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 Contents vii

7. SnO2 dye-sensitized solar cells 205

Qamar Wali and Rajan Jose
7.1 Introduction 205
7.2 Various SnO2 nanostructures employed as photoanodes in
dye-sensitized solar cells 208
7.3 Photoanode based on SnO2 one-dimensional nanostructures 228
7.4 Dye-sensitized solar cells fabrication and testing 240
7.5 Photoanode based on SnO2 composite or hybrid 249
7.6 Doped photoanode 268
7.7 Three-dimensional SnO2 nanostructures 270
7.8 Photoanodes based on SnO2 core
shell 270
7.9 Outlook and future recommendations 277
References 278

8. Nb2O5 dye-sensitized solar cells 287

Barbara N. Nunes, Leandro A. Faustino, Andressa V. Muller,
Andre S. Polo and Antonio Otavio T. Patrocinio
8.1 Introduction 287
8.2 Nb2O5 and its thin films
preparation methods, typical
morphology, crystalline phases, optical, and electronic properties 288
8.3 Nb2O5 in dye-sensitized solar cells 297
8.4 Other photoelectrochemical applications of dye-sensitized
Nb2O5 films 314
8.5 Final remarks and perspectives 315
References 316

Part III Nanowire, nanorod and nanoporous

materials-based solar 323
9. Silicon nanowire-based solar cells 325
Subramani Thiyagu and Naoki Fukata

9.1 Introduction 325

9.2 Formation of silicon nanowires 327
9.3 Silicon nanostructure properties 331
9.4 Solar applications using silicon nanowires 337
9.5 Summary 345
References 346
viii Contents

10. Nanorod-based dye sensitized solar cells 349

Sawanta S. Mali, Jyoti V. Patil, and Chang Kook Hong
10.1 Introduction 349
10.2 Dye-sensitized solar cells 350
10.3 Conventional dye-sensitized solar cells 352
10.4 TiO2 nanorod-based dye-sensitized solar cells 365
10.5 Conclusions and outlook 371
Acknowledgment 372
References 372
Further reading 374

Part IV Others 375

11. Quantum dots for solar cell applications 377
El Hadji Mamour Sakho and Oluwatobi S. Oluwafemi

11.1 Introduction 377

11.2 Theoretical background 379
11.3 Photoanode in quantum dot-sensitized solar cells 387
11.4 Counter electrode in quantum dot-sensitized solar cells 394
11.5 Electrolytes in quantum dot-sensitized solar cells 397
11.6 Experimental background in quantum dot-sensitized solar cells 398
11.7 Summary and future prospects 402
Acknowledgments 403
References 403
Further reading 415

12. Perovskite solar cells 417

Junming Li, Qiong Wang and Antonio Abate

12.1 Introduction 417

12.2 Halide perovskite materials 418
12.3 Perovskite solar cells 422
12.4 Characterization 432
12.5 Remaining challenges 436
12.6 Summary and outlook 439
Reference 440
 Contents ix

13. Metal nanostructures for solar cells 447

Saniat Ahmed Choudhury, Fatema Fairooz, Rashid Ahmed Rifat
and Mustafa Habib Chowdhury
13.1 Section 1—Introduction 448
13.2 Section 2—Photovoltaic technologies involving metals 451
13.3 Section 3—Surface plasmon resonance 462
13.4 Section 4—Plasmonic solar cells—metals and configuration 470
13.5 Section 5—Plasmonic nanostructures on the surface 479
13.6 Section 6—Embedded plasmonic nanostructures 491
13.7 Section 7—Conclusion 500
Acknowledgements 500
References 501
Further reading 511

14. Electrolyte for dye-sensitized, quantum dots, and

perovskite solar cells 513
Sawanta S. Mali, Jyoti V. Patil, Hyungjin Kim, Pramod S. Patil
and Chang Kook Hong
14.1 Introduction 513
14.2 Electrolytes for dye-sensitized solar cells 516
14.3 Electrolytes for quantum dot sensitized solar cells 533
14.4 Ternary CuInSexS22x-based solar cells 541
14.5 Electrolytes for perovskite solar cells 542
14.6 Role of dopant in solid-state hole-transporting materials for
perovskite solar cells 546
14.7 Role of additives 548
14.8 Future aspects in solid-state electrolytes 548
14.9 Conclusion and outlook 549
Acknowledgment 549
References 549

15. Polymer nanocomposites for solar cells: research trends

and perspectives 557
Iliya E. Kuznetsov, Alexander V. Akkuratov and Pavel A. Troshin
15.1 Introduction 557
15.2 Improving fundamental parameters of organic solar cells
using rational material design 564
15.3 Summary and outlook 589
Acknowledgment 591
References 591
x Contents

Part V Nano-carbon materials-based solar cells 601

16. Graphene and carbon nanotube-based solar cells 603
Xiaoxiao Lin and Peng Gao
16.1 Introduction 603
16.2 Graphene-based solar cells 605
16.3 Carbon nanotube-based solar cells 634
16.4 Conclusions and outlook 644
References 645

17. Fullerene-based solar cells 661

Takeo Oku
17.1 Introduction 661
17.2 Organic solar cells and excitons 662
17.3 Bulk-heterojunction 665
17.4 Poly[3-hexylthiophene]:6,6-phenyl C61-butyric acid methyl ester 666
17.5 Phthalocyanine dimer 669
17.6 ZnTPP:C60 672
17.7 Diamond:C60 675
17.8 Ge nanoparticles 679
17.9 Polysilane-system 681
17.10 6,6-Phenyl C61-butyric acid methyl ester:poly[3-hexylthiophene]
with silicon phthalocyanine or silicon naphthalocyanine 685
17.11 Summary 691
Acknowledgments 691
References 691

18. Metal-assisted chemical etching
based nanostructured

silicon solar cells 699
Fatima Toor, Wenqi Duan, Bingtao Gao and Marcie Black
18.1 Introduction 699
18.2 Motivation for industrial applications of metal-assisted catalyzed
etching
based solar cells 700
18.3 Optical properties 701
18.4 Device design 710
18.5 Concluding remarks 722
References 722

Index 727
List of Contributors

Antonio Abate
Helmholtz Center for Materials and Energy, Berlin, Germany
Y. Akila
Department of Physics, Coimbatore Institute of Technology, Coimbatore, India
Alexander V. Akkuratov
Institute for Problems of Chemical Physics of Russian Academy of Sciences,
Chernogolovka, Russian Federation
Marcie Black
Advanced Silicon Group, Lincoln, MA, United States
Daniel Chemisana
Applied Physics Section of the Environmental Science Department, Polytechnic School,
University of Lleida, Lleida, Spain
Saniat Ahmed Choudhury
Independent University, Bangladesh (IUB), Dhaka, Bangladesh
Mustafa Habib Chowdhury
Independent University, Bangladesh (IUB), Dhaka, Bangladesh
Wenqi Duan
Electrical and Computer Engineering Department, University of Iowa, Iowa City, IA,
United States
Fatema Fairooz
Independent University, Bangladesh (IUB), Dhaka, Bangladesh
Leandro A. Faustino
Laboratory of Photochemistry and Materials Science, Institute of Chemistry, Federal
University of Uberlandia, Uberlandia, Brazil
Naoki Fukata
International Center for Materials Nanoarchitectonics, National Institute for Materials
Science, Tsukuba, Japan
Bingtao Gao
Electrical and Computer Engineering Department, University of Iowa, Iowa City, IA,
United States
Peng Gao
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian
Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, P.R. China; Laboratory of Advanced Functional
Materials, Xiamen Institute of Rare Earth Materials, Haixi Institute, Chinese Academy of
Sciences, Xiamen, P.R. China

xi
xii List of Contributors

Chang Kook Hong

Polymer Energy Materials Laboratory, School of Applied Chemical Engineering,
Chonnam National University, Gwangju, South Korea
Rajan Jose
Nanostructures Renewable Energy Materials Laboratory, Faculty of Industrial Sciences &
Technology, Universiti Malaysia Pahang, Gambang, Malaysia
Hyungjin Kim
Polymer Energy Materials Laboratory, School of Applied Chemical Engineering,
Chonnam National University, Gwangju, South Korea
P. Senthil Kumar
Department of Chemical Engineering, SSN College of Engineering, Chennai, India
Iliya E. Kuznetsov
Institute for Problems of Chemical Physics of Russian Academy of Sciences,
Chernogolovka, Russian Federation
Chrysovalantou Lamnatou
Applied Physics Section of the Environmental Science Department, Polytechnic School,
University of Lleida, Lleida, Spain
Junming Li
Helmholtz Center for Materials and Energy, Berlin, Germany
Xiaoxiao Lin
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian
Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, P.R. China; Laboratory of Advanced Functional
Materials, Xiamen Institute of Rare Earth Materials, Haixi Institute, Chinese Academy of
Sciences, Xiamen, P.R. China
Sawanta S. Mali
Polymer Energy Materials Laboratory, School of Applied Chemical Engineering,
Chonnam National University, Gwangju, South Korea
Andressa V. Muller
Federal University of ABC, Santo André, Brazil
N. Muthukumarasamy
Department of Physics, Coimbatore Institute of Technology, Coimbatore, India
Mu. Naushad
Department of Chemistry, College of Science, King Saud University, Riyadh, Saudi
Arabia
Barbara N. Nunes
Laboratory of Photochemistry and Materials Science, Institute of Chemistry, Federal
University of Uberlandia, Uberlandia, Brazil
Takeo Oku
Department of Materials Science, The University of Shiga Prefecture, Hikone, Japan
 List of Contributors xiii

Oluwatobi S. Oluwafemi
Centre for Nanomaterials Science Research, University of Johannesburg, Johannesburg,
South Africa; Department of Chemical Sciences (Formerly Applied Chemistry), University
of Johannesburg, Doornfontein Campus, Johannesburg, South Africa
Gerko Oskam
Departamento de Física Aplicada, CINVESTAV-IPN, Mérida, México
Sundararajan Parani
Department of Chemical Sciences (Formerly Applied Chemistry), University of
Johannesburg, Doornfontein Campus, Johannesburg, South Africa; Centre for
Nanomaterials Science Research, University of Johannesburg, Johannesburg, South Africa
Jyoti V. Patil
Polymer Energy Materials Laboratory, School of Applied Chemical Engineering,
Chonnam National University, Gwangju, South Korea; Thin Film Materials Laboratory,
Department of Physics, Shivaji University, Kolhapur, India
Pramod S. Patil
Thin Film Materials Laboratory, Department of Physics, Shivaji University, Kolhapur,
India
Antonio Otavio T. Patrocinio
Laboratory of Photochemistry and Materials Science, Institute of Chemistry, Federal
University of Uberlandia, Uberlandia, Brazil
K. Grace Pavithra
Department of Chemical Engineering, SSN College of Engineering, Chennai, India
Andre S. Polo
Federal University of ABC, Santo André, Brazil
Dena Pourjafari
Departamento de Física Aplicada, CINVESTAV-IPN, Mérida, México
Rashid Ahmed Rifat
Independent University, Bangladesh (IUB), Dhaka, Bangladesh
A. Riverola
Applied Physics Section of the Environmental Science Department, Polytechnic School,
University of Lleida, Lleida, Spain
El Hadji Mamour Sakho
Department of Chemical Sciences (Formerly Applied Chemistry), University of
Johannesburg, Doornfontein Campus, Johannesburg, South Africa; Centre for
Nanomaterials Science Research, University of Johannesburg, Johannesburg, South Africa
Subramani Thiyagu
International Center for Young Scientists (ICYS), National Institute for Materials Science,
Tsukuba, Japan; International Center for Materials Nanoarchitectonics, National Institute
for Materials Science, Tsukuba, Japan
xiv List of Contributors

Sabu Thomas
International and Inter University Centre for Nanoscience and Nanotechnology,
Mahatma Gandhi University, Kottayam, India
Fatima Toor
Electrical and Computer Engineering Department, University of Iowa, Iowa City, IA,
United States
Pavel A. Troshin
Institute for Problems of Chemical Physics of Russian Academy of Sciences,
Chernogolovka, Russian Federation; Skolkovo Institute of Science and Technology,
Moscow, Russian Federation
R. Jose Varghese
International and Inter University Centre for Nanoscience and Nanotechnology,
Mahatma Gandhi University, Kottayam, India; Department of Chemical Sciences
(Formerly Applied Chemistry), University of Johannesburg, Doornfontein Campus,
Johannesburg, South Africa; Centre for Nanomaterials Science Research, University of
Johannesburg, Johannesburg, South Africa
Dhayalan Velauthapillai
Department of Chemical Sciences (Formerly Applied Chemistry), University of
Johannesburg, Johannesburg, South Africa
A. Vossier
CNRS-PROMES, Odeillo, France
Qamar Wali
NUTECH School of Applied Sciences and Humanities, National University of
Technology, Islamabad, Pakistan
Qiong Wang
Helmholtz Center for Materials and Energy, Berlin, Germany
Jihuai Wu
Professor of Materials and Chemistry, Vice-President of Huaqiao University, Director of
Engineering Research Center of Environment-Friendly Functional Materials, Ministry of
Education, Director of Institute of Materials Physical Chemistry, Huaqiao University,
Xiamen, Fujian, P.R. China
Preface

The interests of developing renewable, sustainable, and clean energy

sources have become very high because of the emergence of global
warming and the vast use of nonrenewable energy sources, such as natural
gas, oil, and coal. Several renewable energy sources, such as wave and
tidal power, wind turbines, hydropower, solar cells, fuel cells, and solar
thermal are being investigated to evaluate their potential to address large-
scale demand. Among these sources, solar photovoltaic (PV) technology,
which uses solar radiation energy, has been considered as the most abun-
dant, inexhaustible, clean, and sustainable energy resource. Solar cells
directly convert the incident solar radiation into electricity via the PV
effect and can convert up to about 20% of incoming solar radiation. Solar
cells are classified into three generations, which are based on their materi-
als and manufacturing process. Silicon (Si) single crystal wafers and bulk
polycrystalline Si wafers are the first generation of solar cells. These cells,
according to the manufacturing procedures and wafer quality, give solar
conversion efficiencies between 12% and 16% and are largely leading the
solar cells market. The thin-film solar cells that are made from different
materials, such as amorphous silicon, a-Si, cadmium telluride, cadmium
indium selenide, or thin silicon films on indium tin oxide, t-Si, are the
second generation of solar cells. This technology provides less expensive
solar cells with lower solar energy conversion in comparing to the silicon
wafers technology. The third and emerging solar cells generation, which
can produce high efficiency devices at low production costs of solar cells,
are based on polymer solar cells, dye synthesized solar cells, quantum dots
solar cells, and perovskite solar cells.
Recently, nanomaterials have emerged as the new building blocks to
construct solar cell assemblies. The use of nanomaterials in solar cell appli-
cation is gaining tremendous interest and building great expectations in
the academic community, industry, and governments. A motivation to
develop high efficiency and cost-effective nanostructured materials for
solar cells is growing and a specific contribution of nanotechnology to
various solar energy is being developed. Nanomaterials provide new
methods to approach solar energy conversion with a flexible and promis-
ing material platform. Therefore nanostructured materials, such as metal
oxide, quantum dots, perovskite, graphene, carbon nanotubes, and

xv
xvi Preface

fullerene play a significant role in solar cell applications. Hence, it has

been demonstrated that nanostructured materials can improve the perfor-
mance of solar cells by enhancing both light trapping and photo-carrier
collection. Furthermore, the synthesis, characterizations, and utilization of
these novel nanostructures lie at the interface among physics, chemistry,
engineering, and materials science. The structure, size, and shape of these
nanomaterials have significant effect over the efficiency of the solar energy
conversion.
Over the last two decades there are numerous research papers on
nanostructured materials for solar cell applications. A few research papers
are based on metal oxide-based solar cells, quantum dot sensitized solar
cells, dye sensitized solar cells, and polymer nanocomposites solar cells.
Recently, nano-carbon based materials such as graphene, graphene deriva-
tives, carbon nanotube, and fullerene have been extensively investigated
on solar cells. However, up to now, no systematic efforts have been made
to come out with a book that exclusively covers the synthesis, characteri-
zations, and properties of nanomaterials for solar cell applications that are
very much required for academe and industry.
Thus this book reports on the developments in the synthesis and
characterizations of nanomaterials for solar cells. The book starts with a
discussion on the fundamentals of nanomaterials for solar cells, including a
discussion on the life-cycle assessments and characterization techniques. It
then follows with a review of the various types of solar cells: thin film,
metal oxide, nanowire, nanorods, and nanoporous materials, and con-
cludes with nanocarbon materials. In addition, it includes a review of
quantum dot sensitized, perovskite, and polymer nanocomposites-based
solar cells.
PART I

Fundamental of
nanomaterials for
solar cells

1
This page intentionally left blank
CHAPTER 1

Fundamentals of solar cells

A.
1
Riverola1, A. Vossier2 and Daniel Chemisana1
Applied Physics Section of the Environmental Science Department, Polytechnic School, University of
Lleida, Lleida, Spain
2
CNRS-PROMES, Odeillo, France

Contents
1.1 Introduction 3
1.2 The solar resource, solar energy 4
1.3 Principles of photovoltaic energy conversion 7
1.4 Semiconductors 7
1.4.1 Bands, electrons, and holes 8
1.4.2 Doping, n and p types 9
1.4.3 Generation and recombination of electron
holes pairs 11
1.5 Solar cell structure, operation, and main parameters 13
1.5.1 p
n Junction 13
1.5.2 Structure, operation, and main parameters of solar cells 15
1.6 Upper limit for solar energy conversion 20
1.7 Reducing Boltzmann losses: optical concentration and angular restriction 22
1.7.1 Optical concentration 23
1.7.2 Angular restriction 25
1.8 Reducing thermalization and below-Eg losses: advanced concepts of
photovoltaic cells 26
1.8.1 Multijunction (MJ) solar cells 26
1.8.2 Other concepts 28
References 32
Further reading 33

1.1 Introduction
During the last decades, photovoltaics (PVs) have become one of the
most promising renewable energy technologies, with installed capacity of
PV panels approaching 100 GW in 2018. High conversion efficiencies at
reasonable costs undoubtedly represent a sine-qua-non condition to be ful-
filled toward promoting an even wider deployment of solar electricity.

Nanomaterials for Solar Cell Applications © 2019 Elsevier Inc.

DOI: https://doi.org/10.1016/B978-0-12-813337-8.00001-1 All rights reserved. 3
4 Nanomaterials for Solar Cell Applications

The development of strategies aiming at an improved PV efficiency has

instigated a broad range of research activities in the most recent decades.
With this objective, strategies involving nanomaterials, implementation of
nanoobjects, or manipulation of light at a nanometer scale, has prompted
a considerable amount of research. These different strategies will be care-
fully reviewed in the next book chapters. In this chapter, we aim to pro-
vide several fundamental concepts necessary to better grasp the underlying
physical mechanisms governing PV cells (A detailed explanation of these
concepts can be found in other textbooks [1,2]).
The PV effect, which was discovered by Edmund Becquerel in 1839,
basically implies direct conversion of sunlight into electricity using a PV
cell made of a semiconductor material tailored to ensure both a high
absorption of sunlight and an efficient extraction of the photogenerated
carriers.

1.2 The solar resource, solar energy

The spectral distribution of sunlight spans a broad range of wavelengths
ranging from the ultraviolet to the near infrared. The relation between
the photon energy (E) and its wavelength (λ) is given by:
hc
E5 (1.1)
λ
where c is the light speed in vacuum (approximately 3.00 3 108 m s21)
and h is the Planck’s constant (6.63 3 10234 J s).
The spectral distribution of sunlight may vary noticeably depending
on (1) the position of the sun in the sky (which is function of the charac-
teristic latitude of the site where the PV cell is supposed to operate, the
time of the day, and the day in the year) and (2) typical atmospheric para-
meters values, which are likely to change noticeably depending on the cli-
matic and atmospheric conditions.
Air mass (AM) is the atmospheric variable to which the solar spectrum
is normally more sensitive. It is defined as the distance, relative to the short-
est (vertical) path length, that sunrays traverse through the atmosphere
before impacting on the Earth’s surface. AM can simply be defined as:
1
AM 5 (1.2)
cosθ
 Fundamentals of solar cells 5

where θ is the so called solar zenith angle, that is, the angle between the
zenith and the center of the sun’s disc.
Nonetheless, a more accurate expression that considers the Earth’s cur-
vature is commonly used to predict or define the solar spectrum [3]
1
AM 5 (1.3)
cosθ10:50572ð96:079952θÞ21:6364
Fig. 1.1 shows two commonly used solar spectra: AM0 (standard
extraterrestrial solar spectrum mainly used by the aerospace community)
and AM1.5 Global (where the receiving surface is defined as an inclined
plane at 37 degrees tilt toward the equator, facing the sun).
The spectral distribution corresponding to AM0 solar spectrum can be
approximated, with a good accuracy, to the spectrum of a blackbody at
5758K (The spectral distribution for blackbody radiation being only
determined by its temperature, as stated by Planck’s law).
The AM1.5 Global spectrum often serves as the terrestrial standard
(reference), and is measured on a surface that faces the sun, with a tilt
angle of 37 degrees over the horizontal plane, under specified atmospheric
conditions [aerosol optical depth (AOD) of 0.084, precipitable water

Figure 1.1 Extraterrestrial solar spectrum (AM0) and the standard terrestrial spec-
trum (AM1.5 Global). Retrieved from ASTM, G173-03 Standard tables for reference solar
spectral irradiances: direct normal and hemispherical on 37° tilted surface, Book of
Standards, 14.04.2004 [4].
6 Nanomaterials for Solar Cell Applications

(PW) of 1.42 cm and total column ozone equivalent of 0.34 cm]. An

AM of 1.5 corresponds to a solar zenith angle of approximately 48
degrees. Passing through the atmosphere, the spectrum is attenuated dif-
ferently for each wavelength due to absorption or scattering by atmo-
spheric particles. For instance, water vapor absorption bands are mainly
located in the near-infrared and infrared regions of the spectrum
(around 0.94, 1.10, and 1.40 μm). The amplitude of light scattering in
the atmosphere is correlated to the AM value: the higher the AM, the
higher the light scattering by atmospheric molecules (such as nitrogen
and oxygen). Consequently, the terrestrial irradiance (which is com-
monly normalized to 1000 W m22) is lower than the extraterrestrial
irradiance (around 1353 W m22). The peak solar irradiance, which cor-
responds to wavelengths typically comprised between 0.4 and 0.8 μm, is
associated with “visible” light in the sense that human vision evolved to
be particularly sensitive to this spectral range. One should distinguish
different definitions for solar irradiance: direct normal irradiance (DNI)
refers to the photons coming directly from the sun. It should be noted
that the definition of DNI is not univocal. This ambiguity stems from
the fact that the angular distance from the center of the sun and the
penumbra function are not well limited. Several definitions of DNI can
be found in the literature, explicitly or implicitly referring to different
limit angles and penumbra functions, which inherently lead to varying
amounts of integrated radiance in the vicinity of the sun [5]. Global
Horizontal Irradiance refers to the total irradiance received from above
by a horizontal surface, and includes both the contributions of DNI and
diffuse radiation, associated to photons scattered in the atmosphere. The
amount of diffuse radiation changes depending on the climate (and
especially the cloud cover) and the latitude, and typically represent
B15% of the total radiation. AM1.5D solar spectrum is commonly used
as a reference spectrum for the characterization of concentrator solar
cells (because of the fundamental inability of these cells to concentrate
diffuse light).
The other atmospheric variables that significantly affect the solar
spectrum characteristics are AOD and PW. AOD characterizes the radia-
tive strength of aerosols (urban haze, smoke particles, desert dust, sea salt
. . .) in the vertical direction while PW is the amount of condensed
water corresponding to the total water vapor contained in a vertical
atmospheric column above any location. Water vapor has strong absorp-
tion bands in the near infrared, which directly impacts the spectrum.
 Fundamentals of solar cells 7

1.3 Principles of photovoltaic energy conversion

Solar cells should be designed to ensure maximum absorption of photons
coming from the sun, and to promote electrons to high-energy states
where they are able to move. The material should have at least two ener-
getically separated bands to guarantee an efficient extraction of the charges
carried from the PV cell. The bandgap (Eg) of PV cell corresponds to the
energy gap separating the maximum energy level in the low-energy band
[referred as “valence band” (VB)], from the minimum energy level in the
high-energy band [known as “conduction band” (CB)], where the elec-
trons should be promoted. The typical time during which the electron is
maintained in a high-energy state should be high enough to guarantee an
efficient extraction of the excited carriers [a constraint that may be fulfilled
if the bandgap is higher than the thermal energy kBT (where kB is the
Boltzmann’s constant and T the temperature)].
Only photons with energy higher than Eg are able to pump electrons
from the VB to the CB. The charge separation mechanism, which is
required to extract charge carriers from the PV cells, involves the use of a
“membrane” to separate the different charge carriers. This is commonly
achieved with an electric field originating from the potential difference
between contacts.
Semiconductor materials have historically been seen as a very attractive
option toward efficiently converting sunlight into electricity using the PV
effect. Emerging technologies using organic or/and inorganic substances
such as Perovskite or polymer solar cells are currently instigating a great
amount of research work, but these technologies will not be addressed in
this chapter, since the underlying physical mechanisms are sensibly differ-
ent (the reader should refer to the following chapters for deeper insights
into these technologies).

1.4 Semiconductors
Materials can be classified into three main categories, depending on their
typical electronic properties: Semiconductors and insulators both show an
energy gap between their valence and CBs, whereas metals show an overlap
between energy levels in the VB and the CB (and, as a consequence, no
energy gap). The development of efficient PV cells requires both an efficient
absorption of solar photons, and the establishment of two distinct charge car-
rier populations, which can only be achieved with semiconductor materials.
8 Nanomaterials for Solar Cell Applications

In this section, some basic concepts related to semiconductor physics

will be introduced. Electrons, holes, and electronic bands will first be
explained. The principles of semiconductor doping will then be detailed,
before concluding this section, by a description of generation and recom-
bination of electron
holes pairs in semiconductors.

1.4.1 Bands, electrons, and holes

In an atom, electrons move in orbitals around the nucleus and can only
have certain energy values, called energy levels. In a solid material consisting
of an immensely high number of atoms, the original orbitals are combined
to form orbitals with a large number of energy levels. Because of the huge
number of atoms involved, these levels are very close one from another so
that they form energy bands. The bonds between atoms and their electronic
properties determine the bands’ energy distribution, as well as the crystalline
structure. For instance, silicon atoms share four electrons of the outermost
shell (valence shell) with the neighboring atoms, creating stable and strong
covalent bonds that result in a diamond lattice type crystalline structure.
The atoms’ chemical properties are determined to a great extent by
the number of electrons in the valence shell. In a similar manner, the last
occupied bands define the electronic properties of crystals. The occupied
band with the highest energy, which contains the valence electrons, is
called the Valence Band (VB), whereas the unoccupied band with the
lowest energy is called the Conduction Band (CB). The energy between
both bands is the previously mentioned bandgap energy (Eg).
In metals, electrons move without difficulty from one energy level to
another, since the valence and the conduction bands overlap in energy
(Eg 5 0), giving rise to a high electrical conductivity. In semiconductors,
the valence and conduction bands are separated (0.5 , Eg , 3 eV), and
the VB is filled with bonded electrons that do not have sufficient energy
to overcome the energy gap and freely move in the crystalline network.
At a temperature higher than 0K, a fraction of these electrons has suffi-
ciently high thermal energy to be expelled to the CB (this fraction being
a function of both the temperature and the energy gap of the semicon-
ductor material). Insulators have very high bandgaps, which practically
avoid electrons from the VB to be ejected to the CB because of the high
energy required to overcome the bandgap. As a consequence, the absence
of free electrons in the CB precludes efficient electrical transport, and
these materials are characterized by a low conductivity. Fig. 1.2 shows a
scheme of insulators, semiconductors, and conductors.
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partial unconsciousness, or even by more marked congestive
symptoms. The pain may seem to fill the whole cranium, may be
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cannot directly depend upon the cerebral lesion, but must be a reflex
phenomenon or due to a neuritis. According to my own experience,
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periosteum. In many cases, especially when the headache is
persistent, there are distinct nocturnal exacerbations.
39 Book Y., p. 88, 1879.

It will be seen that there is nothing absolutely characteristic in the

headache of cerebral syphilis; but excessive persistency, apparent
causelessness, and a tendency to nocturnal exacerbation should in
any cephalalgia excite suspicion of a specific origin—a suspicion
which is always to be increased by the occurrence of slight spells of
giddiness or by delirious mental wandering accompanying the
paroxysms of pain. When an acute inflammatory attack supervenes
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headache of intolerable severity.

When the headache in any case is habitually very constant and

severe, the disease is probably in the dura mater or periosteum; and
this probability is much increased if the pain be local and augmented
by firm, hard pressure upon the skull over the seat of the pain.

Disorders of Sleep.—There are two antagonistic disorders of sleep,

either of which may occur in cerebral syphilis, but which have only
been present in a small proportion of the cases that I have seen.
Insomnia is more apt to be troublesome in the prodromic than in the
later stages, and is only of significance when combined with other
more characteristic symptoms. A peculiar somnolence is of much
more determinate import. It is not pathognomonic of cerebral
syphilis, yet of all the single phenomena of this disease it is the most
characteristic. Its absence is of no import in the theory of an
individual case.

As I have seen it, it occurs in two forms: In the one variety the patient
sits all day long or lies in bed in a state of semi-stupor, indifferent to
everything, but capable of being aroused, answering questions
slowly, imperfectly, and without complaint, but in an instant dropping
off again into his quietude. In the other variety the sufferer may still
be able to work, but often falls asleep while at his tasks, and
especially toward evening has an irresistible desire to slumber, which
leads him to pass, it may be, half of his time in sleep. This state of
partial sleep may precede that of the more continuous stupor, or may
pass off when an attack of hemiplegia seems to divert the
symptoms. The mental phenomena in the more severe cases of
somnolency are peculiar. The patient can be aroused—indeed in
many instances he exists in a state of torpor rather than of sleep;
when stirred up he thinks with extreme slowness, and may appear to
have a form of aphasia; yet at intervals he may be endowed with a
peculiar automatic activity, especially at night. Getting out of bed;
wandering aimlessly and seemingly without knowledge of where he
is, and unable to find his own bed; passing his excretions in a corner
of the room or in other similar place, not because he is unable to
control his bladder and bowels, but because he believes that he is in
a proper place for such act,—he seems a restless nocturnal
automaton rather than a man. In some cases the somnolent patient
lies in a perpetual stupor.

An important fact in connection with the somnolence is that it may

develop suddenly without marked premonition. Thus in a case
reported by J. A. Ormerod40 a man who had been in good health,
save only for headache, awoke one morning in a semi-delirious
condition, and for three days slept steadily, only arousing for meals;
after this there was impairment of memory and mental faculties, but
no more marked symptoms.
40 Brain, vol. v. 260.
Apathy and indifference are the characteristics of the somnolent
state, yet the patient will sometimes show excessive irritability when
aroused, and will at other periods complain bitterly of pain in his
head, or will groan as though suffering severely in the midst of his
stupor—at a time, too, when he is not able to recognize the seat of
the pain. I have seen a man with a vacant, apathetic face, almost
complete aphasia, persistent heaviness and stupor, arouse himself
when the stir in the ward told him that the attending physician was
present, and come forward in a dazed, highly pathetic manner, by
signs and broken utterances begging for something to relieve his
head. Heubner speaks of cases in which the irritability was such that
the patient fought vigorously when aroused; this I have not seen.

This somnolent condition may last many weeks. T. Buzzard41 details

the case of a man who after a specific hemiplegia lay silent and
somnolent for a month, and yet finally recovered so completely as to
win a rowing-match on the Thames. I have seen a fair degree of
recovery after a somnolence of four months' duration.
41 Clinical Lectures on Dis. Nerv. Syst., London, 1882.

In its excessive development syphilitic stupor puts on the symptoms

of advanced brain-softening, to which it is indeed often due. Of the
two cases with fatal result of which I have notes, one at the autopsy
was found to have symmetrical purulent breaking down of the
anterior cerebral lobes; the other, softening of the right frontal and
temporal lobes, due to the pressure of a gummatous tumor, and
ending in a fatal apoplexy.

This close connection with cerebral softening explains the clinical

fact that apoplectic hemorrhage is very apt to end the life in these
cases of somnolent syphilis. But a prolonged deep stupor in persons
suffering from cerebral syphilis does not prove the existence of
extensive brain-softening, and is not incompatible with subsequent
complete recovery. As an element of prognosis it is of serious but not
of fatal import.
Paralysis.—When it is remembered that a syphilitic exudation may
appear at almost any position in the brain, that spots of encephalic
softening are a not rare result of the infection, that syphilitic disease
is a common cause of cerebral hemorrhage, it is plain that a specific
palsy may be of any conceivable variety, and affect either the
sensory, motor, or intellectual sphere. The mode of onset is as
various as the character of the palsy. The attack may be
instantaneous, sudden, or gradual. The gradual development of the
syphilitic gumma would lead us, a priori, to expect an equally gradual
development of the palsy; but experience shows that in a large
proportion of the cases the paralysis appears suddenly, with or
without the occurrence of an apoplectic or epileptic fit. Under these
circumstances it will be usually noted that the resulting palsy is
incomplete; in rare instances it may be at its worst when the patient
awakes from the apoplectic seizure, but usually it progressively
increases for a few hours, and then becomes stationary. These
sudden partial palsies probably result from an intense congestion
around the seat of disease or from stoppage of the circulation in the
same locality; whatever their mechanism may be, it is important to
distinguish them from palsies which are due to hemorrhage. I believe
this can usually be done by noting the degree of paralysis.

A suddenly-developed, complete hemiplegia or other paralysis may

be considered as in all probability either hemorrhagic or produced by
a thrombus so large that the results will be disorganization of the
brain-substance, and a future no more hopeful than that of a clot. On
the other hand, an incomplete palsy may be rationally believed to be
due to pressure or other removable cause; and this belief is much
strengthened by a gradual development. The bearing of these facts
upon prognosis it is scarcely necessary to point out.

Although the gummata may develop at almost any point, they

especially affect the base of the brain, and are prone to involve the
nerves which issue from it. Morbid exudations, not tubercular or
syphilitic, are rare in this region. Hence a rapidly but not abruptly
appearing strabismus, ptosis, dilated pupil, or any paralytic eye
symptom in the adult is usually of syphilitic nature. Syphilitic facial
palsy is not so frequent, whilst paralysis of the nerve from rheumatic
and other inflammation within its bony canal is very common.
Paralysis of the facial nerve may therefore be specific, but existing
alone is of no diagnostic value. Since syphilitic palsies about the
head are in most instances due to pressure upon the nerve-trunks,
the electrical reactions of degeneration are present in the affected
muscles.

There is one peculiarity about specific palsies which has already

been alluded to as frequently present—namely, a temporary,
transient, fugitive, varying character and seat. Thus an arm may be
weak to-day, strong to-morrow, and the next day feeble again, or the
recovered arm may retain its power and a leg fail in its stead. These
transient palsies are much more apt to involve large than small brain
territories. The explanation of their largeness, fugitiveness, and
incompleteness is that they are not directly due to clots or other
structural changes, but to congestions of the brain-tissues in the
neighborhood of gummatous exudations. Squint due to direct
pressure on a nerve will remain when the accompanying monoplegia
due to congestion disappears.

Motor palsies are more frequent than sensory affections in syphilis,

but hemianæsthesia, localized anæsthetic tracts, indeed any form of
sensory paralysis, may occur. Numbness, formications, all varieties
of paræsthesia, are frequently felt in the face, body, or extremities.
Violent peripheral neuralgic pains are rare, and generally when
present denote neuritis. Huguenin, however, reports42 a severe
trigeminal anæsthesia dolorosa, which was found, after death from
intercurrent disease, to have depended upon a small gumma
pressing upon the Gasserian ganglion. A somewhat similar case has
also been reported by Allen McLane Hamilton.43
42 Schwiez. Corr. Blät., 1875.

43 Alienist and Neurologist, iv. 58.

The special senses are liable to suffer from the invasion of their
territories by cerebral syphilis, and the resulting palsies follow
courses and have clinical histories parallel to those of the motor
sphere. The onset may be sudden or gradual, the result temporary
or permanent. Charles Mauriac44 reports a case in which the patient
was frequently seized with sudden attacks of severe frontal pain and
complete blindness lasting from a quarter to half an hour; at other
times the same patient had spells of aphasia lasting only for one or
two minutes. I have seen two cases of nearly complete deafness
developing in a few hours in cerebral syphilis, and disappearing
abruptly after some days. Like other syphilitic palsies, therefore,
paralyses of special senses may come on suddenly or gradually, and
may occur paroxysmally.
44 Loc. cit., p. 31.

Among the palsies of cerebral syphilis must be ranked aphasia. An

examination of recorded cases shows that syphilitic aphasia is
subject to vagaries and laws similar to those connected with other
specific cerebral palsies. It is usually a symptom of advanced
disease, but may certainly develop as one of the first evidences of
cerebral syphilis. Coming on after an apoplectic or epileptic fit, it may
be complete or incomplete: owing to the smallness of the centre
involved and the ease with which its function is held in abeyance, a
total loss of word-thought is not so decisive as to the existence of
cerebral hemorrhage as is a total motor palsy. Like hemiplegia or
monoplegia, specific aphasia is sometimes transitory and
paroxysmal. Buzzard45 records several such cases. Mauriac46 details
a very curious case in which a patient, after long suffering from
headache, was seized by sudden loss of power in the right hand and
fingers, lasting about ten minutes only, but recurring many times a
day. After this had continued some time the paroxysms became
more completely paralytic, and were accompanyed by loss of the
power of finding words, the height of the crises in the palsy and
aphasia being simultaneously reached. For a whole month these
attacks occurred five or six times a day, without other symptoms
except headache, and then the patient became persistently paralytic
and aphasic, but finally recovered. To describe the different forms of
specific aphasia and their mechanism of production would be to
enter upon a discussion of aphasia itself—a discussion out of place
here. Suffice it to say that every conceivable form of the disorder
may be induced by syphilis.
45 Loc. cit., p. 81.

46 Aphasie et Hemiplégia droite Syphilit., Paris, 1877.

Owing to the centres of speech being situated in the cortical portion

of the brain, aphasia in cerebral syphilis is very frequently associated
with epilepsy. Of course right-sided palsy and aphasia are united in
syphilitic as in other disorders. If, however, the statistics given by
Tanowsky47 be reliable, syphilitic aphasia is associated with left-
sided hemiplegia in a most extraordinarily large proportion. Thus in
53 cases collected by Tanowsky, 18 times was there right-sided
hemiplegia, and 14 times left-sided hemiplegia, the other cases
being not at all hemiplegic. Judging from the autopsy on a case
reported in Mauriac's brochure, this concurrence of left-sided
paralysis and aphasia depends partly upon the great frequency of
multiple brain lesions in syphilis, and partly upon the habitual
involvement of large territories of the gray matter secondarily to
diseased membrane. An important practical deduction is that the
conjoint existence of left hemiplegia and aphasia is almost diagnostic
of cerebral syphilis.
47 L'Aphasie syphilitique.

Probably amongst the palsies may be considered the disturbances

of the renal functions, which are only rarely met with in cerebral
syphilis, and which are probably usually dependent upon the specific
exudation pressing upon the vaso-motor centres in the medulla.
Fournier speaks of having notes of six cases in which polyuria with
its accompaniment, polydipsia, was present, and details a case in
which the specific growth was found in the floor of the fourth
ventricle. Cases have been reported of true saccharine diabetes due
to cerebral syphilis,48 and I can add to these an observation of my
own. The symptoms, which occurred in a man of middle age, with a
distinct specific history, were headache, nearly complete hemiplegia,
and mental failure, associated with the passage of comparatively
small quantities of a urine so highly saccharine as to be really a
syrup. Under the influence of the iodide of potassium the sugar in a
few weeks disappeared from the urine.
48 Consult Servantié, Des Rapports du Diabète et de la Syphilis, Paris, Thèse, 1876;
also, case reported by L. Putzel, New York Med. Record, xxv. 450.

Epilepsy.—Epileptic attacks are a very common symptom of

meningeal syphilis, and are of great diagnostic value. The
occurrence in an adult of an epileptic attack or of an apoplectic fit, or
of a hemiplegia after a history of intense and protracted headache,
should always excite grave suspicion.

Before I had read Fournier's work on Nervous Syphilis I taught that

an epilepsy appearing after thirty years of age was very rarely, if
ever, essential epilepsy, and unless alcoholism, uræmic poison, or
other adequate cause could be found was in nine cases out of ten
specific; and I therefore quote with satisfaction Fournier's words:
“L'épilepsie vraie, ne fait jamais son premier dêbut à l'âge adulte, à
l'âge mûr. Si un homme adulte, au dessus de 30, 35, à 40 ans, vient,
à être pris pour la première fois d'une crise épileptique, et cela dans
la cours d'une bonne santé apparente, il y a, je vous le répète, hui
ou neuf chances sur dix pour que cette épilepsie soit d'origine
syphilitique.”

Syphilitic epilepsy may occur either in the form of petit mal or of haut
mal, and in either case may take on the exact characters and
sequence of phenomena which belong to the so-called idiopathic or
essential epilepsy. The momentary loss of consciousness of petit
mal will usually, however, be found to be associated with attacks in
which, although voluntary power is suspended, memory recalls what
has happened during the paroxysm—attacks, therefore, which
simulate those of hysteria, and which may lead to an error of
diagnosis.

Even in the fully-developed type of the convulsions the aura is only

rarely present. Its absence is not, however, of diagnostic value,
because it is frequently not present in essential epilepsy, and it may
be pronounced in the specific disease. It is said that when in an
individual case the aura has once appeared the same type or form of
approach of the convulsion is thereafter rigidly adhered to. The aura
is sometimes bizarre: a severe pain in the foot, a localized cramp, a
peculiar sensation, indescribable and unreal in its feeling, may be
the first warning of the attack. An aura may affect a special sense.
Thus, I have at present a patient whose attacks begin with blindness.

In many, perhaps most, cases of specific convulsions, instead of a

paroxysm of essential epilepsy being closely simulated, the
movements are in the onset, or more rarely throughout the
paroxysm, unilateral; indeed, they may be confined to one extremity.
This restriction of movement has been held to be almost
characteristic of syphilitic epilepsy, but it is not so. Whatever
diagnostic significance such restriction of the convulsion has is
simply to indicate that the fit is due to a cortical organic lesion of
some kind. Tumors, scleroses, and other organic lesions of the
brain-cortex are as prone to cause unilateral or monoplegic epilepsy
when they are not specific as when they are due to syphilis.

Sometimes an epilepsy dependent upon a specific lesion implicating

the brain-cortex may be replaced by a spasm which is more or less
local and is not attended with any loss of consciousness. Thus, in a
case now convalescent in the University Hospital, a man aged about
thirty-five offered a history of repeated epileptic convulsions, but at
the time of his entrance into the hospital, instead of epileptic attacks,
there was a painless tic. The spasms, which were clonic and
occurred very many times a day, sometimes every five minutes,
were very violent, and mostly confined to the left facial nerve
distribution. The trigeminus was never affected, but in the severer
paroxysms the left hypoglossal and spinal accessory nerves were
profoundly implicated in all of their branches. Once, fatal asphyxia
from recurrent laryngeal spasm of the glottis was apparently averted
only by the free inhalation of the nitrite of amyl. The sole other
symptom was headache, but the specific history was clear and the
effect of antisyphilitic remedies rapid and pronounced.
It is very plain that such attacks as those just detailed are closely
allied to epilepsy; indeed, there are cases of cerebral syphilis in
which widespread general spasms occur similar to those of a
Jacksonian epilepsy, except that consciousness is not lost, because
the nervous discharge does not overwhelm the centres which are
connected with consciousness.49 On the other hand, these epileptoid
spasmodic cases link themselves to those in which the local brain
affection manifests itself in contractions or persistent irregular clonic
spasms. Contractures may exist and may simulate those of
descending degeneration,50 but in my own experience are very
rare.51
49 Case, Canada Med. and Surg. Journ., xi. 487.

50 Case, Centralbl. Nerv. Heilk., 1883, p. 1.

51 A case of syphilitic athetosis may be found in Lancet, 1883, ii. 989.

The clonic spasms of cerebral syphilis may assume a distinctly

choreic type, or may in their severity simulate those of hysteria,
throwing the body about violently.52 It is, to my mind, misleading, and
therefore improper, to call such cases syphilitic chorea, as there is
no reason for believing that they have a direct relation with ordinary
chorea. They are the expression of an organic irritation of the brain-
cortex, and are sometimes followed by paralysis of the affected
member; in other words, the disease, progressing inward from the
brain-membrane, first irritates, and then so invades a cortical centre
as to destroy its functional power.53
52 See Allison, Amer. Med. Journ., 1877, 74.

53 Case, Chicago Med. Journ. and Exam., xlvi. 21.

Psychical Symptoms.—As already stated, apathy, somnolence, loss

of memory, and general mental failure are the most frequent and
characteristic mental symptoms of meningeal syphilis; but, as will be
shown in the next chapter, syphilis is able to produce almost any
form of insanity, and therefore mania, melancholia, erotic mania,
delirium of grandeur, etc. etc. may develop along with the ordinary
manifestation of cerebral syphilis, or may come on during an attack
which has hitherto produced only the usual symptoms. Without
attempting any exhaustive citation of cases, the following may be
alluded to.

A. Erlenmeyer reports54 a case in which an attack of violent

headache and vomiting was followed by paralysis of the right arm
and paresis of the left leg, with some mental depression; a little later
the patient suddenly became very cheerful, and shortly afterward
manifested very distinctly delirium of grandeur with failure of
memory. Batty Tuke reports55 a case in which, with aphasia,
muscular wasting, strabismus, and various palsies, there were
delusions and hallucinations. In the same journal56 S. D. Williams
reports a case in which there were paroxysmal violent attacks of
frontal headache. The woman was very dirty in her habits, only ate
when fed, and existed in a state of hypochondriacal melancholy.
Leiderdorf details a case with headache, partial hemiplegia, great
psychical disturbance, irritability, change of character, marked
delirium of grandeur, epileptic attacks, and finally dementia,
eventually cured by iodide of potassium.57 Several cases illustrating
different forms of insanity are reported by N. Manssurow.58
54 Die luëtischen Psychosen.

55 Journ. Ment. Sci., Jan., 1874, p. 560.

56 April, 1869.

57 Medicin Jahrbucher, xx. 1864, p. 114.

58 Die Tertiäre Syphilis, Wien, 1877.

That the attacks of syphilitic insanity, like the palsies of syphilis, may
at times be temporary and fugitive, is shown by a curious case
reported by H. Hayes Newington,59 in which, along with headache,
failure of memory, and ptosis in a syphilitic person, there was a brief
paroxysm of noisy insanity.
 59 Journ. Ment. Sci., London, xix. 555.

DIAGNOSIS.—In a diagnosis of cerebral syphilis a correct history of the

antecedents of the patients is of vital importance. Since very few of
the first manifestations of the disorder are absolutely characteristic,
whilst almost any conceivable cerebral symptoms may arise from
syphilitic disease, treatment should be at once instituted on the
appearance of any disturbance of the cerebral functions in an
infected person.

Very frequently the history of the case is defective, and not rarely
actually misleading. Patients often appear to have no suspicion of
the nature of their complaint, and will deny the possibility of syphilis,
although they confess to habitual unchastity. My own inquiries have
been so often misleading in their results that I attach but little weight
to the statements of the patient, and in private practice avoid asking
questions which might recall unpleasant memories, depending upon
the symptoms themselves for the diagnosis.

The general grounds of diagnosis have been sufficiently mapped out

in the last section, but some reiteration may be allowable. After the
exclusion of other non-specific disease, headache occurring with any
form of ocular palsy or with a history of attack of partial monoplegia
or hemiplegia, vertigo, petit mal, epileptoid convulsions, or
disturbances of consciousness, or attacks of unilateral or localized
spasms, should lead to the practical therapeutic test. Ocular palsies,
epileptic forms of attacks occurring after thirty years of age, morbid
somnolence, even when existing alone, are sufficient to put the
practitioner upon his guard. It is sometimes of vital importance that
the nature of the cephalalgia shall be recognized before the coming
on of more serious symptoms; any apparent causelessness,
severity, and persistency should arouse suspicion, to be much
increased by a tendency to nocturnal exacerbations or by the
occurrence of mental disturbance or of giddiness at the crises of the
paroxysms. Not rarely there are very early in these cases curious,
almost indefinable, disturbances of cerebral functions, which may be
easily overlooked, such as temporary and partial failures of memory,
word-stumbling, fleeting feelings of numbness or weakness,
alterations of disposition. In the absence of hysteria an indefinite and
apparently disconnected series of nerve accidents is of very urgent
import. To use the words of Hughlings-Jackson, “A random
association or a random succession of nervous symptoms is very
strong warrant for a diagnosis of a syphilitic disease of the nervous
system.” Cerebral syphilis occurring in an hysterical subject may be
readily overlooked until fatal mischief is done. When any paralysis
occurs a study of the reflexes may sometimes lead to a correct
diagnosis. Thus in a hemiplegia the reflex on the affected side in
cerebral syphilis is very frequently exaggerated, whilst in hysteria the
reflexes are usually alike on both sides. When both motion and
sensation are disturbed in an organic hemiplegia, the anæsthesia
and motor paralysis occur on the same side of the body, whilst in
hysteria they are usually on opposite sides.

In all cases of doubtful diagnosis the so-called therapeutic test

should be employed, and if sixty grains of iodide of potassium per
day fail to produce iodism, for all practical purposes the person may
be considered to be a syphilitic. No less an authority than Seguin
has denied the validity of this, but I believe, myself, that some of his
reported cases were suffering from unsuspected syphilis. I do not
deny that there are rare individuals who, although untainted, can
resist the action of iodide, but in ten years' practice in large hospitals,
embracing probably some thousands of cases, I have not met with
more than one or two instances which I believed to be of such
character. Of course in making these statements I leave out of sight
persons who have by long custom become accustomed to the use of
the iodide, for although in most cases such use begets increase of
susceptibility, the contrary sometimes occurs. Of course the
physician who should publicly assert that a patient who did not
respond to the iodide had syphilis would be a great fool, but in my
opinion the physician who did not act upon such a basis would be
even more culpable.

PROGNOSIS.—Cerebral meningeal syphilis varies so greatly and so

unexpectedly in its course that it is very difficult to establish rules for
predicting the future in any given case. The general laws of
prognosis in brain disease hold to some extent, but may always be
favorably modified, and patients apparently at the point of death will
frequently recover under treatment. The prognosis is not, however,
as absolutely favorable as is sometimes believed, and especially
should patients be warned of the probable recurrence of the affection
even when the symptoms have entirely disappeared. The only safety
after the restoration of health consists in an immediate re-treatment
upon the recurrence of the slightest symptom. The occurrence of a
complete, sudden hemiplegia or monoplegia is sufficient to render
probable the existence of a clot, which must be subject to the same
laws as though not secondary to a specific lesion. If a rapid decided
rise of temperature occur in an apoplectic or epileptic attack, the
prognosis becomes very grave. An epileptic paroxysm very rarely
ends fatally, although it has done so in two of my cases.

The prognosis in gummatous cerebral syphilis should always be

guardedly favorable. In the great majority of cases a more or less
incomplete recovery occurs under appropriate treatment, and I have
seen repeatedly patients who were unconscious, with urinary and
fecal incontinence, and apparently dying, recover. Nevertheless, so
long as there is any particle of gummatous inflammation in the
membrane the patient is liable to sudden congestions of the brain,
which may prove rapidly fatal, or he may die in a brief epileptic fit. On
the one hand there is an element of uncertainty in the most favorable
case, and on the other so long as there is life a positively hopeless
prognosis is not justifiable.

PATHOLOGY.—Gummatous inflammation of the brain probably always

has its starting-point in the brain-membranes, although it may be
situated within the brain: thus, I have seen the gummatous tumors
spring from the velum interpositum in the lateral ventricle. The
disease most usually attacks the base of the brain, and is especially
found in the neighborhood of the pons Varolii and the optic tract. It
may, however, locate itself upon the vault of the cranium, and in my
experience has seemed to prefer the anterior or motor regions. The
mass may be well defined and roundish, but more usually it is
spread out, irregular in shape, and more or less confluent with the
substance of the brain beneath it. It varies in size from a line to
several inches in length, and when small is prone to be multiple. The
only lesion which it resembles in gross appearance is tubercle, from
which it sometimes cannot be certainly distinguished without
microscopic examination.

The large gummata have not rarely two distinct zones, the inner one
of which is drier, somewhat yellowish in color, opaque, and
resembles the region of caseous degeneration in the tubercle. The
outer zone is more pinkish and more vascular, and is semi-
translucent.

On microscopic examination the most characteristic structures are

small cells, such as are found in gummatous tumors in other portions
of the body. These cells are most abundant in the inner zone, which,
indeed, may be entirely composed of them. In the centre of the
tumor they are more or less granular and atrophied; in some cases
the caseous degeneration has progressed so far that the centre of
the gumma consists of minute acicular crystals of fat. In the external
or peripheral zone of the tumor the mass may pass imperceptibly
into the normal nerve tissue, and under these circumstances it is that
it contains the spider-shaped cells or stellate bodies described by
Jastrowitch, and especially commented upon by Charcot and
Gombault and by Coyne. These are large cells containing an
exaggerated nucleus and a granular protoplasm, which continues
into multiple, branching, rigid, refracting prolongations, which
prolongations are scarcely stained by carmine. Alongside of these
cells other largish cells are often found without prolongations, but
furnished with oval nuclei and granular protoplasm. Amongst these
cells will be seen the true gummatous cells, as well as the more or
less altered neuroglia and nerve-elements. In the perivascular
lymphatic sheaths in the outer part of the gumma is usually a great
abundance of small cells. The spider-shaped cells are probably
hypertrophied normal cells of the neuroglia, and have been
considered by Charcot and Gombault as characteristic of syphilitic
gummata of the brain. In a solitary gumma, however, of considerable
size from the neighborhood of the cerebellum, studied by Coyne and
Peltier, there were no stellated cells. Coyne considers that their
presence is due to their previous existence in the normal state of the
regions affected by the gumma. Exactly what becomes of syphilitic
gumma of the brain in cases of recovery it is difficult to determine. It
is certain that they become softened and disappear more or less
completely, and it is probable that the cicatrices or the small
peripheral cysts which are not rarely found in the surfaces of the
brain are sometimes remnants of gummatous tumors. In a number of
cases collected by Gros and Lancereaux there were small areas of
softened tissue or small calcareous and caseous masses or cerebral
lacunæ corresponding to the cicatrices of softening or imperfect
cysts, coincident with evidences of syphilis elsewhere. V. Cornil also
states that he has found small areas of softening with well-
established syphilitic lesions of the dura mater and cranium, but
believes that the lacunæ or cysts depend rather upon chronic
syphilitic lesions of cerebral arteries than upon gummatous
inflammation.

When a gummatous tumor comes in contact with an artery, the latter

is usually compressed and its walls undergo degeneration. The
specific arteritis may pass beyond the limit of the syphilome and
extend along the arterial wall. Not rarely there is under these
circumstances a thrombus, and if the artery be a large one
secondary softening of its distributive brain-area occurs.

TREATMENT.—The treatment of cerebral syphilis is best studied under

two heads: First, the treatment of the accidents which occur in the
course of the disease; second, the general treatment of the disease
itself.

It must be remembered that in the great majority of cases in which

death occurs in properly-treated cerebral syphilis the fatal result is
produced by an exacerbation—or, as I have termed it, an accident—
of the disease. Under these circumstances the treatment should be
that which is adapted to the relief of the same acute affection when
dependent upon other than specific cause. In a large proportion of
cases the acute outbreak takes the form either of a meningitis or
else of a brain congestion. In either instance when the symptoms are
severe free bleeding should be at once resorted to. The amount of
blood taken is of course to be proportionate to the severity of the
symptoms and the strength of the patient. I have seen life saved by
the abstraction of about a quart of blood, whilst in other cases a few
ounces suffice. Care must be, of course, taken not to mistake a
simple epileptic fit for a severe cerebral attack; but when this fit has
been preceded by severe headache and is accompanied by stupor,
with marked disturbance of the respiration, measures for immediate
relief are usually required; and if the convulsions be perpetually
repeated or if there be violent delirious excitement, the symptoms
may be considered as very urgent. In taking blood the orifice should
be large, so as to favor a rapid flow, and the bleeding be continued
until a distinct impression is made upon the pulse. In some cases
which I have seen in which the action of the heart continued to be
violent after as much blood as was deemed prudent had been taken,
good results were obtained by the hypodermic injection of three
drops of the tincture of aconite-root every half hour until the
reduction of the pulse and the free sweating indicated that the
system was coming under the influence of the cardiac sedative.

Of course, I do not mean to encourage the improper or too free use

of the lancet in these cases, but in the few fatal cases which I have
seen I have almost invariably regretted that blood had not been
taken at once very freely at the beginning of the acute attack. In
most of these cases the symptoms had progressed too far for good
to be achieved before I reached the patient. After venesection, or in
feeble cases as a substitute for it, the usual measures of relief in
cerebral congestion should be instituted. I shall not occupy space
with a discussion of these measures, as they are in no way different
from those to be employed in cases not syphilitic.

The most important part of the treatment of cerebral syphilis itself is

antisyphilitic, and the practitioner is at once forced to select between
the iodide of potassium and the mercurial preparations. In such
choice it must be remembered that even a very small amount of
syphilitic deposit in the brain may at any time cause a sudden
congestion or other acute attack, and is therefore a very dangerous
lesion. I have seen a cerebral syphilis which was manifested only by
an epileptic attack occurring once in many months, and in which
after death the affected membrane was found to be not larger than a
quarter of a dollar, and the deposit not more than an eighth of an
inch in thickness, suddenly produce a rapidly fatal congestion; and I
have known a case fast progressing toward recovery suddenly
ended by the too long continuance of the arrest of respiration during
an epileptic fit. I have, myself, no doubt of the superiority of the
mercurials over the iodide of potassium as a means of producing
absorption of gummatous exudates; and as these exudates in the
brain are so very dangerous, a mercurial course should in the
majority of cases of cerebral syphilis be instituted so soon as the
patient comes under the practitioner's care. When, however, there is
a history of a recent prolonged free use of the mercurial, or when
there is marked specific cachexia, the iodide should be chosen.
Cachexia is, however, a distinctly rare condition in cerebral syphilis,
the disease usually developing in those who have long had apparent
immunity from the constitutional disorder. In my opinion the best
preparation of the mercurial for internal use is calomel. It should be
given in small doses, one-quarter of one grain every two hours,
guarded with opium and astringents, so as to prevent as far as
possible disturbance of the bowels, and should be continued until
soreness of the teeth, sponginess of the gums, or other evidences of
commencing ptyalism are induced. After this the dose of the
mercurial should be so reduced as simply to maintain the slight
impression which has been created, and the patient should be kept
under the mercurial influence for some weeks.

A very effective method of using the mercury is by inunction, and

where the surroundings of the patient are suitable the mercurial
ointment may be substituted for the calomel. It should be applied
regularly, according to the method laid down in my treatise on
therapeutics. I have sometimes gained advantage by practising the
mercurial unction and at the same time giving large doses of iodide
of potassium internally.
After a mercurial course the iodide of potassium should always be
exhibited freely, the object being not only to overcome the natural
disease, but also to bring about the complete elimination of the
mercury from the system. There is no use in giving the iodide in
small doses; at least a drachm and a half should be administered in
the twenty-four hours, and my own custom has been to increase this
to three drachms unless evidences of iodism are produced. The
compound syrup of sarsaparilla covers the disagreeable taste of the
iodide of potassium better than any other substance of which I have
knowledge. Moreover, I am well convinced that there is some truth in
the old belief that the so-called “Woods” are of value in the treatment
of chronic syphilis. I have seen cases in which both the iodide of
potassium and the mercurials had failed to bring about the desired
relief, but in which the same alteratives, when given along with the
“Woods,” rapidly produced favorable results. The old-fashioned
Zittmann's decoction, made according to the formula of the United
States Dispensatory, may be occasionally used with very excellent
effect. But I have gradually come into the habit of substituting a
mixture of the compound fluid extract and the compound syrup of
sarsaparilla in equal proportions. The syrup itself is too feeble to
have any influence upon the system, but is here employed on
account of its flavor. A favorite method of administration is to furnish
the patient with two bottles—one containing a watery solution of the
iodide of potassium of such strength that two drops represent one
grain of the drug, and the other the sarsaparilla mixture above
mentioned. From one to two drachms of the solution of the iodide
may be administered in a tablespoonful of the sarsaparilla well
diluted after meals. When the patient has been previously
mercurialized, or there is any doubt as to the propriety of using
mercurials, corrosive sublimate in small doses may be added to the
solution of the iodide, so that one-tenth to one-fifteenth of a grain
shall be given in each dose. I have never seen especial advantage
obtained by the use of the iodides of mercury. They are no doubt
effective, but are not superior to the simpler forms of the drug.
 Syphilitic Disease of the Brain-Cortex.

The psychical symptoms which are produced by syphilis are often

very pronounced in cases in which the paralysis, headache,
epilepsy, and other palpable manifestations show the presence of
gross brain lesions. In the study of syphilitic disease of the brain-
membranes sufficient has been said in regard to these psychical
disturbances, but the problem which now offers itself for solution is
as to the existence or non-existence of syphilitic insanity—i.e. of an
insanity produced by specific contagion without the obvious
presence of gummatous disease of the brain-membranes. Very few
alienists recognize the existence of a distinct affection entitled to be
called syphilitic insanity, and there are some who deny that insanity
is ever directly caused by syphilis. It is certain that insanity often
occurs in the syphilitic, but syphilis is abundantly joined with
alcoholism, poverty, mental distress, physical ruin, and various
depressing emotions and conditions which are well known to be
active exciting causes of mental disorder. It may well be that syphilis
is in such way an indirect cause of an insanity which under the
circumstances could not be properly styled syphilitic.

If there be disease of the brain-cortex produced directly by syphilis,

of course such disease must give rise to mental disorders; and if the
lesion be so situated as to affect the psychic and avoid the motor
regions of the brain, it will produce mental disorder without paralysis
—i.e. an insanity; again, if such brain disease be widespread,
involving the whole cortex, it will cause a progressive mental
disorder, accompanied by gradual loss of power in all parts of the
body, and ending in dementia with general paralysis; or, in other
words, it will produce an affection more or less closely resembling
the so-called general paralysis of the insane, or dementia paralytica.

As a man having syphilis may have a disease which is not directly

due to the syphilis, when a syphilitic person has any disorder there is
only one positive way of determining during life how far said disorder
is specific—namely, by studying its amenability to antisyphilitic
treatment. In approaching the question whether a lesion found after