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Published on 22 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782624042-FP001
Thermoelectric Materials and Devices

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Thermoelectric Materials and

Devices
Edited by
Iris Nandhakumar
University of Southampton, UK
Email: iris@soton.ac.uk
Neil M. White
Email: nmw@ecs.soton.ac.uk
Stephen Beeby
Email: spb@ecs.soton.ac.uk
Published on 22 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782624042-FP001 View Online
RSC Energy and Environment Series No. 17
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r The Royal Society of Chemistry 2017
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Preface
The publication of this book is motivated by a number of recent and

ground breaking advances in the field of thermoelectrics (TE), which has
seen a renaissance in recent years. Thermoelectric devices have the ability
to convert waste heat into useful electricity, which potentially makes TE a
transformative technology for renewable energy generation. Despite this
enormous potential, historically thermoelectrics have only been utilised in
niche market applications, such as the powering of satellites and space
probes due to the low efficiency of current TE generators. However, nano-
technologies in particular have caused a paradigm shift in thermoelectric
performance through nanostructuring/nanoengineering of materials, en-
abling thermoelectrics to be catapulted from niche product to mainstream.
Indeed, the future is extremely bright for TE technology and thermal energy
harvesting is predicted to become a global multibillion dollar market by
2020 in a range of application scenarios. The current focus on fuel efficiency
in vehicles and stringent legislations on carbon emissions are the main
drivers for the market growth of TE technology by automobile manufacturers
to extract electricity from the hot exhaust stream of cars.
This book aims to provide an up-to-date topical perspective on thermo-
electric materials, fabrication and characterization, devices and applications
to capture the seismic shifts that have recently occurred in this field within
the UK and beyond. Whilst thermoelectrics are well-established within
the US, Japan and China, they are still in their infancy within the UK and
this book is intended as a reflection that many of the recent advances and
innovations within this field have resulted from activities within the UK
thermoelectrics community, whilst not trying to exclusively focus on them.
In fact, the intention is to provide a balanced view of topics such as ther-
moelectric materials, devices and applications.

Edited by Iris Nandhakumar, Neil M. White and Stephen Beeby
Published by the Royal Society of Chemistry, www.rsc.org
v
View Online
vi Preface
Bismuth telluride and lead telluride have been the core materials used for
commercial TE generators targeted at low and medium power generation
and refrigeration since the 1950s and new materials are clearly needed to
disrupt the sustainability issues associated with tellurium as well as to
address the toxicity of lead telluride. The first three chapters provide an
excellent overview of recent developments in materials synthesis that in-
clude zintl phases (Kauzlarich et al.), thermoelectric oxides (Freer et al.) and
novel metal chalcogenides (Powell et al.) that hold great promise for future
thermoelectric applications on the basis of their enhanced thermoelectric
performance and being composed of abundant and sustainable elements.
A fundamental and detailed theory of how nanostructures affect the
electric conductivities, thermal conductivities and Seebeck coefficients in
nanostructures is presented in Chapter 4 (Paul) that also focuses on how
enhanced performance can be achieved through low dimensional structures.
The importance of the complexity of the phenomenon and the uncertainties
associated with existing thermoelectric measurement methods is high-
lighted in Chapter 5 (Cuenat et al.), which is followed by a description
of novel high-throughput thermoelectric measurement techniques in
Chapter 6 (Gao et al.) that enable rapid characterization of thermoelectric
materials and devices. Stobart et al. provide a comprehensive assessment of
all aspects associated with the practical design considerations of thermo-
electric generators, starting from models based on the physical parameters
and empirical correlations for the heat exchange processes to provide a re-
liable basis for design choices that lead on to numerical models supported
by experimental validation to provide the next level of refinement in the
formulation of design guidelines. Naylor et al. illustrate how electrochemical
deposition methods can be employed as a low temperature and low-cost
route without the need for a vacuum or extensive equipment for the
fabrication of thermoelectric materials, in contrast to commonly employed
high-cost approaches such as MBE and MOCVDE. The final chapter by
Simpson et al. discusses the tremendous opportunities for thermoelectric
devices in automotive power-harvesting applications with a particular em-
phasis on systems for electrical energy generation from automobile
exhaust gases.
I would like to thank the authors of this book and my co-editors Professors
Neil White and Stephen Beeby who have contributed to the making of this
book, which was an elaborate and time-consuming process. I would wish for
this book to become an important landmark in the thermoelectrics field that
goes well beyond a ‘laboratory handbook’ but provides a fresh perspective of
this important research field that deserves to be mainstream.
Iris Nandhakumar
Southampton
Contents
Chapter 1 Zintl Phases: Recent Developments in Thermoelectrics and

Future Outlook 1
Susan M. Kauzlarich, Alex Zevalkink, Eric Toberer and
G. Jeff Snyder
1.1 Introduction 1
1.1.1 Definition of Zintl Phases 1
1.1.2 Charge Counting/Formal Valence Rules 2
1.1.3 Thermoelectric Zintl Compounds 4
1.2 Thermal Properties 7
1.2.1 Theory behind Low kL in Complex Materials 8
1.2.2 Case Studies 11
1.3 Electronic Transport 13
1.3.1 Controlling and Optimizing Carrier
Concentration 14
1.3.2 Limits to Controlling Carrier Concentration 15
1.3.3 Band Structure Requirements 16
1.3.4 Carrier Relaxation Time 18
1.4 Future Opportunities for Zintl Thermoelectric
Materials 19
Acknowledgements 19
References 19
Chapter 2 Chalcogenide Thermoelectric Materials 27

Anthony V. Powell and Paz Vaqueiro
2.1 Introduction 27

vii
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viii Contents
2.2 Synthesis 30
2.3 Low-dimensionality in Chalcogenides 32
2.3.1 Layered Dichalcogenides 32
2.3.2 Intercalated Phases 35
2.3.3 Structurally-related Phases 37

2.4 Shandite-related Phases 37
2.5 Rocksalt-derived Chalcogenides 40
2.6 Tin Selenide and Related Materials 45
2.7 Oxychalcogenides 47
2.8 Copper-containing Chalcogenides with
Low Thermal Conductivities 49
2.9 Concluding Remarks 51
References 52
Chapter 3 Thermoelectric Oxides 60

Colin Norman, Feridoon Azough and Robert Freer
3.1 Introduction 60
3.2 Manufacture 63
3.3 Composition and Atomic Structure 67
3.3.1 Strontium Titanate Based Materials 67
3.3.2 Cobaltites 70
3.3.3 Calcium Manganate Based Materials 73
3.3.4 Zinc Oxide 74
3.4 Microstructure 74
3.5 Module Manufacture 76
3.6 Conclusions 77
References 78
Chapter 4 Nano- and Micro-fabrication Techniques for Improving

Thermoelectric Materials and Generators 83
Douglas J. Paul
4.1 Introduction 83
4.2 Low-dimensional Electrical Conductivity 85
4.3 The Seebeck Coefficient and Low-dimensional
Modifications 92
4.4 Thermal Conductivity 93
4.5 Potential Improvements to Thermoelectrics from
Nano- and Micro-structures 97
4.6 Micro-fabrication of Thermoelectric Generators 102
4.7 Conclusions 107
References 107
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Contents ix
Chapter 5 Review of the Methods for Thermal Conductivity

Measurements Most Appropriate for Thermoelectric
Materials 109
Ekaterina Selezneva, Clark Stacey, Pablo Dı́az-Chao,
Andres Muñiz-Piniella and Alexandre Cuenat
5.1 Introduction 109

5.1.1 Thermoelectric Challenges 109
5.1.2 Thermal Conductivity Measurements 110
5.2 Steady-state Methods 112
5.2.1 Guarded Hot Plate 112
5.2.2 High-temperature Measurements 116
5.2.3 Radial Heat Flow Method 117
5.2.5 Longitudinal Heat Flow 119
5.2.7 Heat-flow Meter 123
5.3 Transient Methods 125
5.3.1 Metrological Approach 126
5.4 Conclusions 128
Acknowledgements 128
References 128
Chapter 6 High-throughput Thermoelectric Measurement

Techniques 133
Jorge Garcı́a-Cañadas and Gao Min

6.2 Multifunctional Probes 134
6.2.1 Measuring Principles 134
6.2.2 Design and Fabrication of Multifunctional
Probes 135
6.2.3 Measurement Systems and Procedures 137
6.2.4 Precision, Accuracy and Rapidness 143
6.3 Impedance Spectroscopy 146
6.3.1 Fundamentals of Impedance Spectroscopy 146
6.3.2 Theoretical Framework 147
6.3.3 Experimental Set-up 150
6.3.4 Measurement Analysis and Applications 151
6.4 Conclusions 154
References 155
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x Contents
Chapter 7 System Design Considerations for Thermoelectric

Energy Recovery 156
Richard Stobart, Zhijia Yang and Song Lan

7.1.1 The Potential for Waste Heat Recovery 156
7.2 Modelling TEG Performance 163
7.3 The Role of the Heat Exchanger in TEG Design 165
7.4 Modelling a Thermoelectric Generator 166
7.4.1 Defining the Structure of TEG 167
7.4.2 Calculating Temperature Distributions 169
7.4.3 Thermal Resistance Network in a CV 170
7.5 Electrical-resistance Network of a TEG 175
7.6 Model Structure 176
7.7 Validation Strategy for Models 178
7.8 Using the Model to Optimize TEM Geometry 180
7.8.1 Geometric Factors 180
7.8.2 Influence of Geometric Parameters on
Maximum Power 181
7.8.3 Influence of Operating Environments on
Optimal Geometric Parameters 183
7.8.4 Three-dimensional Figures to Identify the
Optimal Geometry Parameters 183
7.9 Selecting and Evaluating Heat Exchange Designs
for TEG Applications 183
7.9.1 Identifying the Design Parameters of a
Plate Fin Heat Exchanger 183
7.9.2 Comparing Heat Exchange Architectures 189
7.10 An Example of a Family of Heat Exchangers 193
7.11 Observations on TEG Design 198
7.12 Concluding Remarks 199
Appendix A: Exhaust Gas Properties Employed
in the Simulation Model 200
Appendix B: Properties of the Simulated
Thermoelectric Module 201
References 202
Chapter 8 Electrodeposition of Thermoelectric Materials 204

A. J. Naylor, N. M. White and I. Nandhakumar

8.1.1 Electrodeposition of Nanostructured Materials 204
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Contents xi
8.1.2Recent Advances in the Electrodeposition of

Thermoelectric Materials 211
8.2 Experimental 215
8.3 Results and Discussion 217
8.3.1 Sodium Lignosulfonate as an Additive in the

Electrodeposition of Bismuth Telluride 217
8.3.2 Electrodeposition of n-type Copper-doped
Bismuth Tellurium Selenide 222
8.4 Conclusions 226
References 226
Chapter 9 Automotive Power Harvesting/Thermoelectric Applications 230

States Chiwanga, Richard Tuley, Katarzyna Placha,
Mark Robbins, Bob Gilchrist and Kevin Simpson
9.1 Why are Thermoelectric Devices Suitable for

Automotive Applications? 230
9.2 Automotive TEG Systems 232
9.3 Challenges/Trade-offs in Automotive TEGs 235
9.3.1 Thermoelectric Modules Packaging 235
9.3.2 TEG Hot and Cold Heat Exchangers 236
9.3.3 Exhaust Gas Flow Control (Valves and
Sensors) 240
9.3.4 TEG Overall Mechanical Packaging 241
9.3.5 TEG Electrical Output Control
Measurement and Control 244
9.4 Failure of Thermoelectric Modules in Automotive
Applications 244
9.4.1 Ceramic Failures 246
9.4.2 Pellet Failures 247
9.4.3 Interconnect and Joint Failures 247
9.4.4 Failure Modelling 247
9.4.5 Failure Summary 250
References 251
Subject Index 252

Published on 22 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782624042-FP007 View Online
Published on 22 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782624042-00001
CHAPTER 1
Zintl Phases: Recent

Developments in
Thermoelectrics and Future
Outlook
SUSAN M. KAUZLARICH,*a ALEX ZEVALKINK,b ERIC TOBERERc
AND G. JEFF SNYDERd
a
Department of Chemistry, University of California, One Shields Ave,
Davis, CA 95616, USA; b Max-Planck-Institut für Chemische Physik fester
Stoffe, Nöthnitzer Straße 40, 01187 Dresden, Germany; c Department of
Physics, Colorado School of Mines, 1500 Illinois St., Golden, Colorado
80401, USA; d Materials Science and Engineering, Northwestern University,
Evanston, IL 60208, USA
*Email: smkauzlarich@ucdavis.edu
1.1 Introduction
1.1.1 Definition of Zintl Phases
The term Zintl phase was first used by F. Laves1 to indicate a subset of
compounds within the general class of intermetallics, named after Eduard
Zintl, a German scientist who was the first to systematically prepare and
structurally characterize these phases.2 Zintl’s interest was in determining
what combination of elements would form salt-like structures, focusing
on the heavier elements of group 13, 14 and 15. During this time,

1
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2 Chapter 1
Hume-Rothery and Westgren had demonstrated the correlation of structure

and valence electron concentration for intermetallics, and the compounds
that Zintl studied did not fall within those structure–electron count rules. As
more compounds were discovered and the transition between salt-like and
metallic structures became less clear, this definition proved to be too lim-
iting. Schäfer, Eisenmann, and Müller3 proposed a more general definition
where electron transfer is essentially complete between the alkali or alkaline
earth cation and the electronegative elements that utilize the electrons such
that they achieve a filled valence either by covalent bonding or by the
formation of lone pairs of electrons. Therefore, these phases exhibit salt-like
characteristics from the ionic bonding between the cation and the anionic
unit. The anionic unit can be isolated anions; if there are not enough elec-
trons for a filled octet, then they form covalent bonds and polyanionic
units.4 The Zintl concept provides a simple idea concerning ionic and
covalent bonding within intermetallic phases, allowing for a simple de-
scription of bonding that provides insight into the structure and properties
of intermetallic phases.3,5,6 One simple way to define a Zintl phase was ar-
ticulated by Nesper7 and Miller8 as the following: there exists a well-defined
relationship between chemical and electronic structures in a Zintl phase
and a chemist can understand the structure by using simple electron
counting rules.
1.1.2 Charge Counting/Formal Valence Rules

Since Zintl phases fall between insulators and metals, it can be difficult to
devise a consistent set of rules governing their classification. The salt-like
nature of these phases often results in high melting points, high heats of
formation, poor conductivities and greater brittleness than many inter-
metallics. There is the requirement for a well-defined relationship between
their chemical and electronic structures, but that can also be a difficult
criterion to implement since it requires a detailed knowledge of the structure
and bonding. This particular criterion implies that Zintl phases are line
compounds with narrow homogeneity widths, a restriction that would
make this classification of compounds difficult to dope or manipulate
electronically, and therefore uninteresting to those pursuing optimization of
thermoelectric properties. In order to understand how to think about these
phases, let’s start by restating the obvious: all Zintl phases are composed of
an electropositive atom, which is treated like a fully ionized element that
provides its electrons to the more electronegative elements in the structure.
These electronegative elements either use those electrons to form a closed-
shell ion or, if there are not enough electrons for this, to form bonds in order
to achieve a full octet of electrons.9 These compounds are distinguished
from insulators by the size of the band gap10,11 and are typically considered
to be semiconductors.
In binary Zintl phases, AaXx (A ¼ electropositive metal, X ¼ electronegative
element) 8x electrons are required in order to achieve an octet (or closed
View Online
Zintl Phases: Recent Developments in Thermoelectrics and Future Outlook 3
shell) for the x X atoms, e(A) and e(X) are the number of valence electrons of
A and X.
a e(A) þ x e(X) ¼ 8x (1.1)

Typically, it is assumed that there are no bonds between A atoms and that X
can have X–X bonds that are considered to be two-centre, two-electron
bonds, and that the octet rule is satisfied for both elements. If this is the
case, then the number of the valence electron count per formula unit of AaXx
(VEC) is:
a
ðVECÞ ¼ a eðAÞ ¼ x eðXÞ ¼ x eðAÞ þ eðXÞ : (1:2)
x
While this equation provides the VEC for the compound formula, the term
in the parentheses represents the average number of valence electrons per
anion, Nx. In general, this results in the classical valence rule for
insulators—the 8 N rule proposed by Mooser and Pearson—which pro-
vides the number of covalent bonds required to satisfy the anion valence.12
W. Klemm proposed an additional nuance where the more electronegative
partner is described as an element with the same number of electrons: a
pseudoatom concept.3 Consider the charged XðaeA = xÞ unit: if Nx is non-
integral, then a set of pseudoatoms is required to describe the observed
coordination environments. For example, heteroanions with tetrahedral
units can be described as the analogous orthooxosilicate or germanate
anions: [SiP4]8, [SiAs4]8 or [GeP4]8 and [GeAs4]8 where the large formal
charge is balanced by means of the alkaline earth metal cation. The com-
bination of Zintl’s original proposal and Klemm’s pseudoatom description
is now called the Zintl–Klemm concept. Based on this electron counting
model, these compounds should all be semiconductors. However, the
difference between insulators and semiconductors is somewhat arbitrarily
based on the bandgap and there are suggestions in the literature of either
2.5 eV10 or 2.0 eV.7 Because of the simple electron counting scheme, the
Zintl–Klemm concept is a powerful tool for the assessment of complex
main group solids and there are a number of groups working to put this on
firm theoretical grounds.13–18
The incorporation of transition metals into these structures adds
complexity and has expanded the original criteria.9,19–23 Some of the first
research in this area focused on transition metal containing compounds that
are isostructural to known main group Zintl compounds.9,20,24 Analogous to
main group compounds, these compounds contained anionic units that
showed isoelectronic relationships with transition metal halides and chal-
cogenides. The Zintl–Klemm idea of bonding has been successfully used to
probe changes in electronics and bonding within the ThCr2Si2 structure
type.19,25–28 Using the Zintl concept, totally new compounds have been
prepared and novel properties obtained.9,29–32 The addition of both transi-
tion metals and rare earth ions have expanded this area considerably.33–37
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4 Chapter 1
1.1.3 Thermoelectric Zintl Compounds

Good thermoelectric materials have low electrical resistivity, low thermal
conductivity and a large Seebeck coefficient. Typically, small band-gap
semiconductors with carrier concentrations within 1019–1021 cm3 work
better than metals or insulators. Also, a large unit cell, heavy atoms, and
structural complexity generally result in good thermoelectric (TE) efficiency.
Many Zintl materials fulfill these qualifications; however, relatively few
were investigated for their thermoelectric properties until the last few
years.38–40 Since these compounds are valence precise and possess the
requisite small band gap as well as having complex structures, it is expected
that new thermoelectrics with high efficiency may be discovered. The po-
tential of this area for further research is demonstrated so far with a few
structure types that will be described below.
1.1.3.1 Yb14MnSb11 Structure Type

Yb14MnSb11 is one of the first recognized phases with excellent thermo-
electric performance (zTB1 at 1200 K).38 This compound is of the Ca14AlSb11
structure type (shown in Figure 1.1).41 A variety of compounds of this
structure type have been reported for the heavier alkaline earth cations (Ca,
Sr, Ba) with Al, Ga, In, Zn, Cd, Mn, and Nb and the pnictides from P to
Bi.9,20,22,24,41–56 The rare earths, Eu and Yb, have also been prepared, along
with isovalent solid solutions of a variety of compounds.21,34–36,38,57–77 This
structure type has also been prepared with a small amount of Ln31 replacing
some of the Yb21 and a small amount of Te replacing some Sb in
Yb14MnSb11.78–80 In general, all of the compounds can be synthesized by
reacting the elements in sealed Nb or Ta tubes. The tubes are sealed in fused
silica tubes either under vacuum or 0.25 atmosphere of Ar and heated to
Figure 1.1 Views of the Ca14AlSb11 structure type down the (a) [001] and (b) [101]
direction. Ca, Al, and Sb are indicated by the green, blue and gold
spheres, respectively, and the tetrahedron is shaded.
View Online
temperatures of up to 1250 1C for periods of 24–300 h. There is evidence for

reaction of the Nb tubes with some of the elements,53 so Ta is considered the
more ideal container. Quantitative yields can be obtained at low tempera-
tures for some of the phases, but X-ray quality single crystals are formed only
at higher temperatures. Yb14MnSb11 can be prepared by high temperature

inductive heating.81 In addition to direct reaction of the elements, large
crystals can be prepared from Sn flux; this work provided the initial steps
forward for preparing large amounts of phase pure material for detailed
property measurements, including thermoelectric properties.58,82
The compounds crystallize in the tetragonal system, I41/acd (Z ¼ 8). In the
framework of valence rules, the structure of these compounds can be
understood according to one formula unit (A14MPn11) corresponding to
14A21 cations þ 4 Pn3 anions þ MPn49 tetrahedron þ Pn37 linear unit.
The tetrahedron has 4̄ point symmetry and is translated by half along the c
axis, while the Pn3 units have 222 point symmetry and are staggered by 901
along the c axis with respect to each other. The isolated Pn atoms are
6-coordinated by cations and are located between the tetrahedral and the
Pn3 units, forming a spiral along a screw axis coincident with the c axis. The
linear anion, Pn37 unit, can be either symmetric or asymmetric, depending
on both the identity of the cation and anion. The lighter pnictides with large
cations tend to be asymmetric. The structure can also be related to the Cu2O
structure type, but forming two interpenetrating networks. The oxygen
atoms are substituted by the tetrahedron and the Cu atoms are substituted
by the pnictide octahedron. The central Pn atoms of the linear polyanions
connect the nets with the remaining cations.53,63,64
1.1.3.2 CaAl2Si2 Structure Type

The CaAl2Si2 structure type (space group P3̄m1, Z ¼ 1) is prevalent for com-
pounds with the AB2X2 composition.83 There has been extensive research into
compounds of this structure type.84–103 An apparent requirement for this
structure type is that the B atoms are either main group or transition metals
with d0, d5, or d10 electronic configuration.104,105 Several of the compounds
with the CaAl2Si2 structure type have been shown to have zT values near
unity.96,106–110 In particular, the solid solution of Ca1xYbxZn2Sb2 was first
shown to have promise.106 The layered structure can be described as
consisting of two adjacent puckered hexagonal nets of alternating Al and Si.
The An1 cations alternate between the [B2Xx]n double layers (Figure 1.2).
Structural relationships to other structure types, such as BaAl3 and CaSi2, have
been described.104
1.1.3.3 Sr3GaSb3 Structure Type

Compounds with the A3MPn3 stoichiometry can crystallize in four different
structure types. Sr3GaSb3 crystallizes in the monoclinic crystal system (space
group P21/n)111 and the three other structure types include orthorhombic
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6 Chapter 1
Figure 1.2 A view of the structure of YbZn2Sb2 (CaAl2Si2 structure type) showing the
unit cell. Yb, Zn, and Sb are indicated by sky blue, blue and gold spheres,
respectively.
Figure 1.3 Views of Sr3GaSb3, showing (a) the unit cell and (b) the connectivity of
the chain. The Sr, Ga, and Sb atoms are represented by blue, green and
gold spheres, respectively.
Ba3GaSb3 (Z ¼ 8) and Ca3InP3 (Z ¼ 4) both in space group Pnma112 and

Ba3AlSb3, which crystallizes in the space group Cmca, Z ¼ 8.113 All structures
of A3MPn3 contain MPn4 tetrahedra and the structures differ depending on
how these tetrahedra are connected. Sr3GaSb3, shown in Figure 1.3, contains
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Figure 1.4 Views of Ca5Al2Sb6 showing (a) the unit cell and (b) the connectivity of
the chains. Ca, Al, and Sb atoms are represented by blue, green and gold
spheres, respectively. The tetrahedral polyhedra are shaded.
infinite non-linear chains of corner sharing tetrahedra.111,114 Various

combinations of A ¼ Ca, Sr, Ba, Eu; M ¼ Al, Ga, In; Pn ¼ P, As, Sb have been
reported; however, a systematic study has not been performed. For example,
A3GaSb3 (A ¼ Sr, Ba)111,112 have been reported, but Ca3GaSb3 or Eu3GaSb3
have not. The only Eu containing phase reported is Eu3InP3, which is
described as very air-sensitive with high electrical resistivity.115 To date, the
thermoelectric properties of Ca3AlSb3, Sr3GaSb3, and Sr3AlSb3 have been
reported.116–118
1.1.3.4 Ca5Ga2As6 Structure Type

The Zintl compound, Ca5Al2Sb6,119 is well known and crystallizes in the
Ca5Ga2As6 structure type (space group Pbam, Z ¼ 2)120 Compounds of
Ca5M2Sb6 formula (with M ¼ Al, Ga, In) have been prepared and all belong to
this structure type.119,121 Similar to the Sr3GaSb3 compound, this structure
type is another example of MSb4 tetrahedra that are connected in a unique
fashion. The structure type is composed of chains of corner-linked MSb4
tetrahedra, connected through Sb–Sb bonds to form ladder-like moieties
(Figure 1.4).
1.2 Thermal Properties

The thermal conductivity of Zintl compounds is found to be extremely low,
particularly at high temperature. This low thermal conductivity generally
overcomes the lower electronic mobility found in these materials and pro-
vides the foundation for high zT.122,123 Additionally, the complex structures
enable phonon behaviour not observed in more simple lattices.124,125
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8 Chapter 1
Figure 1.5 The experimental kL for many Zintl compounds is much lower than that
observed in the heritage SiGe material used in radioisotope thermo-
electric generators.
Figure 1.5 shows that the lattice thermal conductivity, kL, for many Zintl
compounds is significantly below that of heritage Si0.8Ge0.2.117,126–131 Near
room temperature, many of these materials show a decaying lattice thermal
conductivity due to increased phonon–phonon scattering, while others ex-
hibit thermal conductivity values with little temperature dependence. The
latter behaviour will be explored below. Many of these materials display a
slight upturn in thermal conductivity near their maximum measurement
temperature. At these high temperatures, minority carrier contributions to
the conductivity become significant, leading to a bipolar contribution.132
The standard Wiedemann–Franz approach to removing the electronic con-
tribution does not capture this contribution.
1.2.1 Theory behind Low jL in Complex Materials

A simple kinetic theory approach to phonon transport and heat conduction
reveals that the three primary descriptors of thermal conductivity are the
volumetric heat capacity (Cv), phonon group velocity (v) and mean free path
between collisions (l).133,134 As Zintl compounds are largely dense materials,
there is relatively minor variation in the heat capacity. However, the group
velocity and phonon relaxation time (tph ¼ l/v) are critically dependent on
material composition and crystal structure.
The phonon relaxation time is determined by several scattering sources,
including phonon–phonon, defect, and boundary scattering. In most
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materials at high temperature, Umklapp (phonon–phonon) scattering is the

dominant scattering mechanism. Shown in Figure 1.5, kL in Ca5Al2Sb6
provides an excellent example of the 1/T temperature dependence expected
when Umklapp scattering dominates.128 Umklapp scattering is governed by
the anharmonicity of the lattice, typically parameterized by the Grüneisen

parameter.135 The Grüneisen parameter has been characterized using ther-
mal expansion measurements for few Zintl compounds to date, and mod-
erate values between 1.5–2 have been found.136 However, in ‘rattling’
compounds, the mode-specific Grüneisen parameter can be quite high near
the rattling frequency and leads to increased scattering of phonons in that
frequency regime. Such mode-specific values are obtained from temperature
dependent inelastic scattering measurements.
In addition to Umklapp scattering, point defect scattering137 in Zintl
compounds has been harnessed to scatter high frequency phonons. One
early example is Yb1xCaxZn2Sb2.138 Here, the thermal conductivity responds
as predicted from classic thermal scattering theory (Figure 1.6), with the
most substantial reduction to kL occurring at 300 K near x ¼ 0.5. Likewise,
Yb9Mn4.2Sb9 has Mn interstitials that act as scattering sources and also
reduce kL at room temperature.131 To scatter low frequency phonons,
boundary scattering from grain boundaries, nanostructures, for example,
can be used.139 Despite the success of nanostructures in reducing kL in other
materials, little work has been devoted to nano-structuring Zintl
Figure 1.6 Alloying has a profound effect on the room temperature thermal
conductivity of Yb1xCaxZn2Sb2; the effect is less pronounced at high
temperature due to increased Umklapp scattering.
Reprinted with permission from E. S. Toberer, A. F. May and G. J. Snyder,
Chem. Mater., 2010, 22, 624–634.122 Copyright (2010) American Chemical
Society.
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10 Chapter 1
compounds. Extended defects (stacking faults) have been observed in the

layered Zintl compound SrZnSb2, and have been shown to significantly
reduce kL near room temperature.140
Phonon group velocity, n g, has been found to play a critical role in
explaining the low thermal conductivity in Zintl compounds.136 Like many

thermoelectric materials, the low frequency limit of n g, (speed of sound) in
many Zintl compounds is quite low, arising from a combination of heavy
atoms and soft bonding between covalent moieties. Furthermore, Zintl
compounds often possess large mass contrast, which increases the gap
between phonon modes at the Brillouin zone edges and at the zone
centre.141 Such large gaps flatten the phonon modes and lead to reduced
group velocity. When this phenomenon is combined with extremely complex
structures (here, complexity refers to the number of atoms within the
primitive cell), the group velocity throughout much of the dispersion can be
significantly suppressed. As the size of the real-space cell grows, the
Brillouin zone shrinks, and the fraction of optical phonon modes with low
velocity increases rapidly. As the number of atoms in the primitive cell (N)
increases, the acoustic contribution to kL shrinks, scaling roughly as 1/N1/3.
Figure 1.7 shows the experimental kL in selected Zintl phases as a function of
N, illustrating the benefit of a large unit cell and correspondingly small
contribution from acoustic phonons. Further reduction in the acoustic
group velocity can be achieved through the inclusion of ‘rattling’ modes that
flatten the phonon dispersion near the resonant frequency of the rattling
species.142–144
Figure 1.7 Structural complexity, as estimated from the number of atoms in the
primitive cell, is a good indicator for low phonon group velocity, and
thus low thermal conductivity materials.
Adapted with permission from E. S. Toberer, A. F. May and G. J. Snyder,
Chem. Mater., 2010, 22, 624–634.122 Copyright (2010) American Chemical
Society.
View Online

Figure 1.8 The experimental kL can be readily predicted (within a factor of 2) from
knowledge of speed of sound, Grüneisen parameter, atomic density, cell
volume and average atomic mass. The current approach thus success-
fully captures the underlying relevant physics.
At high temperature, the optical branches in complex materials can be

approximated via Cahill’s minimum thermal conductivity description
(kmin),145 and the remaining phonons in the acoustic branches can be ap-
proximated via a Debye–Callaway model.134 We have extensively considered
the accuracy of this ‘Debye þ kmin’ approach in ref. 136. Experimental
measurements of the thermal conductivity were compared with kL predicted
using experimental measurements of the speed of sound, Grüneisen par-
ameter, atomic density, cell volume and average atomic mass. The results of
this approach are shown in Figure 1.8 for all materials where a complete
property characterization was available from the literature. This approach
was found to be predictive to a factor of two on average for the compounds in
this study.
1.2.2 Case Studies

1.2.2.1 Complex Antimonides – SrZn2Sb2 vs. Yb14MnSb11
The role of complexity can be observed nicely by considering a pair of Zintl
compounds: SrZn2Sb2 and Yb14MnSb11.146,147 In Figure 1.9, we show the
experimental lattice thermal conductivity for these two compounds, as well
theoretical curves for the acoustic, optical, and total contributions to kL.
From the Cahill theory of minimum thermal conductivity, we can estimate a
lower bound on the optical phonon contribution to the lattice thermal
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12 Chapter 1
Figure 1.9 The minimum optical mode contribution to the thermal conductivity of
structurally simple SrZn2Sb2 and complex Yb14MnSb11 (five and 104
atoms in the primitive cell, respectively) is shown in orange. The corres-
ponding maximum possible acoustic contribution (modeled as Umklapp
scattering-dominated with a T1 dependence) is shown in green. The
sum of the acoustic and optical contributions are shown in blue. While
acoustic modes are typically considered the primary vehicle for thermal
conduction, the optical modes represent the dominant source of thermal
conduction at high temperature in structurally complex materials.
conductivity. In the case of SrZn2Sb2, which has only five atoms in the
primitive cell, the optical contribution is fairly minor compared to the ex-
perimental kL. In contrast, Yb14MnSb11 has 104 atoms in the primitive cell
and a corresponding large relative optical contribution. At high tempera-
tures, the optical contribution accounts for more than half of the total
thermal conductivity. We emphasize that this model predicts the minimum
contribution from the optical modes and is likely an underestimate. From
this understanding, the maximum acoustic contribution can be estimated,
assuming Umklapp scattering dominates the phonon transport. As shown in
Figure 1.9, kL in the relatively simple SrZn2Sb2 is comprised primarily of the
acoustic contribution, while in Yb14MnSb11 the acoustic contribution be-
comes almost insignificant, particularly at very high temperatures. Thus,
there is much greater reduction potential available for scattering the
acoustic phonons of SrZn2Sb2 than in more structurally complex solids like
Yb14MnSb11.
1.2.2.2 SrZnSb2 vs. SrZn2Sb2 – Stacking Faults

The simplified consideration of acoustic and optical phonons presented
above is a helpful way to discriminate between low- and high-frequency
phonons. However, classical scattering theory provides a more nuanced view
of phonon behaviour. In particular, it can be helpful to consider the fre-
quency dependence of phonon scattering when more than one scattering
source is present. The two closely related Zintl phases, SrZnSb2 and
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Figure 1.10 (a) The lattice thermal conductivity of SrZnSb2 is significantly lower
than SrZn2Sb2 (left). Bright-field TEM indicates planar defects in
SrZnSb2 (right) but not in SrZn2Sb2 (not shown). (b) This difference in
kL can be successfully modeled using a Debye–Callaway approach that
includes both Umklapp and boundary scattering of the acoustic
branches. Here, the boundary scattering is limited by grain boundaries
(B1 mm) for SrZn2Sb2 and stacking faults (B100 nm) for SrZnSb2.
SrZn2Sb2, provide an excellent example. Despite extremely similar chemical

structures, these two compounds exhibit a factor of two difference in ther-
mal conductivity (Figure 1.10) at room temperature; by 600 K this difference
disappears.146,148 Here, SrZnSb2 is found by transmission electron micro-
scopy (TEM) to possess a high density of stacking faults.140 Qualitatively, the
expectation is that these stacking faults significantly decrease thermal con-
ductivity at room temperature, but the effect is washed out by Umklapp
scattering at high temperature.
To develop a more quantitative assessment of these stacking faults, we
turn to classic phonon transport theory and the Debye–Callaway model. To
begin, the Umklapp scattering is treated as an identical contribution in these
two chemically similar materials. Based on the difference in grain structure,
the boundary scattering mean free path is approximated as 0.1 and 1 mm for
SrZnSb2 and SrZn2Sb2, respectively. These calculations reveal that the
decreased relaxation time due to boundary scattering reduces thermal con-
ductivity by approximately 30% at room temperature. This impact can be
seen in Figure 1.10(b), with the significantly lower relaxation time due to
enhanced boundary scattering.
1.3 Electronic Transport

Electronic transport in Zintl compounds varies widely, stemming from large
differences in the electronic band structures, carrier relaxation times and
carrier concentration (n). While the relationship between the thermal
properties of Zintl compounds and readily available crystallographic infor-
mation is relatively well understood, the electronic properties are often more
difficult to predict from the structure alone. Fortunately, calculated elec-
tronic structures are becoming increasingly available due to improvements
in computational capabilities and can be used to gauge the potential of a
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14 Chapter 1
new Zintl thermoelectric material by predicting the effective mass and band
degeneracy. However, prediction of the electron relaxation time remains a
significant challenge.
1.3.1 Controlling and Optimizing Carrier Concentration

Optimizing the zT of a thermoelectric material requires controlling the
carrier concentration, n, through either electronic doping or by varying the
stoichiometry.122,123 By definition, classic Zintl compounds are valence
precise, suggesting a fully filled valence band and empty conduction
band.149,150 Provided the bandgap is greater than zero, Zintl compounds
generally behave as intrinsic semiconductors with very low n (less than 1019
carriers per cm3), low electronic conductivity (s) and high Seebeck co-
efficients (a). Doping with aliovalent elements leads to a valence imbalance
and an increased concentration of free carriers, allowing for a transition
from semiconducting to metallic behavior. By rationally optimizing the
electronic properties, large improvements in zT relative to undoped Zintl
phase material can be achieved.117,127,128,147
The Ca5M2Sb6 system (M ¼ Al, Ga, or In) provides a straightforward ex-
ample of controlling and optimizing the carrier concentration via doping.
Ca5M2Sb6 compounds are valence precise when M is a trivalent element,
and, consistent with the Zintl formalism, samples with M ¼ Al, Ga or In have
similar, low carrier concentrations (B1018 h1 cm3).151 As in most Zintl
phases,122 the Ca5M2Sb6 system is naturally slightly p-type and apparently
can only be doped p-type. Substituting divalent elements such as Mn or Zn
on the trivalent M site leads to an electron deficiency and the resulting
carrier concentration can be predicted as a function of dopant content (x) by
assuming that each substitution yields one free hole (see dashed line in
Figure 1.11(a)). Experimentally, we find that Zn-doping in the
Ca5In2xZnxSb6 system increases the Hall carrier concentration as expected
at low concentrations of Zn, while the doping effectiveness is reduced above
x ¼ 0.05 (shown as symbols in Figure 1.11(a)),152 Similar trends were ob-
served in Zn-doped Ca5Al2Sb6 and Ca5Ga2Sb6153,154 and in the substitution of
a monovalent element (Na1) on the divalent cation site in Ca5Al2Sb6.127
The transition from non-degenerate to degenerate semiconducting be-
haviour is illustrated for Ca5In2xZnxSb6 in Figure 1.11(b) by the decreasing
a and increasing s with increasing Zn content (x). As the Zn concentration
increases, the peak zT increases from 0.1 to 0.7 when x ¼ 0.1 (Figure 1.11(c)).
In several doped Zintl phases, a single parabolic band model (SPB model)
has been used to approximate the dependence of a and s on carrier con-
centration (see dashed curves in Figure 1.11(b)) by assuming that the band
mass (m*) is invariant with doping (rigid band approximation), and that
acoustic phonons are the predominant scattering mechanism. The figure of
merit can then be modeled as a function of carrier concentration if kL is
assumed to be independent of doping, reducing the need to synthesize a
large number of samples. In the Ca5In2xZnxSb6 system, a SPB model
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Figure 1.11 (a) Doping Ca5In2Sb6 with Zn21 on the In31 site leads to an increase
in p-type carrier concentration and (b) a transition from non-degenerate
to degenerate semiconducting behaviour. Dashed lines were generated
using an SPB model with m* ¼ 2me and mo ¼ 6.9 cm2 V1. (c) This leads
to an increase from a peak zT of 0.2 to zT ¼ 0.7 in extrinsically doped
samples. (d) The optimum carrier concentration predicted using a SPB
model at 700 K corresponds to x ¼ 0.05.
accurately describes the relationship between zT and n, as shown in

Figure 1.11(d) for several temperatures. A more detailed description of the
SPB model and its limitations can be found in ref. 129.
1.3.2 Limits to Controlling Carrier Concentration

In traditional Zintl phases, the maximum carrier concentration that can be
achieved is often limited by the solubility of the dopant. However, the
chemistry and electronic structure of the Zintl phase also plays a role.
The charge imbalance in a heavily doped material impacts the stability of
the structure, potentially leading to the spontaneous formation of charge-
compensating defects.155
Some Zintl phases are able to tolerate very large dopant concentrations
and show highly degenerate behaviour, while in others, doping is very
limited (Figure 1.12). For example, the Yb14Al1xMnxSb11 system, the most
successful high temperature p-type thermoelectric material to date,156
tolerates nH41021 h1 cm3. A14MSb11 compounds are valence precise
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16 Chapter 1
Figure 1.12 Left panel: The carrier concentration in Yb14Al1xMnxSb11 increases

linearly with increasing x. Right panel: In contrast, the substitution of
Mn on the Al site in Ca5Al2Sb6 is limited to very low concentrations.
when the A ion is 2þ and the M ion is 3þ . Yb14MnSb11 (in which Mn is

divalent) can thus be regarded as a heavily doped analogue of the valence
precise Zintl phase, Yb14AlSb11.147 The carrier concentration in the
Mn-analogue (nH ¼ 1.2 1021 h1 cm3) is consistent with simple charge
counting predictions, assuming that each Mn substitution leads to one free
hole. This high doping tolerance in A14MSb11compounds may be partly
explained by the presence of several heavy bands (and thus a large density of
states) slightly below the valence band edge.157 In contrast, the Ca5Al2Sb6
system tolerates only 5 atomic % Mn on the Al site, leading to a maximum
carrier concentration of 2 1020 h1 cm3.158
Stretching the limit of the Zintl formalism are compounds that cannot be
synthesized with a valence precise composition, such as Yb9Mn41xSb9. The
Yb9Mn41xSb9 system is valence precise when x ¼ 0.5. However, when x is
greater than zero, the additional Mn atoms must occupy interstitial lattice
sites.159,160 The competing energetic requirements of charge balance and
structural stability lead to an electron deficient composition of approxi-
mately Yb9Mn4.2Sb9. The resulting high p-type carrier concentration
(21020 h1 cm3) is very close to the optimal n predicted by an SPB model,
leading to excellent thermoelectric performance without the need for doping.131
1.3.3 Band Structure Requirements

When selecting and optimizing Zintl phases for thermoelectric applications,
several key characteristics of the electronic band structure should be con-
sidered. The most critical requirement is the presence of a band gap (Eg 4 0),
which allows for a single carrier type to dominate transport. The magnitude
of Eg determines the temperature at which minority carrier effects begin to
negatively impact thermoelectric performance (e.g., bipolar thermal
View Online
conductivity and degradation of the Seebeck coefficient). Generally the band

gap in Zintl phases arises due to the energy difference between the bonding
and anti-bonding states of the covalently bonded anions.161 Many Zintl
compounds are semiconductors with small band gaps (Ego1 eV), although
semi-metallic Zintl phases have also been reported (Ego0 eV).162 Good
thermoelectric performance is most often found in phases with band gaps in
the range of 0.2 and 0.6 eV.
While a band gap is the only strictly necessary band structure criterion,
the band mass and the number of bands involved in transport (band
degeneracy, Nv) also play an important role in determining thermoelectric
performance. In the optimization of thermoelectric materials, the
effective mass presents a fundamental conflict: while a light inertial effective
mass (m*I) along the direction of transport is desired for high mobility, a
heavy ‘density of states effective mass’ (m*DOS) is necessary for a high Seebeck
coefficient. The density of states effective mass is related to the band
2=3
degeneracy and the inertial effective mass by m*DOS ¼ m*i Nv . Thus, when Nv
*
is large and mi is small, a high Seebeck coefficient and high mobility can be
obtained simultaneously.163 When electrons are scattered primarily by
acoustic phonons, as is the case in most known thermoelectric materials, the
improvement in m conferred by a light band mass outweighs the detrimental
effect on a.
The presence of Nv and m*i in the thermoelectric quality factor highlights
the value of calculated electronic structures. The electronic densities of
states of many Zintl compounds have been reported, providing estimates of
the magnitude of Eg. However, the electronic band structures from which
both Nv and m*i can be obtained are often omitted in published computa-
tional studies. To date, band structures have been published for only a
handful of Zintl compounds, including Ca14MnBi11, Ca5M2Sb6 (M ¼ Al, Ga,
In), Sr3GaSb3, Ca3AlSb3, and several AZn2Sb2 compounds (A ¼ Sr, Ca, Yb, Eu).
Among these reported band structures, the number of bands involved
in p-type transport is typically between one and three. This is far less than
that of PbTe and its alloys, which have up to Nv ¼ 16.163 This disparity is
partly explained by the higher symmetry of the latter compounds, which
leads to multiple symmetrically equivalent carrier pockets.164 However, there
is no theoretical limitation on Nv in Zintl compounds, suggesting that a
computational survey may reveal Zintl phases with high Nv.
Because electronic mobility is higher in covalent materials than in ionic
materials, it is often assumed that charge transport in Zintl compounds
occurs preferentially through the anionic framework. This is supported by
the influence that the dimensionality and orientation of the covalently
bonded substructure appears to have on the anisotropy of the electronic
band structure in some Zintl phases. For example, in Ca5Al2Sb6, transport
parallel to the chains of corner-linked AlSb4 tetrahedra exhibits the lightest
band mass.117 In AZn2Sb2, the lightest bands correspond to the directions
within the plane of the covalent Zn2Sb2 slabs.146 In contrast, Ca14MnBi11,
which is characterized by isolated MnBi4 tetrahedra, has a relatively isotropic
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“Bring it here.... Hickson’s ... and what does she want to be buying
more dresses for will you tell me that.... Hickson’s.... Open it up. If it
looks expensive I’ll send it back.”
The maid gingerly pulled off a layer of tissuepaper, uncovering a
peach and peagreen evening dress.
Mr. Densch got to his feet spluttering, “She must think the war’s
still on.... Tell em we will not receive it. Tell em there’s no such party
livin here.”
The maid picked up the box with a toss of the head and went out
with her nose in the air. Mr. Densch sat down in the little chair and
began looking over the telegrams again.
“Ann-ee, Ann-ee,” came a shrill voice from the inner room; this
was followed by a head in a lace cap shaped like a libertycap and a
big body in a shapeless ruffled negligée. “Why J. D. what are you
doing here at this time of the morning? I’m waiting for my
hairdresser.”
“It’s very important.... I just had a cable from Heintz. Serena my
dear, Blackhead and Densch is in a very bad way on both sides of
the water.”
“Yes ma’am,” came the maid’s voice from behind him.
He gave his shoulders a shrug and walked to the window. He felt
tired and sick and heavy with flesh. An errand boy on a bicycle
passed along the street; he was laughing and his cheeks were pink.
Densch saw himself, felt himself for a second hot and slender
running bareheaded down Pine Street years ago catching the girls’
ankles in the corner of his eye. He turned back into the room. The
maid had gone.
“Serena,” he began, “cant you understand the seriousness...? It’s
this slump. And on top of it all the bean market has gone to hell. It’s
ruin I tell you....”
“Well my dear I dont see what you expect me to do about it.”
“Economize ... economize. Look where the price of rubber’s gone
to.... That dress from Hickson’s....”
“Well you wouldnt have me going to the Blackhead’s party looking
like a country schoolteacher, would you?”
Mr. Densch groaned and shook his head. “O you wont
understand; probably there wont be any party.... Look Serena there’s
no nonsense about this.... I want you to have a trunk packed so that
we can sail any day.... I need a rest. I’m thinking of going to
Marienbad for the cure.... It’ll do you good too.”
Her eye suddenly caught his. All the little wrinkles on her face
deepened; the skin under her eyes was like the skin of a shrunken
toy balloon. He went over to her and put his hand on her shoulder
and was puckering his lips to kiss her when suddenly she flared up.
“I wont have you meddling between me and my dressmakers.... I
wont have it ... I wont have it....”
“Oh have it your own way.” He left the room with his head
hunched between his thick sloping shoulders.
“Ann-ee!”
“Yes ma’am.” The maid came back into the room.
Mrs. Densch had sunk down in the middle of a little spindlelegged
sofa. Her face was green. “Annie please get me that bottle of sweet
spirits of ammonia and a little water.... And Annie you can call up
Hickson’s and tell them that that dress was sent back through a
mistake of ... of the butler’s and please to send it right back as I’ve
got to wear it tonight.”
Pursuit of happiness, unalienable pursuit ... right to life liberty

and.... A black moonless night; Jimmy Herf is walking alone up
South Street. Behind the wharfhouses ships raise shadowy
skeletons against the night. “By Jesus I admit that I’m stumped,” he
says aloud. All these April nights combing the streets alone a
skyscraper has obsessed him, a grooved building jutting up with
uncountable bright windows falling onto him out of a scudding sky.
Typewriters rain continual nickelplated confetti in his ears. Faces of
Follies girls, glorified by Ziegfeld, smile and beckon to him from the
windows. Ellie in a gold dress, Ellie made of thin gold foil absolutely
lifelike beckoning from every window. And he walks round blocks and
blocks looking for the door of the humming tinselwindowed
skyscraper, round blocks and blocks and still no door. Every time he
closes his eyes the dream has hold of him, every time he stops
arguing audibly with himself in pompous reasonable phrases the
dream has hold of him. Young man to save your sanity you’ve got to
do one of two things.... Please mister where’s the door to this
building? Round the block? Just round the block ... one of two
unalienable alternatives: go away in a dirty soft shirt or stay in a
clean Arrow collar. But what’s the use of spending your whole life
fleeing the City of Destruction? What about your unalienable right,
Thirteen Provinces? His mind unreeling phrases, he walks on
doggedly. There’s nowhere in particular he wants to go. If only I still
had faith in words.
“How do you do Mr. Goldstein?” the reporter breezily chanted as

he squeezed the thick flipper held out to him over the counter of the
cigar store. “My name’s Brewster.... I’m writing up the crime wave for
the News.”
Mr. Goldstein was a larvashaped man with a hooked nose a little
crooked in a gray face, behind which pink attentive ears stood out
unexpectedly. He looked at the reporter out of suspicious screwedup
eyes.
“If you’d be so good I’d like to have your story of last night’s little
... misadventure ...”
“Vont get no story from me young man. Vat vill you do but print it
so that other boys and goils vill get the same idear.”
“It’s too bad you feel that way Mr. Goldstein ... Will you give me a
Robert Burns please...? Publicity it seems to me is as necessary as
ventilation.... It lets in fresh air.” The reporter bit off the end of the
cigar, lit it, and stood looking thoughtfully at Mr. Goldstein through a
swirling ring of blue smoke. “You see Mr. Goldstein it’s this way,” he
began impressively. “We are handling this matter from the human
interest angle ... pity and tears ... you understand. A photographer
was on his way out here to get your photograph.... I bet you it would
increase your volume of business for the next couple of weeks.... I
suppose I’ll have to phone him not to come now.”
“Well this guy,” began Mr. Goldstein abruptly, “he’s a welldressed
lookin feller, new spring overcoat an all that and he comes in to buy
a package o Camels.... ‘A nice night,’ he says openin the package
an takin out a cigarette to smoke it. Then I notices the goil with him
had a veil on.”
“Then she didnt have bobbed hair?”
“All I seen was a kind o mournin veil. The foist thing I knew she
was behind the counter an had a gun stuck in my ribs an began
talkin ... you know kinder kiddin like ... and afore I knew what to think
the guy’d cleaned out the cashregister an says to me, ‘Got any cash
in your jeans Buddy?’ I’ll tell ye I was sweatin some ...”
“And that’s all?”
“Sure by the time I’d got hold of a cop they vere off to hell an
gone.”
“How much did they get?”
“Oh about fifty berries an six dollars off me.”
“Was the girl pretty?”
“I dunno, maybe she was. I’d like to smashed her face in. They
ought to make it the electric chair for those babies.... Aint no security
nowhere. Vy should anybody voirk if all you’ve got to do is get a gun
an stick up your neighbors?”
“You say they were welldressed ... like welltodo people?”
“Yare.”
“I’m working on the theory that he’s a college boy and that she’s a
society girl and that they do it for sport.”
“The feller vas a hardlookin bastard.”
“Well there are hardlooking college men.... You wait for the story
called ‘The Gilded Bandits’ in next Sunday’s paper Mr. Goldstein....
You take the News dont you?”
Mr. Goldstein shook his head.
“I’ll send you a copy anyway.”
“I want to see those babies convicted, do you understand? If
there’s anythin I can do I sure vill do it ... Aint no security no more....
I dont care about no Sunday supplement publicity.”
“Well the photographer’ll be right along. I’m sure you’ll consent to
pose Mr. Goldstein.... Well thank you very much.... Good day Mr.
Goldstein.”
Mr. Goldstein suddenly produced a shiny new revolver from under
the counter and pointed it at the reporter.
“Hay go easy with that.”
Mr. Goldstein laughed a sardonic laugh. “I’m ready for em next
time they come,” he shouted after the reporter who was already
making for the Subway.
“Our business, my dear Mrs. Herf,” declaimed Mr. Harpsicourt,

looking sweetly in her eyes and smiling his gray Cheshire cat smile,
“is to roll ashore on the wave of fashion the second before it breaks,
like riding a surfboard.”
Ellen was delicately digging with her spoon into half an alligator
pear; she kept her eyes on her plate, her lips a little parted; she felt
cool and slender in the tightfitting darkblue dress, shyly alert in the
middle of the tangle of sideways glances and the singsong modish
talk of the restaurant.
“It’s a knack that I can prophesy in you more than in any girl, and
more charmingly than any girl I’ve ever known.”
“Prophesy?” asked Ellen, looking up at him laughing.
“You shouldnt pick up an old man’s word.... I’m expressing myself
badly.... That’s always a dangerous sign. No, you understand so
perfectly, though you disdain it a little ... admit that.... What we need
on such a periodical, that I’m sure you could explain it to me far
better.”
“Of course what you want to do is make every reader feel Johnny
on the spot in the center of things.”
“As if she were having lunch right here at the Algonquin.”
“Not today but tomorrow,” added Ellen.
Mr. Harpsicourt laughed his creaky little laugh and tried to look
deep among the laughing gold specs in her gray eyes. Blushing she
looked down into the gutted half of an alligator pear in her plate. Like
the sense of a mirror behind her she felt the smart probing glances
of men and women at the tables round about.
The pancakes were comfortably furry against his gin-bitten
tongue. Jimmy Herf sat in Child’s in the middle of a noisy drunken
company. Eyes, lips, evening dresses, the smell of bacon and coffee
blurred and throbbed about him. He ate the pancakes painstakingly,
called for more coffee. He felt better. He had been afraid he was
going to feel sick. He began reading the paper. The print swam and
spread like Japanese flowers. Then it was sharp again, orderly,
running in a smooth black and white paste over his orderly black and
white brain:
Misguided youth again took its toll of tragedy amid the
tinsel gayeties of Coney Island fresh painted for the season
when plainclothes men arrested “Dutch” Robinson and a girl
companion alleged to be the Flapper Bandit. The pair are
accused of committing more than a score of holdups in
Brooklyn and Queens. The police had been watching the
couple for some days. They had rented a small kitchenette
apartment at 7356 Seacroft Avenue. Suspicion was first
aroused when the girl, about to become a mother, was taken
in an ambulance to the Canarsie Presbyterian Hospital.
Hospital attendants were surprised by Robinson’s seemingly
endless supply of money. The girl had a private room,
expensive flowers and fruit were sent in to her daily, and a
well-known physician was called into consultation at the
man’s request. When it came to the point of registering the
name of the baby girl the young man admitted to the
physician that they were not married. One of the hospital
attendants, noticing that the woman answered to the
description published in the Evening Times of the flapper
bandit and her pal, telephoned the police. Plainclothes men
sleuthed the couple for some days after they had returned to
the apartment on Seacroft Avenue and this afternoon made
the arrests.
The arrest of the flapper bandit ...
A hot biscuit landed on Herf’s paper. He looked up with a start; a
darkeyed Jewish girl at the next table was making a face at him. He
nodded and took off an imaginary hat. “I thank thee lovely nymph,”
he said thickly and began eating the biscuit.
“Quit dat djer hear?” the young man who sat beside her, who
looked like a prizefighter’s trainer, bellowed in her ear.
The people at Herf’s table all had their mouths open laughing. He
picked up his check, vaguely said good night and walked out. The
clock over the cashier’s desk said three o’clock. Outside a rowdy
scattering of people still milled about Columbus Circle. A smell of
rainy pavements mingled with the exhausts of cars and occasionally
there was a whiff of wet earth and sprouting grass from the Park. He
stood a long time on the corner not knowing which way to go. These
nights he hated to go home. He felt vaguely sorry that the Flapper
Bandit and her pal had been arrested. He wished they could have
escaped. He had looked forward to reading their exploits every day
in the papers. Poor devils, he thought. And with a newborn baby too.
Meanwhile a rumpus had started behind him in Child’s. He went
back and looked through the window across the griddle where
sizzled three abandoned buttercakes. The waiters were struggling to
eject a tall man in a dress suit. The thickjawed friend of the Jewish
girl who had thrown the biscuit was being held back by his friends.
Then the bouncer elbowed his way through the crowd. He was a
small broadshouldered man with deepset tired monkey eyes. Calmly
and without enthusiasm he took hold of the tall man. In a flash he
had him shooting through the door. Out on the pavement the tall man
looked about him dazedly and tried to straighten his collar. At that
moment a police-wagon drove up jingling. Two policemen jumped
out and quickly arrested three Italians who stood chatting quietly on
the corner. Herf and the tall man in the dress suit looked at each
other, almost spoke and walked off greatly sobered in opposite
directions.
V. The Burthen of Nineveh
S
eeping in red twilight out of the Gulf
Stream fog, throbbing brassthroat that
howls through the stiff-fingered streets,
prying open glazed eyes of skyscrapers,
splashing red lead on the girdered thighs of
the five bridges, teasing caterwauling
tugboats into heat under the toppling
smoketrees of the harbor.
Spring puckering our mouths, spring
giving us gooseflesh grows gigantic out of
the droning of sirens, crashes with
enormous scaring din through the halted
traffic, between attentive frozen tiptoe
blocks.
r. Densch with the collar of his woolly ulster up round his ears
M and a big English cap pulled down far over his eyes, walked
nervously back and forth on the damp boat deck of the
Volendam. He looked out through a drizzly rain at the gray wharf
houses and the waterfront buildings etched against a sky of
inconceivable bitterness. A ruined man, a ruined man, he kept
whispering to himself. At last the ship’s whistle boomed out for the
third time. Mr. Densch, his fingers in his ears, stood screened by a
lifeboat watching the rift of dirty water between the ship’s side and
the wharf widen, widen. The deck trembled under his feet as the
screws bit into the current. Gray like a photograph the buildings of
Manhattan began sliding by. Below decks the band was playing O
Titin-e Titin-e. Red ferryboats, carferries, tugs, sandscows,
lumberschooners, tramp steamers drifted between him and the
steaming towering city that gathered itself into a pyramid and began
to sink mistily into the browngreen water of the bay.
Mr. Densch went below to his stateroom. Mrs. Densch in a cloche
hat hung with a yellow veil was crying quietly with her head on a
basket of fruit. “Dont Serena,” he said huskily. “Dont.... We like
Marienbad.... We need a rest. Our position isnt so hopeless. I’ll go
and send Blackhead a radio.... After all it’s his stubbornness and
rashness that brought the firm to ... to this. That man thinks he’s a
king on earth.... This’ll ... this’ll get under his skin. If curses can kill I’ll
be a dead man tomorrow.” To his surprise he found the gray drawn
lines of his face cracking into a smile. Mrs. Densch lifted her head
and opened her mouth to speak to him, but the tears got the better of
her. He looked at himself in the glass, squared his shoulders and
adjusted his cap. “Well Serena,” he said with a trace of jauntiness in
his voice, “this is the end of my business career.... I’ll go send that
radio.”
Mother’s face swoops down and kisses him; his hands clutch her
dress, and she has gone leaving him in the dark, leaving a frail
lingering fragrance in the dark that makes him cry. Little Martin lies
tossing within the iron bars of his crib. Outside dark, and beyond
walls and outside again the horrible great dark of grownup people,
rumbling, jiggling, creeping in chunks through the windows, putting
fingers through the crack in the door. From outside above the roar of
wheels comes a strangling wail clutching his throat. Pyramids of dark
piled above him fall crumpling on top of him. He yells, gagging
between yells. Nounou walks towards the crib along a saving
gangplank of light “Dont you be scared ... that aint nothin.” Her black
face grins at him, her black hand straightens the covers. “Just a fire
engine passin.... You wouldn’t be sceered of a fire engine.”
Ellen leaned back in the taxi and closed her eyes for a second.
Not even the bath and the halfhour’s nap had washed out the
fagging memory of the office, the smell of it, the chirruping of
typewriters, the endlessly repeated phrases, faces, typewritten
sheets. She felt very tired; she must have rings under her eyes. The
taxi had stopped. There was a red light in the traffic tower ahead.
Fifth Avenue was jammed to the curbs with taxis, limousines,
motorbusses. She was late; she had left her watch at home. The
minutes hung about her neck leaden as hours. She sat up on the
edge of the seat, her fists so tightly clenched that she could feel
through her gloves her sharp nails digging into the palms of her
hands. At last the taxi jerked forward, there was a gust of exhausts
and whir of motors, the clot of traffic began moving up Murray Hill. At
a corner she caught sight of a clock. Quarter of eight. The traffic
stopped again, the brakes of the taxi shrieked, she was thrown
forward on the seat. She leaned back with her eyes closed, the
blood throbbing in her temples. All her nerves were sharp steel
jangled wires cutting into her. “What does it matter?” she kept asking
herself. “He’ll wait. I’m in no hurry to see him. Let’s see, how many
blocks?... Less than twenty, eighteen.” It must have been to keep
from going crazy people invented numbers. The multiplication table
better than Coué as a cure for jangled nerves. Probably that’s what
old Peter Stuyvesant thought, or whoever laid the city out in
numbers. She was smiling to herself. The taxi had started moving
again.
George Baldwin was walking back and forth in the lobby of the
hotel, taking short puffs of a cigarette. Now and then he glanced at
the clock. His whole body was screwed up taut like a high
violinstring. He was hungry and full up with things he wanted to say;
he hated waiting for people. When she walked in, cool and silky and
smiling, he wanted to go up to her and hit her in the face.
“George do you realize that it’s only because numbers are so cold
and emotionless that we’re not all crazy?” she said giving him a little
pat on the arm.
“Fortyfive minutes waiting is enough to drive anybody crazy, that’s
all I know.”
“I must explain it. It’s a system. I thought it all up coming up in the
taxi.... You go in and order anything you like. I’m going to the ladies’
room a minute.... And please have me a Martini. I’m dead tonight,
just dead.”
“You poor little thing, of course I will.... And dont be long please.”
His knees were weak under him, he felt like melting ice as he
went into the gilt ponderously ornamented diningroom. Good lord
Baldwin you’re acting like a hobbledehoy of seventeen ... after all
these years too. Never get anywhere that way.... “Well Joseph what
are you going to give us to eat tonight? I’m hungry.... But first you
can get Fred to make the best Martini cocktail he ever made in his
life.”
“Tres bien monsieur,” said the longnosed Roumanian waiter and
handed him the menu with a flourish.
Ellen stayed a long time looking in the mirror, dabbing a little
superfluous powder off her face, trying to make up her mind. She
kept winding up a hypothetical dollself and setting it in various
positions. Tiny gestures ensued, acted out on various model stages.
Suddenly she turned away from the mirror with a shrug of her
toowhite shoulders and hurried to the diningroom.
“Oh George I’m starved, simply starved.”
“So am I” he said in a crackling voice. “And Elaine I’ve got news
for you,” he went on hurriedly as if he were afraid she’d interrupt him.
“Cecily has consented to a divorce. We’re going to rush it through
quietly in Paris this summer. Now what I want to know is, will you...?”
She leaned over and patted his hand that grasped the edge of the
table. “George lets eat our dinner first.... We’ve got to be sensible.
God knows we’ve messed things up enough in the past both of us....
Let’s drink to the crime wave.” The smooth infinitesimal foam of the
cocktail was soothing in her tongue and throat, glowed gradually
warmly through her. She looked at him laughing with sparkling eyes.
He drank his at a gulp.
“By gad Elaine,” he said flaming up helplessly, “you’re the most
wonderful thing in the world.”
Through dinner she felt a gradual icy coldness stealing through
her like novocaine. She had made up her mind. It seemed as if she
had set the photograph of herself in her own place, forever frozen
into a single gesture. An invisible silk band of bitterness was
tightening round her throat, strangling. Beyond the plates, the ivory
pink lamp, the broken pieces of bread, his face above the blank
shirtfront jerked and nodded; the flush grew on his cheeks; his nose
caught the light now on one side, now on the other, his taut lips
moved eloquently over his yellow teeth. Ellen felt herself sitting with
her ankles crossed, rigid as a porcelain figure under her clothes,
everything about her seemed to be growing hard and enameled, the
air bluestreaked with cigarettesmoke, was turning to glass. His
wooden face of a marionette waggled senselessly in front of her. She
shuddered and hunched up her shoulders.
“What’s the matter, Elaine?” he burst out. She lied:
“Nothing George.... Somebody walked over my grave I guess.”
“Couldnt I get you a wrap or something?”
She shook her head.
“Well what about it?” he said as they got up from the table.
“What?” she asked smiling. “After Paris?”
“I guess I can stand it if you can George,” she said quietly.
He was waiting for her, standing at the open door of a taxi. She
saw him poised spry against the darkness in a tan felt hat and a light
tan overcoat, smiling like some celebrity in the rotogravure section of
a Sunday paper. Mechanically she squeezed the hand that helped
her into the cab.
“Elaine,” he said shakily, “life’s going to mean something to me
now.... God if you knew how empty life had been for so many years.
I’ve been like a tin mechanical toy, all hollow inside.”
“Let’s not talk about mechanical toys,” she said in a strangled
voice.
“No let’s talk about our happiness,” he shouted.
Inexorably his lips closed on to hers. Beyond the shaking glass
window of the taxi, like someone drowning, she saw out of a corner
of an eye whirling faces, streetlights, zooming nickleglinting wheels.
The old man in the checked cap sits on the brownstone stoop with
his face in his hands. With the glare of Broadway in their backs there
is a continual flickering of people past him towards the theaters down
the street. The old man is sobbing through his fingers in a sour reek
of gin. Once in a while he raises his head and shouts hoarsely, “I
cant, dont you see I cant?” The voice is inhuman like the splitting of
a plank. Footsteps quicken. Middleaged people look the other way.
Two girls giggle shrilly as they look at him. Streeturchins nudging
each other peer in and out through the dark crowd. “Bum Hootch.”
“He’ll get his when the cop on the block comes by.” “Prohibition
liquor.” The old man lifts his wet face out of his hands, staring out of
sightless bloodyrimmed eyes. People back off, step on the feet of the
people behind them. Like splintering wood the voice comes out of
him. “Don’t you see I cant...? I cant ... I cant.”
When Alice Sheffield dropped into the stream of women going

through the doors of Lord & Taylor’s and felt the close smell of stuffs
in her nostrils something went click in her head. First she went to the
glovecounter. The girl was very young and had long curved black
lashes and a pretty smile; they talked of permanent waves while
Alice tried on gray kids, white kids with a little fringe like a gauntlet.
Before she tried it on, the girl deftly powdered the inside of each
glove out of a longnecked wooden shaker. Alice ordered six pairs.
“Yes, Mrs. Roy Sheffield.... Yes I have a charge account, here’s
my card.... I’ll be having quite a lot of things sent.” And to herself she
said all the while: “Ridiculous how I’ve been going round in rags all
winter.... When the bill comes Roy’ll have to find some way of paying
it that’s all. Time he stopped mooning round anyway. I’ve paid
enough bills for him in my time, God knows.” Then she started
looking at fleshcolored silk stockings. She left the store her head still
in a whirl of long vistas of counters in a violet electric haze, of
braided embroidery and tassles and nasturtiumtinted silks; she had
ordered two summer dresses and an evening wrap.
At Maillard’s she met a tall blond Englishman with a coneshaped
head and pointed wisps of towcolored mustaches under his long
nose.
“Oh Buck I’m having the grandest time. I’ve been going berserk in
Lord & Taylor’s. Do you know that it must be a year and a half since
I’ve bought any clothes?”
“Poor old thing,” he said as he motioned her to a table. “Tell me
about it.”
She let herself flop into a chair suddenly whimpering, “Oh Buck
I’m so tired of it all.... I dont know how much longer I can stand it.”
“Well you cant blame me.... You know what I want you to do....”
“Well suppose I did?”
“It’d be topping, we’d hit it off like anything.... But you must have a
bit of beef tea or something. You need picking up.” She giggled. “You
old dear that’s just what I do need.”
“Well how about making tracks for Calgary? I know a fellow there
who’ll give me a job I think.”
“Oh let’s go right away. I dont care about clothes or anything....
Roy can send those things back to Lord & Taylor’s.... Got any money
Buck?”
A flush started on his cheekbones and spread over his temples to
his flat irregular ears. “I confess, Al darling, that I havent a penny. I
can pay for lunch.”
“Oh hell I’ll cash a check; the account’s in both our names.”
“They’ll cash it for me at the Biltmore, they know me there. When
we get to Canada everything will be quite all right I can assure you.
In His Majesty’s Dominion, the name of Buckminster has rather more
weight than in the U.S.”
“Oh I know darling, it’s nothing but money in New York.”
When they were walking up Fifth Avenue she hooked her arm in
his suddenly. “O Buck I have the most horrible thing to tell you. It
made me deathly ill.... You know what I told you about the awful
smell we had in the apartment we thought was rats? This morning I
met the woman who lives on the ground floor.... O it makes me sick
to think of it. Her face was green as that bus.... It seems they’ve
been having the plumbing examined by an inspector.... They
arrested the woman upstairs. O it’s too disgusting. I cant tell you
about it.... I’ll never go back there. I’d die if I did.... There wasnt a
drop of water in the house all day yesterday.”
“What was the matter?”
“It’s too horrible.”
“Tell it to popper.”
“Buck they wont know you when you get back home to Orpen
Manor.”
“But what was it?”
“There was a woman upstairs who did illegal operations,
abortions.... That was what stopped up the plumbing.”
“Good God.”
“Somehow that’s the last straw.... And Roy sitting limp over his
damn paper in the middle of that stench with that horrible adenoid
expression on his face.”
“Poor little girl.”
“But Buck I couldn’t cash a check for more than two hundred....
It’ll be an overdraft as it is. Will that get us to Calgary?”

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Thermoelectric Materials and

RSC Energy and Environment Series No. 17

Print ISBN: 978-1-78262-323-6

r The Royal Society of Chemistry 2017

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Published by The Royal Society of Chemistry,

Registered Charity Number 207890

For further information see our web site at www.rsc.org

The publication of this book is motivated by a number of recent and

RSC Energy and Environment Series No. 17

Chapter 1 Zintl Phases: Recent Developments in Thermoelectrics and

Chapter 2 Chalcogenide Thermoelectric Materials 27

RSC Energy and Environment Series No. 17

2.3.3 Structurally-related Phases 37

Chapter 3 Thermoelectric Oxides 60

Chapter 4 Nano- and Micro-fabrication Techniques for Improving

Chapter 5 Review of the Methods for Thermal Conductivity

Andres Muñiz-Piniella and Alexandre Cuenat

5.1 Introduction 109

Chapter 6 High-throughput Thermoelectric Measurement

6.1 Introduction 133

Chapter 7 System Design Considerations for Thermoelectric

7.1 Introduction 156

Chapter 8 Electrodeposition of Thermoelectric Materials 204

8.1 Introduction 204

8.1.2Recent Advances in the Electrodeposition of

8.3.1 Sodium Lignosulfonate as an Additive in the

Chapter 9 Automotive Power Harvesting/Thermoelectric Applications 230

9.1 Why are Thermoelectric Devices Suitable for

Subject Index 252

Zintl Phases: Recent

RSC Energy and Environment Series No. 17

Hume-Rothery and Westgren had demonstrated the correlation of structure

1.1.2 Charge Counting/Formal Valence Rules

Zintl Phases: Recent Developments in Thermoelectrics and Future Outlook 3

a e(A) þ x e(X) ¼ 8x (1.1)

1.1.3 Thermoelectric Zintl Compounds

1.1.3.1 Yb14MnSb11 Structure Type

Zintl Phases: Recent Developments in Thermoelectrics and Future Outlook 5

temperatures of up to 1250 1C for periods of 24–300 h. There is evidence for

at higher temperatures. Yb14MnSb11 can be prepared by high temperature

1.1.3.2 CaAl2Si2 Structure Type

1.1.3.3 Sr3GaSb3 Structure Type

Ba3GaSb3 (Z ¼ 8) and Ca3InP3 (Z ¼ 4) both in space group Pnma112 and