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New Topics in Superconductivity Research 1st Edition
Barry P. Martins Digital Instant Download
Author(s): Barry P. Martins
ISBN(s): 9781594549854, 1594549850
Edition: 1
File Details: PDF, 11.46 MB
Year: 2006
Language: english
NEW TOPICS IN
SUPERCONDUCTIVITY RESEARCH

No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or
by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no
expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of information
contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in
rendering legal, medical or any other professional services.
NEW TOPICS IN
SUPERCONDUCTIVITY RESEARCH

BARRY P. MARTINS
EDITOR

Nova Science Publishers, Inc.


New York
Copyright © 2006 by Nova Science Publishers, Inc.

All rights reserved. No part of this book may be reproduced, stored in a retrieval system or
transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical
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LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA


Available upon request

ISBN 978-1-61668-113-5 (E-Book)

Published by Nova Science Publishers, Inc.  New York


CONTENTS

Preface vii
Chapter 1 Hot Electron Non Equilibrium High Temperature 1
Superconductor THz Radiation Sensing and the Integrated
Electron Cooling
M.M. Kaila
Chapter 2 Use of Acoustic Emission in Studying High-Tc 45
Superconducting Phenomena
E. Dul’kin and M. Roth
Chapter 3 Van Hove Scenario for High Tc Superconductors 73
J. Bok and J. Bouvier
Chapter 4 Studies of YBCO Electromagnetic Properties for High- 107
Temperature Superconductor Maglev Technology
Honghai Song, Jiasu Wang, Suyu Wang, Zhongyou Ren,
Xiaorong Wang, Oliver de Haas, Gunter Fuchs, Ludwig
Schultz
Chapter 5 Study of High Temperature Superconductor 157
Liang FangYing
Chapter 6 Studies of Cu-based High Temperature Superconductors by 195
Using Coincidence Doppler Broadening of the Electron
Positron Annihilation Radiation Measurement Technique
Mahuya Chakrabarti, D. Sanyal, A. Sarkar, S. Chattopadhyay
Chapter 7 Comparative Study of Statisics of Cooper’s Electron Pairs in 223
Low-Temperature Superconductors and Coupled Holes Pairs
in High Tc Ceramics
I.G. Kaplan and O. Navarro
Chapter 8 Unified Explanation for the Nine Features of Inhomogeneities 239
of Gap and Superconductivity in the High-Tc Cuprates
Fu-sui Liu and Yumin Hou
vi Barry P. Martins

Chapter 9 About the Superconductivity Theory 253


R. Riera, J.L. Marín, R. Rosas and R. Betancourt-Riera
Index 307
PREFACE

Superconductivity is the ability of certain materials to conduct electrical current with no


resistance and extremely low losses. High temperature superconductors, such as La2-
xSrxCuOx (Tc=40K) and YBa2Cu3O7-x (Tc=90K), were discovered in 1987 and have been
actively studied since. In spite of an intense, world-wide, research effort during this time, a
complete understanding of the copper oxide (cuprate) materials is still lacking. Many
fundamental questions are unanswered, particularly the mechanism by which high-Tc
superconductivity occurs. More broadly, the cuprates are in a class of solids with strong
electron-electron interactions. An understanding of such "strongly correlated" solids is
perhaps the major unsolved problem of condensed matter physics with over ten thousand
researchers working on this topic. High-Tc superconductors also have significant potential for
applications in technologies ranging from electric power generation and transmission to
digital electronics. This ability to carry large amounts of current can be applied to electric
power devices such as motors and generators, and to electricity transmission in power lines.
For example, superconductors can carry as much as 100 times the amount of electricity of
ordinary copper or aluminum wires of the same size. Many universities, research institutes
and companies are working to develop high-Tc superconductivity applications and
considerable progress has been made. This new volume brings together new leading-edge
research in the field.
The recently discovered high temperature superconductors ( HTSCs ) have been found, to
be a very suitable class of materials, for the development of THz radiation sensors. They are
easy to manufacture and operate, over the efficiently achievable,thermoelectric temperature
control interval of, 80-140K. The temperature control over this range, can easily be
manipulated by liquid nitrogen as a refrigerant. But the recently developed, low temperature
thermoelectric refrigeration materials ( e.g. Zr, Hf penatellurides ), provide an efficient and a
very convenient alternative. The THz, hot electron thermal sensor ( HETS ) technique, has
now reached an advanced stage of development. Here the electrons are heated by a local
femtosecond pulsed laser pump, above the lattice temperature. This copious supply of
electrons, is then modulated by the chopped, remote THz radiation signal, which is to be
detected. The chopped radiation, modulates the non equilibrium, electron-phonon thermal
dynamics.
The associated response of the dynamics, of the electrical resistance of the
superconductor, on a femtosecond time scale, is the key,to the THz radiation detection. This
is facilitated by adding to the sensor an external heterodyne electronic system. Pulsed boost
viii Barry P. Martins

power of the laser pump, provides for the electrons, the AC ( alternating current ) bias. The
DC ( direct current ) bias is carried out by, a fixed, I ( current ) through or V ( Voltage )
across the device. The sensor is operated, in the hot electron mode i.e. near the critical
temperature Tc of the superconductor.The THz thermal sensors based on the ' hot electron
phenomena',like any other thermal sensor, require cooling of the electrons.This may be an
external, and or an internal ( self ) cooling. A convenient, thermoelectric method of cooling,
for the HTSC sensors, is the aim in the development of the sensor.The heated electrons, due
to Ac and DC bias, are above the lattice temperature. Hot electrons, are easy to manipulate,
at the THz frequencies. The quasiparticle excitations, resulting from the electron-phonon
thermaldynamics, provide the desired tool of sensing. These excitations have relaxation time
of 10-12 - 10-15s, in the HTSCs. The superconducting coherence length in HTSCs, is much
shorter in comparison to that found in low temperature superconductors ( LTSCs ). This puts
a much lower limit, on the workable dimensions in space,in the superconducting film, for use
as an HTSC sensor.HTSC thermal sensing provides a tool, between temperatures 50-140K,for
making a convenient class of THz band of radiation sensors. This window of the
electromagnetic radiation spectrum ( 10-5 m to 10-3 m wavelength ), provides a faster and yet
invisible light,for applications, in communication, astronomy and medicine. In order for the
electrons, to be an efficient means of sensing the THz radiation, they must loose heat, at a
very fast rate.This should happen as close as possible to the point of incidence, of the incident
radiation. This means electrons need to travel as short a distance, as possible, in the sensor,
before being collected. The devices developed so far, have electron heat dissipation, mainly
via the sensor film-substrate, system. In this system, the electron-phonon interactions, with
the relaxation time 10-12-10-15s, lasting on a much wider space,control the ultimate speed of
the sensor. The phonons are an obstruction to the fast movement of the electrons, away from
the sensitive areas of the sensor. They originate, in the sensor film material, and also as a
result of the back flow from the substrate. This is after the sensitive area has been heated by
the laser beam. The DC boas also adds its share of heating to the sensor,raising the average
temperature of the sensor, above that of the substrate.
It is an easy way out, but costly and cumbersome, to use mK range of temperatures, to
reduce electron-phonon interactions. The much reduced phonon specific heat, at mK
temperatures, provides the much desired environment, for the easy transport of the electrons,
but with the added complexity of a cryogenics infrastructure. One can produce scatter free
travel, of the electrons in the film, in various alternate ways. One possible way would be, to
design, a regiment of superconducting dots, on a low dimensional structure,thermeolectric
film. The interface of the, HTSC-thermeolectric junctions, so produced, can be used, as an
efficient source of highly mobile electrons.The output can then be collected, as an integrated
signal from the dots. May be one can sandwich, an insulating layer, in between, the
superconducting and thermeolectric layers, to achieve tunneling of the electrons, with
minimum back flow of the heat. The materials considered highly efficient, in thermal
sensing, at present, are the low temperature superconductors ( LTSCs ).Typical examples are
Al, Pb, Nbn, etc. and are operated at mK temperatures.The specific heat of the phonons at mK
temperatures, is very low ~ 102J/K/m3. The specific heat of the electrons may be, slightly
higher or lower than that of the phonons. At these low temperatures, electrons travel almost
free of interactions with the phonons. In the case of HTSCs, e.g. YBaCuO, BiSrCaCuO,
etc., the scenario is quite different. Here, the specific heat of the electrons is high ~
104J/K/m3. The specific heat of the phonons is much higher ~106J/K/m3. The phonons, play a
Preface ix

very deleterious role, in the performance of an HTSC thermal sensor. A new ray of hope, in
the direction of efficient electron cooling, with minimum involvement of phonons, has now
emerged. It is by virtue of the nano structure, thermoelectric cooling, materials and devices,
operating between 50 and 200K. Band gap engineering using nano structures, can channel
much faster electrontransport in low dimensions. Integrated cooling, can be provided by the
already well known thermoelectric cooling materials e.g. Bi-Sb-Te compounds, or the
recently developed Zr,Ti penta-tellurides. The low dimensional materials and structures,
under investigation world wide, now form a suitable class of materials, for the required
thermoelectric cooling. They have the capability, to bridge the cooling gap, 50 to 200K.
These new materials, have a strong potential, for developing self ( Peltier ) cooling devices,
for an efficient operation of the HTSC thermal sensors. It is the purpose of Chapter 1 to bring
home, the importance of the HTSCs, as a suitable class of thermal sensing materials, with
integrated electronic cooling, as compared to the LTSCs. In the case of the HTSCs, it is
convenient to use, liquid nitrogen as a refrigerant. A thermoelectric or a combination with
liquid nitrogen, if required, as the cooling technique, would also be an
achievement.Thermoelectric cooling, is very economical in space, and does not involve,
moving parts, thus very quiet in operation. A simple current manipulation of the devices,
provides the desired temperature control.
As discussed in Chapter 2, acoustic emission is widely known as a nondestructive method
for investigating the dislocation movement and accumulation accompanying plastic
deformation as well as the generation and propagation of cracks in solid state materials
subjected to mechanical stress. Other extensively studied sources of acoustic emission include
martensitic phase transitions in metals and alloys under thermal ramping and martensitic-like
structural phase transitions in ferroelectric and ferroelastic materials under both thermally and
electric field induced stresses. During the last decade, the acoustic emission method has been
successfully applied to studying the physical properties of high-Tc superconductors under
variable temperature, electric current and external magnetic field conditions. The most
important issues emphasized in the present review are: (i) superconducting and structural
phase transitions in a wide temperature range, (ii) kinetics of superconducting ceramics
sintering and oxygenation, (iii) dislocation mechanisms of mechanical work hardening during
long term thermal cycling and (iv) magnetic flux penetration into the superconductor and flux
lines pinning and interaction. Most of the results have been obtained with YBCO
(YBa2Cu3Ox) ceramics, yet some properties of BISCCO (Bi2Sr2CaCu2Ox) high-Tc
superconducting composite tapes have been also addressed. The authors show that by
monitoring the acoustic emission bursts it is possible to measure the temperature hysteresis of
phase transitions and to reveal their order, to determine the temperature of maximal oxygen
absorption (and calculate the absorption kinetic coefficient) as well as to measure the lower
critical magnetic field Hc1 and the full penetration field H* under electrical current transport.
The cumulative results demonstrate that acoustic emission method is an indispensable tool for
studying the high-Tc superconducting phenomena.
In Chapter 3, the authors give a general description of their approach which explains
many physical properties in the superconducting and normal states of almost all 2D high Tc
superconductors (HTSC). This 2D character leads to the existence of Van Hove singularities
(VHs) or saddle points in the band structure of these compounds. The presence of VHs near
the Fermi level in HTSC is now well established. They review some physical properties of
these materials which can be explained by this scenario, in particular: the critical temperature
x Barry P. Martins

Tc, the anomalous isotope effect, the superconducting gap and its anisotropy, and
thermodynamic and transport properties (eg: Hall effect). The effects of doping and
temperature are also studied, and they are directly dependent of the position of the Fermi level
relative to the VHs position. They show that these compounds present a topological transition
for a critical hole doping p ≈ 0.21 hole per CuO2 plane. Most of these compounds are
disordered metals in the normal state, they think that the Coulomb repulsion is responsible for
the loss of electronic states at the Fermi level, leading to a dip, or the so-called “pseudo-gap”.
Melt textured YBa2Cu3O7−δ superconductor has been widely used in the field of high
temperature superconductor (HTS) Maglev technology, such as the flywheel energy storage
system and the transportation system. The induced (shielded) current may flow at large
density without loss, circulating in large single-grained superconductors. So they can be used
as permanent magnet, but with much higher magnetic fields. However, before good
engineering designs for these applications can be derived, a deeper understanding of the
magnetic behavior of YBCO superconductor must be obtained. Therefore, the studies on the
electromagnetic properties of HTS YBCO bulks are reported for Maglev technology in
Chapter 4. Both experimental and computational results have been discussed in terms of
Electromagnetic Properties of Bulk High Temperature Superconductor for HTS Maglev
Technology. It was found that not only growth sector boundaries (GSB) between the five
growth sectors (GS) but also superconduction property variations in these growth sectors
contribute to inhomogeneities of bulk YBCO. Experiments were designed to investigate the
macroscopic anisotropy of magnetization critical current density of bulk YBCO. While the
field is kept constant at 1.0 T, the ratio increases as the temperature decreasing from 85 K to
20 K. Although levitation force has linear relationship with the applied field in the case of
symmetrical, such a linear relationship disappears once the applied field becomes
unsymmetrical. However, levitation stiffness has linear relationship with the associated
levitation force, whether the applied field is symmetrical or unsymmetrical. The multiple
seeded melt growth (MSMG) bulk has grain boundary (GB), but it still can be regarded as
single larger grain bulk in the perpendicular mode due to the inter-grain critical currents
flowing across GBs, and it has much larger levitation force than the stacked bulk array.
During the lateral movement, the decay of levitation force is dependent on both the maximum
lateral displacement and the movement cycle times, while the guidance force hysteresis curve
does not change after the first cycle. Moreover, A variational approach was presented for the
studies on the field dependence of the critical current density in YBCO Superconductor.
When the anisotropy ratio into account in the HTS computation modelling, the calculated
levitation forces between superconductor and magnet agree with the experimental ones. This
work may be helpful to the system optimization and may provide scientific analysis for the
HTS Maglev system design.
Chapter 5 addresses five important issues:
1. Anomalous transport characteristics of high temperature superconductors and
Josephson currents
The electric currents of superconductor and electrical field are relation of direct
proportion; the currents and magnetic field are relation of inverse ratio. In a special
condition, the Josephon currents has anomalous characteristic.
2. Thermodynamic properties of high temperature superconductor
A new systematic calculation of the specific heat contributions of vortex liquids and
solids is presented. Three derivatives of the free energy with respect to the
Preface xi

temperature of superconductor, the entropy, the specific heat, the temperature of


superconductor derivative of the specific heat are continuous across the phase
transition.
3. The study of characteristics of superconductive rings
The current of superconductive rings is change with jump in theory. The magnetic
field of superconductive rings is quantization. If increasing magnetic field, the order
parameter is gradually decreasing, leads to a decrease of the size of the jump of the
flux in the vorticity. In a special condition, if the outer magnetic field is gathering,
the sign of supercurrent can reversal.
4. Study of thermodynamic properties of type I superconductive films
The specific heat of the type I superconductive films

⎧⎪ ⎛ 2k ρ 3 2 ⎞ 3 ⎛ k T ρ3 2 ⎞ 2
CV = 2a03 ⎨5⎜⎜ ba0 − B 0 ⎟T + 6⎜1 − 2ba0Tc 0 + B C 0 0
⎟ ⎜
⎟T

⎪⎩ ⎝ 3L0 ⎠ ⎝ L0 ⎠
⎛ k T 2 ρ3 2 ⎞ k T ρ ⎪⎫
3 32
− 9⎜⎜ TC 0 − ba 0TC20 + B C 0 0 ⎟T + 3TC20 − 2ba 0TC30
⎟ + B C0 0 ⎬
⎝ 3L0 ⎠ 3L0 ⎪⎭
.

5. Study of high temperature superconductor under pressure


When outer pressure is a constant on superconductor, the pressure intensity with the
temperature is the relation of quadratic curve. The temperature is increasing with the
pressure intensity. When outer pressure on superconductor is not a constant, the
external pressure intensity has a relation of partial differential equation with the
temperature of superconductivity. As increasing the external pressure intensity, the
temperature is rising. The critical temperature is decreasing quasi-linearly with
applied hydrostatic pressure for superconductor, and observed negative pressure
coefficient of the critical temperature of superconductor. In another special case, the
authors obtain the critical temperature increases quasi-linearly with applied pressure
on superconductor.
In chapter 6 an attempt has been taken to study the variation of positron annihilation
parameters, specially those which are probing the electron momentum distributions, due to
superconducting transition in three different high Tc superconducting oxides (single
crystalline Bi2Sr2CaCu2O8+δ, single crystalline SmBa2Cu3O7+x and polycrystalline
La0.7Y0.3Ca0.5Ba1.5 Cu3Oz) and also to identify the core electrons with which positrons are
annihilating in these cuprate HTSC systems. This will help to understand the reasons of the
variation of positron annihilation parameters due to superconducting transition in these HTSC
systems in a better way. The anisotropy of the EMD in different crystallographic orientations
in the layered structured HTSC system has also been studied by using the positron
annihilation technique. The two detector coincidence Doppler broadening of the electron
positron annihilation radiation (CDBEPAR) measurement, having peak to background ratio
better than 14000 : 1, have been used to study the temperature dependent (300 K to 30 K)
electron momentum distributions in these high Tc superconducting oxides. The CDBEPAR
data are analysed both by conventional lineshape analysis and the ratio curve analysis.
It is well known that the system of Cooper’s pair is described by boson symmetric wave
functions, but Cooper’s pair operators are bosons only when the moments k are different and
xii Barry P. Martins

they are fermions for equal k. The analysis of trilinear commutation relations for the Cooper
pair (pairon) operators reveals that they correspond to the modified parafermi statistics of
rank p = 1. Two different expressions for the Cooper pair number operator are presented in
Chapter 7. The authors demonstrate that the calculations with a Hamiltonian expressed via
pairon operators is more convenient using the commutation properties of these operators
without presenting them as a product of fermion operators. This allows to study problems in
which the interactions between Cooper’s pairs are also included. The problem with two
interacting Cooper’s pairs is resolved and its generalization in the case of large systems is
discussed. It is shown that in site representation, the hole-pair operators obey the same
commutation relations (paulion) as the Cooper pair operators in impulse representation,
although the latter describe delocalized quasiparticles. In quasi-impulse representation, the
hole-pair operators are also delocalized and their exact commutation relations correspond to a
modified parafermi statistics of rankM (M is the number of sites in a ”superlattice” formed by
the centers of mass of each hole pair). From this follows that one state can be occupied by up
to M pairs. Even in the absence of dynamic interaction, the system of hole pairs is
characterized by some immanent interaction, named after Dyson as kinematic interaction.
This interaction appears because of the deviation of the quasiparticle statistics from the Bose
(Fermi) statistics and its magnitude depends on the concentration of hole pairs. In spite of the
non-bosonic behavior, there is no statistical prohibition on the Bose-Einstein condensation of
coupled hole pairs.
Recent scanning tunneling microscope (STM) experiments on Bi2212 have shed new
light on the nature of superconducting state in high-Tc cuprates and have emphasized the
important role played by inhomogeneities of superconductivity and energy gap in the CuO2
plane of the high-Tc cuprates. Summarizing all related observations, they find that there are
nine features altogether for the inhomogeneities. Chapter 8 demonstrates that the thermal
perturbation leads to the fluctuation of antiferromagnetic short-range coherence length
(AFSRCL) in the CuO2 plane, and further leads to the fluctuation of pairing potential. The
latter can cause the inhomogeneities of the gap and the superconductivity. This chapter gives
a unified explanation for the nine features of the inhomogeneities. The physical picture of the
inhomogeneities of superconductivity and gap in the CuO2 plane is as follows. The values of
the gap and the critical temperature Tc in bulk measurements are determined by the most
probable value of AFSRCL. At T = Tc, a superconducting percolation channel is established
by the locations with the most probable AFSRCL and the locations with AFSRCL larger than
the most probable one. The proximity effect and pair tunneling effect exist in the locations
with lower values of Tc. However, both effects are not important for the inhomogeneities.
The authors think that the mobile Opσ holes in the CuO2 plane are of homogeneous
distribution. The gap and the superconductivity themselves are stable, and the stability does
not need the help of nodal Cooper pair. This chapter also reconciles Lang et al.’s
experimental observations with the basic concept of superconductivity.
A General Theory of Superconductivity with points of view differing from those of the
BCS Theory is presented. In Chapter 9 The formation of electron pairs in a conductor
material is investigated upon arriving to the critical temperature where the conductor-
superconductor transition occurs. A general equation for the superconductivity is obtained
based on the stable pairing of two electrons bound by a phonon for any type of
superconductor material. This equation comes from a self-consistent field calculation with a
screening, which is temperature dependent, showing that the total energy of the electron pairs
Preface xiii

is constant and the local energy of the paired electrons is equal to that of the phonon in the
range 0 to TC . A specific condition for the existence of the superconducting state is
established, allowing the prediction of the critical temperature. The dispersion law of the
elementary excitements produced by the superconductivity is obtained and correctly
interpreted. The method is based on represent to the operators of Bose that characterize to
phonons and to the electron-phonon interaction as a combination of products of Fermi
operators corresponding to the electrons that form the pairs. The expression obtained for the
critical temperature is compatible with those obtained by G.M. Eliashberg and W.L.
McMillan. An expression for the bond energy of the pairs, or better known as superconductor
gap, is also obtained as a function of the temperature and the critical temperature, resulting
very similar to that formulated by Buckingham. This theory is reached in the frame of self-
consistent field equations for any natural or artificial solid where free electrons exist. The
necessity of the electrons must be coupled by phonons for the existence of the
superconducting state is also justified, arriving to a general conclusion: the superconductivity
theory is based only on the theory used to carry out the electron-phonon interaction and more
concretely of the phonons (harmonic or anharmonic theory, low, intermediate and high
temperature). The theory is applied to the particular case of low temperature superconductors,
obtaining an excellent agreement with the results of other theories (phenomenological and
microscopic) as well as with experimental data. An application of the general equation
obtained for low critical temperature superconductors utilizing a phononic theory is
developed. Then, the authors arrive to a specific expression for the bounding energy as a
function of temperature. The density of states of the electron pairs is calculated and used to
obtain an equation for the critical magnetic field. This result is needed to determine the
electrodynamical properties. Finally, they obtain the specific heat as a function of
temperature, they compare it to experimental data for Sn , and they calculate its jump at TC
for eight superconductors. The authors have also determined the variation of the energy gap
or bond energy with the temperature of the MgB 2 superconductor and they have compared
the results with another theoretical and experimental results reported in the literature,
obtaining an excellent agreement with the experimental results.
In: New Topics in Superconductivity Research ISBN: 1-59454-985-0
Editor: Barry P. Martins, pp. 1-44 © 2006 Nova Science Publishers, Inc.

Chapter 1

HOT ELECTRON NON EQUILIBRIUM HIGH


TEMPERATURE SUPERCONDUCTOR THZ
RADIATION SENSING AND THE INTEGRATED
ELECTRON COOLING

M.M. Kaila*
School of Physics, University of New South Wales, Sydney, NSW 2052, Australia

..curiosity is the mother of all inventions .


….necessity is the mother of all battles…

It is the curiosity, that creates the urge in humans,


to do the impossible, e.g. to go to the Mars.
This my be a small step, for a few individuals,
who are privileged to be involved to do the task.
But a giant step, by the mankind, at large.
They are prepared to pay the price, nevertheless.

Dr. Madan M. Kaila

Abstract
The recently discovered high temperature superconductors (HTSCs) have been found, to
be a very suitable class of materials, for the development of THz radiation sensors. They are
easy to manufacture and operate, over the efficiently achievable,thermoelectric temperature
control interval of, 80-140K. The temperature control over this range, can easily be
manipulated by liquid nitrogen as a refrigerant. But the recently developed, low temperature
thermoelectric refrigeration materials (e.g. Zr, Hf penatellurides), provide an efficient and a
very convenient alternative. The THz, hot electron thermal sensor (HETS) technique, has now
reached an advanced stage of development. Here the electrons are heated by a local
femtosecond pulsed laser pump, above the lattice temperature. This copious supply of
electrons, is then modulated by the chopped, remote THz radiation signal, which is to be

*
E-mail address : [email protected], Ph: 612-93854561, Fx .: 612-93856060
2 M.M. Kaila

detected. The chopped radiation, modulates the non equilibrium, electron-phonon thermal
dynamics.
The associated response of the dynamics, of the electrical resistance of the
superconductor, on a femtosecond time scale, is the key,to the THz radiation detection. This is
facilitated by adding to the sensor an external heterodyne electronic system. Pulsed boost
power of the laser pump, provides for the electrons, the AC (alternating current) bias. The DC
(direct current) bias is carried out by, a fixed, I (current) through or V (Voltage) across the
device. The sensor is operated, in the hot electron mode i.e. near the critical temperature Tc of
the superconductor.The THz thermal sensors based on the ' hot electron phenomena',like any
other thermal sensor, require cooling of the electrons.This may be an external, and or an
internal (self) cooling. A convenient, thermoelectric method of cooling, for the HTSC sensors,
is the aim in the development of the sensor.The heated electrons, due to Ac and DC bias, are
above the lattice temperature. Hot electrons, are easy to manipulate, at the THz frequencies.
The quasiparticle excitations, resulting from the electron-phonon thermaldynamics, provide
the desired tool of sensing. These excitations have relaxation time of 10-12 - 10-15s, in the
HTSCs. The superconducting coherence length in HTSCs, is much shorter in comparison to
that found in low temperature superconductors (LTSCs). This puts a much lower limit, on the
workable dimensions in space,in the superconducting film, for use as an HTSC sensor.HTSC
thermal sensing provides a tool, between temperatures 50-140K,for making a convenient class
of THz band of radiation sensors. This window of the electromagnetic radiation spectrum (10-5
m to 10-3 m wavelength), provides a faster and yet invisible light,for applications, in
communication, astronomy and medicine. In order for the electrons, to be an efficient means
of sensing the THz radiation, they must loose heat, at a very fast rate.This should happen as
close as possible to the point of incidence, of the incident radiation. This means electrons need
to travel as short a distance, as possible, in the sensor, before being collected. The devices
developed so far, have electron heat dissipation, mainly via the sensor film-substrate, system.
In this system, the electron-phonon interactions, with the relaxation time 10-12-10-15s, lasting
on a much wider space,control the ultimate speed of the sensor. The phonons are an
obstruction to the fast movement of the electrons, away from the sensitive areas of the sensor.
They originate, in the sensor film material, and also as a result of the back flow from the
substrate. This is after the sensitive area has been heated by the laser beam. The DC boas also
adds its share of heating to the sensor,raising the average temperature of the sensor, above that
of the substrate.
It is an easy way out, but costly and cumbersome, to use mK range of temperatures, to
reduce electron-phonon interactions. The much reduced phonon specific heat, at mK
temperatures, provides the much desired environment, for the easy transport of the electrons,
but with the added complexity of a cryogenics infrastructure. One can produce scatter free
travel, of the electrons in the film, in various alternate ways. One possible way would be, to
design, a regiment of superconducting dots, on a low dimensional structure,thermeolectric
film. The interface of the, HTSC-thermeolectric junctions, so produced, can be used, as an
efficient source of highly mobile electrons.The output can then be collected, as an integrated
signal from the dots. May be one can sandwich, an insulating layer, in between, the
superconducting and thermeolectric layers, to achieve tunneling of the electrons, with
minimum back flow of the heat. The materials considered highly efficient, in thermal sensing,
at present, are the low temperature superconductors (LTSCs).Typical examples are Al, Pb,
Nbn, etc. and are operated at mK temperatures.The specific heat of the phonons at mK
temperatures, is very low ~ 102J/K/m3. The specific heat of the electrons may be, slightly
higher or lower than that of the phonons. At these low temperatures, electrons travel almost
free of interactions with the phonons.
In the case of HTSCs, e.g. YBaCuO, BiSrCaCuO, etc., the scenario is quite different.
Here, the specific heat of the electrons is high ~ 104J/K/m3. The specific heat of the phonons is
much higher ~106J/K/m3. The phonons, play a very deleterious role, in the performance of an
HTSC thermal sensor. A new ray of hope, in the direction of efficient electron cooling, with
minimum involvement of phonons, has now emerged. It is by virtue of the nano structure,
thermoelectric cooling, materials and devices, operating between 50 and 200K. Band gap
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 3

engineering using nano structures, can channel much faster electrontransport in low
dimensions. Integrated cooling, can be provided by the already well known thermoelectric
cooling materials e.g. Bi-Sb-Te compounds, or the recently developed Zr,Ti penta-tellurides.
The low dimensional materials and structures, under investigation world wide, now form a
suitable class of materials, for the required thermoelectric cooling. They have the capability,
to bridge the cooling gap, 50 to 200K. These new materials, have a strong potential, for
developing self (Peltier) cooling devices, for an efficient operation of the HTSC thermal
sensors.
It is the purpose of this work to bring home, the importance of the HTSCs, as a suitable
class of thermal sensing materials, with integrated electronic cooling, as compared to the
LTSCs. In the case of the HTSCs, it is convenient to use, liquid nitrogen as a refrigerant. A
thermoelectric or a combination with liquid nitrogen, if required, as the cooling technique,
would also be an achievement.Thermoelectric cooling, is very economical in space, and does
not involve, moving parts, thus very quiet in operation. A simple current manipulation of the
devices, provides the desired temperature control.

Foreword
It is my intention, in this work, to provide the reader, with a broad base of physics, to appraise
oneself, with the present status, in the area of non equilibrium hot electron thermal sensing
and electronic cooling.The non equilibrium electron-phonon thermal dynamics, in the sensor
film, is the result of the power boost by a femtosecond laser pump. In a hot electron
operation, an HTSC is operated close to its critical temperature Tc (transition from
superconductor to normal state), for developing thermal sensors. I have included, in this
work, a comparison of the HTSC and the LTSC materials. But the work, is particularly aimed
at the HTSC sensors. It is the efficient cooling of the sensor, that is a necessary step,in the
overall performance of the sensor. One can today, develop, a low dimensional materials
based, THz (1012, cycles/second) radiation thermal sensor, with an integrated electronic
cooling. This work, creates the direction, in the knowledge required,so as to enable the
application, of the developed low temperature bulk thermoelectric cooling materials, to the
HTSCs thin film thermal sensors.
Room temperature bulk thermoelectric cooling materials, were developed during the
sixties and seventies. There has been little development since then. One can see today, a rapid
surge in research and development efforts, towards the low dimensional (nano structure)
thermoelectrics. There is now an urgent demand, to create,
a conveniently operated, low temperature electronic refrigeration system, for the hot
electron thermal sensor (HETS).All thermal sensors basically, have to be cooled. This is to
keep their noise equivalent power, NEP (the minimum power of a signal that can be detected,
below which it is dominated by the noise), very low, and the responsively (voltage or current
output / power of the input signal) very high. A sensor based on an LTSC (e.g. Al, NbN, etc),
enjoys a very good performance. But the price paid, in terms of cryogenics, is very high. They
need to be operated at mK temperatures. Semiconductor Ge, has equivalent performance, but
requires close to 1K, as the operating temperature.
The III-V strain tuned, super lattice semiconductors, HgCdTe, InGaAs, have limited
performance capabilities. This is due to their narrow band gap, resulting in easy generation of
thermal noise.But the conveniently operated, thermoelectric temperature control, over the
range, 300K and 200K, makes them commercially, very popular at present.Semiconductors,
4 M.M. Kaila

in general, due to their band gap restriction, are not suitable for the THz band of radiation.
HTSC thermal sensors operate, over the achievable electronic cooling range of 50-140K. The
new materials (Zr,Hf pentatellurides) are a suitable candidate, for developing, HTSC-
integrated or otherwise, electronic cooling devices, over this range. The liquid helium,
mechanical cryo-coolers, etc. are an option to use milli Kelvin temperatures. But they require
a large infrastructure and involve noisy equipment. Thermoelectric cooling, is a solid-state
phenomena. It offers the technology, with potential of developing, miniaturized cooling
devices. Micro, Peltier coolers, can be in integrated with the sensors. These coolers can be
designed, using quantum wells, wires and dots. LTSC materials, have a much sharper
resistive transition, as compared to the HTSC materials, and thus are much faster in operation.
But the added complication of the cryogenics involved, makes them less attractive.
The possible extension of thermnoelectric cooling down to 50K, using the old (Bi-Sb-Te
compounds) and or the new (Zr, Hf pentatellurides) materials, using low dimensional designs,
is challenging, as much as tempting. Electrons used, in the hot electron thermal sensing
technique,in HTSC materials, are derived, from the top end, of the superconductor- normal
state transition, close to the critical temperature Tc.They require, a very small excitation (nW-
μW) power and are capable of performing same function as a normal electron does, in a
semiconductor. Their ability to revert back to the cold state (cooper pairs), makes them more
efficient and less susceptible, to thermal noise. Thus they are more suitable as thermal
sensors.Some information, in preparing this work, has been used from other sources. The
author gratefully acknowledges those sources.Information, in some cases, is reproduced, in
the appendices, at the end, as an illustration. I express my highest gratitude, to those origins of
information. This work, I am sure would be very valuable to young scientists, who wish to
pursue research and development career, in he area of thermal sensors. It will be equally
valuable, I am sure, to the scientific community at large.

I Introduction
The semiconductors so far, e.g. GaAS[1], have provided, as a suitable class of materials, for
the development of the THz radiation sources and sensors. But over the last decade, the
attention has shifted to the HTSCs, as a better alternative[2-5]. In order to be able to make the
THz radiation sources or sensors, using HTSCs, it is essential to understand first, the basics of
the physical processes involved, i.e., the electron and lattice (phonon) interactions, band gap,
quasi particle excitations, etc., etc[Appendix A1]. There results, a rapid increase in the
electrical resistance, of a superconducting thin film, when it is irradiated by a
femtosecond,optical or thermal laser pulses. A suitable choice of current or voltage bias, can
be used to operate the superconductor, near the upper end of the resistive transition
(superconductor to normal) width, in a hot electron mixerarrangement[ Appendix A2. A3].
When the superconductor is biased, to operate, at a temperature, much below the critical
temperature, the sensing is in a different mode of operation. In that case, the excitation of the
supercurrents (circulating electrical currents over small areas) are used for sensing.
These currents can be externally initiated in the superconductor, by a momentary
application, of a small magnetic field, and then removed. What results is a mixed
(superconducting electrons and normal electrons) state. This is the familiar Meissner effect
state. A cooper pair, is a bound state of two electrons, with zero spin and momentum. Large
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 5

number of these pairs, constitute, the supercurrents. Some paired electrons, can be made to
oscillate, between free and bound state, by cyclic heating, of the pairs. The result is a in an
oscillatory electric filed, being generated in the film. The superconductor in this way, can be
so devised, as to have, a beam of THz electromagnetic waves emanating, from the back of, a
suitable thin film superconductor/substrate system[2]. In this case, the electron-phonon
thermal dynamic processes happening, in an HTSC, can be read, by means, other than the
usual, I-V heterodyne electronic read out system.This is the time Domain Terahertz
Transmission Spectroscopy (TDTTS) technique [3]. Here the transmitted beam through the
superconductor, provides a convenient tool to study the electron-phonon thermal
dynamics.This transmission, if modulated by the signatures of an unknown THz signal, can
be unscrambled, by a video technique[Appendix A4, A5].
The TDRTS (time domain reflection THz spectroscopy), uses reflection from the
superconductor surface instead, and has been found equally valuable[4].Thus one can use, the
electron-phonon dynamics, via the reflected beam, for thermal imaging. The readout may be
through a low temperature grown Gallium Arsenide sensor or an another HTSC sensor. Other
useful superconducting properties of the HTSC thin films, e.g., the penetration of the
electromagnetic waves through the surface, which leads to a change its surface resistance, the
kinetic inductance (resulting from the oscillations of the super current carriers), etc., etc., can
be used to design a THz radiation sensor. The hot electron phenomena, has already been
extensively and successfully used, in the design of THz thermal sensors. In the hot electron
technique, the heated electrons, being more mobile, can be manipulated easily, for a desired
operation.High performance THz sensors, have been produced, among the HTSC
materials[5]. At present the LTSCs e.g. Nbn (response time ~ ps, responsivity~ 104 V/W) are
the materials, considered up to the mark, for designing fast and sensitive, hot electron thermal
sensors. An efficient LTSC nano structure thermal sensor, with integrated
Peltier cooling has already been developed. This is the S(Superconductor)
I(Insulator) N(Normal Metal) I S (SINIS) pair junction, operated at 300mK
One can effectively realize, the self thermoelectric (Peltier) cooling, of the metal
electrode, which is, the sensing element. This is achieved, provided one uses, a bias voltage
across the sensor, close to the band gap energy, of the superconductor.A temperature drop
from 300mK to 100 mK, was easy to produce[6].Peltier cooling is only current controlled.
This simple factor makes it an ideal technique, of temperature control, particularly, when a
small wattage of heat, and a small area is involved. The nano-engineering design, of the
thermoelectric cooling materials, is now gaining a fast momentum world wide.
It is anticipated, this will lead to the development of fast and efficient, much needed
cooling devices. The low dimensional space, could be, the quantum wells, where the space is
a two dimensional plane in which electrons and phonons move. The other structures are,
quantum wires, the one dimensional structure and the quantum dots, providing the zero
dimensional space. Electronic cooling, using semiconductors, so far has provided a very
beneficial technique for the range of temperatures, 300K-200K. The materials developed for
this purpose were, Bi2Te3 - Sb2Te3 alloys. Commercial cooling devices based on these
materials have found applications in medicine, infrared sensors, etc.
The efficiency of a thermoelectric material, cooling or generation, is measured, through
the coefficient of performance, called as the thermoelectric figure of merit (TEFM).In its
simplicity, one can writ, for a single material leg, the TEFM, as ZT = (α2 σ / K). Here Z is
the dimensional figure of merit, ZT the dimensional less figure of merit, T the temperature in
6 M.M. Kaila

degrees Kelvin, α the thermoelectric power (Seebeck coefficient) and σ and K are the
electrical and thermal conductivity respectively.of the leg. The thermal conductivity, K = Ke
+ Kph, where Ke and Kph, are respectively the electronic and thermal (phonon) parts of the
thermal conductivity. In any material suitable for applications, one need to optimize, α, σ and
K. in such a way that ZT >>1.It is now possible, to engineer, the phonon-electron
propagation through a material, so as to achieve the highest TEFM. Recently, there have
been extensive studies for the design of thermoelectric nano structures. These studies have
been performed, towards the materials previously well known,in the bulk form[Appendices
B1-B4]. It is due to the easy access, to the experimental data available on those materials.
These studies can equally well be applied to the Zr, Hf pentatelurides[Appendix B5].
The typical low dimensional structures studied are, quantum wells, PbTe/PbEuTe[7,
Appendix B6, B7], quantum wires, PbTe, GaAs[8], Bi2Te3[9, Appendix B8], Bi[10,
Appendix B9], quantum dots, Ge on Si[11, Appendix B10]. Detailed experimental studies on
these new devices, have yet to be performed. The new class of thermoelectric materials, e.g.
the quasi-crystals AlPdMn[12], the Skutterudites CoAs3, etc[13], etc., may develop into
efficient thermal sensors, when designed as low dimensional structures. The penta-tellurides
Hf,Zr(Ti)Te(Se), on the other hand, need special mention, due to their efficient performanceas
cooling materials, over the temperature interval 200-50K[14]. One can engineer quantum
wells, wires, etc. of the Zr/Hf pentatellurides, and develop thermoelectric cooling devices,
with an efficient operation. An HTSC/ Zr/HfTe5/HTSC, heterostructure, could be developed
as a self cooling thermal sensor. The non equilibrium dynamic superconductivity in HTSCs,
has electron-phonon relaxation times of 10-12-10-15s. The HTSCs and the new thermoelectric
materials, have a strong potential to develop THz radiation sensors with integrated
cooling[15].
It has been recently demonstrated, that one can use femtosecond laser pulses to excite
thermally, the bound antiferromagnetic (anti parallel) spins in a rare earth, e.g. theorthoferrite
TmFeO3. The iron moments order antiferromagnetically, but with a small canting of the spins
on different sublattices. This small anisotropy is very sensitive to temperature. It can oscillate,
through a maximum and minimum, over the temperature interval, 80-90K, in a
picosecond[16].Spin oscillation phenomena, in conjunction with an HTSC,can be an
incentive for developing, a THz radiation sensor. The study of dynamic superconducting-
antiferromagnetic interface, on the time scale[17], would provide a good base to understand,
spin-lattice relaxations, in HTSCs.In the area of ultra high density magnetic recording media,
the nano structures of the ferromagnetic materials[18, 19], present good candidates, for the
study of optical and thermal phonon-spin relaxations. The study of antiferromagnetic-
ferromagnetic phase in conjunction with HTSC materials, may open, another interesting area
of exploration, in the field of THz radiation[20].
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 7

II Theory and Experiment


II A Hot Electron Thermal Sensor (HETS)

II A.1 Non Equilibrium Dynamic High Temperature Superconductivity :


Theoretical Modeling
One should note that there is a critical difference between a superconducting Hot Electron
Thermal Sensor and a conventional superconduicting bolometer.They are both operated in the
transition-edge (superconductor to normal)regime. In the bolometer, thermal equilibrium
between electrons and phonon is established instantly. In the HETS, these two systems are
not in equilibrium. A two temperature, electron (te) and phonon (tp)dynamics, is in operation.
Electron-phonon interactions, in the case of [HTSCs[5], play a crucial role in thermal
sensing.. This is in contrast to the LTSCs, where the electrons, have little involvement with
the phonons. The sensors therefore perform much better. The author has recently carried out
detailed modeling studies, among HTSCs, applied to the THz radiation sensing. I have
particularly endeavored, to obtain responsivity and conversion gain, of the device,
particularly, in the form of analytic, mathematical equations.
The present work, should provide the reader, with the platitude, of the problems involved,
and the possible solutions, in the design of a THz thermal integrated sensing-cooling device.
Modeling, in the performance studies of the THz sources and sensors in HTSCs, is a difficult
task. This is basically, due to the lack of understanding and not enough experimental data
available, on the properties of the materials involved. It is the right time now, to make nano
HTSC- THz devices,with integrated electronic cooling, and test their performance. In
developing the theoretical modeling, of an HTSC thermal sensor, I have used lower case
letter, symbols, in the mathematical equations.This may be considered as contradictory, to the
normal practice of the use of the capital letters. The author apologizes for that. But there is
advantage in doing so when, one is using ' Mathmatica Computer Pacakage ' for the
computations. In the ' Mathematica' program, capital letters are reserved for standard
mathematical functions. Thus the use of lower case letters allows, easy back and forth
movement, between the development of mathematics and carrying out the computations. One
can write the heat dissipation in a thin film device, under the two temperature (electron and
phonon), model in the form of two coupled linear differential equations, as follows[5, 21].

cel vs d te / dt = - lep vs (te3 - -tp3) + I vb + abs prad (1)

cph vs dtp / dt = lep vs(te3 - tp3) - (sflm / rb) (tp-ts) - 8 Kph vs (tp-ts) / lb2 (2)

The diffusion term, i.e. the third on the right hand side of the equation (2),is taken as
negligible in this study. This is what happens, if the sensorlength lb, is greater than, the
diffusion length; this is the distance traveled by an electron before scattered by a phonon. A
normal meander (length >> lb)sensor, would automatically satisfy this condition. In order to
keep the length of the analytic equations, within limit, one should reduce the number of
independent variables, in the equations. In the heat transfer by the phonons in the sensor, to
the substrate, in the equation (2), for the second term on the RHS, I have replaced,ts (substrate
temperature) by the electron temperature te. This means, electrons and phonons maintain, a
8 M.M. Kaila

non equilibriumheat exchange, within the electron-phonon thermal dynamics.This condition


can be considered equivalent to the case, where the sensor remains thermally isolated from
the substrate. A thermally insulating layer e.g. Silicon Nitride (Si3N4)[22], Yttria stabilized
Zirconia[23],etc., in between the sensor and the substrate, would enable to achieve the desired
environment, for the electron transport. The meaning of various terms and symbols is as
follows.

lep = γ / (3 tmes ts) = electron-phonon interaction (cooling) parameter (units W / m3 K3)


γ= Somerfield constant (units W / m3 K2)
ts = the temperature of the substrate
kph = electron phonon diffusion thermal conductivity
lb = length from the sensitive (middle of the bow tie antenna) area to the metal contacts
at the end
cel = electron specific heat per unit volume
cph = phonon specific heat per unit volume
tmes = phonon escape time to the substrate
abs = the coupling factor between incident radiation and the detector
cel = electron specific heat per unit volume
cph = phonon specific heat per unit volume
vs = volume of the sensor = tflm sflm
tflm = thickness of the sensor film
sflm = area of the sensor film
tmes = phonon escape time in to the substrate
rb = thermal boundary resistance = tmes / cph / tflm
lep = electron-phonon coupling constant
te = electron temperature = te0 + te1 exp (I ω tminst)
tp = phonon temperature = tp0 + tp1 exp (I ω tminst)
prad = total (signal + local pump) = Dc power + AC power = prad0 + prad1 exp(I ω tminst)
vb = source voltage; = vb0 + vb1 exp (I ω tminst)
i= total current bias through the bolometer = i0 + i1 exp (I ω tminst)
ω1 = frequency of the fast elctro-optic switch (chopper) through which the remote THz
signal passes
ω2 = frequency of the local laser boost pump
ω= ω1 - ω2 = the intermediate frequency (IF)
rl = AC resistance of the load at IF = vb1 / i1
r0 = dc resistance of the device (bolometer + load) = vb0 / i0

Carrying out the solution of the equations (1) and (2) simultaneously,and retaining terms
to the order of ω4 only, one leads to the following analytical result, for the responsivity
vrspf[15].

vrspf = { √[{(cel2 sflm2 te12 tflm2) + (cel2sflm2te12tflm2) tmes2ω2 }ω2 ]/(i0 prad1)
/√ [(6(lep / cph) tmes tp02 + 9 (lep / cph)2 tmes2 tp04 + (1 + tmes2 ω2) ] (3)
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 9

The conversion gain gcnvrsn, in the THz dynamic case, is evaluated from the equation (3) by
using, the following expression[15].

gcnvrsn = (1/10)Log10 [ 2 (vrspf 2 plo1 i1) / vb1 ] (4)

The resulting expression is long, and it would be out of space to reproduce here. I feel, the
simplifications below, under the extreme conditions, ωtmes >> 1 and ωtmes << 1, for the
responsivity, will provide the reader, with an interesting overview, of the importance of the
various processes involved.
In the approximation, tmes ω << 1, equation (3) would reduce to

vrspf = (cel sflm tflm ω) te1 / (i0 prad1) (5)

In this simplification process, the first and second term in the denominator within the
square brackets, have been taken as << 1, and thus neglected. Various outputs can be
achieved by suitably choosing the material properties, cph, tmes, etc., and the operating
parameters, to a desired effect. The above simplified voltage responsivity, can be expressed as
follows.

vrspf = { (USP) / (prad1) } [ te1 / i0 ] (6)

USP = cel sflm tflm ω (7)

The equation (6), exposes, the physics of the THz sensing, in a much clearer manner. USP
can be regarded as, useful sensing power, per unit increase, of the electron temperature, te1.
Change in the electron temperature alone, would then drive the sensing technique. This is
exactly, one is trying to do, by taking an easier path, i.e. going to mK temperatures. A tacit
assumption has been made, about the thermal resistance, between the electrons and the
phonons, in the sensor film, in this model.It is realized, through the second term on the RHS,
in the equation (2). Electron-phonon thermal resistance within the sensor film, is taken as the
highest limit rb; this is the thermal resistance (phonon-phonon)between the sensor and the
substrate.
A suitable insulating layer over the substrate, makes the substrate relatively unimportant.
In actual practice however, there will always be some heat transferred to the substrate.
One can consider, this as a limiting case, where heat transfer within the film, is just little
bit better, than the heat transfer to the substrate. The following simplifications are included
for a useful insight.

vrspf = [ cel sflm te1 tflm tmes ω2 ] / (i0 prad1) / [√(6(lep / cph) tmes tp02 + tmes2 ω2)]

ωtmes >> 1; 6(lep/cph)tmestp02) >> 1 ~ ωtmes (8)

[ cel sflm te1 tflm ω ] / (i0 prad1)

ωtmes >> 1; 6(lep/cph)tmestp02) << ωtmes (9)


10 M.M. Kaila

vrspf = [ cel sflm (te1) tflm ω2 (√ tmes) ] /


√ [ (6 (lep / cph) ] / tp0 / (i0 prad1)
ωtmes >> 1; 6(lep/cph)tmes tp02) >> ωtmes (10)

vrspf = [ cel sflm te1 tflm ω ] / (√tmes /)


/ [√(6(lep / cph) ] / (tp0)] / (i0 prad1)
ωtmes << 1, 1; 6(lep/cph)tmestp02) >> ωtmes (11)

The various parametric manipulations, of the responivity in the above equations, provides
the designer, with a wide range of possibilities, those can be achieved.In the equation (11),
one sees that, the responsivity is inversely proportional to (√tmes). This is a character,
particularly exhibited, in this chosen model. An improvement (a decrease)in tmes, also
improves the responsivity.This is just opposite to what is observed in a normal static
superconductivity sensor i.e. a bolometer. In that situation, tmes, is the response time of the
device.It would be interesting to fabricate, a THz sensor, using one lobe of the bow tie
antenna (normally used in THz source, sensor technology), as a thermoelectric material. This,
will result in, addition of a Peltier heat term in the equation (1). This term will be – I (Π ). I is
the current bias and Π the Peltier coefficient.
In order to be able to cope with the high speed of the response of the sensor, the
thermoelectric materials should provide for the electrons an easiercooling route of
transport[7-11]. This may just be possible, by using the nano fabrication technology. In the
above analysis, it is found that the term 6(lep/cph)tmes tp02) plays a very crucial role. Solving
this term for tmes, by putting it = 1, taking cph = 106 J/K/m3, tp0 = 85K, and lep = 1010
W/m3K3(the case of a YBCO sensor), one gets tmes ~ 10-9s. The time of escape of the phonons
to the substrate (tmes = rb cph tflm)should be interpreted as the upper limit on the electron-
phonon relaxation time.The lower limit, which will extend the frequency band, towards the
higher THz frequencies, will come from, the quickest possible removal, of the electrons for
conduction. One should realize that the thermal resistance rb ~5x10-8K m2 / W, between the
YBaCuO sensor and the MgO substrate, should be higher than that, between the electron-
phonon cooling process, within the film. If the speed of transmission of the electrons, to the
readout system, is fast enough, then this model can be realized in practice. How fast the
electrons are transported, is limited, by the low dimensional structure designed, through
which the electrons move. In the limit, however, the speed of the sensor, is controlled by the
speed of the read out system.
II Figures 1 and 2 (below), included here are from a more detailed study [15]. They are
reproduced here for the sake of illustration.Figure 1, depicts, the variation of the conversion
gain vs intermediate frequency (IF), and the electron specific heat. One can notice, that ωtmes
is between 1 and 10. Under this condition, the rate of change of the electron temperature, due
to the incident radiation, is much faster, than, the rate of heat transfer, from electrons to the
phonons in the film. One should note, the phonon specific heat, is much higher (by 102), than
the electron specific heat. This results in a slower heat exchange between electrons and
phonons,thus, a quicker saturation, in the conversion gain vs ω (Figure 1). Figure 2 is another
interesting illustration. Here the conversion gain is plotted vs lep and cph. The higher the
phonon specific heat, the greater the thermal mass of the phonons, the slower the heat
exchange between the electrons and the phonons. One can see that the effect, starts around cph
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 11

~ 104 J/K/m3. From here on, the conversion gain is independent of lep (Figure 2). Thus
electron-phonon cooling (lep), in an HTSC sensor, is much less effective, than in an LTSC.
Not much change in conversion gain is observed for cph > 104 J/K/m3.One should compare
this cph, with that for an LTSC i.e., 102 J/K/m3.The theory of the thermal sensing remains
practically the same, whether it is the LTSC or the HTSC. It is the magnitude of the specific
heats of the electrons and the phonons in these materials, which makes them so different.

II A Figure 1. Plot of Conversion Gain gcnvrsn (dB) vs, Intermediate Frequency ω (Hz) and Electron
Specific Heat Cel (J/K/m3). The Fixed parameters are Cph = 1x106 J/K/m3, lep = 1x104 (W/K3/m3), tmes =
1x10-9 s, tflm = 1x10-6 m, sflm = 1x10-6 m2, te1 = 5K, te0 = tp0 = 77 K, abs = 0.5, prad1 = 1x10-6 W, i0 = 1x10-6
A, i1 =1x10-9 A, vb0 = 1x10-5 V, vb1 = 1x10-6 V.

II A Figure 2. Plot of Conversion Gain gcnvrsn (dB) vs Electron-Phonon Interaction Parameter lep(W/K3/
m3) and Phonon Specific Heat. Cph (J/K/m3). The Fixed parameters are tmes = 1x10-9 s, tflm = 1x10-6 m,
sflm = 1x10-6 m2, i0 = 1x10-6 A, te1 = 5K, te0 = tp0 = 77 K, abs = 0.5, prad1 = 1x10-6 W, ω = 1x109 Hz, vb1 =
1x10-6 V, Cel = 1x104 (J/K/m3).
12 M.M. Kaila

II B Thermoelectric Cooling for a HETS : Bulk Materials

II B.1 Developments Past and Present


Research and development in the area of thermoelectric refrigeration during sixties and
seventies, was very much limited to the bulk materials[Appendices B1-B4]. Cooling devices
developed were restricted in use, close to room temperature applications only. The best
materials found were Bi2-Sb2-Te3 compounds. The author fabricated and tested a bulk
material three stage cascaded cooler and obtained a temperature drop of 100K at 300K.The
cooling area was 1cm2 across and had a heat load of half a Watt[24]. There has been little
progress, in the area of thermoelectric cooling,since then. But the field has recently
experienced, a complete turnaround. This is particularly so in the area of low temperature
control applications.The thermal sensors of interest today are 10-12 cm2 acrossand dissipate
around a micro Watt of power.This film thermoelectric cooling, external or internal, thus
makes a sense.Low dimensional thermoelectric materials and structures e.g. superlattice naao
two dimensional heterostructures, quantum wires and quantum dots have raised the hope of
designing, highly efficient cooling devices for the low temperature control applications.
Quantum well devices of, Si-Ge, Bi2Te3, etc., have actually been fabricated and the
dimensionless thermoelectric figure of merit, ZT >> 1, has been demonstrated[25, Appendix
B11]. It is anticipated, that the nano fabrication developments in the field of the hot electron
thermal sensing, together with convenient thermoelectric control of temperature, would
revolutionize, the field of thermal sensing. The new class of bulk thermoelectric materials,
ZrHf Te5, have the right material parameters i.e. the thermoelectric power (Seebeck
coefficient), lattice thermal conductivity and the electrical conductivity, for the development
of 50 - 140K range, efficient refrigeration devices[14, Appendix B5]. Low dimensional
thermoelectric materials–structures, raise much hope for developing the desired thin film
thermoelectric cooling devices[25]. But a researcher in the field need to have a knowledge
thresh hold, in the area ofthe thermoelectric phenomena[26-28]. Unfortunately the
development of the text, in this area, has not kept pace with the recent developments. The task
for a beginner, in the field thus become all the more difficult. This work, I feel, will make the
task easier, foe a new researcher, as well as, for the scientific community, on the whole.

II B.2 Efficiency of a Thermoelectric Refrigerator


Most efficient, thermoelectric materials are semiconductors.At the low dimensional materials
level, a high level of theoretical and experimental understanding, of the thermoelectric
phenomenawould be necessary. A simplified relationship between theory and experiment, for
the bulk materials, developed mainly during seventies, is available e.g. in [28, Appendices
B1- B4].A good knowledge of the Band Theory of Solids, is a prerequisite, to make a good
progress in the field[29]. It is essential to comprehend the steps involved in the systematic
theoretical development,of he mathematical relations. What is reproduced here, in the
sections IIB 3.1 and IB 3I.2 below, is only a a summary. Details can be found in a standard
text[26-28]. They are included here, to show a direct relevance,to the low dimensional
thermoelectric situation. The most basic component of a thermoelectric heat pump, is a
thermo-junctionfabricated form one, n-type (negative) and the other, p-type (positive) leg of a
semiconductor material. The diagram shown in Appendix B1 is for a thermoelectric
generator. In a cooler, one need to replace the load RL by an external source of DC power.
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 13

The thermo junction is reverse biased by an electrical current. The electrons (in n leg) and
holes (in p leg), carry heat away from the junction, and thus the cooling produced. The hotter
ends of the legs are electrically insulated from, a thermally conducting heat sink. An
equilibrium temperature difference ΔT = T2 (temperature of the hot end) -T1 (temperature of
the cold end) will ultimatelybe established, between the cold end and the heat
sink.Thermoelectric refrigerators, are designed to operate at the maximum heat pumping. The
coefficient of performance of the heat pump (COP), can be written as follows.

COP = Cooling Power (Heat Extracted)/Input Power (Electrical Energy Consumed) (1)

The current through the device for maximum COP is given as

I max (COP) = λ (T2 - T1) [ √(1 + ZcT) + 1) ] / (αnp Tav) (2)

Here Tav = (T1 + T2) / 2, is the average temperature of the pump,λ = is the average
thermal conductance (in parallel) of the two leg across cooler-sink interface.
αnp = (αn - αp), αn and αp being the thermoelectric power of the n and p leg respectively. ZcT
= the dimensionless thermoelectric figure of merit of the couple. The maximum possible
value for the COP is

COPmax = η γ (3)

where η = T1 / (T1 - T2) is the normal carnot cycle efficiency and

γ = [√ (1 + ZcT) - (T2 / T1) ] / [ √(1 + ZcT) + 1) ] (4)

is the thermoelectric efficiency. ZcT for a couple, in terms of the material properties of the
two legs of the couple can be written as follows

ZcT = (α2np) / [ (λn / σn)1/2 + (λp / σp)1/2 ] (5)

It is convenient to address ZT as for a single type of material, as follows.

Z = (α2 σ) / K (6)

α = the Seebeck Coefficient, σ = the electrical conductivity, and


K = the thermal conductivity.
In an integrated HTSC sensor-thermoelectric situation, one would in fact be interested in
a single type of material, being involved. Electrons with higher mobility (i.e. an n type
material), would be a preferred choice.

II B.3 Optimization of ZT
II B.3.1 Single Band (Conduction) Approach
A more realistic approach to the theory of optimization of ZT requires,a two band conduction
model, for carrier (electrons and holes) transport. The two bands are conduction(CB), where
14 M.M. Kaila

electrons freely move and valence bands(VB), where holes freely move. Consideration of the
carriers within a single band over simplifies the calculation for the transport parameters.
This may be the ideal model for the design of an efficient electronic cooler. It will
provide for the beginner, a smoother transition, to adapt oneself later, to the understanding
required for the more complex physics involved, in real models. In a single band approach,
the conduction band, considered here, only electrons (no holes) participate in the transport.
For a complete mathematical treatment, i.e. taking into account, multi valley (more than one
electron energy ellipsoid participating), multiple types of electron scattering, the reader
should follow a more rigorous text. The following, is only an outline for, a single valley
conduction, acoustic, ionized impurity and optic phonon scattering. The calculation of charge
and heat transport, in any device,involves first finding, the density (number per unit volume)
of the free carriers (electrons here) in a band. This is done by multiplying the density of states
D(E) (energy states available per unit energy and per unit volume of the material, in the
band), within a small interval of energy, dE, the probability, of occupation (f ) of the energy
levels E, and integrating over various energies.The statistics controlling the occupation of
energy levels, is the familiar Fermi Dirac statistics f.
The important mathematical expressions involved in the transport processes are.

D(E) = (4π / h3)(2 m *e)3/2 E1/2 (E > 0) (conduction band edge) (7)

= (4π / h3)(2 m *e)3/2 (E - Eg)1/2 (E < - Eg) (8)

f = 1 / (E - Ef / kT) (9)

Ef = Fremi Level, k = Boltzmann Constant, T = temperature in degree Kelvin


Eg = energy band gap, between valence and conduction band,
m *e = the effective (expressed in terms of the free electron mass me and
h = the Planck's constant.

Eg = the gap of energy, which the electrons have to overcome,before being in the
conduction state. Refer to adjacent IIB.3 Figure 1, below, for the positions of the various
energy levels, in the two band perspective.When the material is pure (intrinsic), the Fermi
level (FL) (with respect to which the electron energy is measured) is in the middle of the gap.
While when the material is impure (doped), the FL, is closer to the conduction ban edge, for
the electron, and to the valence band edge, for the holes, if present[Appendix B14].E is the
spread of energy levels, available in a band, which the carriers can occupy. The above D(E) is
peculiar to a bulk material.
In a low dimensional situation, it would have a different expression and a discrete
structure. The reader is referred to a standard text on Solid State Physics e.g. [29] for a good
understanding of the Band Theory of Solids and the scattering dynamics of the electrons.The
evaluation of the transport parameters, α (Seebeck Coefficient), σ (electrical conductivity)
and K (thermal conductivity), is first carried out.
Then on substitution in the equation (6) one gets ZT, as follows. II B.3 Figure 1 . Energy
Levels in a Semiconductor Model, showing Valence and Conduction Bands, separated by an
Energy Gap
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 15

II B.3 Figure 1. Energy Levels in a Semiconductor Model, showing Valence and Conduction Bands,
separated by an Energy Gap

ZT = (δ - ξ)2 / (⎢ + 1 / βe) (10)

δ = [ (S + 5/2) FS+3/2(ξ) ] / [ (S + 3/2) FS+1/2(ξ) ] (11)

The meaning of various terms and symbols is as follows.

Fl = o°≡ (xl dx / [ (1 + exp(x - ξ / kT) ] (Fermi Integral of order l) (12)


(x = E / kT = integral variable , ξ = Ef / kT, l = S + 1/2, S + 3/2. etc.),

⎢ = Ke / (σ T) (= the Lorentz Number, Ke = Electronic Thermal Conductivity)


= { [ (S + 7/2)FS+5/2(ξ) ] / [ (S + 3/2)FS+1/2(ξ) ]
- [ (S + 5/2)FS+3/2(ξ) ] / [ (S + 3/2)FS+1/2(ξ) ]2 (13)

α(Seebeck Coefficient) = -/+ (k / e) (δ - ξ), - for electrons and + for holes (14)

The calculations for the transport parameters, can based on the relaxation time
approximation approach.What it means is that as the carriers move through the solid, various
scattering processes, modify the occupation of the higher energy levels,for the electrons. The
electrons move, between the excited and the groundstates of energy, according to a resultant
relaxation time. This relaxation time corresponds to the various scattering mechanisms
16 M.M. Kaila

involved.The change in occupation, in time, as a result of scattering, in the statistics f, can be


written as, δf / δt = [ (f – f0) / τ) ], Here f is the scattered and f0 is the unscathed, statistics of
the occupation of the electrons. Where, one takes the relaxation time, as energy dependent,
according to the relation

τ(E) = a Es (15)

a is a parameter independent of energy but may depend upon temperature.


τ = the energy dependent relaxation tome of the scattering of the carriers,
S = -1/2, for acoustic phonon scattering, = +3/2, for ionized impurity scattering, = +1/2, for
optical phonon scattering, etc. The meaning of more terms and symbols is as follows.

σ = n e μ = σ0 ε (16)

σ0 = 2 (2 π m* k T / h2)3/2 e μc (17)

Here μc = carrier mobility, n = the carrier density and m* = the density of states effective
mass

ε = FS+1/2(ξ) / (S + 1/2)! (18)

n = (4 / √π) (2 π m* k T / h2)3/2 F1/2 (ξ) (19)

μ = (2/3) a (kT)5 (e / mc) [ (FS + 1/2) / F 1/2 ] (20)

Here μc = the carrier mobility, mc = the carrier mass and

μc = (e / mc) < τ > (21)

< τ > = o°≡ [ τ(E) E3/2 ( f0 / E) dE ] /


[ E3/2 ( f0 / E) dE ] (22)

τ(E) would have different energy dependence for different scatterings.Taking various
scattering mechanisms, as independent of each other, one can write (1 / < τ >) > = 1 / < τac
(acoustic phonon) > + 1 / < τ I (ionized impurity) > + etc. Detailed mathematical expressions
for τac (acoustic or lattice scattering), τI (impurity scattering), etc., can be found in a standard
text. In the literature a special material parameter, has been used to gauge, the effects of
various material properties, on ZT (Appendix B2). The parameter can be written as follows.

= [ (k / e)2 T σ0 ] / (Kph)), Kph = lattice thermal conductivity (23)

= (k / e)2 2 (2 π k T / h2)3/2 e (m*3/2 μc) / KL (24)


Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 17

The above mathematical summary is only an oversimplified picture.One need to take the
following into account for a complete treatment.Non parabolic, multiple valley carrier
conduction pockets. This leads to higher carrier concentration and is in favor of ZT.2. Mixed
scattering mechanisms rather than one or tow, dominant ones. This will reduce the mobility of
the carriers and thus the conductivity. It may however enhance kinetic energy transport in a
particular situation. The material parameter , depends upon the basic material properties
e.g. the effective mass of the carriers, mobility, etc. 3. The two band approach (including
minority carriers, bipolar conduction, etc.)
The higher ZT values will be found in materials, with (s) deep in the band gap Eg, ((s) <
0), smaller carrier effective masses, higher carrier mobility, small KL, etc. There is no single
material which will meet all the optimization requirements. It is by performing experiments
on selected materials, comparing with their theoretical modeling, one really can find, what
exactly is in favor of ZT. This was done for the materials in their bulk form, during sixties
and seventies. Extensive data is available for materials like S-Ge alloys, Bi-Sb-Te
compounds, etc. A summary of the results can be seen in the literature [Appendices B3-B4].
Mathematical description of the phenomenology, of the two band approach, is included
below, for the sake of completion.

B 3.2 Two Band (Conduction and Valence) Approach


Assuming that the thermal conductivity K results exclusively from the freecarriers, one can
write

K = Kc = (k/e)2 T ΣNi=1 ⎢I σ I (25)

The suffix i runs over N extrema (energy ellipsoids) in the conduction (I = 1) and
valence (I = 2) band. The total electrical conductivity is

Σi σ i = Ne σ1e + Nh σ1h (26)

where Ne and Nh are the number of equivalent extrema in the conduction and valence bands
(non degenerate) and σ1 is the contribution to electrical conductivity from one extrema. The
other relations, as part of the ZT formulation are

α = (k/e) ΣNi=1 [ (Ai σI) / σi ] (27)

where Ai = δi - ξi , and involves the equations (11) – (14).

For simplicity one assumes, that the electrons obey classical statisticsand that equal
contribution from scattering parameters,are in operation, for the electrons and holes i.e. re =
rh = (s + 1/2). Here r comes from the energy dependence of the mean free path (l)approach
for the transport of the carriers, i.e. l = l0 Er. The relaxation time, equation (15), and the mean
free path approaches, are equivalent.
On substitution of the respective electrical conductivities, one gets

σe = Ne σ1e and σh = Nh σ1h in (26) one gets


18 M.M. Kaila

α = (k/e) [ Ae / (1 + σh / σe) + Ah / (1 + σe / σh) ] (28)

σe / σh = γ2 [ Fre (ξe) / re ! ] / [ Frh (ξh) / rh! ] (29)

Fri (ξi) = o°≡ (x)ri [ 1 + exp (x - ξi) ]-1 dx (30)

γ = [ (m*e / m*h)3/2 (μce / μch) ]1/2 (31)

Here μc, represents the mobility in the low carrier (classical) limit. m*e, m*h are the
density of sates effective mass for electrons and holes respectively.

m* = N2/3 (m*1 m*2 m*3)1/3 (32)

m*1 , m*2, m*3 are the masses along the principal directions of ellipsoids of energy.
Information on the upper bound of ZT can be more easily worked out from the model

Ai = [ r + 2 - ξi ] (33)

⎢i = (r + 1/2) (34)

σe / σh = γ2 exp (ξg + 2 ξ) (35)

Here ξg = Eg / kT, is the reduced energy gap. From these equations, it is apparent that in
this model, the Lorentz number, Ke / (σ T), i.e. ⎢i, is independent of ξ, ξg and γ, and therefore
the variation in these parameters will affect ZT, only through the Seebeck coefficient α
(equation (27)). It is worth noting in this model, that the upper bound in ZT, crucially
depends upon γ. For lattice (acoustic) scattering

γL = χL (m*h / m*e)1/2 (36)

χL = (Ne / Nh)5/6 (σh / σe)1/2 (εh / εe) (ε refers to the deformation potentials) (37)

For ionized impurity scattering

γI = χI (m*e / m*h)1/2 (38)

χI = (Ne / Nh)1/6 (ah / ae)1/4 (39)

The mass anisotropy a is given by

a = 3 / [ (m2 m3 /m12)1/3 + (m1 m3 /m22)1/3 + (m1 m2 /m32)1/3 ] (40)

One finds that for higher ZT, a high value for the ratio m*h / m*e is required and a small m*e /
m*0 (m*0 = the free electron mass). In addition, acoustic lattice scattering should be the
dominant scattering process in the negative branch of the thermocouple and impurity
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 19

scattering in the positive branch. The conduction band should also have a largenumber of
extrema with a small number in the valence band. A large mass anisotropy for the electrons,
but not for the holes, is another requirement for a large ZT. The energy gap also matters. For
a reduced energy gap (Eg / kT) of 4, ZTmax = 8, while for energy gap of 16, a value = 70 is
predicted, assuming a solubility of 1027m-3.

II C Generalized Thermoelectric Theory Applied to a Junction

II C.I Peltier Cooling, Ref[28, Bulk Device Structure, Appendix B14]


Ideally the Peltier heat transported per second, dQP, away from a junction, constructed from
two materials a and b, should result exclusively (reversible effect)from the charge transport.
The phonons should not interfere with electrons. This heat is proportional, to the magnitude
of the external current applied, and the duration dt, over which it is applied. Mathematically it
can be expressed as

dQP ~ I dt (1)

= Πa,b Ia,b (2)

= Πa,b (de / dt) (3)

Here Πa,b is called as the Peltier coefficient, or the Peltier voltage, and (de/dt)is the rate of
charge transported. It is positive, if the current flows from a to b (Appendix B14). dQP > 0
means, that the heat is absorbed, at the junction.From the reversible thermodynamic
consideration, one can also write,the effect, in reverse to (1), i.e. the thermoelectric power, as

αa,b = Πa,b / T (4)

Here, αa,b is the Thermolectric power (or the Seebeck coefficient), and is the Voltage
generated per unit temperature difference, across the junction (material a and b), as a result of
the heat absorbed at the hot junction. A third effect, called the Thomson effect, is also part of
the heat equilibrium in the circuit. There will also be an evolution or absorption of heat,
whenever, an electric current, passes through a single homogenous conductor, along which a
temperature gradient is maintained. This, is called as the Thomson heat, is generated or
absorbed (throughout the length of a single conductor)and is in proportion to the current I
passing, for a time dt i.e.

dQT ~ I dt dT (5)

= τ I dt dT (6)

= τ e dT (7)
20 M.M. Kaila

τ is referred to as the Thomson coefficient. It is positive, if the heat is absorbed, when current
flows to the hotter region.All the three, thermoelectric effects, are expressed as the reversible
effects,In the equations (1) - (7).
The Joule heat, which forms a part of the thermal effects in the circuit,is irreversible and
is not included in the equations, just for the sake of simplicity. As a result, of the temperature
gradient between the hot and cold the junction, an irreversible loss of heat (conduction,
radiation, etc.) also occurs.Disregarding, the irreversible effects, one can write, the net rate of
absorption of heat, required to maintain equilibrium, in the ab circuit as follows.

Q = [Πa,b (TH) - Πa,b (Tc) + ∫(τa - τb) dT ] (8)

By combining first and second law of thermodynamics, one can write[28]

d(αa,b)/dT = (τa - τb)/T (9)

τa = d (αa,) / dT, for a single couple (10)

This means, a standard reference conductor can be defined as having τa = 0, at all


temperatures, down to absolute zero (T = 0).A superconductor, is taken as a reference
material (α = 0),in the thermoelectric phenomena.
Electrons as they travel, get scattered by different targets e.g. phonons, impurities, etc.
All these scatterings are dependent on the electron energy.The relation between mean free
path l and energy E is expressed as follows.

l = l 0 Er (11)

α = (k / e) (A + ξ*) (12)

ξ* = Ef / kT, is the reduced Fermi Energy.

A = [ (< v ■ l >) ] / [ (< v l >) < (k T) > ] (13)

■ is the electric field and v is the velocity of the charge carrierA = r + 2, is referred to as the
average kinetic energy transported by the carriers. One can view, that Seebeck voltage arises,
from two sources, thermo EMF, Π, at the junction, and a distributed array of sources
(Thomson), along each of the conductors, = [ d (τ) / dx ] dx. The total Seebeck voltage arises,
solely from the change with temperature, of the continuous Fermi level Ef (electrochemical
potential, Appendix B14).

α = (1 / e) [d(Ef)/ dT) } (14)

It would be a nice illustration, to see the meaning, of the equation (1 4), in terms of the
application of the new low temperature materials, ZrHf tellurides[ appendix B5], to
thermoelectric refrigeration.The two stationary values of α, with respect to temperature,
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 21

Happen to be at 80 and 200K respectively. These two d(Ef)/dT values, produce the highest
values, of the power factor.

Pf = α2σ = K(ZT) (15)

The calculations, amount to, Pf = 0.5 (W/mK) at 80K and 1.5 (W/mK) at 250K.In between
these two limits, Pf, is higher than that of Bi2Te3, over 150 to 200K, and less than that of
Bi2Te3, over 80 to 100K. The ZT magnitude, would be the same as Pf, as the thermal
conductivity is around 1W/mK, in these materials. This is the situation, for the case of,a bulk
material. In the case of low dimensional materials, the situation is expected to be much more
favorable[Appendices B6-B11]. It is important to pint out, the difference between the Fermi
energy and the Fermi level. The Fermi energy is measured from the conducting band edge,
whereas, the Fermi level, is measured from some arbitrary fixed energy level (Appendix
B14). One can express, the Peltier voltage as

Πa,b (T) = T αa,b = [ (1 / e) (ηa - ηb) ] – [(1 / e) { (r + 2)a – (r + 2)b } ] (16)

Here the first term, is the change in potential energy, when a charge crossesthe junction, and
the second term is the average kinetic energy transported.The Thomson coefficient can be
similarly expressed as

τ = T (dα / dT) = (1 / e) (dη/dT - η / T) (17)

II C.2 Thermoelectric Theory Applied to the Mixed State in an HTSC


In conventional superconductors, dominant contribution to the heat flow is that due to the
moving vortices, at least at temperatures sufficiently far below Tc, and magnetic fields H <<
Hc2 (upper critical magnetic field). On the other hand, in the HTSCs, both quasiparticle
excitations and vortices (to a lesser extent) carry heat. Peltier effect has been observed in the
mixed stateof the HTSCs. For the electric field flux (Ex, electric field per unit area, A) and the
heat current flux (Jhx, heat current per unit area A), along x direction, one can write

■x = ρ Jex + α ∇Tx + transverse effects (18)

Here, ∇Tx = ΔT/ΔX is the temperature gradient, internally created

Jh,x = Π Jex + K ∇Tx + transverse effects (19)

where, Π = Peltier Voltage, internally created, i.e. no external heat input.

Π=αT (20)

When no external heat is present (Jh,x = 0), from (19), one gets
Π = (K / Jex) ∇Tx (Jhx = 0, adiabatic condition, no external heat input) (21)
22 M.M. Kaila

In order to measure the Peltier coefficient (Π), one has to determine, the temperature gradient
∇Tx (no external heat, Jhx = 0), induced by the electric current, Jex. This is a difficult task,
trying to do directly.An indirect approach is considered more convenient. First the
measurement of ΔT; this is done by finding, the thermal voltage generated, across the sample,
for each direction (reversal), of the electric current. The two voltage values, will have
opposite (+ and -) signs. Subtracting and dividing by two gives the Peltier voltage.
This is then converted into temperature difference using the Seebeck coefficient, of the
HTSC, measured in the normal state. Also there is need to,measure the thermal conductivity
K. This done by an independent, exclusive thermal (Jex = 0) experiment. In the thermal
conductivity experiment, a differential thermocouple, connected across two points, little away
from the ends of the sample (to avoid contact effect), is used to measure the temperature
difference and hence the gradient, across the sample, using, the length of the sample. The
thermal conductivity is then calculated, from the familiar relation, Q (External Heat Input) =
(K A (ΔT/ΔX)]. Then from the equation (20), the Peltier voltage for an HTSC- metal junction,
can be found.

III Optimization of ZT: A.Low Dimensional Materials/Structures


The following are some interesting results, worth noting, found in the recent studies, on the
low dimensional materials. The materials used in the modeling studies, were the conventional
room temperature bulk materials. This is due to the well documented details of the material
properties being available. One finds that there is a substantial improvement ZT. It makes, a
very strong incentive, to develop nano structure devices, for cooling applications. The
improvements found in the low dimensional material studies;the following included as
examples, should be interpreted, in view of thetheoretical formulation, outlined in the section
II above.

III A.1 Quantum Wells

II A. 1 n- type PbTe/PbEuTe–planar multi layer Structure, Ref[7, ZT results :


Appendix B6 and B7 ]
Special Features : Narrow gap class of semiconductors, effects of energy band non-
parabolicity, increased carrier density of states, decreased in-plane phonon thermal
conductivity, anisotropic effective masses, the multi valley characteristics.PbTe (ell) : mIIW
(electron mass parallel to well plane) = 0.35 m0, m0 = mass of free electron, mLW (electron
mass perpendicular to well plane)= 0.034 m0, EgW (Band Gap energy) = 321 meV, U (z) (well
confinement potential) = 173 meV, d = well widthPbEuTe (Barrier) : mIIB = 0.495 m0, mLB
= 0. 049 m0, EgB = 635 meVIn the case of (100) orientation all the four ellipsoids of constant
energy of the bulk PbTe are equivalent and the energy subbands in them coincide.In the case
of (11 1) oriented QW, the valley degeneracy is partially lifted.
Two sets of sub bands arising from different valleys appear. One set is from the
longitudinal ellipsoid perpendicular to the QW and is situated below the second one from the
oblique ellipsoids. The values of ZT were found greater than in the bulk case and grow with
the decrease of well width. uch a behavior is connected with the effect of density of states
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 23

increase. At large d (> 2 nm), the ZT depends on QW orientation and its maximum value o.4
is achieved at carrier concentration ~ 1018cm-3, as in bulk. For small d (~ 2 nm) the optimal
carrier concentration is higher. ~ 1019cm-3 and ZT ~ 0.8 is achieved.

III B Quantum Wires

III B. 1 One Dimensional Wire, Bi2Te3 Ref[9, ZT Results : Appendix B8]


Special Features : Anisotropic one band material, constant relaxation time, parabolic bands
in the direction of conduction, free electron like motion in the wire direction, bound state
(infinite potential barriers) in the perpendicular directions, only lowest band considered.
Bi2Te3 has ZT = 0.7 at 300K. It has a trigonal structure, lattice parameters (expressed in
terms of a hexagonal unit cell) are a0 = 4.3 A, co = 30.5 A, anisotropic effective mass
components aremx = 0.02 m0, my = 0.08 m0, mz = 0.32 m0, KL = 1.5 Wm-1K-1and mobility
along a0 (x direction) = 1200 cm2V-1s-1. There are has 6 carrier pockets each with a slightly
different orientation in the Brillouin Zone (BZ). The increase in ZT found, is due to the
change in density of states, but an additional factor is the reduced thermal conductivity due to
the increased phonon scattering.

III B.2 Cylindrical Bi Nanowires, Ref[10, ZT Results, Appendix B9],


Special Features : Bi is a semimetals with one anisotropic hole pocket at the T point of the
Brillouin zone and three highly anisotropic and non parabolic electron ellipsoids at he L
points, has small electron effective mass and the highly anisotropic Fermi surface is a special
attraction, the model takes into account anisotropic carrier effective mass tensor, i.e., non
parabolic features of the L-point , conduction and valence bands, and the multiple carrier
pockets, in ZT, there is a rapid increase, with decreasing wire diameter (< 10 nm), for
semiconducting Bi nanowire with Fermi energies close to the optimal levelthe system can be
approximately described by a one band model at low temperatures, in which the thermal
energy kT is much smaller than the band gap and adjacent subband separations, the Seebeck
coefficient in a one band system is fairly independent of the band character and is determined
by the position of the Fermi energy only, the dependence of ZT on the carrier effective mass
is only influenced by the electrical connectivity and the electronic contribution to the thermal
conductivity.

III B.3 Quantum Dots, Ge Dots on Si, Ref[11, ZT Results : Appendix B10 ]
Special Features : A configuration of regimented quantum dots, with strong coupling among
the dots, the carrier transport is facilitated by the extended 3D mini band formation, rather
than the localized QD states,the analysis is restricted to heavy holes, the single valley
effective mass approximation thus becomes valid, since a single energy maximum in the
valence band is located in Γ point, the light hole subband in compressed (superlattice) Ge is
well separated from the heavy hole subband, and have much smaller effective mass, the
curves show ZT for p type Ge/Si QDS, normalized to the Si values,the constant relaxation
time of 10-12 s is used, there is relatively large region of Fermi energies where ZT, is one or
two orders of magnitude larger than the bulk Si value.experimental value for bulk Si is 0.05 at
300K and of the bulk p type Si 0.95 Ge0.05 ~ 0.06.
24 M.M. Kaila

IV Conclusion
IV A General Considerations

Thermoelectric cooling, at the low dimensional material level, is the much wanted
temperature control, for the nano HTSC, THz devices. The ultimate speed of the of the device
is determined by the fastest possible heat dissipation by the electrons, without a back
flow.Self cooling of the electrons by the Peltier technique, in the HTSC sensorsis the right
approach to follow. Making a junction between Zr,Hf Te5 and YBCO, as a nano structure
would,make a good sensor-cooler to investigate. In a hot electron situation, a full description
of the electron-phonon thermal dynamics, in an HTSC, requires inclusion of coexisting
systems, i.e. cooper pairs, quasiparticles (electrons from broken cooper pairs), phonons in the
film, and phonons in the substrate, etc. When there is, thermal equilibrium, all of these can be
described by equilibrium functions with same temperature.That is the case, of a bolometer. If
a distribution does not satisfy these conditions, the situation is considered as nonequilibrium.
That is what an HETS is about. A treatment of a nonequilibrium state requires, a solution of
the space and time dependent,thermal distribution functions equations..
The assumption of a uniform non equilibrium state, spread over the entire volume of the
film, is applicable only, when the sensor is operated close to the critical temperature Tc.
Below Tc, the electron specific heat exhibits an exponential temperature dependence. That
requires non linear heat transfer equation for even small deviations from the equilibrium.
Near Tc, the superconducting energy gap is strongly suppressed. The concentration of cooper
pairs is very small, and the unpaired electrons exhibit no significant superconduting
peculiarities. They are regarded as normal electrons, and obey the normal Fermi distribution
function. One should notice that there are a wide varieties, of similarities and dissimilarities,
among the LTSCs (e.g. NbN) and the HTSCs (e.g. YBaCuo), [Appendices A1-A3]. The
thermalization dynamics, in the case of an HTSC is an order of magnitude faster. In YBaCuO,
Cp/Ce ~40, while in NbN, it is ~10. On the femtosecond time scale, the non-thermal (hot
electron), and thermal, bolometric (phonon) processes are practically, de-coupled in an
HTSC. Thus the former, totally dominates the early stages of electron relaxation. In a case,
when an HTSC is operated much below Tc,the hot electron approximation is not adequate.
Several alternative models, of using the non equilibrium state of electron and phonons, in
an HTSC, for thermal sensing, have been suggested in the literature. It is worth mentioning
the virtues of, a hot spot HETS.In this approach, a particular selected area on the film, under
irradiation, evolves as a hot spot in the film. What this hot spot means is, that the material
within the hot spot behaves like a normal material,surrounded by superconducting volume all
around. The spatial extent of the spot, increases with the energy received in the spot. The
spot, which is in the normal state, thus has a variable interface with the surrounding
superconducting phase. The ratio of the normal electrons, inside the spot, as compared to the
supreconducting cooper pairs, outside, can be adjusted, by using a suitable bias current and
the power of the laser pump. A study can be carried out on the response of the sensor, by
gradually reducing the photon flux, to almost zero. The response for a single photon, can thus
be manipulated. There may be a one spot, or several sots, working in coherence. A practical
device has been developed, as a single photon, hot electron thermal sensor[5]. It is possible to
design a low dimensional structure e.g. a regiment of quantum dots, of a thermoelectric
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 25

material, on a superconducting lattice, or vice a versa.The ratio of the thermoelectric (T)-


Superconducting (S) phase, can be varied. It would make a good study, to investigate a
current or a voltage biased, ST sensing-cooling integrated device.
One can use a current bias, in the superconduting film, for the destruction, of a certain
number of cooper pairs. The remaining pairs, accelerate to carry the same current. Because of
nonzero inertia of pairs, acceleration requires an electric field. This intrinsically generates a
voltage V kin ~ Lkin (kinetic inductance), in he exterior of the film. Thus this can be an
alternative, and may be a better way, of THz radiation detection. One should also realize that
in an HTSC thin film sensor, there is a strong potential, to develop, a video technique for the
THz radiation sensing , i.e. the thermal imaging [Appendix A4, A5].

IV B Concepts from the LTSCs, Those Can Be Applied to the HTSCs

LTSC Electron Tunneling-Cooling in NIS(Normal Metal / Superconductor / Insulator/)


Sensors
Peltier studies in LTSCs, at mK temperatures have brought out interesting results, Ref[6,
Appendices B12, 13]. The physics of the Peltier heat, in superconductors, in general, becomes
much clearer, by examining the much studied LTSC (mK), NIS sensors. The tunneling of the
electrons from N to S, warms up, the quasiparticles in the S electrode. If it does not
backtunnel S to N, each quasiparticle carriesan energy = Δ - eV, (V = bias voltage and Δ =
superconductor band gap).
The number of cooper pairs breaking per unit time, per unit area, Ns,in the
superconductor, is determined, by a balancing current. This is the current of the quasipartcles,
in the S electrode, due to their decay or out diffusion. If (k Tn), the thermal heat of the
electrons, Tn = normal metal temperature, < < Δ - eV, the relation between, electron number
current number flux (je) and the quasiparticle number flux (jq), is jq = je - (1 / τbt) Ns. The
cooling power Pc can be written approximately as Pc ~ [ Δ (1 – τs / τbt) – eV ] je, τs = the
relaxation time of the quasi particle (superconductor) excitations, and τbt = back scattering
relaxation time.The back flow of the quasipartcles has to be reduced to minimum i.e. one
should have τbt >> τs. The phonons emitted in the process of self recombination, can also
reduce cooling power (Pc) by being absorbed in the N electrode, when thy deposit energy 2Δ.
In competition with Pc, is the phonon electron heat exchange, in the N material. The achieved
cooling power in the LTSC case was approximately 2 pW/μm2.

IV C Achievements HTSCs

Electronic Cooling : Mixed State : Bi 1.7Pb 0.24Sr2 ca2Cu3Oδ (BSCO,Tc = 120K), (Bulk
Material) Ref[30 ]
Thermoelectric-thermomagnetic phenomena in the mixed state of the HTSC materials has
been extensively studied. The BSCO-Cu junction, is good example to consider[30]. In a bulk
material superconductor situation, a direct measurement of the Peltier coefficient (due to its
small magnitude), is very difficult. There is need to take into account, effects of both the
electrical and thermal currents, across the junction.The mixed state of the superconductor, has
a fraction of the volume,where electrons are free and behave like normal electrons.When heat
26 M.M. Kaila

is transported, due to an electric current I (Peltier heat), through the superconductor, a


temperature gradient is established,across the ends of the superconductor.Knowing the
thermal conductivity (K) of the superconductor, and measuring the temperature gradient
across the sample, produced by the Peltier heat (refer section II C.2), one can find the Peltier
coefficient Π, from the relation

Π = (K / Je) (ΔT / Δx) (1)

In an experiment on the (Bi, Pb)2Sr2Ca2Cu3Oδ, (Tc = 120K)-Cu junction, Π was found to


be 0.5 mV at 100K, at the middle of the transition width [30]. This corresponds to a
temperature drop (ΔT = Π / α) of 10-5K,across the sample. This electronic cooling, is much
smaller, than that (0.25K) observed in a thick film situation, in the YBCO-Bi junction[23].
One should compare these results with that of the case of a nano film LTSC sensor i.e. the
SIN (superconductor / insulator / normal metal) IS sensor[6, Appendices B12, B13]. A
cooling of 200mK (at 300mK) was produced, in that device. It is seen in the above BSCO,
mixed state HTSC experiment, that the Peltier heat current is, due mainly to the excitations,
over the nergy gap of the superconductor. These are he so called, quasiparticle
(QP)excitations. Since the electric field (disregarding the small Hall angle) is mainly parallel
to the electric current J , the QPs move parallel to the electric current and contribute to the
longitudinal heat current., i.e. the Peltier heat. The Peltier coefficient, due to total current J,
including contributions fromthe supercurrent (Js) and the QP current (JQP) , can be written as
under. It I believed that the QP excitations carry all the heat.

Π = ΠQP (JQP / J) + Πs (Js / J) (21)

~ ΠQP (JQP / J) (22)

IV D Detectivity

Noise Equivalent Power / Temperature : Hot Electron Thermal Sensor (HETS) :


[Appendices C1-C3 ]
The detectivity of a sensor, is a parameter, which determines, the ultimate sensitivity of a
sensor. It is inversely proportional to the noise equivalent power (NEP) of the sensor.The
NEP, in a sensor, is taken as the square root, of the sum of the squaresof the NEPs, from all
possible sources, e.g. the thermal noise (TN), the resistance or the Johnson Noise (JN), etc.
Detectvity modeling in the case of a YBaCuO-Bi junction was the first oneto involve
thermeoelctric-voltage responsivity, though it was for a bolometric case[32]. The same
technique can be applied to modelNEP in an HETS environment[33]. Remote sensing
detectivityanalysis performed in the YBaCuO-BiSb bolmeter case, can similarly be easily
applied to an HETS.
In a practical device, the specific detectivity D*, rather than detectvity D,is considered as
an appropriate parameter. The D*, D and the NEP are related as follows.

D = 1 / NEP (1)
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 27

D* = D A1/2 Δf1/2 (2)

A = the sensitive area, and Δf = the frequency band of interest and

NEP = NEV / Vrsp(ω) (3)

Here NEV is the noise equivalent voltage and Vrsp(ω) is the frequency dependent voltage
responsivity of the sensor.In a particular, the open circuit (no current bias) case, for the
YBCO-BiSb junction, a specific detectivity, D*, of 1011 Cm Hz1/2/W was estimated [34]. A
detailed noise performance analysis for the YBaCuO-HETS case, has been carried out
before[35]. Noise equivalent temperature, NET, rather than NEP, is considered as more
appropriate parameter. The following mathematical expressions, involved in the noise
analysis ofan HETS, are worth reproducing here[35, 36, Appendices C3, C4].

NET = (NEV)2 / [ 2 a kB RL gcnvrsn(ω) ] (4)

NET = (NEP)2 / [ 2 a kB PLO ] (5)

gcnvrsn(ω) = [ 2 a V2rsp (ω) PLO ] / RL (6)

Here a = the coupling facto between the incident radiation and the sensor,kB = the
Boltzmn constnt, RL = the external (to sensor) load resistance and gcnvrsn(ω) = the frequency
dependent conversion gain of the sensor. In a single side band (SSB) situation, for the case of
thermal noise TN, the noise equivalent temperature, NET can be written as

NET = 2 t2e1 ge / (atcr2 plo) (7)

Here te1, is the electron temperature the substrate temperature, atcr, is the dimensionaless
temperature coefficient of resistance of the sensor, ge is the thermal conductance between
electrons and phonons. In a complete treatment, noises due to, the thermal resistance between
sensorand the substrate, electrical resistance or the JN noise, etc, should all be taken into
account.
In the case of a model where electro-phonon thermal conductance,is the dominant one in
the heat transfer process, the ge, is expressed as follows

ge = 3 lep Vs t2e1 (8)

where Vs is the volume of the sensor, te1 is the amplitude of the electron temperature pulse, lep
= γ / (3 tmep ts),ts is the temperature of the substrate, tmep is the electron phonon temperature
relaxation time and γ is the Somerfield constant. For a 10 nm thin and a 0.1 μ wide, YBaCuO
sensor, a NET of 3000K is obtained. An optimum bias of PLO (local laser pump boost power)
~ 10 μW and I = 50 μA, makes JN much less than the TN noise.Where phonon are in
equilibrium with the substrate, so that the electrons,can easily diffuse to the end electrical
contacts, is called as the diffusion limit.In this limit, one can write
28 M.M. Kaila

NET (TN) = 3 lep te4 LD2 / [ 4 Kp (Tc - te) ] (9)

Here Kp = is the phonon thermal conductivity and LD = the diffusion length of the
electrons. The phonon diffusivity cab be written as

Dp = kp / Cp (10)

~ 0.15 Cm2/s, in the YBaCuO case[35, Appendix C3].

In order to make the device operate under this condition, the lengthof the sensor has to be
< 70 nm and need to be < 2 nm across.The electron temperature relaxation time, tme, is
limited by the electron-phonon relaxation time, tmep and the phonon escape time tmes, as
follows

tme = tmep + tmes (ce / cph) (11)

When a detector can not operate under the diffusion limit, but rather involve, the
substrate, then tmeshas to be small enough, so that, tmep > tmes (ce / cph). Then the band width
of the sensor will be[36]. In the lowest noise temperature limit, one can write[36, Appendix
C4].

NET (TN) = [ 4 Tc/ (atcr) ] (12)

Under this limit the band width of the sensor becomes

Δf (TN) = (1 / tmep) [ √ (1 + (Tc / ΔTc) ] (13)

This is he case when the substrate is highly thermally conducting, with conductance
much better than between electrons and phonons. With Tc = 100K and ΔTc = 10K (HTSC),
Δf = √11 THz (tmep ~ 10-12s). In an LTSC, on the other hand, Tc = 10K, ΔTc = 1K, one gets
Δf = √11 THz.
Thus in the low noise limit, the HTSC results in the sane possible band width, as the
LTSC. One should notice however that the restrictions on the dimensions of an HTSC sensor,
are much more critical, to achieve same level of performance. In the HTSCs, the electrons,
have a much shorter mean free path, and thus have to be collected over a much shorter space,
for conduction. I feel, a, S (superconductor)I (insulator) T (thermoelectric material) – I S, i.e.
a SITIS, pair junction, as a sensor, analogous to the LTSC, SINIS sensor, should form a good
study, for an experimental and theoretical analysis. This should lead. to the much desired
design, of an HTSC junction sensor, with an integrated electronic cooling[Appendix B13].
One can then extend it, to a hot electron HTSC-Peltier cooling,integrated THz thermal sensor.
This can be done by using both, old[Appendices, B3, B4] and new [Appendix B5], class of
thermoelectric materials.
Hot Electron non Eqilibrium High Temperature Superconductor Thz Radiation... 29

Acknowledgements
Family

This work is written in respect of the sufferings of my mother Mrs P.W. Kaila, late, father Dr.
M. R. Kaila, brother Dr. K. L. Kaila, and many millions, living or dead, who became innocent
victims, least to mention, as refugees, at the independence of India, in 1947.This carnage,
resulted from the division of India, which accompanied the freedom.Our family, and many
other millions, during 1947-1948, were made refugees twice. We first moved from our home
at Lahore, and created another one at Jammu (Kashmir). Then later due to the unsettled fate
of Kashmir, moved from Jammu to Delhi. I ma grateful to my wife Mrs Veena Kaila, for her
interest and encouragement.My gratitude also goes to my daughter, Dr. Rakhi Kaila. She
showed lot of interest in my research work, during her stay at,the University of New South
Wales (UNSW), while completing her studies, towards her MBBS degree. I am also thankful
to my son, Rohit Kaila, for his support, during family movements, interstate within Australia,
and also overseas. The movements became an unnecessary evil, to keep myself, in job and my
profession.

Scientific Community

I am grateful to the authors of the publications, both virtual and real, from where some of the
information has been used, to prepare this work. The information available, at present is from
the specialists in the area.This is disseminated, at isolated spots, and intelligible, by non
specialists.I am grateful to those who have made available such publications.This has enabled
me to prepare this work. The preparation is in a in a manner, so that a beginner, in the field,
has a good starting point. On the other hand, scientific community, at large, would have, at
their disposal, a directed information, for research,development, education and training. The
research community, realizes, that it there is need for a thermal sensor, which will have an
integrated cooling, for its best performance. Thermeolectric cooling, by the researchers in
field,is believed, to be the right direction to follow. The way the information is as available at
present, is beyond the comprehension, of many non specialist members of the community.
There has been, little research and development effort, in creating a suitable knowledge bank,
over the last three decades, particularlyin the area of thin film themoelectrics.
The inspiration to take up this task has, originated from the research experience, I
gathered, in the area of high temperature superconductors, while working,in association with
late A/ Professor, G, J. Russell, at the UNSW, during the nineties.Useful research articles, by
several workers in the field, at isolated locations, have been very useful to me. They have
helped me to prepare this work, in comprehensible format. I hope this work will stimulate
participation, in the development, from a much wider section, of the scientific community.
The small step I have endeavored here, I feel, will become a giant step, with the enthusiasm,
of the community at large.My association with Emeritus Professor H. J. Goldsmid, during
seventies,and part of eighties, at the UNSW, provided me with training, in the area of
thermoelectric materials and devices, which helped me to make,this work, a modest one. I
much appreciate that association.I am also grateful to Professor J. W. V. Storey, for his
continuous support andinterest, including, in the field of thermal sensors. The best ‘ present ‘
Exploring the Variety of Random
Documents with Different Content
“There must be a dozen or more!” gasped Frank, in amazement.
CHAPTER XII
A NEW “U-13” APPEARS

Eagerly the lads gazed at the strange sights before them. On their
right rose several huge buildings; evidently workshops. On the left
they could see a field devoted to the erection and testing of several
gigantic dirigibles. Everywhere they saw bustling activity on the part
of the numerous workmen. Sentries paced about with arms in
readiness.
“That fleet of submarines looks to me as if Germany were
preparing to destroy every ship in the world!” stated Jack presently,
as the destroyer on which they stood passed the undersea craft.
“The workmen seem to be fitting out some of the divers, too!”
ventured Jimmie. “See them carrying packages aboard that outside
one!”
“Maybe the grocer is coming to deliver the goods in the rear!”
laughed Ned. “Those packages look like groceries in disguise!”
“I’ll bet Mackinder would like to see those submarines!” Harry
said. “He’d give his eyes almost for one good long look at them!”
“Mackinder won’t see enough to carry any news back home from
this place!” declared Frank. “Didn’t you see the officer take him
below?”
“Yes, I did! I also saw the black look he gave us as he was being
taken away from this deck house. He likes us a lot—nit!”
“I believe the commander of this craft is favorably disposed
toward us,” put in Ned. “He probably realizes that we want to be
neutral and that our presence in this neighborhood is due to our
misfortune and not to our fault. I do wish, though,” the lad added,
“that we could leave!”
“How much would you give to get away?” questioned Jimmie.
“I’d give a good deal!” replied Ned. “I don’t like the idea of
remaining on this island a prisoner for any length of time!”
“Well, if you’ll make it worth while,” Jimmie offered, “I’ll take you
along as a passenger. You must behave, though!”
“Ah!” smiled Ned, thinking Jimmie was indulging in another of his
jokes. “May I ask when your ship leaves?”
“I’m thinking of leaving about midnight or a little after,” stated
Jimmie, gravely. “It will depend somewhat on the wind and weather.
If it comes on to blow and the sea is rough I believe we’ll get out on
time. However, if this breeze should die away, we may not go!”
“You’re rather reversing the order of things,” commented Ned.
“Most captains want clear weather and smooth seas for their
departure!”
“Well, if it remains stormy, as it has every prospect of doing and
you want a swift ride, you just keep watch of your uncle!”
“Thanks!” laughed Ned. “You may surely count on me!”
“May we go along, too, Jimmie?” asked Harry.
“Sure, you may all go!” answered the lad. “But I warn you right
now,” he added, “that you’ll have to work your passage!”
“That suits me!” returned Harry, greatly amused at carrying on
what he considered as a pleasant joke to while away the time.
But to Jimmie, at least, the matter was not by any means to be
regarded as anything but a serious proposition. The lad had quickly
formulated a plan of escape. The very daring of his intended action
was its best guarantee of success. Failure meant disaster, but Jimmie
was prepared to risk all in the attempt.
For a time the lad said no more. His tightly shut jaws showed the
determination that possessed him. The others became absorbed in
observing and discussing the monster Zeppelin dirigibles, hence they
said nothing more upon the subject. There was much to attract their
attention.
Directly they were summoned before the commander. As they
entered the cabin the Sturmvogel drew up alongside a dock.
“Young men,” the officer began as the lads entered the cabin, “I
regret keenly the circumstances that seem to make it necessary for
us to detain you. I understand how anxious you must be to reach
your homes, but it is not possible to permit you to depart at this
time. You will be given every consideration during your stay at this
place.”
“Can’t we go with you when you leave here?” asked Frank.
“No, that is impossible!” the other replied, shaking his head.
“Then maybe some other vessel will call and we can get passage
on it? We are not particular about the class of accommodations!”
“You forget that for some distance in every direction the sea is
mined. No vessels approach this island unless they know the
channels.”
“Then I guess we’ll have to be contented,” sighed the lad.
“Is Mackinder going to remain here also?” questioned Ned.
“I am very sure of it!” smiled the commander. “I believe that
several members of the guard are quite prepared to insist upon his
staying here until the knowledge he now possesses would be of no
use to his own country. Yes,” he added, “Mackinder will remain!”
“I hope matters will be arranged so that we shall soon be able to
leave for home,” stated Ned. “We are not anxious to leave good
company, but we would like to get away from the scene of so much
trouble. We want to remain strictly neutral, and think the best place
for that is at home!”
“I haven’t a doubt of your neutrality!” declared the officer heartily.
“You may be assured that I shall do everything to help you. I believe
I can arrange so that certain privileges will be granted. It will not be
necessary, I am sure, to confine you to one of the buildings.”
“Thank you!” replied Ned, gratefully. “You are most kind.”
“And now, if you please, we will go ashore to meet the officer in
charge of this place,” stated the other. “You will like him, I’m sure.”
Congratulating themselves on the kindness shown in their behalf
the boys prepared to leave the Sturmvogel. They collected the kits of
the four who had left Amsterdam on the Lena Knobloch. As they
gained the dock they found the small boat in which they had left the
schooner. It was evidently being preserved as evidence of the
circumstance of the rescue.
Already the work of provisioning and fitting the vessel was in
progress. The wireless had been busily used during the last few
hours of their voyage to the end that just the supplies needed were
waiting at the wharf. A huge coal barge fitted with a “whirlie” had
drawn up alongside. Great buckets of coal were pouring into the
bunkers, while porters carried all sorts of stores and supplies aboard.
Cases of ammunition were being hoisted aboard and stowed in their
proper compartments.
Stepping along the dock, dodging wagons loaded with fresh
provisions and stores, the boys kept pace with their friend, the
commander.
Presently they reached one of the buildings given over to the use
of offices. Here they were admitted into a room, where they found
the officer in command of the island.
A short conversation in German served to inform this gentleman of
the situation so far as the commander of the destroyer could report.
At the end of the recital the boys were addressed by the one they
had been brought to visit, who had been introduced as General
Gruenwold.
“I understand that you young gentlemen lost an airship when the
schooner sank?” he inquired of Ned, motioning the boys to chairs.
“Yes, sir!” replied Ned. “It was, of course, a complete loss.”
“Then you understand machinery pretty well?”
“We have always thought so,” was the modest reply.
“And electricity?”
“Yes, sir. We understand wireless, also.”
“Then I am fortunate. Perhaps you would consent to assist us in
some difficult technical tasks we have on hand.”
“We shall be glad to do what we may to reimburse you for our
keep if you will be good enough to assist us to return to the United
States!”
“Let us discuss that at another time, if you please,” replied
Gruenwold. “Just now we are short of practical electricians. If you
will offer your services in that direction we shall be very grateful. You
may be sure that we shall not be forgetful when it is possible to
reciprocate.”
“Thank you,” replied Ned in acknowledgment of the indirect
promise. “Now, if you will show us what you want done we shall be
most happy to proceed. I believe we have nothing else to do.”
“Here are some plans,” stated the other, opening a cabinet at one
side of the room. “In these compartments are plans of certain
vessels. You will observe on these sheets marked ‘elek.’ complete
diagrams of the plan of wiring. Take this one, for instance. Do you
think you could understand what is meant by these tracings?”
Ned studied the diagram for a few moments. The other boys
leaned over his shoulder. Presently, after conferring with his friends,
the lad announced that he understood the drawings perfectly, even
though he was unable to read the explanations which were in the
German language.
A smile lighted the face of Gruenwold as this statement was made.
Evidently the need for completing the work was urgent.
“In that case, we will ask you to accompany this orderly on board
the vessel and proceed with the work. I will write an order directing
the ones in charge of the vessel to admit you and render such aid as
may be necessary. Later I will send a man who can speak English.”
While the general was writing the necessary order to the ones in
charge of the vessel to which he had referred the boys were busy
communicating with each other by means of the mute language, in
which they were quite adept. By supreme efforts they were able to
suppress the excitement under which they were laboring.
“What a piece of luck!” rapidly signalled Jimmie to Ned.
“Keep cool!” cautioned Ned in reply. “Don’t give it away!”
“Insist that we stay together on the job,” returned Jimmie.
“You may be sure I shall do that!” came the answer instantly.
“I hope the storm increases!” was Jack’s contribution.
“Now, gentlemen,” announced the general, “if you are ready to
proceed you may accompany this man. He will direct you to the
work.”
Ned bowed in acknowledgment and the party turned to
accompany the orderly, who appeared in answer to the summons of
his superior.
They were led away from the dock at which the Sturmvogel lay. In
a short time they had traversed a goodly distance toward the mouth
of the harbor. Their destination proved to be the building adjacent to
the group of submarine vessels. By inquiries both direct and indirect
Ned and his companions decided that the orderly was unable to
comprehend English, but for the sake of absolute safety they
continued to use the sign language largely in their conversation as
they proceeded.
In a short time they had been admitted to the outermost craft,
which lay moored to its fellows. Communication had been
established between the vessels by means of a row of planks laid
from deck to deck.
Once inside the submarine the boys made a hurried yet thorough
examination of every part, taking a complete inventory of the exact
state of affairs. Frank and Jimmie managed to overhaul the stores.
Harry and Jack looked over the mechanical equipment. Ned, with the
plans in his hands, went carefully over every detail of the electric
system.
“I say, fellows,” announced Ned at length, as all the lads met
beneath the hatch, “this wagon is nearly complete. It looks a lot like
the ‘U-13’!”
“That’s what it does!” agreed Jimmie. “What more is needed?”
“A few pieces of wire and about an hour’s work for me.”
“Frank and I have found enough food to last a couple of months if
we can count hard-tack, sausage, and the supply of canned goods.”
“Jack and I,” announced Harry, “have found the engines and
pumps apparently ready for duty in a moment. My idea is that they
are trying to get this vessel ready for a cruise at the first possible
moment.”
“It looks as if they are expecting a crew from some place and
want the boat ready for duty as soon as the crew arrives!” stated
Ned.
Further conversation was cut short by the arrival of the orderly.
“Essen?” he inquired, pointing at his mouth and rubbing his belt.
“Don’t say it twice!” cried Jimmie. “We heard you the first time!”
The boys prepared to follow the orderly, who evidently intended to
escort them to the mess hall, where they would secure dinner.
As they turned toward the iron ladder leading to the hatch Jimmie,
who had followed close upon the orderly’s heels, cried out:
“Hello, Mackinder, where you from?”
CHAPTER XIII
A THREATENING SITUATION

“Who’s there, Jimmie?” asked Ned, pressing forward.


“Nobody now,” answered the other. “I thought I saw our friend
Mackinder looking down the hatchway, but possibly I was mistaken.
At any rate he’s gone now and we’d better hurry on for dinner.”
“Mackinder’s a prisoner here,” stated Ned, positively.
“Maybe he broke loose,” suggested Harry.
“All right, I’m going up to the deck and look about,” said Ned.
As the boys reached the narrow confines of the small deck at the
top of the conning tower they saw a figure hastening along the foot
planks that led from vessel to vessel. The fleeing person was now
almost at the building on the wharf. In a moment the shelter of this
structure had been gained. The figure dodged out of sight.
“Now, that’s a funny thing to do!” mused Ned. “I wonder just what
the fellow wanted. Are you sure it was Mackinder, Jimmie?”
“No, I’m not,” admitted the lad. “Of course, the face was in
shadow as he looked down the hatch. I’m not positive, but thought
it was he.”
“Well, let’s not bother about it any more,” said Ned, apparently
dismissing the subject. “We’re too hungry for any more mysteries!”
As only hungry boys can the five attacked the ample dinner
provided for them. The dishes were strange but appetizing. Jimmie
declared that he intended to remain in that location for some time in
order to become acquainted with the chef. He said that he would be
the envy of the entire Wolf Patrol if he could cook in German style.
After dinner the boys gathered in the lee of a small building,
where they would be protected from the chilling blasts. Puffy squalls,
bearing dashes of snow, sleet or rain, came threshing out of the
west. It appeared to the lads that the weather was growing
decidedly worse.
In spite of the inclement weather a number of the hardy workmen
were indulging in out of door sports during their rest hour.
For some time the lads watched the games as the hardy men
relaxed their work-tensed muscles. The sullen booming of surf on
the rocky coast constantly sounded in their ears.
“There goes our late rescuer!” announced Jimmie presently.
“Where?” asked Frank. “Whom do you mean?”
“The Sturmvogel!” answered Jimmie, pointing toward the harbor,
where could be seen the speedy destroyer slipping quietly out to
sea.
“Here’s hoping you have a good voyage, friend!” said Frank.
“Yes,” added Jimmie, “we’ll see you a little later!”
“That reminds me,” put in Ned, “we might as well get back to the
‘U-13’ and begin work. There’s no use delaying the game!”
“That’s right,” agreed Harry. “These fellows are probably in a hurry
for that submarine. We might as well be decent.”
“Wait a minute,” suggested Jimmie. “You’ve given me an idea!
Your mention of the name of a certain undersea craft started a train
of thought in my alleged brain. Take it easy for a moment!”
“Yes,” cried Jack, in mock sympathy, “stand back! Give him air! If
Jimmie is really going to think, let’s give him lots of room!”
“Aw, you go on!” scorned Jimmie. “I’ve got a right to think if I
want to, haven’t I? I guess that’s my privilege!”
“Not unless you have a union card!” protested Jack, laughing.
“That’s all right,” retorted Jimmie with a grin as he wrinkled a
freckled nose at the other. “I was going to think about a scab,
anyhow, so I don’t need a card. Besides, this is on overtime!”
“All right, you win!” declared Jack, submissively. “Go ahead!”
“If you’ll promise to never, never tell, I’ll let you in on the
scheme!” whispered Jimmie, glancing about to make sure that no
strangers were within earshot. “Do you solemnly promise?”
“I do!” answered the boys in chorus, anxious to receive the news.
“Then here it is: If we could paint the name ‘U-13’ on that tub
there’s nothing to prevent our getting away in it!”
“Hush, Jimmie!” cautioned Ned, in a startled tone.
“Hush nothing!” declared the other boldly. “It’s now or never! The
destroyer’s gone—everything’s gone that could chase us. Mackinder’s
loose on this island. He’ll make us trouble if we stay. If we go now
we are safe from pursuit until another German boat comes in unless
they flash the news by wireless. In that case, we have an even
chance of getting away. If we don’t go now tell me when we can get
home?”
“I guess you’re right, Jimmie, but how are you going to work it?”
“Simply putter along this afternoon,” explained the lad, “fixing the
wiring and so on. If necessary, rip out some and replace it. We can
get in one another’s way enough to kill a lot of time. After supper
we’ll manage to slip back to the submarine, paint ‘U-13’ on the side,
every man to his post, let go lines easy and skedaddle for the open
sea.”
“It sounds easy enough,” assented Harry.
“Yes, unless you happen to get caught!” agreed Ned.
“What is there to catch us?” asked Jimmie, bristling at this hint of
opposition. “The guards are all wise to the fact that the channel is
mined. They will be sleepy and lazy. They know that the torpedoes
are not aboard yet and believe it impossible for the submarine to
leave without a crew. The weather looks as if it were going to be
rough. What more can you want? It looks to me as if we’d never
have another chance like it!”
“Right you are, Mr. Wolf!” declared Frank. “I, for one, am willing to
take a chance. I’ll go with you to the limit!”
“Here, too!” heartily agreed Ned. “How about it, boys?”
Eagerly the others signified their willingness to undertake the task
suggested. They felt no compunction over the seizure of the boat.
“Now, we’ll have to do some tall thinking before night comes!”
stated Jimmie. “Each of us’ll have his station and we must know just
what to do at the proper time. I had this in mind ever since we came
up the harbor past those boats. I noticed particularly the buoys
marking the safe channel leading into this harbor.”
“Good for you!” cried Ned, administering an affectionate slap upon
Jimmie’s shoulder. “I knew you had something up your sleeve!”
“So did I!” added Jack. “I couldn’t guess what it was, though!”
“It was my arm!” declared Jimmie, with mock gravity. “Now, let’s
go back to this ‘Untervasserbootschiff’ and stall around a while.”
“Correct!” cried Harry. “We’ll rehearse for this evening. We shall
depend on Jimmie to be the pilot, though!”
“Leave it to me!” declared the younger lad. “I know where the
buoys are! I have them all located in my head!”
“But we must be mighty careful,” declared Ned. “We don’t know
how much English these fellows understand. They must not
suspect!”
“Mum’s the word!” put in Frank. “Everybody mum!”
First visiting the warehouse at the wharf, where they procured a
quantity of supplies, such as might be needed to carry out the work
which they were supposed to be doing, the lads proceeded aboard
the submarine.
Upon their arrival they found a painter at work inscribing the
vessel with identifying marks. He had proceeded so far as to place
“U-1—” on each side of the vessel. Jimmie joyfully declared that
fortune was playing into their hands in this respect, and that if
something would compel the man to quit work for a while the
disguise could be quickly made.
At Ned’s request Harry began fitting wires from the storage
batteries to the motors used for propelling the vessel. The boys were
startled to hear him utter an exclamation of dismay. They found
upon inquiry that he had endeavored to strip the insulation from a
wire by using his pocket knife and had cut a finger badly.
“Pooh, pooh!” stated Jimmie, upon discovering the wound. “Don’t
make so much fuss over a little thing like that. We’ll soon have you
fixed up. Here, just hold the wound closed with your other hand
while I hunt up some bandages. You’ll be all right in a minute!”
But Harry declared that the wound pained excessively. He refused
to treat the matter lightly, but gathered up the tools with which he
had been working. These he deposited in a canvas bag in which they
had been brought aboard the vessel.
Presently Jimmie located a first aid kit among the stores. He was
not long in cleansing and bandaging the wound.
“There you are!” he stated. “Just as good as new! Now go lie
down for a little while. I’ll finish this job if I know enough.”
Chatting together in a somewhat nervous manner the boys
anxiously awaited the approach of evening. As the time wore on
their restlessness increased. Again and again they carefully went
over each detail of their proposed plan for escape in the submarine.
It was decided that Jimmie should take the wheel while Harry
stood watch at the engines. The others were assigned to various
other duties at favorable positions. Nothing remained except to wait
for night.
A short time before darkness settled an orderly visited the craft.
He was able to converse slightly in English.
“How are you getting along, boys?” he asked, as he stepped down
the iron ladder. “Can we put the torpedoes aboard tomorrow?”
“Yes, I think you will be able to place the torpedoes after
tomorrow morning,” replied Ned. “We will have our work all done
then.”
“That is good!” was the other’s comment. “Where is Mackinder?”
was his next question. “He will have to come ashore now!” he
added.
“Mackinder?” was Ned’s startled response. “He’s not here.”
“But he was here!” firmly declared the orderly. “He was seen by
one of the sentries to come aboard this vessel, and has not since
been noticed going ashore, although a close watch has been kept!”
“We haven’t seen him at all!” stated Ned, just as firmly.
“We shall have to search the vessel!” affirmed the orderly. “You
will please remain aboard for a short time.”
Quickly ascending the ladder the man summoned another soldier
from the shore. Together the two made a hasty examination of the
boat.
Unable to discover any trace of the missing prisoner they shook
their heads as if greatly puzzled. Now and again they glanced at the
boys, exchanging at the same time comments in German.
“Come with us,” finally said the first visitor.
Obediently the lads followed ashore. They were conducted to the
office building, where they were shown into the presence of General
Gruenwold at once. In a few words the orderly stated the case.
“This looks serious, boys,” commented the General. “Can you not
explain the whereabouts of Mackinder? He is a prisoner, you know!”
“We know nothing of the man!” declared Ned, earnestly. “We don’t
like him and surely would not think of assisting him to escape!”
“If you please, sir,” began the orderly, “it is the opinion of my
comrade and myself that the boys have done away with Mackinder!”
“What!” almost shouted Gruenwold, rising from his chair.
“Yes, sir,” continued the man. “There was found in the boat much
blood. A hammer in their tool kit was also blood-stained. We think
they possibly made away with him and might have dropped his body
into the harbor very quietly without being seen from shore!”
“This is serious, indeed!” gasped Gruenwold. “We shall investigate
this in the morning. Meanwhile, search the vessel again. The boys
will be put in the guardhouse until tomorrow.”
Protests on the part of the lads were unavailing. Gruenwold was
determined in his decision. Ned’s explanation of the presence of the
blood in the vessel was listened to, but without influencing the
general.
Directly the lads found themselves in a room used for the
accommodation of such prisoners as might need confinement for a
time. The island boasted no regular prison, but a house not far from
the water had been utilized for the purpose. A guard paced a beat in
the vicinity.
Disappointed and angry at the turn of affairs the lads made but a
poor supper of the food that was brought to them. Presently, they
composed themselves to sleep on the floor.
A tapping at the window attracted their attention.
CHAPTER XIV
HELPED BY AN ENEMY

“What’s that?” inquired Ned, startled at the unexpected sound.


“Loose board, I guess,” replied Jimmie, rather disgruntled at the
turn affairs had taken. “The wind’s ripping everything loose!”
Again the tapping was repeated in an insistent manner.
“I’m going to see what’s going on here!” declared Ned, rising from
his position. “Some one is trying to communicate with us!”
“Some bloomin’ Dutchman’s tryin’ to ask us whether we want
sausage with our pancakes for breakfast!” growled Jimmie. “Let ’em
alone!”
Disregarding this statement the older lad proceeded toward the
window, where fitful gusts of sleet beat. Outside the darkness
covered everything. Only an occasional point of light indicated a
sentry hut.
“Who’s there?” demanded Ned in a low tone.
“Sh-h-h!” came a hiss from the darkness. “Open the window!”
Ned fumbled a moment at the fastening. Presently he found the
catch sliding the sash back in its channel. An exclamation escaped
him as he did so. The face of the visitor was none other than that of
their missing acquaintance, Mackinder. Ned was astounded.
“Thought you were dead!” he cried in amazement.
“Hush!” cautioned the other. “Not so loud. Now, if you lads want to
get out of here this is your time. Everybody’s busy or asleep!”
“How do you know we want to get out of here?” demanded
Jimmie in a low tone as he approached the opening.
“Don’t you suppose I have eyes? I saw what you were up to!”
“Oh, you did, eh? Then what do you want us to do?”
“If you want to get away from this place according to your plan,
now is the time to take action,” replied Mackinder in a whisper. “If
you prefer to wait until tomorrow and stand trial for an offense of
which you are innocent I cannot offer any objection of course.”
“Ned, I think we’d better make our getaway while the going’s
good!”
“Second the motion!” declared Harry, who had softly approached
the window. “Let’s make a noise like a drum!”
“I’m with you!” stated Frank, raising a foot to the window sill.
“Easy there!” cautioned Jimmie. “Mind your step!”
Frank was through the window in an instant. He landed on the
earth with Mackinder’s assistance without noise. Quickly the others
followed. Ned took the precaution to slide the window shut.
Cautiously the little group of six made their way in the direction of
the wharf where the submarines were moored. Mackinder took the
lead as if familiar with the ground. Once he paused, extending a
warning hand to Jimmie, who was directly behind him. The lad
performed a similar service for those in the rear. A sentry was
approaching.
Mackinder sank upon the ground. Although the night was too dark
for the lads to see this action they were close enough to be aware of
the movement. Instantly all followed suit.
In a moment they breathed more freely. The sentry had passed
within a few paces of their position. Evidently his feeling of security
in the isolation of the island had made him somewhat negligent of
his duties. He proceeded against the storm with head bent low.
Again Mackinder rose to his feet. Cautiously he crept forward.
On tiptoe the party gained the shelter of the warehouse.
“Gee!” declared Jimmie as the edge of the wharf was gained, “I
clean forgot my kit! What shall we do?”
“Hush!” warned Ned. “Don’t even dare think of your kit!”
“I should say not!” put in Harry. “Think of your head instead!”
“And the mines at the harbor entrance,” added Frank.
“All right!” submissively agreed Jimmie. “I’ll keep quiet!”
The wind had risen to such an extent that walking on the narrow
planking was not only uncertain but extremely dangerous. Mackinder
solved the problem by dropping to all fours. The boys followed suit.
Directly, they gained the submarine, the hatch was placed quietly
in position for prompt closing and the lines which held the boat were
let go.
Owing to the movement of the boats caused by the roughened
surface of the harbor creakings and groanings of the fenders had
served to drown any noise the party had made in crossing the
narrow bridge of planks.
Jimmie held the wheel as Ned gave the signal for casting off the
lines. A touch of Harry’s hand on the lever started the engines. The
submarine began to move. Suddenly a loud splash alongside
attracted the attention of all. Frank came scuttling down the ladder.
“Now I’ve done it!” he gasped. “I forgot to shove the plank back
onto the next boat and it fell into the water as we started!”
“Wonder if the guard has heard it!” speculated Ned. “Let me up!”
Under protests from his companions the lad mounted the iron
ladder and thrust his head through the hatch.
“I hear someone running along the dock!” he announced
presently. “I’ll bet they have heard that noise! I see a light!” he
added.
“What are they doing?” inquired Jimmie, holding the boat directly
in the center of the channel as he peered anxiously ahead.
“A fellow with a lantern is running out along the planks,” replied
Ned. “They’ve got to the outside boat now. Now they’re turning
back.”
“Better get that hatch closed so we can dive,” admonished Jimmie.
“This is our time for getting out of sight in a hurry!”
“There goes their searchlight!” shouted Frank, who had crowded
up the ladder close beside Ned. “They’re going to spot us in a
hurry!”
“Ah,” cried Ned as a sullen roar came to their ears. “They’re taking
a chance shot at us from that cannon on the hill. Let’s dive!”
Quickly the two boys adjusted the hatch. As they signaled to their
companions that this task was completed Harry and Jack turned the
deflecting rudders. The half-manned submarine slowly began to
descend.
“Get some water into the tanks quick, Harry!” called Jimmie.
“Pump’s going right now!” declared the other. “We’re going down!”
“Take a look through the periscope, Ned,” requested the pilot,
“and let me know what you can make out. Can you see any buoys
ahead?”
“Try to see if they’ve located us with their searchlight,” suggested
Mackinder. “Maybe they are getting our range with that gun!”
“Never mind about that searchlight,” snapped Jimmie. “I want to
find out what’s ahead, not what’s behind us. We’ll run this boat!”
“I simply wanted to know,” objected Mackinder somewhat ruffled
at the lad’s peremptory manner. “No objection, is there?”
“All the objection in the world!” declared Jimmie. “You’re quite
welcome aboard as a passenger, but we’ll navigate the vessel,
please!”
Scarcely knowing whether to be amused or defiant at this attitude
Mackinder chose the wiser course and refrained from further
comment.
Although the boys could not be sure that the persons on the
island were making efforts to hinder their escape they felt the better
course was to remain beneath the surface until well out of the
harbor.
Directly Jimmie called the attention of his comrades to an object in
the water at no great distance ahead. The rays of the searchlight
with which the submarine was provided indistinctly revealed a huge
bulk slightly above the level at which they were traveling.
“What is that, a ship?” asked Harry wonderingly.
“I’ll bet a cookie that’s a mine!” declared Jimmie positively. “I’m
going to give it a little more leeway, anyhow. It pays to be safe!”
Ned was working the periscope in an effort to locate the buoys as
directed by Jimmie. Occasionally he turned the glass toward the
group of buildings they had just left.
“They’re shooting at us, I guess!” he stated presently. “I can see
the flash of that cannon. It seems to be pointed this way!”
“Let ’em shoot, they can’t see anything but the periscope and
they’d have an awful time hitting that!” boasted Jimmie.
Scarcely had the lad spoken before the vessel was shaken by the
force of a mighty concussion. A gigantic wave tossed the craft up
and forward with a heave that threw the boys off their feet.
“What was that?” gasped Jimmie glancing at his companions with
a terrified face. “Has one of the fuel tanks blown up?”
“Nothing doing!” replied Harry. “I think that cannon hit the mine
we just passed. I’m glad we were no closer!”
“We’ll soon be out of their range!” stated Jimmie. “Shut up your
periscope and we’ll go deeper. Give us a little more speed, Harry!”
In an hour Jimmie declared that they should be out of sight of the
island altogether. The engines had been working at full speed ahead.
Harry nursed the machinery constantly, knowing that it was new and
would, therefore, require considerable care. Their urgent need for
speed induced the lads to crowd the machinery to the limit, and
Harry was gratified to note that every part responded properly to its
task.
“Well, Mackinder,” stated Ned as the tension on their nerves began
to relax with the increasing distance traveled, “we’re surely grateful
to you for suggesting that we get away as you did!”
“My motive was largely a selfish one, I must confess,” returned
Mackinder. “I wanted very badly to get away from that island.”
“How did they ever get hold of you, anyhow?” questioned Jack.
“I left Amsterdam the same evening you did. After the Lena
Knobloch went past us as she did I knew there was little use trying
to delay you. Therefore, my aide and myself left at once on a train
for Rotterdam. There we found a fishing boat which we thought
would answer our purpose. We induced the captain to take us
aboard, intending to cross to England. After traveling some distance
the storm overtook us. We were blown far out of our course. The
vessel was badly battered. The crew left in a panic, leaving me on
board. Just in time the German destroyer came along and took me
off. That’s it in a nutshell.”
“Yes, and then when you discovered us in our little boat you went
and told the captain of the destroyer a lot of nonsense, didn’t you?”
questioned Jimmie in a somewhat aggressive manner. “Why did you
do it?”
“I only told him that you had at one time a package that belonged
to me. I wanted the package badly. I thought he would assist me.”
“That wasn’t a very nice way to go about it,” declared Jimmie with
emphasis. “After searching our baggage twice, and after we had told
you how the package was in our kits without our knowledge, also
that it had been stolen away from our possession, why didn’t you
believe us?”
“There is an old saying that all is fair in love and war!” replied
Mackinder. “You know that my country and Germany are at war. As
an officer in the British army, it is my duty to do everything possible
to assist my country. I believe that package contains information
that my country could use. That is my justification for my acts, and I
hope you boys are fair-minded enough to hold no resentment.”
“I’m just fair-minded enough to be neutral,” declared Jimmie, “if I
have to fight for the right to remain that way. I’m just a little sore at
you for supposing that four boys who are citizens of a neutral
country would be carrying information around for another country at
war!”
“I’m sorry you feel that way,” said Mackinder. “I assure you there
was nothing personal in my acts. I simply tried to do my best!”
“Well, you did a lot, at that!” returned the lad.
“All right, folks, let’s drop the subject,” spoke up Ned. “I feel that
the air in here is getting bad. Suppose we go to the surface.”
“Right you are,” agreed Harry. “Let’s rise and fill the tanks!”
Jimmie, in compliance with this wish, steered the craft upward.
At the surface the boys found the water much smoother than they
had expected would be the case. Jimmie declared that he intended
painting the balance of the name “U-13” on the vessel while the
other lads were occupied in airing out the vessel and refilling the
compressed air tanks.
Slung in a boatswain’s chair over the sloping deck the lad soon
completed this task. Feeling a considerable degree of elation at the
success of his undertaking Jimmie returned with his brush and paint.
“If you’re ready now we’ll dive again and proceed!”
“Wait a minute, Mackinder’s still on deck!” stated Jack.
“He wasn’t there when I came below!” protested Jimmie.
CHAPTER XV
MISTAKEN IDENTITY

Ned looked at Jimmie in astonishment. He could scarcely credit his


senses. He began ascending the iron ladder leading to the deck.
Eagerly the lad glanced about the upper portion of the submarine
which now showed black and gleaming above the surface of the
water.
“Harry,” he called down the hatchway, “didn’t Mackinder say he
was coming on deck to see if he could be of service to Jimmie?”
“He certainly did!” answered Harry. “Then we went on working at
the pumps. I was busy with the starboard pump, because it wasn’t
working just as it should. I saw him start up the ladder!”
“And I saw him when he was about half way up!” put in Jack.
“I’m equally certain he didn’t return, but it may be well enough to
stop a minute to search the interior. Perhaps he came back.”
In a moment all five boys were busily going over every corner of
the craft. From stem to stern they ransacked every place where it
would have been at all possible for their guest to have hidden.
At length they met in the space directly below the hatchway.
“Find anything?” queried Ned glancing about the group.
“Not a hint of anything at all resembling an Englishman!” stated
Jimmie. “Perhaps it would be a good idea to put an ad. in the paper.”
“Yes,” scorned Jack. “Like this: ‘Lost—one perfectly good
Englishman. Finder please return to the “U-13” and receive reward’!”
“Sure!” agreed Jimmie. “Have them charge it, please!”
“Hush this nonsense, boys!” cried Ned. “This may be serious!”
“Well, where is he?” protested Jimmie. “We haven’t got him!”
“Maybe he fell overboard!” suggested Ned. “Let’s have a look.”
Again the lad mounted the ladder. As he reached the small deck
he peered anxiously about the vessel seeking what he hoped he
might not find.
The others came crowding after their chum, filling the space.
“There he goes!” cried Jimmie pointing away to the north.
“Where?” inquired Ned looking in the direction indicated. “Oh, I
see him,” the lad went on. “He’s swimming a good stroke, too!”
“Is he crazy or just disgusted with the company on board the ‘U-
13’?”
“Perhaps he thinks he’ll be picked up by that boat!” stated Jimmie
again directing the attention of his comrades to a small fishing craft.
“They seem to be heading a course that will reach Mackinder.”
“He was wise enough to take one of the life preservers,” said
Harry indicating a space from which a buoy was missing.
“Sure enough!” agreed Ned. “He’s no fool at any rate!”
“Let’s wait a while to see if they pick him up,” suggested Jimmie.
“If they don’t get him, we’ll chase over there and take him aboard
again. What do you say?” asked Ned of the others.
There was no dissenting voice raised to this suggestion. Eagerly
the lads watched the boat momentarily drawing nearer the swimmer.
In a short time the boat rounded to, losing her way in the water. A
sharp skiff was quickly launched over the side. Into this tumbled two
men. They soon covered the distance between their vessel and the
swimmer. Without difficulty they succeeded in assisting Mackinder
into the skiff, then put quickly back to the sailing vessel.
“Ah, he’s safe at any rate!” gladly stated Ned. “Now we can go on
and finish our voyage in peace! I’m glad he’s gone!”
“So am I!” declared Jimmie. “He’s a good fellow as one might say,
but he’s too awfully stuck on getting some information for that
bloomin’ Hinglish Harmy, don’t you know!”
“That’s hardly fair, Jimmie!” laughed Ned. “He didn’t drop his ‘H’s’
and he did only what he considered his duty.”
“He will probably get that fisherman to set him ashore on English
soil as soon as possible,” conjectured Jack. “Suppose we follow
them.”
“What for?” asked Harry. “Why should we chase after those
chaps?”
“Unless we do something of the sort, we’ll have to go at it blindly!”
urged Jack. “We don’t really know where we are!”
“That’s so,” admitted Harry reluctantly. “We haven’t a chart nor a
course. We don’t know how far we are from anywhere at all!”
“We might keep on steering just as we started,” stated Frank. “I
believe southeast was the course we used coming away from
Helgoland.”
“That course would surely bring us up somewhere,” put in Ned,
“but it would be much better if we could find out exactly where we
are. Then we could steer a course with intelligence.”
“Aw, what do we need of a chart?” scorned Jimmie. “We know
that England lies to the southwest of us. It’s big enough so we can’t
miss it. If we blunder into the coast we can just cruise along a ways
until we come to some place or other and then head in.”
“That’s a good idea, too,” agreed Frank. “When we get to a port
we can turn the submarine over to the English authorities as a prize
of war. They’ll probably be glad enough to get the machine.”
“Then we’ll head for the little old U. S. A.!” cried Jimmie.
“You’re right we will. When we get there, we’ll chase ourselves out
to Long Island. The first thing I’ll do will be to get the factory started
on another engine like the Grey Eagle’s!” declared Harry.
“Good enough! Now let’s be ‘wenting’!” added Jimmie.
“But, boys,” objected Ned, “this hit or miss fashion of navigating is
not correct. Something may happen to change our course. If we
don’t know what we are doing, we might get into lots of trouble!”
“Maybe you’re right, Ned!” assented Frank. “What shall we do?”
“I think we’d better cruise carefully along on the surface until we
see a ship. We can ask them for our latitude and longitude. From
that we’ll be able to lay a course to any point.”
“Maybe they’ll give us a chart, too!” put in Harry.
“All right, then, here goes!” shouted Jimmie preparing to slide
down the ladder. “Somebody’ll have to keep on deck.”
Harry at once followed Jimmie into the interior. The engines
responded to his touch. The new “U-13” sprang forward half
submerged.
“We’ve got plenty of gas in the tanks, Harry,” stated Jimmie to his
chum as the latter moved about the interior looking after the
machinery. “We’re making only about fifteen miles now by this log.”
“I’ll give them another touch,” responded Harry. “The sooner we
get there, the quicker we’ll arrive, so here goes!”
The increased speed of the engines urged the submarine ahead at
a goodly rate. Jimmie presently declared that the log indicator
showed a good twenty-five miles an hour. Those on the little deck
above the conning tower found the increased speed uncomfortable
by reason of the dashing spray, but all felt that this was not
unendurable.
“Sail, ho!” Ned presently called down the hatchway.
“Where away?” asked Harry, looking up at his comrade.
“Almost dead ahead!” replied Ned. “We’re overhauling them fast.
It looks to be a three masted ship as nearly as I can make out!”
“Hold your course, Jimmie!” directed Jack. “We’ll come up close
enough to hail them in a little while just as we are heading!”
In a few minutes the ship was so close that all could make out the
details of her rigging. It was a large three masted square-rigged
vessel evidently in ballast for the hull was high out of water.
“I believe they see us!” announced Frank, using a pair of
binoculars he had found among the fittings of the submarine.
“Can you make out the flag at the peak?” asked Jack.
“Yes, I think so. I believe it is the British flag.”
“Then, they’ll be glad to help us out, especially if they find that we
intend to turn the ‘U-13’ over to their government!”
“I don’t know about that!” doubted Frank. “I see men running
aloft. It looks as if they’re rigging out studding sail booms on the
main yards. And I see others on the topsail yards,” declared the boy.
“Why, in that case, they’re trying to get away from us!”
“It certainly looks that way. Now I can see men setting the
studding sails on the booms. They are putting on every rag the old
hooker will carry!” cried the lad excitedly.
“I know why,” stated Harry. “They think we’re a German
submarine chasing them and they’re trying to get away!”
“Let’s run up a white flag, then,” urged Ned. “They ought to know
what that means. They’ll stop for that!”
In response to this suggestion the lads quickly overhauled the flag
locker finding just what they sought. The white flag was at once
brought to the deck where it was bent on to the halliards. It
fluttered gaily at the top of the short flagstaff. Some difficulty was
experienced in securing the staff because of an improperly fitting
socket.
“Do they seem to be making any change?” inquired Harry
presently.
“Yes,” answered Ned. “They’re crowding on more sail!”
“Then we might as well give it up!” stated the other. “They’ll never
stop for us. Our only hope is to dive and come up close to some
vessel so they can’t get away before we ask the questions.”
“Maybe that would be a good idea,” admitted Ned. “Anyhow, we’ll
have to take down this flag. The signal staff don’t fit!”
Disappointed because their efforts had been unavailing, the lads
regretfully folded the flag. It was restored to its proper place.
Harry, however, continued to urge the engines forward in the hope
of eventually overhauling the ship. This seemed to be within the
range of possibilities, but the boys all knew the maxim concerning a
stern chase, and were somewhat discouraged. Knowing that their
intentions were of the best, they felt slightly aggrieved that the
other did not stop.
“I see a smoke away ahead of the ship!” announced Frank after a
few moments. “I can’t tell which way they are headed, though!”
“At this rate of traveling, we’ll soon find out!” declared Jack.
Evidently the smoke had been discovered by those aboard the
sailing vessel, for the course was altered slightly in that direction.
This change was noted by the boys. Jimmie shifted the helm
slightly in order to keep the submarine directly in the track of the
ship.
“I wonder what that other vessel can be,” puzzled Ned. “Let me
take the glasses a moment, Frank. I wish we were higher in the
water,” he added, “then we could get a better range of vision.”
Long and earnestly the boy inspected the strange vessel. Presently
he returned the glasses to Frank with a sigh.
“What is it?” asked Jack with keen interest.
“I believe it is a warship of some sort!” replied Ned.
“Then they’ll capture us and take us to port mighty quick!”
“I guess they’ll capture us all right!” put in Frank. “I can see the
sailing vessel making signals. They’ve got a string of flags flying
from the foretopmast head. I don’t know what they mean, but
they’re calls for help, or I’ll miss my guess! They are something like
the U. S. flags!”
Those on board the steamer had evidently seen the string of flags
or else by the peculiar actions of the sailing vessel guessed that
something was wrong, for the boys saw that their course was at
once altered. From the clouds of dense black smoke pouring from
the funnels they knew that the stokers were being urged to their
best efforts.
In a short space of time the combined speeds of the two vessels
brought them close together. As the other approached, Harry shut
off the power of the engines, checking them to little more than
steerageway.
As the steamer passed the ship Ned could see that some
communication had been made between the two. The steamer came
quickly on.
“Pass me up that white flag again, Harry,” requested Ned. “I think
they’re coming up to speak to us, and I’d just as soon have that
handy. Maybe these fellows might misunderstand our motives, too!”
“I wish now I hadn’t painted that ‘U-13’ quite so plainly on the
sides!” grumbled Jimmie. “I’ll bet they’ve seen that!”
“Of course, they’ve seen it, but if we show a white flag they won’t
do anything to us. They’ll let us ask questions!”
In answer to this statement, a shot echoed across the water. A
ball striking the crest of a wave sent a cloud of spray over the “U-
13.”

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