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Science and Applications
of Nanoparticles
Science and Applications
of Nanoparticles
edited by
Waqar Ahmed
Ehsan Nourafkan
Published by
Jenny Stanford Publishing Pte. Ltd.
101 Thomson Road
#06-01, United Square
Singapore 307591
Email: editorial@jennystanford.com
Web: www.jennystanford.com
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.
Science and Applications of Nanoparticles

Copyright © 2023 by Jenny Stanford Publishing Pte. Ltd.
All rights reserved. This book, or parts thereof, may not be reproduced in any form
or by any means, electronic or mechanical, including photocopying, recording
or any information storage and retrieval system now known or to be invented,
without written permission from the publisher.
For photocopying of material in this volume, please pay a copying fee through
the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923,
USA. In this case permission to photocopy is not required from the publisher.
ISBN 978-981-4267-34-2 (Hardcover)

ISBN 978-1-003-28029-3 (eBook)
Contents
Preface xv
1. Application of Nanoparticles in the Field of Photonics 1

Syed Asad Hussain
1.1 Introduction 2
1.2 Nanoparticles for Bioimaging 3
1.3 Conclusion 21
2. What We Need to Know about Quantum Dots

Nanoparticles 29
Shiv Prakash Singh, Sudheer Kumar Yadav,
and Kunal Mondal
2.1 Introduction 30
2.2 Synthesis Techniques 32
2.2.1 Chemical Route Synthesis 32
2.2.2 Physical Vapor Deposition 33
2.2.3 Chemical Vapor Deposition 33
2.3 Characterization 33
2.3.1 X-Ray Diffraction 33
2.3.2 Transmission Electron Microscopy 35
2.3.3 X-Ray Photoelectron Spectroscopy 35
2.3.4 Fourier Transform Infrared
Spectroscopy 36
2.3.5 Photoluminescence 38
2.3.6 UV-Visible Spectroscopy 40
2.4 Applications 40
2.4.1 Qubits 41
2.4.2 Quantum Dot Solar Cell 43
2.4.3 Optoelectronics 44
2.4.4 Drug Delivery 45
2.4.5 Single-Electron Transistor 46
2.4.6 Photocatalysis 47
2.5 Conclusion and Future Scopes 49
vi Contents
3. Micro-/Nano-Encapsulation and Encapsulation

Applications 55
Hayrunnisa Nadaroglu, M. Kaan Yeşilyurt,
and Ömer Çomakli
3.1 Introduction 56
3.2 Chemical Methods 59
3.2.1 Interfacial Polymerization 59
3.2.2 Suspension Polymerization 61
3.2.3 Emulsification/Emulsion
Polymerization 62
3.2.4 Miniemulsion Polymerization 63
3.2.5 In situ Polymerization 64
3.2.6 Condensation Polymerization 68
3.2.7 Solvent Evaporation 69
3.2.8 Emulsification-Diffusion 69
3.2.9 Molecular Encapsulation/Inclusion
Complexation 70
3.3 Physical Methods 73
3.3.1 Spray Drying 73
3.3.2 Spray Chilling/Spray Congealing 76
3.3.3 Freeze Drying 79
3.3.4 Fluid Bed Coating 79
3.3.5 Air Suspension Coating 81
3.3.6 Melt Extrusion 81
3.3.7 Annular Jet (Vibrational Nozzle) 82
3.3.8 Entrapment in Liposome Vesicles 82
3.3.9 Electrostatic Precipitation 84
3.3.10 Electrohydrodynamic Processes 84
3.3.11 Hydrogel-Based Microgel Particles 85
3.4 Physicochemical Methods 87
3.4.1 Complex Coacervation/Phase
Separation 87
3.4.2 Sol–Gel Method 90
3.5 Conclusion 90
4. Nanoplatforms for Anticancer Therapy Based on

Reactive Oxygen Species 103
Shameer Pillarisetti, Veena Vijayan,
Saji Uthaman, and In-Kyu Park
4.1 Introduction 103
Contents vii
4.2 Significance of ROS in Anticancer Therapy 106

4.3 Strategies for ROS-Based Anticancer Therapy 107
4.4 Stimulation of ROS Production 108
4.4.1 Near-Infrared Irradiation 108
4.4.2 Ultrasound 109
4.4.3 Self-Luminescence 111
4.4.4 Radiation 111
4.4.5 Molecular Dynamics 112
4.5 ROS-Based Monotherapies 114
4.5.1 Photodynamic Therapy 114
4.5.2 Sonodynamic Therapy 116
4.5.3 Molecular Dynamic Therapy 117
4.5.4 Molecular Drug Therapy 118
4.6 ROS-Based Combination Therapy 118
4.6.1 Chemotherapy 118
4.6.2 Immunotherapy 119
4.6.3 Photothermal Therapy 120
4.6.4 Combination Therapy 121
4.7 Clinical Implications of ROS Therapy 122
4.8 Conclusion and Future Perspectives 123
5. Nanotechnology in Textiles 133

Subhankar Maity, Sukumar Roy, and
Ashis Narayan Banerjee
5.2 Nanofibers and Nanoengineered Textiles
Manufactured by Electrospinning 135
5.3 Nanofinishing of Textiles 138
5.3.1 Achieving Water and Oil Repellence
Property through Nanotechnology
Route 138
5.3.2 Antistatic Properties by
Nanotechnology 140
5.3.3 Enhancement of Wrinkle and
Crease Recovery Properties of
Textiles 141
5.3.4 Enhancement of Mechanical
Properties of Textiles by
Nanotechnology 141
viii Contents
5.3.5 Nanofinished Textiles for

Protection from Ultraviolet (UV)
Radiation 142
5.3.6 Antibacterial Nanofinishing of
Textiles 143
5.3.7 Self-Cleaning Textiles 143
5.4 Nanopretreatments of Textile:
Nanoscouring, Nanobleaching,
Nanosoftening 144
5.5 Nanodyeing 148
5.6 Process Involved in the Preparation of Dye
Nanoparticles 150
5.6.1 Ultraviolet and Microwave
Treatment 150
5.6.2 Ultrasound Treatment 150
5.6.3 Mechanical Milling 151
5.7 Testing and Analysis of Nanomaterials 151
5.8 Economic and Environmental Aspects of
Using Nanoparticles 152
5.9 Conclusion 153
6. An Update on Nanotechnology and Sustainable

Agriculture 159
Allah Ditta and Naseer Ullah
6.2 Classification of Nanomaterials 161
6.3 Nanotechnology in Agriculture 162
6.3.1 Precision Farming 163
6.3.2 Crop Production 166
6.3.2.1 Nanopesticides 166
6.3.2.2 Potential delivery
agents for nutrients
and fertilizers 173
6.3.2.3 Nanomaterials and
abiotic stresses 175
6.3.2.4 Biosensors to identify
pathogens/contaminations 176
6.4 Nanotechnology Application in Seed Science 176
6.5 Nanotechnology and Storage of Agricultural
Commodities 177
Contents ix
6.6 Nanobiotechnology for Crop Improvement 177

6.7 Nano-Barcode Technology and Identity
Preservation 179
6.8 Conclusion and Future Perspectives 179
7. Application of Nanocomposites and Nanomaterials

for Treatment of Wastewater Containing Pollutants 199
Hossein Esmaeili
7.2 Nanomaterials Properties 203
7.3 Toxic Metals Removal from Wastewater 204
7.4 Dye Removal from Wastewater 209
7.5 Phosphate, Sulfate, and Nitrate Removal
from Wastewater 214
7.6 Drugs Removal from Wastewater 218
7.7 Hydrocarbon Removal from Wastewater 222
7.8 Reusability of Nano-Sorbents 224
7.9 Effective Factors on Wastewater 227
7.10 Conclusion 227
8. Application of Nanotechnology in Cosmetics 243

Adriana de Melo, Marcelo Lancellotti, and
Daisy Machado
8.2 Definition of Nanoparticles 245
8.3 General Characteristics of Nanoparticles 247
8.4 Nanoparticles for Cosmetic Formulation 247
8.5 Types of Nanoparticles Used in Cosmetics 248
8.5.1 Non-metallic Nanoparticles 249
8.5.1.1 Liposome 249
8.5.1.2 Applications of
liposomes in cosmetics 251
8.5.1.3 Nanoemulsions 254
nanoemulsions in
cosmetics 254
8.5.1.5 Nanocapsules 256
8.5.1.6 Complications of
nanocapsules in
cosmetics 257
x Contents
8.5.1.7 Solid lipid nanoparticles

(SLNs) 258
8.5.1.8 Applications of SLNs in
cosmetics 259
8.5.1.9 Dendrimers 260
dendrimers in cosmetics 260
8.5.1.11 Niosomes 261
8.5.1.12 Applications of niosomes
in cosmetics 262
8.5.2 Metal Nanoparticles 264
8.5.2.1 Silver nanoparticles 264
8.5.2.2 Applications of silver
nanoparticles in
cosmetics 264
8.5.3 Carbon Nanoparticles 265
8.5.3.1 Fullerenes (Buckyballs) 265
fullerenes in cosmetics 266
8.6 Advantages and Disadvantages of
Nanoparticles in Cosmetics 267
8.7 Final Considerations 267
9. Oral Lipid-Based Carriers: Overcoming the

Challenges Associated with Conventional
Treatments of Non-Small Cell Lung Cancer 277
James Glover, Sakib Yousaf, and Iftikhar Khan
9.2 Non-Small Cell Lung Cancer (NSCLC)
Pathophysiology 280
9.3 Current FDA-Approved Therapies for
Non-Small Cell Lung Cancer 281
9.3.1 Chemotherapy 282
9.3.2 Targeted Therapy 283
9.3.3 Immunotherapy 284
9.4 Oral Lipid-Based Formulations and Their
Importance 285
9.4.1 Mechanism of Intestinal Lymphatic
Absorption 286
9.4.2 Phospholipid Nanocarriers 288
Contents xi
9.4.2.1 Self-emulsifying drug-

delivery systems 290
9.4.2.2 Solid lipid nanoparticles
(SLNs) 291
9.4.2.3 Nanostructured lipid
carriers (NLCs) 293
9.4.2.4 Liposomes 294
9.4.2.5 Lipid–polymer hybrid
systems (LPHS) 295
9.4.3 Future of Oral Dosage Forms for
Anticancer Therapy and Lipid-
Based Drug-Delivery Systems 297
9.5 Conclusion 297
10. Skin Aging and Vesicular Delivery Systems 309

Eleni Axioti, Maria Apostolou, Sakib Yousaf,
and Iftikhar Khan
10.1.1 Skin 310
10.1.1.1 Epidermis 311
10.1.1.2 Dermis 313
10.1.1.3 Hypodermis 316
10.2 Skin Aging 316
10.2.1 Categories of Aging 316
10.2.1.1 Chronological aging 317
10.2.1.2 Extrinsic aging 319
10.2.2 ROS and Skin Aging 322
10.2.3 Aging within the Epidermis 323
10.2.4 Aging within the Dermis 324
10.2.5 Aging of the Skin Appendages
and Nerves 326
10.2.6 Changes on Facial Skin throughout
the Years 326
10.2.7 Antiaging Strategies 327
10.3 Delivery through the Skin 333
10.3.1 Factors Affecting Permeation
with Age 333
10.4 Delivery Systems 335
10.4.1 Topical Delivery Systems 338
xii Contents
10.4.2 Nanocarriers as Cosmetic Delivery

System 338
10.4.3 Factors Influencing Nano-Based
Delivery Systems 339
10.4.3.1 Zeta potential 340
10.4.3.2 Particle size and shape 340
10.4.3.3 Saturation 340
10.4.3.4 Temperature and viscosity 340
10.4.4 Use of Vehicles in Delivery Systems 341
10.4.4.1 Liposomes 341
10.4.4.2 Ultradeformable
liposomes
(transferosomes) 345
10.4.4.3 Flexible vesicular
nanocarriers containing
ethanol (ethosome) 347
10.4.4.4 Niosomal nanocarriers
(Niosomes) 347
10.4.5 Use of Delivery Systems in Cosmetics 348
10.4.6 Antiaging Formulations Using
Vesicular Delivery Systems 350
11. Nanoparticle Dispersions for Engineering Application 369

Maje A. Haruna and Saminu M. Magami
11.2 Nanoparticle Production Methods 372
11.2.1 “Bottom-Up” Process 372
11.2.2 “Top-Down” Process 372
11.3 Nanoparticle Dispersions in Polymer Matrices 373
11.3.1 Direct Mixing or ex situ Process 374
11.3.2 In situ Polymerization Method 375
11.4 Concept of the Dispersibility of Nanoparticles 376
11.5 Concept of the Stability of the Dispersions 377
11.6 Concept of Additives that Promote
Dispersibility and Stability 378
11.7 Key Analyses Methods and Performance Tests 380
11.7.1 Sedimentation and Centrifugation
Methods 381
11.7.2 Zeta Potential Technique 381
11.7.3 Spectral Absorbency Techniques 382
Contents xiii
11.7.4 Centrifugal Techniques 383

11.7.5 Analysis of Specific Surface Area 384
11.7.6 Particle Morphology Analyses 384
11.7.7 Light Scattering in Dispersions 385
11.7.8 Rheology and Flow Behavior 387
11.8 Selected Applications 390
11.8.1 Nanoparticle Dispersions in
Enhanced Oil Recovery 390
11.8.1.1 Interfacial tension 391
11.8.1.2 Wettability 392
11.8.1.3 Structural disjoining
pressure 392
11.8.1.4 Retention in porous media 393
11.8.1.5 Mobility control 393
11.8.2 Nanoparticle Dispersions in
Fire-Resistant and Fire-Retardant
Applications 395
11.9 Conclusion 397
12. Effect of Ultrahigh Pressure on Nanomaterials

Structure 407
Ehsan Nourafkan and Yaser Kashcooli
12.2 High-Pressure Instrumentation 409
12.2.1 Large-Volume Press 409
12.2.2 Diamond Anvil Cell 409
12.3 Effect of Pressure on Soft Matter
Nanostructures 410
12.4 Effect of Pressure on Hard Nanomaterials 418
12.4.1 Gold Nanoparticles 428
12.4.2 Quantum Dots 431
12.4.3 Carbon-Based Nanotubes 433
12.5 Conclusion 438
Index 443
Preface
Nanoparticles are materials with overall dimensions in the nanoscale,

i.e., under 100 nm. In recent years, these materials have emerged as
important players in modern techniques, having applications from
medicine and drug delivery to textile and agriculture. Nanoparticles
are already integrated into our everyday lives in various forms, such
as sunscreen lotions containing nanoparticles, dirt-resistant glass
with nanocoatings, and nanodrugs. Much has already been written
on the fundamental aspects of nanoparticles. This book is refreshing
because it deals with recent studies and techniques to produce
nanoparticles for practical application in diverse industrial fields.
Although several aspects of nanoparticles have been dealt with in
innumerable journal articles individually, sources covering this area
comprehensively are limited, and this book tries to fill this gap. Some
other interesting topics, including nanoencapsulation, nanoparticle
formation, and surface functionalization of nanoparticles, have been
covered in detail to make it a valuable resource for practical use.
Waqar Ahmed
Ehsan Nourafkan
Summer 2022
Chapter 1
Application of Nanoparticles
in the Field of Photonics
Syed Asad Hussain

Department of Engineering Science, University of Oxford,
Parks Road, Oxford, OX1 3PJ, UK
asad.hussain@outllook.fr
In this chapter, we have presented applications of nanoparticles

in the field of photonics. The field of photonics is very vast, and
nanoparticles have proved to be a valuable tool in this field. We have
limited and focused our discussion by providing in-depth discussion
about microscopy, laser, nonlinear optical conversion, solar cells,
and therapy. Nanoparticles are very useful in all these areas due
to the unique properties they offer in comparison to their bulk
counterpart. Although these materials are entering the commercial
markets of microscopy, laser, and therapy, further understanding is
required to optimize the properties and make them superior.

Edited by Waqar Ahmed and Ehsan Nourafkan
Copyright © 2023 Jenny Stanford Publishing Pte. Ltd.
ISBN 978-981-4267-34-2 (Hardcover), 978-1-003-28029-3 (eBook)
www.jennystanford.com
2 Application of Nanoparticles in the Field of Photonics
1.1 Introduction
Due to reduction in size, nanoparticles with size in the range of 1
to 100 nm give rise to properties that are not observable from their
bulk counterparts as we reach quantum confinement at the atom
scale (Pavitra et al., 2019; Yanhong et al., 2004). Various properties of
these nanoparticles are very important, which include high surface
area, dedicated surface characteristic, electrical, optical, thermal,
magnetic, and their interaction with the other systems. Intensive
work has been done on their synthesis (Murphy et al., 2005; Panáček
et al., 2006; Lu et al., 2007; Narayanan and Sakthivel, 2010; Tang et al.,
2012). The landscape is rich in various methods, and each has its own
advantages and disadvantages. This also includes various bottom-up
or top-down routines. Due to the pressing climate issues and making
them in an environmentally friendly manner, focus is now on making
them without using chemicals. In this connection, using lasers to
create organic or inorganic particles or making nanoparticles from
natural elements has become a primary focus of the field (Eliezer
et al., 2004; Hu et al., 2009; Amendola and Meneghetti, 2009; Bar
et al., 2009; Iravani, 2011). Apart from environmental issues, these
methods are important due to the cost involved in buying chemicals
and deposing them. In this comparison, the capital cost of utilizing
laser is one off, including its occasional maintenance.
Figure 1.1 Various properties that need to be modified for the nanoparticles
to be used for applications in optics.
Nanoparticles for Bioimaging 3
Understanding the interaction and dynamics of different

biological system is a key process to apply different strategies to
find the cure of diseases. These processes are hard to understand
by using conventional microscopes as the biological dynamics is not
possible to image. Moreover, they are limited in terms of resolution.
To overcome this problem, various nanoparticles have been made
in the past that could be attached to different parts of microscopic
biological systems. As an example, silicon, which is available in
abundance and extensively used in the electronics industry, shows
size-dependent photoluminescence at room temperature (Park et
al., 2009; Pavitra et al., 2019). Once attached, they could then be
used for imaging. Gold attracted a lot of attention in the past and has
been used for many years. Not only silicon and gold, semiconductors
and iron-based nanoparticles have also attracted attention. By using
them inside the biological system, key imaging matrixes such as
signal-to-noise ratio, spatial resolution, and selectivity go high.
In this chapter, we will mainly focus our attention on the
application of nanoparticles in the field of optics. The chapter will
highlight progress that has been made so far and will also provide
knowledge about the science behind each application.
1.2 Nanoparticles for Bioimaging

Iron-based nanoparticles can provide magnetic properties. The
properties of these nanoparticles could be tuned to provide functional
properties that could be applied for magnetic resonance imaging
(MRI) (Hadjipanayis et al., 2008; Ris et al., 2010; Wen et al., 2014).
In the family of these nanoparticles, iron oxide is the most important
material. One problem associated with this type of nanoparticles
is stabilization, which could be overcome by using them inside
composites (Masotti et al., 2009; Santra et al., 2012). However, this
could affect the capabilities of these nanoparticles. Another factor is
to make these types of nanoparticles with multifunctionality.
In MRI, a strong magnetic field is applied that helps to align
the protons present in the tissue (Fig. 1.2). This helps to align the
proton along the field direction. In the next step, a radiofrequency
pulse is applied, which helps them to align in another direction. The
radiofrequency is then turned off, due to which the protons relax

back to their original orientation. In MRI, a unique image is obtained
due to this relaxation. The magnetic nanoparticles could be attached
to different types of tissues and, therefore, could interact with the
relaxation process, making it faster or slower in comparison to other
types of tissues in the surrounding. Once this is done, the MRI images
generated from the setup have much better contrast in comparison
to those without them.
Figure 1.2 Dynamics of atoms in the presence of magnetic field and

radiofrequency pulse. The atoms are aligned in one direction due to a magnetic
field. The radiofrequency signal aligns them in another direction. By turning off
the radiofrequency signal, the atom will relax back to its original aligned state
emitted radiofrequency signal to be detected by the detector. This generated
signal will be used to create an image.
As an example, Fig. 1.3 shows the results for

Zn0.2Fe2.8O4 nanoparticles with sizes 4, 7, and 10 nm for their
magnetic properties (Ma et al., 2019). Figure 1.3(a–c) shows the sizes
of these nanoparticles in transmission electron microscopy (TEM).
When a similar magnetic field is applied to these nanoparticles,
they show different behavior and depending upon the size give
rise to magnetization different in aptitude. Figure 1.3d shows this
phenomenon; in this case for the same magnitude of the magnetic
field, the nanoparticles with size 10 nm attain higher magnetization
and then 4 and 7 nm particles. Moreover, it was also shown that if

a magnet is placed next to the solution of these nanoparticles, they
will also be attracted toward the magnet due to the presence of iron.
Figure 1.3 (a–c) Zn0.2Fe2.8O4 nanoparticles of different sizes. From left to right,
4, 7, and 10 nm. (d) Magnetic field applied to these particles and magnetization
obtained. (e) Nanoparticles attracted toward the magnet. Reproduced from Ma
et al. (2019) with permission.
Although the technique based on MRI has proved to provide

superior spatial resolution, the setup cost is expensive. To overcome
this difficulty, we could use nanoparticles for optical microscopy. The
optical properties are highly dependent on size and shape. Based on
the size of these particles, fluorescence wavelength changes. They
could be injected or delivered into the body where the imaging
is required. However, they need to be connected to distinguish
between different bodies. To do so, the surface is modified to allow
the attachment of different molecules (McConnell et al., 2000; Cheng
et al., 2006; Kango et al., 2013). These molecules act as a linker
between the nanoparticles and the biological tissue. After these
molecules are attached, they provide superior signal-to-noise ratio
and are resistant to photobleaching in comparison to staining alone
with organic or fluorescent dye molecules.
Let us now focus on different types of optical microscopes

available. All microscopes normally consist of a light source that
excites the nanoparticles, a detector to detect the light coming
from the sample, an optics to direct the light toward the sample, a
microscope objective to focus the light beam on the sample, and a
set of optical filters that allow light beams of certain wavelengths
and block light beams of other wavelengths. The microscope creates
a spot diameter by using a microscope objective, which has a set of
lenses packed inside a body to give better optical performance. The
focused light creates a diameter of light known as the point spread
function (PSF) (Fig. 1.4). We can see that the light has an intensity
peak at the center and the decaying side lobes around it. This is
because when the light, which is an electromagnetic field, is solved in
three-dimensional space considering a microscope objective gives a
mathematical expression known as the Airy pattern. This PSF could
be made smaller by using a high numerical aperture (NA) objective
lens (Fig. 1.4a). The inverse relation between the numerical aperture
number and spot diameter can be simplified by using the following
equation:
Wavelength of light
Spot diameter = 1.22
Numerical aperture of microscope objective
On the other hand, the relation between the focusing angle (a)
of the light and the numerical aperture and refractive index of the
medium is given by
Numerical aperture of
= Refractive index ¥ sin a
microscope objective
When the light is focused inside the tissue and if within the
region there are nanoparticles that could emit light, we will get more
than one PSF originating from each nanoparticle. In this case, it will
be possible to distinguish between each nanoparticle if the distance
between them is at least the Rayleigh limit; otherwise, they will look
one single quantity. Finally, in the lateral dimension, the PSF is a
regular ring and an elongated ellipsoid in the other direction. To do
the imaging of smallest molecules and to study their dynamics, we
need to wisely select a microscope objective to get the smallest PSF.
However, after a certain limit, it is not possible to go further down
and we need to use clever optical techniques.
Numerical Aperture (NA)

(a)
Numerical Aperture
NA = nsinα
Light
cone
Optical
nods
a
Objective
aperture angle Objective
Fluorophore Airy disks
lens
(point source) (diffraction pattern)
(b)
Resolution (R)
Resolved Airy disks Rayleigh Limit Unresolved Airy disks
0.61l
R=
NA
Intensity
(C) (d)
Point Spread Function (PSF) Numerical Aperture, Airy disk size and resolution
Lateral view Numerical Aperture Airy disk size Resolution

Point spread function
y
a
x
Small objective
Axial view aperture angle
Unresolved
a
z Large objective
aperture angle Resolved
x
Figure 1.4 (a) Focusing of a light source or beam to a spot by using a lens
or microscope objective. (b) Resolution of the microscope objective defined
by different situations. Two spots will be distinguishable only when the
distance between them is at least equal to the Rayleigh length. (c) The PSF of
the microscope objective in lateral and axial view and (d) various situations
when a large and small numerical aperture is used. Reproduced from Dunst
and Tomancak (2019) under CC-BY 4.0 (http://creativecommons.org/licenses/
by/4.0/).
Figure 1.5 shows different types of microscopes with which we

can carry out many observations. Figure 1.5a shows a conventional
microscope with white light in which wavelengths could be selected
by using a filter in front of it. When a laser is used instead of white
light, we achieve a smaller spot due to a narrow spectrum (Fig. 1.5b).
Selected regions could be excited by using light sheet geometry by
using a cylindrical lens or by using a pin hole (Fig. 1.5c,d). There are
several types of super-resolution microscopes. All have the same
target to go below the PSF limit to obtain the images. Two of them
are shown here: One is structured illumination in which N images
are captured for various orientations of the grating in front of the
light source. This creates dark and bright regions for the PSF. By
mathematical processing, we can obtain the final image that has
contributions from each nanoparticle (Fig. 1.5d). Another type
shown here is stimulated emission depletion (STED) in which by
using a combination of excitation and deexcitation of the light beam,
super-resolution images can be obtained (Fig. 1.5e).
Since there are several microscopes, nanoparticles, and
tissues, the landscape of various studies that could be found in the
literature is huge. By using interferometric scattering microscopy, it
has been shown that it is possible to attach gold nanoparticles to
giant unilamellar vesicles (GUVs) (Taylor and Sandoghdar, 2019)
(Fig. 1.6a). By attaching these nanoparticles to them, they have
achieved tracking of these in real time, which is useful to understand
their behavior in the environment. On the other hand, Deka et al.
presented the application of gold nanoparticles for deep tissue
imaging. Figure 1.6b shows the images of these nanoparticles at
different depths. When the depth is increased, the intensity of
these nanoparticles goes down due to the scattering of the tissue.
Still imaging at the depth of 200 µm has significant light, which is
important for imaging in cells and small microbodies (Deka et al.,
2018). Figure 1.6c shows the image of the HeLa cell with and without
the two-photon photothermal microscope (Bijeesh et al., 2017).
When the two-photon capability was not used, the images produced
no significant information. However, the figure on the right shows
that as soon as the two-photon capability was used, small features
inside the cell became visible and clear.
EMCCO PMT EMCCO

Pinhole
Excitation filter
Emission Emission
filter filter
Dichroic Light source Dichroic Laser Objective lens

mirror mirror Cylindrical
Objective lens lens
Objective lens Laser
z z z
x x x
Depletion
EMCCO laser
PMT
Emission
filter
Dichroic
mirror
Dichroic Laser
mirror Grating Excitation
laser
Objective lens
z z
x x
Image 1 Image 2 Image 1 Image 2
Image N Final image Image N Final image
y y
x x
Figure 1.5 Examples of a few microscopes that could be found in the literature:
(a) widefield microscope, (b) laser microscope, (c) light sheet microscope,
(d) structured illuminations, and (e) stimulated emission depletion. Reproduced from
Dunst and Tomancak (2019) under CC-BY 4.0 (http://creativecommons.org/licenses/
by/4.0/).
Figure 1.6 (a) Gold nanoparticles attached to giant unilamellar vesicles (GUVs)
to show tracking inside the tissue. Gold nanoparticles could also be used for
tracking deep inside the tissue. Reproduced from Taylor and Sandoghdar (2019)
under CC-BY 4.0 (http://creativecommons.org/licenses/by/4.0/). The authors
have managed to do imaging up to 200 µm. (b) This is significantly deep for
most of the tissues in which biologist do study. Reproduced from Deka et al.
(2018) under CC-BY 4.0 (http://creativecommons.org/licenses/by/4.0/). In the
left, we can observe the HeLa cell in the widefield image; no useful information
is available in this. On the other hand, the figure on the right shows the same
structure with a two-photon photothermal microscope where small features of
the cell are visible (c). Reproduced from Bijeesh et al. (2017) under CC-BY 4.0
(http://creativecommons.org/licenses/by/4.0/).
Applications in lasers: Laser is an acronym for Light Amplified by

Stimulated Emission by Radiation. Since its discovery in 1960, it has
provided many useful properties, including power as well as shorter
pulse duration and wavelength. Depending upon the characteristic
of the laser, one type of laser may be cost effective in one application
but not the other (Kärtner and Keller, 1995; Hussain et al., 2012;
Plamann et al., 2016; Coddington et al., 2016; Anastasiou et al.,
2016; Hussain et al., 2017; Anastasiou et al., 2017; Singh et al., 2018;
Anastasiou et al., 2018; Fu et al., 2018; Hussain, 2019c; Hussain,

2019a; Hussain, 2019b; Hussain, 2020). Even after several decades,
there are still areas that require advancement in different aspects.
The laser consists of a gain medium that is sandwiched between two
mirrors to provide optical feedback (Fig. 1.7a). The laser consists
of an electrical or optical source that provides pumping from the
ground state to a higher state and, therefore, providing lasing. The
laser medium needs to be based on different energy levels that are
different from the two-level system (Fig. 1.7b left). This is due to the
fact that in a two-level system, the same photon will be absorbed and
transmitted, making the system transparent (Silfvast, 2004; Svelto,
2010; Renk, 2017). In the laser system, we have three-level and
four-level systems (Fig. 1.7b center and right). They are designed
in such a way that the wavelength of the pumped photon is at the
lower end of the spectrum and the emitted photon is at the higher
end. Let us consider a three-level system. In this system, the atom
will absorb the photon, and the electron will jump from the ground
state to the excited state. Next it will decay in a non-radiative process
followed by a radiative decay. For the system to act as a laser, we
need an optical feedback system that could be achieved by using,
in the simplest case, two mirrors. So far, we have talked about
absorption and emission. This emission is known as spontaneous
emission. In order to get a laser, we need gain. This gain is achieved
through a stimulated process, also known as stimulated emission.
In this process, the photon, which is already in the excited state,
is stimulated to deexcite due to the presence of the same energy
photon. These two photons will give rise to four photons, and these
four photons will give eight photons. This will fill up the laser cavity
quickly. To extract a useful amount of laser power from the cavity,
one of the cavity mirrors is made semitransparent, which will give
us the laser light (Fig. 1.7a).
To achieve lasers from nanoparticles, extensive work has been
done on quantum dots and wells due to their compatibility with
the current fabrication procedures in the silicon industry. The push
on this kind of laser is achieved due to silicon being a non-direct
bandgap material. Without going into details, non-direct bandgap
materials cannot produce light when their electrons are excited.
Although various optical components could be made from silicon,
especially waveguides, it is not possible to get laser action from it
12
Application of Nanoparticles in the Field of Photonics
Figure 1.7 (a) The laser cavity consists of a laser gain material and two mirrors to provide the optical feedback. One of the mirrors is made
semitransparent to take useful light out from the cavity. (b) Two three- and four-level systems. The laser will only work for three- and four-
level systems.
due to this reason. Still researchers are trying to get laser from it,
and a huge amount of investment is made every year. Therefore, the
only possible route adapted by researchers is growing quantum dot
structures on it to get lasing. There is always a strong competition
between the quantum dot and well structures, and a lot of work has
been done on it. Recently, it seems that the dot structure is winning
the battle due to its low energy consumption for the same optical
data transmission (Huang et al., 2020).
Figure 1.8 Various types of lasers that have been achieved by using the
quantum nature of atoms. By using the quantum dots of InGaAs, near-infrared
wavelengths were obtained (a). Reproduced from Zhou et al. (2020) under CC-
BY 4.0 (http://creativecommons.org/licenses/by/4.0/). (b) In another study,
100 nm tunability was obtained (Wang et al., 2018). Reproduced from Wang
et al. (2018) under CC-BY 4.0 (http://creativecommons.org/licenses/by/4.0/).
Finally, a structure based on InGAs and GaAs was also capable of producing
laser (Huang et al., 2020). Reproduced from Huang et al. (2020) under CC-BY 4.0
Figure 1.8a–c shows structures for the fabrication of lasers based

on these. As discussed before, the basic idea is to make them over
silicon structures. On a silicon wafer, several layers are fabricated

along with the gain medium. The gain medium is sandwiched
between these layers. The task of these additional layers is to
provide optical feedback and electrical contacts and to make the
crystal structure compatible with silicon. The figure also shows
the wavelength obtained in each case. In Fig. 1.8a, the wavelength
could be tuned from 1280 to around 1350 nm (Zhou et al., 2020).
Figure 1.8b presents a tuneability of 100 nm for this kind of laser
(Wang et al., 2018). The same picture also shows an atomic force
microscope with various active layers on it. Finally, Fig. 1.8c shows
the change in wavelength at 1300 nm with temperature (Huang et
al., 2020).
Apart from using the semiconductor nanostructures, other
types of nanostructures are also used. Recently, CsPbBr3 Perovskite
quantum dot lasing was achieved in the green region of the
electromagnetic spectrum (Huang et al., 2017). Fernandez-Bravo
et al. developed a microlaser my enclosing Thulium nanoparticles
inside polystyrene. This provided lasers at 800 and 450 nm
wavelengths (Fernandez-Bravo et al., 2018).
Nonlinear optical processes based on nanoparticles: In this
universe, substances around us are made of atoms arranged in
such a way that gives us solid, liquid, or gas. When light, which is an
electromagnetic field, is incident on them, it polarizes the material,
which reemits the same electric field. This makes linear optical
processes such as reflection or refraction. However, when the
value of this electric field starts reaching 105–108 V/m, nonlinear
processes start to happen, which cannot be described by using a
linear relation and additional terms need to be considered (Murti
and Vijayan, 2014; He, 2014; Boyd, 2019). In such a case, we need to
write the equation in the following form:
P = eo (c(1)E1 + c(2)E2 + c(3)E3)
where P is the polarization of the atoms, E is the electric field, c is
susceptibility, and eo is the permittivity of free space. In this equation,
the numbers on c represent the order number. The first elment
in the equation represents linear processes such as reflection and
refraction. As we go higher in terms, other processes can be found
such as second or third harmonics. We can also observe third-order
processes such as saturable absorption, sum or difference frequency
generation, optical parametric oscillation, optical parametric

generation, and so on (Murti and Vijayan, 2014; He, 2014; Boyd,
2019). In this part of the chapter, we will discuss different nonlinear
processes. Each process will be briefly introduced followed by
applications of nanoparticles for this purpose.
Figure 1.9 Energy level diagram for second-order (left) and third-order (right)
effect.
Second and third harmonic generation: These two processes

are widely applied in the industry and based upon c(2) (second
harmonic generation) and c(3) (third harmonic generation) of the
equation above. Considering the second harmonic generation, two
photons are combined inside the nonlinear medium to provide a
photon whose frequency is twice that of the incident photons. In
this medium, the first photon excites the medium to an imaginary
virtual state followed by another photon that excite it to another
virtual state. After relaxation, the system will generate a photon
whose frequency will be double (Fig. 1.9 left). In the third-order
process, the same approximations are applied and, in this case,
instead of two photons, three photons combine. For this situation,
the frequency is thrice the incident photon frequency (Fig. 1.9 right).
Their application in the industry and academia becomes obvious
because one source of photons could give frequency at other parts of
the electromagnetic spectrum. All we need is an efficient nonlinear
medium whose conversion efficiency is high. The second and
third harmonic generations are studied a lot in the past and a few
systems have shown to be very promising, such as KDP (potassium
dihydrogen phosphate), BBO (β-barium borate), lithium niobite, and
KTP (potassium titanyl phosphate) to name a few (Murti and Vijayan,

2014; He, 2014; Boyd, 2019). Still, nanoparticles can reach small
places where these cannot reach. Therefore, the main application of
nanoparticles is in the area where an extremely small footprint is
required.
One of the simplest ways to show their usefulness is to mix
them with the host material. Butet et al. used gold nanoparticles of
150 nm diameter, which were dispersed in gelatin to obtain SHG.
In the study, they used femtosecond laser operating at 794 nm to
achieve its second harmonic at 397 nm. Since the pumped laser
provided femtosecond laser pulses, the obtained converted pulses
could also be used in the applications where femtosecond pulses
are required (Butet et al., 2010). Another paper presented an
increase in the efficiency of the second harmonic signal due to the
use of nanoparticles. When silicon nanoparticles were arranged in a
manner that gives rise to Mie resonance, it has been shown that the
efficiency of the SHG could be increased. In this case, a magnitude
of at least two orders could be achieved (Makarov et al., 2017). A
similar approach was applied to obtain THG (Shcherbakov et al.,
2014). Gold nanoparticles, on the other hand, provided both SHG
and THG (Lippitz et al., 2005).
Nanoparticles as saturable absorbers: A saturable absorber is
a third-order nonlinear effect also observed in many materials,
including nanomaterials. In a saturable absorber, the lower
intensity light is blocked whereas high-intensity light can pass
through the sample. This could be explained in terms of a two-level
system (Fig. 1.10) when the light pulse contains a small number of
photons and the number of electrons is enough to block the laser
pulse. However, as the laser pulse starts to rise, the sample starts
to become more and more transparent until the sample becomes
completely transparent. This is because the number of photons is
becoming higher and there are not enough electrons to block them.
In some cases, the sample could be damaged before it could become
completely transparent. Therefore, a saturable absorber sample can
act like a switch that could be opaque for low-intensity pulse and
transparent for high-intensity pulses. The experimental setup to test
a saturable absorber normally has a light source that could produce
nano to femtosecond laser pulses followed by a lens, the sample, and
the detector to measure the power. Since a saturable absorber acts

like a switch, such a switch is very useful for the creation of ultrashort
laser pulses from the laser cavity. Apart from having a saturable
absorber, another condition is to have a wide bandgap laser gain
material inside the laser cavity. This supports longitudinal modes of
the cavity. The saturable absorber will then provide modulation for
the cavity. Another requirement is the absorption of the saturable
absorber at the laser cavity wavelength. Moreover, the electron
relaxation time should be faster than the cavity round trip time and
the intracavity power should be high enough to make the absorber
at least semitransparent.
Figure 1.10 Energy level diagram to understand saturable absorption inside

the material. For the low-intensity case, the light will be absorbed by the
material. For the high-intensity case, the light will manage to pass through the
material.
Various materials have been used in the literature as saturable

absorbers inside the laser to obtain laser pulses from the laser cavity.
They include semiconductors (Tilma et al., 2015), two-dimensional
materials (Martinez and Sun, 2013), and other nanomaterials
(Ahmad et al., 2016; Mohanraj et al., 2016; Song et al., 2016; Chu et
al., 2018) that could be made by using different methods. Figure 1.11
shows the image of obtaining ultrashort laser pulses by using
different materials. Figure 1.11a shows results that were obtained
for carbon nanotubes. In this figure, the extreme left shows change
in transmission as the power increases. In this case, the maximum
change of 6.44% was obtained. Beyond 2000 MW/cm2, the sample
was damaged due to excessive power. By working with this saturable
absorber below this power, we could use it inside the laser (Hussain,
2019a). Since carbon nanotubes have broad absorption, this absorber
could be used for the tunability of wavelength. In this, we can see a
tunability of 40 nm. For this laser, the pulse separation was found to
be 59 ns. In another paper, by using a titanium disulfide saturable
absorber, the authors showed pulsed operation at around 1530 nm.
In this case, the optical transmission increased as they increased the
power. The pulse separation in this case was found to be 291.3 ns
(Shang et al., 2020). Finally, a saturable absorber based on tellurene
could also be used for the same purpose (Xu et al., 2020). The same
kind of observations were also made in previous papers. The sample
showed an increase in transmission with the power. In this case, the
pulse separation was 82.17 ns. Although we have shown examples
of wavelengths around 1550 nm, several examples in the literature
use different wavelengths. All these wavelengths depend on the
availability of gain materials either for research or for commerce.
Nanoparticles for other miscellaneous applications: So far, we
have shown applications of nanoparticles for microscopy, nonlinear
conversion, and generation of laser pulses. The application is not
just limited here. This is because of their quantum nature, and the
dependence on size and shape could give so many applications
that still need to be further discovered. Nanoparticles, for example,
could be used for chemotherapy. For this application, the substance
used, cisplatin, can be toxic for the tissue. Therefore, a platform is
needed where this could be minimized while providing at least the
same performance. Gold (Ajnai et al., 2014), carbon-based systems
(Liu et al., 2011), polydopamine nanoparticles (Zhu and Su, 2017),
and polymer also proved for such applications (Priya James et al.,
2014). For this, Zhu et al. prepared the required nanoparticles by
first modifying them with glycol followed by attaching cisplatin (Zhu
and Su, 2017) (Fig. 1.12).
(a)
8 1.25
1.0
6 1.00
4 0.8
0.75
2
DT (%)
0.6
0 0.50
Intensity (a.u.)
0.4
Intensity (a.u.)
1 10 100 1000 10000 0.25
Pin (MW/cm2) 0.2
0.00
1520 1525 1530 1535 1540 15451550 1555 -150 -100 -50 0 50 100 150
Wavelength (nm) Time (ns)
(b) 84 -10 1.4

82 -20 1.2
-30 1.0
80
-40 0.8
78
-50 0.6
Intensity (dB)
Intensity (a.u.)
76 -60 0.4
Transmission (%)
74 -70 0.2
-80 0.0
72 -2 -1 0 1 2
0 20 40 60 80 100 1518152115241527153015331536153915421545
Optical intensity (MW/cm2) Wavelength (nm) Time (ms)
(c) 42 –30 1.8

1.6
41
–40 1.4
40 1.2
1.0
39 –50
0.8
38 0.6
Intensity (dB)
Intensity (a.u.)
Transmission (%)
–60 0.4
37
0.2
36 –70 0.0
0 20 40 60 80 100 120 140 160 180 200 1540 1550 1560 1570 1580 1590 0.0 0.5 1.0 1.5 2.0
Optical intensity (MW/cm2)
Wavelength (nm) Time (ms)
Nanoparticles for Bioimaging
Figure 1.11 Use of various saturable absorbers to obtain laser pulses from the cavity. By using carbon nanotubes (a), titanium disulfide
(b), and tellurene (c). Reproduced from Hussain (2019a), Xu et al. (2020), and Shang et al. (2020) under CC-BY 4.0 (http://creativecommons.
19
org/licenses/by/4.0/).
Figure 1.12 Modified polydopamine nanoparticles by attaching glycol and

cisplatin for chemotherapy. Reproduced from Zhu and Su (2017) under CC-BY
4.0 (http://creativecommons.org/licenses/by/4.0/).
Another very hot area is using nanoparticles for energy

applications. In this field, solar cells are one of the key areas as
perovskite solar cells have shown better performance. These
nanoparticles are used in the structure to make the performance
superior. One example is to use plasmonic structures inside the
solar cells to increase their absorption (Ghahremanirad et al.,
2019). Ghahremanirad et al. (2019) used gold nanoparticles inside
the structure (Fig. 1.13 left), which has proved to be very effective.
The infrared absorption at 800 nm increased significantly (Fig. 1.13
right). We can see that the absorption increased with the radius of
gold nanoparticles.
Figure 1.13 The structure used in solar cell application with gold nanoparticles
(left). This showed high absorption with the increase in the radius of gold
nanoparticles. Reproduced from Ghahremanirad et al. (2019) under CC-BY 4.0
References 21
1.3 Conclusion
In this chapter, we discussed various applications of nanoparticles
in optics. We presented various applications in microscopy, laser,
nonlinear conversion, solar cells, and cancer therapy. Nanoparticles
have been successfully applied in these areas. Due to their unique
properties of size and shape, their applications are unlimited.
Nanoparticles are being researched, where they must be fully
applied in all commercial areas.
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Chapter 2
What We Need to Know about

Quantum Dots Nanoparticles
Shiv Prakash Singh,a Sudheer Kumar Yadav,b

and Kunal Mondalc
aCentre for Ceramic Processing, International Advanced Research Centre for
Powder Metallurgy and New Materials (ARCI), 500005 Hyderabad, India

bEduard-Zintl-Institut für Anorganische und Physikalische Chemie,
Technische Universität Darmstadt, 64287 Darmstadt, Germany

cMaterials Science and Engineering Department, Idaho National Laboratory,
Idaho Falls, ID 83415, USA

spsingh67@gmail.com
Quantum dots (QDs) have engrossed huge research interest over

the last 10 years. QDs are within the range of a few nanometers
(<10 nm), and to be part of photonic structures, they are usually
entrenched in thin films or other micro- and nanostructures. After
briefly reviewing the various fabrication methods of QDs, examples
of results concerning the characterization of these nanostructures
were discussed. Properties of QDs containing CdSe/ZnS, TiO2, and
other QDs are presented describing their optics, optoelectronics,
absorption, and photoluminescence, including different ways of

Edited by Waqar Ahmed and Ehsan Nourafkan
Copyright © 2023 Jenny Stanford Publishing Pte. Ltd.
ISBN 978-981-4267-34-2 (Hardcover), 978-1-003-28029-3 (eBook)
www.jennystanford.com
30 What We Need to Know about Quantum Dots Nanoparticles
characterization of these nanostructures. Finally, we discussed

applications of QDs for drug delivery, energy materials, catalysis,
and electronics with brief future prospects. It is important to
enhance the understanding of QDs to explore the possibility of new
properties and applications toward the advancement of technology
as well as scientific discoveries.
2.1 Introduction
We are dealing with nanotechnology in our daily life by using
different materials such as oxides, semiconductors, metals,
polymers, etc. In all these cases, atoms play an important role. A
group of atoms of semiconductors have revolutionized the whole
world of materials science from simple home lights to modern
computers and photovoltaic solar cells, several types of sensors,
biomedical applications, and many in more advanced technologies.
These groups of atoms of semiconductors are known as QDs [1–3].
It is essential to understand the importance of these QDs and their
functions. The QDs are extremely small in diameter that they are
effectively concentrated into a single point or we can say into a zero-
dimension structure [4, 5]. Due to their size effect, the particles
inside them are trapped and have well-defined energy levels
according to the quantum theory. The QDs are nanocrystalline, with
sizes within a few nanometers meaning a few dozens of atoms. These
QDs are made up of semiconductors such as silicon, germanium,
etc. and are nanocrystalline but behave as a single atom. Hence,
QDs are also called artificial atoms [6, 7]. Recent developments in
the processing of semiconductors allowed the artificial design of
quantum confinement of only a few electrons [1, 8, 9]. This type of
finite fermion structure has many similarities with atoms; however,
they are artificial in structure, design, and development in the
laboratory. The properties of QDs can be altered in a precise way by
electrostatic gates, modifications in the dot geometry, induction of
magnetic fields, etc. Their technological understanding provided the
opportunity for quantum effects in a finite low-dimensional system
that was generally unexplored. If the particle size of a semiconductor
is below the Bohr radius of both the holes and electrons, strong
quantum confinement or quantum effect will occur. The quantum
Introduction 31
confinement will lead to the breaking of continuous energy levels

into discrete energy levels. The bandgap and the spacing between
these energy levels increase with a decrease in the particle size of
the semiconductor. Thus, the optical absorption peak shifts toward
higher energies as the particle size decreases [10]. Figure 2.1a shows
a schematic presentation of energy bands of a bulk semiconductor
showing the continuity of conduction and valence bands separated
by a bandgap, Eg. For QDs, the continuity of energy bands is broken
into discrete atom-like energy levels whose energy is determined by
the size of the quantum dot [11].
Figure 2.1 (a) Energy bands of bulk semiconductor (Eg) and for a quantum dot
(QD) [11], (b) visual images of samples excited by a broadband UV lamp, and (c)
UV-visible absorption (black) and PL emission (red) spectra (excitation at 350
nm) of CdSe quantum dots with different sizes [12]. Reproduced from Refs. [11]
and [12] with permission from the Royal Society of Chemistry.
In recent developments, some QDs have attracted immense

attention from researchers. Carbon QDs are one of them, which have
inspired many studies for their potential technological applications.
Some other types of QDs are known as III–V and II–VI semiconductors.
The III–V semiconductors are compounds of the III and V groups
of elements in the periodic table. One best-known example of this
category of semiconductors is gallium arsenide (GaAs) used as
an amplification medium in lasers. The II–VI semiconductors are
compounds of elements that belong to groups II and V of the periodic
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I have got Jack’s horse on board in the Westmorland with my
horses, and, as he will have thus two horses at Lisbon, think he is
very right in taking out his groom with him. Adieu.
Hd. Qrs., St Olaia, June 20, 1811.

My Dear Father,
... I am very much obliged to Arbuthnot and to you for your trouble
about my promotion, which, I suppose, is by this settled. I think your
letter to Torrens a very proper one, and I myself wrote to him by last
packet and to M’Mahon, which I thought right, and really felt a strong
inclination to do, expressing my gratitude for all his and Mrs
M’Mahon’s kindness, which has been uniform and most obliging, but
we must not press any business there for the present, though after
all, what I have got, I must have had without any interest, except
Beresford’s.
The Marshal is, I am happy to observe, somewhat better, though
he will require some time of quiet of body and mind to put him quite
right again, and I really hope, if Marshal Soult leaves us alone for the
present, as I think most likely, that the Marshal will go to Lisbon for a
month or six weeks, and try sea-bathing and a change of air. But till
the intentions of the enemy can be positively ascertained, I know he
will not be persuaded to move to the rear.
This movement of the army to the rear will, I hope, satisfy our
newsmongers as to the propriety of raising the siege of Badajos. It
was about just in time, or we should have had to fight a battle,
perhaps against a very superior force, and under every
disadvantage. It would have been a good thing to have taken the
place, but we had a very limited period to do it in, much too much so
for an attack en rêgle. It was worth attempting, and our failing only
proves that the place required a more regular attack, for which it is
evident we had lost time. It is now free again, and our Army has
retired, leaving Elvas to its right, and now occupies this place,
Campo Mayor, towards Portalegre, and Hill’s and Cole’s Divisions
and the heavy Cavalry the woods round Torre de Mouro, about 4
miles, half-way between this and Campo Mayor, in which is the 1st
Dns. and some P. Cavalry, and the 11th Lt. Dns. and 12 Hussars are
at Elvas and near it, and give that outpost duty.
We dined yesterday with Ld. Wellington at St Vincente, about ½-
way (5 miles) between this and Elvas, where he has a very pretty
Quinta, and after dinner we rode to the Camp (4 miles) and Torre de
Mouro, and nearly to Campo Mayor, to look over the positions (4
more), and we had then 8 to ride back to this, which is not a bad
afternoon’s ride, and it was very late when we got here. This is a little
town, and we are pretty well off, notwithstanding its being a good
deal crowded with 13th Lt. Dns. and General Castanhos’ Hd. Qrs.,
who has now no army. He is a good-natured well-meaning man, but
not remarkable either for talent or judgement. I do not think the
enemy will advance immediately, though greatly superior to us in
number. They must be as anxious as we can be to rest and refit, and
can hardly have recovered their defeat at Albuera, though in
numbers increased by the junction of Marmont and Drouet with their
Corps, and he must first besiege and take Elvas, which, (though I
have no very high opinion of either its Governor, or the principal part
of its garrison, and know it to have very weak points,) would I hope
at all events delay him some weeks....
The Portuguese Government are wretchedly off for money.
Nothing whatever is paid for. The Officers have not had a farthing for
four months, and when I sent for my pay, the answer was não ha
dinheiro. Things cannot long go on so, and I fear all the Marshal’s
exertions hitherto will have been to no avail, and the country go
completely to ruin in spite of him and all his zeal and activity, unless
some remedy is applied to the horrid mismanagement and almost
torpid want of energy in the Government. We want for everything,
and have not the means, or are we likely that I can see to have
them, for the most trifling occurrences. I feel for the Marshal, to
whom these disgusts are, I am sure, a great cause of his illness.
No event has given me individually greater pleasure, or will be
received by the army in general with more satisfaction than the
appointment of the Duke of York, who, notwithstanding the malice of
his enemies, and the mischievous revolutionary exertions of a set of
low-bred soi-disant reformers, was a most excellent Commr. in Chief,
and certainly brought the Army to a point of discipline and systematic
order that claims from it its utmost gratitude. As to his private amours
they are nothing to us, and most indecently brought forward by that
set, who perhaps the least ought to have agitated it, from motives
most unwarrantable, as we all know. Pray remember me most kindly
to General Ferguson and Farrer, and to Ross, Campbell, my friend
John Brown, of whom I rejoice to hear such good accounts, and to
his brother. With kindest love to all, etc., etc. Ever, my dear Father,
etc.,
Wm. W.
We have a report of a brilliant victory by Sir C. Cotton in the
Mediterranean against 9 sail and 2 frigates of the enemy with 10,000
men for Catalonia from Toulon, but it requires confirmation. Don Josè
desires to be remembered to you. Pray make my best respects to his
Excellency the Ambassador.
I hear from dear Jacko that he is quite well, amusing himself very
pleasantly. The Marshal desires to be most kindly remembered to
you; pray do also say the same from me to his brother.
St Olaia, June 27, 1811.

My Dearest, Kind Father,
Though I have little to add to what I wrote to you, and my letters to
dear Emily and my Uncle William contain all the no news I have to
send, I will not delay thanking you for yours of the 5th and 8th and
for the newspapers.... We have been kept very alert lately by a
reconnaissance Marshal Soult made on the 22nd on Campo Mayor,
with 14 Squadrons, pushing at the same time 1000 Cavalry and as
many Infantry close up to Elvas. He saw nothing, but I am sorry to
say we lost upwards of 100 men and horses, which is a very serious
loss to us at present, mostly of the 10th and 2nd German Hussars. It
is attributed to some mismanagement in posting our Pickets (which I
thought very apparent), and by no means the fault of the Officers
commanding them. Poor Lutyens while retiring from a party which
had crossed the Guadiana in his rear, most unfortunately mistook a
French body of Cavalry for his own reserve, and did not find out his
mistake till too late. He then, however, very gallantly attempted to
fight his way through them, but was at last overpowered, losing 5 or
7 killed and 20 wounded, and the remainder of 40 taken with himself
and another Officer. One Officer escaped wounded. We have not
since seen anything of the enemy, and it is my opinion that they will
not at present attack us, as some think, though it is very difficult to
say what those fellows may risk, they are so presumptuous and
insolent, though Albuera and the other beatings they have received,
must have at least given them prudence and a better opinion of us,
and I am unwilling to believe that, now that Badajos is relieved, and
he can have no immediate object to gain, he will risk an action which
if unsuccessful to him must have the most disastrous consequences,
and perhaps decide the fate of the Peninsula, if he should have a
war to divide his attention to the North. It is the largest army they
have in Spain, and all they can collect from all parts of the South.
It would appear to me the height of rashness to venture it at one
cast against troops which have just beaten the two Corps of which it
is composed, and without any positive advantage to gain, for they
cannot yet be in a state to advance far into Portugal. I am well aware
of the consequences which would attend a defeat of us, against their
superior Cavalry and numbers, but I feel so confident that this is
scarce possible from the state and high spirits of our brave troops,
that I have not the least uneasiness about it, and I also am much
pleased with our position, which, I think, though not strong by nature,
will enable us to bring all our troops into play in the manner best
suited to them, and for the use of the bayonet, which in the hands of
a British soldier is always decisive. Nor are our brave Portuguese by
any means unaware of its utility or backward in applying it with full
vigour. The whole army are in the best spirits and most willing to give
these boasting miscreants another dressing before we go into
quarters, which are, however, very necessary.
I think, when it is decided that the enemy do not mean to attack
us, and that they retire from before us, that the Marshal will go to
Lisbon, which I shall be most glad of for his sake, as I think he
requires rest both of body and mind, though, thank God, he is much
better than when I first arrived. I quite agree with all you say in his
praise. He has indeed deserved all that can be said, and it has been
truly gratifying to read the manner in which the thanks of the House
were voted to him. He is of course much pleased and flattered by the
approbation of his country, but he is as modest and diffident of what
concerns himself as he is brave and clever in the field. We are on
the very best terms, and I am as happy as I can be, notwithstanding
the heat and turning out at 3 a.m. and then riding all day. We sleep
the better for it, and in this respect I am in great luxury, as I have a
little camp bed of Count D’Alva’s, with sheets, etc., etc., which I like
so well, and so much better than my cloak and bearskin, since he
went away, that I intend to buy a camp bed at Lisbon and always
carry one in future.
Pray have my newspaper, The Day, sent regularly every day; it is
a great comfort, and besides enables me to oblige a great many
people. Though I sincerely rejoice when anything can be done for my
cousins at Rugby, I am extremely sorry that anything should have
been asked of Lord Mulgrave, however obligingly granted. I have
good reasons for being decidedly against any application whatever
being made to him on any account, and do intreat you that you will
never allow any; not knowing him, you can have no idea what harm it
does, though a very worthy old man, and though we should call and
shew him every respect which is his due. I did wish to be under no
obligation, and am much vexed that anything should have been
asked. It was my intention to have tried by another channel, to have
had the boy admitted, but would not have consented to this. It is,
however, now too late, and he has behaved very kindly, but for the
future pray never think of such a thing....
[MS. torn, part wanting.]
... it must have handsome round Staff “tawsels” and ribbons at the
sides, but must not be gold laced, as the new regulation is, Deos nos
livre. I suppose our good chiefs do not think our Generals or Staff get
killed off fast enough that they order them cocked hats with gold
binding. It must only be meant for Wimbledon. There are no
Voltigeurs there, and a gold laced cocked hat, though very ugly, is a
very harmless thing—not here.
Extract from Letters to his Sisters.

July 1, St. Olaia.
We move to-morrow to Lisbon for a few weeks, which I am not
sorry for, as the French are not likely to disturb us, and this place is
horribly dull unless we had something to do.
I daresay the whole army will go into Quarters during the hottest
months....
We are here four in a very small quarter, and not a pane of glass
in the whole house, or a wooden floor, which we should not mind at
all, if there was anything going on or likely, but the French are as
glad, and as likely to be quiet, as we are for the present....
I see I am gazetted as Major at last, and the Marshal has
recommended me for the Portuguese Lt.-Colonelcy, as I am nearly
the eldest Major in their Army, and several have gone over my head,
to whom I am to be antedated.
Lisbon, July 5, 1811.

I am quite well after my very tiresome journey with the Hd. Qrs.
baggage, for the Marshal has been here these two days and left me
to bring the Hd. Qrs. Staff. A pretty set to be bear leader to indeed!
Lisbon, August 2nd, 1811.

My Dearest Father,
... Nothing can give us greater pleasure than to see you in this
country, and I assure you the Marshal will also be very happy to see
you, and I think your presence may be useful in the north at Porto. I
think this country for the present quite safe, and if Russia declares
against France, or even continues her threatening posture, so as to
occupy a large portion of his force in the north of Germany, things
have never looked better in the Peninsula. If not, it is quite
impossible to foretell the events of a Campaign, or what may happen
from one moment to another, particularly if the Spaniards persist in
not doing anything. It is a curious perverseness their dislike to a
foreign command, particularly where they confess they want it, in
their armies, and their pride and vain-glory, which one would
naturally expect would be the stimulus to anything, in order to avoid
subjugation, will probably be the real causes, with the ignorance and
treason of their gentry, of their ultimate fall.
As to a battle immediately I do not see the least chance of it. I
think the army will shortly make some movement, but as yet I know
nothing about it. I pay no attention, and wish you would not, to the
nonsense of our wise politicians of London, who speculate mostly,
either from very bad information, or as best suits their views.
As to your informant about Ld. Wn. starving the South as well as
the North of Portugal, I confess the speech savours as much of
roguery as of ignorance, and I should have a very poor opinion of
any Englishman who could make such an observation, unless he
wishes purposely to discourage the people from continuing this
glorious struggle for everything that is dear to man. He shews
himself as ignorant of the country as of the means it offers for
defence, and of the enemy’s decided superiority in numbers, which
can only be overcome by drawing him away from his resources, and
weakening him before we can strike.
In the action of Mina near Vittoria the French were completely
beaten by his guerilla, which for that sort of corps is more organised
than usual, and consists of 4 Bns. and a Regt. of Cavalry, from 4 to
5000 men. They make a good partisan corps, but have neither
solidity nor system enough to be much better than a rather more
disciplined and subordinate mob, as yet.
The Galicians and Asturians, like the other parts of Spain, I do not
think likely to do much at present. Their Government gives them no
encouragement, and but little hope of any effectual support, and
they, poor devils, have felt how inadequate they are alone to resist
regular troops.
The fall of Tarragona was a serious disaster, though expected, and
may have a bad moral effect upon the mind of the populace, besides
giving a handle to the ill disposed, which order of people I cannot say
have increased in Spain, though I fear the indifferents, who are
nearly as bad, certainly have. At the same time I have not a doubt
that, where the people are not kept under by force, was there any
fair prospect of success, or any disaster to happen to the French, the
whole would rise against their oppressors, whom they detest—at
least, I think, the whole of the lower orders.
I am much obliged to you for the papers with the vote of thanks
from the City to the Marshal. They were never better bestowed. He
had never heard of them before. I am very glad Le Marchant is
coming out, as I think it is what he wished, and I have no doubt that
with his extensive theoretical knowledge, and the practice he
formerly had, he will be a great acquisition to our Army. I hope my
friend Johnstone will get leave to come out with him.
I have heard of no disagreement amongst our Generals, or that
the Marshal ever had any idea of going home. We are for the
present very quietly settled, and most comfortably, at that lovely
place Cintra, where we are likely to remain till some general
movement takes place, and something to be done. The air agrees
extremely well with the Marshal, who is very well. I never was so well
for many years. It is very remarkable that the climate of Cintra is as
different from Lisbon as London is. We have not had a day of heat,
while here they have suffered very much. The fog morning and
evening keeps us, with the number of trees, constantly cool. The
rash I had continues, and has increased, but the Doctors tell me it is
rather beneficial than otherwise, and desire me to do nothing to it. It
gives me no inconvenience. They call it “Morphen,” and most
certainly, notwithstanding, my general health never was better. I
came in yesterday on business and return to-morrow. The Marshal
also. He is at Caxias, nr. St Julians, at the Admiral’s.... I have just
heard that a Packet is coming in with a mail in 4 days from Falmouth,
but have not heard that the bag is landed....
Wm. W.
Cintra, August 17, 1811.

My Dear Father,
I have not written to you by the last Packet, as I wrote to some of
the family, and had really nothing in particular to communicate. We
have been for the last four or five days in Lisbon, as the Marshal had
a good deal to arrange with the Government, who, as usual with the
people in power in this country, are the more impracticable in
proportion as the danger is removed; and foresight or a liberal policy
is not to be expected from people who cannot carry their views
beyond the present moment, and though quite impotent in affairs of
State, and as ignorant as obstinate, are extremely jealous of the
power entrusted to them. Scarce a plan or arrangement, even
military, is proposed by the military chiefs, but becomes a subject of
discussion, and if not rejected, mostly so delayed that the object is
either lost, or rendered far less effective. It is most disgusting, and if
they do not alter, it is quite impossible but the army must go to
pieces in spite of even the exertions and firmness of the Marshal.
The Brother[25] to your friend is the worst. Nothing can exceed his
vanity and self-sufficiency except his ignorance.[26]
The Marshal is quite well. The coolness and fine air of this
beautiful spot agrees wonderfully with him, and, if we remain a week,
or a fortnight longer, I think he will have acquired so much bracing
and strength, that he will be fully equal to a campaign, and after next
month the heat is not very oppressive.
Lord W. has invested Ciudad Rodrigo with his cavalry and light
troops, but not quite closely. I hope we shall be more successful in
this siege than our last, and have acquired a little more experience.
The accounts we have of the number and state of the garrison are
very favourable to us, and you know I have not a very great opinion
of the strength of the place, but we have but very little experience in
this sort of warfare. Hd. Qrs. are, I believe, at Fuentes Guinaldo. I
hope the Marshal will have arranged his business and move up in
time, as I do not expect we shall break ground for this some time.
Jack is returned from his tour, with which he is much pleased,
though it does not seem to have increased his military zeal. He saw
some Divisions on the march, which has given him some idea of the
miseries of even a summer campaign, and of the fatigue and
inconvenience to which Regt. Officers and men are exposed. What
would he think of one in winter? I think it will do him a great deal of
good. I wish a great many more of our English country gentlemen
could see a little of real warfare, which they affect to discuss so
freely. Jack is quite well, and both Lord Balgonie and he were, I
believe, heartily glad to get back to Lisbon again. They had not time
to get used to fleas, mosquitoes, and no beds.
I am extremely anxious to hear when you determine upon coming
to this country, though I fear it will not be before we leave this and
Lisbon, as I was in great hopes you might have contrived. If you are
to come, I think it is a pity you should put it off till much later in the
year. But pray let me know, and what you wish me to do. Such as
they are, I hope you will take my rooms at Cathariz, which I will have
prepared for you, though I am afraid that, if we are out of town, a
large empty house is not the most pleasant abode. I can make no
arrangement for you till I know whether and when you come. It will
be most provoking if we should have marched to the army, and
therefore pray do not delay longer than indispensable....
The Marshal has sent the Brigadier Lemos his military secretary to
the Rio de Janeiro on business. He will return almost immediately.
As I think it not unlikely the Prince may send some honours by him to
his officers, it may be a good opportunity to get Dr Ds.[27] to write
directly to the Count de Linhares[28] about the Commandos. As to
the other business we spoke of, from what I hear and know of things
in this country the idea gives me far more pain than pleasure, and I
hope it may never take place. You must be careful that Dr Ds. has
not a hint of my extreme dislike to his brothers and their ministry.
Yrs., etc.,
Wm. Warre.
[25] Principal Sousa.

[26] See Oman, iii., 193 ff. and 415 ff.
[27] Domingos Antonio de Sousa Contentro, afterwards Conde
de Funchal.
[28] The eldest of the Brothers Sousa, Prime Minister at Rio
Janeiro.
Cintra, August 23, 1811.

My Dear Father,
... I hope you will not delay your departure for this country till much
later in the year, and expect by next Packet some further information
of your intentions on the subject. I should doubt your finding us here
at all events, as I think it very likely we shall join the army again early
next month, when the siege of Ciudad Rodrigo will be going on. At
present our troops are all around it at a distance, in cantonments,
quite quiet, though the place is invested, and for the present the
enemy do not show any intention of disturbing us; at least, I have
heard of no movement on their part that indicates it. But I cannot
think they will quietly allow us to take the place. It is to them well
worth risking a battle for, if they intend ever to enter Portugal again. I
cannot even guess whether Ld. Wn. will think it worth his while. At
this distance I have but general and very imperfect information of the
army, and it is dangerous to venture upon conjectures on such a
subject.
The Spaniards continue to do nothing, at least on a great scale,
and my hopes of any great effort on their part gradually diminish as
the accounts arrive of reinforcements entering from France, though it
is true in very inconsiderable numbers. We cannot make out that
they yet exceed 9 to 12,000 men, which is nothing for the Peninsula.
I look to Russia with some anxiety, as much must depend upon her
conduct in our future operations. Your opinion, I am sorry to observe,
is not favourable, though I think it evident there is some great
misunderstanding or resistance to the Tyrant’s will on the part of that
Emperor, and, from the nature of the man, I should suppose he will
not allow him to oppose him long with impunity. In the disordered
state in which we understand the Russian finance to be, it is perhaps
better, till she can make peace with the Turk, that she should hold
her doubtful posture.
I am surprised you have not received a letter I sent you with the
Gazette containing my Portuguese promotion. For the present, at
least, I am Lt.-Colonel. Except the rank, I have not one advantage
pecuniary or otherwise by my Brevet Majority, but I keep my Staff
situation, and unless I should get an effective majority of Cavalry, it is
as good a situation as I can have, and I have not the least inclination
to quit that service.
I am vexed that I have been able to get nothing done for Casey,
who is well deserving his promotion. I have written several times to
Brown, but have no answer, and I know, from my own situation, how
very unpleasant it is to be importuned upon these subjects. Perhaps
Greenwood could do something for him. The purchase money is, I
believe, in Tom’s hands.
We have yet no account of the honours conferred by the P. R. of P.
on the Marshals, and at any rate I do not think them equal to their
deserts, and, unless their Pensions are better paid than usual in
these cases, they will not be much the richer for them.
I am glad that you have met the Douglas family. There cannot be a
finer fellow or better Officer than he is, and more universally
respected and beloved. He is a very great friend of mine. I saw him
just before we left St Olaia. He was quite well. General Houston is
gone home unwell. Campbell arrived the day before yesterday, and
writes that he is quite well.
We are in daily expectation of accounts of the poor King’s death,
but while I believe every one must regret the loss of such a
Sovereign and such a man, considering his sufferings and the
present state of the nation, I hardly think it can be a subject of great
sorrow to lose him, however much we loved and respected the royal
and excellent qualities of such a King.
Your accounts of the internal politics of the country are extremely
interesting, but with you I think it is quite impossible to guess the
Prince Regent’s intentions, or what his conduct may be after the
King’s death, and we all naturally look with great anxiety to the first
steps of his reign as a criterion to judge of what we are to expect....
Campbell is this moment arrived. I never saw him looking better.
He was detained 5 weeks at Portsmouth and nearly a month on his
passage.... Jack is also here quite well after his trip to Castello
Branco, where he saw some Divisions marching, and the sight of
their hardships, even in a peaceable move distant from the enemy,
has not increased his military zeal. It does these English amateurs a
vast deal of good to see a little how things are carried on, and what
soldiers go through on service, though I think it quite folly for any
person, whose duty does not demand it of him, to expose himself as
many have, and been laughed at. For after all they but prove what
nobody doubted, that they are not afraid of their flesh....
We continue to spend our time very pleasantly. The Marshal has a
slight cold and lumbago, which will, I hope, soon pass away. He is
otherwise very well....
Aug. 24—The Marshal is much better to-day. He desires to be
most kindly remembered to you. We have nothing new. The Duke of
Leinster, Lords Clare and Delaware, are arrived in Lisbon, and going
up to the army. Yrs., etc.,
Wm. Warre.
The Marshal is Count of Francozo, and Lord W. of Vimiero, but
they have not yet the Regent’s permission to accept the titles—
which, being compared with Silveira, are not at all flattering to any
person but him, and completely marred the P. Regent of P.’s
intention of obliging them, for though nobody will deny Silveira
considerable merit, it is folly to rank him with the other two. Nor has
he ever done anything to deserve such a rank. Poor Baçelar, who
commands him, was at least entitled to H. R. H. notice.
Cintra, Sept. 7, 1811.

My Dear Father,
I am much disappointed at not hearing from any of you the last two
packets, though from my not having any letter at all, I must think it is
owing to some mistake either at the Horse Guards, or at the Army
Post Office, Lisbon.... I hope this will find you preparing to give me
the pleasure of seeing you in this country, as I should be extremely
sorry, if you intend to come at all, that you should delay it till much
later in the year, and I had hoped you might come while we remain at
this place or at Lisbon. The Marshal does not yet talk of moving, but I
should guess we shall not remain longer than this month, as the
business that called him to the Capital appears now to be nearly
concluded.
We continue to amuse ourselves very well, and certainly if we are
to be quiet, could not be in pleasanter or better quarters. Jack is with
us and very well, and, whenever the time comes, I shall part with him
with great regret. I have met few better hearted or more sensible
fellows, and he has made himself much liked and esteemed by the
whole of our Staff.
I do not think the siege of Ciudad Rodrigo is now likely to take
place. The supineness of our Spanish neighbours would enable the
enemy to collect a force much superior to us for its relief, without any
risk to themselves, and Ld. Wn. would fight to a very great
disadvantage encumbered with the stores and train necessary for a
siege; and, in case of disaster, the loss of them would be serious
indeed. In the present demolished state of Almeida, that place could
be of no assistance to him. Were it otherwise, the siege might be
undertaken, as in case of their advancing in force to relieve it, he
could in a few hours place it (the train) in comparative safety, and in
case of a defeat, it would enable him to cover his retreat, and get
some part of it away. At present Almeida is rather a weight than
otherwise to us.
Marmont has moved up part of his Corps through the Puerto de
Baños, but I do not know that he has advanced himself, though it is
not improbable he may draw near our cantonments to observe Ld.
W.’s motions. He is not strong enough to prevent his Lordship from
undertaking the siege, if he wished it, but I rather suspect that the
Corps which was collecting at Benevente, whatever its previous
destination might have been, will also move to that quarter, in
consequence of the advance of the allied army, and perhaps join
with him, for I can never suppose that the enemy will allow us to take
that town, which is of such importance to them, if they ever intend to
enter Portugal again, and which I cannot doubt they will; and, for
many reasons, notwithstanding the happiness it would be to me to
see you, I should recommend, unless your plans are fixed, and that
you can come immediately, or that your presence is quite necessary,
that you would delay it till the spring, for I think this winter will decide
much as to the fate of the Peninsula, which, (this is quite entre nous)
I fear, if great reinforcements arrive, and that Napoleon’s attention is
not otherwise diverted, the unaccountable folly of the Spanish
Government, and the consequent apathy and acquiescence of the
people, has again placed in the balance; and it appears probable we
shall have another active winter in this country again.
The Spanish Government have received, I hear, within the last
twelvemonths 18 millions of Dollars, of which latterly 5 millions; and,
notwithstanding, I do not hear that their rabble, called an army, is a
bit better provided, or that any effectual step has been taken to
organise them, or oppose more effectual resistance to their invaders.
It is truly lamentable. It appears that Blake has been defeated at
Grenada, and I believe it. It was to be expected, and will always
happen where he commands, for I do not believe there was ever a
worse General; and these defeats completely destroy even the slight
remains of confidence the naturally brave Spaniards had left. They
will soon not fight at all, and I am sure it is not to be wondered at....
Genl. Le Marchant has been here for a day or two, and has been
quite delighted with the beauty of the place. He is quite well. We
have had the Duke of Leinster and Lords Clare and Delaware and
Mr Fitzgerald, who left us this morning. They are remarkably
unaffected fine young men, and an excellent sample of our young
Fidalgos. Ever yrs., etc.,
Wm. Warre.
Lisbon, 17th Oct. 1811.

My Dearest Father,
... I am extremely anxious for the arrival of another Packet, which
is due, to be able to form some idea of when I may expect you in this
country, as I find you still continue your intention of giving us the
happiness of a visit.
Things are now quiet on the frontier, and I think may continue so
for some time longer. Indeed I should not suppose anything will be
now seriously undertaken by the Enemy till the spring. I therefore
think the sooner you can come the better, and I certainly would not
wait till the season is much further advanced, as what you say about
the Wine Company is true, and nobody feels the tyranny and
oppression of this monopolizing Body more than the inhabitants of
this country themselves, you know. But with regard to the fulfilment
of treaties with the English, no nation seems to think that necessary,
and we are consequently always laughed at. John Bull is a noble
beast, and has more good qualities than any other animal in the
world, but en fait de politique he is generally a great gull. Witness
Sicily, Portugal, Spain, Prussia, Russia, etc., etc., etc., etc. But, as I
should not suppose your presence in London necessary to forward
its execution, I think it would be a great advantage for you to be here
on the spot, and make your own arrangements, which so many
others are doing before you. The name alone in the country would
have weight, but it must not be allowed to be forgotten if you resolve
ever to resume the business, as people will seek other channels for
their business, and not be able to disengage themselves for you,
even if they wished it. But, as you know all this much better than I
do, I hope next mail to hear your decision on the subject.
The Marshal, poor fellow, has been very unwell, and that has
delayed us much longer here than we expected. We left the Prayas
4 days ago, as the air very much disagreed with him, and are at our
old Head Quarters. He is more comfortable in his own house than
anywhere else, and he requires in his present state every
indulgence. I have been very anxious indeed about him, but he is
now, thank God, much better, though still very weak, and it is
therefore uncertain when we may be able to move as there is
nothing likely to be doing for the present, and I am very anxious
about it, as I think he is as well here as anywhere. His complaint is a
low fever and great debility, which has been hanging about him for
some months, and which, though it sometimes leaves him for a few
days, has never given him time to gain strength; and his constant
employment and hard work of mind and body have also greatly
retarded his getting well. I should much fear we shall be gone before
your arrival notwithstanding, which I shall regret extremely, as it
would have been a great comfort and happiness to have seen you
while we are quietly settled.
With regard to the honours to Officers I can tell you that Forjas[29]
had nothing whatever to do with the List, or could he send any in
without an order from the Regency, who are alone to blame. Much
has been said upon the subject, and it seems very extraordinary that
they should ever have thought of conferring Military Honours, without
reference to the Commander in Chief of their army, who most
certainly is the best judge of who deserves them. But these, like
most other things in this country, are ruled by meanness, jealousy,
and intrigue, nor can we expect any good and energetical measures
while the Principal and Patriarch, ignorant, bigoted, and
presumptuous, and mean enough to have recourse to any dirtiness
to attain their ends, are in the Regency, and Count Linhares in the
Ministry, for he backs his ignorant meddling brother through
everything, even in spite of the opinions of the other members.
Forjas is often blamed, and most undeservedly so. I do believe him
to be a very honorable and well-intentioned man, and certainly a
man of good abilities, and no intrigue and meanness has been
neglected to ruin him in Brazil. The P—h hates him, and would
willingly, if he dare, replace him by any of his creatures, whom he
tries to force into every situation. Quite entre nous there never was a
more mischievous little animal, or a more treacherous one. And pray
be very careful in any opinions you give to Dn.—Ds. that he may
suppose from me. He is of the same party and may do a great deal
of harm. For they at present rather suppose I never trouble my head
about them.
As to my own Honours, I shall be proud of any military ones, when
they come, if conformable to my rank. But I put no trust in promises,
and quite think with you that your friend knows nothing of the matter.
But his strong recommendation to that quarter must have
considerable weight. I feel an unconquerable aversion to soliciting
any honours, and would not for the world appear to have given any
opinion on the subject.
With regard to the representation he made of the poverty of this
Government, I do not believe it to the extent he says, though they
are certainly distrest, and must be, while there is so much
mismanagement, and so many useless hangers-on to be satisfied.
As to a Loan, I quite agree with you, that they must be honest, or,
what is not an easy undertaking at present, they must persuade the
lenders that they are honest, in their intentions at least.
I should be glad to hear that the Princess Charlotta really again
got into power. She is at least energetical, and the changes you fear
are most desirable from their consequent changes here.
We have no news from the army except an account of Don Julian
Sanchez and his guerrilla having taken the General, Governor of
Ciudad Rodrigo, Regnioux, while taking his promenade outside the
town, and most of the cattle belonging to the garrison. I do not know
the particulars, but it appears to have been a neat business enough.
We all miss dear Jack very much....
Remember me to General Leith, should you see him. I have a
great regard for him. He is generally much esteemed. I am not likely
to see Douglas for some time. When I do I will give him your
message. Hardinge desires me to thank you most kindly for
undertaking his commission of seals. Yrs., etc.,
Wm. Warre.
[29] General Miguel Forjaz. See Oman, iii., 418.
Lisbon, Nov. 23rd, 1811.

My Dearest Father,
After a very long delay I was at length made very happy by your
most kind letter from Cowes....
I quite agree with you about the infamous Wine Company at Porto,
but I think that it cannot stand long, even supposing we are such
dupes as to allow the P. Government to infringe so directly on the
Treaty. It is a grievous oppression on the farmer, and so generally
disliked, that I much doubt, when the terror of French dominion is
removed, they will submit either to this or many other oppressions. O
Povo esta mto. desabusado, e seria mto. melhor conceder ehe
algums destes privilegios, que em nada contribuem para o bem do
estado, mas mto. para o bem de hums poucos de individuos, ò
menos penso que o que contribue não sofre o odio de huma tão
sega politica.[30]
I therefore hope to have the happiness of giving you an abraço
early in the spring, and am not sorry you did not come out at this
advanced period of the year, when you would have found very great
difficulty in travelling in a country desolate and almost depopulated,
in bad weather, and as I could not foresee that our excellent Marshal
would fall ill again, I had given up all hopes of meeting you in Lisbon,
at all events. We were to have moved to-day, but H. E. has been
very unwell, and though now, thank God, much better, our departure
cannot take place till the beginning of next month. He has great
confidence in the good effects of a change of air and travelling. I
confess I rather dread the effects of any fatigue or cold for him after
what happened lately, when a not very long ride quite threw him
back. If good wishes, not only from his own family, but from all ranks
of the people could avail, he would have been long since well, and it
is, and must at all events be, a pleasant reflection to him in illness to
see how universally he is regretted, and the fears his illness has
raised amongst almost the whole nation.
I have not a word of public news to send you. The Prince
d’Aremberg, Colonel of the 27th Chasseurs à Cheval, and married to
the Empress Josephine’s niece, is arrived here, and 1400 prisoners
taken at Arroio del Molino by Hill. He is an insignificant looking
creature, and not reckoned a great Officer. Genl. Bron is not yet
arrived. I have dined with the Lt.-Col. of their 40th Regt. He is a fine
intelligent young man, but quite a Frenchman. He lies without the
least hesitation. He half cries at times at his misfortune, but, when he
has drank a little wine, sings and dances, and seems to forget
entirely that he is a Prisoner. I am going this morning to take the Lt.-
Col. of 34th F.A. to make some purchases he wants, and then to
dine at Hardinge’s. I think him steadier a good deal than the other,
who is a most amusing companion, and less of a soldier. This man is
reserved, but I know what he says is true, and therefore we intend to
try what the bon vin de Bordeaux will do towards opening his heart,
[31] for we often get very interesting information in this way, and,
though I hate and despise the fellows, I am rather amused by them
now and then.
I think we are likely to remain quiet at Villa Formosa beyond the
Coa, where we fix our Hd. Qrs. It was entirely destroyed by the
French, but we have had doors and window-shutters put to some of
the Houses. But I expect we shall passar m’tos. frios, and I dread it
for the Marshal. I do not think the French will make any movement till
Ciudad Rodrigo is again distressed for provisions, and then they will

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Science and Applications of

Nanoparticles Wagar Ahmed

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Resolved Airy disks Rayleigh Limit Unresolved Airy disks

Lateral view Numerical Aperture Airy disk size Resolution

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EMCCO PMT EMCCO

Dichroic Light source Dichroic Laser Objective lens

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Image N Final image Image N Final image

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(b) 84 -10 1.4