Nanomaterials for Sensing and

Optoelectronic Applications (Micro and

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N A N O M AT E R I A L S F O R
SENSING AND
OPTOELECTRONIC
A P P L I C AT I O N S
N A N O M AT E R I A L S F O R
SENSING AND
OPTOELECTRONIC
A P P L I C AT I O N S
Edited by

M. K. JAYARAJ
Cochin University of Science and Technology, Kochi, India;
University of Calicut, Malappuram, India

SUBHA P. P.
Cochin University of Science and Technology, Kochi,
Kerala, India

SHIBI THOMAS
Department of Physics, Bharata Mata College,
Thrikkakara, Kochi, India
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 Contents v

Contents

Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .xi
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv

Chapter 1 Facet-dependent gas sensing properties of metal oxide

nanostructures 1
M.J. Priya, Subha P.P. and M.K. Jayaraj
1.1 Introduction 1
1.2 Metal oxide–based gas sensors 2
1.3 Strategies for improving the performance of metal
oxide–based gas sensors 8
1.4 General synthesis routes of high-energy crystal
facet–exposed metal oxides 14
1.5 Facet-dependent gas sensing properties of zinc oxide gas
sensors 15
1.6 Challenges and approaches 17
1.7 Application 19
1.8 Summary 19
References 20

Chapter 2 Metal oxide semiconductor thin-film transistors for gas

sensing applications 25
Manu Shaji, K.J. Saji and M.K. Jayaraj
2.1 Introduction 25
2.2 Various types of gas sensors 26
2.3 Metal oxide TFT–based gas sensors 27
2.4 Hybrid TFT sensors 39
2.5 Summary 41
References 41
vi Contents

Chapter 3 Recent developments in 2D MoS2 thin films for gas

sensing applications 45
P.S. Midhun, K.J. Saji and M.K. Jayaraj
3.1 Introduction 45
3.2 Sensing mechanism in 2D-based gas sensors 46
3.3 2D-based gas sensing devices 47
3.4 MoS2 -based gas sensors 51
3.5 Summary 58
References 59

Chapter 4 Template-assisted nanostructures for gas sensing

applications 63
P.M. Aswathy and M.K. Jayaraj
4.1 Introduction 63
4.2 Templated nanostructures: synthesis techniques and
applications 64
4.3 Prospects of biocages as templates in nanotechnology 72
4.4 Summary 78
References 79

Chapter 5 An introduction to biosensors 91

Shibi Thomas, K.J. Saji and M.K. Jayaraj
5.1 Introduction 91
5.2 Fundamentals of biosensors 92
5.3 Classification of biosensors 93
5.4 Coupling/Immobilization methods 97
5.5 Field-effect transistor biosensors 98
5.6 Applications of biosensor 103
5.7 Summary 104
References 104
 Contents vii

Chapter 6 Luminescent nanoparticles for bio-imaging application 107

T.K. Krishnapriya, M.K. Jayaraj and A.S. Asha
6.1 Introduction 107
6.2 Luminescence 108
6.3 Bioimaging 113
6.4 Luminescent nanoparticles used for bioimaging 115
6.5 Summary 123
References 124

Chapter 7 Nanophotonic biosensors for disease diagnosis 129

R. Anjana and M.K. Jayaraj
7.1 Introduction 129
7.2 Plasmonic biosensors 130
7.3 Evanescent field waveguide biosensors 137
7.4 Förster resonance energy transfer sensors 140
7.5 Multimodal sensors 143
7.6 Summary 144
References 145

Chapter 8 Precision nanoclusters: promising materials for sensing,

optoelectronics, and biology 149
J.V. Rival, P. Mymoona and E.S. Shibu
8.1 Introduction 149
8.2 LED fabrication 171
8.3 Solar energy harvesting 173
8.4 Photocatalysis 177
8.5 Bioimaging 179
8.6 Photodynamic and photothermal therapies 184
8.7 Summary 187
References 187
viii Contents

Chapter 9 Recent trends in core–shell nanostructures–based

SERS substrates 199
K.S. Anju, K.K. Rajeev and M.K. Jayaraj
9.1 Introduction 199
9.2 Surface-enhanced Raman spectroscopy 199
9.3 SERS substrates: an overview 203
9.4 Core–shell nanostructures 204
9.5 Core–shell nanostructures for biological applications 213
Summary 216
References 216

Chapter 10 Noninvasive biomarker sensors using

surface-enhanced Raman spectroscopy 221
Navami Sunil and Biji Pullithadathil
10.1 Introduction 221
10.2 Non-invasive biological fluids 225
10.3 Challenges and future perspectives 237
10.4 Summary 238
Acknowledgment 238
References 239

Chapter 11 Nanomaterials-based flexible electrochemical

sensors for health care monitoring 245
A.M.V. Mohan and A.M. Starvin
11.1 Introduction 245
11.2 Wearable electrochemical sensors for sweat monitoring 246
11.3 Flexible microfluidic sensors for sweat analysis 256
11.4 Flexible sensors for saliva monitoring 258
11.5 Flexible sensors for interstitial fluid analysis 261
11.6 Flexible sensors for tear fluid analysis 263
11.7 Challenges and future perspectives 265
 Contents ix

11.8 Summary 266

References 266

Chapter 12 Resistive switching in metal oxides for various

applications 273
P.S. Subin, K.J. Saji and M.K. Jayaraj
12.1 Introduction 273
12.2 Types of resistive switching 274
12.3 Mechanism of resistive switching 277
12.4 Chalcogenides-based RRAM 280
12.5 Carbon-based RRAM 282
12.6 Perovskite-based RRAM 282
12.7 Multilayer RRAM 283
12.8 High-density memory (crossbar memory) 284
12.9 In-memory digital computing 286
12.10 Neuromorphic computing with RS memory 289
Summary 291
References 292

Chapter 13 Mechanical bottom-up nanoassembling and

nanomanipulation using shape memory alloy nanogripper 299
V. Sampath, S. von Gratowski A. Irzhak, P. Lega, Z. Song,
M. Alonso Cotta and V. Koledov
13.1 Introduction 299
13.2 Materials and methods 301
13.3 Experiment 302
13.4 Results and discussions 303
Summary 304
Acknowledgments 306
References 306
x Contents

Chapter 14 Diamond deposition on WC–Co substrates with

interlayers for engineering applications 311
Maneesh Chandran
14.1 Introduction 311
14.2 WC-Co substrates 313
14.3 Diamond deposition 316
14.4 Characterizations and analyses 319
14.5 Applications of CVD diamond 324
14.6 Summary 325
References 325

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
 Contributors xi

Contributors

M. Alonso Cotta
Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas,
13083-859 Campinas, São Paulo, Brazil.
R. Anjana
Cochin University of Science and Technology, Kochi, India; Department of
Physics, St. Albert’s College (Autonomous), Ernakulam, India
K.S. Anju
Cochin University of Science and Technology, Kochi, India
A.S. Asha
Cochin University of Science and Technology, Kochi, India; Centre of
Excellence in Advanced Materials, Cochin University of Science and
Technology, Kochi, India
P.A. Aswathy
Cochin University of Science and Technology, Kochi, India; Department of
Physics, St. Stephen’s College, Kollam, India
Maneesh Chandran
Department of Physics, National Institute of Technology Calicut, Calicut,
India
A. Irzhak
Institute of Microelectronics Technology, Russian Academy of Sciences,
Chernogolovka, 142432, Russia
M.K. Jayaraj
Cochin University of Science and Technology, Kochi, India; University of
Calicut, Malappuram, India
V. Koledov
Kotelnikov Institute of Radio Engineering and Electronics of the Russian
Academy of Sciences, Moscow, Russia
T.K. Krishnapriya
Cochin University of Science and Technology, Kochi, India
P. Lega
Magnetic Phenomena Laboratory, Kotelnikov Institute of Radio
Engineering and Electronics, Russian Academy of Sciences, Mokhovaya
11-7, 125009, Moscow, Russia
P.S. Midhun
Cochin University of Science and Technology, Kochi, India
xii Contributors

A.M.V. Mohan
Electrodics & Electrocatalysis Division, CSIR-Central Electrochemical
Research Institute (CECRI), Karaikudi, India
P. Mymoona
Electroplating and Metal Finishing Division (EMFD), Council of Scientific
and Industrial Research (CSIR)-Central Electrochemical Research Institute
(CECRI), Karaikudi, India; Academy of Scientific and Innovative Research
(AcSIR)-CSIR, Ghaziabad, India
Subha P.P.
Department of Physics, Cochin University of Science and Technology,
Kochi, Kerala, India
M.J. Priya
Centre of Excellence in Advanced Materials, Cochin University of Science
and Technology, Kochi, Kerala, India
Biji Pullithadathil
Nanosensor Laboratory, PSG Institute of Advanced Studies, Coimbatore,
India
K.K. Rajeev
Department of Instrumentation, Cochin University of Science and
Technology, Kochi, India; Centre of Excellence in Advanced Materials,
Cochin University of Science and Technology, Kochi, India
J.V. Rival
Smart Materials Lab, Department of Nanoscience and Technology,
University of Calicut, Kerala, India
K.J. Saji
International School of Photonics, Cochin University of Science and
Technology, Kochi, India; Centre of Excellence in Advanced Materials,
Cochin University of Science and Technology, Kochi, India
V. Sampath
Indian Institute of Technology Madras, Chennai-600 036, India
Manu Shaji
Cochin University of Science and Technology, Kochi, India
E.S. Shibu
Smart Materials Lab, Department of Nanoscience and Technology,
University of Calicut, Kerala, India
Z. Song
International Research Centre for Nano Handling & Manufacturing of
China, Changchun University of Science and Technology, Changchun
130022, China
A.M. Starvin
Department of Chemistry, Christian College, Kattakada,
Thiruvananthapuram, India
 Contributors xiii

P.S. Subin
Centre of Excellence in Advanced Materials, Cochin University of Science
and Technology, Kochi, Kerala, India
Navami Sunil
Nanosensor Laboratory, PSG Institute of Advanced Studies, Coimbatore,
India
Shibi Thomas
Department of Physics, Bharata Mata College, Thrikkakara, Kochi, India
S. von Gratowski
Laboratory of Spectroscopy and Millimeter and Submillimeter Wave
Measurements, Kotelnikov Institute of Radio Engineering and Electronics,
Russian Academy of Sciences, Fryazino Branch, FIRE RAS, Vvedenski
Sq.1, Fryazino, Moscow Region, 141190, Russia
 Preface xv

Preface

This book on “Nanomaterials for sensing and optoelectronic ap-

plications” is designed for postgraduate and research students. Nano-
materials are defined by their nanoscale dimensions, where surface or
interface qualities take precedence over bulk features. The large surface
area of nanomaterials gives rise to novel physical and chemical proper-
ties, which make them suitable for developing devices and instruments
for a variety of applications in fields of life sciences, chemical industry,
pharmaceuticals, energy conversion and storage, electronics, photon-
ics, aviation and space, food safety, and information technology. This
book leans more toward experimental methods and practical appli-
cations rather than detailing the fundamental principles. We believe
that the framework of this book will better benefit a novice researcher.
This book brings together reviews, recent studies, and knowledge on
nanomaterials for sensing and optoelectronic applications.
Developing sensors with a high response, improved selectivity,
and a faster recovery time are the prime goals for researchers work-
ing on sensors. A nanostructured design helps the miniaturization
of the sensing device with improved performance, paving the way
for portable sensors. Such sensors can be a breakthrough in vari-
ous fields, including biomedical research and environmental moni-
toring. Intriguing results using metal oxide semiconductor–based and
thin-film transistor–based gas sensors have been reported in recent
years. Metal oxide semiconductors with exposed high-energy facets
have been reported to have improved gas sensing performance. The
first three chapters provide an overview of nanostructured gas sen-
sors using metal oxide semiconductors and two-dimensional tran-
sition metal dichalcogenides. Chapter 4 details the significance of
developing nanostructures with interesting features using template-
assisted synthesis. Chapter 5 gives an introduction to biosensors and
the phenomenon of luminescence, as well as various types of lumi-
nescent nanoparticles employed in bioimaging, which are thoroughly
explained in Chapter 6. The major challenges in bioimaging and the
use of luminescent nanoparticles as a bioimaging probe are also dis-
cussed. Early, fast, accurate disease diagnosis is the most demanding
need from biomedicine, the first step toward fighting against diseases.
Chapter 7 details the different nanophotonic techniques that can be
used for disease diagnosis. Precision nanoclusters have been used
for a broad spectrum of applications, such as molecular/metal ion
sensing, device fabrication, green energy harvesting, photocatalysis,
xvi Preface

and in the biomedical field. The use of atomically precise nanoclus-

ters in these applications is discussed in Chapter 8. Surface-enhanced
Raman spectroscopy (SERS) has evolved as a unique sensing tech-
nique since it combines molecular fingerprint specificity with single-
molecule sensitivity. Recent advancements in developing core–shell
nanostructures for the development of SERS substrates are also dis-
cussed in Chapter 9. SERS is also a label-free technique for monitoring
biomarkers in biological matrices at trace-level concentrations. The
recent advances in the field of SERS-based sensors for biomarker de-
tection in body fluids such as sweat, saliva, and tear with an emphasis
on the analysis of biomarkers, fabrication techniques, and potential
real-time applications for biochemical sensing are included in Chapter
10. There is always growing demand for flexible and skin-interfaced
sensors capable of the real-time monitoring of relevant biomarkers
from human body fluids, like sweat, saliva, tear, and interstitial fluid.
The design of nanomaterials-based electrochemical sensors enhances
the sensitivity of detection, and Chapter 11 discusses nanomaterials-
based flexible electrochemical sensors for healthcare monitoring. Ar-
tificial synaptic devices are one of the most far-fetched applications of
nanostructured materials. Artificial neural networks based on resistive
switching (RS) devices are considered one of the most straightforward
and cost-effective ways of realizing this technology. Apart from that, RS
has found immense applications in semiconductor electronics as well.
The mechanism of RS in nanostructures and its numerous applications
are discussed in Chapter 12. Shape memory alloys (SMAs) are smart
materials that exhibit the unique property of a shape change upon
exposure to a change in temperature. The combination of nanomate-
rials and SMAs helps to tailor the properties and to fabricate several
nanodevices based on individual nanoobjects. One of the emerging
technologies of nanotweezers based on shape memory composite ma-
terials and their application for manipulating real nanoobjects like
nanotubes and nanowires is discussed in Chapter 13. The final chap-
ter of this book elaborates on the outstanding physical and chemical
properties of diamond. Various techniques for the growth of diamond
in the form of thin films on different substrates and their characteristics
are explained.
It is very exciting to finally publish this book on “Nanomaterials
for sensing and optoelectronic applications.” There are many people
to whom we are grateful for their valuable contributions. We extend
our sincere thanks to Ms. Priya, M. J., Mr. Manu, S., Mr. Midhun, P. S.,
Ms. Krishnapriya, T. K., Ms. Anju, K. S., Mr. Subin, P. S., Ms. Navami,
S., Mr. Jose, V. R., Dr. Anjana, R., Dr. Pillai, A. M., Dr. Saji, K. J.,
Dr. Asha, A. S., and present and former researchers at Nanopho-
tonic and Optoelectronic Devices Laboratory (NPOED), Department
of Physics, Cochin University of Science and Technology. They have
 Preface xvii

contributed their research results meticulously for each chapter of

this book. We also take this opportunity to thank with due regards,
Prof. Kumar, K. R., Department of Instrumentation, Cochin Uni-
versity of Science and Technology; Dr. Shibu, E. S., Department of
Nanoscience and Technology, University of Calicut; Dr. Biji, P., Depart-
ment of Chemistry and Nanoscience and Technology, PSG Institute
of Advanced Studies; Dr. Vinu, M. V. M., CSIR-Central Electrochem-
ical Research Institute (CECRI), Karaikudi; Prof. Sampath, V., Indian
Institute of Technology Madras, India; Von Gratowski, S. and Koledov,
V., Kotelnikov Institute of Radio Engineering and Electronics of the
Russian Academy of Sciences, Moscow, Russia; and Dr. Chandran,
M., Department of Physics, National Institute of Technology, India, for
their contribution.
It was a pleasant experience to work with the Elsevier Editorial
team, who have enabled the timely publication of this book.
Dr. M.K. Jayaraj
Dr. P.P. Subha
Dr. T. Shibi
Facet-dependent gas sensing
1
properties of metal oxide
nanostructures
M.J. Priya a, Subha P.P. b and M.K. Jayaraj b,c
a
Centre of Excellence in Advanced Materials, Cochin University of Science
and Technology, Kochi, Kerala, India. b Cochin University of Science and
Technology, Kochi, India. c University of Calicut, Malappuram, India

1.1 Introduction
Recently, nanostructured metal oxides have attracted much atten-
tion in many industrial and domestic applications for the detection
of toxic, flammable, and explosive gases due to their high sensitivity,
flexibility in production, small size, low cost, and ability to detect both
reducing and oxidizing gases (Miller et al., 2014; Wang et al., 2010). The
sensing properties of these nanomaterials strongly depend on their
size, structure, shape, surface-to-volume ratio, and physical and chem-
ical properties. With the increasing demand for selective and sensitive
gas sensors, researchers are following different strategies to improve
the gas sensing properties of the metal oxide semiconductor (MOS)–
based gas sensors, such as changing the morphology of nanostructures
(Gurlo, 2011; Shouli et al., 2010; Sun et al., 2012), noble metal dop-
ing (Luo et al., 2017; Sarkar et al., 2015), the formation of hierarchical
nanostructures (Miller et al., 2014; Walker et al., 2019), core–shell (CS)
structures (Yan et al., 2018), hollow heteronanostructures (Guo et al.,
2019), and exposing high energy crystal facets (Jia et al., 2014; Liang
et al. 2019a; Liu, et al., 2012). Among these strategies, scientists are
more interested in the development of nanostructures with selectively
exposed high-energy facets.
The numbers of dangling bonds (unsaturated bonds), number of
active site for gas adsorption, and the arrangement of surface atoms
are important factors that play a crucial role in gas sensing proper-
ties since gas sensing processes occur on the surface. Different crystal
facets with distinctive surface atomic arrangements possess different
gas sensing properties. High-energy facets possess a large number of

Nanomaterials for Sensing and Optoelectronic Applications. DOI: https://doi.org/10.1016/B978-0-12-824008-3.00015-1

Copyright 
c 2022 Elsevier Inc. All rights reserved. 1
2 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures

dangling bonds, atomic steps, and edges, which leads to more active
sites for gas adsorption; hence sensing materials exposed with high-
energy facets show greater reactivity than those exposed with the low-
energy facets (Gao & Zhang, 2018; Kuang et al., 2014; Pal & Pal, 2015;
Shang & Guo, 2015).
This chapter gives a basic idea regarding MOS-based sensors, in-
cluding their gas sensing mechanism, the design of the gas sensor, the
design of the gas sensing measurement unit, different performance
parameters, and different strategies adopted for the improvement of
the performance of MOS gas sensors. The importance of MOSs with
exposed high-energy facets in the improvement of gas sensing perfor-
mance has been discussed in detail. Also, the effects of dangling bond
density on gas sensing properties have been discussed. According to
the research and calculation, surface engineering by selectively expos-
ing high-energy facets provides an effective way to obtain MOS gas-
sensitive materials with superior performance. The understanding of
the facet-dependent properties of MOS will lead to the fabrication of
more effective gas sensors in the future.

1.2 Metal oxide–based gas sensors

1.2.1 Gas sensing mechanism
The fundamental principle of MOS–based chemoresistive sensors
is the change in the conductivity of the MOS due to the oxygen ad-
sorption and desorption reactions on the metal oxide surface. In the
case of an n-type MOS-based gas sensor the sensing mechanism is as
follows: in ambient air atmosphere, oxygen adsorbed on the surface of
the sensing layer by extracting electrons from the conduction band of
the MOS, which results in the formation of a Schottky potential barrier
in MOS (Shankar et al., 2016). The adsorption of oxygen on the surface
of MOS depends on the operating temperature of the sensor. At lower
temperatures (<150°C), oxygen molecules are adsorbed in the form of
molecular oxygen ions (O2 − ) via the trapping of a comparably fewer
number of electrons; however, at higher temperatures (>150°C), more
electrons are trapped by the adsorbed oxygen and form atomic oxygen
species (O− and O2 − ) (Kashif et al., 2013). The processes involved in
the adsorption of oxygen on the metal oxide surface can be described
as follows:

O2 (gas) → O2 (ads) (1.1)

O2 (ads) + e− → O2 − (ads), T < 150◦ C (1.2)

O− − − ◦
2 (ads) + e → 2O (ads), T > 150 C (1.3)

O− (ads) + e− → O2− (ads), T > 150◦ C (1.4)

 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures 3

The extracted electrons from the

conduction band (Ec ) leave behind pos-
itively charged ions, resulting in upward
band bending and the formation of an
electron-depletion region or a space-
charge layer in the MOS, as shown in
Fig. 1.1. The height and depth of the
band bending depend on the amount
and type of adsorbed oxygen. Due to
the formation of the electron depletion
region, an increase in the resistance of
the MOS can be observed. When this
surface is exposed to reducing gases
such as acetone and ammonia, the ad-
sorbed oxygen ions interact with the tar-
get gases and the trapped electrons are
released back onto the MOS surface. The amount of oxygen removed Figure 1.1. Schematic
from the surface is proportional to the concentration of the reducing representation of band bending
after the adsorption of oxygen
gas. Thus the height and depth of band bending and the resistance
species (Priya et al., 2021).
of the MOS decrease (Ananya, 2018; Shankar et al., 2016; Wang et al.,
2010). The oxygen desorption from the MOS surface in the presence of
a reducing gas (say, R) can be described as follows:
R + nO− → a CO2 + b H2 O + ne− (1.5)
These electrons are released back onto the MOS surface and the
produced gas and water molecule are released into the atmosphere. On
the other hand, an oxidizing gas depletes the charge carriers, leading to
an increase in resistance. Similarly, in the case of p-type MOS, where
positive holes are the majority charge carriers, a decrease in the resis-
tance is observed in the presence of an oxidizing gas and an increase
in the resistance in the case of a reducing gas (Barsan et al., 2012; Neri,
2015; Subha & Jayaraj, 2019). Table 1.1 clearly summarizes the response
of n- and p-type MOS toward reducing and oxidizing gases.

1.2.2 Design of MOS gas sensors

The commonly available configurations for the design of
semiconductor-based gas sensors are (1) sintered pellet gas sensors
(Kazemi et al., 2016), (2) thick-film gas sensors (Arshak & Gaidan,
2005), and (3) thin-film gas sensors (Mirzaei et al., 2019). The
disadvantage with the use of sintered pellet gas sensors is their
relatively low gas response due to the limited surface area (Mirzaei
et al., 2019). Therefore researchers are more interested in the use
of thin- or thick-film gas sensors either in the tubular or planar
configuration, as shown in Fig. 1.2.
4 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures

Table 1.1 Change in the resistance of n- and p-type MOS when exposed
to reducing and oxidizing gases.

When exposed to When exposed to

Type of MOS reducing gases oxidizing gases
n-type Resistance decrease Resistance increase
p-type Resistance increase Resistance decrease

(A) (B)

Figure 1.2. Schematic diagram

of metal oxide gas sensor
configurations: (A) tubular and
(B) planar (SE and HE represent
the sensor electrode and heater
electrode, respectively).
Reproduced with permission
from (Lee, 2018), Copyright 2018,
Elsevier.

Thin- or thick-film sensors are prepared by depositing a sensitive

layer on an insulating substrate such as alumina (Al2 O3 ) and Si/SiO2
wafer. The metal oxide powder is ground together with suitable sol-
vents like ethanol and terpineol using an agate mortar to form a slurry
for the tubular configuration. Then the slurry is coated on an alumina
tube, on which a pair of Au electrodes had been printed previously,
followed by drying and subsequent annealing at high temperatures.
Finally, a small Ni–Cr alloy coil is inserted into the tube as a heater so
as to adjust and optimize the working temperature of the gas sensor.
The tubular configuration is shown in Fig. 1.2A. Si/SiO2 or alumina sub-
strate with preprinted interdigitated gold electrodes is commonly used
for the fabrication of planar sensors (Fig. 1.2B). A schematic diagram
of the interdigitated pattern is shown in Fig. 1.3. The use of platinum
electrodes is limited due to their high cost. In such cases Au electrodes
are more preferred. The working temperature is obtained by placing
the device on the external heater or with the help of an internal heater
printed at the back of the substrate. The planar configuration is more
 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures 5

Figure 1.3. Schematic diagram

of the interdigitated electrode
pattern.

preferred for large-scale production due to the improved fabrication

productivity and quality of the sensor (Lee, 2018; Mirzaei et al., 2019).
When we consider the substrate material, alumina is the best avail-
able substrate material due to its high thermal conductivity and sta-
bility, low thermal expansion coefficients, high mechanical strength,
and low electrical conductivity (Lee, 2018). The high thermal stability of
alumina is an important feature since most MOS-based sensors work
at relatively higher temperatures. However, for the fabrication of elec-
trodes in the micrometer range (<10 μm), microfabrication techniques
such as UV or electron-beam lithography has to be employed, which
leads to the preference of a Si/SiO2 wafer as the substrate material
over the alumina substrate due to the surface roughness of alumina
substrate.
Plastic foils can also be used as supporting materials due to the
increasing demand for flexible gas sensors. The advantages of plastic
foils are their foldable and wearable design, lightweight, transparency,
and mass productivity due to roll-to-roll printing processes. Polymers
such as polyimide (PI), with relatively high thermal stability, have been
widely used as supporting materials for flexible sensors operating at a
relatively higher temperature. However, the operation of MOS sensors
above 400°C is difficult using PI substrates (Wang et al., 2016).

1.2.3 Gas sensing measurement system

Generally, two types of measurement systems are commonly used
for studying the gas sensing properties of the device: static and dy-
namic. Fig. 1.4 shows the schematic diagram of a static measurement
system. The system consists of a transparent gas chamber of a defined
volume with a gas inlet. The sample is placed inside the chamber under
a controlled temperature and humidity. The operating temperature of
the sample can be adjusted by varying the heating voltage. During the
measurement, a fixed amount of analyte gas is injected through the gas
6 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures

Figure 1.4. Schematic diagram

of the static gas sensing
measurement system (Mirzaei
et al., 2018, 2019; Patil, 2007).

Figure 1.5. Schematic diagram

of the dynamic gas sensing
measurement system.

inlet with the help of a syringe. To uniformize the distribution of the

injected test gas, an electrical fan is installed inside the chamber. The
concentration of analyte gas is calculated with the ratio of the volume of
the injected gas to the volume of air under standard atmospheric pres-
sure. After reaching saturation in the current, the chamber is opened
to recover to the initial current in the air atmosphere. The procedure
is repeated for different analyte gases at different conditions (Mirzaei
et al., 2018, 2019).
A dynamic system consists of gas cylinders with a known concen-
tration, mass flow controllers (MFCs), a test chamber with a gas in-
let and outlet, heating arrangement, electrical measurement arrange-
ments, and data acquisition systems, as shown in Fig. 1.5. With the
help of MFCs, the flow rate of analyte gases and synthetic air can
be controlled. The concentration of analyte gases can be changed by
mixing properly with synthetic air or nitrogen in a mixing chamber
connected prior to the test chamber. Then the mixed volume of gas
 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures 7

is passed into the test chamber through

the gas inlet. The sample is placed on
an external heater and the working tem-
perature can be controlled with a tem-
perature controller. The sample is con-
nected to a measurement unit to record
the current variation continuously. Dur-
ing measurement, the current through
the sample in air and in the presence
of analyte gas at different temperatures
is recorded. Finally, after the measure-
ment, the gas from the test chamber is
removed with the help of a rotary pump
arrangement.

1.2.4 Performance parameters

Figure 1.6. Typical response
The gas-sensing performance of sensors is evaluated using the fol- curve of an MOS-based gas
lowing important parameters (Balaguru 2004; Tonezzer et al., 2015; sensor.
Tshabalala et al., 2016).

1.2.4.1 Gas response and sensitivity

Generally, the response of a semiconductor-based gas sensor is
defined as follows:  
Rg − Ra 
Response = (1.6)
Ra
where Ra and Rg represent the resistances of the gas sensor in the
presence of air and target gas, respectively. A typical response curve
is shown in Fig. 1.6. Sensitivity is the change in measured resistance
(R) with a change in analyte concentration (C), i.e., the slope of a
calibration graph: S = S = R/C .

1.2.4.2 Selectivity
It is the ability of a sensor to differentiate a specific target gas from
a mixture of gases. A good sensor will detect a particular gas while
remaining insensitive to other gases. The selectivity coefficient (K) of
a gas sensor can be written as
SI
K= (1.7)
SII
where SI and SII are the sensing responses of the sensor toward two
different gases, I and II, respectively.

1.2.4.3 Stability
Stability is defined as the reproducibility of the device in the sensing
measurement after long use. To avoid the effects of nonrepeatability
8 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures

after repeated use, the materials are subjected to a thermal pretreat-

ment.

1.2.4.4 Response time and recovery time

Response time is defined as the time taken for the sensor to reach
90% of the maximum response and recovery time is the time taken for
the sensor to reach back to 10% of the maximum response after the
removal of analyte gas. For practical applications, rapid response and
short recovery times are always preferred for the efficient detection of
toxic or explosive target gases.

1.2.4.5 Operating temperature

Generally, the working temperature of metal oxide gas sensors is in
the range of 30°C–500°C. The response is limited at low temperatures
because of the slow rates of the chemical reactions, and it is limited
at high temperatures due to the high diffusion rate of gas molecules.
The optimum temperature should be chosen to get maximum sensor
response and short response time and recovery time etc.

1.2.4.6 Limit of detection (LoD)

The detection limit is defined as the lowest concentration of gas that
can be detected by the sensor and is expressed as follows:
3 × noiserms
LoD = (1.8)
Slope
where noiserms represents the standard deviation of the sensor re-
sponse, and the slope is the first derivative of the response vs. the gas
concentration curve.

1.3 Strategies for improving the performance

of metal oxide–based gas sensors
1.3.1 Changing the sensing layer morphology
The morphology of the sensing materials plays a critical role in the
sensing performance of metal oxide gas sensors (Dong et al., 2020).
Exposed surface area and porosity are different for different morpholo-
gies; thus the number of active sites for gas adsorption is also different,
which affects the gas sensing performance. Investigations are carried
out on different dimensional nanostructures to get an enhanced sens-
ing response (Lin et al., 2017). Fig. 1.7 shows the ethanol sensing prop-
erties of SnO2 sensors with different morphologies. From the figure, it
 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures 9

is clear that SnO2 nanosheets show

the best sensing performances with the
largest surface area and a porous struc-
ture that has large number of active sites
for gas adsorption than the other mor-
phologies (Zeng et al., 2013).
Zero-dimensional (0D) nanoparti-
cles are used in the field of gas sensors
but the agglomeration of such particles
limits its application in this field. One-
dimensional (1D) nanostructures such
as nanotubes, nanorods, nanowires,
and nanofibers have a high aspect ratio
and hence a large surface-to-volume
ratio, thus having enhanced gas sensing
Figure 1.7. Response–recovery
properties. Also for 1D structures, electrons flow along the axial direc-
characteristics of the SnO2
tion, which increases the speed of charge transfer, thus further enhanc- sensors with different
ing the sensing performance. Two-dimensional (2D) nanostructures morphologies at 340°C toward
have also garnered interest due to their large surface area. Also, they 100 ppm ethanol. Reproduced
can be used as building blocks for three-dimensional (3D) hierarchical with permission from (Zeng
structures. 3D hierarchical nanostructures are potential candidates as et al., 2013), Copyright 2013,
sensing materials compared to 0D, 1D, and 2D nanostructures because Elsevier.
of their large surface area, abundance of active sites, high porosity,
a less agglomerated configuration, and fast interfacial transport. For
porous nanostructures, analyte gas interacts with the surface; also the
gas penetrates into the sensing material, which improves the sensing
response (Lin et al., 2017; Németh et al., 2007; Zeng et al., 2013). Hollow
nanostructures show a better response than solid nanostructures. In
the case of hollow structures analyte gas can be adsorbed on the in-
ner and outer surfaces of the sensing materials, which facilitates the
superior performance of sensors. For example, Guo et al. studied the
ethanol sensing properties of Cu2 O hollow and solid sphere sensors
(Guo et al., 2019). Fig. 1.8(A&B) shows the scanning electron micro-
scope (SEM) images of Cu2 O solid and hollow spheres. The hollow
spheres show superior gas sensing performance over solid spheres, as
shown in Fig. 1.8C. The enhanced performance is due to their unique
hollow structure, which provides plenty of active sites on both the inner
and outer surfaces.

1.3.2 Doping with noble metals

Noble metals such as Pt, Pd, Au, and Ag are widely used as doping
materials for metal oxide–based sensors due to their catalytic activ-
ities. They can reduce the activation energy and hence increase the
adsorption on the MOS surface. This will lead to fast response and
10 Chapter 1 Facet-dependent gas sensing properties of metal oxide nanostructures

Figure 1.8. SEM images of

(A) solid Cu2 O microspheres and
(B) hollow Cu2 O microspheres.
(C) Response–recovery
characteristics of hollow and
solid sphere Cu2 O sensors at
350°C toward 200 ppm ethanol.
Reproduced with permission
from (Guo et al., 2019), Copyright
2019, Elsevier.

Figure 1.9. Sensitization

mechanisms of noble
metal–doped metal oxide
surface by (A) Fermi-level
control and
(B) spillover effect (Degler et al.,
2019; Franke et al., 2006).

recovery times and lower the operating temperature (Luo et al., 2017).
Also, they can produce more active sites on the surface. Analyte gas
can be adsorbed on the noble metal and then spilled into the MOS.
For example, noble metals can dissociate H atom from H2 , which then
spills over and is adsorbed on the surface of metal oxide, as shown
in Fig. 1.9. The role of a noble metal is to bring down the reaction
activation energy. Generally, the work function of noble metals is more
than that of semiconductors; hence the Fermi level of a noble metal lies
below that of MOS. Due to the work function difference, the electrons
from the semiconductor flow into the noble metals to equal the Fermi
levels, as shown in Figs. 1.9 and 1.10. This electron transfer generates
the Schottky barrier at the interface and energy bands in the MOS are
bent upward due to positive charge, which makes the material more
sensitive to analyte gases, as shown in Fig. 1.10 (Degler et al., 2019;
Sarkar et al., 2015).

1.3.3 Forming hierarchical structures

For a better gas sensing response, heterostructures have been syn-
thesized from two different metal oxides having different Fermi levels.
The metal oxides can be either p-type or n-type. By the combination
of these metal oxides, p–p, n–n, and p–n junctions can be formed.
During the formations of heterostructures, due to the difference in
Fermi level, electrons flow from areas of higher Fermi level to areas
of lower Fermi level until the two Fermi levels are equal, as explained
before. This charge transfer creates a depletion region at the interface
of the two metal oxides and increases the resistance of the materials.
Another random document with
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lesion is in the cerebellum, so that, if continuous, it is not likely to
mean that anything worse is coming. It has been said to be strongly
significant if occurring without the digestive derangements or
circulatory disturbances likely to cause it, and be unconnected with
disease of the ear. Unfortunately for diagnosis, but fortunately for the
patients, the so-called vertigo a stomacho læso, may arise in cases
where the stomach trouble is very difficult or impossible to detect,
and it often continues for weeks or months after the most careful
regulation of the diet, and yet is followed by no cerebral lesion.
Although a vertigo for which every other cause can be excluded
certainly justifies a suspicion of cerebral trouble, the tendency to
exaggerate its prognostic importance should not be encouraged by
the physician, as it may exist a long time, and disappear without
another sign of the catastrophe which has been keeping the patient
in dread.

Among the more significant and immediate symptoms are to be

reckoned paræsthesiæ of the side about to be paralyzed, such as
numbness or tickling. Headache of great severity is often, but not
invariably, present. It has nothing characteristic about it, except that
it may be different from those the patient has been in the habit of
having, or may be of unusual severity, so that the patient says it is
going to kill him. Such a headache in a person in whom there is good
reason, from age, interstitial nephritis, or other symptoms, to suspect
the existence of vascular lesions is likely to be an immediate
precursor of a hemorrhage. Persistent early waking with a slight
headache, which passes off soon after rising, is said by Thompson29
to be a somewhat frequent premonition. Vomiting is hardly a
premonitory, but may be an initial, symptom, especially in
hemorrhage of the cerebellum.
29 N. Y. Med. Record, 1878, ii. p. 381.

Reference is had in these statements chiefly to the ordinary form of

cerebral hemorrhage. Of course if, during a leucocythæmia or
purpura, large hemorrhages occur elsewhere, it may be taken as a
hint that possibly the same thing may take place in the brain.
These signs of arterial disease must be considered as of the highest
importance among the (possibly remoter) premonitory signs, not only
of cerebral hemorrhage, but of the other lesions treated in this
article. Atheroma and calcification of the tangible arteries place the
existence of peri-endarteritis among the not remote possibilities.
High arterial tension has already been spoken of in connection with
etiology, and its presence should be sought for. An irregular and
enfeebled cutaneous circulation has been spoken of as an indication
of value.

OCCLUSION OF THE CEREBRAL ARTERIES may take place from several

causes other than those which concern us here, as from the
pressure of tumors or endarteritis, usually syphilitic. Thrombosis and
embolism are grouped together from their great anatomical
resemblance and their frequent coexistence, but the symptoms
produced, although ultimately the same, are often different enough
to make it necessary to bear in mind the fact that there is a
distinction—that is, that embolism is rapid and thrombosis is slow.

A cerebral artery may be occluded from the presence of a plug of

fibrin more or less intermixed with the other elements of the blood.
This plug may have been formed in situ, and is then somewhat firmly
attached to the walls of the vessel, and partly decolorized at its
oldest portion, while on each side of it, but especially on the side
away from the heart, it is prolonged by a looser and darker clot of
more recent origin. This is a thrombus.

When the plug has been transported from elsewhere it is embolus.30

It may consist of various substances, as described in the article on
General Pathology, but is usually of fibrin which has formed a
thrombus or vegetation elsewhere, and, having been broken off, is
carried by the blood until it comes to a place too narrow for it to pass,
or where it lodges at the bifurcation of a vessel. The piece of fibrin
thus lodged has a strong tendency to cause a still further deposition
—that is, a secondary thrombus—which may progress until it comes
to a place where the blood-current is too strong for the process to go
on any farther. It may in such cases not be obvious at the first glance
whether the whole process is thrombosis or whether it started from
an embolus.
30 The Greek word εμβολος (εν, in, and βαλλω, to throw) signifies the beak or rostrum
of a ship of war. Εμβολον signifies wedge or stopper, and would certainly seem the
appropriate form to be adopted for anatomical purposes. As uniformity of
nomenclature, however, seems more to be desired than etymological accuracy, the
writer has conformed in this article to the general usage.

It is probable that a thrombus forming at one point in a cerebral

vessel may break to pieces and its fragments be carried farther
along, forming a number of small emboli. (See Capillary Embolism.)
Embolism or thrombosis may take place anywhere in the brain or
body generally, but has certain points of preference. Of these, the
most usual in the brain is in the neighborhood where the internal
carotid divides into the anterior and middle cerebral, or in either of
these arteries, especially the middle, beyond this point. The plug
may be situated in the carotid just before this point, or even as low
down as its origin from the common trunk. Emboli lodge in this
region, somewhat more often upon the left side. The brain is said to
be third in the order of frequency with which the different organs are
affected by embolism, the kidneys and spleen preceding it. It has
been found that small emboli experimentally introduced into the
carotids are found in much larger numbers in the middle cerebral
than elsewhere. It is the largest branch, and most nearly in the direct
line of the carotid. Position undoubtedly influences the point at which
an embolus lodges, as it probably moves slowly along the vessels
and along their lower side. It has been remarked that, on account of
this course of the embolus, it is doubtful whether it can get into the
carotid when the patient is standing, but it certainly can do so when
he is sitting up; which, so far as the direction of the carotids is
concerned, is the same thing. The frequency with which a
hemiplegia is observed when a patient awakes in the morning may
perhaps be accounted for by the position favoring the passage of an
embolus into the carotid, which otherwise would reach organs more
remote.
The vertebrals and basilar are not infrequently affected.

The sources whence cerebral emboli may spring are various, but
cannot be found outside a certain range. They may, in the first place,
be torn off from vegetations upon either the mitral or aortic valves;
and this source is probably the most common. The appendix of the
left auricle may furnish a plug from the thrombi formed among its
trabeculæ, or the aorta from an aneurism or from parietal thrombi
formed, upon spots roughened by atheroma. The pulmonary veins
are occasionally the source of the embolus, though this is not very
common.

It is rather doubtful whether an embolus can find its way from the
systemic veins through the lungs to the brain, but it is possible that
small emboli may do so, and increase in size from the addition of
fresh fibrin when floating in the blood-current. The occurrence of
pyæmic abscesses in the brain would suggest the possibility of this,
though it is, on the other hand, possible that the brain abscesses are
secondary to older ones in the lungs. In some cases, however, a
careful examination does not disclose the source of the embolus.

In the blood-current the embolus may give rise to no symptoms

whatever, and even after its arrival in the cerebral circulation it may
lodge in such a way as not entirely to obstruct the current. In most
instances, however, it does not stop until it plugs the vessel
completely and arrests the current of blood beyond it for a moment.
Whether it shall completely deprive the portion of brain to which it is
distributed depends upon its situation as regards anastomoses and
upon the formation of secondary thrombus. Hence the knowledge of
the distribution of the arteries supplying the brain—that is, the two
carotids and two vertebrals—is of more importance in reference to
embolism and thrombosis than to cerebral hemorrhage, where the
effusion takes place from quite small branches.

The anterior portion of the brain, including the anterior and posterior
central convolutions and the first temporal, are supplied with blood
by the two terminal branches of the internal carotid, the anterior and
middle cerebral, the ganglia underlying these portions of the cortex
being supplied, as already stated, by small branches arising near the
origin of these two trunks, and principally the second. The anterior
cerebrals of the two sides are connected by the anterior
communicating, which is a short and usually wide vessel. Sometimes
one anterior cerebral branches in the longitudinal fissure, and
supplies a part of both sides. Hence in plugging of one internal
carotid which does not reach its bifurcation a collateral supply may
be received from the other side. If, however, an embolus or thrombus
has penetrated beyond the origin of the middle cerebral, this vessel
can no longer receive a supply from the anterior.

The posterior communicating arteries are two small vessels which

connect on each side the posterior cerebrals and either the carotid,
just as it gives off its two chief cerebral branches, or else the middle
cerebral close to its origin. These arteries may be of quite unequal
size, that upon the right usually being the larger, and sometimes so
large as to give the appearance of being the principal origin of the
posterior cerebral. When this happens the part of the posterior
cerebral which arises from the basilar may be reduced to a minute
arteriole, and the basilar, almost entire, goes to supply the left side of
the brain. This condition of the posterior communicating may exist to
some extent on both sides in the same brain. It is probable that in
many cases these arteries are too small to be of great value in re-
establishing the circulation in the anterior portion of the brain when it
is suddenly interrupted by an embolus.

When the large trunks leave the circle of Willis to be distributed upon
the surface of the brain, after giving off from the first centimeter or
two of their course the nutrient arteries for the deep-seated ganglia,
they break up into several branches which ramify upon the surface,
but, as Duret has shown, undergo very few anastomoses. Instead of
forming, as was once supposed, a richly inosculating network, small
branches penetrate into the brain-substance perpendicularly from
the superficial vessels, but these do not communicate freely with
each other by vessels larger than capillaries.
From these anatomical conditions it happens that when a vascular
territory is deprived of its normal supply by an embolus, it cannot be
supplied with blood from surrounding districts. A certain limited
amount of collateral supply is possible through the capillaries and the
rare anastomoses, but it is only around the edges, and the centre of
the territory becomes destitute of circulating blood. Thus an embolus
does not in the brain produce, as it does in other organs with more
abundant collateral supply, a large hemorrhagic infarction.

Small hemorrhages may, however, take place around the edges of

the softening, and when a number of small emboli are present, so as
to afford a number of overlapping areas with their borders of
congestion, a red softening may be the result. When the emboli are
very small, and at the same time not numerous enough to occlude all
the ultimate ramifications of a trunk, the vascular compensation may
be rapidly completed.

The change produced in the cerebral substance from cutting off its
supply of blood is known as anæmic necrosis, and includes what has
been known as white softening, with probably some yellow, and
possibly a little red softening, the latter in case where simple
softening has been complicated by hemorrhage.

When the circulation ceases the substance that should have been
nourished loses its firmness and acquires a custard-like consistency.
The gray and white substances are no longer so distinct in
appearance, the latter losing its milky-white color, the whole surface
of a section becoming of a dirty yellowish-white, somewhat shining,
and looking as if it contained more moisture than normal. When a
considerable portion of the interior of the hemisphere is thus
affected, the brain outside, with its membranes, bags down, looks
swollen, and feels to the fingers as if there were present a sacful of
fluid. The boundaries of such an area of softening are marked off
from the healthy substance with some distinctness, though less than
that of a hemorrhage. There may be some hemorrhage around the
edges or into the cavity, so that the presence of a little blood-pigment
is no proof that the original lesion was not softening from occlusion.
In the further progress the contents of the cavity become more fluid,
and finally a somewhat distinct cyst is formed, not unlike that from a
hemorrhage, with an internal areolar structure from the remains of
connective tissue, and contents of a slightly yellowish or brownish
color, or often of a chalky white. These cysts have little to distinguish
them, when old, from similar ones left by hemorrhage, except the
much greater amount of pigment in the latter. The smaller spots of
softening may after a time lose their fluidity, and remain as yellowish
patches as firm as, or firmer than, the surrounding brain. The region
of the brain involved becomes atrophied, the convolutions shrink,
and the membranes become filled with serous fluid, to compensate
for the sinking of the surface.

The microscope shows gradually increasing fatty degeneration,

disorganization of the nervous tissue, and degeneration of its
elements. The pyramidal cells are sometimes distinctly recognizable
by their form, and show gradual transition into the indeterminate
round granulation-corpuscles. The vessels exhibit fatty degeneration
of their coats, as well as accumulation of fatty granules between the
vessel and the lymphatic sheath. The clot which blocks the artery
becomes adherent to its walls, and the vessel with its contents forms
a round solid cord.

In a few instances the thrombi have become perforated through the

centre, so that a channel is formed for a renewal of the circulation.
There is no reason to suppose that this takes place soon enough to
be of any advantage in restoring the nutrition of the necrosed
portions of brain.

The region involved in softening depends upon the artery which is

plugged and the location of the obstructing body. The place of
election seems to be the carotid near its separation into its large
branches, or these branches after the separation, especially the
middle cerebral, this being peculiarly liable because it is the largest
branch and is the continuation in a direct line of the carotid. It is more
frequent upon the left side. Cases have been observed where the
whole of one hemisphere was softened from obstruction of the
carotid at its bifurcation; which may be accounted for, as Charcot
suggests, by an unusual distribution of the arteries, as described
above, the posterior cerebral as well as the other two being derived
almost entirely from the carotid. In a case recently observed by the
writer the whole right cerebral hemisphere, with the exception of the
tip of the frontal and tip of the occipital lobes, was softened to the
consistency of custard, a thrombus extending from the bifurcation of
the common carotid into all the ramifications of the middle cerebral.
The most common form, however, is where more or less of the brain
around the fissure of Rolando and fissure of Sylvius, with or without
the underlying ganglia, is softened. This happens from a lodgment of
the embolus in the middle cerebral. If the obstruction be close to the
origin of the artery, the corpus striatum suffers, from the mouths of its
small nutrient arteries arising in this part of its course being stopped,
while if it have passed along a little farther, these remain open, and
the cortex, to which the larger branches are distributed, alone is
softened.

The anterior cerebral is not infrequently affected, either alone or with

the middle, and in these arteries as well as the posterior the
embolus, if of small size originally, may penetrate so far as to give
rise only to quite a limited anæmia. The basilar is an artery not very
rarely occluded, though more commonly by thrombus than embolus.
This occlusion may be so limited as to affect only the nutrient
arteries of the pons and cause a very limited softening, the parts
before and behind it being supplied by the unobstructed portion or by
collateral circulation from the carotids. Occlusion of the cerebellar
arteries and softening of the cerebellum are among the rarer forms.
The vertebrals themselves are sometimes plugged. A thrombosis
has been observed in the only inferior cerebellar artery which
existed, causing softening in both lobes. There was atheroma of the
heart and arteries, and a thick calcareous plate in that which was
occluded.31
31 Progrès méd., 1876, 373.
In a general way, it may be said, with many exceptions on both
sides, that thrombosis and embolism tend to affect the cortex, and
hemorrhage the central ganglia.

What has just been written applies to the simple mechanical action
of emboli. If, however, they have a septic origin, as notably in cases
of ulcerative endocarditis, the region in which they lodge becomes,
instead of a simple spot of necrosis, a septic focus or abscess, with
its results of compression or irritation. In such a case there are likely
to be abscesses of similar origin in other organs, and the cerebral
lesion is only a part of the general pyæmic condition.

ETIOLOGY.—So far as the lodgment of an embolus in an artery is

concerned, it can hardly be said that there is any etiology, for the
detachment of the plug from its place of origin is purely a matter of
accident, and may take place at any time. As to its origin in the form
of fibrinous deposit on the valves of the heart or a roughened spot on
the aorta, we must refer to the article on General Pathology. The
most important condition for embolism is disease of the valves of the
heart, rheumatic or otherwise. Next comes arterial disease,
producing roughening of the inner coat and subsequent deposition of
fibrin. So far as we can tell, the causes leading to endarteritis or
atheroma are essentially the same as those which produce the
periarteritis described in connection with cerebral hemorrhage, and
we may therefore put down old age, alcohol, and strain as among
the causes of cerebral embolism. Injuries of the lungs leading to
thrombosis of the veins may be considered as possible sources for
the formation of an embolus, and we might suppose that phthisis and
pneumonia would furnish plugs which would lodge in the brain,
though as a matter of fact they seldom do so.

Experience shows that embolism, unlike hemorrhage, is not specially

a disease of advanced life, but is distributed over different periods,
with preference for old age less marked than with hemorrhage.
Andral gives the ages of patients with softening—which, however,
includes thrombosis as well as embolism—as follows: the average
would undoubtedly be displaced in the direction of youth if
thrombosis could be taken out of the list:

Andral: Andral: Cases (with autopsies) of

Beginning of softening Death with softening embolism, thrombosis, and
in 27 cases. in 153 cases. softening—25 cases.
17–20 4 15–20 10 20–30 4
27 2 20–30 18 30–40 3
30–37 2 30–40 11 40–50 3
43–45 2 40–50 19 50–60 1
53–59 4 50–60 27 60–70 5
63–69 7 60–70 34 70–80 2
76–78 6 70–80 30 Young 1
80–89 4 Middle-aged 1
Old 5

In the etiology of cerebral arterial thrombus there seem to be two

factors of prime importance, although there are cases which seem to
demand a third, and Charcot32 suggests the possibility of some
hæmic dyscrasia favoring the formation of a thrombus, and relates a
case of thrombosis of the middle cerebral, with three others of the
same process in other arteries, occurring in patients with uterine
cancer, where all the usual sources of emboli were explored with
negative results. The first of the two is disease of the cerebral
arteries, not necessarily extensive, but sufficient to form a starting-
point on the inner wall for the deposit of fibrin. In this respect the
etiology of thrombosis may be various. Syphilitic endarteritis, for
instance, may very easily give rise to this lesion, but it is likely to be
accompanied by others, and has a symptomatology more or less
peculiar to itself. It is not, of course, to be included with the form we
are considering.
32 Comptes Rendus Soc. de Biol., 1865, p. 24.

The second factor—one which is perhaps capable of giving rise to

coagulation of the blood or deposit of fibrin without any arterial
disease—is weakness of the heart, connected or not with anæmia.
The causes of this condition may be manifold, and are likely to lead
to many other consequences than cerebral thrombosis. A thrombus
may form upon a very small basis of atheroma. Several of these
points are illustrated in the following case: A lady, aged about sixty-
five, had had for many months vague symptoms of want of strength,
fatigue, want of appetite, and so on, with complaints of distress and
fulness in the abdomen, for which no special cause could be found.
On one occasion she was unusually long in dressing, and her
expression was noticed to be changed and her voice altered for a
few moments. The pulse was habitually 60 or less, and at times
irregular, but nothing abnormal could be detected in the sounds or
position of the heart. Fatty degeneration was suspected. One
morning, after going to bed in her usual health, she was found on the
floor of her room unconscious and with left hemiplegia. She lived
about thirty-six hours. The autopsy showed nothing abnormal in the
abdomen except a considerable accumulation of fat; and in the
thorax the heart appeared normal, and was not fatty. There was very
little atheroma. In the end of the internal carotid artery was a
thrombus, of which the lower and firmest part was connected with a
very small spot of roughening just at the point where the artery
comes through the base of the skull. It extended just beyond the
origin of the middle cerebral artery, which was of course occluded.
The corresponding region of the brain was converted into a vast
mass of softened tissue.

The SYMPTOMS of the lodgment of an embolus in the brain may

closely resemble, or even be precisely the same as, those of
hemorrhage. Unless, however, an embolus makes a pause on its
journey, giving rise to a partial obstruction before there is a complete
one, or unless the obstruction is not absolute until after the formation
of a secondary thrombus, the attack may be absolutely sudden.

A thrombus, however, is slower in its formation, and may produce

gradually increasing anæmia of the region of brain supplied before it
is absolutely complete, with a gradually increasing paralysis and loss
of consciousness slowly approaching. Thus we may have the early
symptoms in the form of headache, vertigo, heaviness, and
drowsiness, peculiar sensations in the limbs about to be paralyzed or
in the head, delirium of various kinds, or hysterical manifestations.
Prévost and Cotard33 lay special stress upon the importance of
severe vertigo (étourdissement) as a prodrome or warning of
softening, especially in the aged. It is dependent upon anæmia of the
brain, and this, in its turn, upon atheroma of the arteries, and
sometimes at least upon feebleness of the circulation, both of these
being conditions likely to cause the deposit of a thrombus. As,
however, the thrombus does not necessarily result from these
conditions, and as the vertigo may arise from other sources, as
stated under the head of Cerebral Hemorrhage, it is to be looked
upon with special suspicion chiefly in those cases where other
symptoms might lead in the same direction, and when other causes
can be excluded.
33 Mémoires de la Soc. de Biol., 1865, p. 171.

The same authors also speak of less defined symptoms, like delirium
and stupor, occurring among the inhabitants of the Salpêtrière (old
women), with intervals of comparative health, as being premonitory.

It is possible, however, for the symptoms of thrombus to be

developed rapidly when, as in the case last described, the thrombus
begins to form in a place which does not entirely interrupt the
current, but afterward reached the mouth of a large vessel, which it
closes.

The loss of consciousness, coma, and all the phenomena of the

apoplectic attack, with the possible exception of early rigidity, may be
as fully developed from occlusion of the cerebral vessels as from
their rupture; but it must be said that it is more common to meet with
them in cases of large hemorrhage than with either embolism or
thrombosis.

The general functions are even less disturbed than with a

hemorrhage producing an equal extent of paralysis. The temperature
follows nearly the same course as in hemorrhage, except that the
initial fall, if present—which is not always the case—is said to be less
than with cerebral hemorrhage. To this succeeds a rapid rise, which,
even in cases which are to terminate fatally, gives place to a fall to
the neighborhood of normal, and another rise before death. These
are the statements of Bourneville. The rise is said not to be so high
as with hemorrhage.

The annexed chart is from a man (W. I. W.) who was in the hospital
with ill-defined nervous symptoms, and was suddenly attacked with
convulsions, vomiting, and unconsciousness. He had a small tumor
at the point of the right temporal lobe, and softening of the left corpus
striatum. The apoplectic symptoms occurred on the 15th—that is, as
will be seen by the chart, one day after the temperature began to
rise. The pulse and respiration show no characteristic changes.

FIG. 40.
It is much more common for the embolus or thrombus to give rise to
a set of symptoms less severe than a fully-developed apoplectic fit.
During such a fit—or, more clearly, as it is passing off—we find more
or less marked paralytic symptoms, but these are quite as frequently
present without the loss of consciousness. The patient states that he
waked up and found one side of his body helpless, or that he was
reading the paper when it fell from his hand, and upon trying to walk
found that he could not do so. Loss of speech may be an initial
symptom. It has been spoken of as premonitory, but it is probable
that it is in reality only the beginning, which, in some cases may go
no farther, but is usually succeeded by more extensive paralysis,
which makes its meaning unmistakable. These symptoms may be
hours or even days in developing, with occlusion as well as with
hemorrhage. Very slight attacks may occur which hardly excite
attention, and lesions are found after death in many cases to which
there is nothing in the history to correspond.

Improvement may begin very rapidly in some cases where the lesion
is small, a sufficient amount of collateral circulation being developed
to prevent the structure from being disorganized. In others a
specially favorable anastomosis may preserve even a larger area,
but in others still it is not easy to account on entirely anatomical
grounds for the amount of improvement which takes place.

From this point onward the history of hemorrhagic and of embolic

and thrombotic paralysis is essentially the same, and the description
of the principal phenomena and progress of hemiplegia will apply to
all.

SYMPTOMS AND PROGRESS OF HEMIPLEGIA DEPENDING ON CEREBRAL

HEMORRHAGE OR OCCLUSION OF THE CEREBRAL VESSELS.—The cerebral
cortex represents the centres for many of the higher nervous
functions, spread out in such a way that they may be more or less
separately affected, while the corpora striata and internal capsules
are the regions where the various conductors are crowded together,
so that embolism, when affecting small vessels and limited areas of
the cortex, more frequently gives rise to narrowly-defined groups of
symptoms than hemorrhage, which, taking place oftener in the
central ganglia, is able to cut off the communication from large
masses of cerebral tissue at once. This is a general remark, tending
to explain why aphasia, for instance, is often spoken of as especially
a symptom of embolism, while it is in reality common to all the
lesions that affect the proper locality.

The motor paralysis, more or less complete, which has been

described under the head of Hemorrhage continues indefinitely. It
may disappear rapidly, so that motion begins to return in a day or
two, and goes on to complete recovery in a short time. On the other
hand, it may be months before the flexion of a finger or a toe gives
the slightest token of the will resuming its control. The face often
recovers its symmetry before the limbs are fully restored, but the leg
may be used in locomotion before the complete recovery from
paralysis, since the tone of the muscles is sufficient to keep the knee
straight enough for support, as if the leg were all in one piece, while
it is swung around at each step by the pelvic muscles. We may meet
with all degrees of recovery—from that which is absolutely complete
and comparatively rare, through the case where a little want of play
upon one side of the face, a little thickness of speech, a feeble or
awkward grasp of the hand, betrays what has happened, or that of
the man so often seen in the streets with a mournful or stolid face,
the arm in a sling or dangling straight down by the side, and
swinging one leg awkwardly around, to the helpless paralytic lifted in
and out of his chair or lying almost motionless in bed, and living only
to be fed and be kept clean.

Involuntary movements may take place in limbs entirely incapable of

voluntary ones, and may occur under conditions of excitement or
with other involuntary movements, such as gaping. On the other
hand, the patient often moves the well hand while making utterly
ineffectual attempts on the paralyzed side. Involuntary twitching of
the feet may be annoying. Reflex movements, especially of the feet,
are often exaggerated, and in fact the twitching just spoken of is
often excited by some trifling, perhaps unperceived, irritation. A
touch with the point of a penknife upon the sole of the foot may call
out a movement which the patient is utterly incapable of executing by
the force of the will, and the appearance of volition is often increased
by the grimace or exclamation of pain or annoyance.

Epileptiform attacks may be a sequence of hemiplegia, occurring at

irregular intervals, and not of great severity. Sometimes the patient
seems depressed or less talkative for a day or two previously, and
relieved after the fit has occurred, as in true epilepsy.

Comparatively little attention has been given to the condition of

sensation in hemiplegia. In the more complete apoplectic stupor it is
apparently abolished, like nearly all the functions above those of
respiration and circulation, but it often happens when the patient is
unable or unwilling to make any voluntary response to the voice, and
lies apparently perfectly indifferent, that any moderate irritation like a
pinch will bring out evidence of sensation. It is often stated that in
hemiplegia the sensation is not at all affected; and this is probably
true of many cases, but a more attentive examination will often
disclose a decided diminution on the affected side. Broadbent, who
has tested with pricking, touch, the compasses, and hot substances,
says that it is frequently diminished, and often greatly so, and not
only in the limbs, but in the face, chest, and abdomen. Tripier34 says
that a lesion of the larger part of the fronto-parietal region determines
at the same time a paralysis of motion and a diminution of sensibility;
and one may conclude that this region holds under its dependence
sensitive as well as motor phenomena intimately connected with
each other. The zone called motor, of which the limits are difficult to
fix, may with more reason be called sensori-motor.
34 Revue mensuelle de Méd. et Chir., 1880, p. 18.

Anæsthesia probably in most instances disappears more rapidly

than motor paralysis, which accounts for its being frequently
overlooked. The more common location of lesions causing motor
paralysis—i.e. the corpus striatum and the motor portion of the
cortex—is one not likely, unless extensive, to concern sensation; but
there are cases where a very complete hemianæsthesia, including
the special senses, may be found; and when, in such cases, the
motor paralysis is slight, a picture is presented almost identical with
that of hysterical hemianæsthesia with great diminution or abolition
of the special senses, hearing, taste, smell, with concentric
diminution of the field of vision and of the color-field, or complete
color-blindness on the affected side.

A man aged thirty-five while at work suddenly felt a prickling

sensation upon his left side, and became unconscious. The
bystanders say he was convulsed. On returning to consciousness
after three hours he had lost his speech, which, however, was rapidly
recovered, and his left side was not so strong as his right, though
there was no distinct history of paralysis. Two or three days
afterward it was noticed that sensation was much diminished upon
the left side, two sharp points of the æsthesiometer being felt as one
at two inches on the forearm and three-quarters of an inch on the
tongue. He could feel the touch of a spoon, but could not tell whether
it was cold or hot. Odors were not recognized upon the left side of
the nose, except faintly ammonia and chloroform, and a watch was
heard on that side only when in contact with the ear. The field of
vision was much diminished and color-blindness was almost
complete. A few days later the field of vision had increased, and
there was color-sense, the field of perception for the different colors
being arranged almost exactly as laid down by Charcot, vision for
red being largest, but not so large as for simple perception of
objects; those for blue, green, and yellow nearly the same and
smaller; and that for violet limited to a small space in the centre of
the field.

Less regular forms of anæsthesia may be met with, as well as

hyperæsthesia. These are said to be especially connected with
various lesions of the pons.35 A case is recorded36 of complete
hemianæsthesia in a man, coming on like a blow. There was no loss
of motor power; the face was symmetrical, sight and hearing
unimpaired. Taste was lost and smell doubtful. There was aortic and
mitral disease. Hughlings-Jackson speaks of a man who
experienced a severe apoplectiform attack which it was thought
would be fatal in a few hours. He recovered, however, with almost
complete loss of hearing.
35 Conty, Centralblatt f. d. Med. Wiss., 1878, 571.

36 Med. Times and Gaz., 1871, i. 246.

Neuralgic pains of long continuance are not infrequent

accompaniments of hemiplegia, and may be lasting even after nearly
complete recovery from the paralysis. A peculiar restlessness, a
constant desire for change of position, has been referred to
derangement of the muscle-sense. It is sometimes very distressing,
and causes much annoyance to attendants as well as to the sufferer,
as the patient is no sooner placed in one position, no matter how
comfortable, than he desires to change it.

The mental condition seldom fails to suffer more or less in cases of

hemiplegia, but the limits are very wide between a slight emotional
excitability on the one hand and almost dementia on the other. This
is, of course, applicable to cases where the lesion is a single or
limited one, and not where a hemorrhage or thrombus is merely a
part of a general vascular degenerative change with chronic
meningitis or atrophy of the brain, where the mental decay can
hardly be called the result of any single lesion. In cases of aphasia
the mental condition is harder to make out, from the peculiar inability
to communicate ideas if present. It is very safe to say, however, that
many such patients possess much greater intelligence than would
appear to a casual observer, and yet the apathy with which they
often bear the deprivation of speech and consequent isolation
speaks more strongly in favor of some blunting of the perceptions
than of Christian resignation. A patient whose general appearance is
that of tolerable comfort is likely to cry when attention is called to the
helpless condition of the hand. It is probable that memory suffers in
such cases, if not the reasoning faculties.

Trousseau cites the case of Lordat, who became aphasic, and after
recovery described his own case. The learned professor claims to
have been in full possession of his faculties, and to have arranged a
lecture with the divisions and subdivisions of the subject, and all this
without the thought of a single word passing through his mind.
Trousseau ventures to doubt the possibility of carrying on
complicated mental processes without words, and thinks Lordat may
have overestimated the precision of his mental processes. It appears
in confirmation of this view that after his attack he always read his
lectures, whereas before he had been distinguished as an
extempore speaker.

McCready, in an excellent article in the New York Journal of

Medicine (September, 1857), discusses this subject at length, and
details a number of cases where it was evident that paralytics and
aphasics (who, however, he did not know by that name, nor the
special lesion connected with their condition) possessed not only
ordinary intelligence, but excellent business judgment and ability. He
says that the confusion of mind and difficulty in pursuing a train of
thought of which apoplectics are apt to complain is, to a great extent,
the mere result of diminished nervous energy—that they
comprehend well and judge correctly. It is fair to say that while the
mind is almost certainly impaired, it is not necessarily in exact
proportion to the severity of other symptoms, aphasia included. The
memory, either special or general, is most apt to be impaired.

The testamentary capacity of a person who has had an apoplectic fit

or who is paralyzed at the time of making a will may be called in
question. The only general remark to be made is that these facts
alone are not sufficient to prove incapacity; neither should the
presence of aphasia or agraphia do so without further evidence of
want of comprehension of the meaning of language used by others;
so that if, for instance, a person were seized with hemiplegia and
aphasia between the drawing up of a will and its signature, it should
not be invalidated unless there be further evidence to show that the
testator was incapable of understanding it when read over to him. In
cases of word-blindness, a patient, like one described by Magnan,
may be able to draw up a will with full comprehension of what he is
doing, and yet be unable to read it understandingly. Inability to
signify intelligibly assent or dissent would, of course, entirely
disqualify one from signing a will.

It is seldom that a paralytic attack fails to leave its mark, though

perhaps slight, for years, if not for the remainder of life. An extreme
ease of shedding tears is a very common symptom, and sometimes
laughter comes on very slight provocation.

Among the most interesting groups of phenomena connected with

hemiplegia, and sometimes the sole representative of this condition
—that is, existing alone without any motor paralysis—is that
embracing the means of communicating with the outer world by
means of language spoken or written. Corresponding to, and usually