Table Of ContentNanoscopy and
N anospectroscopy
This book builds a narrative on the near- field optical and spectroscopic studies with an emphasis
on p lasmonic- and p hotonic- assisted nano- optics as a tool for superlensing. Deliberations on n ear-
field studies using confined light in various applications are included along with their commercial
implications. Single- molecule detection utilizing efficient s urface- enhanced Raman scattering phe-
nomenon in the far- field and plasmonic t ip- enhanced Raman scattering studies in the near- field
measurements for fast analysis up to trace level is discussed.
Features:
• Covers the broad area of nano-o ptical spectroscopy from the perspective of putting the
concepts and innovations in the field to use.
• Discusses entire spectra of near- field optics and spectroscopy using light.
• Explores gas/ chemical sensing using surface plasmon resonance ( SPR) in the Kretschmann
configuration.
• Includes dielectric nano- photonics and optical confinement.
• Studies phonon behaviour using confined light for the analysis of chemical, biological, and
other materials.
This book is aimed at graduate students and researchers in material science, analytical chemistry,
nanotechnology, and electrical engineering.
Nanoscopy and
N anospectroscopy
Edited by
Sandip Dhara, Deep Jariwala, and Soumen Das
Designed cover image: © Shutterstock; Sandip Dhara, Deep Jariwala, and Soumen Das
First edition published 2023
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© 2023 selection and editorial matter, Sandip Dhara, Deep Jariwala, and Soumen Das; individual chapters, the
contributors.
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ISBN: 9781032163888 ( hbk)
ISBN: 9781032163895 ( pbk)
ISBN: 9781003248323 ( ebk)
DOI: 10.1201/9 781003248323
Typeset in Times
by codeMantra
Contents
Editors ..............................................................................................................................................vii
Contributors ......................................................................................................................................ix
Preface...............................................................................................................................................xi
Chapter 1 Theory of Light Scattering and Applications ...............................................................1
T. R. Ravindran and Sandip Dhara
Chapter 2 Plasmonic and Optical Confinement ..........................................................................39
Binaya Kumar Sahu, Pratap K. Sahoo, and Sandip Dhara
Chapter 3 Dielectric and Metallodielectric Nanophotonics and Optical Confinement ..............51
Sushil Mujumdar, Rabisankar Samanta, and Sandip Mondal
Chapter 4 Optical Nanoscopy .....................................................................................................75
Kishore K. Madapu
Chapter 5 Far- Field Spectroscopy and Surface- Enhanced Raman Spectroscopy ( SERS) .........97
Debanjan Bhowmik and Chandrabhas Narayana
Chapter 6 Near- Field Nanospectroscopy and Tip- Enhanced Raman Spectroscopy ( TERS) ...131
Andrey Krayev, Jeremy F. Schultz, Nan Jiang, Sreetosh Goswami,
Agnès Tempez, Sharad Ambardar, Dmitri V. Voronine, Naresh Kumar,
Kaiyuan Yao, Shuai Zhang, Emanuil Yanev, Kathleen McCreary,
Hsun- Jen Chuang, Matthew R. Rosenberger, Thomas Darlington,
Berend T. Jonker, James C. Hone, D. N. Basov, P. James Schuck,
and Avinash Patsha
Chapter 7 Conclusions and Future Directions ..........................................................................253
Index ..............................................................................................................................................255
v
Editors
Prof. Dr. Sandip Dhara completed his Ph.D. on Magneto- optic Recording Materials from National
Physical Laboratory, New Delhi in 1994 and joined Indira Gandhi Centre for Atomic Research
( IGCAR), Kalpakkam in 1996. Presently he is the Head of the Surface and Sensors Studies Division,
Materials Science Group and a Professor in Homi Bhabha National Institute. He was also a visiting
Professor in the Institute of Atomic and Molecular Sciences, Academia Sinica, Taiwan. Dr. Dhara
has more than 300 research publications including several review articles, books, book chapters,
several conference presentations, etc. He has delivered more than 100 invited and plenary talks and
is the recipient of Homi Bhabha Gold Medal for 2019 and Department of Atomic Energy- Science
Research Council ( DAE- SRC) outstanding researcher award for 2012. He is also in the editorial
board of many national and international scientific journals. Dr. Dhara is specialized in studies of
light- matter interaction at the nanoscale in the sub- diffraction limit. He is a Fellow of Institute of
Physics ( FInstP) and a Fellow of the Royal Society of Chemistry ( FRSC). He is among World’s Top
2% Scientists in 2021.
Deep Jariwala is an Assistant Professor in the Department of Electrical and Systems Engineering
at the University of Pennsylvania ( Penn). His research interests broadly lie at the intersection of
new materials, surface science, and s olid- state devices for computing, sensing, o pto- electronics,
and e nergy- harvesting applications. Deep completed his undergraduate degree in Metallurgical
Engineering from the Indian Institute of Technology, Banaras Hindu University in 2010. He com-
pleted his Ph.D. in Materials Science and Engineering at Northwestern University in 2015. At
Northwestern, Deep made contributions to the study of charge transport and electronic applica-
tions of two- dimensional ( 2D) semiconductors and pioneering the study of g ate- tunable, mixed-
d imensional, and Van der Waals’ heterostructures. He was Resnick Prize Postdoctoral Fellow at
Caltech from 2015 to 2017 working on nanophotonic devices and ultrathin solar cells before joining
Penn in 2018. Deep’s research has earned him awards from multiple professional societies includ-
ing the Russell and Sigurd Varian Award and Paul H. Holloway Award of the American Vacuum
Society, the Richard L. Greene Dissertation Award of the American Physical Society, Johannes
and Julia Weertman Doctoral Fellowship, the Hilliard Award, the Army Research Office Young
Investigator Award, Nanomaterials Young Investigator Award, TMS Frontiers in Materials Award,
Intel Rising Star Award, IEEE Young Electrical Engineer of the Year Award, IEEE Photonics
Society Young Investigator Award, and IUPAP Early Career Scientist Prize in Semiconductors
in addition to being named in Forbes Magazine list of 30 scientists under 30 and is an invitee to
Frontiers of Engineering conference of the National Academy of Engineering as well as a recipi-
ent of the Sloan Fellowship. In addition, he has also received the S. Reid Warren Jr. award. He also
serves on the editorial board of the journals Electronics and Micromachines. He has published over
100 journal papers with more than 14,000 citations and 7 patents.
Dr. Soumen Das is a Scientific Officer at Indira Gandhi Centre for Atomic Research ( IGCAR),
Kalpakkam, Tamil Nadu, India. His research interests involve semiconductor, ferroelectric and
magnetic oxide thin films, high- temperature materials, protective coating, and nanostructures. At
present, he is a program leader in the Materials Chemistry and Metal Fuel Chemical Group, IGCAR,
looking after materials processing, qualification, and studying LASER- based surface phenomena.
vii
Contributors
Sharad Ambardar Naresh Kumar
Department of Medical Engineering, Department of Chemistry and Applied
University of South Florida, Tampa, Florida Biosciences, ETH Zurich, Zurich,
Switzerland
D. N. Basov
Department of Physics, Columbia University, Andrey Krayev
New York, New York Horiba Scientific, Novato, California
Debanjan Bhowmik Kishore K. Madapu
Ramanujan Faculty Scientist, Transdisciplinary Surface and NanoScience Division,
Biology, Rajiv Gandhi Centre for Materials Science Group, Indira
Biotechnology, Thiruvananthapuram, India Gandhi Centre for Atomic Research,
Kalpakkam, India
H sun-J en Chuang
Materials Science and Technology Division, Kathleen McCreary
Naval Research Laboratory, Washington, Materials Science & Technology Division,
District of Columbia and Naval Research Laboratory, Washington,
Nova Research, Inc., Washington, District of District of Columbia
Columbia
Sandip Mondal
Thomas Darlington Nano- Optics and Mesoscopic Optics
Department of Mechanical Engineering, Laboratory, Tata Institute of Fundamental
Columbia University, New York, New York Research, Mumbai, India
Sandip Dhara Sushil Mujumdar
Surface and Sensors Studies Division, Nano- Optics and Mesoscopic Optics
Materials Science Group, Indira Gandhi Laboratory, Tata Institute of
Centre for Atomic Research, A CI of Homi Fundamental Research,
Bhabha National Institute, Kalpakkam, Mumbai, India
India
Chandrabhas Narayana
Sreetosh Goswami Rajiv Gandhi Centre for Biotechnology,
National University of Singapore, Singapore Thiruvananthapuram, India. On
Deputation from Professor Chemistry and
James C. Hone Physics of Materials Unit,
Department of Mechanical Engineering, School of Advanced Materials,
Columbia University, New York, Jawaharlal Nehru Centre for
New York Nan Jiang Advanced Scientific Research, Bangalore,
Department of Chemistry, University of India
Illinois, Chicago, Illinois
Avinash Patsha
Berend T. Jonker Department of Materials Science and
Materials Science & Technology Division, Engineering, Tel Aviv University, Tel Aviv,
Naval Research Laboratory, Washington, Israel
District of Columbia
ix
x Contributors
T. R. Ravindran P. James Schuck
Condensed Matter Physics Division, Department of Mechanical Engineering,
Materials Science Group, Indira Columbia University, New York, New York
Gandhi Centre for Atomic Research, A
CI of Homi Bhabha National Institute, Jeremy F. Schultz
Kalpakkam, India Nanoscale Spectroscopy Group, National
Institute of Standards and Technology,
Matthew R. Rosenberger Gaithersburg, Maryland
Department of Aerospace and Mechanical
Engineering, University of Notre Dame, Agnès Tempez
Notre Dame, Indiana HORIBA France SAS, Palaiseau, France
Pratap K. Sahoo Dmitri V. Voronine
School of Physical Sciences, Department of Medical Engineering,
National Institute of Science University of South Florida, Tampa, Florida
Education and Research, and
An OCC of Homi Bhabha Department of Physics, University of South
National Institute, Bhubaneswar, India Florida, Tampa, Florida
Binaya Kumar Sahu Emanuil Yanev
School of Physical Sciences, Department of Mechanical Engineering,
National Institute of Science Columbia University, New York, New York
Education and Research,
An OCC of Homi Bhabha National Institute, Kaiyuan Yao
Bhubaneswar, India Department of Mechanical Engineering,
Columbia University, New York, New York
Rabisankar Samanta
N ano-O ptics and Mesoscopic Optics Shuai Zhang
Laboratory, Tata Institute of Fundamental Department of Physics, Columbia University,
Research, Mumbai, India New York, New York
Preface
The prime attraction of the present book is the elaborate discussion on optical microscopy and
Raman spectroscopy in the nanoscale of molecular dimension with an additional emphasis on its
applications to decipher the cause- a nd- effect relations of physical, chemical, and biological samples
of interest. The unique perspective of the discussion sets the present book apart from other books
available in the market. There are books on plasmonics, photonics, and the basics of n ano- optics
phenomenon, but they hardly shed light on its applications in contemporary research. Interestingly,
many books are available on the s urface- enhanced Raman spectroscopy ( SERS) for analytical,
biomolecular, and medical diagnostics applications, yet there is no book available for tip- enhanced
Raman spectroscopy ( TERS) and its applications. Most discussion on TERS is available barely as
review chapters in journals or sporadic discussion as book chapters. In contrast, the present book
is a n ear- comprehensive collection of relevant topics to comprehend and analyze properties at the
nanoscale using TERS.
Fundamentals of phonon properties in material and Raman spectroscopy as a diagnostic tool
are deliberated in great detail, covering molecular symmetry and group theoretical analysis. A
brief analysis of elastic properties in nanomaterials and its application in finding structural modes
are discussed. The size and shape of nanomaterials are determined using confinement of acoustic
phonon mode and radial breathing mode is analyzed for the atomically thin wall of a nanotube.
In this regard, l ow- frequency bosonic mode ( spin wave) is also discussed in the magnetic lattice.
The essence of plasmonics, photonics, and n ear- filed optics is also included while discussing the
latest developments. Similarly, the principle and various models of SERS and TERS are discussed
in great detail for the s tate- of- the- art development of the technique as well as its applications. We
envisage that doctoral and graduate students looking for comprehensive guidance, referral, and sug-
gestion may find this book immensely helpful. For example, simple techniques in assigning Raman
mode will attract Master’s students doing their advanced projects and researchers investigating
inter- disciplinary subjects dealing with Raman spectroscopy as a tool. A comprehensive discussion
on all techniques, including n ear- field studies for analyzing properties of nanomaterials and char-
acterization at the nanoscale, will serve as a ready reference for most readers. This book reviews
contemporary plasmonics, photonics, and their advanced optical and o ptical- mode spectroscopic
applications which will be very attractive topics for many readers.
The book is a chronicle on the present status and progress related to nanoscopy and nanospec-
troscopy. The detail of Raman spectroscopy probing different materials, including nanomaterials,
are described in Chapter 1. P lasmonic- b ased research and applications found tremendous impetus
in modern science and technology in the last decade. Abbe’s diffraction limit was overcome and
made technologically acceptable by confining light. The confinement of light using plasmonics and
later photonics brought a renaissance in optical nanoscopy that resulted in the development of super-
lensing, leading to the Nobel Prize in Chemistry in 2014. The subjects are detailed in C hapters 2
and 3. Near- field studies using confined light have made nanoscopy available for i n- vitro studies
of biological samples and have helped in observing surface plasmon polariton waves, achieving
sub- micron lithography at sub- diffraction limit and medical diagnostic applications ( Chapter 4).
Earlier, confinement of light was achieved by utilizing efficient SERS phenomenon in the far- field
measurements to study a single molecule. The technique has proved to be so versatile that nowa-
days, it is routinely used for compositional analysis of biological samples in the pharmaceutical
industry with trace- level detection limits ( Chapter 5). In C hapter 6, the techniques have been made
further sophisticated by combining surface probe microscopy ( SPM), where a plasmonic tip was
raster scanned for site- specific analysis in inorganic crystal and semiconducting nanostructures of
strategic importance, e.g., strained Si and quantum dots, along with other layered MXenes and Van
der Waals’ bonded materials in the TERS technique. At low- temperature and ultrahigh- vacuum
xi
xii Preface
conditions, TERS study can achieve s ub- nanometer resolution for single nanostructure analysis
and chemical sensitive imaging for studying various catalytic activities. The use of TERS for both
DNA and RNA sequencing, including the study of bacteria and viruses, is in the ambit of the book.
The nano- spectroscopic study is further extended to imaging 2D transition metal dichalcogenide
stacking as excitons greatly enhance near- field second harmonic generation efficiency. Finally, the
chapter concludes with its important application of tip- enhanced photoluminescence measurements
for understanding excitonic properties of semiconductors. The final Chapter 7 offers a summary of
the expected future developments.
Plasmonics- and photonics- assisted “ nanoscopy and nanospectroscopy” are very efficient mate-
rial characterization techniques for surface, s ub- surface, and trace- level detection up to the level of
molecular imaging. There is a persistent interest in developing optical- based characterization tech-
niques at the sub- nanometer or atomic scale ( superlensing) for quick and non- destructive studies of
material. Optical characterization techniques are popular for their ease of use in batch processing,
attracting researchers and scholars alike. This book thus will be suitable as a reference for graduate,
undergraduate, and doctoral students looking for quick guidance for material characterizations at
the nanoscale using optical techniques.
