal to that of the bulk
recombination time. It was shown [28–30] that surface recombination can
be as well presented in a more intuitive way through the surface recombi-
nation velocity (cm/s),
L
s= (11)
2[τ s − L (π 2 D 2 )]
2
where L is the device thickness, and D is the carrier diffusion coefficient.

As an illustration, we mention the fitting results from Ref. [3] related to the
above mentioned asymmetric p-n junction parameters, sn = 3 × 104 cm/s
and sp = 100 cm/s and demonstrating again strong asymmetry between
highly defective n- and more perfect p-materials. Some of the existing pho-
tovoltaic technologies use surface passivation (with Hydrogen, sulphur, or
other suitable materials) to suppress the corresponding recombination
velocities.
The current voltage characteristic of Eq. (6) can be readily derived for
the case of p-n diode by relating p- and n-type layers to the metals with
electrodes having Fermi levels EF2 and EF1 in Fig. 9. However, the satura-
tion current density is presented now as [12]
1 LDn 1 LDp G
J0 eN c N v exp . (12)
Nd n Na p kT
The activation energy G (instead of the Fermi energy) reflects the

nonequilibrium nature of the process where thermally generated charge
carriers are swept away of the system (not enough time for the electron
thermalization down to Fermi energy).
A historically significant advantage of the Fig. 15 p-n model is its suit-
ability for analyses utilizing the drift-diffusion kinetics, defect facilitated
recombination processes, and light absorption. That made it possible to
relate the device performance with its constituting material and structure
parameters and provided a solid guide for crystalline PV developments.
Here, we will not reproduce the corresponding cumbersome analytical
results found with many standard textbooks [2−12] and not practically
important nowadays due to the availability of simple modeling software
solving 1D diode problems.
D. Heterojunctions
Two dissimilar semiconductors form a heterojunction. Its band diagram is
obtained by the same general rule that Fermi levels in the component mate-
rials must be equal. It is always true that the Fermi level is uniquely related
to the work function, which is the energy difference between the electron
at the vacuum and Fermi levels. However, in semiconductors, the Fermi
energy depends on doping and thus is not a material parameter. Instead,
band edges should be considered as the parameters uniquely related to a
semiconductor. The position of conduction band edge relative to vacuum
level is described by the electronic affinity, defined as the energy obtained

by moving an electron from the vacuum just outside the semiconductor
to the bottom of the conduction band just inside the semiconductor. The
electronic affinities are generally different for different semiconductors.
Because of that difference matching band diagrams for heterojunctions can
exhibit discontinuities (conductive band offsets) illustrated in Fig. 16 of the
type that depends on the electron affinities involved.
Shown in Fig. 17 is a commonly used (‘baseline’) band diagram of
CdTe or CIGS based thin film PV. Most of researchers tend to interpret
it in terms of p-n heterojunction assuming p-type CdTe (or CIGS) and
n-type CdS. That interpretation dominates even though there is no exper-
imental proof for n-type CdS. Furthermore, the existing data show that
CdS performs best when prepared highly resistive, thin, and significantly
non-crystalline of rather p-type. The miraculous CdS layer appears hardly
replaceable with significantly different materials, and a possible resolution
CBO>0 G2 CBO=0 CBO<0

G2
energy
G2
G1 G1 G1
Fig. 16 Possible band diagram alignments with positive, zero, and negative Conductive
Band Offset (CBO) corresponding to the cliff, smooth, and barrier type of band structure.
CdTe or CIGS
–
+
TCO
+
+
CdS Back
buffer
metal
Fig. 17 A rough sketch of the commonly used band diagram for CdTe and CIGS based
thin film PV. The CdS forbidden gap (≈ 2.4 eV) is greater than that of CdTe (≈ 1.5 eV)
or CIGS (≈ 1 − 1.7 eV depending on composition). Such combinations of different gap
materials are called heterojunctions. The dash and dot depicted features in the CdS region
represent a hypothetical energy barrier or a cliff introduced by some researchers to better
fit data; they can be related to the band structure mismatches.
of that mystery can be related to the piezo-photovoltaic coupling that

becomes possible due to the well-known (mostly beyond the PV com-
munity) piezo- and pyro-electric properties of CdS in combination with
the compressive stress created by the deposition and postdeposition pro-
cesses. While these issues will be addressed in what follows (Sec. XVIII)
we note here that all the ‘successful’ replacement of CdS layer (such as e.g.
MgZnO) utilized materials that are piezo-active as well.
The same figure presents other barrier features. On the back, there is a
Schottky barrier originating from the difference between work functions
of CdTe and the metal electrode. The front part can accommodate either
an energy cliff or energy barrier (according to different authors) reflecting
the data used for determining the band structure mismatch between CdS
and front electrode or buffer layer. More sophisticated diagrams presenting
this or other specific device recipes can include other barriers. However,
regardless of all these complementary details, the mainstream understand-
ing of such devices is that of p-n junction.
E. Other Relevant Types of Diodes

p-i-n barriers presented in Fig. 18 have been historically important with
a-Si:H thin film PV technology [31]. They consist of two heavily doped p-
and n- layers separated by the undoped intrinsic region. In the latter, both
the screening lengths of Eqs. (7) and (8) exceed the layer thickness leaving
the field in it practically uniform, which provides efficient drift of photo-
generated charge carriers towards the electrodes. In reality, such a diagram
may not be limited to a-Si:H. It may approximately apply to CdTe based
devices where screening length is of the same order as the layer thickness.
We shall end this section by noting that the current voltage characteristic
of Eq. (6) can be readily extended over all the above mentioned diodes by
relating the junction forming layers to the metal electrodes having Fermi
levels EF2 and EF1 in Fig. 9. The expression for saturation current density is
p intrinsic n
EF
Fig. 18 The schematic structure and band diagram of a p-i-n diode.

not immediately apparent and remains a model parameter extracted from

the data or further theoretical estimates.
It is important that any of the above discussed or other conceivable
diodes can be described in detail based on the established equations, which
are the electrostatic Poisson equation and the continuity equation includ-
ing the recombination processes. The corresponding analytical treatments
can be rather involved. However there exists various software packages
that generate all the required characteristics given the input of material
parameters. They will be introduced in Sec. III B below.
F. Field Reversal Diode: A Counterintuitive Case

The versatility of diode concept exhibits itself with a rather counterintui-
tive arrangement where the electric field undergoes sign reversal includ-
ing its discontinuity, and the electric potential distribution shows a gull
wing singularity shape as illustrated in Fig. 19. Here we will not provide
its analytical and numerical analysis referring to Sec. XVIII below where
it is presented for a more general case including photocurrent. We would
like to note however that the field reversal diode can be quite realistic
corresponding to the case where one of the components (A in Fig. 19)
is ferroelectric, i.e. it has structural electric dipoles that can align to the
electric field.
Indeed, aligning its dipoles in such direction that their negative
poles point
  right in Fig. 19 will decrease the system electrostatic energy
Wel p E (another wording of the same would be that the positive
(negative) poles move along (against) the field decreasing the system
Electron energy
Field
Electron energy
A B
Field
A B
Fig. 19 The electron energy and field distribution for a two-layer (A,B) system where
one of the components is ferroelectric, capable of aligning its dipoles to the external field.
Left: the standard distribution where the left side layer has n- and the right-side layer
p - type of conductivity and the built-in filed is significant in the junction proximity.
Right: the distributions after the electric dipoles in the ferroelectric layer (A) are aligned
minimizing the system energy. Their created electric field is opposite to the original one
leading to field reversal. The field discontinuity at the material contact plane is due to the
polarization surface charge density.
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There is no peace, nor ever can be, for the soul of man, but in the
purity and perfection of its first-created nature; nor can it have its
purity and perfection in any other way, than in and by the spirit of
love. For love is the purity, the perfection of all created things; and
nothing can live in God but as it lives in love. Look at every vice,
pain, and disorder, in human nature, it is in itself nothing but the spirit
of the creature turned from the universality of love to some self-
seeking in created things. So that love alone is the cure of every evil;
and he that lives in the purity of love, is risen out of the power of evil,
into the freedom of the one spirit of heaven. The schools have given
us very accurate definitions of every vice, whether it be
covetousness, pride, wrath, or envy, and shewn us how to conceive
them as notionally distinguished from one another. But the Christian
has a much shorter way of knowing them, and what they all are, and
do, in himself. For, call them by what names you will, they are all,
that same one thing, and all do that same one work, as the Scribes,
the Pharisees, and rabble of the Jews, who crucified Christ, were all
but one and the same thing, and all did one and the same work,
however different they were in outward names. If you would
therefore have a true sense of the nature and power of pride, wrath,
covetousness, envy, they are in their whole nature nothing else but
the murderers and crucifiers of the true Christ of God; not as the
high-priests did many hundred years ago, nailing his outward
humanity to an outward cross, but crucifying afresh the Son of God,
who is the Christ that every man crucifies as often as he gives way
to wrath, pride, envy, or covetousness. For where pride, and envy,
and hatred, are wilfully indulged, there the same thing is done, as
when Christ was killed, and Barabbas was saved alive.
In all the universe, nothing but heaven and heavenly creatures
could have been known, had every creature continued in that state in
which it came forth from God. For God can will nothing in the life of
the creature but a manifestation of his own goodness, happiness,
and perfection. And therefore when this is wanted, it is certain, the
creature hath lost its first state that it had from God. Every thing
therefore, which is the vanity, the torment, and evil, of man, or any
intelligent creature, is solely the effect of his will turned from God.
Misery and wickedness can have no other root; for whatever wills
and works with God, must partake of the happiness and perfection of
God.
This therefore is a certain truth, that hell and death, curse and
misery, can never be removed from the creation, till the will of the
creature is again as it came from God, a spirit of love, that willeth
nothing but goodness. All the whole fallen creation, stand it never so
long, must groan and travel in pain, till every contrariety to the divine
will is entirely taken from every creature.
Thus, Sir, you have seen the original, immutable ground of the
spirit of love. It is no imaginary refinement, or speculative curiosity;
but is of the highest reality. It stands in the immutability and
perfection of God; and not only every intelligent creature, be it what
and where it will, but every inanimate thing must work in vanity till it
works under the spirit of love.
*Every son of fallen Adam is under this same necessity of
working and striving after something that he neither is nor hath. All
evil as well as good men, all the wisdom and folly of this life, are a
proof of this. For the vanity of wicked men in their various ways, and
the labours of good men in faith and hope, proceed from the same
cause, viz. from a want and desire of having and being something
that they neither are nor have. The evil seek wrong, and the good
seek right; but they both are seekers, and for the same reason;
because their present state has not that which it wants to have. And
this must be the state of every creature that has fallen from its first
state. It must do as the polluted fluid does; it must ferment and work,
either right or wrong, to mend its state. The muddled wine always
works right to the utmost of its power, because it works according to
nature; but if it had an intelligent free will, it might work as vainly as
man does; it might continually thicken itself, be always stirring up its
own dregs, and then it would seek for its purity, just as well as the
soul of man seeks for its happiness in the lusts of the flesh, the lust
of the eyes, and the pride of life. All which must fall away from the
heart of man before it can find its happiness in God, as the dregs
must separate from the wine before it can have its perfection and
clearness.
*Purification therefore is so necessary, that nothing will do in the

stead of it. But man is not purified, till every earthly, wrathful,
sensual, selfish temper is taken from him. He is not dying to himself,
till he is dying to these tempers; and he is not alive in God, but as he
is dead to them. It is the purity and perfection of the divine nature
that must be brought again into him: nor are you to think that these
words, the purity and perfection of God, are too high to be used on
this occasion; for they only mean, that the will of the creature must
will and work with the will of God; and whatever does not thus, is at
enmity with God, and cannot have life and happiness with him.
Now, nothing wills and works with God but the spirit of love;
because nothing else works in God himself. The Almighty brought
forth all nature for this only end, that boundless love might have its
infinity of height and depth to dwell and work in; and all the
properties of nature are only to give life and strength to the spirit of
love, that it may come forth into outward activity, and manifest its
blessed powers; that all creatures may communicate the spirit of
love and goodness, give and receive delight to and from one
another. All below this state of love, is a fall from the one life of God,
the only life in which the God of love can dwell.
Now who can restore this life? The unbelieving Jews said of our
Lord, How can this man forgive sins? Christ shewed them how, by
appealing to that power which they saw he had over the body:
whether, says he, is it easier to say, Thy sins are forgiven thee, or to
say, Arise, take up thy bed, and walk? But the delusion of the
unbelieving Deist is greater than that of the Jew. For the Deist sees,
that his reason has no power over his body; can remove no disease,
blindness, deafness, or lameness, from it; and yet will pretend to
have power enough from his reason, to help the soul out of all its
evil; not knowing that he only, who can say to the dead body of
Lazarus, Come forth, can say to the soul, Be thou clean. The Deist
therefore, if he pleases, may stile himself a natural, or a moral
philosopher, but with no more truth, than he can call himself an
healer of all the maladies of the body. And for a man to think himself
a moral philosopher, because he has made a choice collection of
syllogisms, in order to quicken and revive a divine goodness in the
soul; or that no Redeemer need come from heaven, because human
reason, when truly left to itself, has great skill in chopping of logic;
may justly be deemed such an ignorance of the nature of things, as
is seldom found in the transactions of illiterate and vulgar life. But
this by the by.
To return to our chief subject: the sum is this: all evil, all misery of
every kind, is nothing else but nature left to itself; and therefore,
there is no possibility for the natural, earthly man to escape eternal
wrath, but solely in the way the gospel teacheth, by denying and
dying to himself. On the other hand, all the goodness and perfection,
all the happiness, glory, and joy, that any intelligent creature can be
possessed of, is, and can be, from nothing else, but the invisible
uncreated light and Spirit of God manifesting itself in the creatures,
filling, blessing, and uniting them all in one love.
And thus again: there is no possibility of man’s attaining to any

heavenly perfection and happiness, but only in the way of the
gospel, by the union of the divine and human nature, by man’s being
born again from above, of the Word and Spirit of God. There is no
possibility of any other way, because there is nothing that can
possibly change us into an heavenly state, but the presence and
power of the Deity united with, and working in us. And therefore the
Word was made flesh, and must of all necessity be made flesh, if
man is to have an heavenly nature. Now as all evil, sin, and misery,
have no beginning, nor power of working, but in the manifestation of
contrary properties; so man has nothing to turn to, seek, or aspire
after, but the lost spirit of love. And therefore it is, that God only can
be his Redeemer; because God only is love; and love can be no
where else, but in God, and where God dwelleth and worketh.
Now the difficulty you find in attaining this spirit of love, is
because you seek for it, in the way of reasoning: you would be
possessed of it only from a rational conviction of the fitness and
amiableness of it. And as this clear idea does not put you into the
possession of it, your reason begins to waver; and suggests to you,
that it may be only a fine notion, that has no ground but in the power
of imagination. But this, Sir, is all your own error; as if you would
have your eyes do that, which only your hands or feet can do for
you. The spirit of love is a spirit of nature and life; and therefore can
only be produced in you, by that Almighty power which produced all
nature, and gave life to every living thing. Life can only arise in its
own time and place from its proper cause, and as the genuine effect
of it. Nature and life do nothing by chance, or accidentally, but every
thing in one uniform way. Fire, air, and light, do not proceed
sometimes from one thing, and sometimes from another: but
wherever they are, they are always born in the same manner, and
from the same working in the properties of nature. So in like manner,
love is an immutable birth, always proceeding from the same cause,
and cannot be in existence till its own true parents have brought it
forth.
*How unreasonable would it be to doubt whether strength and

health of body were real things, or possible to be had, because you
could not by the power of your reason take possession of them? Yet
this is as well as to suspect the purity and perfection of love to be
only a notion, because your reason cannot bring it forth in your soul.
For reason has no more power of altering the life and properties of
the soul, than of altering the life and properties of the body. That, and
that only, can cast devils, and evil spirits, out of the soul, that can say
to the storm, Be still; and to the leper, Be thou clean.
And now, Sir, you see the absolute necessity of the gospel-
doctrine of the cross; viz. of dying to ourselves, as the only way to
life in God. This is the one morality that does man any good. Fancy
as many rules as you will, of modelling the moral behaviour of man,
they all do nothing, because they leave nature still alive; and
therefore can only help a man to an art of concealing his own inward
evil. But still nature can no more change from evil to good, than
darkness can work itself into light. The one work therefore is to resist
and deny nature, that a supernatural power may take possession of
it.
There is no standing still, life goes on, and is always bringing

forth its realities, which way soever it goeth. You see the true state of
every natural man, whether he be Cæsar or Cato, whether he
gloriously murders others, or only stabs himself; blind nature does all
the work, and must be the doer of it, till the light of God has helped
them to one common good, in which they all willingly unite, rest, and
rejoice. In a word, goodness is only a sound, and virtue a mere strife
of natural passions, till the spirit of love is the breath of every thing
that lives, and moves in the heart. For love is the one only blessing,
and goodness, and God of nature; and you have no true religion, are
no worshipper of the one true God, but in and by that Spirit of love,
which is God himself living and working in you.
An Extract from Mr. Law’s
Spirit of L O V E.
P A R T II.
A dialogue between Theogenes, Eusebius, and Theophilus.
Y heart embraces you both with the greatest

Theophilus. M affection, and I am much pleased at the occasion
of your coming, which calls me to the most
delightful subject in the world, to help both you and myself, to rejoice
in that adorable Deity, whose infinite being is an infinity of mere love,
an unbeginning, never-ceasing, and for ever over-flowing ocean of
meekness, sweetness, delight, blessing, goodness, patience, and
mercy; and all this, as so many blessed streams breaking out of the
abyss of universal love. Father, Son, and Holy Ghost, a triune infinity
of love and goodness, for ever and ever, giving forth nothing but the
same gifts of light and love, of blessing and joy, whether before or
after the fall, either of angels, or men.
Look at all nature, through all its height and depth, in all its variety
of powers, it is what it is, for this only end, that the hidden riches, the
invisible blessings, glory and love of the unsearchable God, may
become visible, sensible, and manifest in it, and by it.
Look at all the variety of creatures, they are what they are, for this
only end, that in their infinite variety, degrees, and capacities, they
may be as so many speaking figures, so many sounds and voices,
preachers and trumpets, giving glory and praise, and thanksgiving to
that Deity of love, which gives life to all nature.
For every creature, call it by what name you will, had its form,
and power, and state, and place in nature for no other end, but to
open and enjoy, to manifest and rejoice in some share of the love
and happiness, and goodness of the Deity.
Now this is the one will and work of God, in, and through all
creatures. From eternity to eternity he can will, and intend nothing
towards them, in them, or by them, but the communication of various
degrees of his own love, goodness and happiness to them,
according to their state and place, and capacity. This is God’s
unchangeable disposition towards the creature; he can be nothing
else, but all goodness towards it; because he can be nothing
towards the creature, but that which he is, and was, and ever shall
be in himself.
Theogenes. Pray, Theophilus, let me ask you, Does not patience

and pity, and mercy begin to be in God, and only then begin, when
the creature has brought forth itself into misery? They could have no
existence in the Deity before.
Theophilus. ’Tis true, Theogenes, that God can only then begin to
make known his mercy and patience, when the creature has lost its
rectitude and happiness; yet nothing then begins to be in God, or to
be found in him, but that which was always in him, in the same
infinite state, viz. a will to all goodness, and which can will nothing
else. And his patience and mercy, which could not shew forth
themselves, till sin had brought forth misery, were not new tempers,
or the beginning of some new disposition, that was not in God
before, but only new and occasional manifestations of that
boundless, eternal will to all goodness, which always was in God in
the same height and depth. The will to all goodness, which is God
himself, began to display itself in a new way, when it first gave birth
to creatures. The same will to all goodness began to manifest itself
in another new way, when it became patience and compassion
towards fallen creatures. But neither of these ways are the beginning
of any new tempers or qualities in God, but only new and occasional
manifestations of that true eternal will to all goodness, which always
was, and always will be, in the same fulness in God.
And salvation is, and can be nothing else, but the manifestation
of the life of God in the soul. How clearly does this give the solid
distinction between inward holiness, and all outward practices. All
that God has done for man by any particular dispensations, whether
by the law or the prophets, by the scriptures, or ordinances of the
church, are only as helps to an holiness, which they cannot give, but
are only suited to the death and darkness of the earthly life, to turn it
from itself, from its own workings, and awaken in it a faith and hope,
a hunger and thirst after that first union with the Deity, which was lost
in the fall of the first father of mankind.
*How unreasonable is it, to call perpetual inspiration fanaticism,

and enthusiasm, when there cannot be the least degree of goodness
or happiness in any intelligent being, but what is in its whole nature,
merely and truly the breathing, the life, and the operation of God in
the life of the creature? For if goodness can only be in God, if it
cannot exist separate from him, if he can only bless and sanctify by
himself becoming the blessing and sanctification of the creature,
then it is the highest degree of blindness to look for any goodness,
and happiness from any thing but the immediate indwelling, union
and operation of the Deity in the creature. Perpetual inspiration,
therefore, is in the nature of the thing as necessary to a life of
goodness, holiness, and happiness, as the perpetual respiration of
the air is necessary to animal life.
*For the life of the creature, whilst possessing nothing but itself, is
hell; that is, it is all pain and want and distress. Now nothing can help
it to be in light and love, in peace and goodness, but the union of
God with it, and the life of God working in it, because nothing but
God is light, and love, and heavenly goodness. And, therefore,
where the life of God is not become the life and goodness of the
creature, it cannot have the least degree of goodness in it.
What a mistake is it, therefore, to confine inspiration to particular
times and occasions, to prophets and apostles, and extraordinary
messengers of God! and to call it enthusiasm, when the common
Christian looks, and trusts to be continually led and inspired by the
Spirit of God! For tho’ all are not called to be prophets, or apostles,
yet all are called to be holy, as he who has called them is holy, to be
perfect as their heavenly Father is perfect, to be like minded with
Christ, to will only as God wills, to do all to his honour and glory, to
renounce the spirit of this world, to have their conversation in
heaven, to set their affections on things above, to love God, with all
their heart, soul, and spirit, and their neighbour as themselves.
Behold a work as great, as divine and supernatural, as that of a

prophet and an apostle. But to suppose that we ought, and may
always be in this spirit of holiness, and yet are not, and ought not to
be always moved and led by the Spirit of God, within us, is to
suppose, that there is a holiness and goodness which comes not
from God; which is no better than supposing, that there may be true
prophets and apostles who have not their truth from God.
Now the holiness of the common Christian is not an occasional

thing, that begins and ends, or is only for such a time, or place, or
action, but is the holiness of that, which is always alive, and stirring
in us, namely, of our thoughts, wills, and affections. If therefore these
are always alive in us, always governing our lives, then a perpetual
operation of the Spirit of God within us, is absolutely necessary. For
we cannot be inwardly led and governed by a spirit of goodness, but
by being governed by the Spirit of God himself.
If our thoughts, wills, and affections, need only be now and then
holy and good, then, indeed, the Spirit of God need only now and
then govern us. But if our thoughts and affections are to be always
holy, then the holy Spirit of God is to be always operating within us.
The scripture saith, We are not sufficient of ourselves to think a
good thought. If so, then we cannot be chargeable with not thinking,
and willing that which is good, but upon this supposition, that there is
always a supernatural power ready, and able to help us to the good,
which we cannot have from ourselves.
How firmly our established church adheres to this doctrine of the

necessity of the perpetual operation of the Holy Spirit, as the one
only source of any degree of divine light, wisdom, virtue, and
goodness in the soul of man; how earnestly she requires all her
members to live in the most open profession of it, and in the highest
conformity to it, may be seen by many such prayers as these in her
ordinary, public service.
O God for as much as without thee, we are not able to please

thee, grant that thy Holy Spirit may in all things direct and rule our
hearts. Again we pray thee, that thy grace may ALWAYS prevent and
follow us, and make us CONTINUALLY to be given to all good
works. Again, Grant to us, Lord, we beseech thee, the Spirit to think
and do ALWAYS such things as be rightful, that we, who cannot do
ANY THING that is good, WITHOUT thee, may, by thee, be enabled
to live according to thy will. Again, Because the frailty of man,
WITHOUT thee, CANNOT BUT FALL, keep us EVER, by thy HELP,
from all things hurtful, and LEAD us to all things profitable to our
salvation, &c. Again, O God from whom all good things do come,
grant to us, thy humble servants, that by THY holy INSPIRATION,
we may THINK those things that be good, and, by thy merciful
GUIDING, may PERFORM the same.
And now, Eusebius, how is the great controversy about religion,

and salvation, ♦shortened.
♦ “shortned” replaced with “shortened”

For since the one work of Christ as your Redeemer, is to take
from the earthly life of flesh and blood, its usurped power, and to
raise the smothered spark of heaven, out of death, into life, your one
work also, under your Redeemer is fully known. And you have the
utmost certainty, what you are to do, where you are to seek, and in
what you are to find your salvation. All that you have to do, is to
oppose, resist, to renounce the evil tempers, and workings of your
earthly nature. You want no deliverance, but from the power of
yourself. This is the one murderer of the divine life within you. And
every thing that your earthly nature does, is under the influence of
self-will, self-love, and self-seeking, whether it carries you to
laudable, or blameable practices, all is done in the nature and spirit
of Cain, and only helps you to such goodness, as when Cain slew
his brother. For every action and motion of self, has the spirit of
antichrist, and murders the divine life within you.
Judge not therefore of yourself, by considering how many of

those things you do, which divines and moralists call virtue and
goodness, nor how much you abstain from those things, which they
call sin and vice.
But daily and hourly, in every step that you take, see to the spirit
that is within you, whether it be heaven, or earth that guides you.
And judge every thing to be sin and Satan, in which your earthly
nature, has any share of life in you; nor think that any goodness is in
you, but so far as it is an actual death to the pride, the vanity, the
wrath, and selfish tempers of your fallen, earthly life.
Again, here you see, where and how you are to seek your
salvation, not in taking up your travelling-staff, or crossing the seas
to find out a new Luther or a new Calvin, to cloath yourself with their
opinions. No. The oracle is at home, that always speaks the truth to
you; nothing is your truth, but that good and that evil which is within
you. For salvation or damnation is not an outward thing, but springs
up within you. What you are in yourself, what is doing in yourself, is
either your salvation or damnation.
Again nothing that we do is bad, but for this reason, because it
resists the power, and working of God within us; and nothing that we
do, can be good, but because it conforms, to the Spirit of God within
us. And therefore, you have the utmost certainty, that God, salvation
and the kingdom of heaven, are within you, and that all outward
religion, from the fall of man to this day, is not for itself, but merely for
the sake of an inward and divine life, which was lost when Adam
died his first death in paradise. So that it may well be said,
circumcision is nothing, and uncircumcision is nothing, because
nothing is wanted, but a new creature, called out of the death and
darkness of flesh and blood, into the light, life and perfection of its
first creation.
And thus also, you have the fullest proof in what your salvation
precisely consists. Not in any historic faith, or knowledge of any thing
absent, or distant from you, not in any variety of restraints, rules, and
methods of practising virtues, not in any formality of opinion about
faith and works, repentance, forgiveness of sins, or justification, and
sanctification, not in any truth, or righteousness, that you can have
from yourself, from the best of men or books, but wholly and solely in
the life of God.
Theogenes. I have not the least doubt about any of these things.
It is visible, that there can be no medium in this matter, either religion
must be all spiritual, or all carnal; that is, we must either take up with
the grossness of the Sadducees, who say, there is neither angel nor
spirit, or with such purification as the Pharisees had from their
washing of pots and vessels, and tithing their mint and rue; we must,
I say, either acquiesce in this carnality, or we must profess a religion,
that is all spirit and life, and merely for the sake of raising up an
inward spiritual life of heaven, that fell into death in our first father.
*Theophilus. Oh Theogenes! What an eternity is that, out of
which, and for which thy eternal soul was created? What little,
crawling things are all that an earthly ambition can set before thee?
Bear with patience for awhile the rags of thy earthly nature, the veil
and darkness of flesh and blood, as the lot of thy inheritance from
father Adam, but think nothing worth a thought but that which will
bring thee back to thy first glory, and land thee safe in the region of
eternity.
An Extract from Mr. Law’s
Spirit of L O V E.
P A R T III.
A dialogue between Theogenes, Eusebius, and Theophilus.
HE doctrine of the spirit of love, cannot have more

Eusebius. T power over me, or be more deeply rooted in me, than
it is already. It has so gained possession of my whole
heart, that every thing else must be under its dominion. I can do
nothing else but love; it is my whole nature, I have no taste for any
thing else. Can this matter be carried higher in practice?
Theophilus. No higher, Eusebius. And was this the true state of
your heart, you would bid fair to leave the world as Elijah did. For
was there nothing but this divine love alive in you, your fallen flesh
and blood would be in danger of being burnt up by it. What you have
said of yourself, you have spoken in great sincerity, but in a total
ignorance of yourself, and of the spirit of divine love. You are as yet
only charmed with the sight, or rather the sound of it; its real birth is
as yet unfelt, and unfound in you. Your natural complexion has a
great deal of the animal meekness and softness of the lamb, and the
dove; your blood and spirit are of this turn; and therefore a God all
love, and a religion all love, quite transport you; and you are so
delighted with it, that you fancy you have nothing in you, but this
religion of love. But, my friend, bear with me, if I tell you, that all this
is only the good part of the spirit of this world, and may be in any
unregenerate man, that is of your complexion. It is so far from being
a genuine fruit of divine love, that if it be not well looked to, it may
prove a real hindrance of it, as it oftentimes does, by its appearing to
be that which it is not.
You have quite forgot all that was said in the letter to you on the
spirit of love. You may love it as much as you please, think it the
most charming thing in the world, fancy every thing but dross and
dung, in comparison of it, and yet have no more of it in you, than the
blind man has of that light, of which he has got a most charming
notion.
Eusebius. But if I am got no farther than this, what good have I

from giving in so heartily to all that you have said of this doctrine?
Theophilus. Your error lies in this; you confound two things, which
are entirely distinct from each other. You make no difference betwixt
the doctrine, that only sets forth the nature, excellency, and
necessity of the spirit of love, and the spirit of love itself; which yet
are two things so different, that you may be quite full of the former,
and at the same time quite empty of the latter. I have said every
thing that I could, to shew you the excellency and necessity of the
spirit of love: it is of infinite importance to you to be well established
in the belief of this doctrine. But all that I have said of it, is only to
encourage you to buy it, at its own price, and to give all that for it,
which alone can purchase it. But if you think you have got it,
because you are so highly pleased with that which you have heard of
it, you only embrace the shadow, instead of the substance.
Eusebius. What is the price that I must give for it?
Theophilus. You must give up all that you are, and all that you
have from fallen Adam; for all that you are and have from him, is that
life of flesh and blood, which cannot enter into the kingdom of God.
Adam, after his fall, had nothing that was good in him, nothing
that could inherit an eternal life in heaven, but a seed of grace. Every
thing else in him was devoted to death, that this incorruptible seed
might grow up in Christ Jesus.
Theogenes. I am afraid the matter is much worse with me, than it

is with Eusebius. For tho’ this doctrine, seems to have got all my
heart, as it is a doctrine; yet I am continually thrown out of it in
practice, and find myself as much under the power of my old
tempers and passions, as I was before I was so full of this doctrine.
Theophilus. You are to know, my friends, that every kind of virtue
and goodness, may be brought into us, by two different ways. They
may be taught us outwardly by men, by rules and precepts; and they
may be inwardly wrought in us. In the former way, as we learn them
only from men, they at best, only change our outward behaviour,
leave our heart in its natural state, only put our passions under a
forced restraint, which will occasionally break forth, in spite of
precept and doctrine. Now this way of learning goodness, tho’ thus
imperfect, is yet absolutely necessary, in the nature of the thing, and
must first have its time, and place, and work in us; yet it is only for a
time, as the law was a school-master to the gospel. We must first be
babes in doctrine, as well as in strength, before we can be men. But
of all this outward instruction, whether from good men, or the letter of
scripture, it must be said, as the apostle saith of the law, that it
maketh nothing perfect.
The true profitableness of the written word of God, is fully set

forth by St. Paul to Timothy: from a child, saith he, thou hast known
the scriptures, which are able to make thee wise unto salvation,
which is by faith in Christ Jesus. Now these scriptures were the law
and the prophets, for Timothy had known no other from his youth.
And as they, so all other scriptures since, have no other good, or
benefit in them, but as they lead us to a salvation, that is not to be
had in themselves, but from faith in Christ Jesus. Their teaching is
only to teach us, where to seek and to find the fountain of all light
and knowledge.
Of the law saith the apostle, it was a school-master to Christ. The

same thing is to be affirmed of the letter of the New Testament; it is
but our school-master unto Christ. Nor can the thing possibly be
otherwise; no instruction that comes under the form of words can do
more for us, than sounds, and words can do; they can only direct us
to something that is better than themselves, that can be the true
light, life, spirit, and power of ♦holiness in us.
♦ “hoiliness” replaced with “holiness”

Eusebius. I cannot deny what you say, and yet it seems to me to
derogate from scripture.
Theophilus. Would you then have me to say, that the written word
of God, is that word of God, which liveth, and abideth for ever; that
word, which was with God, which was God, by whom all things were
made; that word of God, which was made flesh for the redemption of
the world; that word which lighteth every man, that cometh into the
world; that word, which in Christ Jesus is become wisdom, and
righteousness, and sanctification in us; would you have me say, that
all this is to be understood of the written word of God? If this cannot
possibly be, then all that I have said is granted, namely, that Jesus is
alone that word of God, that can be the light, life, and salvation of
fallen man. And how is it possible more to exalt the letter of scripture,
than by owning it to be a true, outward direction to the one only true
light, and salvation of man.
Suppose you had been a true disciple of John the Baptist, whose
office was, to prepare the way to Christ, how could you have more
magnified his office, than by going from his teaching, to be taught by
Christ? The Baptist was indeed a burning and a shining light, and so
are the holy scriptures; but he was not that light, but was sent to bear
witness of that light. That was the true light, which lighteth every
man, that cometh into the world.
What a folly would it be to say that you had undervalued the

office, and the character of John the Baptist, because he was not
allowed to be the light itself, but only a true witness of it, and guide to
it? Now if you can shew, that the written word can have any other, or
higher office, or power, than such a ministerial one as the Baptist
had, I am ready to hear you.
Eusebius. There is no possibility of doing that.

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A. Band Transport in Random Potential 144

XXVII. Categories of Degradation 225

spectrum of localized states, operations of nonocrystalline junctions, and,

of subjects so established that they appear “carved in stone” for ages as

I. Introduction to Thin Film PV

A. The Origin of PV. Junctions

chemically different metal electrodes of a capacitor will spontaneously

B. Fundamental Material Requirements

metal semiconductor metal

Fig. 2 Band diagram of a metal/semiconductor/metal structure where EF1 and EF2

C. Charge Transport. Definition of Thin Film PV

τE = l/v = l2/(μqV) and τD = l2/D, (1)

shorter than τr in thin PV where recombination becomes almost immate-

D. Distinctive Features of Thin Film PV

inevitable with inexpensive fast deposition techniques not giving enough

Back metal Glass

extreme views ranging from that these materials cannot be effectively

degradation processes. Some PV companies went under being unable to

12. W. Shockley and H. J. Queisser, Detailed Balance Limit of Efficiency of p-n

Fig. 7 represents the energy band diagram of a nonmetal layer sand-

Fig. 8 Current-voltage characteristic of a system with symmetric barrier illustrated in Fig. 7.

(a) (b) (c) (d)

thermal fluctuations. The probability of such fluctuations is proportional

J1 = J00 exp(−qW1/kT) and J2 = J1 exp (–qV/kT)

and the current voltage characteristics, J = J1 – J2 takes the form

It saturates as illustrated in Fig. 8.

W1,eff = max{W1, W2 − qV}, (5)

The corresponding currents are given by,

They have exponentially different saturated values:

Fig. 10 Current voltage characteristic of a system with asymmetric barrier illustrated in

B. Schottky, Reach-Through, and Field-Compensation

Eq. (7) assumes discrete energy levels of donors or acceptors responsible

Fermi level Fermi level

Metal Semiconductor Metal Semiconductor

2. Reach Through Diodes

Wh1 Wh2 Wh1

Fig. 13 Reach-through structure of a semiconductor layer sandwiched between two

The reach-through related issues will be further discussed in connection

3. Field Compensation Diode

compared to WE and omitting all the numerical multipliers of the order of

LDp Lsp LDn

300 μm, and LDn ~ 12 μm vs. LDp ~ 1100 μm corresponding to τn ~ 350

where L is the device thickness, and D is the carrier diffusion coefficient.

The activation energy G (instead of the Fermi energy) reflects the

level is described by the electronic affinity, defined as the energy obtained

CBO>0 G2 CBO=0 CBO<0

of that mystery can be related to the piezo-photovoltaic coupling that

E. Other Relevant Types of Diodes