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21st Century Nanoscience – A Handbook
21st Century Nanoscience – A Handbook: Nanophysics Sourcebook (Volume One)

21st Century Nanoscience – A Handbook: Design Strategies for Synthesis and Fabrication (Volume Two)

21st Century Nanoscience – A Handbook: Advanced Analytic Methods and Instrumentation (Volume Three)

21st Century Nanoscience – A Handbook: Low-Dimensional Materials and Morphologies (Volume Four)

21st Century Nanoscience – A Handbook: Exotic Nanostructures and Quantum Systems (Volume Five)

21st Century Nanoscience – A Handbook: Nanophotonics, Nanoelectronics, and Nanoplasmonics (Volume Six)

21st Century Nanoscience – A Handbook: Bioinspired Systems and Methods (Volume Seven)

21st Century Nanoscience – A Handbook: Nanopharmaceuticals, Nanomedicine, and Food Nanoscience (Volume Eight)

21st Century Nanoscience – A Handbook: Industrial Applications (Volume Nine)

21st Century Nanoscience – A Handbook: Public Policy, Education, and Global Trends (Volume Ten)
 21st Century Nanoscience – A Handbook
Exotic Nanostructures and Quantum Systems (Volume Five)

Edited by

Klaus D. Sattler
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Library of Congress Cataloging-in-Publication Data

Names: Sattler, Klaus D., editor.
Title: 21st century nanoscience : a handbook / edited by Klaus D. Sattler.
Description: Boca Raton, Florida : CRC Press, [2020] | Includes bibliographical references and index. | Contents: volume 1. Nanophysics
sourcebook—volume 2. Design strategies for synthesis and fabrication—volume 3. Advanced analytic methods and instrumentation—
volume 5. Exotic nanostructures and quantum systems—volume 6. Nanophotonics, nanoelectronics, and nanoplasmonics—volume 7.
Bioinspired systems and methods. | Summary: “This 21st Century Nanoscience Handbook will be the most comprehensive, up-to-date
large reference work for the field of nanoscience. Handbook of Nanophysics, by the same editor, published in the fall of 2010, was embraced
as the first comprehensive reference to consider both fundamental and applied aspects of nanophysics. This follow-up project has been
conceived as a necessary expansion and full update that considers the significant advances made in the field since 2010. It goes well
beyond the physics as warranted by recent developments in the field”—Provided by publisher.
Identifiers: LCCN 2019024160 (print) | LCCN 2019024161 (ebook) | ISBN 9780815384434 (v. 1 ; hardback) | ISBN 9780815392330 (v. 2 ;
hardback) | ISBN 9780815384731 (v. 3 ; hardback) | ISBN 9780815355281 (v. 4 ; hardback) | ISBN 9780815356264 (v. 5 ; hardback) | ISBN
9780815356417 (v. 6 ; hardback) | ISBN 9780815357032 (v. 7 ; hardback) | ISBN 9780815357070 (v. 8 ; hardback) | ISBN 9780815357087
(v. 9 ; hardback) | ISBN 9780815357094 (v. 10 ; hardback) | ISBN 9780367333003 (v. 1 ; ebook) | ISBN 9780367341558 (v. 2 ; ebook) |
ISBN 9780429340420 (v. 3 ; ebook) | ISBN 9780429347290 (v. 4 ; ebook) | ISBN 9780429347313 (v. 5 ; ebook) | ISBN 9780429351617
(v. 6 ; ebook) | ISBN 9780429351525 (v. 7 ; ebook) | ISBN 9780429351587 (v. 8 ; ebook) | ISBN 9780429351594 (v. 9 ; ebook) | ISBN
9780429351631 (v. 10 ; ebook)
Subjects: LCSH: Nanoscience—Handbooks, manuals, etc.
Classification: LCC QC176.8.N35 A22 2020 (print) | LCC QC176.8.N35
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 Contents

Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
1 Novel Nanoscience in Superfluid Helium Arin Mizouri, Charlotte Pughe, Berlian Sitorus,
Andrew M. Ellis, and Shengfu Yang . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1
2 Stimuli-Responsive Polymeric Nanomaterials Siyang Wang and Marek W. Urban . . . . . . 2-1
3 Nanoparticle Superlattices Steffi S. Thomas and Fabian Meder . . . . . . . . . . . . . . . . . . 3-1
4 Heptacene Holger F. Bettinger and Peter Grüninger . . . . . . . . . . . . . . . . . . . . . . . . . 4-1
5 Epitaxial Silicene Dmytro Solonenko and Patrick Vogt . . . . . . . . . . . . . . . . . . . . . . . . 5-1
6 Emissive Nanomaterials and Liquid Crystals Marianne E. Prévôt, Julie P. Vanegas,
Elda Hegmann, Torsten Hegmann, Julia Pérez-Prieto, and Yann Molard . . . . . . . . . . . . . 6-1
7 Nanoscale Alloys and Intermetallics: Recent Progresses in Catalysis Arnab Samanta
and Subhra Jana . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1
8 Nanoionics: Fundamentals and Applications Joachim Maier . . . . . . . . . . . . . . . . . . . . 8-1
9 Structure-Dynamic Approach of Nanoionics A.L. Despotuli and A.V. Andreeva . . . . . . . . 9-1
10 Energetic Processing of Molecular and Metallic Nanoparticles by Ion Impact
A. Domaracka, A. Mika, P. Rousseau, and B.A. Huber . . . . . . . . . . . . . . . . . . . . . . . . . 10-1
11 Nanoscale Fluid Dynamics Ravi Radhakrishnan, N. Ramakrishnan, David M. Eckmann,
and Portonovo S. Ayyaswamy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-1
12 Transport in Nanoporous Materials Saad Alafnan and I. Yucel Akkutlu . . . . . . . . . . . . . 12-1
13 Beyond Phenomena: Functionalization of Nanofluidics Based on Nano-in-Nano Integration
Technology Yan Xu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-1
14 Classical Density Functional Theory and Nanofluidics: Adsorption and the Interface
Binding Potential P. Yatsyshin, M.-A. Durán-Olivencia and S. Kalliadasis . . . . . . . . . . . 14-1
15 Water Flow in Graphene Nanochannels Seungha Shin . . . . . . . . . . . . . . . . . . . . . . . . 15-1
16 Transport of Water in Graphene Nanochannels Chinh Thanh Nguyen, Alper Tunga Celebi,
and Ali Beskok . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16-1
17 Nanoscale Magnetism Roopali Kukreja and Hendrik Ohldag . . . . . . . . . . . . . . . . . . . . 17-1
18 Physics of Nanomagnets Ralph Skomski, Balamurugan Balasubramanian,
and D. J. Sellmyer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18-1
19 Magnetic Disorder at the Nanoscale Nader Yaacoub and Rodaina Sayed Hassan . . . . . . . 19-1
20 The Study of Hexagonal Fe2 Si: In Terms of Its Structure and Electronic Properties
Chi Pui Tang and Kuan Vai Tam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20-1
21 Tunable Picosecond Magnetization Dynamics in Ferromagnetic Nanostructures
Samiran Choudhury, Sucheta Mondal, Anulekha De, and Anjan Barman . . . . . . . . . . . . . 21-1
22 Nanothermodynamics: Fundamentals and Applications Vladimir Garcı́a-Morales,
Javier Cervera, and José A. Manzanares . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22-1
23 Characterization of Nanoscale Thermal Conductivity Weidong Liu, Liangchi Zhang,
Alireza Moridi, and Mohammad Ehsan Khaled . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23-1
24 Nanothermometers: Remote Sensors for Temperature Mapping at the Nanoscale
Blanca del Rosal and Dirk H. Ortgies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24-1
25 Luminescence Nanothermometry Oleksandr A. Savchuk and Joan J. Carvajal . . . . . . . . . 25-1
26 Diamond Nanothermometry Yuen Yung Hui, Oliver Y. Chen, Huan-Cheng Chang, and
Meng-Chih Su . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26-1
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-1
Taylor & Francis
Taylor & Francis Group
http://taylorandfrancis.com

Klaus D. Sattler pursued his undergraduate and master’s
courses at the University of Karlsruhe in Germany. He
earned his PhD under the guidance of Professors G. Busch
and H.C. Siegmann at the Swiss Federal Institute of Tech-
nology (ETH) in Zurich. For three years he was a Heisenberg
fellow at the University of California, Berkeley, where he
initiated the first studies with a scanning tunneling micro-
scope of atomic clusters on surfaces. Dr. Sattler accepted a
position as professor of physics at the University of Hawaii,
Honolulu, in 1988. In 1994, his group produced the first
Editor
carbon nanocones. His current work focuses on novel nano-
materials and solar photocatalysis with nanoparticles for the
purification of water. He is the editor of the sister refer-
ences, Carbon Nanomaterials Sourcebook (2016) and Silicon
Nanomaterials Sourcebook (2017), as well as Fundamen-
tals of Picoscience (2014). Among his many other accom-
plishments, Dr. Sattler was awarded the prestigious Walter
Schottky Prize from the German Physical Society in 1983.
At the University of Hawaii, he teaches courses in general
physics, solid state physics, and quantum mechanics.
Taylor & Francis
Taylor & Francis Group
http://taylorandfrancis.com

Saad Alafnan
Petroleum Engineering
King Fahd University of Petroleum
and Minerals
Dhahran, Saudi Arabia
I. Yucel Akkutlu
Petroleum Engineering
Texas A&M University
College Station, Texas
A.V. Andreeva
Institute of Microelectronics
Technology and High Purity
Materials
Russian Academy of Science
Moscow Region, Russia
Portonovo S. Ayyaswamy
Department of Mechanical
Engineering and Applied
Mechanics
University of Pennsylvania
Philadelphia, Pennsylvania
Balamurugan Balasubramanian
Nebraska Center for Materials and
Nanoscience
University of Nebraska
Lincoln, Nebraska
and
Department of Physics and
Astronomy
University of Nebraska
Lincoln, Nebraska
Anjan Barman
Department of Condensed Matter
Physics and Material Sciences
S. N. Bose National Centre for Basic
Sciences
Kolkata, India
Ali Beskok
Department of Mechanical
Engineering
Southern Methodist University
Dallas, Texas
Contributors
Holger F. Bettinger Anulekha De
Institute for Organic Chemistry and Department of Condensed Matter
Institute for Physical and Physics and Material Sciences
Theoretical Chemistry S. N. Bose National Centre for Basic
University of Tübingen Sciences
Tübingen, Germany Kolkata, India
Joan J. Carvajal Blanca del Rosal
Departament Química Física i Faculty of Science
Inorgànica Engineering and Technology
Física i Cristallografía de Materials i Centre for Micro-Photonics
Nanomaterials (FiCMA-FiCNA) - Swinburne University of Technology
EMaS Hawthorn, Australia
Universitat Rovira i Virgili
Tarragona, Spain A.L. Despotuli
Institute of Microelectronics
Alper Tunga Celebi Technology and High Purity
Department of Mechanical Materials
Engineering Russian Academy of Science
Southern Methodist University Moscow Region, Russia
Dallas, Texas
A. Domaracka
Javier Cervera ENSICAEN, UNICAEN, CEA,
Faculty of Physics CNRS, CIMAP
Department of Thermodynamics Normandie Université
University of Valencia Caen, France
Burjasot, Spain
M.-A. Durán-Olivencia
Huan-Cheng Chang Department of Chemical Engineering
Institute of Atomic and Molecular Imperial College London
Sciences London, United Kingdom
Academia Sinica
Taipei, Republic of China David M. Eckmann
Department of Bioengineering
Oliver Y. Chen University of Pennsylvania
Institute of Atomic and Molecular Philadelphia, Pennsylvania
Sciences and
Academic Sinica Department of Anesthesiology and
Taipei, Republic of China Critical Care
University of Pennsylvania
Samiran Choudhury Philadelphia, Pennsylvania
Department of Condensed Matter
Physics and Material Sciences Andrew M. Ellis
S. N. Bose National Centre for Basic Department of Chemistry
Sciences University of Leicester
Kolkata, India Leicester, United Kingdom
x Contributors

Vladimir García-Morales S. Kalliadasis Sucheta Mondal

Faculty of Physics Department of Chemical Engineering Department of Condensed Matter
Department of Thermodynamics Imperial College London Physics and Material Sciences
University of Valencia London, United Kingdom S. N. Bose National Centre for Basic
Burjasot, Spain Sciences
Mohammad Ehsan Khaled Kolkata, India
Peter Grüninger Laboratory for Precision and Nano
Institute for Organic Chemistry and Processing Technologies
Institute for Physical and School of Mechanical and Alireza Moridi
Theoretical Chemistry Manufacturing Engineering Laboratory for Precision and Nano
University of Tübingen The University of New South Wales Processing Technologies
Tübingen, Germany Sydney, Australia School of Mechanical and
Manufacturing Engineering
Rodaina Sayed Hassan Roopali Kukreja The University of New South Wales
Multidisciplinary Physics Laboratory University of California Davis Sydney, Australia
(MPLAB) Davis, California
Faculty of sciences Section I
Lebanese University Weidong Liu Chinh Thanh Nguyen
Beirut, Lebanon Laboratory for Precision and Nano Department of Mechanical
Processing Technologies Engineering
Elda Hegmann School of Mechanical and Southern Methodist University
Liquid Crystal Institute Manufacturing Engineering Dallas, Texas
Kent State University The University of New South Wales
Kent, Ohio Sydney, Australia Hendrik Ohldag
and
Lawrence Berkeley National
Department of Biological Sciences Joachim Maier
Laboratory
Kent State University Max Planck Institute for Solid State
University of California Santa Cruz
Kent, Ohio Research
Santa Cruz, California
Stuttgart, Germany
and
Torsten Hegmann
Stanford University
Liquid Crystal Institute José A. Manzanares
Stanford, California
Kent State University Faculty of Physics
Kent, Ohio Department of Thermodynamics
and University of Valencia Dirk H. Ortgies
Department of Chemistry and Burjasot, Spain Nanobiology Group
Biochemistry Instituto Ramón y Cajal de
Kent State University Fabian Meder Investigación Sanitaria IRYCIS
Kent, Ohio Center for Micro-BioRobotics Madrid, Spain
Istituto Italiano di Tecnologia and
B.A. Huber Pontedera, Italy Fluorescence Imaging Group
ENSICAEN, UNICAEN, CEA, Departamento de Física de Materiales
CNRS, CIMAP A. Mika
Facultad de Ciencias
Normandie Université ENSICAEN, UNICAEN, CEA,
Universidad Autónoma de Madrid
Caen, France CNRS, CIMAP
Madrid, Spain
Normandie Université
Yuen Yung Hui Caen, France
Institute of Atomic and Molecular Julia Pérez-Prieto
Sciences Arin Mizouri Instituto de Ciencia Molecular
Academic Sinica Department of Chemistry (ICMol)
Taipei, Republic of China University of Leicester University of Valencia
Leicester, United Kingdom Paterna, Spain
Subhra Jana
Department of Chemical, Biological & Yann Molard
Macro-Molecular Sciences Institut des Sciences Chimiques de Marianne E. Prévôt
S. N. Bose National Centre for Basic Rennes Liquid Crystal Institute
Sciences Université de Rennes 1, CNRS Kent State University
Kolkata, India Rennes, France Kent, Ohio
Contributors xi

Charlotte Pughe Berlian Sitorus Julie P. Vanegas

Department of Chemistry Department of Chemistry Liquid Crystal Institute
University of Leicester University of Leicester Kent State University
Leicester, United Kingdom Leicester, United Kingdom Kent, Ohio
and
Ravi Radhakrishnan Department of Chemistry Patrick Vogt
Department of Bioengineering Tanjungpura University Institut für Physik
University of Pennsylvania Pontianak, Indonesia Technische Universität Chemnitz
Philadelphia, Pennsylvania
Chemnitz, Germany
and Ralph Skomski
Department of Chemical and Nebraska Center for Materials and Siyang Wang
Biomolecular Engineering Nanoscience Department of Materials Science and
University of Pennsylvania University of Nebraska Engineering
Philadelphia, Pennsylvania Lincoln, Nebraska Clemson University
and Clemson, South Carolina
N. Ramakrishnan
Department of Physics and
Department of Bioengineering
Astronomy
University of Pennsylvania Yan Xu
University of Nebraska
Philadelphia, Pennsylvania Department of Chemical Engineering
Lincoln, Nebraska
Graduate School of Engineering
P. Rousseau Osaka Prefecture University
ENSICAEN, UNICAEN, CEA, Dmytro Solonenko
Sakai, Japan
CNRS, CIMAP Institut für Physik
and
Normandie Université Technische Universität Chemnitz
Japan Science and Technology Agency
Caen, France Chemnitz, Germany
(JST), PRESTO
Kawaguchi, Japan
Arnab Samanta Meng-Chih Su
and
Department of Chemical, Biological & Department of Chemistry
NanoSquare Research Institute
Macro-Molecular Sciences Sonoma State University
Osaka Prefecture Universit
S. N. Bose National Centre for Basic Rohnert Park, California
Sakai, Japan
Sciences
Kolkata, India Kuan Vai Tam
Nader Yaacoub
Lunar and Planetary Science
Oleksandr A. Savchuk Institute of Molecules and Materials
Laboratory
Nanophotonics Department of Le Mans (IMMM) CNRS
Macau University of Science and
Ultrafast Bio- and Nanophotonics UMR-6283
Technology
Group Le Mans University
Macau, China
International Iberian Nanotechnology Le Mans, France
Laboratory (INL)
Chi Pui Tang
Braga, Portugal Shengfu Yang
Lunar and Planetary Science
Laboratory Department of Chemistry
D. J. Sellmyer
Macau University of Science and University of Leicester
Nebraska Center for Materials and
Technology Leicester, United Kingdom
Nanoscience
University of Nebraska Macau, China
P. Yatsyshin
Lincoln, Nebraska
Steffi S. Thomas Department of Chemical Engineering
and
School of Chemistry Imperial College London
Department of Physics and
Trinity College Dublin London, United Kingdom
Astronomy
University of Nebraska Dublin, Ireland
Lincoln, Nebraska Liangchi Zhang
Marek W. Urban Laboratory for Precision and Nano
Seungha Shin Department of Materials Science and Processing Technologies
Mechanical, Aerospace, and Engineering School of Mechanical and
Biomedical Engineering Clemson University Manufacturing Engineering
The University of Tennessee Clemson, South Carolina The University of New South Wales
Knoxville, Tennessee Sydney, Australia
Taylor & Francis
Taylor & Francis Group
http://taylorandfrancis.com
 1
Novel Nanoscience in Superfluid Helium
1.1 The Properties of Superfluid Helium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2
Viscosity • Thermal Conductivity • Quantized Vortices
1.2 Growth of Nanomaterials in Bulk Superfluid Helium . . . . . . . . . . . . . . . . . . . . 1-4
Mechanism for Nanowire Formation • Typical Bulk Superfluid Helium
Arin Mizouri, Charlotte Pughe, Apparatus • Nanostructures Formed in Bulk Superfluid Helium
Berlian Sitorus, Andrew M. 1.3 Synthesis of Nanomaterials in Superfluid Helium Droplets . . . . . . . . . . . . . . 1-7
Ellis, and Shengfu Yang Basics of Helium Droplets • Formation of Nanoparticles in Helium Droplets •

University of Leicester Quantized Vortices and the Growth of Nanowires Using Superfluid Helium
Droplets
Berlian Sitorus 1.4 Perspectives and Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-12
Tanjungpura University References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-12

Nanoscience and nanotechnology are broad interdisciplinary
areas of research that span chemistry, physics, materials
science and biology. The motivation for studying these areas
is driven partly by the fascinating properties offered by new
materials at the nanoscale, which can differ drastically from
their bulk counterparts, and can be exploited for appli-
cations in medicine,1,2 electronics and opto-electronics,3,4
catalysis,5−7 and nowadays in consumer products such as
clothing and cosmetics.8,9 The properties of nanomaterials
are strongly dependent on their shapes, sizes, morphology,
structures and chemical composition, and it is critical to
have control over these parameters in order to obtain novel
materials with desired properties.
To date, the vast majority of nanomaterials have been
synthesized at the room temperature or above, but low-
temperature techniques have also emerged in recent years,
e.g., by employing solid matrices or superfluid helium
as the solvents. In the solid matrix method, hot atoms
collide with a cold solid matrix formed by the condensa-
tion of rare gases, nitrogen or carbon dioxide,10−12 which
then melts and allows atoms to aggregate. This is the
first step occurring in the formation of nanomaterials in
the solid matrix. While the clusters are being formed,
the binding energy between atoms is released, stimulating
further melting and thereby allowing subsequent migra-
tion and clustering of the added materials. In contrast, the
formation of nanomaterials in superfluid helium occurs in
the liquid phase, where the migration and aggregation is
easier than in solid matrices. The extraordinary properties
of superfluid helium, such as near-zero viscosity, ultrahigh
thermal conductivity and quantized vortices,13 allow the
creation of a variety of nanostructures, many being inacces-
sible by conventional synthetic methods. However, super-
fluid helium is intrinsically a poor solvent as helium atoms
interact very weakly with other atoms and molecules. As a
result, materials added tend to locate at the walls of the
container, rather than reside within the fluid, in bulk super-
fluid helium.
Problems associated with the condensation of samples on
the container walls can be circumvented by using liquid
helium droplets, which are isolated, self-contained large
clusters of helium typically composed of 103 –1011 helium
atoms.14,15 Unlike bulk liquid helium, helium droplets have
no container wall; so foreign species can be trapped and
then confined by the surface of the droplet. Toennies et al.
were the first to demonstrate that the superfluidity of bulk
liquid helium also occurs on the nanoscale,16,17 to which
atoms/molecules can be added by a pickup technique,18
i.e., by collisions between the droplets and gas-phase
atoms/molecules. Helium droplets are highly “sticky”, with
a near unity pickup probability. In other words, the number
of atoms/molecules being added to the droplets is approx-
imately the number of collision events. By controlling the
pickup conditions, formation of nanoparticles containing a
few dozens to millions of atoms are possible, which depends
on the size of the droplets and the number density of
atoms/molecules in the pickup region. Although still in
its infancy, a number of metallic nanoparticles have been
synthesised using this technique. In 2011, Loginov et al.
performed the first transmission electron microscopy (TEM)
imaging of spherical metallic nanoparticles formed in helium
droplets.19
One of the unique advantages of using helium droplets
as nano–reactors to grow nanomaterials is the ease of
forming core–shell structures, which can be achieved simply
by pickup of different types of materials when they pass
through two sequential pickup regions. Such a scenario
was first demonstrated by the formation of molecular

1-1
1-2
clusters, where a core–shell structure was deduced using
mass spectrometry.20 Evidence for the formation of a core–
shell bimetallic structure was obtained in Ni/Au nanoparti-
cles formed by sequential addition of Ni and Au to helium
droplets, for which the core–shell structure was evident from
X-ray photoelectron spectroscopy (XPS).21 In this process
the inter-diffusion between layers is also minimized as the
reactions occur in very cold superfluid helium, giving rise
to core–shell structures with clear boundary at the inter-
face, which is difficult to achieve using conventional “hot”
approaches.
This chapter is divided into three sections: (i) the prop-
erties of superfluid helium (in bulk helium and droplets),
and how and why each property is useful in the synthesis
of nanomaterials; (ii) fabrication of nanostructures in
bulk superfluid helium; and (iii) the new possibilities for
the synthesis of nanomaterials using superfluid helium
droplets, and the recent advances in this emerging field of
nanoscience. Finally, we will close by considering some of the
remaining challenges and the prospects for superfluid helium
being employed in the development of next-generation
materials.
1.1 The Properties of Superfluid
Helium
Helium is the only element that remains as a liquid at 0 K.
This is a consequence of the very weak van der Waals inter-
action between helium atoms (5 cm−1 ) and the low atomic
mass (4 amu). This results in a zero-point vibrational energy
being comparable to the interatomic attraction, preventing
helium atoms from being pinned to a solid lattice unless
a very high pressure is imposed. This very weak inter-
action also means a very low temperature is needed to
liquefy helium. Liquid helium was first discovered in 1908
by Kammerlingh-Onnes, who cooled the element to 4.2 K.
At this temperature, helium behaves as a normal liquid (He
I phase)22 but upon further cooling below 2.17 K it enters a
superfluid phase (He II, see Figure 1.1 for the phase diagram
of 4 He). Superfluidity is the consequence of Bose-Einstein
condensation (BEC), in which all of the bosonic particles
occupy the same quantum state.23 In contrast, 3 He is a
fermion and has a distinctly different phase diagram when
compared with 4 He. Although 3 He can become a super-
fluid, the transition temperature is far lower (3 mK)24 in
order for the fermionic 3 He atoms to pair up and form
quasi-bosons.
One of the major differences between bulk helium and
helium droplets is that the temperature of bulk liquid
helium can be varied via cooling or heating its container. In
contrast, helium droplets have a steady-state temperature
that is determined by the balance of the surface tension of
the droplets and the kinetic energy carried by helium atoms.
For 4 He, this steady-state temperature is 0.37 K, which is
well below the “kick-in” temperature for forming superfluid
helium.25
Exotic Nanostructures and Quantum Systems
FIGURE 1.1 Phase diagram of helium. The three dots at
2.17 K, 1.76 and 4.2 K highlight the λ-point, upper λ-point and
boiling point of helium, respectively.
1.1.1 Viscosity
Kapitza, Allen and Misener performed the first experi-
mental measurements showing the superfluidity of liquid
helium below 2.17 K. In these experiments, performed
in 1938, they investigated the viscous flow of helium
through narrow channels.26,27 Above 2.17 K, the liquid
helium was found to be viscous, just like any normal
liquids but below the λ-point the viscosity was found
to decrease by a factor of 106 , allowing liquid helium
to flow through microchannels at driven by a tiny pres-
sure difference. From this observation, Kapitza coined
the name “superfluid” to describe frictionless flow in the
He II phase.
Some of the unusual properties of bulk superfluid helium
irrelevant to the growth of nanomaterials, such as the foun-
tain effect, film flow and creeping, will not be covered here.
Instead, we will focus only on properties that are possessed
by both bulk superfluid helium and helium droplets and
that are important for the growth of nanomaterials, such as
superfluidity (which allows the free motion of dopants and
thus easy aggregation), the ultrahigh cooling rate (allowing
different species to be incorporated) and quantized vortices
(allowing the formation of 1-D nanostructures).
Not only does the superfluid flow unhindered, but also
species contained within the fluid are able to move freely,
almost unperturbed by the surrounding helium atoms. Due
to the poor solubility of dopants in liquid helium, frictionless
motion of impurities makes it difficult to suspend a species
inside the bulk superfluid. This difficulty can be circum-
vented by using helium droplets. In 1998, Toennies et al.
showed for the first time that atoms and molecules can be
confined in very small droplets of liquid helium,16 which
can be retained for further investigations, e.g., by mass
spectrometry and/or optical spectroscopy. The first experi-
mental evidence for the superfluidity of helium droplets was
Novel Nanoscience in Superfluid Helium
FIGURE 1.2 Absorption spectrum of OCS in 4 He droplets
(HeN = <6000>). The factor 10 enlarged spectrum shows
the results for the OC34 S isotope measured with an improved
time constant. (Reprinted with permission from Ref. [28], AIP
Publishing.)
obtained by Grebenev et al., who measured the rotationally
resolved infrared spectrum of the OCS molecule.28 The spec-
trum obtained showed well-resolved P and R branches (see
Figure 1.2), suggesting that the OCS molecule is able to
rotate in a way similar to gas phase molecules. However,
liquid helium does have some significant influence on rota-
tional spectra, e.g., by increasing the rotational moment
of inertia and thus reducing the rotational constant.29 The
reduced rotational constant was interpreted as the attach-
ment of a layer of helium atoms which follows the rotation
of the OCS molecule in the droplet. The relative intensities
of the vibration-rotation transitions allowed the determina-
tion of the temperature of helium droplets, which was found
to be ∼0.37 K. In the same study, OCS was also added to
3
He droplets for comparison. In this case no rotational struc-
ture can be resolved, suggesting that 3 He droplets are in the
normal liquid phase. Indeed, this is consistent with the very
low onset temperature of superfluidity for 3 He (3 mK) and a
higher steady-state temperature of 3 He droplets (∼0.15 K).
1.1.2 Thermal Conductivity
Superfluid helium has very unusual thermal properties,
which were first observed by Allen.30 When a torch was
shone on a superfluid liquid helium reservoir, helium was
found to spout from the capillary, an effect known as the
fountain effect. This can be explained by the so-called
two-fluid model in the He II phase, in which the fluid is
assumed to consist of both a normal fluid fraction and a
superfluid fraction. Upon heating, the superfluid fraction
decreases in the region being heated, creating a concentra-
tion gradient. As a result, superfluid helium rapidly flows
through the porous membrane in order to minimize the
chemical potential, leading to spray of the fluid out of the
capillary. Keesom et al. quantified the heat conductivity of
He II as 800 times greater than that of copper at room
temperature and a magnitude of 1.3 × 107 times greater
1-3
than the He I phase.31,32 This ultrahigh thermal conduc-
tivity leads to bubble-free evaporation of superfluid helium
when excess energy is introduced to the system.
A similar rapid cooling seems to occur when atoms or
molecules are added to helium droplets: a cooling rate for
the dopants as high as 1016 K/s has been proposed.33,34 As a
result, cluster formation in helium droplets involves succes-
sive binding of atoms/molecules to a pre-cooled cluster while
the energy released from each binding event is instantly
dissipated by the evaporative loss of helium atoms at the
surface. As the helium-helium binding energy is only 5 cm−1 ,
each 1 eV of energy stimulates the evaporative loss of
∼1,600 atoms.35 Clusters grown under such conditions may
have unusual structures as thermal energy is being rapidly
removed; so they might localize in a shallow potential well
along the potential energy surface. This has been demon-
strated in several experiments, such as the formation of
linear HCN clusters and cyclic H2 O hexamers,36,37 and more
recently in metallic nanoclusters.38 New properties can be
envisaged from entities with new structures.
1.1.3 Quantized Vortices
The quantization of circulation in superfluids and supercon-
ductors is one of the most remarkable macroscopic illustra-
tions of quantum mechanics. In superfluids, the circulation is
carried by the continuant atoms, each possessing an angular
momentum equal to an integer multiple of ħ. The investi-
gation of the rotational behavior of superfluid 4 He can be
traced back to the 1950s when Osborne,39 Andronikashvili,
and Kaverkin40 found that the liquid rotates uniformly as a
whole in rotating containers, and the shape of the meniscus
generated in the containers is independent of the tempera-
ture. This was puzzling until Onsager proposed quantized
vortices and modeled rotation in a bucket of superfluid
helium as an array of concentric vortices rotating around
a fixed point with quantized circulation41 :
h
Quantized circulation = n (1.1)
m4
where h/m 4 represents a quantum of circulation, h is
Planck’s constant, m 4 is the mass of a 4 He atom, and
n represents the quantum number (n = 1, 2. . . ) of the
vortex. Later, Feynman proposed a slightly different theory,
in which rotation of superfluid helium is manifested in the
form of many vortex filaments (also called vortex lines).42
He predicted that the radius of a vortex filament is on the
order of the atomic scale (∼0.5 Å) and that the centrifugal
force associated with it would be balanced by the Bernoulli
force due to a pressure gradient.43,44
In 1976, Packard et al. provided the first visual evidence
supporting Feynman’s theory.45,46 This was achieved by
dissolving electrons in a bath of superfluid helium over which
a fluorescent screen was placed. By applying an electric
potential, the electrons were accelerated from the superfluid
towards the phosphor screen. The resulting image showed
1-4
electrons arranged into circular arrays, with each spot repre-
senting a vortex.47 Analogous experiments by Bewley et al.
in 2006 used light scattering of H2 clusters pinned to vortex
lines to determine the vortex density of bulk He II.48 By
injecting a premixed gaseous solution of hydrogen, which
was highly diluted by helium gas, into liquid helium in
a steadily rotating container, micron-sized hydrogen clus-
ters were formed. Below 2.17 K, the otherwise randomly
distributed particles above the phase transition tempera-
ture were found to collect into slender filaments, and arrange
themselves along uniformly spaced lines parallel to the axis
of rotation, forming a rectilinear array.48 The vortex density
depends on the angular velocity of the container, Ω, and in
this case was found to be 2,000 Ω vortex lines per cm2 .
Imaging of pinned particles has shown that vortex lines do
not have to be linear: they can also adopt circular, closed
ring or curved shapes and can even tangle together.49−51
Quantized vortices have recently been found to be present
in large helium droplets with diameters >300 nm, which
allow the growth of nanostructure in one dimension, i.e., the
nanowires. The first evidence for the presence of quantized
vortices in helium droplets was obtained by Gomez et al.,52
who added Ag atoms to helium droplets and then investi-
gated the deposits obtained by allowing the doped helium
droplets to collide with a solid target. By using TEM, track-
like silver deposits were observed, which were attributed to
the preferential growth of silver chains along the quantized
vortices. In superfluid helium, the weak Bernoulli force is
sufficient to trap dopants in the vortex so quantized vortices
can serve as intrinsic 1-D templates that can be employed
to fabricate ultrathin 1-D nanowires.53 Both the length and
diameter of these wires can be controlled by varying the
helium droplet size and the rate of doping.
1.2 Growth of Nanomaterials in
Bulk Superfluid Helium
Although bulk superfluid helium is intrinsically a poor
solvent and it does not appear to be a good medium to grow
nanomaterials, effort has been made recently to grow nanos-
tructures, the vast majority of which are 1-D nanostructures
formed by pinning metal atoms to the vortex lines instead
of forming spherical particles. Due to the high thermal
conductivity and the very low temperature of superfluid
helium, atoms/molecules, once entering a quantized vortex,
can no longer escape as helium rapidly removes all the
kinetic energy; hence, the addition of materials to bulk liquid
helium containing quantized vortices can lead to the forma-
tion of nanostructures in the shape of vortices – nanowires.
By this route, long and thin metallic nanowires have been
recently produced using bulk superfluid helium.54,55
1.2.1 Mechanism for Nanowire Formation
It had been thought that all processes following the laser
ablation of impurities in superfluid helium are controlled by
Exotic Nanostructures and Quantum Systems
diffusion and thus are slow and strictly isothermal, forming
loose products. However, recent studies by Gordon et al.
have convincingly shown that the fast coagulation process
in superfluid helium is in fact not controlled by diffusion.56
Instead, it is the concentration of impurities within the
cores of quantized vortices that make thin and long wires
the predominant products. In this process the coagulation
is not isothermal in the initial stages and leads to vast
local overheating. It is believed that this process results in
melting of the coagulation products, forming densely packed
structures.
Figure 1.3 illustrates the process.56 The signal decay
is different in the superfluid phase and the normal liquid
phase, which provides evidence for the difference in mech-
anisms. In superfluid helium, two stages are proposed in
the coagulation process, the first being the “hot” stage
where atoms and nanoclusters coalesce and form molten
nanospheres, releasing heat as a result of the condensa-
tion, which is sufficient to evaporate the surrounding liquid
helium. The second stage is the aggregation of nanospheres
into nanowires. The behavior is remarkably different in the
normal liquid phase, which has three stages: the growth
begins with a “hot” stage of spherical cluster growth,
followed by clusters coalescing, eventually leading to a lump.
These experiments suggest that each metal has a critical
cluster size, beyond which nanoclusters can no longer melt
and form spherical particles. Instead, they stick to each
other in the vortex to form nanowires, where the critical
cluster size determines the diameter of the wires.
Gordon et al. have recently proposed a mechanism for
the condensation of atoms and nanoparticles in quantized
vortices of superfluid helium.57 In their model, vortex forma-
tion is caused by the impact of a laser pulse on the metal
target, which generates a vortex near the focus of the laser.
Small metal clusters and metal atoms generated by the laser
ablation of a metal target then migrate into the vortex core.
They can move freely along the vortex line, where there
is a higher probability of collision compared with particles
outside the vortex, and can aggregate into larger clusters.
The coagulation releases energy that is sufficient to melt
the clusters, resulting in a dense structure, which acquires a
spherical shape due to the surface tension.57,58 Meanwhile,
the liquid helium surrounding the vortex line boils, and the
cavitation by the gas bubbles in the normal liquid fraction
then leads to the formation of further vortices. This process
continues until the cluster size increases to an extent that
the heat released during coagulation can no longer melt the
cluster; so the aggregate starts to grow along the vortex
core. Eventually, this results in elongated wires. Since the
Bernoulli force is very short-ranged, the formation of larger
particles during condensation leads to an increase in the
particle-vortex attraction, and thus extending their lifetime
in the trapped state, making it the prevalent process.59 As a
result, the main products of condensation are not spherical
particles but long and thin filaments.
It was the structure and thicknesses of wires grown in
bulk superfluid helium that led to the conclusion that the
Novel Nanoscience in Superfluid Helium
FIGURE 1.3 Temporal dependence of the temperature developed during tungsten coagulation in (a) superfluid and (b) normal
helium. (a) The first stage is the hot stage of spherical cluster growth followed by the nanowire growth (stage II). (b) The first stage is
the hot stage of spherical clusters growth; in the second stage, clusters coalesce. (Reprinted with permission from Ref. [56], American
Chemical Society.)
nanowires pass through a stage in which molten nanoclus-
ters coalesce. Such a suggestion seems counterintuitive,
since the very high thermal conductivity of superfluid
helium should eliminate any local overheating.60 In a recent
experiment, Gordon et al. investigated time-dependent
thermal emission accompanying metal coagulation in He
II, which showed huge local overheating of several thou-
sand degrees.56,61 Although superfluid helium possesses a
high thermal conductivity, it can only maintain this for low
heat flow. Otherwise, turbulence kicks in and suppresses
the heat transfer, converting the superfluid helium into the
normal fluid. The normal fluid has a much lower thermal
conductivity, which then evaporates and forms an insulating
envelope filled with low-pressure helium gas.
Time-resolved shadowgraph photography has been
employed recently to study the laser ablation of copper
and silver targets submerged in bulk normal and superfluid
4
He, allowing the dynamics of the vortex-assisted metal
condensation to be investigated.62 Following the laser
ablation pulse, the plasma produced by ablation is confined
by the surrounding solvent, causing a transient increase of
the local temperature and pressure. The cavitation bubble
surrounding the plasma then expands due to the high
initial internal pressure, leading to a rapid reduction in
both pressure and temperature inside the bubble. Since
the expansion dynamics of the cavitation bubble is highly
non-linear, there are shockwaves that pass into the liquid,
which occur in both normal liquid helium and in superfluid
helium. Therefore, when the bubble cools towards thermal
equilibrium, two stages are involved, including both the
gas-normal liquid and normal-superfluid. The sudden
formation of large clusters occurs at the latter stage, where
the fluid reaches the superfluid lambda transition.
In the experiments by Zurek and Kibble, the temper-
ature of liquid helium was quickly reduced by a sudden
pressure drop.63,64 The rapid phase transition between the
1-5
normal liquid and the superfluid provides an ideal system for
observing vortex formation, which explains the formation of
a thermally excited vortex near a superfluid phase transi-
tion. For laser ablation of metals in bulk superfluid helium,
essentially a similar scenario occurs as the short laser pulse
produces instant heating, and the system then undergoes
rapid cooling by the surrounding superfluid helium. Hence,
the vorticity observed during laser ablation of metal targets
in superfluid helium can be interpreted by the Zurek-Kibble
mechanism.
A recent review provides a thorough summary on the
successes of density functional theory (DFT) in modeling the
structure and dynamics of doped liquid helium droplets.65
However, despite the success with DFT, a detailed theory
of nanowire or filament growth in superfluid helium vortices
does not exist. One of the remaining puzzles is the filament
formation at the later stages, where individual nanowires
become entangled and twisted together to form “ropes” and
networks.66 Many of the observed filaments and nanowires
have rich structures that could not form from a single vortex.
Furthermore, nanowires also form in normal fluid of helium
at temperatures above 2.17 K. However, these are only small
structures without networks or filaments, and the wires have
a less smooth structure when compared with those formed
in superfluid helium.69
1.2.2 Typical Bulk Superfluid Helium
Apparatus
Figure 1.4 shows a typical bulk superfluid helium apparatus
for the formation of nanowires by Gordon et al.67 A metal
target is submerged in superfluid helium, which is ablated
by a pulsed laser through a pair of sapphire windows. At
the base of the cell sits a TEM grid for the collection
of metallic deposits, which can subsequently be removed
from the liquid helium cryostat for imaging. In addition,
1-6
FIGURE 1.4 Apparatus for the formation of nanowires in superfluid helium by laser ablation of a metal target.67 ,69 (a) A target onto
which a pulsed laser is focused. The expansion of the gas and rapid cooling leads to the formation of quantized vortices. (b) A typical
experimental cell immersed in liquid He II showing the target, electrode system, and a holder of TEM grids. (c) A new cell design.69
The cell can be rotated by a motor.
an electrode system is positioned near the target which can
be used to study the electrical conductivity of nanowires in
liquid helium.68
A major drawback of using the “standard” laser ablation
technique in the synthesis of nanowires is that the coagula-
tion of the metal occurs very close to the plasma bubbles,
adjacent to which the hydrodynamic instabilities can lead
to structural distortion of the nanowires and thus a rela-
tively short length. Consequently, a different cell design used
mechanical rotation in superfluid helium to overcome this
problem.69 By using a miniaturized low-power electric motor
in superfluid helium (see Figure 1.5c), an organized array of
parallel quantized vortices can be generated by the rota-
tion of superfluid helium inside the cryostat. The number of
vortices generated by the rotation of the liquid adjacent to
the target will exceed that by the laser pulse, provided that
the rotation is sufficiently fast.69 Unfortunately, this new
design only worked for the duration of one set of measure-
ments, as the motor behavior was unstable at 1.6 K, which
led to the deformation of the components of the motor.
1.2.3 Nanostructures Formed in Bulk
Superfluid Helium
Nanowires grown in bulk superfluid helium are generally
densely packed due to the melting process, and can
have crystalline, polycrystalline, and amorphous structures.
Although relatively large spherical nanoparticles are often
seen, the vast majority of the nanostructures formed are
nanowires, which often entangle each other. Theoretical
modeling by Volk et al. suggests that the large particles
Exotic Nanostructures and Quantum Systems
do not exist initially; instead, they are formed during the
heating of the samples when they were removed from cold
helium to ambient conditions prior to imaging,70 in which
nanoscale wires can fission into particles because of Rayleigh
instability. Figure 1.5 shows typical nanostructures formed
by laser ablation of metals, e.g., Au, Cu, and their alloys, in
bulk superfluid helium.71 For the latter, the growth mecha-
nism is expected to be identical to that of pure metals due
to the universal nature of processes occurring during the
growth of nanostructures in superfluid helium.
Formation of ultrathin nanowires from refractory metals
(e.g., Nb, Re, W, Mo) by laser ablation in bulk super-
fluid helium has also been explored. For these metals, the
diameters of the wires are found to be different, e.g., 4.0,
2.0, and 2.5 nm for niobium, molybdenum, and tungsten,
respectively,67 which, clearly, is due to the critical particle
sizes of different metals. Nanowebs have also been produced
for other metals such as gold, platinum, and mercury, where
the difference in diameters has also been observed. For
instance, gold and platinum nanowires have diameters of
4.5 and 3.0 nm, respectively.72 The observation of metal
nanowires with different diameters provides circumstantial
evidence for the mechanism proposed by Gordon et al.56 As
all the metal nanowire webs are electrically interconnected,
they can potentially be used as electrodes in electrochem-
istry with no support.
Recent experiments have found that nanowires made
from binary metal alloys may have more diverse structures
than pure metals, such as periodic alternation of elemental
composition and core–shell nanostructures, produced by
laser ablation of metal alloy targets.73 The growth of
Novel Nanoscience in Superfluid Helium
FIGURE 1.5 TEM images of sediments formed following the laser ablation of metal targets submerged in superfluid helium for (a, b)
silver; (c, d) copper; (e, f) their alloys. (Reprinted with permission from Ref. [71], Royal Society of Chemistry (Great Britain).)
nanowires starts with the formation of spherical “proto-
clusters” with diameters larger than 2 nm, which is large
enough for spatial phase separation to occur. This is due to
the fact that the phase diagram of a nanocluster correlates
with surface tension rather than with free energy. Before
the protoclusters stick together to form nanowires, they
have a core–shell structure, with the shell material being
more fusible than that of the core. When these clusters
stick together in the vortex, the shell material can then fuse
to allow interconnection for the core and shell respectively,
leading to the formation of core–shell structures or periodic
structures, respectively.
1.3 Synthesis of Nanomaterials in
Superfluid Helium Droplets
Helium droplets possess important properties for the forma-
tion of nanostructures, including (i) the superfluidity, which
allows the free motion of atoms and molecules inside the
droplets and subsequent aggregation into nanoparticles;
(ii) a very low temperature (0.37 K), which helps in the
incorporation of volatile substances into the nanomaterials;
(iii) the chemical inertness of helium, which allows the
formation of nanomaterials with highly reactive species;
(iv) the sequential pickup of different types of materials,
1-7
easing the formation of core–shell nanostructures. Other
important properties include quantized vortices, which, as
in the case of bulk superfluid helium, allow the formation
of 1-D nanostructures. The following sections discuss how
these properties can be exploited for the formation of both
spherical and 1-D nanostructures.
1.3.1 Basics of Helium Droplets
The formation of superfluid helium droplets requires a low
temperature in order to reach the He II phase. Helium
droplets can be formed from bulk superfluid helium, for
example, by agitation using a piezoelectric transducer,74
laser levitation,75 or magnetic field levitation.76 However, in
practice these methods are rarely used because the droplets
formed are very large and are hard to control. In the context
of nanomaterial synthesis, it is extremely challenging to
separate and dope them with atoms and molecules. Instead,
the commonly used method for forming superfluid helium
droplets is expansion of pre-cooled and pressurized helium
into the vacuum (see Figure 1.6 for a typical helium
droplet apparatus), which is more cost-effective and is also
a method consuming less helium. This generally involves
forcing helium gas or liquid through a pinhole nozzle, often
with a diameter of 2–10 μm. The droplets are then formed
either by the condensation of helium gas or by the breakup
1-8 Exotic Nanostructures and Quantum Systems

FIGURE 1.6 Typical helium droplet apparatus for the fabrication of nanoparticles. (a) Nozzle (5 μm diameter), (b) skimmer (with
an aperture of 0.5 mm diameter), (c) helium droplet beam, (d) metal evaporator, (e) translation arm, (f) load-lock chamber, and
(g) deposition target to align the helium droplet beam. The expanded view (i) illustrates addition of metal atoms to the helium droplets
as they pass through the metal vapor. The expanded view (ii) shows the collision of nanoclusters formed in helium droplets with a
surface.

of a liquid droplet beam. After their formation, the helium

droplets cool rapidly by evaporative loss of helium atoms
until a steady-state temperature of 0.37 K is reached.25
They are then collimated into a beam by passing through a
skimmer and enter the pickup region where dopants can be
added.
Depending on the nozzle temperature and the stagna-
tion pressure, the formation of helium droplets undergoes
one of three different expansion regimes,35,77 each having
different average droplet sizes and different size distribu-
tions. Between 10 and 30 K, it is the subcritical expan-
sion zone, where helium gas ejects from the nozzle as a gas
and expands along the isentropes,78 which crosses the gas-
liquid phase separation line from the gas phase side (see
Figure 1.7). The droplets are then formed by the condensa-
tion of atoms via three body collisions, with typical mean
sizes <N He > = 103 –104 , where N He is the number of helium
atoms within a droplet of helium. From 6 to 10 K, the
expansion is in the supercritical region, where the isentrope
crosses the phase separation line from the liquid side. In
this case, liquid helium emerges in the nozzle, which breaks
into helium droplets. The droplets formed in this regime
are much larger, with <N He > = 104 –107 . With further
cooling of helium gas to a lower temperature, e.g., below
6 K, the curve plateaus and the expansion is subsonic. The
phase separation line has already been crossed before the
liquid leaves the nozzle. Rather than helium gas, liquid
helium appears from the nozzle as a continuous liquid beam,
which then breaks up due to Rayleigh instability and forms
very large but mono-dispersed droplets containing over 1010
atoms. 78 Droplets nearly visible to the naked eye can be
made at temperatures near 0 K, with diameters close to
the diameter of the nozzle orifice. These very large droplets
are important for the formation of sizeable nanoclusters
as the aggregation of dopants in helium droplets releases
FIGURE 1.7 Expansion isentropes (dotted lines) of 4 He at
the various expansion regimes. The stagnation pressure is 20 bar.
(Reprinted with permission from Ref. [14], American Institute of
Physics.)
substantial energy that needs to be dissipated, i.e., by evap-
oration of helium atoms.
In the pickup zone, helium droplets can acquire gas-
phase dopants, as illustrated in Figure 1.6. No evapora-
tion is necessary for gas samples and while the vapor above
liquids can also be used. For solid samples, a resistively
heated oven evaporator is often needed to produce vapors.
Compared with bulk superfluid helium, helium droplets
are far more efficient at retaining impurities because they
have a boundary that can confine the dopants. After being
captured by helium droplets, most species will migrate and
reside in the interior of the droplets, somewhere near the
center of the droplets where the potential energy is the
lowest.79 The exceptions are alkali metal atoms and small
alkali clusters, as well as some alkaline earth metals, which
tend to reside on the surface of helium droplet due to
short-range repulsion between the diffuse valence electrons
and helium atoms.80 However, as the size of the clusters
Novel Nanoscience in Superfluid Helium
increases, the London force between the cluster and helium
droplets will increase, which might surmount the short-
range repulsion. Once such a critical size is reached, the
metal clusters will submerge and be located inside the
droplets, e.g., n ≥ 21 for Nan clusters81 and n ≥ 78 for
Kn clusters.82
The pickup probability is near unity on collision between a
dopant atom/molecule and a helium droplet. Consequently,
the total number of atoms/molecules added to the droplets
is determined by the number of collisions, which follows a
Poisson distribution:
zk
Pk (z) = exp (−z) (1.2)
k!
Here, k is the number of species picked up by the droplet;
z is the collision parameter defined by z = σnl, where
σ is the geometric cross-section of the droplets, n is the
number density of dopants, and l is the length of the
pickup region. The number of dopants picked up by the
droplets can be controlled by the size of the droplets and
the number density of gas-phase dopants in the pickup
region. Clearly, the former depends on the stagnation pres-
sure and the nozzle temperature of the helium droplet source
while the latter can be controlled through fine tuning of
the partial pressure(s) of gas-phase atoms/molecules in the
pickup region.
1.3.2 Formation of Nanoparticles in
Helium Droplets
The nanocluster growth process starts with the addition of
a single atom/molecule to the droplets. As a dopant enters
the droplet, its kinetic energy will be instantly removed and
its internal energy, such as vibrational and rotational energy,
can also be removed. Experiments showed that the cooling
rate can be as high as 1016 K/s.34 Hauser et al. modeled the
formation of metal clusters inside helium droplets by using
DFT and molecular dynamic simulations.83 The simulations
suggested that a metal atom will follow a planar rosette-like
trajectory, rather than a straight-line path to the center of
FIGURE 1.8 TEM images of Ag nanoparticles formed in superfluid helium droplets. The nanoparticle density increases from image
(a) to (d) as the deposition time is increased. (Reprinted (adapted) with permission Ref. [19], American Chemical Society.)
1-9
the droplet, until aggregation occurs. Continuous addition
of atoms causes the evaporation of helium droplets in order
to dissipate the kinetic energy of the metal atoms and the
binding energy released in the aggregation. Meantime, the
droplets decrease in size, accounting for energy released at
a rate of 5 cm−1 energy/atom.
Formation of Large Clusters in Helium Droplets
Formation of metallic clusters in helium droplets was first
carried out in 1996. By passing helium droplets through a
heated oven containing silver, indium, or europium, Bartelt
et al. showed that metal clusters with masses up to 2,000
amu could be formed by using mass spectrometry.84 UV-
depletion spectroscopy of silver clusters formed in helium
droplets was then measured, which was very similar to
the spectrum of silver clusters in bulk liquid helium. This
suggested that these particles reside in the interior of the
droplets. Later on, Diederich et al. demonstrated that larger
magnesium clusters consisting of over 1,000 atoms can be
formed.85 Following these early experiments, very large
molecular clusters of (NH3 )n (n = 2 − 104 ), (CH4 )n (n =
1 – 4 × 103 ), and (C3 H6 )n (n = 10 – 104 ) were produced in
helium droplets and were investigated by spectroscopy.86,87
The ability to form sizeable clusters has stimulated novel
nanoscience by using superfluid helium droplets as the nano-
reactors. The first experiment intending to form nanopar-
ticles in helium droplets was performed by Mozhayskiy
et al., who added both Ag and Au to helium droplets and
formed binary metal clusters containing ∼500 metal atoms
and investigated these clusters by spectroscopy.88 The first
deposition experiment was performed by Loginov et al.,
who employed TEM to image silver clusters containing
300–6,000 atoms after they were deposited on a carbon
surface (Figure 1.8).19 In a different experiment, photoab-
sorption spectra were recorded for Agn clusters with the
average number n = 6, 60, 300, 2,000, and 6,000.89 All of the
spectra featured a plasmon peak around 3.6–3.8 eV, which
is consistent with the formation of spherical Ag particles.
However, an additional broad absorption band extending
1-10
down to 0.5 eV was observed for large clusters. This addi-
tional peak was unexpected and was interpreted by a multi-
center growth mechanism, i.e., the growth of multiple small
clusters at different sites within the droplets before they
migrate and coagulate at the center of the droplet. Multi-
center growth occurs if the time between the successive
pickup events is shorter than the time required for a silver
atom to reach the center of the droplets and aggregate with
the existing cluster. Eventually, these small particles migrate
to the center of the droplets and form a single loosely packed
cluster, exhibiting broadband absorption at low frequency
region. As each small cluster can have its own lattice orienta-
tion, multi-center growth can result in polycrystalline struc-
ture. This was confirmed by Ernst’s group, who investigated
Ag and Au nanoparticles by use of high-resolution TEM and
observed polycrystalline structures.90,91
Formation of Core–Shell Nanoparticles
in Helium Droplets
The synthesis of nanomaterials using superfluid helium
droplets is not limited to the formation of spherical nanopar-
ticles containing only one type of materials. Other possibil-
ities are core–shell nanoparticles, alloy nanoparticles, and
nanowires. Besides, it is also possible to synthesize nanopar-
ticles with new properties, e.g., magnetic properties and
catalytic properties. Core–shell nanoparticles consisting of
a core surrounded by a shell made from a different mate-
rial are desirable in many applications because they offer
new electronic, optical, magnetic, and chemical properties.92
By varying the diameter of the core and the thickness
of the shell, the properties of core–shell nanoparticles can
be tuned,93 which is an added advantage of the core–
shell structure. In addition, the surface coating can also
be crafted so that it can be functionalized, making the
nanoparticles compatible with different media. For example,
coating nanoparticles with materials such as silica or gold
is a common strategy for applications of nanoparticles in
medical science.94
Fabrication of core–shell nanoparticles with a well-defined
core and shell structure is often challenging using conven-
tional synthetic methods, such as wet-chemical synthesis
and high-temperature techniques. With these methods,
reactions generally take place at room temperature or above,
and so inter-diffusion between the core and the shell is
difficult to avoid. Furthermore, in wet-chemical synthesis
the overall structure is often loosely packed, which requires
further annealing in order to produce particles with repro-
ducible properties.95 Such treatments can increase the inter-
diffusion between core and shell materials. In the helium
droplet, the strategy for forming core–shell structures is
straightforward: when helium droplets sequentially pass
through two or more ovens containing different types of
materials, these materials will be added to the droplets
following the geometric order. A core will be first grown
in the droplets, and these then travel onwards to the next
pickup cell and acquire a different material. Naturally, this
Exotic Nanostructures and Quantum Systems
atom-by-atom growth allow new materials to grow on the
surface of the existing clusters, resulting in core–shell struc-
tures. As the entire procedure takes place at the very low
temperature of superfluid helium and the deposition is often
at room temperature, inter-diffusion is minimized. In addi-
tion, the growth of core and shell(s) can be independently
controlled, i.e., through the partial pressure in different
pickup cells, and therefore their thicknesses can be indepen-
dently varied. Moreover, nearly any material can be used
as the core due to the very low temperature of superfluid
helium, at which any other substances become solid. These
include solid-phase materials, as well as substances that are
gases or liquids at room temperature.
A proof-of-concept experiment for the formation of core–
shell nanostructures was first carried out by Shepperson
et al.,20 who formed H2 O/X (X = N2 , O2 , CO2 and
CO, etc.) by sequential addition of water and another
molecule to helium droplets, and the core–shell structures
were deduced from mass spectrometric measurements. The
same group also obtained the first evidence for the forma-
tion of core–shell nanoparticles in helium droplets in 2013.21
By sequentially passing helium droplets through a pickup
cell containing Ni vapor and a second cell with gold vapor,
Ni/Au core–shell nanoparticles were formed, which were
investigated by XPS. No shift of the photon energy was
observed for the Ni 2p and Au 4f core levels in the XPS
spectra when compared to pure metals, which excluded the
possibility of alloying between Ni and Au. This confirmed
a well-defined core and shell with a boundary between the
two metals. Later on, Ag/Si core–shell nanoparticles with a
distinct core and shell structure were reported by Ellis and
Yang.96 On TEM images a dark Ag core and a transparent Si
shell are apparently visible due to the difference in electron
scattering cross-sections between Ag and Si. Essentially,
the materials added later grow on the surface of existing
nanoclusters inside the droplets: by this means even core-
multiple shell nanoparticles can be formed, and each layer
can be independently controlled.
Formation of Magnetic Nanoparticles
The unique properties possessed by superfluid helium
droplets make it possible to develop novel nanomaterials
with unusual structures and perhaps unexpected proper-
ties. In contrast to noble metals such as Ag and Au,
strong exchange interactions exist between high-spin transi-
tion metal atoms in addition to metallic bonding. Although
the exchange interactions are still weaker than the metallic
bonding, it is found to play a critical role in the growth of
magnetic nanoparticles inside superfluid helium droplets.
Yang et al. recently synthesized Cr nanoparticles in super-
fluid helium droplets and investigated the magnetic proper-
ties for the first time. Cr is an antiferromagnetic material,
which favors anti-parallel alignment of the atomic spins for
adjacent atoms by its nature, leading to near-zero magneti-
zation in the bulk phase. When grown in superfluid helium
droplets, however, a surprisingly high magnetic moment was
Novel Nanoscience in Superfluid Helium
observed.38 For example, Cr nanoparticles with a diam-
eter of 2.4 nm possess a magnetic moment as high as
1.29 μB /atom at 5 K, and 0.45 μB /atom at room tempera-
ture. The magnetization saturates at a field of ∼0.5 tesla at
room temperature, clearly indicating that the Cr nanopar-
ticles formed are ferromagnetic (see the hysteresis curves in
Figure 1.9).
It is well-known that the magnetic properties of nanoclus-
ters vary with their structures, for example, by purposely
introducing defects and/or lattice strain.97 For Cr nanopar-
ticles grown in superfluid helium, the high ferromag-
netic moments were attributed to defects, as evident from
high-resolution scanning transmission electron microscopy
(STEM). Unlike noble metal nanoparticles grown in helium
droplets,21 Cr nanoparticles were found to be extensively
disordered at the atomic level. This is because of the
rapid continuous cooling offered by superfluid helium, which
instantly removes the excess energy released during the
aggregation of Cr atoms, making the exchange interac-
tions predominant in the absence of thermal effects. The Cr
nanoparticles built atom by atom then have uneven inter-
atomic distances. In the same study, DFT and Monte Carlo
simulations were also performed and a frustrated aggrega-
tion mechanism was proposed.
Formation of Catalytic Nanoparticles
Helium droplets can be used to produce nanoparticles with
diameters <5 nm, which are ideal for catalysis. Under
subsonic expansion conditions, large mono-dispersed helium
droplets can be obtained, which can be used to produce
nanoparticles with a narrow size distribution. This is partic-
ularly important for catalysis, where the particle sizes dras-
tically impact on the catalytic activities.
Wu et al. have recently shown that the size of Au nanopar-
ticles on a titanium dioxide support can be tuned over a
very narrow range of 0.75–3 nm by controlling the helium
droplet size.98 The AuN @TiO2 nanoparticles studied were
shown to be stable up to 473 K and could potentially be
used to catalyze CO oxidation reactions. Stable gold cata-
lysts have been of increasing interest in recent years as
FIGURE 1.9 Hysteresis curves of Cr nanoparticles.38
1-11
gold nanoparticles have displayed superior catalytic activity
compared to the conventional platinum group, especially
when the diameter of the nanoparticles is less than 5 nm.99
Using helium droplets the nanoparticles can be prepared
without surfactants or capping ligands, which might other-
wise impede the catalytic performance.100 Therefore, helium
droplets hold promise as a route to prepare stable and
tunable nanoparticles for catalysis.
1.3.3 Quantized Vortices and the Growth
of Nanowires Using Superfluid
Helium Droplets
Given the presence of quantized vortices in bulk superfluid
helium, the question arises as to whether these might exist
in helium droplets. Theoretical modeling has suggested that
quantized vortices can occur in helium droplets101−103 but
the first evidence for their existence was only obtained in
2012.52 Gomez et al. added silver atoms to helium droplets
with mean diameters of 100, 300, and 1,000 nm (composed
of 107 –1010 helium atoms). Subsequently, the Ag-doped
droplets collided with a thin carbon film substrate, and Ag
nanomaterials were deposited onto the substrate for TEM
imaging. Silver nanoparticles obtained from helium droplets
with a diameter of 100 nm or below are mostly spher-
ical, whereas larger droplets produced track-like deposits
consisting of elongated Ag segments (nanorods). The results
showed that the shapes and overall lengths of the tracks
varied with the helium droplet size, suggesting that Ag
atoms are pinned to quantized vortices spanning the helium
droplets. In a similar experiment, Spence et al. added Ag
to helium droplets at a lower doping rate and observed
spherical nanoparticles aligned in a chain.104 Later on,
Volk et al. performed both experiments and theoretical
modeling on the silver nanowires, suggesting that the ultra-
thin nanowires can fragment due to Rayleigh instability,
which then melt into spheres as in the case of bulk superfluid
helium.70
Direct imaging of quantized vortices in helium droplets
was recently achieved by Gomez et al. using ultrafast X-ray
diffraction.105 In this experiment, xenon atoms were added
to large helium droplets with radius ranging from 100 to
1,000 nm, and these were then illuminated by a free electron
laser source. Bragg patterns from xenon clusters trapped
in the vortex cores are consistent with the presence of an
array of quantum vortices in the droplets. Surprisingly, the
vortex densities in helium droplets appear to be ∼5 orders of
magnitude larger than those observed in bulk liquid helium.
Quantized vortices offer the prospect of creating a range
of 1-D nanostructures in helium droplets. In a recent exper-
iment by Latimer et al., quantized vortices were shown to
lead to ultrathin 1-D nanowires made from elements such
as Au, Ag, Si, Ni, and Cr. Both the length and the diam-
eter of the nanowires can be controlled, i.e., by the size of
the droplets and the partial pressure in the pickup region.53
The diameters of the nanowires are generally in the region
of 3–5 nm, and the length can be increased at higher doping
1-12
rates. This technique has also been employed by Thaler et al.
to grow Au/Ag bimetallic core–shell nanowires.106 Both Au
and Ag were evaporated by resistive heating and were then
added sequentially to the helium droplets. The resulting
nanowires were then investigated by energy-dispersive X-ray
spectroscopy (EDX) to confirm the core–shell structure.
1.4 Perspectives and Challenges
Superfluid helium, with its unique properties, has opened
up many exciting opportunities for novel nanoscience.
Compared with bulk superfluid helium, helium droplets
offer a much higher degree of control and flexibility in
the selection of materials, and also ease the formation of
core–shell and core-multiple-shell nanoparticles. Many of
these are highly challenging and are hard to access by
conventional synthetic methods, making superfluid helium
a uniquely powerful tool for nanoscience and nanotechnolo-
gies.
Despite the fascinating opportunities opened up by super-
fluid helium, there exist some significant challenges for
experiments in both bulk superfluid helium and helium
droplets. Bulk superfluid helium has so far been used to
develop nanowires and nanowebs by laser ablation of metal
targets, yet the underlying physics for the generation of
quantized vortices and subtle reactions for the formation
of 1-D nanostructures remains debatable. The prerequisite
for the formation of quantized vortices is the generation of
angular momentum but it is unclear how laser ablation can
generate this for helium atoms near the focus point of the
laser light, and how the phase transition at the normal liquid
and superfluid interface may assist the process. These are
the key questions that need to be answered from funda-
mental aspects, which require both experimental and theo-
retical effort. Another major weakness of using superfluid
helium in the fabrication of nanomaterials is associated with
the relatively low production rates of nanoparticles and
nanowires, and the high costs of both bulk liquid helium and
helium droplet apparatus. For helium droplets, the produc-
tion rate is restricted by the flux of the droplets; while for
bulk superfluid helium, the intrinsic limitation is the evap-
oration of metals in superfluid helium without significant
disturbance to dismiss the superfluidity. Both approaches
are currently restricted to a production of sub-milligram
quantities per day, and they all require sophisticated high-
vacuum and low-temperature apparatuses. These, in addi-
tion to the scarceness of helium, make the approaches non-
economical for many possible applications. However, this
can be resolved if scale-up approaches can be developed and
thus the practical impact of superfluid helium in nanoscience
and nanotechnology can be promoted.
To close this chapter, we will highlight some new possi-
bilities offered by superfluid helium. The first is the fabri-
cation of core-multiple-shell nanostructures with distinct
boundaries between layers using helium droplets. These
nanostructures are extremely challenging to make with
Exotic Nanostructures and Quantum Systems
conventional techniques, and yet may offer novel properties
that are important for applications spanning spintronics,
photonics, electronics, and biomedical science. From a
fundamental point of view, the fabrication of such new
nanostructures and investigation of the associated prop-
erties are important to develop new theoretical models,
which in turn will stimulate the design of new nanomate-
rials and the development of next-generation technologies.
Another possibility is to form nanostructures with struc-
tures different from the bulk counterparts, as well as those
made from conventional synthetic approaches, as manifested
in the formation of ferromagnetic Cr nanoparticles. In this
process the ultrahigh thermal conductivity of the very cold
superfluid helium plays a critical role to remove thermal
energy released during the growth of nanomaterials, hence
accentuates other effects which may often be overwhelmed
by thermal reactions. The resulting meta-stable structures
may offer new opportunities for applications. Consequently,
superfluid helium technology can impact on the fundamen-
tals of nanoscience and can potentially open up new possi-
bilities in developing next-generation nanotechnologies.
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 2
Stimuli-Responsive Polymeric Nanomaterials
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-1
2.2 Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-3
2.3 Nanowires and Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-8
Siyang Wang and 2.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-11
Marek W. Urban Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-11
Clemson University References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-11

2.1 Introduction advances. For example, one of the questions raised a

Stimuli-responsive nanomaterials play an important role in
modern materials’ design and offer numerous opportunities
for future technological advances. Although continuously
increasing efforts have been devoted to the development of
stimuli-responsive polymers that primarily include synthesis
of stimuli-responsive building blocks and their polymer-
ization, the formation of higher-order structures, from
nano- to micro- and above, remains to be challenging.
Recently published reviews summarized previous and
current efforts in this field along with potential technolog-
ical opportunities.1−4 The main prerequisite for developing
higher-order responsive systems is to control the placement
of the stimuli-responsive building blocks, as their location
may enable or disable responsiveness at higher-order hier-
archical structures. The primary motivation for developing
stimuli-responsive nano- and higher-order assemblies is the
ability to locally or globally alter physical (thermal, elec-
tromagnetic radiations, electric/magnetic fields) and chem-
ical (pH, ionic strength, covalent bonding, or supramolecular
chemistry) responses, while empowering macroscale assem-
blies. Precise control of stimuli-responsive building blocks in
a copolymer can be facilitated by controlled polymerization
(CP) approaches, among which nitroxide-mediated radical
polymerization (NMP)5 , atomic transfer radical polymer-
ization (ATRP)6 , reversible addition-fragmentation chain
transfer polymerization (RAFT)7 along with the recently
developed heterogeneous radical polymerization (HRP)8
capable of producing ultrahigh molecular weight block
copolymers that contain built-in stimuli-responsive nano-
assemblies play an important role.
Numerous studies published as early as 1950s have
reported the synthesis of colloidal nanomaterials, which
primarily focused on spherical colloidal nanoparticles known
as latexes.9,10 While today these technologies represent
significant and mature portion of polymer industries,11,12
every once in a while, this field is rejuvenated by new
while back was how colloidal nanoparticles form films.13,14
The significance of this question had important implica-
tions for several technological advances because film forma-
tion significantly impacts adhesion, mechanical, and optical
properties of polymeric coatings.3,15,16 Also, hollow poly-
meric nanoparticles can effectively alter opacity of poly-
meric films.17−20 During film formation, there are processes
that may have constructive or adverse influence on inter-
facial properties; film–air or film–substrate interfaces may
be hydrophobic or hydrophilic, depending upon the strat-
ification of individual components.15,16,21−25 Today, as
these technologies are mature, and spherical, core–shell,
and hollow colloidal nanoparticles containing hydrophobic
fluoro-monomers can be produced by emulsion polymeriza-
tion in water,26 new opportunities have arisen, which is
reflected by the formation of more complex anisotropic 2-3D
morphologies with stimuli-responsive attributes.27 To place
these advances in prospective, Figure 2.1 illustrates an array
of nanostructures produced over the years, which range
from isotropic spherical,28−29 core–shell,30−34 hollow,35−37
and concentric nanoparticles38−40 to Janus particles41−43 ,
gibbous/inverse-gibbous,4,44,45 or cocklebur46,47 nanoparti-
cles, nanowires48 and nanotubes49 . The advantage of intro-
ducing heterogeneities in stimuli-responsive nanomaterials
offers diverse properties brought about by each individual
phase/component into one nano-object, thus enabling the
creation of larger scale micro- and macro-devices with a
broad spectrum of properties and a small volume. There-
fore, despite maturity of some of these technologies, the
exploration of stimuli-responsive polymeric nanomaterials
continues to be of great interest.
Numerous colloidal nano-objects with various morpholo-
gies, functionalities, and responsiveness were developed.
Figure 2.1a–c depicts isotropic spherical, core–shell, and
hollow nanoparticles capable of uniformly altering size,
shape, color as well as other properties, which were
summarized in several review articles.50−53 Figure 2.1d–g

2-1
2-2 Exotic Nanostructures and Quantum Systems

FIGURE 2.1 Representative examples of morphologies of nanomaterials (I), physical/chemical stimuli (II), responses manifested
by shape, color, and dimensional changes (III), selective examples of polymers/copolymers responsible for responsiveness (IV), and
references (V). Abbreviations: poly(dimethylaminoethyl methacrylate) (pDMAEMA), poly(N-isopropylacrylamide) (pNIPAM), poly-
acrylic acid (pAA), polyhydroxyethylmethacrylate (pHEMA), poly(glycidyl methacrylate) (pGMA), poly(4- vinylpyridine) (p4VP),
poly(methacrylic acid) (pMAA), polycaprolactone (pCL), polythioether ketal (pTEK), β-CD (β-cyclodextrin), poly(amidoamine)
(PAMAM), PEGylated phospholipids (PEGphospholipids), poly(lactic-co-glycolic acid) (pLGA), spiropyran (SP).

illustrates anisotropic nano-objects that are capable of
changing size and morphologies asymmetrically in 3D,
thus enabling orientation or self-assembly of heterogeneous
and hierarchical structures. Stimuli-responsive anisotropic
nanoparticles, such as gibbous and Janus nanoparticles,
nanowires, and nanotubes, are of particular interest not
only in the context of mimicking biological organisms
but also due to potential lithographic and biomedical
applications. It should be noted that limited analyt-
ical tools are available to elucidate the origin of molec-
ular processes responsible for their behavior and prop-
erties, thus making the measurements of asymmetric
responses to external stimuli troublesome. Another chal-
lenge is to imbed stimuli-responsive components, facilitating
directional interactions and multi-dimensional encoded
signaling capable of interacting with an environment.
Another random document with
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 The Project Gutenberg eBook of Early
explorers of Plymouth Harbor, 1525-1619
This ebook is for the use of anyone anywhere in the United States
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Title: Early explorers of Plymouth Harbor, 1525-1619

Author: Henry F. Howe

Release date: November 16, 2023 [eBook #72138]

Language: English

Original publication: Plymouth, MA: Plimoth Plantation, Inc. and the

Pilgrim Society, 1953

Credits: Steve Mattern and the Online Distributed Proofreading Team

at https://www.pgdp.net

*** START OF THE PROJECT GUTENBERG EBOOK EARLY

EXPLORERS OF PLYMOUTH HARBOR, 1525-1619 ***
 Transcriber’s Note
Larger versions of the illustrations may be seen by right-
clicking them and selecting an option to view them separately,
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(Larger)
 Early
Explorers of
Plymouth Harbor
1525–1619

by
Henry F. Howe
Published jointly by
Plimoth Plantation, Inc.
and the Pilgrim Society
Plymouth, 1953
Copyright by Plimoth Plantation, Inc., and the Pilgrim Society, 1953

Henry F. Howe is author of Prologue to New

England, New York, 1943, and Salt Rivers of the
Massachusetts Shore, New York, 1951, both
published by Rinehart & Co., Inc. Much of the
material here presented is condensed from these
volumes.
The cover decoration, which is reproduced from
the London 1614 translation of Bartholomew
Pitiscus, Trigonometry: or the doctrine of
triangles, shows not only early seventeenth
century ships but seamen using a cross-staff and
casting a lead.

Printed in offset by The Meriden Gravure Company, Meriden,

Connecticut
Composition by The Anthoensen Press, Portland, Maine
Early Explorers of Plymouth Harbor,
1525–1619
VISITORS to Plymouth are often amazed to learn that the Mayflower
was not the first vessel to drop anchor in Plymouth Harbor. The
“stern and rock-bound coast” of Massachusetts was in fact explored
by more than twenty recorded expeditions before the arrival of the
Pilgrims. At least six of these sailed into Plymouth Harbor. Plymouth
appeared on five good maps of the Massachusetts coast by 1616,
one of them a detailed map of Plymouth Harbor itself, made by
Samuel de Champlain in 1605. The Harbor had been successively
called Whitson Bay, the Port du Cap St. Louis, and Cranes Bay by
English, French and Dutch explorers, but the name Plimouth,
bestowed on it by Captain John Smith in 1614, was the one the
Pilgrims perpetuated.
The Pilgrim voyage was the successful culmination of a century
of maritime efforts along the New England coast by Spanish
explorers, Portuguese fishermen, French and Dutch fur traders, and
Elizabethan English “sea dogs.” All the western ports of Europe
seethed with ambitious shipmasters in search of opportunities for
profit in commerce or fishing, free-booting, the slave trade, warfare
or piracy. Some, like Henry Hudson, visited New England primarily
as geographers looking for a Northwest Passage through North
America. A few were probing out possibilities for a colonial
beachhead in the New World. One of these, led by French Jesuits,
had, like the Pilgrims, a religious motive. Three or four others
attempted New England colonies, but failed. Only the Pilgrims
succeeded in hanging on, through the inevitable preliminary
disasters of the first year or two, to found a permanent colony.
Indians of Massachusetts probably first saw Europeans during
the four Vinland voyages of Leif Ericsson and his successors
between 1003 and 1015 a.d. There is good reason to suppose that
these voyages touched the shores of Cape Cod and the islands
about Martha’s Vineyard, but no direct evidence connects them with
Plymouth Harbor. Continuous contact with Europeans did not begin
until nearly five hundred years later when John Cabot’s second
Newfoundland voyage coasted North America southward to the
Carolinas in 1498. The Portuguese nobleman, Miguel Cortereal, a
castaway on a voyage of exploration, may have lived among the
Indians at the head of Narragansett Bay from 1502 until 1511.
Certainly these Indians, the ancestors of Massasoit, were visited in
1524 by Giovanni da Verrazano, whose French expedition spent two
weeks in Narragansett Bay in that year. Verrazano wrote that he was
met by about twenty dugout canoes filled with eager people, dressed
in embroidered deerskins and necklaces. The women wore
ornaments of copper on their heads and in their ears, and painted
their faces. These Indians were delighted to trade furs for bright bits
of colored glass. They lived in circular houses “ten or twelve paces in
circumference, made of logs split in halves, covered with roofs of
straw, nicely put on.” From the description, these people were no
doubt the Wampanoags, who a hundred years later were such
friendly allies to the Pilgrims at Plymouth, only thirty miles away.
Verrazano did not enter Massachusetts Bay. But in the spring of
1525 a Spaniard, Estevan Gomez, cruised for two months on the
New England coast. While he left no narrative of his voyage, “Tierra
de Estevan Gomez” appeared immediately on Spanish maps of the
period, notably that of Ribero, 1529. An indentation of the bay shore
behind his “Cabo de Arenas” sufficiently suggests Plymouth Harbor
and Cape Cod Bay to make one speculate whether this is not in fact
the first record of a visit to Plymouth, ninety-five years before the
landing of the Pilgrims. What has been interpreted as Boston Harbor
on this Ribero map bears the name “Bay of St. Christoval,” but the
indentation that suggests Plymouth remains nameless. It seems
likely that Estevan Gomez was the discoverer of Plymouth in 1525.
After these first Massachusetts discoveries, there follows a
period of seventy-five years of documentary obscurity so far as
Massachusetts is concerned. Maritime activities about
Newfoundland, the St. Lawrence River, and Nova Scotia steadily
grew. Cartier founded, and then had to abandon, his French colony
at Quebec. Jehan Allefonsce, one of his shipmasters, was blown
southward from the Newfoundland banks in 1542, into “a great bay
in latitude 42°,” but Massachusetts Bay is not mentioned during the
rest of the century. Both French and English built up an increasing
fur trade on the Maine coast, especially about the Penobscot and in
the Bay of Fundy. Fishermen from all the maritime nations of Europe
crowded in increasing numbers to the Newfoundland banks, carrying
back apparently inexhaustible supplies of codfish to feed Catholic
Europe in the season of Lent. By 1578 as many as 350 fishing
vessels were making the transatlantic voyage, usually twice each
year. Since fishermen and fur traders rarely left written records, we
can only assume that with the increased volume of shipping, some of
these vessels found their way to Massachusetts shores. But we have
no documentary evidence of their visits.
 (Larger)
TIERA DE AYLLON
TIERA DE ESTEVA GOMEZ
TIERA NOVA: DE CORTEREAI
Map of the North American Coast, a portion of the World Map made
by Diego Ribero in 1529, showing the results of the explorations of
Estevan Gomez in 1525
Reproduced from the Map Collection, Yale University Library

Inevitably the tremendous growth of all this free-lance

commercial shipping, in the fur trade and fisheries, must lead to
attempts to organize it either into colonial administrations under
government control, or business companies privately financed.
Everyone could see that permanent bases were needed in the New
World. International quarrels and actual piracy were already
appearing in the Newfoundland fisheries. Sir Humphrey Gilbert
determined to make Newfoundland an English colony. But in 1583
his well-organized expedition came to grief by shipwreck. His half
brother, Sir Walter Raleigh, renewed the attempt, this time at
Roanoke in the Carolinas, but was unable to maintain the colony’s
supply, once it was established. The project failed. But the idea was
right, and men in England like Raleigh and Richard Hakluyt, the
historian of English voyages, kept preaching the necessity of
overseas colonies. Similar ideas were growing in the western ports
of France.
The turn of the century marked the beginning of a concerted
campaign on the part of both France and England to establish
plantations in New England. The first move was made by a group of
free-lance English merchants who in 1602 sent out Bartholomew
Gosnold on a commercial voyage with thirty-two men in the bark
Concord. Its objective was twofold, to get sassafras (a medication
thought to be “of sovereigne vertue for the French poxe”) and to
establish an outpost somewhere in the area described by Verrazano
seventy-five years before. Sir Humphrey Gilbert’s son Bartholomew
was among the company. After brief landings on Cape Cod and
Martha’s Vineyard, the expedition built a hut on the islet in the pond
on Cuttyhunk Island in Buzzards Bay, there traded with the Indians,
cut a cargo of sassafras root and cedarwood, and after a minor
altercation with the natives pulled up stakes and sailed back to
England with two enthusiastic narratives of the country and its
commodities.
Less than nine months later, and obviously because of the
success of the Gosnold voyage, a new expedition of two vessels,
Speedwell and Discoverer, with forty-four men and boys, sailed to
Massachusetts from Bristol under command of Martin Pring, a
Devonshire skipper. This voyage was instigated by Richard Hakluyt,
together with some merchants of Bristol. Robert Salterne, pilot of the
Gosnold voyage, was assistant to Pring. Deliberately avoiding the
long sail around Cape Cod, Pring entered Massachusetts Bay,
coasted its North Shore looking for sassafras, and finding none,
sailed across to “a certaine Bay, which we called Whitson Bay.” It
had a “pleasant Hill thereunto adjoyning,” and a “Haven winding in
compasse like the Shell of a Snaile,” with twenty fathoms at the
entrance, and seven fathoms at the land-locked anchorage. Here
was a “sufficient quantitie of Sassafras.” This was Plymouth Harbor
in 1603.
Ashore, Pring’s men built a “small baricado” or watchtower and
kept it manned with sentinels while the crew worked in the woods.
They also took ashore with them two great mastiff dogs, of whom the
Indians were mortally afraid. Indians appeared in considerable
numbers, “at one time one hundred and twentie at once.” One of the
crew delighted the natives by playing a guitar and they sang and
“danced twentie in a ring” about him and gave him gifts of tobacco,
tobacco pipes, snakeskin girdles and “Fawnes skinnes.” They had
black and yellow bows, and prettily decorated quivers of rushes filled
with long feathered arrows. They used birch-bark canoes “where of
we brought one to Bristoll.” Their gardens were planted with tobacco,
pumpkins, cucumbers and corn. The men wore breech clouts, and
feathers in their knotted hair; the women “Aprons of Leather skins
before them down to the knees, and a Bears skinne like an Irish
Mantle over one shoulder.”
 (Larger)
Martin Pring’s men ashore with a mastiff, Plymouth Harbor, 1603
Reproduced from J. P. Abelin, De Wytheroemde Voyagien der Engelsen (Leiden,
1727) in the Boston Athenæum

For the story of the latter days of their seven weeks’ stay at
Plymouth, we can scarcely do better than read Pring’s narrative in
the original: “By the end of July we had laded our small Barke called
the Discoverer with as much Sassafras as we thought sufficient, and
sent her home into England before, to give some speedie
contentment to the Adventurers; who arrived safely in Kingrode
about a fortnight before us. After their departure we so bestirred
ourselves, that our shippe also had gotten in her lading, during which
time there fell out this accident. On a day about noone tide while our
men which used to cut down Sassafras in the woods were asleep, as
they used to do for two houres in the heat of the day, there came
down about seven score Savages armed with their Bowes and
Arrowes, and environed our House or Barricado, wherein were foure
of our men alone with their Muskets to keepe Centinell, whom they
sought to have come down unto them, which they utterly refused,
and stood upon their guard. Our Master like-wise being very careful
and circumspect, having not past two with him in the shippe, put the
same in the best defence he could, lest they should have invaded
the same, and caused a piece of great Ordnance to bee shot off to
give terrour to the Indians, and warning to our men which were fast
asleepe in the woods: at the noyse of which peece they ... betooke
them to their weapons, and with their Mastives, great Foole with an
halfe Pike in his mouth, drew down to their ship; whom when the
Indians beheld afarre off with the Mastive which they most feared, in
dissembling manner they turned all to a jest and sport and departed
away in friendly manner, yet not long after, even the day before our
departure, they set fire on the woods where wee wrought, which wee
did behold to burne for a mile space, and the very same day that
wee weighed Anchor, they came down to the shore in greater
number, to wit, very neere two hundred by our estimation, and some
of them came in theire Boates to our ship, and would have had us
come in againe, but we sent them back, and would none of their
entertainment.” One would love to know more than is provided in
Martin Pring’s brief narrative in order to estimate fairly whether the
English had given provocation to the Indians for this threatened
attack at Plymouth. The only hint of provocation is the taking of a
canoe back to England.
Had Plymouth been populated by two hundred Indians in 1620 it
seems unlikely that the Pilgrims could have survived. The English
adventurers transferred their explorations to the coast of Maine,
where in 1605 George Waymouth, and in 1606 Martin Pring, made
investigations preparatory to the major colonization attempt of the
English Plymouth Company at Sagadahoc, the mouth of the
Kennebec River. This colony failed after a year through a breakdown
in leadership. For our purposes it is significant that the English sent
no further explorations into Massachusetts waters for eight years
after the voyages of Gosnold and Martin Pring. It looks as though the
enmity of the Massachusetts Indians dissuaded English merchants
from further plans to set up a colony in that region.
Plymouth’s next visitor was that great French explorer and
empire builder, the founder of Canada, Samuel de Champlain. A
group of French merchants organized by the governor of Dieppe,
that old French port which had been sending fishermen to America
for more than a century, succeeded in 1603 in getting from Henri IV
a commission to found a colony. After spending the summer of 1603
exploring the St. Lawrence, the leaders decided that a more
southern climate was desirable. Accordingly in 1604, De Monts and
Pont-Grave, with Samuel de Champlain as geographer and
chronicler of the expedition, explored the Bay of Fundy and founded
a colony on Dochet Island in Passamaquoddy Bay. Half the colonists
died during the first winter, and the colony was moved across the
Bay to a better site at what is now Annapolis, Nova Scotia. Meantime
Champlain spent the summers of 1605 and 1606 exploring the New
England coast, familiarizing himself with all the shores as far south
as Woods Hole in Massachusetts. He wrote a splendid account of
these expeditions, which is still good reading; and for the first time
produced a good map of the Massachusetts coast, with detail maps
of Gloucester, Plymouth, Eastham and Chatham harbors.
 (Larger)
Champlain’s Map of Plymouth Harbor, 1605
Legends on Champlain’s Map of Port St. Louis with comments

A. SHOWS THE PLACE WHERE VESSELS ANCHOR

The figures show the fathoms of water. The depths are now much less than
those indicated on the map, and the difference may represent an actual
change.
B. THE CHANNEL
C. TWO ISLANDS
Clarks Island, a low swell of upland occupied by farms, and Saquish Head,
likewise low upland occupied by a few buildings and some bushes.
D. SAND DUNES
The long line of dune beaches, collectively called Duxbury Beach,
connecting Brant and Gurnet points.
E. SHOALS
A prominent feature of this part of Plymouth Harbor and of Duxbury Bay. As
Champlain states, they are largely bare at low tide.
F. WIGWAMS WHERE THE INDIANS CULTIVATE THE LAND
A number are situated on the slope where now stands the historic city of
Plymouth founded by the Pilgrim Fathers fifteen years after this visit of
Champlain.
G. THE SPOT WHERE WE RAN OUR PINNACE AGROUND
Browns Bank, still an impediment to the navigation of the harbor. Apparently
it was while their pinnace was aground that Champlain landed on the north
end of Long Beach, where he sketched this map.
H. A KIND OF ISLAND COVERED WITH TREES, AND
CONNECTED WITH THE SAND DUNES
The Gurnet, a low-swelling upland island, ending in a low bluff; it is largely
bare of trees and occupied by a group of buildings belonging to the light
station. It was thickly wooded when the Pilgrim Fathers settled here in 1620.
Slafter’s contention that this was Saquish Head he later abandoned.
I. A FAIRLY HIGH PROMONTORY, WHICH IS VISIBLE FROM
FOUR TO FIVE LEAGUES OUT TO SEA
Manomet Hill, 360 feet in height, a plateau ridge cut to an abrupt bluff where
it reaches the sea, thus forming a conspicuous landmark.