Martin Goosey (Auth.), Martin Goosey (Eds.) - Plastics For Electronics-Springer Netherlands (1999)

Plastics for Electronics
Plastics for Electronics

Second Edition
Edited by
Martin Goosey
Chief Scientist and Technology Fellow
Shipley Europe Ltd
Coventry, UK
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

Library of Congress Cataloging-in-Publication Data is available
ISBN 978-90-481-4018-3 ISBN 978-94-017-2700-6 (eBook)

DOI 10.1007/978-94-017-2700-6
Printed on acid-free paper
AII Rights Reserved

© 1999 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1999
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
including photocopying, recording or by any information storage and
retrieval system, without written permission from the copyright owner.
Contents
List of Contributors ix
Preface Xl
Chapter 1 Introduction to polymers and their important properties

for electronic applications 1
Martin Goosey
1.1 Introduction to polymers and their properties 1
1.2 Chemistry of polymers 4
1.3 Important electrical properties of polymers 9
1.4 Important mechanical, chemical and physical
properties of polymers 16
1.5 Summary 24
Chapter 2 Silicone materials for electronic components

and circuit protection 25
Jean-Paul Mollie
2.1 Definition and history 25
2.2 Physical properties 27
2.3 Production of silicones 29
2.4 Silicone applications in electronics 33
2.5 Future developments 47
2.6 References 48
Chapter 3 Engineering thermoplastics 51

Harry van Baal
3.1 Introduction 51
3.2 Engineering thermoplastics 52
3.3 Principal standard tests 65
3.4 Further applications 69
3.5 Post-treatment of engineering thermoplastics 80
vi I I CONTENTS
3.6 Design for recyclability 81

3.7 Conclusion 81
Chapter 4 Epoxide resins and their formulation 83

Martin Goosey, Martin Roth, Thomas Kainmuller
and Wolfgang Seiz
4.1 Introduction 83
4.2 Epoxide resins 87
4.3 Curing agents 93
4.4 Extenders 106
4.5 Flame retardants 112
4.6 Other useful constituents 116
4.7 General formulation considerations 121
4.8 Recycling of cured epoxy-based materials 123
4.9 Toxicological properties and safety precautions 124
4.10 Summary 125
4.11 References 125
4.12 Further reading 125
Chapter 5 Recent developments in the encapsulation

of semiconductors by transfer moulding 131
Martin Goosey and Mike Plant
5.1 Introduction 131
5.2 Transfer moulding equipment considerations 134
5.3 Transfer moulding compound formulation
considerations 140
5.4 Common moulding problems and how to avoid them 151
5.5 Evaluation of epoxide-based transfer moulding
compounds 161
5.6 Challenges into the 21st century 167
5.7 Reference 168
5.8 Further reading 168
Chapter 6 Materials for advanced encapsulation 171

Nigel Hackett
6.2 Material choices for encapsulants 174
6.3 Handling and use 186
6.4 Application techniques 189
6.5 Industry trends 196
6.6 Summary 198
6.7 Acknowledgements 199
CONTENTS
I I vii
Chapter 7 Recent developments in the chemistry of lithography

for electronics production 201
David Merricks
7.2 Photoresists for printed circuit board production 205
7.3 Photoresists for integrated circuit production 223
7.4 Conclusion 238
7.5 References 239
Chapter 8 Ferroelectric polymers 243
John A. Chilton
8.2 Electroactive polymers 246
8.3 Poling 251
8.4 Electroactive composites 253
8.5 Properties of ferroelectric materials 258
8.6 Applications 276
8.7 SMART materials 284
8.8 Conclusions 286
8.9 Acronyms and symbolism 288
8.10 References 289
Chapter 9 Polymers in printed circuit board (PCB) and related
advanced interconnect applications 293
Martin Goosey
9.2 Printed circuit board fabrication 295
9.3 Laminates for rigid printed wiring 297
9.4 Properties and testing of laminates 301
9.5 Polymers used for laminate manufacture 309
9.6 Polymers for flexible printed wiring 320
9.7 Integrated capacitors and resistors 325
9.8 Polymers in advanced interconnect applications 326
9.9 Summary and conclusions 330
9.10 Acknowledgement 332
9.11 References 332
Chapter 10 New polymers for emerging interconnect applications 333

John Everett, Philip Garrou and David Dalman
10.2 PWB substrates with organic reinforcements 334
10.3 PWB substrates without reinforcements 337
10.4 Polymers for thin film microelectronics applications 338
10.5 Tradenames 349
10.6 References 350
viii II
L ___________ C_O_NT_E_NT_S_ _ _ _ _ _ _ _ _ _----...l
Chapter 11 Moulded interconnect devices (MIDs) 355

Frank Pohlau and Klaus Feldmann
11.2 Key advantages and introduction strategies 359
11.3 Manufacturing methods 363
11.4 Assembly and connection technology 377
11.5 Materials used 383
11.6 Example product 384
11.7 Summary 385
11.8 Literature 385
Index 387
List of Contributors
Harry van Baal

General Electric Plastics bv, Bergen op Zoom, The Netherlands
John A. Chilton
Bosworth College, Nazareth House, Barrack Road, Northampton, UK
David Dalman
The Dow Chemical Company, Midland, Michigan, MI 48674, USA
John Everett
Dow Deutschland Inc., Industriestrasse I, D-77836 Rheinmunster, Germany
Klaus Feldmann
F APS, Lehrstuhl fUr Fertigungsautomatisierung und Produktionssyste-
matik, University of Erlangen-Nurnberg, Germany
Philip Garrou
The Dow Chemical Company, c/-MCNC Research Triangle Park, NC
27909, USA
Martin Goosey
Shipley Europe Ltd, Herald Way, Coventry, UK
Nigel Hackett
Dexter Electronic Materials, Langley, UK
Thomas Kainmiiller
Ciba Specialty Chemicals Inc., Basel, Switzerland
David Merricks
Shipley Company Inc., Marlborough, MA, USA
Jean-Paul Mollie
Dow Corning SA, Seneffe, Belgium
x I IL-_______________L_IS_T_O__F_C_O_NT__RI__B_U_T_O_R_S______________~
Mike Plant
Kemtron International, South Woodham Ferrers, UK
Frank Pohlau
F APS, Lehrstuhl fUr Fertigungsautomatisierung und Produktionssyste-
matik, University of Erlangen-Numberg, Germany
Martin Roth
Wolfgang Seiz
Preface
The phenomenal and relentless progress in the development and commer-

cialization of new electronics products has had a major impact on most
people in the civilized world. We are all now familiar with personal
computers, mobile telephones, portable camcorders and a host of other
relatively low cost devices that have transformed our everyday lives. The key
features that characterize the evolution of most of these products from one
generation to the next are typically enhanced performance and functionality
coupled with reduced size. The electronics industry is also one of the few
industries in which the real cost-performance function has continued to
decline significantly over the last 40 years or so since the mass commercial-
ization of semiconductor devices. The now ubiquitous personal computer is
the classic example, where the new product introduction cycle is of the order
of only a few months and where operating speeds, memory capacity and
overall performance are increasing at an incredible rate, yet the prices are
continually reducing.
All of this has been a result of the development of increasingly
sophisticated semiconductor devices along with the supporting discrete
components, packages and interconnection and assembly methods. In
particular, one of the key drivers has been the ability to incorporate more
and more features onto silicon without any appreciable increase in size.
Again, the microprocessor and memory chips used in personal computers
are good examples. These advances have only been made possible because of
both improved and new materials such as the polymer-based photoresists
and packaging materials that have enabled the mass production of these
sophisticated devices on a scale and yield that would have seemed
impossible a few years ago.
Polymeric materials are widely used during nearly all stages of the
manufacturing process of electronics products from photoresists to printed
circuit boards and from encapsulants to equipment cases. In almost every
piece of electronics there is invariably a wide range of polymeric materials to
be found and this book gives an introductory overview of the chemistry,
ni I I~________________P_R_E_FA_C_E________________~
properties and uses of some of the more important classes of materials likely
to be encountered in these applications. It is intended to serve primarily as
an introduction to the use of polymers and plastics in the process~ng and
manufacture of electronic and electrical components and assemblies. No in-
depth knowledge of polymer chemistry is assumed and the book is aimed· at
engineers and material scientists who wish to gain a greater understanding
of the materials both currently in use and emerging. The book begins with
an introduction to polymers, their structures and important properties, after
which the rest of the chapters detail the major materials and their uses.
The original version of this book was written during the first part of the
1980s and published in 1985. As editor of both this new work and the
previous edition, it has been an interesting task to compare and contrast the
key materials from that period with those that are used today and to see how
the technology has evolved in the last 15 years. In some areas the materials
used for a specific application have changed markedly, whereas in other
areas there has been less radical change and a more gradual evolution of
improvements to fundamentally the same types of materials. As a
consequence, I have taken the opportunity, rather than merely updating
the contents of the original book, to make some major changes by
introducing a number of new chapters covering materials and topics which
have come to prominence in the last few years. Where appropriate, I have
also added new sections to certain of those chapters that remain similar to
those in the original version. For example, the chapter on printed circuit
board materials contains details of the many new materials that are now
widely used in addition to those previously described. Additionally, a new
section details the various fabrication methods used to produce advanced
interconnects. Also, the chapter on photoresists has been expanded to cover
some of the newer types of materials used in both microelectronics and
printed circuit board fabrication.
In the last few years there has also been a lot of work carried out on the
development and use of polymers that have important special properties in
addition to those normally associated with conventional polymers. I have,
therefore, also included a chapter that introduces one particular group of
materials exhibiting these special properties: the ferroelectric polymers. The
book also includes new chapters on the high temperature thermoplastics, or
engineering thermoplastics as they are sometimes known, and their use in
so-called moulded interconnect devices, where the polymer is used to
provide a much wider range of functions than has been possible using a
more conventional approach.
In this new version I have given the book a more international flavour
and, in addition to chapters from the UK, I have included contributions by
experts based in Belgium, Holland, Switzerland, Germany and the USA.
While I am extremely grateful to all the authors for their hard work and help
in making this book possible, I would especially like to acknowledge the
PREFACE
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~
Xlll
excellent contributions from those authors whose first language is not

English.
The first version of this book was very well received and indeed is still in
wide use. It is my hope that this second edition will prove to be of equal
value to its readers and of use both to those working with materials in the
electronics industry and to those with a more general interest in the subject.
Martin Goosey
Shipley Europe
Coventry
1998
Introduction to Polymers and 1
their Important Properties for
Electronic Applications
MARTIN GOOSEY
Shipley Europe Ltd, Coventry, England
1.1 INTRODUCTION TO POLYMERS AND THEIR PROPERTIES
The word plastic has its origins in the Greek language where 'plastikos'
meant to form or shape. Today plastic has a number of meanings but the
one which best fits the description of materials detailed in this work is that
referring to any of various substances which harden and retain their shape
after being moulded or formed by heat and pressure. This description is still
rather broad, covering a large number of materials including many such as
tar, clay and even mud which do not really agree with our current
perception of a plastic. In order to qualify the word plastic, a more accurate
description would be synthetic plastic, since this eliminates the naturally
occurring materials that have plastic properties and only includes those
derived by chemical means from relatively simple raw materials. Plastics are
thus man-made polymers where the word polymer is an abbreviation of the
two words poly and monomer and literally means many monomers. It
should also be noted, however, that the word plastic is generally taken to
refer to thermoplastic materials and therefore does not include thermoset-
ting materials. Consequently, in this revision of the original chapter the
word polymer will generally be used unless the reference is specifically to a
thermoplastic material.
Plastics for Electronics, 2nd edn. Edited by Martin Goosey. Published in 1999 by Kluwer
Academic Publishers, Dordrecht. ISBN 978-90-481-4018-3
2 I I INTRODUCTION TO POLYMERS FOR ELECTRONIC APPLICATIONS
During the nineteenth century much interesting work was performed on
polymeric materials beginning with the vulcanization of rubber in 1839
and also including the development of nitrated cellulose (celluloid) in 1868.
It was not until after the tum of the century that the first commercially
successful fully synthetic polymer was produced. This was Bakelite made
from phenol and formaldehyde by Leo Baekeland in 1909. Before the end
of the 1920s a large number of other synthetic polymers had been created,
notable examples being the development of polyvinyl chloride in 1927 and
urea formaldehyde in 1929. Today there are literally hundreds of synthetic
polymers commercially available with ranges of properties making them
suitable for applications in many industries including the electrical and
electronics industries. For every material commercially available, many
more have been synthesized, examined and discarded as of no present use
for various technical or economic reasons. The year of introduction
and typical electronics applications for various polymers are shown in
Table 1.1.
Much of the driving force behind the development of many modem
polymeric materials came from the electrical and electronics industries,
largely because of the numerous areas for application in electrical and
Table 1.1 Year of introduction and uses for various plastics
Year Material Application
1909 Phenol-formaldehyde Equipment cases

1927 Polyvinyl chloride Wire and cable insulation
1938 Polystyrene Capacitor dielectrics
1942 Polyethylene Capacitor dielectrics, wire
insulation
1947 Epoxides Adhesives, potting and
moulding compounds,
printed circuit boards
1957 Polypropylene Capacitor dielectrics, wire
insulation
1964 Polyimide Dielectrics, die attach
adhesives, printed circuit boards
1965 Polyxylylenes Insulation, conformal coatings
1975 Polymethyl pentene Microwave components, cable
dielectrics
1982 Polyether imide High reliability chip carriers,
moulded interconnect
devices (MIDs)
1984 Liquid crystal polymers Connectors, switches, fibre optics
1988 Polyetherketoneketone Injection moulded substrates
1990s Polypyrrole (ICP) Direct plate processes
'--_ _INT_R_O_D_U_C_T_IO_N_T_O_PO_L_y_M_E_R_S_A_ND
_ _T_H_E_I_R_P_R_O_P_E_R_TI_E_S_----III'-_3_-,
Table 1.2 Typical applications for polymers in the electronics and electrical
industries
Integrated circuits, Transfer moulding compounds, injection
transistors, diodes and moulding compounds, casting, potting,
other discrete devices dip and powder coating compounds, die
attach adhesives, photoresists, intermetal
dielectrics, junction coatings.
Wires and cables Sleevings, coatings, varnishes.
Connectors Transfer moulding, injection moulding,
compression moulding compounds.
Hybrids Conductive and non-conductive
adhesives, sealants, conformal
coatings.
Transformers, coils, Transfer moulding compounds, coatings,
bushings potting compounds, coil impregnants,
wire insulation.
Printed circuit boards Laminates, conformal coatings, solder
masks, masking tapes, component
attachment adhesives, vibration
dampers, photoresists and direct plate processes.
Moulded interconnect devices.
electronic components. Typical applications for polymers in the electronics

and electrical industries are shown in Table 1.2.
The principal reasons for this popularity are that polymers are generally
inexpensive, readily shaped dielectric materials with easily controlled
physical, mechanical and electrical properties. A typical radio manufactured
50 years ago would almost certainly have had a case made from a dark
brown 'Bakelite' type phenolic resin and inside this would be components
covered in a variety of strong-smelling sticky waxes or bituminous materials.
Since then steady improvements in technology have paved the way for a
huge selection of materials to be manufactured that are used in electronics
applications unimaginable in the 1950s. Today, polymers are used through-
out all parts of the electronics industry from the manufacturing processes to
the final packaging as well as in the individual microcircuits themselves.
Some further applications for polymers in electronic and electrical compo-
nent manufacture are shown in Table 1.3.
Polymeric materials are used as the basis of photoresists for making
metallization patterns on printed circuit boards, and also on the individual
integrated circuit devices themselves. The circuit boards are typically made
of various glass-fibre or paper filled epoxides and phenolics, and are usually
coated with other polymeric materials such as photoresists and solder masks
to facilitate the final stages of board manufacture and subsequently to
protect the assembled board in service. One major recent innovation is the
use of intrinsically conducting polymers as the conductive species in so-
Table 1.3 Uses for polymers in electronics and suitable materials
Use Suitable materials
Transfer moulding Epoxides, silicones, phenolics, polyimides.

Injection moulding Polyethylene, polypropylene, polyphenylene
sulphide.
ABS, ABS/polycarbonate, polyetherimide.
Encapsulation/casting Epoxides, polyurethanes, silicones.
Adhesives Epoxides, polyimides, cyanoacrylates, polyesters,
polyurethanes.
Coatings Silicones, fluorocarbons, epoxides,
polyxylylenes, polyurethanes, polyimides.
Films Polyesters, polypropylene, polystyrene,
polyimides.
Sealants Silicones, polysulphides, polyurethanes,
epoxide-polyamides, fluoro-silicones.
Substrates Epoxides, polyimides, cyanate esters,
engineering thermoplastics.
Photoresists Epoxides, novolacs, butadienes, acrylates.
called direct plate processes which enable electroplating of through holes in

multilayer printed circuit boards. The devices that are mounted on the
completed printed circuit boards may have been manufactured using
polymeric photoresists or have polymers such as polypropylene and
polyester films in capacitors or epoxide resins in integrated circuits and
transistors. The completed boards containing various devices are often then
coated in another protective polymer if a harsh service environment is likely
to be encountered.
Finally, electrical connections are made with wires coated in one of
several polymers and the finished circuitry is often housed in an attractive
case. Polymers can thus be seen to play an important role throughout all
parts of the electronics and electrical industries' manufacturing process from
the initial fabrication of devices to their final packaging.
1.2 CHEMISTRY OF POLYMERS
Polymers are different from the majority of simple inorganic and organic
molecules commonly encountered in that they typically have very large
molecules with molecular weights sometimes exceeding one million. Even
though these molecules are big, they can be defined by the basic repeat unit
that forms the polymer chain. Many of the overall properties of a particular
type of polymer will be a direct result of the individual atoms and the way
they are arranged in the repeat unit. One of the most important atoms in
~_____________C_H
__EM
__IS_T_R_Y_O_F __L_Y_M_E_R_S______________~I
__PO I 5
polymer chemistry and indeed in all organic chemistry is the carbon atom.
In polymer chemistry carbon is the atom that forms the basis of the main
structural chains found in most polymer molecules. Carbon has a valency of
four, which simply means that it has four sites at which it can combine with
other elements. If a single atom of carbon combines with four atoms of
hydrogen the gas methane is formed:
H
I
H-C-H
I
H
Carbon can combine with many other elements besides hydrogen and
importantly can also form bonds with itself. Examples of carbon atoms
combined with other carbon atoms and hydrogen atoms are the alkanes,
such as ethane and propane, where two and three carbon atoms are joined
together, respectively, and the rest of the unoccupied sites are used to
combine with hydrogen atoms:
H H H H H
I I I I I
H-C-C-H H-C-C-C-H
I I I I I
H H H H H
Propane (C3HS)
One of the key features of carbon which can ultimately lead to the
formation of polymers is its ability to form multiple bonds with itself. For
example, in the molecule ethylene (C2H 4) there are not enough hydrogen
atoms to occupy all of the available bonding sites and so the carbon atoms
form a double bond between themselves
These double bonds are very reactive and under the right conditions
ethylene molecules can polymerize in a chain reaction to form a long linear
molecule of ethylene:
-
H H
I I
n C-C
I I
H H n
Ethylene Polyethylene
Carbon also has the capability of forming ring structures containing
various numbers of carbon atoms; the simplest molecule containing six
carbon atoms in a ring structure is benzene:
For simplicity, the benzene molecule is drawn as a hexagon with a circle

representing the double bonds between the carbon atoms:
If one of the hydrogen atoms of an ethylene molecule is replaced by a

benzene ring the compound styrene is formed. Styrene can also be
polymerized by reacting the carbon--carbon double bond of the ethylene
part of the molecule to give polystyrene:
CHEMISTRY OF POLYMERS II 7
H H
I I
C-C
©
I
H n
Styrene Polystyrene
In addition to the substitution of one of the hydrogen atoms of ethylene

with a benzene ring there are several other substituents that can be used and
these lead to the formation of various well-known polymers:
Substituent Resulting polymer

-H Polyethylene
-CH 3 Polypropylene
-CI Polyvinyl chloride
-CH 2-CH 3 Polybutylene
-OH Polyvinyl alcohol
-C=N Polyacrylonitrile
-OOC-CH3 Polyvinyl acetate
These are known as polymers derived from vinyl monomers and the word
vinyl refers to an ethylene molecule with one of its hydrogen atoms replaced
with another atom or molecule. There is no reason why only one of the four
hydrogen atoms can be replaced and it is quite normal to replace more than
one of these atoms. When two atoms are replaced the resultant polymers are
said to be derived from vinylidene monomers, where vinylidene refers to an
ethylene molecule with two of its hydrogen atoms replaced with other atoms
or molecules. When two hydrogen atoms are replaced they are both from
the same carbon atom of the ethylene molecule. Some examples of linear
polymers based on vinylidene monomers are shown below with their
substituents.
Substituent A Substituent B Resulting polymer

-CI -CI Polyvinylidene chloride
-F -F Polyvinylidene fluoride
8 I I INTRODUCfION TO POLYMERS FOR ELECfRONIC APPLICATIONS
© Poly a. methyl styrene
-C-O-CH3 Poly methyl methacrylate

II
o
One further group of polymers based on ethene is possible and these have all
four hydrogen atoms of the ethylene molecule replaced. When the
substituent is fluorine the resultant polymer is polytetrafiuoroethylene;
alternatively, the hydrogen atoms may be replaced by three fluorine atoms
and one chlorine atom in which case the resultant polymer is polychlorotri-
ftuoroethylene.
F F
I I
C-C
I I
F CI
n
The above examples have been based upon ethylene and its derivative
monomers, all of which have led to the formation of polymer backbones
containing chains of linked carbon atoms. Carbon may join with other
atoms and molecules such that they can also be incorporated into the
polymer backbone. The previous examples have all been formed by the
addition polymerization process in which carbon-carbon double bonds have
been changed to single bonds in order that further carbon atoms could join
together. In many of the polymers containing different atoms in their
backbones polymerization may have occurred by another means such as
condensation polymerization. Typical examples of linear polymers contain-
ing other atoms in addition to carbon in their backbones are shown below:
Structural unit Polymer
to-st Polyphenylene sulphide
1<0>-1-<0)-01 Polyether sulphone

L -_ _IM_P_O_R_T_A_NT_E_L_E_cr_R_IC_A_L_P_R_O_PE_R_T_I_ES_O_F_PO_L_YM_E_R_S_ _ -----.JI I 9
toc-{5\-c-0-~_1-of.
.II~II
0
H1'rH
n
Polyethylene terephthalate
Polycarbonate
Although carbon has the ability to form very large long chain molecules it
is not completely unique in this characteristic. Nitrogen and oxygen can also
form long chain molecules with carbon atoms. Sulphur can be incorporated
either as an individual sulphur atom as in polyphenylene sulphide or it may
form short chains of sulphur atoms. Perhaps the main examples of long
chain polymers not requiring carbon atoms to form their backbones are the
silicones. In these materials the main chain is composed of alternating
silicon and oxygen atoms;
R R R
I I I
-Si-O-Si-O-Si-O-
I I I
R R R
These materials are covered in detail in Chapter 2.
1.3 IMPORTANT ELECTRICAL PROPERTIES OF POLYMERS
One of the main reasons why polymers have become so widely used in
electronics and electrical applications is that they are good dielectric
materials with readily controllable electrical properties. However, the fact
that polymers are good insulators does not mean that they are inert in an
electrical field and the intrinsic properties of a material can usually be related
to performance under specific test conditions. The electrical properties that
have to be considered when selecting a material include dielectric constant,
10 I I INTRODUCTION TO POLYMERS FOR ELECTRONIC APPLICATIONS I
volume resistivity, surface resistivity, dissipation, power and loss factors, arc
resistance and dielectric strength. When selecting a polymer for a specific
application the variation of these properties with changes in the likely service
environment has to be taken into account since many of them are
temperature, frequency, voltage and environmentally variable.
Most polymers serve as electrical insulators and may be required to
operate in conditions of varying voltage with both direct current and
alternating current at frequencies up to and above the GHz region. The
voltage a polymer is exposed to may be as little as a few microvolts in
communications equipment or up to several million volts in power
distribution systems. Similarly, currents can vary from a few picoamps to
many thousands of amps.
All of these variations may be encountered over a wide range of
temperatures, humidities and operating environments. The selection of a
material capable of operating under such variable conditions is obviously
important and thus an understanding of the electrical properties of polymers
and how they vary under these conditions is essential. Some of the more
important electrical properties are now discussed.
1.3.1 Resistance and Resistivity

Most polymers, unless purposely modified, are excellent insulators having
very high resistivities and conduct little electrical current. The insulation
resistance of a material is the ratio of the applied voltage to the total current
passing between two electrodes contacting the material. This resistance is
measured in ohms and is directly proportional to the length and inversely
proportional to the area of the specimen according to the equation
R = pl/A
where R = insulation resistance (Q), I = length (m), A = area (m 2),
p = specific resistivity (Q m).
In order to compare different materials, it is usually more convenient to
compare their resistivities because these values reduce resistance measure-
ments to a common denominator. Volume resistivity is the ohmic resistance
of a cube of dielectric material with sides of length 1 cm or 1 m, and is
expressed in Q cm or Q m, respectively.
All materials may be classified by their resistivities and they range from
the metals which are extremely good conductors to the polymers which are
very good insulators. Between these two extremes are the semiconductors
such as germanium, silicon and gallium arsenide. Most materials can thus be
conveniently placed into one of three groups: those that are good
conductors, those that are good insulators and those in between which
may be semiconductors. The resistivities of a number of materials are given
in Table 1.4. Polymers generally have resistivities of 1012 Q cm or greater
IMPORTANT ELECTRICAL PROPERTIES OF POLYMERS
II 11
Table 1.4 Comparative electrical resistivities of materials
Resistivity Material Classification

(nem)
1018 Polytetratluoroethylene
1017 Polystyrene, polypropylene
1016 Polyethylene, silicone rubber
10 15 Amine-cured epoxides
10 14 Diamond
1013 Polyamides Insulators
1012
1011
1010 Glass
109
108 Silver bromide
107
106
105
104 Silicon Semiconductors
103
102 Germanium
101
100
10-1
10-2 Quinolinium salts
10-3
10-4 Bismuth, mercury, graphite Conductors
10-5 Polypyrrole and polythiophene
10-6 Silver, copper
10-7
and some fluorinated polymers have resistivities in excess of 1018 n em. It

should be noted, however, that intrinsically conducting polymers such as
polyaniline and polypyrrole have been the subject of much study and
development over the last decade or so and it is now possible to produce
these materials with conductivities approaching those of the metals.
Various factors influence the resistivity of a polymer and these have to be
taken into account when formulating or selecting materials for use in
electronics. The chemical structure of the polymer itself will play an
important role in determining the resistivity, as will the concentration of any
impurities remaining in the material such as by-products of manufacture.
The addition of flexibilizing and plasticizing agents is also known to reduce
the resistiv~ty of plastics and the degree of cure or crosslinking density of
thermosetting materials must also be considered.
Resistivity varies with temperature and, in an opposite manner to metals,
the resistivity of polymers decreases with temperature. There is thus the
possibility that a material that has adequate insulative properties at room
temperature may be too conducting at elevated temperatures. The temper-
ature dependence of resistivity is given by the equation
P = Po exp (JE/2kT)
where p = resistivity at temperature T, Po = limiting low temperature
resistivity, k = Boltzmann's constant, I1E = energy, T = absolute tem-
perature.
Other factors influencing the resistivity of a polymer include voltage,
frequency, pressure and the conditioning of the sample. In particular,
environmental conditions are very important since relative humidity
changes alter the resistivity. If a polymer absorbs a significant amount of
moisture, the resistivity may drop to an unacceptably low value. Whilst this
increase in conductivity is generally due to the direct presence of sorbed
moisture within the polymer matrix and is reversible if the material is dried,
some polymers may actually be degraded by the presence of moisture and
high potential gradients. One example of this behaviour can occur with the
polyester materials which, when exposed to high humidities in the presence
of an electric field, may be hydrolysed to the acid and alcohol constituents
from which they were made. In the presence of moisture these then form a
conductive solution which can lead to corrosion or short-circuiting. The
surface resistivities of plastics are also important because moisture and
contaminants affect surface resistivity more than volume resistivity.
Large mOUldings may take several weeks or months to register any
changes in volume resistivity due to varying humidity conditions, but under
the same humidity conditions or in contaminated environments the surface
resistivity may change almost immediately. The surface resistivity of a
material is the ratio of the potential gradient parallel to the current along its
surface to the current per unit width of surface and is numerically equal to
the surface resistance between two electrodes forming opposite sides of a
square. The size of the square is immaterial and the units are a/square. It is
measured as the resistance when a direct voltage is applied between the
surface mounted electrodes of unit width and unit spacing (see IEC93 and
ASTM D257).
For some special applications conductivity may be more important than
resistivity, as is the case with conductive adhesives. The conductance of a
polymer is the reciprocal of its resistance and likewise its conductivity is the
reciprocal of its resistivity. The units of specific conductivity are mhos per
centimetre or preferably Siemens per metre. As most polymers are normally
good insulators, conductivity is often imparted by the incorporation of
finely divided metals such as silver, gold and copper. Conductive polymers
find important uses as electromagnetic and radio frequency shielding, as
well as die attach materials for semiconductors. The newly emerging
intrinsically conducting polymers offer conductivity without the need for the
addition of metallic fillers. These are already being used commercially in
'-----_ _IM_PO_R_T_ANT
__E_L_E_CT_RI_C_A_L_PR_O_P_E_R_TI_E_S_O_F_P_O_L_y_M_E_R_S_ _ ----'1 I 13
electronics applications such as the direct plate processes that form part of
printed circuit board manufacturing.
1.3.2 Relative Permitivity (Dielectric Constant)

IEC 250 states that the relative permittivity of an insulating material is the
ratio of capacitance of a capacitor, in which the space between and around
the electrodes is entirely and exclusively filled with the insulating material in
question, to the capacitance of the same configuration of electrodes in
vacuum.
K= Cm/Cv
where K = relative permitivity, C m= capacitance with material m as the
dielectric and Cv = capacitance with a vacuum as the dielectric.
The relative permittivities of materials vary from just above one to several
thousands for some inorganic materials, and typical examples are shown in
Table 1.5.
The relative permittivities of materials are due to their electronic
polarizability and compounds with polar groups in their molecular structure
have large dielectric constants because their dipoles are able to orient in an
electric field and have large dipole moments. Polar polymers absorb
moisture from the atmosphere and for these reasons non-polar polymers are
normally preferred over polar polymers for insulative applications. For
general insulating or protective coatings dielectric constants up to 8 may be
acceptable but the maximum relative permittivity specified by MIL-I-16923
for materials used in electronic and electrical assemblies is 4.5 at 1 kHz.
Table 1.5 Relative permittivities of various materials at 25°C
Material Relative permittivities
Air 1.00053
Fluoropolymers 1.9--2.6
Polypropylene 2.2-2.3
Polystyrene 2.45-2.65
Benzocyclobutenes 2.6-2.8
Epoxides 2.8-5.5
Polyetherimide (Ultem) 3.15
Polyimide (Pyralin) 3.50
Epoxy-glass laminates 4.4-5.2
Phenolics 5.0-6.5
Ceramic filled PTFE 6.0--10.2
Nitrobenzene 34.9
Water 79.5
Lead titanate 200
Lead zirconate titanate (PZT) 3400
14 I I INTRODUCTION TO POLYMERS FOR ELECI'RONIC APPLICATIONS
Relative permittivities of polymers vary with frequency and can either
increase or decrease depending upon molecular structure, and the presence
of any additives or fillers. In order to be of use in electrical and electronic
applications a polymer should have reasonably constant dielectric properties
over a broad range of temperatures, frequencies and humidities. It is for
these reasons that materials such as polyethylene, polystyrene and the
fluorocarbons find such extensive usage as electrical insulators.
1.3.3 Dissipation, Power and Loss Factors

The dissipation factor (D) is the ratio of the current of the resistive
component (Ir) to the current of the capacitive component (Ie) and is also
equal to the tangent of the dielectric loss angle 0, i.e.
D = Ir/le = tan 0
Typical values of the dissipation factor vary from 0.1 to less than 0.0005.
The power factor (PF) is the ratio of power dissipated to the product of
the effective power output (volts x amps) and is a measure of the dielectric
loss in the insulating plastic (which is effectively acting as a capacitor). The
power factor and dissipation factor are related by the equation
PF
D = ---,=;===
J[I-(PF)2]
Power factors for most plastics are fairly low and so the (pF)2 term in the
equation can be ignored, making the power factor approximately equal to
the dissipation factor. These two terms are often used interchangeably for
dielectric materials.
The loss factor is a measure of the energy absorption of a material and is
given by the product of the dielectric constant and the power factor, i.e.
Loss factor ~ Ktano ~ KD
It is desirable for all of the above parameters to have as low values as
possible and this is particularly important in the case of high-speed, high-
frequency devices and circuitry working at frequencies up to 100 GHz. Low
values are indicative of minimum conversion of electrical energy to heat and
little overall power loss in the system. These factors are again generally
functions of frequency, temperature, humidity and the purity of the
polymer. Both relative permittivity and dissipation factor are measured
using the same test equipment and the test method is detailed in IEC250.
1.3.4 Arc Resistance

The arc resistance of a material is the time (in seconds) that its surface may
be exposed to an arc before electrical breakdown occurs. A high-voltage,
IMPORTANT ELECTRICAL PROPERTIES OF POLYMERS II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~
15
low-current arc is used to simulate the conditions likely to be found in

service. Standard test procedures used in the United States are UL746A and
ASTM-D-495, whilst in Europe the test is to DIN 53484 VDE 0303. A
number of arc testers are commercially available that comply with these
specifications. The specimen to be examined is placed between the electrodes
and an arc generated at specified intervals and currents.
Failure due to arcing can occur in three different ways:
1. By the formation of a thin conductive line between the electrodes known
as tracking.
2. By the formation of a conductive path of carbonaceous material due to
surface heating.
3. By self-ignition of the material without the formation of any visible
conductive path.
The arc resistance of a plastic is very dependent upon its molecular
structure and the presence and amount of any additives in the formulation.
Fillers have a significant effect upon the arc resistance and materials such as
alumina and silica can give considerable improvements. Arc resistance is
also very dependent on the condition of the surface and is easily reduced by
moisture, salts or even grease from skin contact.
1.3.5 Comparative Tracking Index (CTI)

The tracking index is the relative resistance of insulating materials to
tracking when the surface is exposed under electrical stress to water
containing ionic contaminants. This is an important test because it evaluates
the safety of actual components with insulation between live parts.
Insulating materials must obviously be resistant to tracking and the en
is defined as the maximum voltage at which no failure occurs when
contaminant-containing water e.g. a 0.1 % solution of ammonium chloride
in distilled water, is applied to the surface. It is desirable to have as high a
en as possible and materials meeting the en requirements at 600 V are
known as 'high tracking' resins. The test itself is somewhat complex and is
detailed in lEe 112 and ASTM D3638. en values for polymers are
influenced by the presence of additives used in their formulation. They can
be lowered by pigments, especially carbon blacks, flame retardants and glass
fibres and can be raised by the addition of minerals such as titania.
1.3.6 Dielectric Strength and Breakdown Voltage

The dielectric strength of a polymer is a measure of its ability to withstand
voltage without breakdown or the passage of considerable amounts of
current. It is defined as the minimum voltage at or below which no
breakdown occurs. Rather similarly, the breakdown voltage is the voltage
16 I I INTRODUCTION TO POLYMERS FOR ELECTRONIC APPLICATIONS I
above which actual failure occurs and the two items are often used
interchangeably.
The dielectric strength of a material is, like the properties reported above,
very dependent upon molecular structure, the level of impurities and the
relative humidity to which the sample has been exposed. Consequently, the
dielectric strength of a material should be measured under carefully specified
conditions. There are several standardized procedures for measuring
dielectric strength; in the United States ASTM-D-149 is commonly used
whilst the ISO and DIN standards are IEC 243 and 53981 VDE 0303
respectively.
1.4 IMPORTANT MECHANICAL, CHEMICAL AND PHYSICAL

PROPERTIES OF POLYMERS
In addition to having excellent electrical properties for electronic and

electrical applications, polymers also have desirable mechanical, chemical
and physical properties that enhance their capabilities in these fields.
Polymers are available with very high purity and can be easily moulded to
form rigid protective packages for delicate microcircuits, whilst others are
available that are extremely flexible making them useful as wire coatings and
sleevings. These properties are determined largely by the chemical compo-
sition and subsequent formulation of the given material but the way in
which a plastic is manufactured and used sometimes also has a bearing on
the final properties. In this section some of the more important mechanical,
chemical and physical properties of polymers are discussed.
1.4.1 Mechanical Properties

Unlike many metals, polymers are not perfectly elastic, possessing charac-
teristics of both elastic and viscous materials. Consequently, they are often
regarded as being viscoelastic. In order to select the best material for a given
application it is usually important to know how its properties vary with
time, temperature and environmental changes. A number of the more
important physical capabilities of a polymer can be defined by examining the
following properties: elasticity, stiffness, strength, toughness and resilience.
The elasticity of a polymer is its ability to carry stress without suffering a
permanent deformation. The stiffness of a material is a measure of its ability
to carry a stress without changing its dimensions,. and strength determines
its ability to carry a dead load. Toughness represents the ability to absorb
energy and undergo permanent changes without rupturing whilst resilience
is a measure of the work required to deform a material to its elastic limit and
determines the energy that it can absorb without undergoing a permanent
deformation.
IIMPORTANT MECHANICAL, CHEMICAL AND PHYSICAL PROPERTIES I 17
All of these properties can be determined from the stress/strain charac-

teristics of a plastic by plotting its stress/strain curve. Stress is defined as the
intensity (measured per unit area) of the internal distributed forces, or
components of force, which resist a change in the form of a body. Strain is
the change per unit length in a linear dimension of a body accompanying a
stress and is measured in metres per metre or in percent. When under
tension or compression, strain is measured along the dimension under
consideration. Many plastics have stress/strain characteristics that can be
represented by a curve with the general shape shown in Fig. 1.1.
The slope of the curve where stress and strain are almost proportional
represents a measure of the material's stiffness. In this region the ratio of
stress to strain is known as the modulus of elasticity or Young's modulus.
At the first bend in the curve (1) the stress value represents the yield point
and is a measure of the strength of the material and its resistance to
permanent deformation. Before the yield point is reached strains are largely
recoverable and are a measure of elastic deformation. From the yield point
(1) to the break point (2) the strains are no longer immediately recoverable
and they determine the degree of plastic deformation. The area under the
curve represents the work required to fracture the polymer sample and is an
approximate measure of its toughness. The resilience of a material can be
determined from the area under the curve up to the yield point. The various
shapes of stress/strain curve allow polymers to be classified according to five
main types of behaviour:
1. Soft and weak polymers having low moduli of elasticity, yield points and
low elongations at break.
2. Hard and brittle polymers having high moduli of elasticity, no well-
defined yield points and low strain at break.
Strain
Fig. 1.1. A typical stress/strain curve for a polymer.

18 I I INTRODUCfION TO POLYMERS FOR ELECfRONIC APPLICATIONS
3. Soft, tough polymers having low moduli of elasticity, low yield points
and high strain at break.
4. Hard, strong polymers having high moduli of elasticity and yield points
with moderate stress at break.
S. Hard, tough polymers having high moduli of elasticity and yield points
and also high stress and strain at break.
In addition to mechanical failure under conditions of high stress, failure can

also occur at relatively low stress levels under some conditions and this must
again be taken into account when selecting materials for a specific
application. The failure of a polymer at relatively low stress levels can
occur under the following circumstances:
• fatigue
• stress relaxation
• creep
• chemical exposure
Fatigue is the term used to describe the behaviour of a polymer under
repeated cycles of stress or strain which cause a deterioration of the material
and result in progressive fracture. Fatigue is dependent upon frequency,
amplitude, temperature, stress and mode of stressing.
Stress relaxation occurs in a polymer when it has been deformed to a
predetermined shape and then restrained in that shape so that total
deformation neither increases nor decreases. Under these conditions the
phenomenon of stress relaxation can then occur and the initial stress in the
plastic gradually decreases. It can be defined as the time-dependent change
in stress which results from the application of a constant total strain to the
material at constant temperature. Creep is defined as the time-dependent
part of the strain which results from the application of a constant stress to a
plastic. By comparing the definitions of creep and stress relaxation it can be
seen that the two phenomena are closely related. Creep occurs when a
constant stress is applied for an extended period whilst stress relaxation
occurs during long-term exposure to a constant strain.
The loss of mechanical properties during exposure of a polymer to certain
environments may also be important in electrical and electronic applica-
tions. Whilst some chemicals may have little effect upon the strength of an
unstressed part there may be a totally different behaviour with the same part
under stressed conditions. Contact with water, acids, alkalis and solvents
can cause a number of undesirable effects in a polymer such as swelling,
shrinkage, distortion, crazing, cracking, softening, weight loss or gain, and
loss of strength or stiffness. All of these factors must be taken into account
when selecting a material for use in electrical and electronic components,
particularly where mechanical and physical properties are likely to be
important.
A number of other mechanical properties are also often considered

important. The hardness, abrasion resistance and machinability may need to
be considered where some reworking of a compound is needed or where
machining into a particular shape is required. Depending upon the final
usage of the material the tensile, shear and compressive strengths of a
polymer can be important. Such properties would need to be considered
where the polymer was used as a structural component or where it is likely
to be exposed to forces that could cause mechanical failure. The flexibility of
a polymer and, more particularly, maintenance of flexibility over a likely
operating temperature range need to be characterized since wire coatings
must stay flexible at low temperatures and junction coatings used to protect
semiconductors must not become rigid if the equipment in which they are
used happens to be exposed to low temperatures. Shrinkage can be
important when attempting to mould parts to strict tolerances since
thermosetting materials experience shrinkage during moulding because of
the curing reaction which takes place. Another property that is important
with plastic moulding compounds is viscosity. This must be controlled so
that moulds fill properly yet the resinous components do not bleed out of
the mould, and, in the case of wire-bonded semiconductors, so that wire
bonds are not swept off contacts causing shorting or open circuits.
1.4.2 Chemical Properties

The resistance of a polymer to various chemicals is largely determined by its
molecular composition and varies widely from type to type. Some polymers
such as polytetrafluoroethylene are inert even in aggressive chemicals and
solvents whilst others are easily decomposed in the mildest solvents or are
soluble in water. Although exceptions are frequently discovered, it is quite
possible to make predictions of a material's likely behaviour in various
environments by studying its molecular structure. Polymers that have a
backbone made up entirely of carbon-carbon bonds with hydrophobic
groups attached usually have good oxidation resistance and low moisture
absorption. Low moisture sorption obviously helps to minimize attack by
aggressive aqueous solutions. If a degree of double bonding (unsaturation)
is introduced into the chain the oxidation resistance will tend to decrease
although the water absorption characteristics may change only slightly. A
typical example is butyl rubber that contains few double bonds. This is
much more resistant to oxidation than natural rubber which has a larger
number of double bonds in the chain.
Where the polymer backbone contains groups such as the ester or amide
linkages found in polyesters and polyamides, the degree of moisture
sorption is usually high and they are readily attacked by chemicals with
hydrolysing capabilities. They are thus rather unstable in both moderately
strong acids and alkalis. The absolute structure of the material concerned
will play a part in determining the actual degree of hydrolysis that occurs
and the moisture sorption characteristics will also be important. If the
molecular structure dictates a low moisture permeability, transport of
aggressive solutions into the bulk of the material may be retarded with
attack predominantly limited to the material surface.
The introduction of hydrophilic groups onto the main chain of the
polymer results in the enhanced sensitivity of the material to both moisture
and aqueous solutions. The classic example of such a material is polyvinyl
alcohol which is soluble in both water and some other polar solvents.
Interestingly, however, polyvinyl alcohol is not affected by hydrophobic
solvents such as the hydrocarbons. The presence of a hydroxyl group on
every second carbon atom in the main chain of polyvinyl alcohol not only
provides high polarity to the molecule but also allows it to exhibit strong
adhesion to certain substrates. In general the introduction of polar groups
both in the main chain and in the side groups leads to very high surface
energies and surface tensions resulting in good adhesive properties. The
amide linkage in polyamides, whilst being largely responsible for their
moisture sorption, also leads to powerful hydrogen bonding and their good
adhesive properties.
The molecular weight of a polymer molecule also has a significant effect
in determining the chemical properties. A typical example is a polymer's
solubility in a solvent which is usually inversely proportional to its
molecular weight. The swelling, absorption and permeability of polymers to
gases and liquids is also related to molecular weight although the
relationship is not clearly defined and it has been stated that molecular
weight does not affect diffusion and permeation by liquids and gases. The
general chemical reactivity of polymers is known to decrease with increasing
molecular weight. This is thought to be due to the reactivity of the end
groups of the polymer molecule which are usually the most reactive parts of
the whole molecule. Since the number of end groups is inversely
proportional to the number average molecular weight, it is expected that
polymer reactivity will decrease with increasing molecular weight. As ageing
processes are chemical degradation reactions that occur in polymers, their
resistance to this type of deterioration should also be related to molecular
weight. The ageing of polymers by oxygen, ozone, moisture and ultra-violet
light is found to decrease with increasing molecular weight and again this is
because the number of reactive end groups is reduced. The lower mobility
of the higher molecular weight molecules also reduces reactivity and
degradation of very high molecular weight polymers may only degrade
them to medium molecular weight polymers with almost equivalent
properties.
The presence of impurities or monomeric additives in a polymer also has
an important bearing upon its final properties and the applications for
which it will be suitable. No organic chemical reactions give absolutely
100% yields of the desired products and polymerization reactions are no

exception. In addition to by-products, residual monomers may be present
which can degrade the mechanical and thermal properties of the plastic.
Residual solvents can cause softening and degradation of electrical
properties in polymers, particularly where coatings from solution are being
applied or where polymerization is carried out in solution. Moisture and
other small molecules can be generated during condensation polymeriza-
tions or they can be absorbed from unsuitable storage environments. The
presence of moisture, whilst not only causing degraded mechanical and
electrical properties, can lead to difficulties in moulding a polymer and may
even be the source of hydrolytic instability. Contamination can also occur in
the form of ions which are residual impurities from the synthesis of the
polymer's starting materials. Chloride and sodium ions are sometimes found
in epoxide resins as by-products of the synthesis and these can lead to
malfunctioning of epoxide encapsulated semiconductors and early corrosion
of certain conductors such as aluminium. In addition, ions can lead to
reductions in the insulative properties of a polymer. Catalysts used to
promote a polymerization reaction may leave residues that have a
deleterious effect upon thermal stability and electrical properties of a
polymer. Effective post-cures are required with epoxide moulding com-
pounds in order to decompose these catalyst residues and to improve the
bulk resistivity of the cured materials.
In order to evaluate a material for its chemical stability it is necessary to
test it under conditions which as nearly as possible replicate those likely to
be encountered in service. One fairly simple test that can be applied to most
plastic materials as part of an initial screening process, involves immersing
moulded discs or bars for seven days in a variety of liquids at room
temperature. This test uses a number of acids, alkalis and salt solutions of
varying concentrations and a series of solvents with a range of polarities. At
the end of the test, the samples are examined for changes in dimensions,
weight, colour and other physical properties.
Before selecting a polymer for an electrical or electronic application its
chemical properties should be considered just as the electrical, mechanical
and physical properties are taken into account. The final operating
environment and conditions of service will often dictate the type of material
to be used and the required purity.
1.4.3 Physical Properties

A number of other important properties have to be considered when
selecting a polymer for electronic and electrical usage. There may be
restrictions on the amount of material that can be used or perhaps it must
have a certain degree of thermal conductivity to impart heat dissipation to a
circuit. Some of these other physical properties are now briefly discussed.
Polymers have distinct advantages over the majority of other materials in
terms of weight of material used. Most have densities that are considerably
lower than the metals they often replace in structural applications with
values normally between 0.9 and 2.0 (a good number lie between 1.0 and
1.4). Density considerations become important in applications where overall
weight must be minimized such as in aerospace electronics. Since the
approval of a polymer used is normally based on volume rather than weight
and yet the polymer is sold by weight, a reduction in density of the material
will also allow more parts to be made per unit weight and this factor should
be considered where material costs must be carefully controlled.
There are several thermal properties of a polymer that are considered
important, such as its thermal expansion coefficient, thermal conductivity,
thermal stability, melting point and glass transition temperature. The
thermal expansion coefficient of a polymer needs to be taken into account
when it is in intimate contact with another material with a different thermal
expansion coefficient. Polymers have much higher thermal expansion
coefficients than most other materials especially metals, ceramics and the
silicon substrates found in electrical and electronic components. The
thermal expansion coefficient depends partly upon molecular weight and
this is largely because the polymer end groups are one of the major
contributing factors. Increasing the effective molecular weight by crosslink-
ing also assists in reducing the expansion coefficient of a polymer. Where
lower thermal expansion coefficients are required, fillers and fibres are often
added to reduce them as is the case with most moulding compounds and
printed circuit board laminates.
The thermal conductivities of polymers are much lower than those of
other materials and because of this they often find use as thermal insulators.
The thermal conductivity coefficient is the time rate of heat flow under
steady-state conditions through a unit area and unit thickness per unit
temperature gradient. Polymers used with electrical and electronic assem-
blies usually require high thermal conductivities because of the need to
dissipate heat from circuitry. For many applications the polymers are
formulated with high thermal conductivity fillers such as crystalline silica or
alumina. Other high thermal conductivity electrically insulating inorganic
materials include beryllia (BeD), aluminium nitride (AIN), boron nitride
(BN) and silicon carbide (SiC). The use of diamond in high thermal
conductivity applications has also progressed significantly in recent years.
Where possible the thermal conductivity of, for example, an adhesive layer,
can also be improved by using as thin a coating as possible. Thermal
management issues are becoming increasingly important as device, e.g.
microprocessor, operating speeds and power consumptions increase. It is
already common practice to employ chip mounted cooling fans and the
predictions are that thermal dissipations will continue to grow; there is
clearly an opportunity for new high thermal conductivity materials.
IIMPORTANT MECHANICAL, CHEMICAL AND PHYSICAL PROPERTIESi 23
The thermal stability or heat resistance of polymers is obviously of

particular importance when products have to withstand exposure to heat
under a wide variety of service conditions. As polymers are organic
materials they are susceptible to the undesirable reactions of these materials
such as thermal degradation, oxidation and hydrolysis. Thermal stability is
another parameter that is directly related to molecular weight and the
polymer's molecular structure. Much of the instability at high temperatures
is due to the nature of the end groups of the polymer molecules, which are
sites for reactivity. The thermal stability of a polymer can be enhanced by
reducing the number of reactive impurities that can take part in thermal
degradation. Crosslinking a polymer increases its molecular weight and
decreases its volatility leading to increased thermal stability. Molecular
structure also plays a significant part in determining thermal stability and
the presence of aromatic and highly electronegative elements tends to
enhance both the thermal and the oxidative stability. The hydrogen atoms
of polyethylene can be replaced with electronegative fluorine atoms to give
the high thermal stability polymer polytetrafluoroethylene.
The melting point and/or the glass transition temperature (Tg) of a
polymer will also have an important part in the choice of materials for an
application. Both of these thermal characteristics play a large part in
determining many of the mechanical properties of a polymer. The glass
transition temperature of a material represents the point above which it
behaves as a viscous liquid or a rubber. Below the glass transition
temperature the polymer behaves as a hard, brittle, glass-like compound.
Silicone rubbers are examples of materials that have Tg values below room
temperature and Perspex is an example of a material that has a Tg above
room temperature. The Tg of a material is determined by its molecular
structure with factors such as flexibility, symmetry and the bulkiness of the
molecules playing a major part. Obviously, the melting point of a
thermoplastic polymer also determines the acceptable temperature range
over which it can be used and for thermoplastic materials will limit the
maximum service temperature of, for instance, coated wires. The glass
Table 1.6 Glass transition temperatures (Tg) and melting points (Tm) of some
common polymers
Polymer
Polyethylene -120 137

Polypropylene -18 176
Polystyrene 100 240
Polyethylene terephthalate 69 267
Polymethyl methacrylate 105 160
Polyvinyl chloride 87 212
FR4 epoxy laminate 130-140 n/a
transition temperatures and melting points of several thermoplastic mate-
rials are given in Table 1.6.
1.5 SUMMARY
This chapter has given a brief introduction to polymers, their fundamental

chemistries and the key properties that make them useful in electrical and
electronic applications. There are normally many other factors which have
to be taken into account when selecting polymeric materials for a specific
application. Quite often it is not possible to satisfy all application
requirements with one material and some form of compromise has to be
made. For further details of the properties of polymers for electronic
applications the reader is referred to Chapter 2 of the previous edition of
this book.
Silicone Materials for 2
Electronic Components and
Circuit Protection
JEAN-PAUL MOLLIE
Dow Corning SA, Seneife, Belgium
2.1 DEFINITION AND HISTORY
Silicones are synthetic polymers based on a molecular structure of

alternating silicon and oxygen atoms with organic groups also attached to
all or some of the silicon atoms. Their general formula is [Ra SiO(4--a)/21b
where a = I to 3 and b ~ 2. R represents an organic group.
Diagrammatically, their smallest unit structure can be represented by
where R J and R2 may be equal or dissimilar organic groups. Most

commonly these are methyl --{CH3) or phenyl --{C6 H s), but may also be
chemically reactive groups such as -CH=CH2 (vinyl) or -OH (hydroxy)
which can take part in further polymerization reactions.
This unit structure makes up the final silicone polymer by molecular chain
lengthening and crosslinking, for example:
26 1 1-1__S_I_L_IC_O_NE_M_A_T_E_R_IA_L_S_F_O_R_E_L_E_C_TR_O--,--NI_C_CO_M_PO_N_E_NT_S_------'
R R R R
1 1 1 1
-O--Si-O--Si-O--Si-O--Si-
1
R
1
I.
°I.
1
R
1
-Sl-O--Sl-O--
°
1 1
R
1
Physically, silicones are now available in a wide variety of physical forms

e.g. as fluids, greases, gels, elastomers of many kinds and hard resins. The
term 'silicone' was first derived by Professor Kipping and his co-researchers
of Nottingham University, England, at the beginning of the 20th century
under the mistaken belief that new silicon-based materials which they had
synthesized were chemically analogous to ketones based on carbon. 1
Although the term 'organopolysiloxane' in which the word siloxane defines
the -Si-O-Si- constituent is now considered to be a better chemical
description, the name 'silicone' has lived on and is now universally used to
describe organopolysiloxanes which are used for many industrial applica-
tions.
Although Kipping is recognized as the founder of silicone chemistry, a
period of 30 years elapsed before the industrial and development potential
of his work was realized. Coming Glass Works in the USA had by then
developed the first glass fibres, for which electrical insulation was foreseen as
an important end application. Until then only organic textile fabrics were
available, apart from asbestos, to make electrical insulating tapes, sheet and
laminates. The advent of glasscloth offered the prospect of a considerable
increase in thermal endurance, subject to the availability of new bonding
and impregnating resins which would also withstand high temperatures.
Work to achieve such polymers based on Kipping's original discoveries
began under Dr Frank Hyde at Coming Glass Works. As the associated
chemical technology expanded, Dow Chemical joined as a partner and in
1943 Dow Corning Corporation was established and the first commercial
production of silicones began. Today, silicones are manufactured at large-
scale and highly capital-intensive plants in the USA, Europe and Japan.
There are also several plants carrying out formulation and further
processing, although not basic manufacture.
Dow Coming Corporation is the global leader in silicone technology
supplying 38% of the global 1.1 to 1.5 million metric tonnes per year
siloxanes market. Europe accounts for just over 20% of the company's
worldwide sales, which in 1995 reached $2.5 billion. 2
The valuable physical properties of silicones described below have led to
applications in virtually all industries.
PHYSICAL PROPERTIES II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~ 27
2.2 PHYSICAL PROPERTIES
2.2.1 Thermal and Oxidative Stabilities

The most important characteristic of silicones is their resistance to thermal
and oxidative deterioration. This can be largely attributed to the high
average bond energy of the Si-O chemical bond at 452 kJ/mo1. 3 Although
the organic side groups impose temperature limitations, their own thermal
endurance is enhanced by the support of the siloxane (Si-O-Si) molecular
backbone. Excellent resistance to ultra-violet radiation, ozone, electrical
arcing and discharges are also corresponding characteristic features.
2.2.2 Stability in Physical and Dielectric Characteristics with Varying

Temperature
The Si-O-Si bond angle in a silicone polymer can vary between 1000 and
1800 and there is free rotation about these bonds. Such a polymer can adopt
a randomly coiled shape which responds easily to external forces unless
there are sufficient restraining crosslinks. Lightly crosslinked silicones, even
those of high molecular weight, are therefore quite elastic.
Silicones are generally non-polar in behaviour despite the strongly polar
Si-O bond. This is attributed to the organic side groups which form a
protective sheath preventing the Si ± 0 dipoles from approaching each other
closely. This can be seen from the molecular model of Fig. 2.1 which
Fig. 2.1. Model of silicone fluid molecule showing helical arrangement of polymer
chain with silicone atoms bonded to oxygen atoms and to outer organic groups.
28 II SILICONE MATERIALS FOR ELECTRONIC COMPONENTS
~----------------------------------------------------~
conveys a better idea of the molecular form than a planar illustration.

Because of this separation of the Si ± 0 dipoles, the intermolecular forces
between adjacent molecules, following an inverse square law, are also weak.
Many characteristics of silicones are due to this behaviour.
In organic polymers, as the temperature rises the strong attraction
between polymer chains diminishes and dependent properties such as
viscosity, elasticity, tensile strength, permittivity and dissipation factor may
change significantly. For silicones, intermolecular forces which are already
low do not change much as temperature rises or falls, so that physical and
dielectric characteristics of the polymers are also relatively stable. Two
characteristics of this kind are the relatively high compressibility of silicone
fluids and only a small change in their viscosities with temperature variation
when compared with mineral oils.4
Low and stable values of dissipation factor and permittivity under
varying temperatures and also varying frequency became apparent when
electronic applications for silicones were first developed over 40 years ago.
Von Hippel5 measured very stable values of dielectric characteristics for
silicone resin and silicone resin bonded glasscloth laminates at temperatures
up to 200°C and at frequencies from 100 Hz to 100 MHz.
A less favourable consequence of these weak intermolecular forces is that
silicone elastomers, for example, are physically weaker than many organic
rubbers. However, modem polymer and filler technology enables silicone
rubbers to be formulated with fully acceptable mechanical strength for
industrial uses which are very different from the early materials of 40 years
ago.
2.2.3 Surface Properties

The organic side groups in a silicone molecular structure account mainly for
characteristic surface properties. Surface tension at 20 mN/m (for methyl
silicone fluids) is low and characteristic of a completely organic polymer
surface. Such methyl silicones are highly water-repellent. Their low surface
tensions and insolubility in water make them valuable as anti-foam agents
and highly effective in breaking down aqueous foams. They also make
excellent release agents though by contrast, with reactive side groups
present, silicone adhesives can also be formulated.
2.2.4 Health and Environmental Aspects

Polydimethylsiloxanes have been extensively studied and have been found to
present only a low order of toxicity to human health and the environment.
Several studies even used very high concentrations, far higher than exposure
levels to be expected under normal circumstances. 6
Silicone polymers exhibit a low order of toxicity. In a few cases they are
supplied or applied in organic solvents, such as xylene, which require
P_R_O_D_U_CT
L -_ _ _ _ _ _ _ _ _ _ _ _ _ SI_L_IC_O_N_E_S______________~I
__I_O_N_O_F__ I 29
appropriate handling precautions. In certain other cases common curing
catalysts such as peroxides or organometallic salts are used and these
additives again require appropriate safe handling procedures prescribed for
such materials. In other respects, both when used as production materials by
industry and afterwards in service, silicone polymer pose few concerns.
2.2.5 Fire Resistance and Products of Combustion

Silicones are generally very fire resistant although this depends to some
extent on their formulation. Certain silicone elastomers used as encapsulants
and cable insulation have excellent values of limiting oxygen index (LOI) or
UL rating. A specially processed dimethyl silicone fluid, Dow Coming 561,
used as a transformer coolant is far more fire resistant than mineral oil.
When silicones do bum, a residual ash of silica remains. The heat of
combustion is less than for most other polymers, while smoke is also low in
density and relatively non-toxic, consisting mainly of carbon dioxide and
some carbon monoxide. 7 These attributes are increasingly important
nowadays with attention to more stringent fire regulations.
2.2.6 Chemical Purity and Low Water Absorption

Silicones normally contain very low levels of impurities such as mobile ions
and absorb very little water. As already noted, their surfaces are highly
water-repellent. On the other hand, their open molecular structure makes
them more permeable to water vapour than many other polymers. Taken
together, these characteristics mean that a silicone-coated substrate will be
well protected provided that it is not itself absorbent and that surface
contact at the interface is good.
Under these conditions, water vapour may pass relatively freely through
the silicone layer in either direction but is not absorbed and does not form a
moisture film at the interface. Harmful ionic constituents are not
transported to the surface so the protection provided is often superior to
that of other polymers which, although less permeable to water vapour, are
also more impure chemically.
2.3 PRODUCTION OF SILICONES
The most important method of production in use today begins with a

chemical reaction between methyl chloride and 'metallic' silicon at about
300°C, catalysed by copper. This produces a mixture of methyl chlorosilanes
which have the general formula Si(CH3)xCl4-x. Chlorosilanes have differing
boiling points. Unlike the final silicone product, they are highly flammable
as well as volatile and must therefore be separated by fractional distillation
in an inert atmosphere.
30 I IL--__SI_L_IC_O_N_E_M_A_T_E_R_IA_L_S_F_O_R_E_L_E_CT_R_O_NI_C_C_O_M_P_O_N_E_NT_S_ _----'
A silicone manufacturing plant is characterized by its tall distillation
columns.
Methyl chlorosilanes comprise by far the largest volume of silicone
precursors but phenylchlorosilanes are also important. One way in which
they can be produced is by reaction of chlorobenzene with silicon. Other
production processes involve the production of methyl or phenyl
chlorosilanes with reactive groups such as vinyl or hydrogen attached to
some silicon atoms. Thus a series of chlorosilane monomers is first produced
and then separated by distillation as precursors for conversion to useful
polymer products. The next stage is achieved by hydrolysis, in which the
chlorosilanes react with water to form compounds called silanols. Hydrogen
chloride is also formed and removed:
== SiCI + H20 -+ == SiOH + HCI
Chlorosilanes Silanols
Further reaction of silanols leads to silicone polymers

== SiOH+ == SiCI-+== Si-CI-+== Si-o-Si == +HCI
or Silicone
== SiOH+ == SiOH -+== Si-o-Si == +H 20

These equations describe in simplified form a complex production
technology that involves a series of processes to purify, stabilize and
polymerize the final silicone products which are ultimately available as
silicone fluids, gums and resins.
Further processing in which appropriate fillers, catalysts, pigments and
other additives are incorporated leads to typical products such as silicone
greases, elastomers and resin-based transfer moulding compounds. A broad
list of final silicone products is given in Table 2.1.
Most silicone fluids and silicone greases are used in the form in which they
are supplied and require no further polymerization or curing by the
customer. The other products listed, elastomer and resin-based materials,
usually require further curing in the course of extrusion, moulding,
encapsulating or similar processes. They are therefore formulated with
appropriate reactive chemical groups, as already described, which can be
activated by heat, atmospheric moisture or other means to produce the
desired end product.
Table 2.2 lists some of the most common curing reactions. In the first of
these, (a), the reaction of hydroxyl (OH) groups extends and crosslinks the
Si-O-Si chain and is characteristic of many silicone resins. Usually this
reaction is induced by heating the uncured resin which contains some Si-OH
groups, in the presence of an organo-metallic salt as a catalyst that is already
mixed with the resin as supplied. A small amount of moisture is liberated as
a by-product. In the second reaction, (b), alkoxy (RO) groups react with
atmospheric moisture liberating alcohol as a by-product. Chemically
neutral, low consistency elastomers which cure at room temperature
Table 2.1 Typical silicone product families and applications
Volatiles Fluids and pastes Elastomers Resins
Typical product Cyclosiloxane Antifoams RTV sealants Methyl resins

families Emulsions Liquid sil. rubber Phenyl resins
Phenyl fluids Heat cured rubber
2 part elastomers
and adhesives
Typical applications Cleaning solvents Transformer fluids Construction Coatings
Cosmetics Antifoams Automotive Paint additives
Cosmetics Electrical Electronics
Paper coatings Electronics Water repellents
Lubricants Medical
Textile finish Textile coatings
Mechanical engineering
Food processing
Mould making
32 1 1-1___SI_L_IC_O_N_E_M_A_T_E_R_I_A_L_S_F_O_R_E_L_E_C_T_R_O_N_IC~C_O_M_P_O_N_E_NT_S_ _---,
Table 2.2 Silicone polymerization reactions
(a) =8iOH +HOSi= -+ =Si-O-Si= + H 20
(b) (=8iORh +H20 -+ =8i-O-Si= +2ROH
(c) (=8iOOCCH3h +H20 -+ =8i-O-Si= +2CH3COOH
(d) =8iOR +HOSi= -+ =8i-O-Si= +ROH
(c) =8iCH=CH2 + HSi= -+ =8i-CH2-CHrSi=
(RTV materials) generally fall into this category, as do silicone conformal

coatings. To protect against moisture during storage such materials are
supplied in tubes, cartridges or other sealed containers. Again there is
usually an integral catalyst to promote these curing reactions. Unlike most
other curing mechanisms this type of reaction depends on the relative
humidity ofthe atmosphere and cannot be greatly accelerated by heating. (A
faster heat cure is possible with some silicone conformal coatings if a special
heat-sensitive catalyst is added.)
Because reaction (b) is chemically neutral there is no corrosion hazard
affecting electronic equipment. However, the most common family of one-
component RTV elastomers employs the acetoxy reaction shown in (c)
which liberates acetic acid with its characteristic vinegary smell when curing.
This type of elastomer is widely used for general industrial and household
sealants but should be avoided in favour of the neutral variety for most
electronic applications because residual acetic acid can promote corrosion
and undesired electrical conductivity. The neutral alkoxy curing reaction of
(b) can also be incorporated in a two-component system, leading to a cured
polymer by interaction between Si-OR and Si-OH groups as in (d), a type
of cure often used with two-component R TV products. Like the related
reaction (b), curing cannot be appreciably accelerated by heating but no
atmospheric moisture is required. The requisite OH groups are contained in
one component of the polymer. This permits curing in depth, whereas the
one-component systems requiring atmospheric moisture are only suitable
for coatings which are a few millimetres in thickness.
Addition reaction (e) is used with many of the two-component silicone
elastomers and gels. Silicon-hydrogen groups react with silicon-vinyl groups
in the presence of an integral catalyst such as a platinum complex. Unlike
reaction (c), there are no by-products and their absence eliminates or
minimizes shrinkage during cure. Products can be designed to have either
very long or very short pot lives as desired after mixing the two constituent
components. Elastomers cured by addition reaction (e) are also extremely
resistant to reversion or depolymerization, which may occur under adverse
high temperature conditions in confined thick sections of alkoxy cure system
elastomers. 8
A further curing reaction is commonly used for high-consistency silicone
rubbers which are fabricated into insulating components such as extruded
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S_IL_I_C_O_N_E_A_P_P_L_IC_A_T_I_O_N_S_IN_E_L_E_CT_R_O_NI_C_S_ _ _ _ 33
insulation sleeving, cables and moulded components. Reaction between

vinyl and methyl or methyl with other methyl groups is brought about by a
peroxide catalyst under heat and pressure using hot air, a heated mould or
steam pressure as appropriate. 8
2.4 SILICONE APPLICATIONS IN ELECTRONICS
The different types of silicones and their application in the electronics

industry are now reviewed with illustrative examples.
2.4.1 Silicone Encapsulating and Potting Materials

Today's continuing trends towards increased complexity and miniaturiza-
tion of electronic units, assemblies and components, is putting ever more
pressure on the performance of encapsulants and potting materials used to
protect them. Increasingly, the encapsulant is required to function reliably in
extreme and adverse environments.
The typical requirements of an encapsulant used in the electronics
industry are :
• enough electrical strength to withstand an electrical field between the
conductors;
• high insulation resistance to prevent leakage of current across the
conductors;
• good arc resistance to prevent damage in case of arcing;
• mechanically strong enough to resist vibrations and shocks but at the
same time allowing a degree of independent movement by other materials
and components in the unit;
• maintained electrical and mechanical integrity under a wide variety of
environmental conditions such as extremes of temperature, humidity and
radiation.
The key electrical properties which have a bearing on these requirements are
dielectric constant, dielectric strength, dissipation factor, and volume and
surface resistivity, whilst the key mechanical properties are hardness,
elongation at break and modulus.
Of all the commonly used encapsulants, the properties of silicones are
probably the best suited to meet the needs of electronic and electrical
applications. In general, silicones offer a number of unique properties.
Firstly, silicones possess exceptional thermal stability. Fully cured, the
majority of silicone encapsulants remain serviceable at temperatures ranging
from -60°C to + 200°C. Secondly, they offer exceptional performance
under most environmental conditions. They will not harden, crack, peel or
34 I L.I__S_I_L_IC_O_NE
__ M_A_T_E_RI_A_L_S_F_O_R_E_L_E_CT_R_O~N_IC_C_O_M_P_O_N_E_NT_S_---l
become brittle with age. In addition, cured silicones exhibit a low order of
toxicity and are simple and easy-to-use in production. Typically, they
contain no flammable or toxic solvents and require no special handling
precautions, such as ventilation or expensive exhaust systems.
Perhaps one of the most important issues in any electronic unit's design is
the difference in coefficient of thermal expansion (CTE) of the various
materials used in the unit. The differences in the CTEs are transmitted
throughout the unit and create mechanical stresses and potential for stress
related failures. The low modulus of elasticity of silicone encapsulants
allows a reasonable degree of independent movement while absorbing many
of these stresses. Silicones provide an ideal cushion between sensitive
electronic units and external mechanical shocks and vibrations.
For many years, silicone encapsulants and potting materials have been
recognized as among the most durable and reliable in the electrical and
electronics industry. Historically, they were chosen only when superior
perfoIll}.ance properties were essential, such as for use in aerospace and
other high-technology applications. From a performance point of view
silicones are undoubtedly the number one choice, but in many cases they
may not have been considered a first choice due to the misconception that
they were highly priced.
A wide range of silicones for electronics is available for general
industrial use (Table 2.3). Two-component elastomeric encapsulants can
provide protection in depth and offer many opportunities for electronic
packaging design where resistance to high or low temperatures and
physical resilience are required. In general, the cured materials require
further support from mechanical damage by the use of an outer container
unless there is an external cover. Thus they can best be described as
potting materials. Unlike their one-component counterparts, which are
normally applied as pastes or viscous fluids from a tube or cartridge, two-
component silicone elastomers are supplied as fluid polymers which are
mixed before use. Degassing under vacuum is often necessary after mixing
to remove air. (One-component speciality elastomers are also available as
potting materials.) When mixed, the material is then poured into a mould
or container holding the circuit to be protected and cured at room
temperature or by heating if an accelerated cure is desired, as is the case
with addition reaction based products. These procedures are relatively
simple and can be carried out in a laboratory or workshop with relatively
little equipment (Fig. 2.2) while for larger-scale use machinery is available
to mechanize production with airless mixing, dispensing and curing being
possible on a continuous basis.
Table 2.3 lists the properties of a representative selection of one and two-
component products. The first of these (1) is grey-black in colour and easily
handled because the two liquid components as supplied are mixed in equal
weights or volumes. They are white and black, respectively, so that complete
Table 2.3 Typical one- and two-part silicone sealants, adhesives, encapsulants and conformal coatings
Description Colour Viscosity Specific Cure Potlife Cure Hardness Tensile

(mPa.s) gravity system (h at 25°C) (h;oC) (Shore A) strength
(MPa)
1. Flame retardant Black 3.000 1.38 2 pt RTV 0.5 8/25 48 3.5

2. Self-priming Black 1.500 1.23 2 pt heat cure >2 days 2/100 38 1.4
system
3. Optically clear Clear 4.000 1.05 2 pt RTV 8 24/25 40 6.2
4. Self-healing gel Clear/Red 500 0.97 2 pt heat cure 2 1/100 NA NA
5. High thermal Grey 6.000 2.14 2 pt heat cure 24 1/100 88 6.5
conductive
6. Solventless Clear 35.000 1.05 1 pt RTV NA 24/25 25 2.0
elastomer
7. Elastoplastic resin Straw 1.000 1.04 1 pt RTV NA 24/25 30 (Shore D) 3.5
solution in solvent
8. Solventless heat Straw 450 0.97 1 pt heat cure > 30 days 0.5/100 15 2.2
cure elastomer
9. General-purpose White Paste 1.36 1 pt RTV NA 24/25 35 2.3
adhesive/sealant
10. High-strength Grey Paste 1.12 1 pt RTV NA 24/25 50 7.0
adhesive
Table 2.3 (cont.)
Description Colour Elongation Tear Thermal Volume Electrical Volume

(%) strength conductivity CTEx 104 strength resistivity
(kN/m) (W/m.K) (l/K) (kV/mm) (ohm em x 1015 )
1. Flame retardant Black 150 1.7 0.34 8.0 18 1.0

2. Self-priming system Black 100 0.34 8.5 18 1.0
3. Optically clear Clear 100 2.7 0.15 9.6 22 2.0
4. Self-healing gel Clear/Red NA 9.9 17 2.3
5. High thermal Grey 55 1.04 6.0 27 0.88
conductive
6. Solventless Clear 350 3.6 0.12 8.8 20 0.5
elastomer
7. Elastoplastic resin Straw 30 0.12 6.6 43 0.1
solution in solvent
8. Solventless heat Straw 80 0.15 8.0 18 2.0
cure elastomer
9. General-purpose White 650 11.8 0.15 8.0 17 0.7
adhesive/sealant
10. High-strength Grey 675 33 0.17 7.8 21 0.5
adhesive
--.l1 I
L...._ _ _ _S_1_L_IC_O_N_E_A_P_P_L_IC_A_T_I_O_N_S_I_N_E_L_E_CT_R_O_N_I_C_S_ _ _ _ 37
Fig. 2.2. Application of Sylgard@ 567 potting a module for a telecommunication

application with a simple mixing and dispensing equipment. (Alcatel Bell, Antwerp-
en, Belgium)
Fig. 2.3. Easy dispensing of silicone encapsulant in high voltage units.
mixing is apparent when a uniform dark grey colour is obtained. Figure 2.3
shows the use of this encapsulant to insulate and protect high-voltage
cascade units for visual display terminals, with processing in a fully
38 1 ,--I__S_I_L_IC_O_N_E_M_A_T_E_R_IA_L_S_F_O_R_E_L_E_CT_R_O_NI_C_C_O_M_PO_N_E_NT_S_-----'
automated vacuum, mixing and transfer system. The silicone encapsulant is
highly resistant to fire, passing the stringent UL 94-YO standard specified by
the computer manufacturer end user, and it also protects against corona
discharge at high voltage. (It should be noted, however, that in order to
achieve optimum performance a primer is sometimes needed with this
encapsulant.)
Product (2) in Table 2.3 is an example of a product that has been
developed with an integral primer, though a heat cure is necessary for its
activation. This type of self-priming silicone encapsulant is very useful in
cases where priming may be difficult because of small gaps. It is also a cost-
saving process since separate primers need a drying time before encapsu-
lation.
The next product example (3) is a transparent encapsulant, again
processed by mixing two fluid components as supplied. One version will
cure either at room temperature or by heating, while a variant has much
longer pot life at room temperature and is normally cured by heating in the
temperature range 70-150°C. The cured product is optically clear, permit-
ting visual inspection of an encapsulated circuit or components. One specific
application, outside the definition of electronic encapsulation, is the
protective coating of optical fibres. 9 In a continuous process the silicone is
cured in a few seconds as the fibre passes through a radiant curing zone at
over 3OO°C. The absence of any solvent or by-products prevents blistering
and the silicone provides a chemically pure coating which is also soft enough
to prevent mechanical damage to the glass fibre.
Example (4) is a silicone gel. Silicone dielectric gels are polymers with a
low level of crosslinking and they exhibit good pressure-sensitive adhesion
to most substrates. Therefore, they are extremely good in protecting
electronic circuits against corrosion and metal migration. Silicone gels form
a cushioning gel-like mass which combines the stress relief and self-healing
properties of a liquid, thereby preventing stress damage to delicate
components, even when subjected to heat ageing. The unique silicone
dielectric gels retain their softness, adhesion and electrical properties after
more than 1000 cycles from 50°C to 200°C (Fig. 2.3). Silicone gels also have
outstanding dielectric properties. Silicone gels have proven their unique
characteristics in the protection of automotive electronic modules (Fig. 2.4)
where the exposure to environmental extremes including high and low
temperatures, mechanical shock and vibration, water and salt from road
surfaces require excellent and reliable protection. 1o
Typical applications for silicone gels are:
• hybrid encapsulation
• connection sealant
• clean room filter sealing
• potting of high voltage units
L -_ _ _ _ S_IL_I_C_O_N_E_A_P_P_Ll_C_A_T_IO_N_S_IN_E_L_E_CT_R_O_N_I_C_S_ _ _ _ ---'I I 39
Fig. 2.4. Silicone dielectric gels function as durable dielectric insulation, as barriers
against environmental contaminants, and as stress-relieving shock and vibration
absorbers. Here it is applied in an Engine Management Unit from Bosch Germany.
Special gels have been developed for extra low temperature applications
(-80°C) and for the protection of units and circuits in fuel or solvent-rich
environments.
In microelectronic packages high purity silicone gels ll are used to provide
premium moisture protection, due to their good adhesion, and to keep the
packaging material cost low (Fig. 2.5). See also the further information in
section 2.4.4 on high purity electronic coatings and adhesives.
2.4.2 Silicone Conformal Coatings

Unlike the encapsulants described above, conformal coatings provide a
relatively thin protective cover typically ranging from 0.3 to 0.8 mm thick
which is ideally suitable for providing protection to printed circuit boards,
hybrids, multichip modules and other, similar configurations. At this
thickness, the coating can protect against surface moisture and pollution
and thus against unwanted current leakage or tracking, but is not expected
to provide the same in-depth mechanical protection or high voltage
insulation that is given by a thick section encapsulation or potting.
Within these constraints conformal coatings provide an economical way
to ensure circuit reliability. Several different classes of polymer may be used
in this way, among which silicones offer the unique combination of a wide
temperature working range, surface water resistance and low water
40 II'-__S_I_L_IC_O_N_E_M_A_T_E_R_IA_L_S_FO_R_E_L_E_CT_R_O_N_IC~C_O_M_P_O_N_E_N_T_S_----,
Fig. 2.5. Delco Electronics Corporation's Sensing and Diagnostic Module (SDM) is
an active part of a car air bag system. A one-part, solventless silicone conformal
coating protects the unit's electronic components without stressing delicate soldered
joints.
absorption. Several types of silicone conformal coatings are available. Each

is formulated to 'conform', as the generic name implies, by following the
circuit contours and without leaving sharp solder points or other obtrusions
uncovered. Their general properties are also shown in Table 2.3. The first
example of these (6) is a solventless, viscous fluid elastomer which can be
applied directly to a printed circuit board by flow coating, although it is
usually first diluted by solvent to reduce its viscosity. Application may then
be by dipping, spraying or flow coating as convenient. Curing takes place by
reaction with atmospheric moisture at room temperature.
By contrast, the second conformal coating shown in Table 2.3, (7), can
best be described as an elastoplastic resin: a resin with highly elastic
properties. Supplied in solvent, it can again be applied in several ways but
forms a harder, more slippery surface after cure than the elastomeric
formulation. Its maximum elongation at 100% is less than for the
elastomeric product (6) but is adequate for most applications. Curing is
again by reaction with atmospheric moisture at room temperature, although
a fast heat cure is also possible if a suitable catalyst is added.
A paper by Day and WeIIer 12 reported the good fire-resistant character-
istics of this type of conformal coating. When applied to an epoxy-glass fibre
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S_1_L_IC_O_N_E_A_P_P_L_IC_A_T_I_O_N_S_I_N_E_L_E_C_T_R_O_N_I_C_S_ _ _ _ 41
reinforced circuit board, the silicone coating did not improve the assembly
to the same degree of fire resistance as the silicone itself, but the lower value
for the uncoated board was not impaired. Conversely, other types of coating
reduced the fire resistance of the uncoated epoxy-glass fibre circuit board.
The third coating (8) belongs to a new family of one-part solventless
silicone elastomers that cure with heat to a give a flexible and transparent
material. Heat cured conformal coatings offer a significant range of
processing benefits. Their most common application in electronics is to
protect printed circuit boards, and they have been used successfully in this
way for many automotive applications.
One useful attribute of all these silicone coatings is their repairability.
Solder joints can be re-made, often even without removal of the coating. No
carbon is formed and fresh silicone may then be applied to the area which
has been repaired. They also comply with the MIL-I-460S8C specification
for PCB coatings. One limitation, however, is their poor resistance to strong
solvents, such as fluorinated hydrocarbons.
2.4.3 Silicone One- and Two-Part Sealants and Adhesives

A wide range of one-component RTV silicone sealants and adhesives is
available but for many sensitive electronic applications the acetoxy one-
component system should be avoided for reasons already indicated. The
properties of four representative examples are listed in Table 2.3. The first of
these (9) is a free-flowing paste while the second (10) is more thixotropic.
Where high cohesive strength is required, the third material (6) is preferred,
particularly for sticking components on to printed circuit boards and other
substrates. The third material (6) is used both as a sealant and as a
conformal coating, for which purpose it is diluted if necessary with an
aromatic solvent to reduce its viscosity.
All these silicones cure by reaction with atmospheric moisture and
account must be taken of this in application. They are typically used for
coatings up to about 6 mm thick. These products are unsuitable for bonding
large impermeable areas of material together unless adhesive contact only at
the outer edges is sufficient. Figure 2.6 illustrates the use of a non-slump
sealant to bond a large capacitor to a conventional FR-4 epoxy circuit
board.
The disadvantage of all the room temperature vulcanizing (RTV)
adhesives is their long 'full cure' times (24 to 72 hours at 25°C). For fast
production lines a family of primerless silicone adhesives has been developed
for use in the electronics industry.13 These adhesives cure relatively quickly
at temperatures which are compatible with electronic assemblies and, since
they do not require moisture for cure, a uniform cure can be completed in
either a confined or open air environment. The materials will maintain their
flexibility and integrity over a wide range of temperature exposures. Within
42 II SILICONE MATERIALS FOR ELECTRONIC COMPONENTS
~--------------------------------~----------------~
Fig. 2.6. A non-slump sealant/adhesIve provIdes shock and vIbratIOn resIstance to

sensitive and large components.
this family of products, the user can choose from a wide variety of
properties to select the material that is best suited for each specific
application. 14 Properties to consider in product selection are hardness,
elongation, green strength, and tensile strength. Very good adhesion can be
achieved with most metal and reactive plastic surfaces. To meet various
process requirements, the materials are made in a wide viscosity range, from
flowable to thixotropic or non-slump. In addition to the manufacturing time
and space savings offered by a relatively fast cure, some systems are
formulated with a UV dye to offer the capability of optical detection and
inspection. These silicone adhesives also help to accommodate the thermal
expansion coefficient mismatch generated stresses created when two
materials with different coefficients of thermal expansion (CTE) are bonded
together.
Another advantage silicone adhesives bring is moisture resistance.
Moisture absorption is very low and has little effect on these adhesives or
their electrical properties. This quality, together with adhesion and
corrosion protection, is important in harsh environments, such as in
under-the-hood automotive-type applications.
In the same family of primerless silicone adhesives there are materials
available with the additional capability of dissipating thermal energy away
from delicate components. IS A thermally conductive silicone adhesive
basically has four components:
L -_ _ _ _ --'I I
S_1_L_IC_O_N_E_A_P_P_LI_C_A_T_I_O_N_S_I_N_E_L_E_CT_R_O_NI_C_S_ _ _ _ 43
• the silicone polymer (typically polydimethylsiloxane) with crosslinkable

sites either pendent or terminal;
• the thermally conductive filler;
• the cure catalyst;
• an adhesion promoter.
These silicone adhesives are easy to process not only because of the range of
viscosities available and one-part packaging, but also because of the
inherent wettability of silicone polymers. These adhesives can be dispensed
quickly and accurately in many forms. Users have successfully applied these
adhesives in single dot configurations as well as in showered configurations
where 20-50 dots are dispensed at one time. With the addition ofXY and Z
axis translation equipment, lines or beads of the adhesive can be applied
accurately to channels, resulting in mating bonds that are very homo-
geneous after the adhesive is cured. The types of dispensing equipment
available today can apply the same amount of adhesive time after time,
giving extremely good usage rates on already existing production lines, as
well as offering very good design flexibility for future lines.
These types of silicone adhesive are suitable for a variety of applications,
such as bonding substrates to base plates, housings to base plates, covers to
housings, connector sealing, damming to enclose more flowable material
and so forth. They adhere well to ceramics, aluminium, glass and plastics
with low moisture content such as polyethylene teraphthalate (PET),
polyphenyl sulfone (PPS), polybutylene teraphthalate (PBT) and nylon. In
new designs of automotive modules, chips are adhesively bonded directly to
the board conductor. The adhesive allows for a greater degree of
miniaturization and design flexibility (Fig. 2.7).
2.4.4 High Purity Electronic Coatings and Adhesives

In order to protect a semiconductor device surface against adverse physical
and chemical effects from its surrounding environment, and also to increase
the breakdown strength at P-N junction surfaces in many devices, specially
formulated silicone polymers with optimized rheology and chemical purity
have been developed. These high-purity coatings may be applied to a chip
surface before encapsulation, for example prior to transfer moulding, or
they can be used alone to provide surface protection on a naked chip
mounted on a hybrid circuit or in a chip on board type configuration. II
In these products, the combination of low moisture absorption, very low
levels of metallic or chloride ions and compatibility with the chip surface is
of key importance. 16 Diode chips can be protected by a thixotropic silicone
paste which fills the remaining space between the adjoining electrodes and
thus reduces the inverse voltage leakage current. In the case of power
transistors, a high-purity silicone elastomer forms a protective coating not
44 II'-__S_I_L_IC_O_N_E_M_A_T_E_R_IA_L_S_F_O_R_E_L_E_C_T_R_O_N_IC_C_O_M_P_O_N_E_NT_S_------'
Fig. 2.7. Thermally conductive adhesive to quickly dissipate thermal energy away
from delicate components and absorb stresses created when two materials with
different CTE are bonded together.
only for the semiconductor surface but also over the connecting bond wires
(Fig. 2.8). In practice it has been found best to cover the bond wire near to
the chip surface but not along its whole length, in order to avoid failures due
to wire breakage. Similar types of coating are also used to prevent
corrosion,17 current leakage or failure under inverse voltage at thyristor
junctions.
The rheology desired for many of these applications includes high
thixotropy, so that shearing forces during dispensing allow the coating to
flow closely round the chip surface and bond wires. The original viscosity
must then be rapidly restored so that the silicone coating remains in situ
without further flow during the curing stage, whether at room temperature
or by heating at, say, 120-1 50°C. The material is cured by heating and,
typical of silicone polymers, shows a much smaller fall in viscosity as
temperature rises prior to cure than an organic glob top coating such as an
epoxy. This ensures that the glob does not flow away from the chip during
the curing process.
Outside the field of discrete component protection, high-purity silicone
coatings contribute to the growing use of microcircuits combined with
newer forms of interconnection and packaging. In wafer fabrication,
flowable oxide or hydrogen silsesquioxane (HSQ) provides an interlevel
dielectric coating with excellent planarity and gap filling in a simple spin-on
L -_ _ _ _ ---ll I
S_1_L_IC_O_N_E_A_P_P_L_IC_A_T_I_O_N_S_I_N_E_L_E_CT_R_O_N_I_C_S_ _ _ _ 45
Fig. 2.8. High performance protective silicone materials are integral to product
advancement for the semiconductor industry.
application. Another advantage of HSQ/flowable Oxide (FOx) is that it is a

carbon-free polymer. The absence of carbon reduces the potential for
poisoned vias. Because of this, it is not necessary to remove the oxide from
areas surrounding vias, and a non-etchback process can be used. 18 ,19,20
2.4.5 Insulating and Constructional Materials, Wires and Cables

Many fabricated materials made from or based on silicones are also
available for the construction of electronic equipment, including silicone
resin bonded glass-cloth laminates, insulating sleeving cables or wiring and a
wide variety of moulded or extruded components.
Silicone resin bonded glasscloth laminates have low and stable dielectric
losses at temperatures up to 200°C or even higher. They are used in the
construction of radar and high-power communications equipment, and in
dielectric heating apparatus. Copper-clad silicone-glass laminates are
available for PCB manufacture, but find usage mainly where copper-clad
epoxy-glass laminates are unacceptable in terms of thermal endurance or
dielectric loss. The copper to laminate peel strength is lower and more
variable in the case of silicone than epoxy, and the laminate price is higher.
Silicone elastomer sleeving is available in two forms: unsupported
extrusions and with fibreglass reinforcement. The reinforced variety is
mechanically stronger but may be lower in electric strength and has lower
elongation. Liquid silicone rubbers have been developed which cure by an
46 I LI__S_I_LI_C_O_N_E_M_A_T_E_R_IA_L_S_F_O_R_E_L_E_CT_R_O_N_IC_C_O_M_P_O_N_E_NT_S_------'
addition reaction as in (e) of Table 2.2. They have proved to be useful as
coatings for reinforced sleeving. Compared with the other two-component
elastomers in Table 2.3, these liquid silicone rubbers are higher in viscosity
before cure and physically tougher afterwards. They can be economically
handled by airless mix and meter systems with automated production
equipment providing fast throughput. 21
Electrical insulating tapes made from silicone elastomers or silicone resin
coated glasscloth or mica paper are also widely used. Polyester or polyimide
tapes are also available with heat-resistant silicone pressure-sensitive
adhesive coatings.
Silicone elastomer insulated cables and wiring provide connections which
retain their integrity and flexibility over a wide temperature range, e.g. from
-55°C or even lower to + 250°C. They are fire resistant, but if damaged or
destroyed by fire leave an insulating residue of silica and do not evolve toxic
fumes.7 ,22
Keypads for telephones and microcomputers have long been important
end applications for silicone rubber. A number of keypads can be produced
by a single operation in multi-cavity moulds. This eliminates the need for a
much larger number of mechanical components and assembly. The silicone
elastomer used for the microcomputer keypad shown in Fig. 2.9 retains its
Fig. 2.9. Microcomputer keypad made from a single moulding of a liquid silicone
rubber, with its underlying membrane switching circuit (Sinclair Research, Ha-
ffenden and NFl Electronics).
L -_ _ _ _ _ _ _ F_UT_V_R_E_D_EV_E_L_O_P_M_E_NT_S_ _ _ _ _ _ _ ---'I I 47
elastic properties over a long life without the adverse changes due to ageing
characteristics of other elastomers. When the keys are depressed, they
actuate a membrane switching sandwich below and then spring back into
place. The resilience of the keypad shown was tested over five million
operational cycles before entering volume production.
2.4.6 Silicone Aids in Electronic Production

Apart from direct use as insulating and constructional materials, silicones
are also used as processing aids in the production of electronic equipment.
Silicone vacuum pump fluids are used in the diffusion pumps which provide
high vacuums for the production of semiconductors and cathode ray tubes
or other vacuum devices. Many electronic components are encapsulated in
epoxy or other hard organic coating resins. Here silicones find wide use as
release agents, either as fluids or to make elastomeric moulds. Key
properties for those mould-making materials are high elongation and good
values of tensile and tear strength to allow the mould to be used repeatedly
for long production runs.
2.5 FUTURE DEVELOPMENTS
The continuous trend towards miniaturization of components and units is

likely to lead to increased use and development of speciality silicone
elastomers as coatings, adhesives and encapsulants. Flexible, high thermal
conductivity silicone adhesives are going to play a much more important
role in bonding components to substrates where differing thermal expansion
coefficients preclude the use of rigid materials.
Silicone encapsulants and adhesives should continue to be recognized for
their benefits of ease of use, high chemical purity and low order of toxicity.
Silicones will continue to play an important role in applications where
greater reliability and better performances are essential requirements.
Typical areas for growth are high voltage applications, automotive
electronic modules and, last but not least, electronics for home appliances.
The use of electronic control units in domestic appliances (e.g. ovens,
fridges, steam irons, washing machines, etc.) is expanding quickly. Those
assemblies require reliable protection and joining solutions which can
survive the adverse environmental conditions often experienced in normal
service. Speciality silicones have been developed for this fast growing market
segment.
An area of chemistry which is growing in importance concerns silicone--
organic copolymers. In these the silicone polymer chain is interconnected
with large polymeric groups such as epoxides or polyesters. The challenge is
also to continue this present movement together with the merging of
48 I 1<--__S_I_Ll_C_O_N_E_M_A_T_E_R_IA_L_S_F_O_R_E_L_E_CT_R_O_Nl_C~C_O_M_P_O_N_E_NT_S_------,
polymer chemistry and materials science. From the point of view of
materials, silicone-based polymers span the three traditional materials
classifications, i.e. plastics, ceramics and metals. Potential applications are
equally diverse. Silicone-based polymer applications range from use as
structural materials, to optoelectronic devices, and to speciality materials for
many microelectronics applications. Silicone manufacturers are in a unique
position to capture the benefits of this merger of materials and polymer
science. 23
2.6 REFERENCES
1. Kipping, F. S. and Lloyd, L. L., Organic derivatives of silicon, J. Chem. Soc., 79,
449 (1901). .
2. Alperowicz, N., Dow Corning poised for growth in Europe, Chemical Week,
April 3, 1996.
3. Eabom, C., Organosilicon Compounds, Butterworth Scientific Publications,
London, 1960.
4. Noll, W., Chemie und Technologie der Silicone, Verlag Chemie, Weinheim, 1960.
5. Von Hippe!, A., Dielectric Materials and Applications, Technology Press of MIT
and John Wiley & Sons Inc., New York, 1954.
6. Joint Assessment of Commodity Chemicals No. 26: Linear Polydimethylsilox-
anes, ECETOC Brussels, September 1994.
7. Hilado, C. J., Casey, C. J., Christensen, D. F. and Lipowitz, J., Toxicity of
pyrolysis gases from silicone polymers, J. Combustion Toxicology,S, 130-140,
May 1978.
8. Lynch, W., Handbook of Silicone Rubber Fabrication, Van Nostrand Rheinhold
Co., New York, 1978.
9. France, P. W., Dunn, P. L. and Reeve, M. H., Plastic coating of glass fibres and
its influence on strength, Fibre and Integrated Optics, 2, (1979).
10. Mollie, J.-P., and Paquet, R., Performance of new silicone adhesives and
encapsulants at high and low temperature, Proc. lEE Automotive Eighth
International Conference, London, 1988.
11. Kookootsedes, G., and Antonen, R., Selecting protective materials for coating
hybrid circuits, Hybrid Circuit Technology, March 1986.
12. Day, A. G., and Weller, M.G., Flammability testing of printed wiring board
material and the effect of the conformal coating, Proc. Internepcon Conference,
Brighton, 1980.
13. Mollie, J.-P., Klebstoffe aus Silicon, Electronik Produktion Pruftechnik, March
1995.
14. Vanwert, B., One-part thermal cure silicone adhesives, Proc. NEPCON WEST
'96, California, 1996.
15. Wilson, S., Thermally conductive adhesives for high thermally stressed
assembly, Proc. NEPCON WEST '96, California, 1996.
16. Verhelst, V., Capillary zone electrophoresis determination of ionic impurities in
silicone product used for electronic applications, J. Chromatography, Special
Issue, International Symposium, Reading, 1996.
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _R_E_F_ER_E_N_C_E_S______________ ~I I 49
17. Otsuka, K. et al., The mechanisms that provide corrosion protection for silicone
gel encapsulated chips. IEEE Transactions on Components, Hybrids, CUMT-12
(4), December 1987.
18. Ahlburn, B. T. et al., Hydrogen silsesquioxane-based flowable oxide as an
element in the inter-level dielectric for sub 0.5 micron ULSI circuits, Multilevel
Interconnection Conference, Santa Clara, 1995.
19. Ballance, D. S., Scheibert, K. A. and Tietz, J. V., Low temperature reflow
planarisation using a novel spin-on inter-level dielectric, Multilevel Interconnec-
tion Conference (VMIC), 1995.
20. Waeterloos, J. and Meynen, H., Integrating a hydrogen-silsesquioxane spin-on
dielectric in a quarter-micron technology, DUMIC, California, February 1997.
21. Cush, R.J., LSR: the versatile alternative, British Plastics and Rubber, 29-31
(October 1982).
22. Lipowitz, J., Combustion, Flammability and Fire Hazard Properties of Silicones,
Publication NMAB-342, National Academy of Sciences, Washington, DC,
1978.
23. Weyenberg, D. R., and Lane, T. H., Future Directions for Silicon-based
Polymers, American Chemical Society, 1990.
Engineering Thermoplastics 3
HARRY VAN BAAL
General Electric Plastics bv, Bergen op Zoom, The Netherlands
3.1 INTRODUCTION
By using different modifiers, additives, fillers and reinforcements with

various polymers, more than 15000 thermoplastic compounds are now
commercially available. They are often classified as commodity plastics or
engineering plastics. This chapter is dedicated to a review of the so-called
engineering thermoplastics. In it a broad overview will be given of the most
significant of these materials and of their use in the electrotechnical industry,
where they continue to be highly successful because of their unlimited design
flexibilities and their high performance profiles. The substantial use of these
materials is confirmed by the figures for the world-wide market for
engineering polymers used in electrical and electronic components. In 1995
this market was estimated to be valued at around £1300 million.
Engineering plastics command higher prices than commodity plastics
because they offer superior performance over a wide temperature range,
excellent impact performance and stiffness. In addition, they offer many
other benefits including possibilities for optimum part consolidation,
moulded-in assembly, thin wall moulding and smart design for disassembly
and reuse. The inherent quality of engineering thermoplastics also helps to
ensure that recycled materials retain a high performance profile.
Emphasis will be given to the importance of selecting the appropriate
engineering material to enable the designer to tailor part, function and
performance precisely to meet application needs, while offering optimum
engineering flexibility and fulfilling all stringent industry standards. Since
compliance with the industry standards is a fundamental selection criterion,
a description of some of the principal standard tests which are conducted on
52 I ~I____________E_N__G_IN_E_E_R_IN__G__T_H_E_RM__O_P_L_A_S_T_IC_S____________~
thermoplastic materials in electrotechnical applications is also given later in
this chapter.
3.2 ENGINEERING mERMOPLASTICS
The term 'engineering thermoplastic' can be somewhat arbitrary. For

example, it is possible through the use of additives, reinforcement and
alloying to give conventional commodity plastics some of the performance
characteristics normally associated with engineering materials. In this
chapter passing reference will be made to some of the materials of this type
which are used in significant volumes in some parts of the electrotechnical
industry. However, the primary focus will remain on those materials which
are normally considered to be true engineering thermoplastics.
Limitations of space preclude the inclusion of thermosetting materials, or
any detailed discussion of the influence of fillers and additives on the main
polymer types. Similarly, a detailed examination of the features of different
primary processes (injection moulding, extrusion, blow moulding, gas-assist
and structural foam moulding, etc.) will not be undertaken.
3.2.1 Acrylonitrile-butadiene-styrene (ADS)

ABS is an amorphous terpolymer formed from the polymerization of the
monomers acrylonitrile, butadiene and styrene. It is possible to achieve a
wide range of final chemistries and properties by varying the ratios of
monomers used in the polymerization and also by modifying the manufac-
turing conditions. Consequently, a very wide variety of commercial products
is also available and these are typically characterized by a good surface
finish, toughness and impact strength, low water absorption, good dimen-
sional stability, good electrical properties and resistance to chemicals and
ageing. Flame retardant grades are also available. ABS is mainly used as an
injection moulding material, and is typically found in applications such as
domestic enclosures, switches, plugs and sockets and uninterrupted power
supply (UPS) batteries. It has been especially popular as the preferred
material for the moulding of telephone bodies and handsets where its impact
strength, good surface appearance, ease of moulding and reasonable cost
have lead to its widespread use.
3.2.2 Acrylics
Acrylics, specifically those from the polymethylmethacrylate (PMMA)
family, are widely used in the electrotechnical industry. Typical applications
include lighting diffusers, such as those used in street lighting where impact
is not critical. These amorphous materials are characterized by sparkling
ENGINEERING THERMOPLASTICS II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~ 53
crystal clarity, surface hardness and scratch resistance complemented by

superior weatherability, UV stability, good chemical resistance and good
electrical properties. Where better toughness is required to meet safety
requirements, however, polycarbonate becomes the material of choice as
acrylics are inherently brittle.
PMMA has been extensively studied for use in polymeric optical fibres
(POFs) used to transmit optical signals. Polymer optical fibres have many
advantages over glass fibres such as ease of handling, reduced weight, good
ductility and ease of splicing. They also have the potential to be low cost.
Polymethyl methacrylate is attractive for this type of application because it
is easily purified at the monomer level and because no condensation
products are produced during polymerization. PMMA has also been used as
the cladding material for POFs where the core is polystyrene.
PMMA is also used extensively in the formulation of photoresists and has
formed the basis of many positive working electron beam resist formula-
tions. Although PMMA exhibits high resolution, its low sensitivity and poor
thermal stability have encouraged workers to investigate substituted
PMMA and to search for alternative materials.
3.2.3 Liquid Crystal Polymers (LCPs)

The thermotropic liquid crystal polymers are a group of crystalline polymers
that are produced as the random copolymers of a specific group of aromatic
polyesters themselves produced by the polymerization of specific monomers.
Examples of materials used to produce the starting monomers include p-
hydroxybenzoic acid, 2,6-hydroxynaphthoic acid, p,p'-dihydroxybiphenol
and biphenol. The liquid crystalline state is a unique condition in which
long-range molecular orientational order persists in the absence of various
types of short-range translational order. LCPs therefore exhibit a highly
ordered structure in both the solid and molten states and the polymers are
rigid rod-like molecules that pack together tightly to give fibrous crystalline
chains under shear in the melt. A key characteristic of LCPs is their
anisotropic properties caused by the orientation imparted during processing.
Early LCPs had very high melting temperatures ( > 400°C) and were difficult
to process. However, copolymers were subsequently developed which
introduced a degree of disorder into the polymer molecule and made
processing somewhat easier. There are believed to be around 20 companies
world-wide that have LCP development programmes and the world market
for LCPs in 1997 was estimated to be over 8000 tonnes.
Through careful selection of monomers it is possible to meet a wide range
of performance, processing and cost objectives. There are thus many LCP
formulations exhibiting a wide range of properties and so it is not possible
to give other than a general example of some typical properties as shown in
Table 3.1.
54 I I<--______EN_G_IN_E_E_R_IN_G_T_H_E_R_M_O_P_L_A_S_T_IC_S_ _ _ _ _ _--'
Table 3.1 Some properties of a generic liquid crystal polymer
Glass transition temperature (Oq 217
Dielectric constant (1kHz) 4.0-4.5
Dissipation factor (IGHz) 4-6 x 10-3
Volume resistivity (nm) 1013_10 14
Dielectric strength (kV mm-I) 30-43
Moulding temperature (Oq 30-200
Mould shrinkage (%) 0--0.6
Melt temperature ceq 285-325
The commercial introduction of liquid crystal polymers (LCPs) in the

mid-1980s provided new design opportunities for thermoplastics through
their outstanding strength under extremes of temperature, excellent flame
retardancy (UL94 V-O, self extinguishing and non-dripping) with very low
smoke evolution, broad chemical resistance and inherent UV stability. LCPs
are also transparent to microwave energy and are virtually unaffected by
radiation. They exhibit good dimensional stability and their thermal
expansion coefficients can be adjusted over a wide range; in one case
coming close to the value for FR4 epoxy glass fibre printed circuit board
laminate material.
These properties, combined with excellent electrical properties and
consistently good flow, make LCPs ideally suited to demanding applications
such as connectors. For example, a variety of connectors is now commer-
cially available that are manufactured using LCPs and these include
microminiature, D-subminiature, backplane, card edge and board-to-board
types. Board-to-board connectors for flat panel displays are an excellent
example of LCPs being utilized to solve extremely demanding application
requirements. Thermotropic LCPs have also been used in the production of
high performance optoelectronic components such as fibre optic couplers
for light wave communication systems. In this application the LCPs were
ideally suited to the demands of an expansion coefficient matched to the
optical glass fibre as well as small physical size and good dimensional
stability.
The highly attractive features of LCPs and the ability to tailor them for
specific applications means that they will find increasing use, especially in
electrical and electronic applications. However, at the moment they are
relatively expensive and this does tend to limit their use to applications with
very specific high performance profiles.
3.2.4 Modified Polyphenylene Ether (PPE)

Modified polyphenylene ether (PPE) amorphous resins are well established
for use in the electrotechnical industry because of their excellent dimensiohal
stability, low mould shrinkage, very low creep behaviour (even at elevated
EN
__
L -_ _ _ _ _ _ _ _ _ _ _ _ G_IN
__E_ER
__IN_G
__T_H_E_R_M_O_P_L_A_S_T_IC
__ S __________~I I 55
temperatures) and the lowest water absorption of all engineering thermo-

plastics. Another advantage associated with PPE resins is that all the flame-
retardant grades are halogen-free. Developed by General Electric Plastics,
this unique technology blends PPE and high impact polystyrene (HIPS) to
achieve a variety of characteristics in order to fulfil specific requirements:
from flexible wire insulation to rigid profiles, from optical fibre connectors
to electrical enclosures. UPS batteries and kWh meters are typical
application areas where PPE is used.
Special grades have been developed which offer a combination of
halogen-free flame retardancy with low corrosivity and low smoke gener-
ation. These materials fulfil the most stringent industry requirements and
are commonly used in power distribution conduits and cable management
apparatus such as plain and slotted trunking and rigid conduit/pipe.
PPE has also been modified to produce a crosslinkable thermosetting
resin system that can be used like conventional epoxy resin systems to
produce base materials for printed circuit boards. Laminates produced using
this material have low loss factors (0.002) and dielectric constants of around
3.5 at I MHz making them interesting for high frequency applications. With
glass transition temperatures of around 190°C they also offer thermal
stabilities higher than for conventional FR4 resins. Like their thermoplastic
Fig. 3.1. Noryl®, modified PPE, cable profile. Photo: GE Plastics.

56 I LI_____________E_N_G_IN__E_ER__IN_G__T_H_E_R_M_O_P_L_A_S_T~I_C_S__________~
Fig. 3.2. Noryl®, modified PPE, industrial connector. Photo: GE Plastics
analogues, they also conform to UL 94 v-o standards without the need to

add halogenated flame retardants.
3.2.5 Polyamides (PA)

Polyamide (PA) or nylon was the first of the so-called engineering
thermoplastics. Nylon 6/6 is the most widely used, followed by nylon 6
and nylons 11 and 12. This broad family of crystalline materials is
characterized by a balance of strength, stiffness and toughness, comple-
mented by excellent mouldability and ductility. These properties combined
with excellent wear resistance have enabled them to establish their use in
applications such as connectors and wire and cable equipment. All nylons
are inert to biological attack, exhibit good resistance to creep and cold flow
and have electrical properties which are adequate for most voltages and
frequencies. Several grades offer a comparative tracking index (eTI) of
~ 600 volts. There are also many halogen-free self-extinguishing (SE)
grades available based on different flame-retardant systems. SE grades of
nylon 6, for example, which are based on melamine cyanurate, provide a
rating of V-0 according to UL 94.
However, the inherent susceptibility of nylons to dimensional changes and
diminished electrical properties through moisture absorption has opened up
opportunities for alternative materials such as the polyester polybutylene
teraphthalate (PBT).
EN
__
L -_ _ _ _ _ _ _ _ _ _ _ _ G_IN_E _O_P_L_A_S_T_IC_S____________~I
_E_R_I_N_G__T_H_E_R_M I 57
3.2.6 Polybutylene Teraphthalate (PBT) and Polyethylene Terephthalate
(PET)
Polybutylene terephthalate (PBT) is in a class of materials referred to as the
thermoplastic polyesters which also includes polyethylene terephthalate
(PET). PBT is primarily used in injection moulding applications where fast
cycle times and good flow make it particularly suitable for complex parts in
which precise dimensional stability is an important property. Example
applications include industrial power plugs and electrical switchgear.
Commonly used in wiring devices, enclosures and connectors, this crystal-
line material combines high mechanical, thermal and electrical properties
with excellent chemical resistance. PBT is somewhat softer than the
relatively hard and stiff PET and has a slightly lower melting range 224-
228°C versus 255-258°C, which permits faster moulding cycle times and
lower mould temperatures. It is also worth noting that products combining
both PBT and PET chemistry have been produced which offer certain
processing advantages.
Polyethylene terephthalate (PET) is generally similar to PBT but with a
slightly higher short-term heat performance. This makes it suitable for
products such as lamp holders and motor end-frames. However, compared
to PBT, the requirement for pre-drying before processing is more critical for
PET and the processing window is also much smaller.
Fig. 3.3. Valox®, PBT, connector. Photo: GE Plastics.

58 I IL-____________EN__G_IN_E_E_R_I_N_G__TH__E_RM__O_P~L_A_S_T_IC_S____________~
3.2.7 Polycarbonate (PC)
Polycarbonate can be made by the melt condensation of bisphenol A and
diphenyl carbonate and typically has molecular weights of 20000 to 30000
for injection moulding materials and > 60000 for extrudable types.
H0f-<Q)-rQ-0- LOtQ-rQ-OH
CH) n CH)
Polycarbonate
Flame retardency can normally be achieved through the incorporation of
brominated components such as tetrabromobisphenol A.
Amorphous polycarbonate (PC) resins are distinguished by their unique
balance of toughness, heat and flame resistance, dimensional stability and
natural transparency. In the electrotechnical industry they are used in a
broad range of end-use applications including connectors, wiring devices,
terminal blocks and indoor and outdoor lighting diffusers. The insulating
and related electrical properties of polycarbonate are excellent and remain
almost unaffected by changes in temperature. Certain combinations of
chemical environments, temperature and stress can adversely affect moulded
polycarbonate parts. However, grades with improved chemical resistance
are available and special coating systems can be applied to provide
Fig. 3.4. LEXAN@, PC, kWh meter. Photo: GE Plastics.

L -_ _ _ _ _ _ E_N_G_INE_E_R_I_N_G_T_H_E_R_M_O_P_L_A_S_T_IC_S_ _ _ _ _ _----.JI I 59
additional chemical protection for parts requiring moderate solvent resis-

tance such as outdoor power plugs and industrial switches.
3.2.8 Polycarbonate/Acrylonitrile Butadiene Styrene (PC/ABS) Blends

PC;ABS blends offer the processability of ABS, together with the impact
performance and high resistance to heat distortion of polycarbonate. This
versatile blend is typically to be found in kWh meter enclosures, cable
trunking, business machine housings and light fittings. It is also used
extensively in plating on plastics applications outside the electronics
industry such as in car trim parts.
3.2.9 Polyetheretherketone (PEEK)

The polyetheretherketones are one group from a family of polymers that
contain an aromatic ketone group as the major constituent of their polymer
backbones. This group imparts the benefits of high thermal stability, high
temperature performance and chemical resistance. In addition to PEEK
there are also the other ketone-based polymers that have been commercially
exploited and these include the polyketones (PK), polyetherketones (PEK)
and polyetherketoneketones (PEKK). The structures of PEEK and PEKK
are shown below:
t°-@-o-@-~~. PEEK
t°-@-~-@-~~. PEKK
Polyetheretherketone (PEEK) offers prolonged high temperature resis-

tance and high temperature chemical stability, making it one of the most
temperature resistant thermoplastics available. In addition, it has a very low
flammability and minimum smoke and toxic gas emission. However,
because of its high cost, it has yet to be used a great deal commercially other
than in extremely specialized applications.
3.2.10 Polyetherimide (PEl) and Polyamideimide (PAl)

Polyetherimides are one of the members of a group of polymers which can
be described as linear modified polyimides. Polyimides, which contain the
characteristic imide group
60 I LI____________E_N_G_I_N_E_E_R_IN_G__TH__E_RM__O_P_L_A_S_T_IC_S__________~
Typical imide structure
are typically thermosetting, high thermal stability materials. However by

chemical modification it is possible to make thermoplastic injection
mouldable and extrudable versions. Other members of the linear modified
polyimide group include polyamide-imides, and polyimide sulphones. A
typical example of a polyether imide is Ultem which is formed from the
components, trimellitic anhydride, diisocyanates and bisphenol A. The
structure of polyetherimide is as follows:
{
II ~~
~:J§lo-@-T-@-o-©r! 0
0
" 0II .
Me
UlTEM"" (GE) Polyetherimide
From high temperature connectors to metallized halogen light reflectors

and spotlights, polyetherimide (PEl) is ideal for demanding electrical and
lighting applications which require exceptional long-term heat resistance
and strength and modulus at elevated temperatures. This high performance
engineering thermoplastic is also characterized by inherent flame retardancy
with low smoke generation, making it ideal for aircraft interiors. Because it
is an amorphous material, it exhibits much lower levels of post moulding
distortion when compared to similar crystalline materials, thereby offering
excellent dimensional accuracy. This combined with broad chemical
resistance and weldability make it suitable for applications such as gas
meters. Polyetherimides are resistant to mineral acids but are however
attacked by strong bases such as sodium hydroxide. Although PEls are less
moisture sensitive than some other polymers they must still be dried before
melt processing. They typically show comparable properties to the
polyethersulphones and polyarylsulphones although their low dissipation
factors at gigahertz frequencies make them the preferred materials for
microwave applications. Other important features of polyetherimides that
make them suitable for electrical and electronic applications are resistance
to wave and vapour phase soldering temperatures, good electrical properties
and dimensional stability, as well as the above mentioned inherent flame
resistance. PEl has been found suitable for the manufacture of integrated
circuit chip carriers because of its low ionic impurity levels. It has also found
use in military connectors, radomes, and as a printed circuit board
substrate. The latest generation of polyetherimides have glass transition
L -_ _ _ _ _ _ E_N_G_IN_E_E_RIN_G_TH_E_R_M_O_P_L_A_S_T_I_C_S_ _ _ _ _ -----,I 1 61
Table 3.2 Some properties of polyetber-imides and polyamide-imides
Property PEl (Ultem 1000) PAl (Torlon 4203L)
Glass transition temperature eC) 217 275

Dielectric constant (1kHz) 3.15 4.2
Dissipation factor (1kHz) 1.3 x 10-3 2.6 x 10-2
Volume resistivity (am) 6.7 X 10 15 3 X 10 14
Dielectric strength (kV mm-I) 28 24
Moulding temperature eC) 175 204-218
Mould shrinkage (%) 0.7 1.0
Melt temperature eC) 365-390 330-360
Continuous use temperature eC) 170 200-220
temperatures of around 265°C and offer continuous service temperatures of

over 220°C.
Polyamide-imides (PAIs) have the general structure shown below:
°II 0
:~-@-CH2-@-~-~ Polyamide-imide
II H
o
and they have higher glass transition temperatures than polyetherimides.

PAIs exhibit the thermal stability of polyimides with easier processing and
mechanical performance up to 250°C but they are still more difficult to
mould than polyetherimides. PAIs also possess electrical properties that are
inferior to PEl and hence they do not find a great deal of use in electrical
and electronic applications. Notable exceptions are found where they can
provide structural integrity under severe operating conditions and a good
example is their use in integrated circuit bum in sockets. Some typical
general properties of a standard polyetherimide and polyamide imide are
compared in Table 3.2.
3.2.11 Polyoxymetbylene (POM)/Acetal

Polyoxymethylene (POM) is more commonly called acetal. It is formed from
the polymerization of formaldehyde and typically has a melting point in the
region of 160-1 85°C. The polymer is the stiffest and strongest unreinforced
thermoplastic and this is largely due to the capability of formaldehyde to
form regular alternating molecular chains that produce highly crystalline
assemblies. :This high performance crystalline engineering thermoplastic
exhibits excellent electrical properties, complemented by high wear and
62 I ~I____________E_N_G_IN__E_E_R_IN_G__TH__E_RM__O_P_L_A_S_T_IC_S__________~
fatigue resistance, a low coefficient of friction, exceptional dimensional
stability, good solvent resistance and relatively low water absorption. It is,
however, attacked by strong acids (PH < 4) and alkalis and is hydrolysed by
hot water. Acetal is commonly used for moving parts in a wide range oflight
engineering applications such as water meters, and in snap fit parts which
require frequent assembly and disassembly. Self-extinguishing/flame-retar-
dant grades are not available and they tend to bum with a blue flame
accompanied by dripping.
Copolymers of acetal are also produced and these have similar melting
points to the homopolymer whilst offering greater resistance to alkalis and
hot water. This improvement is brought about by the use of a modified
polymerization process which involves the use of the cyclic trimer of
formaldehyde as the main monomer.
3.2.12 Polyphenylene Sulphide (PPS)

Polyphenylene sulphide (PPS) is a crystalline aromatic polymer with the
repeat unit as shown below:
Polyphenylene sulphide
It is produced commercially as a glass or glass/mineral reinforced

engineering thermoplastic which is ideal for products such as connectors,
relay components, outdoor lighting and products using surface mount
technology. PPS is characterized by inherent flame retardancy and filled
grades have received UL94 V-O ratings down to 1/64 inch. It also exhibits
excellent chemical resistance and there are no known solvents that will
dissolve it at temperatures below 200°C, although some do make it swell at
relatively high temperatures. It is, however, attacked by oxidizing acids such
as hot nitric acid. PPS has outstanding high temperature stability, achieving
a continuous use temperature of 200°C even though it has both melting and
glass transition temperatures lower than the ketone-based polymers. It also
exhibits low water absorption although long-term contact with water at high
temperatures may reduce the mechanical strength somewhat. While rein-
forcement provides PPS with a characteristic high strength and modulus,
this also gives the material its brittle nature.
Polyphenylene sulphide's good combination of thermal, mechanical and
chemical resistant properties, coupled with its excellent electrical features,
means that it is ideally suited to many electronic and electrical applications.
Areas where it has already found application are in connectors and sockets
requiring superior dimensional stability. Additional applications are in
switches, bobbins and surface-mounted component housings where stability
to vapour phase soldering is a requisite. At one time PPS was proposed as
'-----_ _ _ _ _ _E_N_G_I_N_E_E_R_IN_G_T_H_E_R_M_O_P_L_A_S_T_IC_S_ _ _ _ _ _ -'1 1 63
an alternative encapsulant to epoxides for the packaging of semiconductor

devices and this was partly due to its low ionic impurity levels. Although it is
attractively priced compared to other engineering thermoplastics used in
moulded interconnect device applications, difficulties in metallization have
prevented its widespread adoption in this area.
3.2.13 Polypropylene (PP)

Polypropylene (PP) is produced by the low pressure polymerization of
propene. With its many different varieties, it accounts for the largest volume
of commodity plastics used world-wide in the electrotechnical industry. In
general these extremely versatile, crystalline materials are characterized by a
good balance of strength and stiffness, excellent chemical resistance and
electrical properties, near-zero moisture absorption and easy processing.
They offer economical bulk production of products such as wire and cable
equipment, but offer limited opportunities for secondary operations such as
printing and metallization. They have been used as the material for battery
cases and as loose fitting sheathings for fibre optic cables. The main
drawbacks of the material are poor UV stability, limited heat resistance and
poor low temperature performance. In addition, requirements with regard
to degradability continue to pose problems.
3.2.14 Polysulpbones (PSU)

Polysulphones (PSU) are one of the three important families of amorphous
thermoplastics with Tgs high enough to make them suitable for electronic
applications (the others are the imide based polymers and the polyarylates).
The PSU polymers have a diphenylene sulphone group as a major
constituent of their chemical backbones:
o
--@-~-@- Diphenylene sulfone group
o
This group imparts thermal stability, oxidative resistance and rigidity even
at elevated temperatures. Some amount of flexibility can be introduced to
give a degree of toughness to these polymers through the incorporation of
ether linkages as in the polyether sulphones.
Polyethersulfone
It is not surprising therefore, that the formulated PSU-based engineering

thermoplastics also exhibit very high heat deflection temperatures, inherent
64 II~____________E_N_G_IN__E_E_~_N_G__T_H_E_RM
__O_P_L_A_S_T_IC_S__________~
Table 3.3 Some typical properties of commercially available sulphone-based
polymers
Property Polysulphone Polyethersulphone
(Udel P1720) (Victrex 3600G)
Glass transition temperature eC) 190 225

Dielectric constant (1kHz) 3.19 3.5
Dissipation factor (1kHz) 1.3 x 10-3 1.0 x 10-2
Volume resistivity (Om) 5.0 X 1014 10 15_10 16
Dielectric strength (kV mm-I) 15 16
Moulding temperature eC) 93-160 140-160
Mould shrinkage (%) 0.7 0.6
Melt temperature eC) 343-399 340-380
flame retardancy, outstanding dimensional stability and excellent mechan-

ical and electrical properties. Some example properties are shown in Table
3.3. Their poor weatherability, however, means that they are not recom-
mended for outdoor applications, unless they are painted, plated or UV
stabilized. Furthermore, their high cost limits their specification to end-use
products with specific, very high performance requirements such as
connectors.
3.2.15 Polyvinyl Chloride (PVC)

Polyvinyl chloride (PVC) is an extremely versatile commodity material
which is widely used in a broad range of products, including wire insulation
and cable sheathing where it accounts for the largest market share. PVC
coated wire insulation was introduced in Germany during the Second World
War but this initially suffered from stress cracking and it was not until
around 1950 that a hard non-cracking PVC insulation was developed. In the
1970s nylon coated PVC jumper wire was used in the UK, the nylon coating
giving toughness and cut-through resistance, although at the same time
having a negative impact on the flammability performance. This was soon
replaced by the introduction of a single shot extrusion of PVC crosslinked
by irradiation. PVC has also been used to seal racks containing telephone
exchange equipment against hostile environments. In general, this amor-
phous material offers excellent water and chemical resistance, strength,
abrasion and stain resistance, weatherability and self-extinguishability.
However, most PVCs are not recommended for continuous use above 60°C,
which limits their suitability for more demanding applications. Chlorination
increases the material's heat resistance and flame retardancy. However, in
the event of fire, the material will release corrosive combustion products
including hydrogen chloride.
k -_ _ _ _ _ _ _ _ _ _ _ _ P_R_I_N_C_I_PA_L__ST_A_N
__D_A_R_D_T_E_S_T_S____________~I I 65
3.2.16 Thermoplastic Elastomers (TPEs)

Thermoplastic elastomers (TPEs) link the strength and processibility of
thermoplastics with the flexibility and impact resistance of rubber. They
comprise a group of materials that exhibit rather complicated molecular
structures containing entangled 'hard' and 'soft' regions. The hard regions
contain linear alignments of polymer chains below their glass transition
temperatures held together by secondary forces (van der Waals etc.). Above
a temperature sufficient to overcome these secondary forces they behave as
thermoplastic materials (the structure of the material determines ultimately
whether it is hard or soft). One example of the thermoplastic elastomers are
the olefinic TPEs which are based upon blends of a crystalline polyolefin
(e.g. polypropylene or polyethylene) with EPM or EPDM rubber, often
lightly crosslinked.
These materials are tailor-made for products such as keypads and wire
and cable equipment and thermoplastic elastomer polyurethanes have been
used in special cable applications such as those being used underwater.
3.3 PRINCIPAL STANDARD TESTS
This section introduces some of the principal standard tests that are used to
characterize thermoplastic materials used in electrotechnical applications.
These can be grouped into flammability, electrical, thermal, mechanical and
weathering tests.
3.3.1 Flammability
In nearly all electrical and electronic applications of polymers, due attention
must be paid to the flammability of the materials used in the construction of
a particular piece of equipment. Polymeric materials must usually pass strict
flammability rating tests and must ideally also be known not to produce
toxic decomposition products if burning or thermally induced decomposi-
tion should occur.
Burning behaviour is not only a material chemistry and formulation
characteristic but it is also dependent on physical dimensions including the
shape and wall thickness of the application, and on the processing
conditions employed. As there are possibly more flammability test methods
than polymer types, this section gives details of only the most commonly
recognized tests.
In the USA, testing is carried out according to Underwriters' Labora-
tories UL 94. The main tests for this classification fall into three categories:
• UL 94HB
• UL 94V
66 I ~1____________E_N_G_I_N_E_E_ru_N_G__TH__E_R_M_O_P_L_A_S_TI_C_S__________~
• UL945V
Of the three tests, UL 94HB is the least stringent and UL 94 5V is the most
stringent with two classifications, 5VA and 5VB. UL 94V classifications
range from V-O, V-I to V-2, with a V-O rating giving the best flammability
behaviour.
In Europe, the flammability of polymeric materials is commonly tested
using two different methods. The first of these is the glow wire test (GWT),
according to lEC 695-2-1, and the second is the needle flame test according
to lEC 695-2-2.
The glow wire test simulates thermal stresses which may be produced by
sources of heat or ignition, such as might be encountered, for example, in
electrical applications by overloaded resistors or glowing elements. A
sample of the insulating material is held vertically for 30 seconds with a
force of I Newton against the tip of an electrically heated glowing wire. The
travel of the glow wire tip through the sample is limited. After withdrawing
the sample, the time for the flames to extinguish plus the presence of any
burning drops is noted. The sample is deemed to have passed the glow wire
test if one of the following occurs:
• if there is no flame and no glowing;
• if flames or glowing of the specimen, of the surroundings and of the layer
below, extinguish within 30 seconds after removal of the glow wire and
the surrounding parts and the layer below have not burned away
completely.
In the glow wire test, actual test temperatures can vary considerably from
650°C for non-current carrying parts, to 850°C and even 960°C depending
on end-use requirements. Most engineering thermoplastics pass this test at
650°C with a I mm sample thickness. To pass at the higher temperatures,
materials are generally at least UL 94V-2 rated, and examples include flame-
retardant grades of modified PPE and polycarbonate.
The Limited Oxygen Index (LOI) according to ISO 4589 is defined as the
minimum concentration of oxygen, expressed as a percentage by volume, in
a mixture of oxygen and nitrogen, which will just support the flaming
combustion of a material. It is a test which measures the relative
flammability of materials by burning them in a controlled environment.
The test atmosphere is an externally controlled mixture of nitrogen and
oxygen and the supported specimen is ignited with a pilot flame which is
then removed. In successive test runs the oxygen concentration is reduced to
a point where the sample can no longer support combustion. The higher the
value indicated, the less the likelihood of combustion. In general, a material
with an LOI of > 21 % will not bum under atmospheric conditions. (Several
French standards, however, require an LOI of > 25%, and even> 28% in
some cases.)
PRINCIPAL STANDARD TESTS
~----------------------------------------------------~
II 67
3.3.2 Electrical
The Comparative Tracking Index (CTI) is one of the key electrical tests
which are carried out to determine the safety of components carrying live
parts. According to IEC 112 and UL 746, the CTI test indicates the voltage
at which a material continues to resist tracking when the surface is exposed
under stress to contaminated water. The CTI test is carried out using two
platinum electrodes of given dimensions placed on the sample surface. A
potential difference is applied between these and the voltage is gradually
increased in steps of 25 volts up to a maximum of 600 V. The surface of the
sample is wetted with 50 drops of a 0.1 % ammonium chloride solution by
allowing the drops to fall centrally between the two electrodes. (The size and
frequency of the drops is specified.) When no current is flowing at the
applied voltage the test is repeated with increasing voltages until there is a
flow of current. This voltage, decreased by one step of 25 volts is called the
CTI. The test is then repeated at this voltage but this time using 100 drops of
the solution. For direct support of live parts, a CTI greater than 175 V is
required. The CTI 'M' test is a similar procedure which creates more severe
conditions for the testing of industrial parts.
Engineering thermoplastics in general have CTIs of > 175 volts. It should
be noted, however, that the CTI can be affected by the addition of flame-
retardant additives, colours/pigments and fillers. Carbon black, flame
retardants and glass fibres for example, have a distinct negative effect on the
CTI whilst minerals such as Ti02 tend to raise the values. Materials meeting
the CTI requirements at 600 volts are known as 'high tracking resins'.
3.3.3 Thermal
All thermoplastics will soften at elevated temperature. According to ISO 75,
the heat deflection temperature (HDT) or the deflection temperature under
load (DTUL) is a relative measure of a material's ability to perform at
elevated temperatures while supporting a load. The test measures the effect
of temperature on stiffness and a standard test specimen is given a defined
surface stress and the temperature is· raised at a uniform rate. In both the
ISO and ASTM standards a loaded test bar is placed in a silicone oil-filled
heating bath. The force is allowed to act for 5 minutes and then the original
bath temperature of 23°C is raised at the rate of 2°Cfminute. The deflection
of the test bar is continuously observed and the temperature at which the
deflection reaches 0.32 mm (ISO) or 0.25 mm (ASTM) is reported as
deflection temperature under load or heat deflection temperature.
In amorphous materials the HDT is almost the same as the glass
transition temperature (Tg ). However, it is worth noting that this measure-
ment does not necessarily represent the upper use temperature of a material.
Many crystalline materials can be used at temperatures well above their
68 I I~___________E_N_G_I_N_E_E_R_IN_G__T_H_E_R_M_O_P_L_A_S_TI_C_S__________~
HDTs, depending on factors such as the load, the time and whether the
material is filled or unfilled. .
The ball pressure test, according to IEC 335-1, is the most common
softening temperature test and is similar to the Vicat method. During this
test a steel ball is pressed against the sample in a heating cabinet for one
hour. After one hour the ball is removed, the sample is cooled in water for
10 seconds and the remaining impression caused by the ball is measured. In
general, the ambient temperature is 125°C for current carrying parts and
75°C for non-current carrying parts. The diameter of the impression caused
by the ball should not exceed 2 mm.
In accordance with UL 746B, the Relative Thermal Index (RTI) of a
material is an indication of the material's ability to retain a particular
property when exposed to elevated temperatures for an extended period of
time. There can be up to three independent RTI ratings assigned to a
material: electrical, mechanical with impact and mechanical without impact.
3.3.4 Mechanical
To withstand stresses imposed during installation and use, components are
tested to ensure that they can resist mechanical damage. The range of
mechanical properties which are tested includes impact strength, E-
modulus, tensile elongation and hardness. Equipment will often be required
to withstand heat ageing and exposure to humidity while retaining its
mechanical properties.
Impact testing gives the opportunity to evaluate a material under
conditions typical of what might be encountered in real life if a component
is dropped or made to absorb rapidly an impact in some other way. Two
tests used to evaluate the effects of impact on a sample are the Izod and
Charpy methods and these are detailed in ISO 180 (ASTM D256) and
ISO 179 (also ASTM D256) respectively. These methods are used to
investigate the behaviour of suitably defined specimens under specified
impact stresses and to estimate the brittleness or toughness of specimens.
Both tests are performed using a pendulum impact machine in which a
clamped notched sample is struck with a hardened steel hammer released
from a pre-determined height. The impact of the hammer causes the sample
to shear from the sudden load and any residual energy carries the pendulum
upwards. The difference in the drop height and the return height can be used
to determine the energy required to break the test bar. The test can be
carried out at various temperatures and also with a number of test bar
designs.
The modulus of a sample can be determined by monitoring the amount of
deformation (strain) introduced by a given load (stress) and stress/stress
strain relationships under tension are the most widely reported property for
comparing materials or designing for a specific application. Tensile stress/
F_U_R_TH
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ AP_P_L_I_C_A_T_IO_N_S______________~I
__E_R__ I 69
strain relationships are determined by elongating a dog-bone shaped sample

at a constant rate. The load applied and the elongation are recorded and
used to calculate the modulus and a number of other important properties
such as stress at yield, stress at break and the elastic modulus. Typical test
conditions are described in ISO R527, DIN 53455 and ASTM D638M.
Hardness can be determined according to a number of well-known tests
including Ball, Rockwell and Shore hardness. The Rockwell hardness test
determines the hardness of a polymer sample after allowing for elastic
recovery of the test specimen. In this respect it differs from the Ball and Shore
tests where the hardness is derived from the depth of penetration under load,
thus eliminating the possibility for any elastic recovery of the material.
Rockwell hardness values cannot therefore be directly compared to Ball and
Shore values. In the ball hardness test (ISO 2039-1) a polished hardened steel
ball of 5 mm diameter is pressed into the surface of a test specimen with a
force of 358 Newtons. After 30 seconds of applied load the depth of the
impression is measured and the hardness is then calculated from the applied
load divided by the surface area of the impression. The Rockwell hardness
test (ISO 2039-2) also uses a steel ball method whereas the Shore hardness
test (ISO 868) uses a durometer containing a defined steel rod.
Care should be taken when attempting to relate indentation hardness to
the fundamental properties of a material since no simple relationship exists.
3.3.5 Weathering
Weathering is the deterioration of a material under the influence of
temperature, oxygen, relative humidity and UV radiation. These can result
in complete degradation of a polymer with the loss of many important
properties and also its colour. The weatherability performance of a material
is therefore vitally important, particularly where the sample is used in critical
exterior applications. Weathering tests are divided into 'real time' exterior
testing and laboratory-accelerated testing and, according to ISO 4892-2,
include both wet and dry cycles for applications intended for external use.
It should be noted that colour, an integral part of a material's
formulation, can have a significant influence on visual appearance in UV
ageing performance as well as affecting other properties.
3.4 FURTHER APPLICATIONS
3.4.1 Wiring Devices

All engineering thermoplastics are normally suitable for use in non-current
carrying parts. For current carrying parts, polycarbonate, flame-retardant
PBT and most grades of flame-retardant modified PPE resin are ideally
70 I ~I____________E_N_G_I_N_E_E_R_IN_G__T_H_E_RM__O_P_L_A_S_T_IC_S__________~
suited. PBT has a good fit where a balance of chemical and heat resistance is
required.
The leading industry standards for industrial wiring devices are EN 60309
which cover plugs, sockets and couplers. For household and similar
purposes, IEC 884 covers plugs and sockets and EN 60998 covers
connecting devices for low voltage circuits.
In addition to complying with stringent safety codes, domestic switches,
plugs and sockets must also satisfy critical aesthetic requirements. ABS
resin, PC and PCIABS blends all offer a good quality surface finish (high
gloss or textured), in a wide range of colours. Certain grades have also been
specifically developed to offer enhanced UV stability.
3.4.2 Enclosures
The characteristic properties required of materials for enclosures include,
most importantly, -surface finish, impact strength and low flammability. In
accordance with the standards EN 60670 and lEC 439, most high
performance engineering thermoplastics meet the diverse requirements of
enclosures for accessories for household and similar fixed electrical instal-
lations, including both current carrying and non-current carrying parts.
Ongoing development in both materials and process technology ensures
that material suppliers keep in step with market trends. Predominantly,
these trends are for an optimum balance of performance and cost, with a
drive towards improved low temperature performance, chemical and UV
resistance and halogen-free flame retardancy. Colourability is also an
important feature as is the suitability for laser printing.
Each engineering thermoplastic offers a different balance of key properties
to meet individual application needs. Power tool housings, for example,
require the chemical resistance and impact performance of a material like
PBT. Housings for fuse boxes and cable distribution frames also require
high impact resistance combined with good tracking resistance and constant
electrical properties in humid conditions. PBT, modified PPE and PC resins
are ideal for these applications. Uninterrupted power supply (UPS) batteries
require flame-retardancy, chemical resistance, dimensional stability and ease
of moulding for which flame retardant grades of modified PPE resin or ABS
are a popular choice.
Structural foam moulding materials are a sound choice for larger
enclosures as they offer cost-effective parts with good aesthetics, rigidity
and strength.
3.4.3 Installations
PVC is the established material for applications such as cable channels,
conduits and industrial trunking. However, where specifications require
L -_ _ _ _ _ _ _ _ FV_R_T_H_E_R_A_P_P_L_I_C_A_T_IO_N_S_ _ _ _ _ _ _ ---->I I 71
halogen-free flame retardancy according to VDEA 72, then extrusion grades

of modified PPE and PC; ABS become the materials of choice. These
engineering polymers satisfy standards lEC 614 and EN 50086 which
require a flame test on the finished part as well as a GWT pass at 750°C on
fittings. Tailor-made grades offer the same benefits and, in addition, give off
very limited fumes under fire conditions.
Polyetherimide resin meets the critical safety and performance demands
of applications such as in the aerospace industry, as it offers inherent flame
retardancy, combined with minimal smoke generation in the event of a fire.
3.4.4 Wire and Cable

For many years PVC has been, and continues to be, a standard material for
wire and cable insulation. However, although PVC offers inherent low
flammability at normal temperatures, at higher temperatures it will burn
readily and emit highly corrosive fumes.
Recent years have seen the development of advanced insulation and
sheathing polymers. For example, special wire and cable grades of modified
PPE resin offer non-halogenated flame retardancy which minimizes the
toxicity and corrosivity of the combustion products in case of a fire. In
addition, these materials offer excellent electrical properties and thin wall
extrusion at very high speeds on conventional equipment, making them
ideal for telephone exchange wiring.
Optical fibre cable materials must be both soft enough to cushion the fibre
as well as hard enough to withstand impact and abrasion. Thermoplastics
play a significant role in this area. A new modified thermoplastic polyester
resin offers low post shrinkage, good chemical and heat resistance and
superior hydrolytic stability for loose buffer tubes, while high performance
polyetherimide resin meets requirements for superior heat resistance. TPEs
offer the necessary flexibility, hardness and thermal expansion for tight tube
systems, and the right balance of flexibility, shape retention and abrasion
resistance for wire insulation and the sheathing of curly cables.
3.4.5 Switchgear, Relays and Circuit Breakers

Polycarbonate, thermoplastic polyester and nylon 6 and nylon 6/6 have
become the standard materials in many switch assemblies and relays. Their
electrical properties and in particular their resistance to tracking and arcing,
provide reliability in contaminated atmospheres and at elevated tempera-
tures. The increasing economies of multi-chassis designs have further
enhanced the popularity of these resins because of their ease of processing.
The current European standards for these applications are EN 60439 and
EN 60947-1 which will place even more stringent demands on materials in
the future.
72 I LI____________E_N_G__N_E_E_R_N_G__T_H_E_R_M_O_P_L_A_s~T_IC_S__________~
Fig. 3.5. LEXA~, PC, switch box. Photo: GE Plastics.
EN 60898 is the European standard for circuit breakers for overload

protection for household and similar installations. When the circuit is
abruptly broken, the part must reliably withstand the high forces and the
temperatures which can exceed 200°C. An excellent material for this
application is glass-reinforced PBT which offers good dimensional stability
and exceptional thermal and electrical properties. Nylons 6 and 6/6 offer a
superior CTI and ductility but are prone to distortion.
3.4.6 Electricity Meters

This application area is governed by EN 61036 with stringent flammability
requirements. Parts which are in contact with current carrying components
must pass the glow wire test at 960°C and have an HDT of 135°C, criteria
which are being met by tailor-made grades of glass-reinforced thermoplastic
polyester and polycarbonate. For electricity meter covers and cases which
are not in direct contact with current carrying parts, the recommended
materials include flame-retardant modified PPE, polycarbonate and PC;ABS
blends. The option of laser marking of serial numbers is an important
advantage, as these materials are all fully compatible with the process.
The use of polycarbonate offers the possibility of integrating a polycar-
bonate window into the part to enhance the cost savings which can be
gained over traditional materials through faster cycle times. If the window
can be assembled into the case without welding, then modified PPE is a good
choice because of a lower material cost per volume.
FURTHER APPLICATIONS
~------------------------------------------------------~
II 73
3.4.7 Connectors
In the connector industry, no specific IEC material criteria exist. However,
different segments require an individual balance of material properties. The
predominant trends in connector technology are high heat soldering,
miniaturization and MIDs (see Chapter 11). Materials must be easily
moulded in intricate moulding tools with thin sections and very close
tolerances.
Manufacturers are offered a wide range of high performance flame
retardant materials which can be broken down into amorphous resins,
offering high dimensional stability, and glass-reinforced semi-crystalline
resins, which feature high chemical and temperature resistance. Materials
which are generally used in this sector are thermoplastic polyesters,
polycarbonate, nylon and modified PPE. Polysulphones offer high heat
distortion temperatures but at a high cost which limits their use to specific
applications.
3.4.7.1 Standard Connectors

Glass-reinforced PBT is a well-established product for standard connectors
which use compliant push-fit contacts, providing the necessary V-O
flammability rating according to UL 94, high impact performance and
excellent flow properties. Unreinforced grades of PBT and TPEs are also
being used in this application area when stiffness is not critical, or where
there is a hinge component.
In automotive connectors, there is a growing trend towards PBT which
offers tight dimensional stability and high heat resistance (typically 10 000
hours at l60-170°C).
In telecommunications connectors, there is an excellent fit for halogen-
free flame-retardant polycarbonate and modified PPE resins, specifically in
large dimension connectors to be used in less aggressive environments.
Specially developed grades of both material types have a V-O flammability
rating at a wall thickness of 0.8 mm according to UL 94 and meet the most
critical performance requirements of thin walled connectors. Furthermore,
both polymers provide engineering latitude for applications like insulation
displacement connectors which are gaining in popularity.
3.4.7.2 Flexible Hinge Connectors

To satisfy the specific design criteria of flexible hinge connectors, TPEs and
tailor-made grades of unreinforced PBT are ideally suited. These materials
offer the necessary flexibility, good flow, chemical resistance, high elonga-
tion and dimensional stability.
74 I I~___________E_N_G_I_N_E_E_R_IN_G__TH__E_RM__O_P~L_A_S_T_IC_S__________~
3.4.7.3 Fibre Optic Connectors
Polyetherimide and glass-filled modified PPE resins have an excellent fit in
the optical fibre connector market where key design specifications include
dimensional stability, tight tolerances and a low, uniform coefficient of
thermal expansion. Unreinforced polyetherimide grades offer an HDT of
200°C at 1.82 MPa, and excellent flame retardancy. These are comple-
mented by glass-reinforced grades which provide even greater rigidity
and improved dimensional stability while retaining excellent processability.
Furthermore, these resins offer the possibility of metallization using
different methods.
3.4.8 Surface Mount Technology

In surface mount technology (SMT) the key material requirements are high
heat resistance, good flow properties and close tolerance mouldability for
consistent reproducibility. The short-term temperature requirements range
from 160°C with conventional wave soldering, to 215°C with vapour phase
or condensation soldering, and to as high as 260°C with infra-red and
double wave soldering techniques. After soldering, the end product must
show no evidence of blistering and the final dimensions must stay within
extremely close tolerances.
In addition to LCPs, PEEK and PPA, there are the other two dominant
groups of SMT materials with different combinations of heat resistance,
ductility and flow. PPS resins are recommended for applications requiring
high heat and chemical resistance combined with good flow properties.
Where superior ductility is a key requirement, PEl resin is commonly used.
3.4.9 Moulded Interconnect Devices

The predominant trends towards miniaturization of electrical components,
combined with the increasing concentration of functions into these smaller
parts, have led to the development of moulded interconnect devices (MIDs)
made of engineering thermoplastics. The materials are required to offer
superior heat resistance and electrical properties, while combining excellent
dimensional stability and mechanical strength. Furthermore, they must
provide consistent processibility while fulfilling the critical demands of
advanced soldering techniques. Further details of MIDs can be found in
Chapter 11.
3.4.10 Insulation Systems

Engineering materials which are specified for use as insulation in trans-
formers and industrial motors operating at up to 600 volts must meet the
L -_______________ FU
__R_T_H_E_R_A_P_P_L_I_CA
__T_IO_N_S______________~I I 75
stringent requirements of UL Standard 1446 and IEC Publication 85.

Specific grades of polyetherimide, thermoplastic polyester and PPS resins
satisfy these criteria and are compatible with the insulation components
listed in UL File E75735, the most extensive material selection guide
available. In addition to outstanding insulation and electrical properties,
these materials offer important advantages including increased strength and
stiffness, excellent dimensional stability, v-o and 5V flammability ratings
according to UL 94, low water absorption and reduced processing steps.
3.4.11 Capacitor Housings

PBT resin is tailor-made for capacitor housings primarily because it
provides the required high dimensional stability and high resistance to heat
deformation. Furthermore, manufacturers are offered easy, consistent
processibility and compatibility with laser marking processes. PC, modified
PPE and PP resins are also used, although the latter have the disadvantage
of UV sensitivity and brittleness.
3.4.12 Lighting
With an extensive portfolio of engineering thermoplastics satisfying low,
medium and high heat requirements, lighting manufacturers have wide
design freedom to replace metal and thermoset materials in a broad range of
applications. The leading European standard for lighting applications is EN
60598: Part 1 covers general requirements on flammability, GWT and cn
and Part 2 covers more specific requirements by application.
3.4.12.1 Lamp Holders

For manufacturers of lamp holder housings and fittings, high performance
engineering thermoplastics have brought unique design capabilities in
compliance with European standards EN 60400 and EN 60238. In addition
to an optimum balance of mechanical, thermal, electrical and optical
properties, these materials offer cost-effective production and unprecedented
strength to weight ratios. Furthermore, they are available in a wide variety
of colours with a long-lasting finish which can be matt, high gloss or
metallized. In general, materials are selected according to the size and the
temperature class of the lamp holder and typically include glass-filled grades
of PBT, PET and nylon 6/6.
3.4.12.2 Diffusers
Polycarbonate is an ideal material for diffusers, produced by injection
moulding, extrusion or blow moulding. This high impact, transparent
material provides an ideal balance of mechanical, optical and thermal
76 I I~___________E_N_G_I_N_E_E_R_IN_G__T_H_E_R_M_O_P_L_A_S_T_IC_S__________~
~.. '. ~_ L. • ~ .' ' - ~ ...... - - - I • oJ ,- • .' .'
Fig. 3.6. VALOX®, lamp holder. Photo: GE Plastics.
properties, complemented by low uniform shrinkage and dimensional

stability and consistent processibility. UV stabilized grades are available
where long-term weatherability is a requirement. Alternatively, PMMA
offers superior UV stability though inferior flame-retardant properties. PS is
an established material for domestic fittings.
3.4.12.3 Housings and Armatures

Engineering thermoplastics provide the necessary high impact strength, high
heat distortion temperatures and weathering resistance, combined with the
design flexibility to produce complicated mouldings with maximum inte-
gration. Material selection is primarily made according to the temperature
requirements. ABS and PC!ABS blends are recommended for low heat;
polycarbonate for medium heat; and polyetherimide, glass reinforced-poly-
phenylenesulphide, PBT and modified PPE alloys for high heat requirements.
3.4.12.4 Street Lamps

Engineering thermoplastics offer designers a balance of light weight and
mechanical strength, combined with snap-fit design and functional integra-
tion for high quality, durable street lamps. The absence of corrosion ensures
easy, inexpensive maintenance with low replacement costs.
F_U_R_T_H_E_R_A_P_P_L_I_C_A_T_IO_N_S
L-_______________ ______________ ~I I 77
Fig. 3.7. LEXA~, PC, street lamp. Photo: GE Plastics.
The choice of material for the lens is often dependent on the height at
which it is mounted. Where risk of damage to the lens through vandalism is
minimal, then PMMA is widely used because of its excellent UV stability
and cost advantages. However, where superior impact resistance is required,
PC is generally specified. PC is also the material of choice for the structural
components, providing excellent creep performance and mechanical prop-
erties. PP or PC are commonly used for the covers, depending on the
required cost/performance balance.
3.4.12.5 Traffic Lights, Warning and Hazard Lights

Polycarbonate is widely used in traffic light production, due to its excellent
balance of mechanical and electrical properties, combined with good
dimensional stability and weatherability. Furthermore, the resin features
fast moulding times and allows the elimination of expensive finishing
operations through snap-fit assembly. For the internal parts of traffic lights,
warning and hazard lights, thermoplastic polyester and modified PPE are
recommended materials as they provide good dimensional stability and low
water absorption.
78 II ENGINEERING THERMOPLASTICS
~----------------------------------------------------~
3.4.12.6 Spotlights
The broad range of engineering thermoplastics provides the design latitude
to meet the varying levels of service temperature, with high performance
polyphenylenesulphide providing a relative thermal index (RTI) of up to
220°C.
Excellent dimensional stability, high temperature resistance and the
ability to achieve tight tolerances make polyetherimide a good choice for
critical components.
3.4.12.7 Emergency Lights

The European luminaire product standard EN 60598 2:22 requires that the
housings on emergency luminaires on escape routes must pass the glow wire
test at 850°C.
Established flame-retardant engineering materials for luminaire bases
include high flow polycarbonate and PCjABS blends. The latter are
characterized by superior impact performance and UV stability, meeting the
high flammability requirements and offering excellent flow properties for
thin wall designs.
Polycarbonate is an established material choice for emergency light
diffusers as, in addition to its glass-like transparency for a high light output,
it provides the design freedom for clean, attractive styling, exceptional
impact resistance, heat resistance, dimensional stability and structural
strength. Furthermore, the luminaire's light weight complements ease of
installation.
3.4.12.8 Explosion-Proof Lights

Explosion-proof lighting is the most demanding of lighting applications,
and, as such, is subject to the most stringent regulatory requirements for
quality and safety. Polycarbonate is the material of choice for diffusers on
the sealed light fixtures which are typically found in hazardous environ-
ments such as in mines and on oil rigs. As specific grades are virtually
shatter-proof, they offer a high degree of safety and durability in service,
even in the event of an explosion, pass the glow wire test at 850°C at I rom
and have a CTI of > 250 volts.
3.4.12.9 Reflectors
Engineering thermoplastics offer reflector manufacturers a brighter future in
terms of greater design freedom and cost efficiency. The excellent combi-
nation of heat resistance and good surface finish make thermoplastic
polyester, polyetherimide and modified PPE/PA alloys ideal for the
FURTHER APPLICATIONS
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~
79
production of highly efficient vacuum metallized reflectors. For applications

requiring exceptional heat resistance, polyphenylenesulphide is recommend-
ed.
Polycarbonate and polyetherimide resins are both suitable for use with
dichroic coatings without the need for a primer. These coatings allow the
transmission of infra-red rays and reduce the quantity of heat reflected by
the metallized surface. This has enabled engineering thermoplastics to make
an important breakthrough into the cool beam reflector market with end-
use applications ranging from the home and office to the hospital.
3.4.13 Smart Cards

Smart card materials and production processes are selected according to the
required balance of performance, quality and cost. New markets and card
applications such as SIM cards and medical cards require long-life, high
performance properties which are beyond the limits of traditional card
materials. In full compliance with ISO standards 7810, 7811 and 7816, a
tailor-made range of injection moulding engineering materials meets a broad
range of card requirements for heat resistance, durability and printability,
and guarantees environment-friendly recyclability.
Injection moulding offers card manufacturers design flexibility, produc-
tivity and consistent quality. Scrap rates can be kept close to zero and the
waste material can be reground and reused in combination with virgin
material. IC module cavities are easily integrated into the mould design,
eliminating the need for milling.
The range of suitable materials includes ABS, PC/ABS and polycarbon-
ate. All three materials are characterized by good flow and by a 'non-juicing'
polymer formulation which provides cards with a first-class surface finish
for optimum printing quality.
PC/ABS blends offer the processibility of ABS, together with the impact
performance and high resistance to heat distortion of polycarbonate,
making them ideally suited for applications such as GSM SIM cards.
The development of high flow grades of ABS and PC/ ABS alloys for thin
wall moulding has answered the specific demands of in-mould labelling,
opening up important opportunities for cost-effective small batch produc-
tion. The next generation of resins will offer even better flow to meet the
design requirements of con tactless cards.
In addition to smart card materials, injection moulding engineering
polymers are established for card reading equipment production. These
materials feature thin wall processing, dimensional stability, impact resis-
tance and halogen-free flame retardancy for both enclosures and internal
components. Moulded interconnect technology concepts are currently being
developed based on polyetherimide resin, which will offer both superior
productivity and performance.
80 I I'-______E_N_G_I_N_E_E_R_IN_G_T_H_E_R_M_O_P_L_A_S~T_IC_S_ _ _ _ _------'
3.5 POST-TREATMENT OF ENGINEERING THERMOPLASTICS
Many engineering thermoplastics are compatible with a diverse range of

post-treatment processes which include metallization, painting, coating,
silicone hardcoating, printing and laser marking.
3.5.1 Metallization
The metallization of engineering thermoplastics is normally undertaken for
either decorative or functional reasons. A very large and growing quantity
of plastic parts is metallized for reasons of electromagnetic compatibility
(EMC) or to shield electronics from electromagnetic interference (EMI), as
plastics are inherently transparent to EM!. EMI is a recognized form of
pollution and since European legislation was introduced in 1992, there have
been strict limitations on the levels of interference that can be emitted from
any computing device. There are various ways to metallize engineering
thermoplastics using both chemical and physical deposition of metal. A
typical route would involve the deposition of metals such as copper, nickel
and chrome depending on the application. For example, for electromagnetic
shielding, the part could be metallized using electroless copper and nickel
chemistry. A layer of around 5 l1IIl of copper would be deposited onto the
textured surface of the part and a thin top coating of nickel would provide
the outer protective layer. The key to the successful metallization of
polymers is the adhesion of the deposited metal and this is largely
determined by the surface morphology of the polymer sample prior to
metallization. Typically, the surface of the polymer may be treated with
strong oxidizing agents such as chromic acid and alkali permanganate
solutions to achieve the desired result.
3.5.2 Painting
Plastic parts today are primarily painted to enhance aesthetics and provide
colour uniformity. The paint layer can also have an additional beneficial
effect on the surface gloss and offer improved scratch and UV resistance.
However, a key advantage of high performance engineering thermoplastics
is that they offer self-coloured grades with superior surface quality which
often avoids the necessity to apply additional paint.
3.5.3 Laser Marking

The laser marking process provides durable, consistently reproducible part
quality, design flexibility and cost-effective finished parts in an unlimited
variety of applications. This includes the marking of complex geometry
surfaces and the production of very fine lines down to 80 ~ or less. Once
CONCLUSION
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~
81
initial investment has been recovered, unit cost savings are achieved through
simplified, faster production processes, reduced inventories and the recy-
clability of in-plant scrap. Furthermore, set-up and change-over times in
production are minimized, allowing greater manufacturing flexibility and
reduced down-time.
A broad range of laser markable materials has been developed using
proprietary combinations of pigments and additives. Furthermore, expand-
ing on the choice of 'light mark on dark background' or 'dark mark on light
background', the technology has recently expanded to allow laser marking
in many contrasting colour combinations, including both transparent and
translucent colours.
3.6 DESIGN FOR RECYCLABILITY
Manufacturing economics combined with growing environmental concerns

are forcing the design engineer to rethink the approach to product design,
and to consider the disposal issues arising after the product is discarded.
Because of the waste disposal problems associated with plastics, it is
necessary to think in terms of design for recyclability.
The key criterion for ease of recyclability is ease of disassembly which, in
turn, is dependent on simplified assembly. The unique design benefits of
engineering thermoplastics allow this criterion to be met by using fewer
components through, for example, component integration and by the
utilization of assembly features that can be 'designed-in'. Furthermore, the
inherent quality of engineering thermoplastics helps to ensure that recycled
materials retain a high performance profile.
3.7 CONCLUSION
Engineering thermoplastics have been extremely successful in the elec-

trotechnical industry because of their high performance profiles and their
unlimited design flexibility. In the broad range of available materials,
designers can find ideal combinations of electrical, mechanical and thermal
properties: from dimensional stability and creep resistance for close point-
to-point tolerances, to halogen-free flame retardancy with low corrosivity
and low smoke generation to satisfy the most stringent industry require-
ments.
By combining plastics expertise with an in-depth knowledge of industry
standards, processing technology and trends, and by working closely with
customers, suppliers of engineering thermoplastics play a vital role in the
production of parts that are not only lighter, stronger and more reliable, but
also more cost effective and, most importantly, more competitive. Ongoing
82 I IL-___________E_N_G_I_N_E_E_R_IN_G__T_H_E_RM__O_P_L_A_S_T_IC_S__________~
investment in materials development, process technology and manufactur-
ing techniques will ensure that engineering thermoplastics continue to offer
tailor-made material solutions.
Epoxide Resins and Their 4
Formulation
MARTIN GOOSEY*, MARTIN ROTHt,
THOMAS KAINMULLER t and WOLFGANG SEIZt
*Shipley Europe Ltd, Coventry, England and
tCiba Speciality Chemicals Inc., Basel, Switzerland
4.1 INTRODUCTION
The epoxide resins are a class of materials that possess all the properties
required to make them useful for a wide range of applications throughout
the electronics industry. When fully cured they have good electrical
properties, low shrinkage, good adhesion and resistance to thermal and
mechanical shock, whilst also possessing resistance to moisture, solvents and
general chemical attack.
Epoxide resins are all based on the epoxide group, a strained three-
membered carbon, carbon, oxygen ring structure (also known as the oxirane
group);
o
/\
-CH-CH2
The first synthesis of an epoxide group was made early in the nineteenth
century, but it was not until 100 years later that the possible uses of epoxides
began to be realized. They were brought to the attention of industry in 1939,
with the publication of a German patent by I. G. Farben l describing liquid
epoxides. P. Castan of De Trey Freres2 in Switzerland (patents licensed to
CIBA) and S. O. Greenlee of Devoe Raynolds3 first identified the
84 I LI____E_P_O_XI_D_E_R_E_S_IN_S_A_ND
__T_H_E_I_R_F_O_R_M_U_LA_T_I_O_N_ _ _ _ .....l
commercial possibilities of epoxy resins, followed soon by Shell, Reichold

and later Dow and other companies. Ciba Ltd introduced this class of
thermosetting resins to industry at the Swiss Industries Fair of 1946. Since
then many new applications ltave been found and the dramatic increase in
their usage is illustrated by the production figures for the USA, where
production rose from virtually zero in 1948 to 15 000 metric tons in 1957,
65000 tin 1968, 140000 tin 1978 and 243500 tin 1988. World production
climbed from 40000 metric tons in 1960 to 180000 t in 1970, 360000 t in
1980, 600000 t in 1990 and 725000 t in 1994. Roughly 20% of this material
found use in the electrical and electronics industry.
One of the most widely used series of epoxide resins is made by reacting
epichlorohydrin with bisphenol A, in the presence of an alkali, to give the
/\ /\
diglycidyl ether of bisphenol A (DGEBA):
o CH 0
-o-I~
H2C-CH-CH2"0 ~ h 9~O-CH2CH-CH2
CH3
Diglycidyletber of bisphenol A
In order to form the familiar crosslinked networks with the desired
physical properties, epoxide resins are cured by the addition of a suitable
chemical known as a hardener or curing agent. The term 'curing' is used to
describe the process in which an epoxide and a curing agent react to give a
highly crosslinked network. The curing agents for epoxides are numerous
and come from well over 100 different classes of chemical compounds. The
curing of epoxides occurs by an addition type reaction, with the interaction
of resin and hardener or by a catalytically induced homopolymerization to
form a crosslinked structure. These types of curing reaction give epoxides a
particular advantage over some other polymers in which a condensation-
type cure leads to the evolution of a small unwanted molecule such as water
or an alcohol. Condensation molecules are an obvious potential source of
problems when polymerization occurs in the proximity of an electronic
circuit, since they can lead to device malfunctioning or corrosion of
metallization. Another advantage offered by the addition type curing
reaction is reduced shrinkage and epoxides are well known to have
unusually low shrinkage values (usually less than 2%).
In order to be useful, a cured epoxide compound should possess as many
of the following properties as possible:
• good adhesion
• environmental and chemical stability
• thermal stability
INT
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ____R_O_D_U_C_T_IO
__ N__________________~I I 85
• long pot and storage lives

• be easily modifiable
• good reproducibility
• mechanical stability
To impart these properties to the final product, very careful selection of the
epoxide resin and hardener system, as well as all the other components of
the formulation, is vitally important. As the cured material is crosslinked,
the structure and properties of the original resin will be completely changed.
The material will no longer be soluble without decomposition and its
chemical resistance will depend as much upon the hardener selected as upon
the epoxy resin. As an illustration of the dependency of the cured system
upon the hardener, acid anhydride-based hardeners offer excellent resistance
to acid environments, whilst amine type hardeners offer maximum resistance
to alkaline environments.
The reaction between an epoxide resin and a hardener, although usually
leading to a solid material, is unlikely to be sufficient to impart all of the
desired properties. In order to obtain the characteristics that will make it
useful for a specific application, a variety of other compounds may be added
to the resin-hardener system during the formulation stages. For the sake of
formulation purposes, an epoxide resin system can be considered to
comprise two principal components known as the binder and the filler. The
binder component of the system contains the reactive ingredients and
additional organic compounds as solvents, diluents, plasticizers, flexibilizing
or toughening agents. It is the part that undergoes the chemical reaction
when exposed to heat or possibly light and pressure. Ultimately, the binder
component is responsible for providing cured properties compatible with the
particular application for which the material is used.
The filler component comprises the other materials that are needed to
complete the formulation. These are generally non-reactive although one
particular exception is the silane coupling agents used as reactive surface
coatings for the filler particles. Many different compounds find application
as filler components but the more generally used ones are extenders such as
silica, alumina, talc and other minerals and pigments used to give the desired
coloration. If necessary, release agents are also employed to prevent sticking
after moulding. The composition of a typical epoxide transfer moulding
compound used for semiconductor device encapsulation is shown in Table
4.1.
As can be seen from this formulation the constituents comprising the filler
portion are very varied. Materials may also be added in order to counteract
the effects of any deleterious impurities in the compound.
Once it is appreciated that a typical epoxide compound may comprise
many individual ingredients, all of which are available with a variety of
chemical and physical forms, it is not surprising that, before a compound
86 I LI____E_PO_XI_D_E_R_E_S_IN_S_A_ND
__T_H_E_I_R_F_O_RM_U_LA_T_I_O_N_ _ ___
Table 4.1 Composition of a typical epoxide transfer moulding compound for

encapsulating electronic components
Binder component Filler component
Epoxy cresol novolac Silica (crystalline or fused)

Cresol novolac Silane coupling agent
Accelerator Pigment (carbon black)
Flame retardant epoxy Flame retardant (antimony oxide)
Release agent (wax)
can be successfully formulated, some knowledge of the likely application is

required. The major considerations that will lead to an initial selection of
materials are:
1. What object is the epoxide to be used with?
2. What are the cost limitations?
3. To what environment is the object to be exposed?
4. How is the epoxide to be applied to the object?
Having decided upon these factors there will then be a set of consider-
ations which will apply with every application:
1. What shelf-life must the material have?
2. What physical properties must the cured material have?
3. What cure time and temperature are required?
4. What viscosity must the epoxide have?
5. What chemical and thermal stability is required?
6. Is good adhesion required?
7. Does the material need to release easily from a mould?
8. Does the material have to be especially pure?
Quite often there will be a large number of contrasting property
requirements and it will be an unusual case where all of the desired
characteristics can be accommodated. For instance, a system that gives the
desired rapid cure may not have the correct storage lifetime. Alternatively, a
system that provides the correct shelf stability may need an expensive latent
catalyst system which exceeds the permitted cost limitations for the
compound.
Not only is there a large degree of latitude in the selection of individual
ingredients for an epoxy resin formulation but there is also a degree of
flexibility in the final physical form of the uncured compound. This will
obviously be determined by the application, but an epoxy formulation may
be required as a powder, a single liquid or a two-part system which reacts
upon mixing. If a single part material is required, whether powder or liquid,
the individual components are mixed thoroughly together either in solution
EPOXIDE RESINS
L -____________________________________________________ ~
II 87
using suitable solvents or by melt blending. In the melt blending process

heat is used to melt the solid ingredients so that they are thoroughly mixed
together and so that the unfusible inorganic constituents are completely
coated and evenly dispersed within the binder materials. This process
obviously has to be carried out at a temperature high enough to fuse the
organic components but also at a temperature low enough to avoid excessive
curing of the binder system. The solvent process simply involves dissolving
the binder system in one or more suitable solvents and then adding the
fillers. The solvents can be carefully removed under elevated temperature
and reduced pressure. In this process the binder must be able to withstand
the temperature of solvent removal if a dry product is required. Two other
processes are also commonly used and these are the liquid process and the
dry process. In the liquid process one or more of the ingredients is a liquid at
room temperature and the final product will be a solvent-free liquid,
although partial curing may be carried out to solidify the material for a dry
product. The dry process simply involves mixing finely divided powders of
the solid ingredients. The process may begin with large particle size
ingredients, but during the mixing the total mix is reduced in particle size
yielding a fine homogeneously blended powder.
In order to obtain an epoxide compound suitable for a particular
application, all the above considerations have to be taken into account and
the successful formulation can only be made with full knowledge of the
intended application. Each of the major components commonly used in
epoxy resin formulations is now individually discussed and the influence of
physical and chemical properties on the properties of the final formulation
described.
4.2 EPOXIDE RESINS
The epoxide resins, whilst being characterized by the epoxy group, are
available with greatly varying physical and chemical properties. They
exhibit widely ranging molecular structures, molecular weights and viscos-
ities. This wide range of epoxide resins means that they find broad usage in
all types of application, particularly in the electronics industry. By careful
selection of the correct resins and other components of the formulation, the
epoxy resins can be made to yield a variety of forms, ranging from soft and
flexible materials to hard, tough, highly crosslinked, chemically resistant
products.
One of the most commonly used groups of epoxide resins is that
comprised of the diglycidyl ethers, and these are made by reacting
epichlorohydrin with a bisphenol such as bisphenol A. Bisphenol A is
easily and inexpensively formed from the reaction between acetone and
phenol, whilst epichlorohydrin is derived from propylene via allylchloride.
88 II
L ____ E_P_O_X_I_D_E_R_E_S_I_N_S_A_ND
__T_H_E_I_R_F_O_R_M_U_L_A_T_IO_N
_ _ _ _-----I
HO-o-to-OH + 2
o
~CI
Bisphenol A Epichlorohydrin
Diglycidylether of bisphenol A (DGEBA)

The pure diglycidylether of bisphenol A formed from these reactions has a
molecular weight of 340 and many of the well known commercially used
liquid resins have average molecular weights in this region. The actual
molecular weight depends on the reaction conditions, however, and the
more general formula is as follows:
For liquid epoxy resins n is generally less than 1, while for the solid types n
is generally 2 or larger, although it should be remembered that a product
will always be a mixture of various molecular weight resins. Higher
molecular weight resins with a value of 1 < n < 4 can be obtained by reducing
the amount of epichlorohydrin relative to bisphenol A and increasing the
reaction temperature gradually to about 95°C. This so-called 'Taffy' process
is used for solid resins up to a molecular weight of about 1500. An
alternative is the 'advancement' process, where difunctional glycidylethers
and bisphenols are submitted to a polyaddition reaction to give higher
molecular weight, solid resins with n as high as 20 or 30. The relatively high
reaction temperatures of 160--200°C necessitate a careful selection of
suitable catalysts in order to avoid side reactions such as branching or even
gelation.
As their average molecular weight increases, the resins become more and
more viscous until they eventually turn into solids with increasing melting
points (Table 4.2).
Besides the diglycidyl ether of bisphenol A, many other glycidyl ether-
type epoxides are of considerable importance. Closely related is the
diglycidyl ether of bisphenol F (dihydroxydiphenylmethane), offering lower
viscosities and being used as an additive to prevent crystallization of
bisphenol-A-based liquid resins with high purity.
L-_________________E_PO
__X_ID
__E_R_E_S_IN_S__________________ ~I I 89
Table 4.2 Melting points of typical epoxide resins
Molecular weight Average value oln/molecule Melting point (0C)
360-380 0.1 Liquid at room temperature

850-1100 2.2 65-75
1750-2050 5.5 95-105
4000-5000 14.4 125-135
Diglycidyletber of bisphenol F
The preparation of an epoxide novolac type resin is shown below:
6 -
OH OH
0
+ HJl H CH 2
n
Novolac resin
o~
0
0
Novolac resin + ~CI- CH 2
n
Epoxide novolac
The epoxide novo lacs are a very important class of compounds, since they
are the basis of the materials used in the formulation of many of the epoxide
moulding compounds. They are ideal in these applications because very high
crosslink densities are achieved in the cured polymer network. This is a
direct result of the large number of epoxy groups available in the resin for
reaction and these also give the added advantage of high temperature
stability. A typical epoxy novolac might have a molecular weight of around
650, with a weight per epoxide of 175-182 and a very high viscosity. In order
90 1 ,-I____E_PO_XI_D_E_R_E_SIN_S_A_ND
__T_H_E_I_R_F_O_RM_U_L_A_TI_O_N_ _ _ -----l
to develop high temperature stability and the other properties characteristic

of the novolac epoxide, a high temperature cure is necessary, usually in the
region of I 60-1 80°C. When an epoxide novolac is used in a room-
temperature curing system the properties are likely to be similar to those of a
bisphenol A based material in the same application.
The tetraglycidylether of tetrakis (4-hydroxyphenyl)-ethane combines
high functionality with relatively low molecular weight.
Diglycidylethers based on dihydroxybiphenyl and dihydroxynaphthalene

derivatives offer other ways towards highly crosslinked materials with
reduced thermal expansion coefficients and improved thermal resistance.
Diglycidylcthcr ofdihydroxybiphcnyl Diglycidylcthcr of 1.5-dihydroxynaphthalcne
The phenomenal rise of the microelectronics industry in the last two

decades has spurred the development of a host of new and highly specialized
materials. Amongst these are epoxide resins systems used primarily as
adhesives, conformal coatings, glob tops, encapsulants for active and
passive devices, potting compounds and sealants. These electronic grade
bisphenol and novolac-based epoxide resins must be of very high purity in
order to fulfil the most stringent quality criteria demanded by this industry.
These resins are characterized by an extremely low content of ionic
E_P_O_X_ID_E__R_E_S_IN_S__________________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 91
impurities, such as Na +, K + and CC Typical values are less than a few

ppm for such ionic contaminants. Particularly important are the high purity
epoxy-cresol-novolac resins for semiconductor encapsulation with a very
low total chlorine content including ionic chloride as well as organic bound
chlorine. Such resins have to be purified by additional process steps in order
to reach the aforementioned values.
Another development especially for the electronics industry are resins
with double functionality containing both epoxy groups and radiation-
curing double bonds crosslinkable by an addition reaction. Typical
examples are the introduction of double bonds via bisphenols containing
an unsaturated bridge or via a partial esterification of epoxide resins with
(meth-)acrylic acid.
o _~ ~ 0
~O~W-CH=CH~O~
o
Dihydroxychalconediglycidy lether
In addition to the diglycidyl ether-based resins, other epoxide resins are
known, that are also synthesized via epichlorohydrin. Glycidyl esters based
on tetra or hexahydrophthalic acid have low viscosities and after cure, e.g.
with cyclic anhydrides, form materials with improved light and arc
resistance.
o
II
c
o~
CC o~
c
I
o
Hexahydrophthalic acid-diglycidylester
Especially suitable for the manufacture of carbon fibre reinforced
materials are triglycidyl-p-aminophenol and N,N,N',N'-tetraglycidyl-4,4'-
diaminodiphenylmethane. 1,3,5-triglycidylisocyanurate is another very im-
portant N-glycidyl-derivative, finding use mainly in powder coatings.
o o 0
o ~~ ~~~~
~O~N'---D ~N~CH~N'---D
o o 0
Triglycidyl-p-aminophenol N,N,N',N'-Tetraglycidyl-4,4'-diaminodiphenylmethane
92 I LI________E_P_O_XI_D_E__R_E_SI_N_S_A_ND
___T_H_E_I_R_F_O_R_M_U_L_A_T_I_O_N________~
1,3,5-Triglycidylisocyanurate
Further materials can usually be prepared by carrying out an epoxidi-
zation reaction on an unsaturated compound using hydrogen peroxide or
peracetic acid:
\ /
C=C
/ \
Products synthesized in this way contain no hydrolysable chlorine and have
very low ash content, two advantages for their use in electronic applications.
They are also available in a variety of forms, but can essentially be divided
into those which contain a ring structure as well as an epoxide group
(cycloaliphatic) and those which have a linear structure attached to the
epoxide group (acyclic aliphatic).
The cycloaliphatic resins are of paler colour than the standard diglycidyl-
ether resins, they show better light stability and often have lower viscosities.
Typical examples are resins based on two cyclohexeneoxide rings connected
by ester or acetal bridges.
3,4-EpoxycycJohexylmethyl- 2-(3,4-EpoxycycJohexyl)-5,5-spiro-
3' ,4'-epoxycycJohexane-carboxylate (3' ,4'-epoxy)-cyclohexane-m-dioxane
These resins are preferably combined with anhydride curing agents or, if a
very quick cure is asked for, with cationic curing catalysts. The more
compact structure leads to a greater crosslinking density than with the
standard diglycidyl-esters. The cured cycloaliphatic resins thus show very
C_U_R_IN
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ __S________________~I
G_A_G_E_NT I 93
high glass transition temperatures, lower dissipation factors, good arc and
arc tracking resistance as well as high heat stability. They are also well suited
for the manufacture of electrical insulators. On the other hand they are
somewhat brittle. Proper formulation with flexibiIizing or toughening agents
leads to high performance cycloaliphatic epoxide systems for electrical
apparatus which provide a good balance of high heat distortion temper-
ature, thermal shock resistance and arc resistance and high temperature
electrical properties. In both filled and unfilled forms they are also suited to
the encapsulation of coils, transformers and other electrical components.
The acyclic aliphatic resins differ from the cyclic aliphatic epoxy resins in
that they do not possess ring structures. They can be subdivided into two
groups: the epoxidized diene polymers and the epoxidized oils. The
epoxidized diene resins are generally more viscous than the diglycidyl
ethers, except when volatile diluents are used. They are also less reactive
with amines than diglycidyl ethers because of the absence of the ether
linkage, although they have similar reactivity with anhydride hardeners. The
epoxidized oils have the following general skeletal structure:
0 0 o
t: "
II I \ I \
0 0
I \
0 0 o
0 II I \ I \
The number of epoxide groups per molecule can vary, although an average
four to six groups would be usual. As with the epoxidized dienes, their
reactivity with amine curing agents is also low because of steric reasons and
the absence of an ether linkage. The epoxidized oils are usually modified
before use by the introduction of hydroxyl groups into the molecule in order
to reduce the spacing between potential crosslinking sites. By introducing
these hydroxyl groups, the modified material can be made to exhibit
increased toughness and rigidity.
4.3 CURING AGENTS
The special properties that have allowed such widespread usage of epoxide
resins are only obtained when the resins are properly cured. The final cured
characteristics of an epoxide resin are largely dependent upon the curing
system that is used to convert the resin into a thermoset product. This
reaction is brought about by a compound generally known as a hardener,
which causes the epoxide resin to undergo either an addition or a catalytic
94 II
L-_ _ _ _ E_PO_X_ID_E_R_E_SIN_S_A_ND
__TH_E_IR_F_O_R_M_V_L_A_T_I_O_N_ _ _------'
reaction. In the case of an addition reaction, the hardener molecule is

chemically combined into the polymer matrix serving as a bridge for
crosslinking several resin molecules. This is a type of polymerization
reaction referred to as heteropolymerization. In the catalytic type of
reaction, the hardener behaves as a catalyst, encouraging the self-polymer-
ization of the resin and this is known as homopolymerization.
There are many different types of hardener and catalyst available and the
curing agent will largely determine the storage life, the reaction rate, the
time and temperature required for curing, and the final properties of the
system. All of the various hardeners and catalysts have distinct advantages
and limitations associated with them and this section details some of the
major curing agents commonly used. When considering the formulation of
an epoxide resin system for a particular application, the final selection of a
curing agent will depend upon several important factors such as:
1. The physical, electrical, chemical, thermal and mechanical properties

required of the cured material.
2. The limitations on cure speed, postcure and temperature.
3. The cost of the curing agent.
4. The limitations on the material concerned, e.g. pot life, curing
exotherm, viscosity and toxicity.
Although there are literally hundreds of curing agents to choose from, the
commonly used ones can be conveniently divided into the major categories
of aliphatic amines, cycloaliphatic amines, aromatic amines, acid anhy-
drides, novolacs and catalytic curing agents.
4.3.1 Aliphatic Amines

The aliphatic amines form a group of low viscosity, low cost, room-
temperature curing agents which are probably the most widely used of all
epoxide hardeners. They can be used unmodified and also in a reacted form
which reduces their reactivity and the curing exotherm. Too rapid a cure
reaction can complicate any attempt to use the materials for a production
process because the resin and hardener have to be mixed prior to use. A
large curing exotherm is also undesirable because it limits the casting of
large piece parts where thermal runaway might occur.
The aliphatic polyamines most commonly used to cure epoxides are
diethylene triamine (OETA) and triethylene tetramine (TETA). These are
both pungent, low viscosity liquids and they are commonly used with the
diglycidyl ether of bisphenol A type resins, where rapid low temperature
cures are required. Three other commonly used polyamines are ethylene
diamine (EOA), tetraethylene pentamine (TEPA), diethylaminopropyl-
amine (OEAPA) and 3,3-dimethyl-5-methyl-I,6-diaminohexane (TMO).
CURING AGENTS
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~
95
~NH2
H2N
Ethylenediamine (EDA) Diethylenetriamine (DETA)
Triethylenetetramine (TETA) Tetraethylenepentamine (TEPA)
lN~NH
~ 2
3,3-Dimethyl-5-rnethyl-1 ,6-diaminohexane (TMD) Diethylaminopropylamine (DEAPA)
The properties of these amines are given in Table 4.3.

Epoxides cured with DETA and TETA usually have similar properties.
They have good chemical resistance to aqueous acids and alkalis, although
they are attacked by strong organic acids and nitric acid. These properties are
maintained up to moderate temperatures, but for high temperature perfor-
mance an aromatic amine would be preferred. DEAPA is very similar to
DETA, yet it offers pot lives of up to 4 hours at room temperature and needs
to be heated in order for full curing to be achieved. It does not crosslink so
densely as the TETA-type amines and thus its chemical properties are
somewhat inferior. 3-Dimethyl-5-methyl-l,6-diaminohexane offers advan-
tages such as prolonged pot-life and improved mechanical properties.
Epoxide polyamine systems are commonly used as the basis for solvent-
type epoxide coatings. They offer excellent coverage of both ferrous and
non-ferrous metals as well as concrete and wood. These coatings are usually
applied by conventional spraying or brushing techniques. They are also
often used as dip coatings for various electronic components and electrical
Table 4.3 Properties of commonly used polyamines and optimized amounts required
to cure epoxides
Amine Molecular weight Active hydrogens Calculated amount State

(phr)
DETA 103 5 11 Liquid

TETA 146 6 13 Liquid
TEPA 189 7 14 Liquid
EDA 60 4 8 Liquid
DEAPA 130 2 7 Liquid
TMD 158 4 25 Liquid
96 I I~_______E_P_O_XI_D_E__R_E_SI_N_S_A_ND
___TH
__E_IR
__F_O_R_M_U_L_A_TI
__ O_N______~
equipment, where the epoxide resins will be based on DGEBA or a low
molecular weight epoxy novolac. The formulated liquid system may then be
modified with a thixotroping filler or filler combination to give regular
coating and non-drip characteristics. A typical basis for a formulation
would be:
Material Quantity
DGEBA 100
Bentonite 16
Iron oxide 4
DETA 10
Several other types of curing agent based upon the aliphatic amine
approach are also commonly used in epoxide formulations. Examples are
polyether-polyamines with a ftexibilizing effect or the glycidyl adducts of the
aliphatic amines, in which the aliphatic amine is partially reacted with an
epoxide to give an adduct with low volatility. Similar types of adduct can
also be made by reacting the amines with ethylene and propylene oxides. By
forming such adducts, reaction rates can be increased and the danger of
allergic reactions can be reduced, but the physical properties may deteriorate
somewhat, and, in the case of the ethylene and propylene oxide adducts, the
compounds are hygroscopic. Polyaminoamides are made from dimerized
fatty acids and polyalkylene polyamines. Besides a ftexibilizing effect they
offer advantages such as low volatility, reduced allergic potential and an
uncritical and high mixing ratio with the resin which facilitates dosage and
mixing.
o
)l ~NH............... NH2
(CH 2h NH
(CH~NH....,/""-NH-......,.,NH2
o
~ (CH 2);CH 3
Polyetber-polyamine Polyaminoamide
4.3.2 Cycloaliphatic Amines
Another group of curing agents based upon the polyamine concept is the
cycloaliphatic amines. These have properties somewhere between those of
the aliphatic amines and the aromatic amines. Typical examples are
isophorone-diamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 1,2-
diaminocyclohexane, aminoethyl piperazine and 1,8-diamino-p-menthane.
__S__________________~I
C_U_R_I_N_G_A_G_E_NT
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 97
Xylylene diamine is closely related in reactivity and properties of the cured
materials.
4N~ ~N-OCH6N~ ONH,

Isophoronediamine 3,3'-Dimetbyl-4,4'-diamino- 1,2-Diaminocyclohexane
dicyclohexylmetbane
£: I NH2
m-Xylylenediamine
HN
1\
~
N~
NH2
Aminoetbyl-piprazine
~H'
NH2
1,8-Diamino-p-mentbane
These materials generally give higher glass transition temperatures than the
aliphatic amines but have poorer thermal stabilities than the aromatic
amines.
4.3.3 Aromatic Amines

The aromatic amines are characterized by having the nitrogen atoms of their
amino groups attached directly to an aromatic ring structure. They offer
several advantages over the aliphatic amines, such as higher glass transition
temperatures, longer pot lives and greater chemical resistance after cure.
Their reactivities are generally much less than those of the aliphatic amines,
with cures often taking several months at room temperature. As a general
guideline, the reaction rates for aromatic amines at around 90°C are roughly
comparable to the room temperature reaction rates achieved with the
aliphatic primary amines. Carefully controlled pre-reaction leads to solid,
still fusible intermediates with relatively long storage stability. B-staged
moulding compounds as well as fibre-reinforced 'pre-pregs' are based on
this technology.
4,4'-diaminodiphenylmethane (DADM), 4,4'-diaminodiphenylsulfone
(DADS), m- and p-phenylenediamine, low molecular weight aniline and
methylaniline-formaldehyde condensation products, 4,4'-oxydianiline as
single curing agents or in the form of low melting or liquid (eutectic)
mixtures and adducts are all used as curing agents for epoxy resins.
2,2'-diethyl-4,4'-diaminodiphenylmethane and similar alkylated DADM-
derivatives offer longer pot life and, hopefully, lower toxicological risks than
the other above-mentioned aromatic amines.
98 II EPOXIDE RESINS AND THEIR FORMULATION
~----------------------------------------------------~
4,4'-Diaminodiphenylmetbane (DADM) 4,4'-Diaminodiphenylsulfone (DADS)
2,2'-Dietbyl-4,4'-diaminodiphenylmethane
DADM, for example, is a solid, melting at around 90o e. It contains four
active hydrogens and is usually used in concentrations of 25-30 parts per
hundred of resin. Mixing is achieved by heating part of the resin to just
above 90 0 e and adding the molten amine. After thorough mixing, the batch
is cooled by the addition of more resin and mixing is continued. DADM
gives relatively high temperature strength and enhanced electrical proper-
ties, such as dielectric constant and dissipation factors.
DADS has an advantage over other aromatic amines in that it gives very
high glass transition temperatures and its strength properties are maintained
to higher temperatures. It is a solid with a melting point around 175°e and
is generally used in the range of 40 phr with DGEBA type epoxides
(although 20-30 phr may be adequate if an accelerator is utilized). In order
to mix the resin and hardener, the resin is heated to above nooe and the
DADS is added slowly with stirring and maintenance of temperature until
all the hardener is dissolved. If an accelerator is to be used, the temperature
should be lowered to 1000e and one part by weight of boron trifluoride-
monoethylamine blended in. This type of system would be suitable for
electrical casting requiring extreme service durability and elevated temper-
ature strength.
As well as the principal aromatic amines reported above, various other
aromatic amines find use in certain applications. Typical examples of these
compounds are:
NH2
2,4-Diaminotoluene 2,6-Diaminopyridine 2-Aminobenzylamine
__S__________________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 99
4.3.4 Dicyanodiamide and Related Products
Used from the beginning in epoxy-resin technology, dicyanodiamide is still

one of the most important latent curing agents. Its main application is with
epoxides used in the production of printed circuit boards.
Latency depends to a great extent on the low solubility of dicyanodiamide
in epoxy resins at room temperature. Reaction at elevated temperature
follows similar routes as for cyanamide via dialkylcyanamides, amino-
oxazoles and iminooxazolidinones. For applications where the reactivity of
dicyanodiamide is too low, alkyl-substituted phenyl-ureas or imidazoles are
the preferred accelerators.
Closely related as latent curing agents are biguanids, finding use in
powder coatings.
Cyanamide Dicyanodiamide Biguanide
4.3.5 Anhydrides
Acid anhydrides are the second most commonly used curing agents, and
they are characterized by the anhydride group, which is derived from a
diacid by dehydration.
aGo
o
OH
OH
o o
They represent a low cost group of hardeners which provide long pot lives,
have excellent heat stability and are especially suited to electrical applica-
tions. Anhydrides also offer advantages in handling, since, unlike the
amines, they are not skin-sensitizing agents. Also, unlike the aliphatic amine
cured epoxide systems, the acid anhydride cured epoxides usually require
long, high temperature cure schedules before optimum properties can be
achieved. This is probably the major limitation to their use, although certain
accelerators are useful in enhancing the reactivity. Acid anhydrides can,
however, provide more rapid cures than amines when used as curing agents
for the cycloaliphatic and epoxidized olefin based resins.
100 II'- -____ E_P_O_X_I_D_E_R_E_S_I_N_S_A_ND
__T_H_E_I_R_F_O_R_M_V_L_A_T_IO_N
_ _ _ _--'
The curing reactions of anhydrides with epoxide resins are quite complex
and may be dependent upon a number offactors, such as the temperature, the
type of epoxide, the amount of anhydride used and the presence and type of
accelerator. The first stage of the curing reaction is the opening of the
anhydride ring by a hydroxyl group, such as may be found in the epoxide resin.
o
~O-R
~o + R-OH
~OH
o o
There are then five further possible types of reaction that can take place but
the two most important ones are (l) the reaction of a carboxylic acid group
«
with an epoxide group:
~O-R +
o I
OO_R
OH
~OH ~ ~ O~
o o
and (2) the etherification of a hydroxyl group by an epoxide group:
I o OH I
H-C-OH + ~ H-C-OA
I I
Anhydrides react relatively slowly and, especially with cycloaliphatic resins,
it is quite often found that approximately equal amounts of the ester and
ether linkages are formed, thus leading to brittle products. Therefore, the
reaction is usually modified in commercial systems by the use of accelerators
such as tertiary amines, quaternary ammonium salts or, in the case of
cycloaliphatic resins, sodium alcoholates.
The tertiary amine accelerators are commonly used with standard resin/
anhydride systems to speed up their curing reactions. They are used in
concentrations of 0.5 to 5 phr and typical examples are:
'NyO~
I I I h
N/ fvNH
N/
I
Benzyl-dimethyl- Dimethyl- Tris- 2-Ethyl-4-methyl-
amine aminomethyl- (dimethylaminomethyl)- imidazole
phenol (DMP 10) phenol (DMP 30)
L -_ _ _ _ _ _ _ C_U_R_IN_G_A_G_E_NT_S_ _ _ _ _ _ _ -'I I 101
There are many types of anhydride available, but one of the most
important groups is that based upon anhydrides with cyclic structures.
Typical examples of anhydrides in common use are:
o 0 0
~o ~o ~o
o 0 0
Phthalic anhydride Tetrahydrophthalic Hexahydrophthalic
m.p.131-133°C anhydride anhydride
m.p. 65-68°C m.p. 35-36°C
CI
o 0
HO~
CI
o~o ~
I 0
CI
0
o 0 0
CI
Pyromellitic Trimellitic anhydride Chlorendic anhydride
dianhydride mp.168°C mp.239°C
m.p. 283-286°C
Phthalic anhydride is used extensively in low cost epoxy formulations

since it is itself very inexpensive. Its main application is with glycidyl ether
type resins, in the production of large electrical castings. The anhydride is
usually mixed with the resin by stirring it into the hot resin at l20-l40 a e
and then cooling to 60a e to prolong the pot life. With low molecular weight
bisphenol A resins, phthalic anhydride is usually used at a concentration of
between 30 and 45 parts per hundred of resin. The curing reaction is fairly
slow, examples being 24 h at 120ae, 16 h at Boac and 6 h at l50ae.
Phthalic anhydride cured systems do not give particularly high glass
transition temperatures and problems may be experienced with sublimation
of the anhydride. The main advantages of phthalic anhydride cured systems
are the very low curing exotherms, which allow the production of large
castings with good chemical resistance and good electrical properties.
Tetrahydrophthalic anhydride is often used in place of phthalic anhy-
dride, since it is of comparable cost and has the advantage of not subliming.
Even more useful is hexahydrophthalic anhydride, which imparts good all-
round properties and is also soluble in epoxide resins at room temperature.
It is used in yoncentrations of between 55 and 80 parts per hundred of resin
and, in the presence of around 0.5% of benzyl dimethyl amine, it gives
~----------------------------------------------------~
similar cure times to phthalic anhydride, with slightly higher glass transition
temperatures. Mixtures of isomeric methyl-tetrahydrophthalic-anhydrides,
as well as methyl-hexahydrophthalic anhydride, have the advantage of being
liquid at room temperature and easily mixable with the resin.
Where higher glass transition temperatures are required with diglycidyl-
ether of bisphenol A based resins, anhydrides with higher functionality have
been employed, such as pyromellitic dianhydride, which contains two
anhydride groups, and trimellitic anhydride which has an additional
carboxylic acid group. Chlorendic anhydride is a member of the family
that, because of their halogen content, imparts flame retardancy upon a
cured resin. Systems cured with chlorendic anhydride have excellent
electrical and mechanical properties although it does have a somewhat
limited thermal stability and a tendency to be hygroscopic.
Similarly to the aromatic amines, eutectic mixtures of two anhydrides are
sometimes used to overcome difficult mixing procedures such as the
requirement for high temperature mixing. One such example is a 70/30
mixture of chlorendic anhydride and hexahydrophthalic anhydride which
imparts nearly the same properties on the cured system as pure chlorendic
anhydride yet allows much simpler mixing to be achieved.
4.3.6 Novolacs
Novolacs mentioned above as starting materials for multifunctional epoxy
resins are also very useful curing agents. Curing needs temperatures in the
range of 160 to 200°C even when accelerators such as tertiary amines or
imidazole-derivatives are added. The resulting crosslinked products com-
bine high Tg with excellent long-term thermal and chemical resistance as
well as relatively good mechanical properties. Novolacs find use in epoxy
moulding compounds as well as in coatings.
4.3.7 Catalytic and Photoinitiated Curing, Latency

The amine and anhydride curing agents described above lead to the
formation of the crosslinked thermoset material primarily by a polyaddition
reaction. Also known as stoichiometric hardeners, they are usually
employed in equimolar amounts of reactive groups relative to the epoxy
group. In contrast to this, the so-called 'catalytic' curing agents achieve the
same result with di- or higher functional epoxide resins by causing the ring
opening homopolymerization of the strained epoxide ring. The resin's
molecules react directly with each other, the catalytic curing agent acting as
an ionic initiator. As it is often incorporated into the polymer chain and
used up during the curing reaction, the term 'catalytic' is actually incorrect
in such a case. Only small amounts of catalytic hardeners are employed and
L - -_ _ _ _ _ _ _ C_U_Rl_N_G_A_G_E_NT_S_ _ _ _ _ _ _---JI 1 103
this results in the crosslinked polymer having predominantly a polyether

type structure.
The absence of secondary hydroxyl groups and the high crosslink
density of catalytically cured resins is reflected in the bulk material
properties, such as high heat and chemical resistance, brittleness and
somewhat inferior adhesive properties compared to amine cured types. A
distinctive feature is also the possibility of broadly varying the cure speed:
systems with very high cure speeds at ambient temperature can be achieved
as well as latent systems with a long pot life at room temperature and a
short gel-time at the cure temperature. As the homopolymerization of the
epoxide group is accompanied by a massive evolution of heat of reaction,
approximately 90-100 kJ per molar equivalent of epoxide group, care has
to be taken to control the exotherm, especially when curing large amounts
of material.
The most prominent classes of catalytic curing agents are: Lewis acids
(BF3-complexes, metal salts with non-nucleophilic anions), Lewis bases
(tertiary amines, N-containing heterocycles), onium compounds (sulfonium
salts) and metal complexes (e.g. metallocenes). A Lewis acid is a species that
can accept an electron pair during a reaction and a Lewis base is one that
can donate an electron pair. Lewis acids and onium salts (I) polymerize the
epoxy group (II) via a cationic reaction mechanism (III), (IV), whereas
Lewis bases act as anionic initiators in the polymerization of the epoxy
group, the result being in both cases a polymer (V) with the same polyether
structure, independent of the type of initiator and with only the end groups
varying.
[~ 0 ~R [E-{O~~~ RJ
E] ~
1+ +)
o
.. X- _ X-
~R
~
initiation R chain growth R
(I) (II) (III)
E+ X - =Lewis acid
X =non-nucleophilic anion
+HX
(V)
104 I LI________E_PO__XI_D_E__R_E_S_IN_S_A_ND
___T_H_E_I_R_F_O_RM~U_L_A_T_I_O_N________~
Boron trifluoride is one of the more important Lewis acids currently used.
However, as it is a corrosive gas which is extremely reactive at room
temperature, it is usually complexed with an amine such as monoethylamine
or benzylamine:
FI H
I
FI H
I
F-S:N~
I I \ F-S:Nb
I I
F H F H -
~ h
BF3-ethylamine complex BF3-benzylamine complex
These complexes have negligible reactivity at room temperature (good

latency) but at around 90°C they begin to dissociate and react with the
epoxide. The complexes are normally used in concentrations of around 3-5
parts per hundred of resin and a typical cure would be 2 hours at 105°C,
with a post-cure of 4 hours at 175°C. Complexation with structurally
different amines can be used to control properties such as reactivity and
solubility over a relatively wide range. The cured products are very hard,
strong and brittle, and have good to average electrical properties. Formu-
lations often contain fiexibilizing reactive diluents in order to toughen them
against impact induced damage. Care should be exercised in the use of these
materials with certain metals or sensitive devices, since the liberated BF3
may cause corrosion.
BF3 and BCl3 complexes are also often used as accelerators for the
anhydride curing of epoxide resins, particularly in electrical casting
applications for the fabrication of large volume parts.
Onium salts are another type of cationic catalytic curing agents which
have gained widespread attention in recent years. Depending on their
structure, they are either used with the standard thermal activation or, even
more importantly, with photoinduced activation, in which case they are
often referred to as 'cationic photoinitiators'.
__S__________________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I lOS
Onium salts as cationic photolnitiators
ROO
Qx-
R'VS'Q R"'
Triarylsulfonlum salt Diaryliodonium salt lron-arene complex
(metallocene)
Onium salts for thermal curing x = non-nucleophilic anion

e.g. PF6-; SbF6-
Mono-benzylsulfonium salt Tris-benzylsulfonium salt
Photoinitiators, either radical or cationic, are the heart of modem

photocurable materials which compete favourably with conventional
thermal methods in various applications, such as coatings, adhesives and
printing inks. Considerable savings in energy, solvent emissions and process
time can be realized. Although radical photoinitiators are still dominant,
cationics of the triarylsulfonium-type and iron-arene complexes, are
becoming more important. When irradiated with UV-light of wavelength
below 350 nm, triarylsulfonium- and diaryliodonium-salts generate very
strong Brensted acids, which in tum initiate the cationic polymerization of
the epoxide group. The UV irradiation of iron-arene complexes (metal-
locenes) leads to metal-organic intermediates with strong Lewis acid
activity, in this case the spectral response is enlarged to longer wavelength
regions, up to about 450 nm. Cycloaliphatic epoxide resins are most reactive
with these photoinitiators, but aromatic glycidylethers derived from
bisphenol A can also be utilized. Often a short post exposure bake at 80-
120°C markedly enhances the cure speed. Oxygen (air) is not an inhibitor
but care has to be taken to exclude any basic components, such as amines
and phosphines, which act as chain terminators.
A number of alkyl substituted sulfonium salts have been proposed as
thermal initiators for epoxide curing. The benzyl substituted compounds
feature an interesting combination of properties. Di- and tribenzyl-
sulfonium salts allow for very short cure cycles at moderate temperatures
of 80-120°C with a relatively long pot life of several days or weeks at
~----------------------------------------------------~
ambient temperature. Mono-benzylsulfonium salts are less reactive but have

even longer open times. A broad range of applications for these thermally
activated benzyl sulfonium salts exists in such fields as encapsulation of
electrical and electronic parts, adhesives, conformal coatings and laminating
resins.
Of the Lewis bases, imidazoles and tertiary amines, already well known as
accelerators for the anhydride curing of epoxides, are used per se as anionic
epoxide hardeners. They are employed in concentrations of 2-10 parts per
100 parts of liquid diglycidylether and curing can take place at moderate
temperatures. IH-imidazoles and I-substituted imidazoles are of special
interest due to their high reactivities.
H3C
~N
~·J"~CH
N \ 2
(~~
N ~ \
I :--...
~ CH3 H
2- Ethyl-4-methyl-imidazole 2-Phenyl-imidazole 1-Methyl-imldazole

(2,4-EMI) (2-PI) (1-MI)
A host of substituted imidazoles and imidazole derived products with

vastly differing curing characteristics are commercially available, with 2,4-
EMI being perhaps the best known. In a typical example, a mixture of 4
parts of 2,4-EMI in 100 parts ofliquid bisphenol A-diglycidylether will show
a gel time of about 3 minutes at 12oDe, a pot life (determined as the time for
doubling of the initial viscosity) of about 9 hours at ambient temperature
and a glass transition temperature of 130D e if given a cure of 100 minutes at
80D e followed by a post cure of 4 hours at 150D e.
Of the Lewis bases, the compounds dimethylaminomethyl phenol (DMP
10) and tris (dimethylaminomethyl) phenol (DMP 30) are also widely used
as curing catalysts. They are employed in concentrations of 4-10 parts per
hundred of resin with liquid diglycidyl ethers and curing takes place rapidly
even at room temperature.
4.4 EXTENDERS
The term extender is very broad and covers a wide range of materials but it
generally applies to inorganic materials that are added to a polymer in
relatively high concentrations. One of the major reasons for using extenders
in an epoxide resin system is to reduce the cost of the final product and this
has become particularly important since the onset of crude oil price
increases in the early 1970s. By using extenders in a resin system, not only
can the price be controlled but their use also allows the properties of the
finished product to be tailored for a particular application. In the electronics
"--_ _ _ _ _ _ _ _
EX_T_E_ND_ER_S_ _ _ _ _ _ _ _ --'I I 107
industry, the use of extenders with epoxides is usually more important from
the point of view of tailoring properties than of cost reduction.
Extenders can be used to control curing exotherms and moisture
permeability, to impart increased strength or to tailor properties such as
hardness, heat distortion, thermal expansion coefficients and thermal
conductivity. More novel fillers can be used to impart electrical conductivity
and magnetic properties or to reduce the compound's density by the
incorporation of small hollow glass spheres. The selection of the correct
filler is of the utmost importance and all the critical desired properties of the
cured compound must be taken into account before a particular filler can be
decided upon.
One of the first problems that is encountered is the selection of an
extender with the correct particle size, shape and particle size distribution.
Since the properties a filler imparts upon a formulated epoxide resin system
may well be very dependent upon surface area, the particle size distribution
of a given type of filler may be critical. For a moulding compound
formulation, particle size will control the flash and bleed characteristics and,
indeed, the mouldability. Another important factor that has to be
acknowledged is the possibility of a reaction occurring between the extender
and the resin system, and since reactivity will be influenced by surface area,
this should be borne in mind when selecting a particular particle size
material.
Perhaps some of the most important considerations of extenders for
epoxides to be used in electronic applications are the changes that they
impart to the electrical properties of the formulated product. If good
insulative properties are required of the compound, the condition and type
of extender selected will be important since ions, salts, moisture or water
soluble impurities may be adsorbed on the particle's surfaces, all of which
can serve to increase the conductivity of the compound. Conversely, high
conductivity may be required, as in the case of conductive die attach
materials where the extender may be a finely divided metal such as silver or
gold. Care also has to be taken when selecting organic extenders, since high
voltages or areas of high current density can cause tracking or carbon
bridges to form. The use of extenders can thus be seen to play an important
part in determining the electrical properties of a finished product and
extreme care should be exercised in their selection.
Extenders are often used to alter the thermal expansion coefficient of a
material and this is particularly true with electronic applications, where the
principal substrate is usually silicon. If a silicon die is encapsulated in an
epoxide based moulding compound, reliability problems can occur because
of the thermal expansion coefficient mismatch between the silicon and the
encapsulant. During any temperature changes, the differential expansion of
the two materials can cause stresses to build up in the package which lead to
wire bond fatigue and possibly even cracking of the chip. The same applies
108 II~________E_P_O_X_I_D_E_R_E_S_I_N_S_A_ND
___T_H_E_I_R_F_O_R_M
__ ________~
U_L_A_T_IO_N
Table 4.4 Advantages and disadvantages of the use of extenders
Advantages Disadvantages
Reduced cure shrinkage Increased density

Reduced cost Reduced flow
Reduced thermal expansion coefficient Increased dielectric constant
Reduced curing exotherms Loss of transparency
Improved thermal stability Promotion of crack propagation
Reduced moisture, solvent and gas permeability Introduction of impurities
Increased thermal conductivity Reduced tensile strength
Increased hardness Reduced flexural strength
Improved compressive strength Variable machinability
Improved dielectric strength
Improved abrasion resistance
Improved adhesive strength
Reduced creep and stress relaxation
Increased heat deflection temperatures
Enhanced flame retardancy
Improved arc resistance
Increased pot life
with die attach materials, particularly when the adhesive used is a fairly
rigid, highly crosslinked type.
It is generally true that nearly all commercial epoxide resin formulations
have extenders incorporated in their formulation, the final selection being
determined by the properties to be altered, the application and the other
components of the system. Some of the properties affected by the addition of
extenders are listed in Table 4.4. (For some specialized applications, certain
of the listed disadvantages may in fact be advantages.)
As can be seen, for the majority of applications the advantages of using
extenders far outweigh the disadvantages and it is hardly surprising that the
inorganic extenders find such widespread usage. Several of the more
important extenders will now be discussed in more detail.
4.4.1 Silica (Si02 )

Silica is usually thought of quite simply as Si02 , but in fact there are over 20
distinct phases of silica, each one still being chemically Si02 . One of the
most important types of silica for use in electronic grade epoxides is fused
silica. This is produced by subjecting high purity crystalline quartz to very
high temperatures in an arc furnace. It has a thermal expansion coefficient of
around 9.54 x 10--6 m/m;oC over the temperature range ~1000°C and a
comparatively low density. The low density means less weight increase in an
epoxide formulation and thus I kg of fused silica will give a larger volume of
L -_ _ _ _ _ _ _ _ EX_T_E_ND_ER_S_ _ _ _ _ _ _ _ ----'I I 109
Table 4.5 Densities of some widely used fillers
Filler Density (g/c~)
Fused silica 2.15

Glass 2.70
Quartz 2.65
Calcium carbonate 2.70
Alumina 3.97
product than the same weight of a denser material. The densities of various
extenders are shown in Table 4.5.
Another commonly used form of silica is quartz, which has advantages
over fused silica for certain applications due to its higher thermal
conductivity. Thus, where enhanced thermal conductivity is required, as
in the encapsulation of power devices or integrated circuits (lCs) with high
circuit density, quartz would be a preferred filler.
Another popular form of silica that is particularly useful with liquid
systems is fumed silica and this is an amorphous form that has a very large
surface area. It can be used in liquid epoxide systems to provide thixotropic
and anti-settling characteristics and in moulding compounds to control flash
and bleed. The thickening effect of fumed silica results from the interaction
of silanol (SiOH) groups on adjoining particles, as well as between the
silanol groups and the reactive groups of the hardener (such as amine
groups). Fumed silica is also useful in elastomeric materials, such as the
silicone rubbers, as a reinforcing agent to improve mechanical properties. It
has the distinct advantage of allowing the formulation of silicones that are
translucent or even transparent.
4.4.2 Silicate-based Fillers
4.4.2.1 Talc
Talc is the name given to hydrated magnesium silicate, which has the
theoretical formula 3MgO.4Si02 ·H20 and it occurs in several ores from
which talc products can be made. The form of most use in plastic
formulations is finely ground talc, which consists of thin platelets. It is
considered to be a reinforcing filler in many compound applications,
although it can also be described as an extender because of its low cost.
Talc possesses a good degree of chemical resistance, being inert to most
acids and it is also a good insulator. This latter property makes it
particularly useful in the manufacture of high frequency electrical insulators.
It has good ~hermal stability up to 900°C, which is considerably higher than
any temperature likely to be encountered in an epoxide resin application.
110 I ~I________E_PO__X_ID_E__R_E_SI_N_S_A_ND __F_O_R_M_V_L_A_T_I_O_N______~
___T_H_E_IR
The use of talc in epoxide formulations leads to higher stiffness and
improved creep resistance at both room and elevated temperatures. In order
to obtain the full benefits from using talc, it is very important that the
correct compounding techniques are used to incorporate high loading into
the resin system.
The machinability of epoxides varies considerably from filler to filler, and,
if ease of machinability is required, the use of talc may provide this property.
Talc is also of use in epoxide resin formulations when the thermal expansion
coefficient has to be lowered by a large amount, since loadings up to 80 parts
per hundred of resin can be tolerated. Loading epoxides with talc has also
been shown to increase their lap shear strengths when they are used as
adhesives.
4.4.2.2 Wollastonite
Wollastonite is a naturally occurring calcium-silicate that is available in
different particle size distributions with or without surface treatment. Due to
its lower coefficient of thermal expansion (CTE ca. 7 ppm/K) compared to
ca. 14 for (crystalline) silica the CTEs of metal substrates can be better
matched by formulations containing Wollastonite. In terms of lowering
CTE, fused silica, with a CTE near to zero is still more efficient. Beside the
effect or reducing stresses from CTE mismatches Wollastonite can also
improve the fracture mechanical properties of epoxy formulations due to its
particular needle shaped form. This property profile leads to materials that
are very resistant to thermal shocks. Wollastonite shows other useful
properties, e.g. a low abrasivity. Disadvantages with this filler are its lower
thermal conductivity compared to crystalline silica and the fact that
additional technical efforts are necessary to manufacture really homoge-
neous dispersions.
4.4.2.3 Clay
Another extender occasionally used in epoxide formulations is clay. Clay is
a hydrated alumino silicate mineral, also known as kaolin, which is available
in a calcined, anhydrous form. The hydrated form is non-abrasive,
chemically inert and has a large surface area. It is naturally acidic and
this must be taken into account when formulating for applications where
corrosion of metallic conductors may be encountered. Hydrated clay
disperses readily in most formulations, particularly when dispersants or
surfactants are used, and is utilized in epoxide transfer moulding com-
pounds to allow control of Bow.
The calcined clays are considerably harder than their hydrated counter-
parts but they impart better electrical properties to both thermosetting
compounds and thermoplastics. Clay is also of particular use in fibre-filled
L -___________________ __E_R_S__________________~I
E_X_T_E_N_D I 111
epoxides, where its plate-like structure and viscosity increasing properties

prevent fibres 'blooming' or appearing at the moulded surface. Calcined clay
is used to increase volume resistivity in the formulation of electrical laminate
type compounds. A hydrophobic surface treated version of calcined clay is
available for applications where enhanced electrical properties are required
even under humid conditions.
4.4.3 Metallic FiUers

Metallic fillers can impart special properties to an epoxide formulation, such
as giving response to magnetic fields and providing a radiation shielding
capability. They are also used to enhance properties such as thermal
conductivity and electrical conductivity and it is this last feature that makes
them so useful in the electronics industry, where they find wide use in die
attach materials. The principal metals used for enhancing electrical
conductivity are silver, copper and gold, although various metal alloys
such as silver/palladium have also been utilized. Generally, however, alloys
have not given the reliability required and the preferred materials for
military applications are gold-filled.
The conductivity of the final product may vary greatly, depending upon
the metallic filler selected, the particle size, shape, previous history and the
amount used. With non-noble metals, the surface of the filler particles has to
be cleaned to remove non-conducting surface oxides. With certain metallic
fillers these oxides can gradually reform, reducing the conductivity as the
material ages.
As already stated, the addition of metallic fillers to a formulation serves to
decrease the electrical insulation, but there may be other effects on the
compound's electrical properties that may need to be taken into account.
The frequency dependence of the dielectric loss factor increases as the
metallic particles offset the low loss factors of the binder system. The loss
factor is defined as the product of the power factor and the dielectric
constant and is a measure of the signal absorption by the compound.
Normally, low loss factors are desirable, particularly where a material is to
be used in devices operating at high speed such as gallium arsenide based
semiconductors, and this should be taken into account when formulating
with conductive extenders. The dielectric strength will decrease with
increasing metal loading and, at the same time, the dielectric constant will
increase. As the loading increases the resistivity decreases and this may
negate any advantages gained from the increased dielectric constant.
The metallic fillers or extenders are usually incorporated into the liquid or
liquefied binder system by planetary mixing accompanied by three-roll
milling. If a solvent-based product is required, the use of the solvent usually
helps with the addition of the extender, although, if the viscosity of the
system is low, some settling may occur.
112 1 1.. -1_ _ _ _E_P_o_XI_D_E_R_E_SIN_S_A_ND
__ T_H_E_IR_F_o_RM_U~L_A_TI_O_N_ _ _- - '
4.4.4 Carbon Black
Carbon blacks can be produced by a number of different processes, each of
which plays an important part in determining the quality of the material
produced. Over 90% of the carbon black currently produced is made by the
furnace process, in which oil or gas is thermally decomposed to form the
carbon black particles. Carbon blacks produced by this process are usually
almost neutral in pH. Other types of carbon black can be made with the
differing processes, examples being thermal blacks, channel blacks, lamp-
black and acetylene black.
The main applications of carbon black are for ultra-violet light and
thermal protection as well as the control of electrical conductivity. It finds
considerable use in wire and cable sheathing, particularly with crosslinked
polyethylene. Carbon black and its analogues are frequently also used as the
black pigment for epoxide transfer moulding compounds at concentrations
of 0.2% or less.
The principal uses of carbon black are:
1. as a pigment
2. to control electrical conductivity
3. to enhance abrasion resistance
4. to increase the tensile strength
5. to increase modulus
4.5 FLAME RETARDANTS
The extensive use of polymeric materials in all areas of the electronics

industry, including consumer electronics, has reinstated the introduction of
flammability regulations to safeguard the end user. Considerable concern
has been expressed about the ability of synthetic polymers to bum and
means have had to be found for controlling their flammability. This concern
encompasses not only suppliers of plastic materials, but also the manufac-
turers of electronic components who have to ensure that the assemblies they
sell to their customers do not represent a fire hazard. The requirement for
reduced flammability often necessitates the addition of flame-retardant
additives into epoxide resin formulations and many materials are now
available that provide valuable service in reducing their flammable nature.
In order to develop effective flame retardants, it has been necessary to carry
out much work on the actual mechanisms occurring when a material bums
and these will be briefly discussed before the currently available flame
retardants are reviewed. During burning, several processes occur, including
heating, degradation, volatilization and oxidation. The flames produced
during the burning process are sustained by the gas phase volatiles evolved
from the decomposing material. Various methods are available for
L--_ _ _ _ _ _ _ _ F_L_A_M_E_R_E_T_A_R_D_A_NT_S_ _ _ _ _ _ _ _ --'I I 113
extinguishing the flames, such as cooling the solid, or altering the

atmosphere available to the flame, so as to change the degradation and
decomposition processes to give non-flammable products. Additives used in
epoxide formulations function both in the solid phase and in the vapour
phase. In the solid phase, flammability is reduced by altering the thermal
degradation mechanisms or by forming a barrier at the surface, whilst in the
vapour phase, flammability is reduced by interfering with the oxidation
processes.
The oxidation that occurs in the vapour phase is a free radical process and
additives that can trap radicals such as H' , 0' ,HO; and OH may be useful
as flame retardants. Halogen-containing compounds are an example of
particularly good radical scavengers and thus halogenated organic com-
pounds find extensive use in flame-retarded compound formulations.
4.5.1 Flame Retardant Epoxide Resins

Early efforts to impart flame retardancy upon epoxide resin formulations
involved blending co-reactive halogenated compounds such as e.g. bromi-
nated phenyl- or cresyl-glycidylethers with liquid epoxides. These merely
served as diluents and quite often resulted in products with markedly
reduced physical properties such as Tg , thermal stability and compressive
strength. In order to avoid these problems, flame-retardant epoxide resins
have been synthesized containing halogen atoms within their molecular
structures and these are now commonly used in epoxide resin based
formulations. Their structures are basically the same as the commonly used
epoxide resins, except that some of the hydrogen atoms attached to the
benzene rings have been replaced by halogen atoms such as chlorine and
bromine. Typical examples are the halogenated derivatives of bisphenol A,
e.g. tetrachlorobisphenol A and tetrabromobisphenol A. Brominated
novolac structures are used when higher Tg values are required.
Br Br
HO OH
Br Br
Tetrabromobisphenol A
When such halogenated epoxides decompose at high temperatures, as is the

case during combustion, various halogen-containing species are formed,
which help to trap the free radicals formed and their removal snuffs out the
flame.
114 II
L ________ E_PO
__X_ID_E__R_E_S_IN_S_A_ND
___TH
__E_IR __U_L_A_T_I_O_N______~
__F_O_RM
Although at the beginning both brominated and chlorinated epoxides
were tested, bromine has become the preferred halogen. This is because less
bromine-containing epoxide resin (by weight) is required to impart flame
retardancy, because the brominated resin shows better thermal stability and
because the danger of forming highly toxic species during combustion is
lower with the bromine-containing resins.
Quantity of halogen required to impart flame retardancy upon a clear epoxide casting
Halogen % (by weight)
Bromine 26--30
Chlorine 13-15
Quantity of halogen in tetra halogenated bisphenol A
Halogenated bisphenol A % (by weight)
Tetrachlorobisphenol A 39
Tetrabromobisphenol A 59
In the case of the diglycidyl-ether of tetrabromobisphenol-A, the weight

percentage of halogen present is about three times greater than is actually
required. This means that halogen-free resin can be added or that halogen-
containing and halogen-free structural elements can be combined in the
same resin backbone without losing the flame-retardant properties. Thus
solid flame-retardant resins used as matrices in the production of printed
circuit boards can be made by an advancement reaction from halogen-free
bisphenol-A-based liquid epoxy resin and tetrabromobisphenol A. Apart
from their use in structural laminate formulations, brominated epoxide
resins find considerable use in both electrical and electronic applications as
components of adhesive, coating, encapsulant and potting compound
formulations.
4.5.2 Antimony Oxides

For certain high reliability electronic applications it is desirable to have as
little halogen as possible present in the epoxide resin formulation. One
convenient way of reducing the halogen content of an epoxide resin system
but maintaining the flame retardancy is by the use of antimony oxides. The
antimony oxide most commonly used is Sb20 3, although Sb20 4 and Sb20 s
also find occasional use. When an antimony oxide is used with halogenated
resins a synergistic effect occurs, allowing a substantial reduction in the
quantity of halogenated resin needed. (Synergism is said to occur when the
effects of two components combined is greater than the sum of their
individual effects.) On its own, antimony oxide has little effect as a flame
FLAME RETARDANTS
L -____________________________________________________ ~
II 115
retardant and may remain totally unaffected during the combustion of an

epoxide. However, in the presence of an organic halide species the
corresponding antimony halide is produced.
6RX + S~03 -> 2SbX3 + 3R20
6HX + Sb20 3 -> 2SbX3 + 3H20
Various hypotheses have been proposed in an attempt to explain how this
synergistic flame retardancy occurs. One theory proposes that a reaction
occurs between the polymer and the resultant antimony trihalide, which
leads to char formation on the polymer surface. This char is formed in place
of volatile flammable gas and also reduces further volatile formation by
acting as a thermal barrier to further polymer breakdown. The antimony
halides formed during the combustion process are very volatile and they
constitute a blanketing atmosphere over the epoxide, thus reducing the
oxygen supply to the flame. Antimony oxides are also very reactive and a
third theory proposes that, once they have volatilized into the flame, they
decompose into antimony compounds and halogen-free radicals. The
antimony compounds function as energy dissipators and the halogen-free
radicals react with other free radicals altering the flame chemistry.
Irrespective of the mechanism by which they work, antimony oxides allow
considerable reductions to be made in the amount of halogenated resin
required to impart a certain level of flame retardancy. A formulation
utilizing an epoxide resin containing 14% bromine by weight would only
need 5% of bromine to achieve the same flame retardancy if 3% of
antimony oxide was also added. This reliable effect is used in many flame-
retardant epoxy-resin based formulations, but the more recently determined
toxicological properties of antimony oxides mean that the development of
alternatives is, however, important.
4.5.3 Alumina and Magnesia Trihydrate

Alumina trihydrate (Ah03·3H20) is another commonly used inorganic
flame retardant, and it is both chemically inert and non-toxic. Polymer
combustion is retarded by an exothermic dehydration reaction in which the
hydrated alumina absorbs part of the heat of combustion, and, being in the
solid phase, acts as a heat sink removing energy from the combustion zone.
The evolution of water vapour may also be important in diluting
combustion gases, reducing the availability of gaseous oxygen. Alumina
trihydrate is normally used in epoxide formulations at between 40 and
60 weight% and it also imparts good arc and arc track resistance, which
is useful in high voltage encapsulation work. Alumina trihydrate filled
cycloaliphatic epoxide resins have been extensively used in transformer,
insulator and switchgear applications. It is not generally thought to exhibit
any synergistic effects with other flame retardants.
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~
For some applications the dehydration reaction of alumina trihydrate

starts at too Iowa temperature, thus causing bubble formation even during
processing of the formulated epoxy resin. In this case the use of magnesia
trihydrate offers advantages.
4.5.4 Other Flame Retardants

Besides brominated epoxide resins, bromine-containing compounds known
as flame-retardant additives for thermoplastic materials are also used in
epoxy resin chemistry. Thus decabromophenyleneoxide, ethylene-bis-
tetrabromophthalimide and trisbromostyrene have successfully been intro-
duced in flame-retardant epoxy-based formulations. Following the trends to
halogen-free flame-retardant products various organic phosphates, phos-
phites and phosphonates are under evaluation. Salts such as ammonium
polyphosphate have been successfully utilized as flame retardants in filled
epoxy resin systems. It is more usual to employ phosphorus/halogen
mixtures in epoxide resins, however. A combination of 1.5--2% phosphorus
with 5--6% chlorine will impart self-extinguishing properties to epoxides.
Nitrogen-containing compounds such as melamine-cyanurate have also
been tested. Whilst antimony oxide and alumina trihydrate are the two most
commonly used inorganic flame retardants, a large number of other
materials are available for use in speciality applications or as cost-saving
alternatives. Encapsulated red phosphorus is an alternative to be used in
halogen-free flame-retardant products. Concentrations of borates in excess
of 20 weight% can impart self extinguishing properties upon certain
epoxide-based formulations. Organic boron compounds such as trimeth-
oxyboroxine, borolene and borinane are particularly useful because of their
solubilities in resin systems.
Finally, apart from using halogenated epoxide resins or additives, it is
also possible to use halogen- or phosphorus-containing curing agents.
When considering the use of flame retardants, considerable thought and
testing effort should be given to the reliability performance required of the
encapsulated or moulded part, since for example halogen ions generated
from halogenated flame retardants may have deleterious effects on certain
metallic conductors, antimony atoms may have can influence on the
performance of semiconductors and phosphorus-based flame retardants
may work very well in one application but fail in another.
4.6 OTHER USEFUL CONSTITUENTS
Even though there are literally hundreds of different epoxide resins and
hardeners commercially available, giving countless formulations with a
diversity of cured properties, further modifications of a material are
L -_ _ _ _ _ _O_T_H_E_R_U_S_E_F_U_L_C_O_N_STIT
__ U_ENT
__S_ _ _ _ _ _ --'I I 117
sometimes still required. These modifications can be achieved by incorpo-

rating a range of compounds known as diluents, flexibilizers and plasticizers
into the epoxide resin system during the formulation process. The properties
of some typical diluents, flexibilizers and plasticizers are now discussed.
4.6.1 Diluents and Plasticizers

For many uses of epoxide resin systems, a low viscosity product is required
and the role of the diluent is usually to reduce the viscosity of the formulated
compound. Diluents can also be used to tailor other characteristics of the
epoxide, such as the chemical resistance, mechanical and electrical proper-
ties, thermal expansion coefficient and glass transition temperature. They
may be conveniently divided into two groups, the reactive diluents and the
non-reactive diluents.
Examples of non-reactive diluents are solvents with elevated boiling
points such as the aromatic hydrocarbons xylene and toluene. These are
used in concentrations of less than 5 phI' and have little effect upon the
cured physical properties, but there may be more significant changes in a
crosslinked product's chemical and solvent resistance. Obviously, as the
concentration of non-reactive diluent is increased, the effect upon the cured
properties becomes more pronounced. Care also has to be taken with
thermally cured systems that the curing temperature does not cause
volatilization of the diluent, as this can result in the formation of voids
and blisters in the cured material.
One of the most popular groups of all the non-reactive diluents comprises
the phthalate esters, which have in addition a plasticizing effect and find
extensive use in many types of other polymer formulation as well as with
epoxides. The properties of several commonly used esters are given in Table
4.6. The most widely used phthalate ester is probably dibutyl phthalate.
o
Q 6 «:==: o
m-Xylene Toluene Dibutyl-phthalate
When used in the range of 15-20 phI' with DGEBA-based resins, four-
fold reductions in viscosity can be achieved, although, by nature of its
chemical structure, it may also bring about a reduction in crosslinking
density. Other materials that are useful under certain circumstances as non-
reactive diluents are the low molecular weight styrenes and the bisphenol-
118 I LI________E_PD__X_ID_E__R_E_SUN ___T_H_E_I_R_F_O_R_M_V_L_A_T_I_O_N______~
__S_A_ND
Table 4.6 Properties of some commonly used phthalate esters
Ester Formula Molecular Boiling point DensilJ.

weight (OC) (g/cm)
Diethyl phthalate C6 H4(COOC2H sh 222 249 1.12

Dibutyl phthalate C6 H4(COOC4H 9)2 278 310 1.05
Dihexyl phthalate C~(COOC~13)2 334 345 1.01
Dioctyl phthalate C~4(COOC8H 17)2 390 340 0.98
and phenolic-based resins. Before selecting a non-reactive diluent for use in

an epoxide resin formulation, careful consideration should be given to the
desired final properties since although certain properties may be improved
others may be deleteriously affected.
4.6.2 Reactive Diluents

Reactive diluents are usually small molecules that contain one or two
epoxide groups in their structure, enabling them to react during the curing
reaction. The monofunctional epoxides reduce the crosslinking density of
the cured products and this is illustrated by resulting lower glass transition
temperatures and reduced thermal stabilities. Examples of commonly used
epoxide-containing reactive diluents are shown below.
~o~
o
Phenyl glycidylether Cresyl glycidylether Butyl glycidylether
o
~o~o~
o
Butanediol diglycidylether Neopentylglycol diglycidylether
Phenylglycidylether and cresylglycidylether help, in addition to their

diluting effect, to reduce the crystallization tendency of low molecular
weight bisphenol-A-diglycidylether. Butylglycidylether is more and more
replaced by the glycidylethers of CS-C IO and C 1rCI4 linear aliphatic
alcohols. These materials have higher molecular weights which result in
odourless compounds with low volatility in air and reduced potential for
skin irritation.
OTHER USEFUL CONSTITUENTS
L -____________________________________________________ ~
II 119
Butanedioldiglycidylether, hexanedioldiglycidylether and neopentyl-

glycoldiglycidylether are examples of di-functional reactive diluents which
show a reduced tendency to lower the properties of the cured product. In
general reactive diluents should be handled with care, since they are more
prone to inducing dermatitis than the epoxide resins themselves.
4.6.3 Flexibilizers and Toughening Agents

For some applications there may be a requirement for a normally brittle and
hard epoxide system to be modified to have greater flexibility and toughness.
There are several ways in which this can be achieved and a typical example
would be to convert a rigid system into one that has improved thermal
shock and impact resistance for castings, improved flexibility for films or
enhanced peel strength for adhesive applications. The best method of
achieving this goal is to incorporate molecules into the formulation that
have long flexible chains and which can be reacted into the polymer network
during curing. This method is known as flexibilization and flexibilized resins,
curing agents or additives can be used. The flexibilizing epoxide resins may
be either monofunctional or polyfunctional in a similar manner to the
reactive diluents. The monofunctional epoxide resins are usually derived
from molecules containing long chains of atoms such as the vegetable oils
and other molecules containing aliphatic chains with more than 12 carbon
atoms. These compounds are epoxidized and, during the curing reaction,
their epoxide groups react with the growing polymer network effectively
inhibiting further propagation of the polymer chains. This leads to the
formation of long floating chains within the crosslinked matrix, which serve
to increase the volume of the crosslinked product, allowing greater
movement of the material under imposed loads. To a large extent, the
monofunctional diluents can also be considered as flexibilizers.
The polyfunctional flexibilizers are composed largely of difunctional
epoxides derived from molecules with flexible structures. The commercially
available flexibilizing resins are commonly based upon the glycidyl
derivatives of glycols and dimerized acids. The general structure of an
epoxidized glycol is:
n
The value of n would be in the range 2-7.
The glycidyl derivatives of fatty acids are also good flexibilizing resins and
such materials generally have viscosities of between 400 and 600 cP at room
120 I ~I________E_PO__XI_D__E_R_E_S_UN_S_A_ND
___T_H_E_I_R_F_O_R_M_U_L_A_T_I_O_N______~
temperature. They can be used with most epoxide curing agents, but their
incorporation into a system generally leads to long pot lives and the need for
longer cure times.
Flexibilization of a formulation can also be achieved by using flexibilizing
curing agents or other additives. Examples are diester-dicarboxylic acids or
low molecular weight polyesters with acidic end groups to be used together
with anhydride curing agents. These materials again have reactive end
groups separated by flexible long chain molecular segments. Another typical
example is dodecenyl succinic anhydride which has the structure:
o
Dodecenyl succinic-anhydride
In certain applications this material can impart outstanding electrical
properties along with increased flexibility. When it is used in a 50/50 adduct
with hexahydrophthalic anhydride it gives a useful eutectic mixture with a
melting point of rvO°C. One other group of flexibilizing hardeners also
worthy of mention is the polysulphides. They have a polymeric structure
which is terminated at each end with a thiol group (-SH). Although the thiol
group can react slowly with the epoxide resins, they are generally used in
conjunction with catalysts such as DMP 10 and DMP 30. The polysulphides
have found considerable usage in the formulation of epoxide systems for the
encapsulation and potting of delicate components.
The third possible way of improving toughness of epoxy formulations,
besides adding plasticizers or flexibilizing agents, consists of dispersing soft
rubbery inclusions in the brittle epoxy matrix. A system family that has
received much attention are the carboxyl-terminated butadiene acrylonitrile
(CTBN) copolymers, that react via end groups with the epoxide and form a
second phase during curing. This second phase acts as a crack stopper. In
contrast to the other two mentioned methods of increasing toughness, the
heat distortion temperature of such two-phase systems is practically not
reduced. The morphology and fracture/mechanical properties of such two-
phase systems formed during curing depends, of course, very much on the
curing conditions. The toughness of other two and multiphase systems that
already contain pre-formed particles before curing is relatively independent
of the curing conditions. The size of such particles can be less than 1 pm.
Core shell type elastomers are typical examples of materials used to provide
such pre-formed particles.
L -_ _ _ _G_EN_E_RA_L_F_O_R_M_U_L_A_T_IO_N_C_O_N_S_I_D_E_R_A_T_IO_N_S_ _ _ ---'I I 121
4.7 GENERAL FORMULATION CONSIDERATIONS
Having been presented with the large number of materials that are
commonly used in the formulation of epoxide encapsulants, the reader
new to this area may be bewildered at the vast range of possibilities for the
composition of a given compound and may be wondering how one begins to
select the individual components to impart the desired properties in the
cured product. It is relatively easy to define the properties required of an
epoxide for a specific application, but it is more difficult to select ingredients
that will allow all of these desired properties to be accommodated and, quite
often, some degree of compromise is necessary. The formulator will have to
make a choice of components from a range ofliterally hundreds of available
resins, hardeners, catalysts and other ingredients, each of which is often
available in a variety of forms, in an attempt to balance their contrasting
properties. The properties of a given formulation can be conveniently
divided into those required before, during and after cure.
The main characteristics of the material required before cure that will
influence ingredient selection are:
1. The overall cost limitations for the product.
2. The required physical form of the compound. Is a liquid or a solid
required?
3. Chemical stability. What storage life is required and does the
compound have to be one or two parts?
Having taken these characteristics of the compound into account, the
properties of the compound during the curing reaction now have to be
considered. The major factors here are:
1. What cure schedule is possible? Does the compound have to cure
within a specific time? Is there a maximum permissible curing
temperature?
2. Are the components of the formulation chemically compatible with the
substrate being encapsulated and coated?
3. How much cure shrinkage can be tolerated?
4. What viscosity is required for both liquid systems and moulding
compounds?
5. What curing exotherm is tolerable under the determined curing
conditions?
Finally, we come to the properties of the cured product. Many of these
properties will obviously be influenced by or influence the properties
required before and during curing of the compound. The more important
characteristics commonly considered when formulating epoxides for elec-
tronic applications are:
122 I LI________E_P_O_X_I_D_E_R__ES_I_N_S_A_ND
___T_H_E_I_R_F_O_R_M ________~
__U_L_A_T_IO_N
1. Colour and optical properties; an epoxide may need to be a specified
colour or it may need good transmissive properties at a given
wavelength for electro-optic applications.
2. Density; there may be limitations on the weight of a product,
particularly if it is intended for aerospace use.
3. Thermal expansion coefficient; the thermal expansion coefficient mis-
match between the epoxide and a substrate may need to be minimized.
4. Adhesion; good adhesive properties may be required, as in die attach
applications.
5. Thermal conductivity; good thermal conductivity may be required for
heat dissipation from power devices and integrated circuits such as the
latest microprocessors.
6. Chemical and solvent resistance; good chemical and solvent resistance
may be required for epoxides exposed to harsh chemical environments.
7. High purity; this is required for epoxides in contact with delicate
microcircuits where impurities may cause corrosion of conductor
metallization.
8. Low gas, moisture and vapour permeability; again, this is required for
epoxides in contact with delicate microcircuits, where corrosion or
parametric shifts may occur.
9. Internal stress; low internal stress may be important with epoxides in
contact with large microcircuits, microcircuits with multi-layer metal-
lization and large I/O count packages.
10. Low alpha particle emission; ingredients may need to be pure with
respect to actinide elements, to avoid alpha particle emission that can
cause soft errors in dynamic random access memories.
11. Thermal stability; stability at high temperatures may be required for an
epoxide operating in a harsh environment where elevated temperatures
are experienced or with high power devices.
12. Tensile and flexural strength, hardness and glass transition tempera-
tures (TJ are all important properties where good mechanical perfor-
mance and physical integrity is required.
13. Flammability; an epoxide may need to be flame retarded to meet certain
customer requirements. Examples would be to achieve Underwriters,
Laboratory listings (UL), such as UL94 1/16 in VO.
14. Electrical properties such as volume resistivity, dielectric constant,
dielectric strength, arc resistance, dissipation factor and loss factor are
all important where the epoxide is in contact with high voltages or
where there is intimate contact with a microcircuit surface. Certain of
these electrical properties are particularly important with high-speed
devices operating in the frequency range above 100 MHz, where low
values are generally desirable.
L -_ _ _R_E_C_y_C_L_IN_G_O_F_CU_R_E_D_E_P_O_X_y_-B_A_S_E_D_M_A_T_E_R_IA_L_S
_ _ _--.JI I 123
Only by carefully considering all of the properties that are required of a

compound formulation before, during and after cure will it be possible to
make a final selection of the ingredients required to give a material suitable
for a specific application.
4.8 RECYCLING OF CURED EPOXY-BASED MATERIALS
Since the oil crisis in the 1970s, the question of recycling has gained
importance with the experience of increasing waste streams and with space
for landfills becoming expensive and more and more scarce.
Epoxies in structural applications with their long usable life and their
excellent chemical resistance offer ecological advantages and play, with less
than about 0.5%, only a minor role in the generation of the plastic waste
streams; nevertheless they are also included in the emerging regulations and
methods for recycling them have to be found.
Particle recycling, e.g. the use of milled cured epoxy-based materials as
additional filler in new formulated epoxy products, is already used in the
processing of epoxy moulding compounds. Up to about 15% of milled
runners can be added to new material. With a proper choice of particle size
distribution (low fines), up to about 30% of the mineral filler in quartz-filled
anhydride cured epoxy-casting formulations can be replaced by recycled
epoxy-based insulating materials etc. without affecting the properties of the
cured materials too much. The use of milled recycled epoxy-based printed
circuit boards as reinforcing filler in thermoplastic materials as well as in
concrete or road building materials is under evaluation.
Feedstock recycling as a way to split plastic waste back to basic chemicals
is also applicable to cured epoxy-based products. Pyrolysis results in a gas
fraction with an energy content similar to that of natural gas and a liquid
fraction consisting mainly of aromatic compounds. Hydrolysis with alkali at
elevated temperature is very easily achieved with anhydride-cured epoxies
and leads to phenolic ethers with OH end-groups and acid-salts. Hydrolysis
of dicyanodiamide-cured epoxies, e.g. from printed circuit boards, needs
more severe conditions. In the case of bromine-containing resins, the
bromine is completely split off and aromatic compounds similar to those
found after pyrolysis are formed. Catalytic hydrogenation of e.g. anhydride-
cured epoxy resin at elevated temperatures under pressure results in a
fraction of phenolic and other aromatic compounds, neopentylglycol-
derivatives and lactones.
Energetic recycling (incineration in power plants) is no problem with
epoxy-based cured materials that contain no critical by-products. Inciner-
ation of chlorine- or bromine-containing materials requires modem equip-
ment with sufficient corrosion resistance and perfect cleaning of the smoke
gases.
124 I LI________E_P_O_X_ID_E__R_E_SfIN
__S_A_ND __F_O_R_M_U_L_A_T_I_O_N________~
___T_H_E_IR
Use of waste plastics instead of coal in blast-furnaces or similar
equipment is a method lying between pyrolysis and incineration. Use is
already made of this technique in the case of printed circuit boards. The
concept behind this is to recover the copper and, if present, the noble metals
contained in the electronic scrap.
Surveys show that the methods used for the recycling of the commodity
plastics are, with proper choice of the reaction conditions, also applicable to
cured epoxies.
4.9 TOXICOLOGICAL PROPERTIES AND SAFETY PRECAUTIONS
Epoxy resins and curing agents are reactive chemicals and have to be
handled with care. Toxicological properties of the numerous products used
in epoxy resin formulations differ very much. Bisphenol-based conventional
epoxy resins, for example, have a low order of acute toxicity and are mild to
moderate irritants; low molecular weight resins are skin sensitizers. Skin
irritation and sensitizing effects are stronger, when certain reactive diluents
are added.
Amongst curing agents, the aliphatic amines are strong bases and thus
corrosive and volatile materials which can cause tissue damage (bums) to
skin, eyes and mucous membranes. Several aromatic amines show evidence
of carcinogenicity in animals and exposure should be strictly avoided.
Anhydrides are eye, skin and respiratory irritants. Solvents may cause fire
hazards and even mineral or reinforcing fillers may be dangerous to health.
It is therefore very important in every case to consult the safety data sheet
for the individual product to be used. It is also important to make a person-
and workplace-oriented risk analysis followed by intensive instruction and
training before work with epoxy-based products starts. To minimize
exposure, the following protective equipment should be provided and used:
rubber or plastic gloves and sleeves, overalls and aprons (to be washed and
cleaned regularly), goggles or face shields, special protective skin cream to
be used before work starts.
After work, and in the case of skin contamination, but also before eating
or using the we etc., operatives should wash with warm water and mild
alkali-free soap and dry themselves with disposable paper towels. Never use
solvents to cleanse contaminated skin.
The working area should be separated from other areas in the factory and
be provided with general and local exhaust systems to remove vapours,
mists etc. where they are generated. Rooms for eating, taking a break or
changing clothes should be separated from the working area.
________________~I
F_U_R_T_H_E_R_R_E_A_D_I_N_G
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 125
4.9.1 First Aid

Contamination of the eyes by resin, hardener or product mix should be
treated by immediate irrigation with running tap water for 15 minutes. A
doctor should then be consulted. Contaminated skin should be treated by
dabbing away the resin etc., washing with warm water and soap and
applying a cleansing cream. A doctor should be consulted in the case of
severe skin irritation and bums. Contaminated clothing should be removed,
isolated and washed before using again.
4.10 SUMMARY
This chapter has described the principal ingredients more commonly used in
epoxide formulations and illustrated the vast selection of choices available
to the prospective compound formulator. The important factors that may
need to be taken into account for a given application have also been
reviewed. For further information and assistance with formulation, the
reader is referred to the list of further reading at the end of this chapter.
4.11 REFERENCES
1. Farben, I. G., German Patent 676,117 (1939).

2. De Trey Fn!res, Swiss Patent 211,116 (1939).
3. Devoe Raynolds, US Patent 2,456,408 (1948).
4.12 FURmER READING
4.12.1 Handbooks and Monograpbs

Batzer, H. and Lohse, F. UI/manns Encyclopddie d. Techn. Chemie, 4th edn, Vol. 10,
Verlag Chemie, Weinheim, 1975.
Bruins, P. F. (ed.), Epoxy Resin Technology, John Wiley and Sons Inc., New York,
1968.
Ellis, B., Chemistry and Technology 0/ Epoxy Resins, Blackie, Glasgow, 1993.
Fluck, E. W., Epoxy Resins, Curing Agents, Compounds and Modifiers, 2nd edn,
Noyes Publications, 1993.
Gannon, J., Kirk-Othmer Encyclopedia o/Chemical Technology, 4th edn, Vol. 9, John
Wiley & Sons Inc., New York, 1994.
Jahn, H., Epoxidharze, VEB Deutscher Verlag fUr Grundstoffindustrie, Leipzig,
1969.
Kubens, R., Meyerhans, K. et al., KunststofJ-Handbuch VoUl, Carl Hanser Verlag,
Munchen, 1971.
126 I LI____E_P_O_X_ID_E_R_E_SI_N_S_A_ND
_ _T_H_E_IR_F_O_RM_D_L_A_T_I_O_N_ _ _ -----.J
Lee, H. and Neville, K., Handbook of Epoxy Resins, McGraw-Hill Inc. New York,
1967, repro 1982.
Lohse F. and Seiz, W., Houhen Weyl Methoden der Org. Chemie, Vol. E 20, Part 3,
Georg Thieme Verlag, Stuttgart, New York, 1987.
May, C. A. and Tanaka, Y., Epoxy Resin Technology, 2nd edn., Marcel Decker, New
York,1988.
McAdams, W. and Gannon, J. A., Encyclopedia of Polymer Sci., Wiley Interscience
New York, 6, 322-82, 1986.
Potter, W. G., Epoxide Resins, Butterworth and Co. (Publishers) Ltd., London,
1970.
Potter, W. G., Uses of Epoxy Resins, Newness Butterworth, Sevenoaks, 1975.
4.12.2 Reviews
4.12.2.1 Epoxy Resins and Technology

Bathnagar, M. S., Paintindia 42, 1992.
Batzer, H., Epoxy compounds, their synthesis and uses. Chimia 37, 9, 329-337,1983.
Bauer, R. S., Epoxy Resin Chemistry ACS-Symp. Ser., 1I4, 1979; 221, 1983; 285,
1985, Am. Chem. Soc., Washington.
Di Stasio, J., Epoxy Resin Technology, Development since 1979, Noyes Data Corp.,
Park Ridge, New York, 1982.
Gannon, J., History and development of epoxy resins. High Perform. Polym., Proc.
Symp., 299-307, 1986.
Gannon, J., Advances in epoxy resin technology. Polym. News, 15(5), 138-144, 1990.
Hodd, K. A., Epoxy resins. Rapra Rev. Rep., 4(2), I-lIS, 1990.
Lohse, F., Epoxy resins - new results and developments. Macromol. Chem.,
Macromol. Symp. 7, 1-16, 1987.
Ranney, N. W., Epoxy Resins and Products, Recent Advances, Noyes Data Corp.,
Park Ridge, New York, 1997.
Reader, C. E. L., Recent developments in epoxy resins. Proc. Int. Con/. Pet. Refis,
Petrochem. Process, 78-97, 1991.
4.12.2.2 Crosslinking and Crosslinking Agents

Ashcroft, W. R., Curing agents for epoxy resins, in Chem. Technol. Epoxy Resins (ed.
B. Ellis), Blackie, Glasgow, 1993.
Dickson, L. and Singh, A., Radiation curing of epoxies, Radiat. Phys. Chem., 31 (4-
6) 587-93, 1988.
Dusek, K., Network build-up and structure in curing of epoxy resins. Macromol.
Chem. Macromol. Symp. 7, 37-53, 1987.
Green, G. E., Stark, B. P. and Zahir, S. A., Photocrosslinkable resin systems. J.
Macromol. Sci. Reviews, Macromol. Chem., C 21 (2), 187-273, 1982.
Hull, C. G. and Sinclair, J. H., Epoxy curing agents. In Handb. Coat. Addit. (ed. L. J.
Calbo) 2, pp. 277-99, Marcel Dekker, New York, 1992.
Kamon, T. and Furukawa, H., Curing mechanisms and mechanical properties of
cured epoxy resins. Adv. Polym. Sci., 80, 173-202, 1986.
F_U_R_T_H_E_R_R_E_A_D_I_N_G________________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 127
Kishore, K., Joseph, M. and Vijayshree, M. N., Epoxide curing, a literature survey.
J. Sci. Ind. Res. 47(11), 662-74, 1988.
Lohse, F. and Zweifel, H., Photocrosslinking of epoxy resins. Adv. Polym. Sci., 78,
62-81, 1986.
Scola, D. A., Novel curing agents for epoxy resins. Dev. Reinf Plast., 4, 165, 1984.
4.12.2.3 Formulation and Toughening

Dewprashad, B. and Eisenbraun, E. J., Fundamentals of epoxy formulation. J.
Chem. Educ., 71 (4), 290-4, 1994.
Drake, R., Review toughening thermoset resins. Polym. Mater. Sci. Eng., 63,802-5,
1990.
Hedrich, J. c., Patel, N. M. and McGrath, J. E., Toughening of epoxy resin
networks with functionalized engineering thermoplastics. Adv. Chem. Ser., 233,
293-304, 1993.
Nielson, P.O., Properties of epoxy resins, hardeners and modifiers. Adhesives Age,
25 (4), 42-6, 1982.
Pearson, R. A., Toughening epoxies using rigid thermoplastic particles - a review.
Adv. Chem. Series, 233, 405-25, 1993.
Price, J. N., An integrated approach to developing tough epoxies. Int. SAMPE
Techn. Conf, 23, 959-63, 1991.
Riew, C. K., Siebert, A. R. S., Smith, R. W., Fernando, M. and Kinloch, A. J.,
Toughened epoxy resins: preformed particles as tougheners. Polym. Mat. Sci.
Eng., 70, 5-6, 1993.
Shaw, S. J., Rubber modified epoxy resin. In Rubber Toughened Engineering Plast.,
pp. 165-209 (ed. A. A. Collyer), Chapman and Hall, London, 1994.
Siebert, A. R., Morphology and dynamic mechanical behavior of rubber-toughened
epoxy resins. Adv. Chem. Series, 208, 179-91, 1984.
The Epoxy Resin Formulators Training Manual, Soc. of Plastics Ind. Inc., New York,
1988.
4.12.2.4 Diluents and Mineral Fillers

Kaiser, T., Role of particle-matrix-interface in the deformation and fracture
behavior of filled epoxy resins. Chimia, 44 (11), 354-59, 1990.
Katz, H. S. and Milewski, J. V., Handbook of Fillers and Reinforcementsfor Plastics,
Van Nostrand Reinhold Company, New York, 1978.
Mieziva, J., Reactive and non-reactive diluents for epoxy resins. Farbe Lack 92 (7),
589-95, 1986.
Roulin-Molonay, A. C., Cantwell, W. J. and Kausch, H. H., Parameters determining
the strength and toughness of particulate-filled epoxy resins. Polym. Compos., 8
(5), 314-23, 1987.
Schnelle, A., Reactive diluents for epoxy resins. Pitture Vernici, 60 (3), 49-56, 1984.
Shaw, S. J., Additives and modifiers for epoxy resins, in Chem. Technol. Epoxy
Resins (ed. B. Ellis) pp. 117-43, Blackie, Glasgow, 1993.
128 I ,-I____E_PO_XI_D_E_R_E_SIN_S_A_ND
_ _TH_E_IR_F_O_R_M_U_L_A_T_I_O_N_ _ _----'
4.12.2.5 Applications in the Electronic Industry

Abshier, C. S., Berry, J. and Maget, H. J. R., Toughening agents improve epoxy
encapsulants. Insulation/Circuits, 27, 1977.
Adell, J. A., Molina, M. and Cavaro, J. M., Adhesives for electronic applications.
Hybrid Circuits, 31,54-6, 1993.
Angerer, G. and Biitcher., Bars, Reuse of Electronic Waste, Fraunhofer-Istitut fUr
Systemtechnik und Innovationsforschung, 1993.
Bauer R. S., Epoxy resins in potting. Polym. Mat. Sci. Eng., 59, 626-8, 1988.
Bauer, R. S., Applications of epoxy resins in high density packaging. Polym. Mat.
Sci. Eng., 59, 626-8, 1988.
Bauer, R. S., Application of epoxy resins in electronics, in Polym. Electron Photonic
Appl. (ed. C. P. Wong), pp. 287-331, Academic, Boston, 1993.
Beyer, M., Epoxy Resins in the Electrical Industry. Expert-Verlag, 1983.
Bolger J. C., Die attach in high-reI. p-dips. Proc. Electron. Compo Conf, 34, 63-7,
1984.
Drain, K., Kropp, Ph. L. and Dreifus, D. W., Surface mount device adhesives. Int.
SAMPE Electron. ConI, 1, 411-20, 1987.
Fujita H. and Mogi, N., High reliability epoxy molding compounds for surface-
mount devices. Proc. Electron. Compon. Technical Conf, 43, 735-41, 1993.
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Hirsch, H., Resin system used for encapsulation of microelectronic packages. Proc.
Soc. Plastics Engineers, 28th Annual Technical Conference, p. 380, New York,
1970.
Kaji, M., Molecular design of epoxy resins for microelectronics packaging. ACS
Symp. Ser., 579, 220-33,1944.
Keirsey, R. A., Evolution of epoxy resins in semiconductor device encapsulation.
Ann. Pack. Tech. Con/ Disp. (Tech. Pap), Society of Plast. Eng. 1981, 6th
Reinforced Plast. Compo Adhes, Thermosets, pp. 172-9.
Kinjo, N., Ogata, M., Nishi, R. and Kaneda, A., Epoxy molding compounds as
encapsulation materials for microelectronic devices. Adv. Polym. Sci., 88, 1-48,
1989.
Kino, N., EP-molding compounds as microelectronics-encapsulants. Adv. Polymer
Sci., 88, 1-48, 1989.
Ludeck, W., Adhesives for microelectronics. Plaste Kautsch, 34, 175-6, 1987.
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and Production, 51, 1981.
Massey, M. L., Epoxy resin technology for the laminating industry. Nat. SAMPE
Symp. Exhibit., 29, 1585-91, 1984.
Oldberg, R. C., The effects of epoxy encapsulant composition on semiconductor
device stability. J. Electrochem. Soc. Solid State Science, 118, 129, 1971.
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(8), 44--51, 1987.
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attach. Annu. Proc. Reliab. Phys. Symp., 23, 164-72, 1985.
Reinhart, J., Epoxy moulding compounds for semiconductor encapsulation. Circuits
Manufacturing, 29, 1977.
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Schultz, N., Potting and encapsulating electronic components. Adhesives Age, 19,
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Recent Developments in the 5
Encapsulation of
Semiconductors by Transfer
Moulding
MARTIN GOOSEY· and MIKE PLANTt
·Shipley Europe Ltd Coventry, England and tKemtron
International South Woodham Ferrers, England
5.1 INTRODUCTION
In the early days of semiconductor fabrication, devices were packaged in

glass, ceramic or metal. However, by the 1960s device manufacturers were
beginning to encapsulate their products in the newly available polymer-
based materials, as an alternative to the traditional methods. The incentives
for this move were the large cost reductions offered over the standard
ceramic and metal parts and compatibility with mass production techniques,
which often allowed several hundred parts to be encapsulated in a single
operation taking less than two minutes.
Motorola introduced the plastic T092 package in the mid-1960s and by
the late 1970s world-wide annual production of plastic encapsulated parts
was estimated to have exceeded 10 billion units. The world market for
semiconductor devices is predicted to reach 300 billion by 2000, and the vast
majority of these will be plastic encapsulated.
There are several ways in which a semiconductor device can be
encapsulated to give it good physical integrity and environmental protec-
tion. The three most commonly used techniques are transfer moulding,
potting and conformal coating, with transfer moulding being by far the
most popular method. In this process, components to be encapsulated are
placed in a mould cavity and a moulding compound, liquefied by heat and
132 IENCAPSULATION OF SEMICONDUCTORS BY TRANSFER MOULDING I
pressure, is transferred into the cavities where it solidifies giving the familiar
plastic encapsulated device. Typical plastic encapsulated parts are shown in
Fig. 5.1.
Whilst the early materials and machinery were fairly basic, considerable
progress has been made in both equipment design and compound
formulation. The main areas where improvements were required were in
device reliability, production rates and material wastage. The major
achievements of the equipment manufacturers in both mould and press
design have allowed the number of parts moulded per cycle to increase
dramatically, so that in some cases 400-500 parts can be finished per shot.
Much larger active devices with higher pin count packages can now be
moulded, while the amount of material wasted in the runner systems has
been reduced. A further breakthrough has been the introduction of
automatic moulding equipment, offering advantages in terms of labour
costs and quality (see section 5.2.7).
The most commonly used materials for transfer moulding both active and
passive components are epoxide based. The longer flowing epoxide
moulding compounds for semiconductors are now largely unrivalled, the
only other materials occasionally used in these applications being silicones,
silicone-epoxides and more rarely, polyimides and polyphenylene sulphide.
(In 1995 about 97% of the total consumption of semiconductor encapsulants
was epoxide resin based.) The main reason for the popularity of epoxides in
this field is that they possess advantages such as:
I. Excellent compatibility with other components of the formulation, e.g.
good bonding to fillers, particularly when coupling agents are used.
2. Dimensional stability in the cured product.
3. Good chemical and solvent resistances due to high crosslinking density.
Fig. 5.1. Examples of transfer moulded devices (courtesy INTEL)

I_NT
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4. Retention of excellent electrical and mechanical properties at elevated
temperatures, up to 180--190°C.
5. Cure by an addition reaction, avoiding the emission of volatile
condensation molecules.
6. Relatively low shrinkage.
7. High hot hardness facilitating release from the mould.
8. Ability to mould at relatively low transfer pressures, thus reducing flash
and/or bleed and giving prolonged intervals before major tool mainte-
nance.
9. Rapid curing, allowing the high-speed production of parts.
However, there are also some disadvantages, the major two being:
1. High adhesive strength; epoxides are good adhesives and release agents
are required to prevent parts from sticking in a mould.
2. Epoxides are inherently flammable and require flame retardant additives
if flammability control is needed.
Just as the moulding equipment suppliers have improved their products,
so have the moulding compound manufacturers and distinct improvements
have been made over the last few years in epoxide moulding compound
formulation. Epoxide moulding compounds now exist with properties that
were totally unattainable only a few years ago, allowing their use in many
new areas, e.g.:
1. Low stress materials are available that enable the moulding of large pin
count devices and large package sizes without the familiar problems
caused by stress such as cracking of passivation layers, moved metal
phenomena and package warping.
2. Low alpha particle emission materials are available enabling the
encapsulation of 1MB and higher dynamic RAMs without the fear of
soft error generation due to alpha particle emissions from the moulding
compound.
3. Faster curing materials are available that are compatible with automated
moulding machinery, allowing mould cycle times of around 35-45 s.
4. Laser markable materials are available that allow identification numbers
to be imprinted directly onto the surface of a package, removing the need
for an ink-marking process.
In addition, many other general improvements have been introduced in the
last few years, examples being:
1. Higher as-moulded and post-cured glass transition temperatures.
2. Reduced mould staining due to the introduction of higher purity and
synthetic release systems.
3. Reduced,flashing and bleeding by use of graded particle size distribution
fillers and better controlled resin viscosities.
4. Improved raw material purity.
S. Improved hot hardness.
As a consequence of these advances in moulding compound formulation,
the packaging of components by transfer moulding has increased in
popularity and will remain by far the most important packaging technique
in terms of volume for the foreseeable future.
5.2 TRANSFER MOULDING EqUIPMENT CONSIDERATIONS
Transfer moulding was the term chosen by L. E. Shaw, the originator of the
process, 'to describe the method and apparatus for moulding thermosetting
materials, whereby the material is subjected to heat and pressure and then
forced into a closed mould cavity by this same pressure and held there under
additional heat and pressure until cure is complete'. Transfer moulding
equipment for electronic components consists of a hydraulic press equipped
with platens, one of which contains a chamber known as a pot, in which the
moulding powder is placed and liquefied by a combination of pressure and
heat. A piston or ram transfers the molten material into cavities of the
mould via a series of channels known as runners. Figure S.2a shows a
modem FICO (Holland) fully automatic moulding machine (with close-up
detail in Fig. S.2b), making an interesting comparison with the conventional
press shown in the first edition of this book (many of which continue to give
excellent and reliable service around the world).
The moulding compound can be introduced into the pot as a ground
powder or more usually as a preheated preform. In this latter case the
powder is compressed to form a solid pellet of material which is
dielectrically heated to around 90°C using a high-frequency preheater.
The preheated preforms are loaded into the pot and transferred by the ram
at pressures typically around 1000 psi, although as little as 50 psi may be
sufficient for some specially formulated epoxides. For an epoxide compound
used for moulding many tens of semiconductor devices in a single shot, a
transfer time of between IS and 20 s is usually typical, although for some
compounds and moulds, operation outside these limits may be necessary.
The mould temperature would normally be around 17SoC and the parts
could be removed after a mould cycle time of I to 2 min. The mould is
usually designed so that, when it opens, ejector pins in the cavities and
runners push the moulded devices free. The moulded strips of components
will then be removed from the mould and subjected to a number of finishing
processes such as defiashing, cropping and forming ofthe lead-frames, post-
curing and marking before the final product is obtained.
Transfer moulding can also be used for the packaging of resistors, resistor
networks, capacitors, coils, reed relays and other discrete components. The
process only becomes economically feasible, however, for mass production
L -_ _T_RA_N_S_FE_R_M_O_V_L_D_I_N_G_EQ_V_IP_M_E_NT
__ C_O_N_S_1D_E_RA_T_I_O_N_S_ _ - 11 I 135
Fig. S.2a. Electromechanical two-station multiplunger moulding system with dual

strip moulds (courtesy FICO).
Fig. S.2b. Detail of dual strip mould for matrix frames (courtesy FICO).
operations since the initial cost of the press, moulds, preheater and
preformer can only be amortized over the production of many hundreds of
thousands of parts.
In order to design a mould for the transfer moulding of semiconductors, it
is essential to define the basic parameters and processing variables that are
likely to be important in order to gain a thorough understanding of what is
actually required before the mould can be manufactured. A mould will
generally be developed for a specific device and encapsulant combination.
Some important basic factors which need to be taken into account before a
mould design can be initiated are:
1. Shrinkage of the moulding compound during cure.
2. Mould release behaviour of the compound and draft angles needed to
enhance component release.
3. Siting of gates to optimize filling of cavities and to give good cosmetic
appearance.
4. Degree of venting required to prevent air and volatile entrapment in the
moulding. .
5. Whether or not ejector pins will be required to release the moulded parts
from the mould and, if so, where they must be located, taking into
account the rigidity and hot hardness of the cured epoxide and the
sensitivity of the encapsulated devices to mechanical damage during
ejection.
6. Whether the surface of the moulded components needs to be glossy or
matte and whether conventional marking or laser marking is to be used.
5.2.1 Gate Location

The dimensions and location of the gate that admits molten moulding
compound into the cavity of the device to be moulded are determined by a
number of considerations. A gate must permit proper flow of the epoxide as
it enters the cavity and it must also be situated so that the moulded parts can
easily be removed from the mould. It should also be situated to facilitate
easy cleaning. For the transfer moulding of dual in-line packages, a single
gate is usually sited at the narrow end of the package and is offset to one side
in the parting line area. The gate depth in a semiconductor application
would typically be in the range 0.010-0.015 in, the width depending on the
volume of material to be transferred. For square packages the gate is usually
in one comer.
5.2.2 Venting
All transfer moulds have to be vented in order that air and volatiles in the
mould can escape, preventing the build-up of back pressure and allowing
complete void-free filling. The size and location of the vents will depend
upon the size and design of the moulding and the position of any pins or
inserts. A vent is a small groove machined from one face of the mould that
allows the expulsion of unwanted gaseous products from the cavity, but
L -_ _ T_RA_N_S_F_E_R_M_O_V_L_D_I_N_G_E_Q_V_I_P_M_E_NT
__ C_O_N_S_ID_E_RA
__ T_IO_N_S_ _-----'I I 137
which is too narrow to allow the passage of any of the moulding compound.
For the moulding of dual in-line packages, a single vent is usually machined
at the opposite end of the package to the gate, as this is normally the area
which fills last with compound. Dimensions for a vent of this type would be
between 0.0005 and 0.0015 in deep and 0.125 to 0.250 in wide, although it is
normal to begin with a minimum gate dimension and enlarge as necessary.
5.2.3 Runner Systems

The runner system of a transfer mould refers to the series of channels that
allow distribution of the moulding compound to the separate chases and
eventually the individual cavities. The runners emanating from the plunger/
cull area which feed each individual chase of the mould are known as the
primary runners and those that distribute the material from the primary
runners to each individual cavity are known as secondary runners. A typical
primary runner would be hemispherical or trapezoidal in shape with a width
and a depth of 3-5 mm. The secondary runners are generally around 25-
35% smaller in area than the primary runners. Runners are usually
machined into the ejection side of the mould and often have their own
ejector pins. The runners are kept short to enhance the material flow and
reduce the transfer time required to fill the cavities. The area of cross-section
is also kept low to avoid wastage of compound.
5.2.4 Parting Line

The surface at which the two halves of a mould separate is known as the
parting line. The optimum parting surface, as far as mould construction is
concerned, is a flat plane which remains flat after all moulded parts and
projections are removed. This is because a flat surface can be easily
machined flat again, should any wear or damage occur. For a standard
chase mould for dual in-line integrated circuits, the parting line is at the
centre of the package in the plane of the lead-frame.
5.2.5 Shrinkage and Draft Angles

Thermosetting moulding compounds shrink when they cure and allowances
must be made for this shrinkage during mould construction. The mould
cavities are made oversized by an amount equal to the shrinkage of the
cured compound. Typical shrinkage allowances range from 0.004 to
0.010 mlm and obviously the use of a material with different shrinkage
characteristics to the one the mould was made for may lead to dimensional
tolerance problems.
Draft angles are the degree of taper machined into a cavity wall in order
to facilitate easier moulded-part removal. By the use of tapers, the distance
required to free the moulded part from the mould is significantly reduced
from the case where the cavity walls are parallel. Less force is required from
ejector pins to free the moulded device and the reduced warping or flexing of
delicate mouldings will give increased yields for sensitive devices.
Material shrinkage and draft angles have become more important in
recent years because the increasing size of both chips and packages has
meant that many devices are susceptible to internal stresses. These stresses
are primarily caused by thermal expansion coefficient mismatches between
the moulding compound, lead-frame and device. One way of reducing these
stresses is to modify the moulding compound formulation to reduce its
thermal expansion coefficient and shrinkage. The draft angle for standard
moulding compounds is around 4° whilst to obtain good release with the
latest low stress compounds draft angles of 8-12° are recommended.
5.2.6 Mould Finish

The finish of the cavity surface of a mould is important because it
determines the quality of the finish of the moulded part, and is influential in
determining release properties. Moulds are often hard chrome plated to seal
any porosity in the steel mould surfaces. Since epoxide moulding com-
pounds are mineral filled, they are abrasive and hard chrome plating can
give an effective decrease in the rate of wear of the runners, gates and
cavities. It is essential that a surface to be hard chrome plated is very highly
polished because the plating effectively replicates the topography of the
underlying steel. Hard chrome plating also tends to prevent corrosion and
allows a smoother material flow through the runner system.
Having taken all of the above factors into account, the mould manufac-
turer can produce a workable design for a mould. Figures 5.3 and 5.4 show
the layout of a typical 320 cavity mould for 14/16 pin dual in-line les.
5.2.7 Automated Moulding Systems

Several manufacturers now offer fully automated moulding systems in an
attempt to reduce labour costs and to increase the productivity of moulding
operations. In the past, many major semiconductor manufacturers were
forced to abandon their indigenous assembly operations because of high
labour costs. As a consequence, much of this so-called back end, or final,
assembly work is performed at low-cost assembly houses in the Far East
which rely upon cheap labour to give assembly costs which could not be
achieved in either Europe or the USA. In order to maximize the productivity
of in-house assembly, new assembly facilities are being equipped with the
latest generation of automated moulding machines.
Modem automated moulding machines are totally enclosed systems that
are fed with assembled lead-frames at one side, the final product appearing
L -_ _ T_RA_N_S_FE_R_M_O_V_L_D_I_N_G_EQ_V_IP_M_E_NT
__ C_O_N_S_ID_E_RA_T_I_O_N_S_ _ -,I I 139
Fig. 5.3. A 320 cavity MTI encapsulation mould for 14/16 pin dual in-line ICs.
Fig. 5.4. A close-up view of the 320 cavity mould illustrating the position of gates,
knock-out pins, runners and runner turn-offs.
at the opposite side ready moulded, trimmed and formed. The lead-frames
are placed in the mould cavities automatically by a robot loading arm fed
from a cassette or magazine. The moulds are of a multiplunger design, with
each plunger having runners to typically only four devices. Each plunger is
automatically fed with mini preforms or tablets or, with some equipment, a
specially ground powder. After loading the preforms and transfer moulding,
the devices are automatically removed from the mould and transferred by a
conveyor system to an automated trim and form operation, which is part of
the equipment, or to storage cassettes ready for trimming and forming on a
separate machine. After each mould cycle a cleaning operation can be
specified and this is performed by revolving brushes.
The principal advantage claimed for these automated presses, apart from
the fact that they can be largely unsupervised when operational, is the
increase in throughput that is achievable. Conventional moulding is limited
not only by the cure time of the moulding compound but also by the speed
at which the operator can load and unload the machine. The main
automated moulding machine manufacturers are Towa, Yamada and
Daichi Seiko of Japan and FICO of Holland. A number of American and
other European manufacturers are also pursuing the manufacture of
automated moulding systems.
5.2.8 Comparison of Conventional and Automated Moulding

We have highlighted the ability of the automatic moulding machine to
process a higher throughput with limited supervision. Typically, one skilled
or semi-skilled supervisor can 'manage' three or four machines and this is
eventually planned to rise to seven or eight machines as the equipment itself
becomes more reliable. There is, however, a strong counter-argument purely
in cost terms for a logical development of the conventional approach, e.g. a
standard press and mould tool, with maximum possible cavity count, using
a fast cure mould compound, giving a 50-70 seconds total cycle time. The
argument is based on the much lower capital cost of the 'conventional
approach' compared with the expensive automatic moulding machine.
However, the industry as a whole has decided to follow the automated
approach, and even if the economic considerations can be interpreted in
more than one way, the overall quality, or uniformity of quality, that results
appears to justify the capital investment. This is especially true for high lead
count devices where moulding parameters may have to be more closely
controlled than for relatively straightforward 14 or 16 lead DIL or 24 lead
quad pack packages.
5.3 TRANSFER MOULDING COMPOUND FORMULATION

CONSIDERATIONS
The development and production of a typical epoxide moulding compound

has usually been determined, as with other epoxide formulations, by the
'----_ _ _
TRA
__
N_SF_E_R_M_O_U_L_D_IN_G_C_O_M_P_O_U_ND_F_O_R_M_U_L_A_TI_O_N
___ --'I I 141
Table 5.1 Typical components of an epoxide moulding compound
Major components Minor components
Epoxide resins Release agents

Hardener resin Pigments
Catalyst or accelerator Flame retardants
Fillers Additives
properties desired for the compound, the availability of raw materials to

manufacture the compound and its selling price. From a practical point of
view, the final product is the result of a series of trade-offs or compromises
between the various end properties required, many combinations of which
are incompatible.
A typical epoxide moulding compound contains a variety of major and
minor components, and the general ingredients found in most products are
shown in Table 5.1. Each of these components is available with a range of
physical and chemical properties, all of which have a distinct role in
determining the product's final properties. The influences these constituents
have on a compound's properties are now discussed.
5.3.1 Filler Content and Resin Viscosity Effects on Spiral Flow

The spiral flow of a moulding compound is a property that determines
whether or not a mould will fill under given moulding conditions and
whether the compound will have acceptable flash and bleed characteristics.
The spiral is moulded under a set of moulding parameters with a charge of
material sufficient to give a cull within a specific thickness range. Moulding
compounds for semiconductors usually have a spiral flow from 20--40 in.
The spiral flow of a typical epoxide moulding compound varies with the
viscosity of the resins and the amount of filler used in the formulation, as
can be seen in Fig. 5.5.
The resin viscosity shown on the left-hand axis in Fig. 5.5 may be taken to
represent the predominant resinous component or the net viscosity of the
combined resin system. In either case, as the viscosity increases the spiral
flow decreases. This means that the viscosity range of the resins that may be
employed is limited, to a large extent, by the desired spiral flow for the
finished products (shown here as 25-35 in). The choice of resin viscosity is,
however, also related to other factors besides spiral flow and these impose
further limitations on the range of usable viscosities. In particular, the use of
very high viscosity resins can cause wire sweep problems during moulding
(see section 5.4.4), whilst low viscosity resins can cause resin bleed.
The right-hand vertical axis in Fig. 5.5 represents filler content and it can
be seen that spiral flow decreases with increasing filler content. The spiral
t
....e-
S
.re
;>
20 30 40
Spiral F10wrmches
Fig. 5.5. Variation of spiral flow with viscosity and filler content.
flow requirement thus has a direct bearing upon the filler content of most
compounds, giving a finite range. Another factor influenced by the filler
content of a compound is the cure shrinkage, with high filler contents giving
lower values. Other aspects of the filler composition can also add further
limitations to the development of a compound. For example, the filler
particle size and particle size distribution affect the flash and resin bleed
characteristics of the finished compound. Oversized filler particles can cause
gate blockage, resulting in incomplete filling of cavities. This is particularly
important when moulding small-sized packages such as chip carriers and
SOT23 devices, where gate depths may be thinner than for conventional
transistor and dual in-line packaged integrated circuit moulds.
5.3.2 Thermal Expansion Coefficient and Filler Content

The thermal expansion coefficient of silicon is 3 ppmrC, whilst that of an
unfilled epoxide is typically 50-60 ppm/DC. This difference results in a
thermal expansion coefficient mismatch between a moulding compound and
a semiconductor die (and also the lead-frame material). Thermal expansion
coefficient mismatch can lead to the build-up of stresses in a device, which
result in premature failure by cracking of passivation layers, failure of wire
bonds and even cracking of the chip or package. One of the main uses of
fillers is to reduce the thermal expansion coefficient mismatch between the
epoxide and the encapsulated parts. For a given epoxide, the thermal
TRANSFER MOULDING COMPOUND FORMULATION II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~ 143
45
30
15
60 70 80
Filler ContentJ%
Fig. 5.6. Variation of thennal expansion coefficient with filler content.
expansion coefficient below the glass transition temperature (1X1) decreases

with increasing filler content, as can be seen in Fig. 5.6.
Of greater significance, however, is the selection of filler and its effect
upon the thermal expansion coefficient. For a specified loading, much lower
values are achieved with fused silica than with alpha quartz. The obvious
choice of filler to give a low thermal expansion coefficient at a given loading
would be fused silica; however, there is a trade-off in properties, since the
filler giving the best thermal expansion characteristics does not give the best
thermal conductivity.
5.3.3 Thermal Conductivity (1) and Filler Content

Unfilled epoxides have relatively low thermal conductivities compared with
the inorganic fillers and thus the incorporation of a filler such as silica into a
formulation not only reduces the thermal expansion coefficient but also
increases thermal conductivity. The variation of thermal conductivity with
filler content for a typical moulding compound is shown in Fig. 5.7.
However, the most significant factor is again the choice of filler with alpha
quartz giving higher thermal conductivity than fused silica at the same
loading. While the choice of filler for highest thermal conductivity is
obviously in favour of alpha quartz, by considering both Figs 5.6 and 5.7,
the trade-off between thermal expansion coefficient and thermal conductiv-
ity can be appreciated. In effect, for the highest thermal conductivity alpha
quartz would be the best filler, whereas for the lowest thermal expansion
coefficient fused silica would be selected. The choice of filler will therefore
have to be carefully considered for a particular application depending upon
50
30
10
60 70 80
Filler Contentl%
Fig. 5.7. Variation of thermal conductivity with filler content.
which property is more important. It is of course possible to blend the two

fillers to give a compromise in properties where moderate expansion and
thermal conductivity properties are required.
5.3.4 Mould Release Agents: Staining and Releasability

Epoxides are good adhesives and epoxide moulding compounds are no
exception. Consequently, in order that moulded parts can be removed from
a mould cavity, a mould release agent is included in the formulation. A
popular release agent used to be camauba wax, a natural product, which
unfortunately contains small amounts of impurity that eventually contribute
to staining of the mould and degraded cosmetic appearance of the moulded
parts. There are thus conflicting requirements with the use of this wax:
enough must be added to facilitate easy release from the mould tool, yet the
smallest amount possible should be used to avoid staining. Figure 5.8
illustrates the relationship between mould release concentration, time to
mould stain and release force.
Increasing the release agent level results in reduced production time
before mould cleaning is required. Simultaneously, however, the energy
required for physical release from the mould is reduced. The physical release
force shown is from an arbitrary laboratory test. By experience, values of
151b or less in this test can be expected to give satisfactory release in
production moulding. A typical concentration of release agent would thus
be in the region of 0.5%. Synthetic release agents are now available and
have been in general use for some years; in most situations they contribute
to a useful reduction in mould stain.
T_RA_N_SF_E_R_M_O_U_L_D_IN_G_CO_M_PO_U_ND_F_O_RM
L -_ _ _ __ U_L_A_T_IO_N
___ - 11 I 145
20 20
10
fi
~
1
o L -____________________________~
o
o 0.5 1.0
Release Concentrationl%
Fig. 5.S. The relationship between mould release concentration, time to stain and
release force.
5.3.5 Mould Release Agents: Concentration versus Adhesion

Much work has been carried out in the last few years to quantify and
enhance the level of adhesion between the epoxy and the lead frame/chip
assembly. This has been driven not only by the general requirement to
increase reliability of the part in terms of reduced moisture ingression, for
example, but more specifically by the requirement to surface mount devices,
with the accompanying thermal shock that causes many devices to
disintegrate unless they have been carefully processed prior to the assembly
operation or stored in a dry bag since manufacture. Testing of devices has
been carried out by X-ray and particularly 'acoustic X-ray' techniques
(scanning acoustic microscopy) and it is acknowledged that it is desirable
that the epoxy and the silicon chip/lead-frame it is encapsulating should
remain as a single unit in intimate contact. Ideally there will be some
bonding to ensure physical contact is maintained during the lifetime of the
device, and through the various thermal excursions to which it will
inevitably be subjected. However, the only realistic way that this can be
achieved is by completely eliminating the release agent from the mould
compound. With present technology, this will result in gluing together of the
two halves of the production mould within just a few shots, and even if the
mould is treated between shots with some form of external release, some of
this will be removed from the cavity walls during the filling part of the
mould cycle, and in so being, will be re-distributed. Some ofit will inevitably
reappear at the interface between the epoxy and the chip/lead frame. Until
such time as a foolproof system can be devised whereby the moulding
compound formulator can eradicate all wax or wax-like equivalents from his
materials, this will continue to be a trade-off in which practical consider-
ations, i.e. the ability to release each shot without too much difficulty from
the mould tool, will continue to dominate. Recently, a Dutch company has
patented an approach that appears to circumvent this difficulty, though at
the time of writing it remains to be seen whether their innovative process will
become widely adopted in production-orientated environments. 1
5.3.6 Glass Transition Temperature (T,J and Stress

The dramatic increase in the number of functions provided by a single chip,
the smaller geometries involved and the conflicting demands of a large chip
in a small package lead to some challenging mechanical compromises. For
instance, stress applied to the chip by the encapsulant is becoming
increasingly important. Even though chip geometries are getting smaller,
the complexity and number of functions is resulting in larger and potentially
more vulnerable chips, with the need for more connections to the outside
interconnect circuitry. Packages with lead counts of 300 or more are
increasing and will become even more common.
Stresses are caused by the thermal expansion coefficient mismatch
between the plastic package and the silicon die and lead-frame it
encapsulates. They can affect the electrical properties of the device, causing
cracking of passivation layers or even the chips themselves. In extreme cases
stresses can even result in cracking of the encapsulant. The internal stress
performance of an epoxide moulding compound is related to several factors,
the important ones being the extent of mismatch of expansion coefficient
between the epoxide, the chip and in some cases the lead-frame material.
Young's modulus also figures and, whereas from some considerations it
could be supposed that a high modulus would provide a superior material, a
compromise must be sought in order to provide the required combination of
low expansion coefficient and low stress on the chip. Figure 5.9 shows the
variation of internal stress with glass transition temperature for a typical
epoxide moulding compound.
In order to obtain optimum stress performance in the past, some sacrifice
in glass transition temperature was often made. However, a high glass
transition temperature is usually required to ensure good device reliability,
particularly where high temperature operation or thermal cycling is likely to
occur. There has thus been a trade-off between stress and glass transition
temperature. Recent developments have shown that for each compound
there is a filler concentration where the thermal expansion coefficient and
Young's modulus interrelationship can be optimized allowing low stress
performance to be achieved whilst simultaneously giving higher glass
transition temperatures.
'--_ _TRA
__N_SF_E_R_M_O_U_L_D_I_N_G_C_O_M_P_O_U_ND_F_O_R_M_U_L_A_T_IO_N
__ -----'I I 147
....w
~
J
6
4
120 150 180
Glass Transition TemperaturerC
Fig. 5.9. Variation of internal stress with T g •
5.3.7 Glass Transition Temperature (Tg) and Curing Conditions

For a given compound, the final glass transition temperature achieved is
determined by the time and temperature of the cure and the level of catalyst
used in the formulation. When formulating a moulding compound, enough
catalyst must be used to provide a good cure within the specified moulding
cycle parameters. As can be seen in Fig. 5.10, Tg increases curvilinearly with
170
oU
~:I
~
100
<II
S'
~ 150
1:1
Q
;e
~
E-4
~
6
130
0 12 24
Post Cure/hours
Fig. 5.10. Variation of Tg with cure time and temperature.
time and temperature to different maximum levels depending upon the post-
cure temperature.
The choice of post-cure conditions has a direct bearing upon the degree of
crosslink density achieved and, in effect, on the overall properties of the
cured compound. The zero point on Fig. 5.10 represents the as-moulded Tg
before post-curing and thus variations in the permissible moulding
conditions play a large part in determining the catalyst type and level to
be selected for a given formulation. Whilst it would seem obvious to use
additional catalyst where a curing schedule is limited, it should be borne in
mind that device reliability usually decreases somewhat with increasing
catalyst concentration. The use of a more reactive catalyst may also lead to
problems with reduced shelf stability.
5.3.8 Shelf Stability

An ideal moulding compound would have indefinite shelf stability at room
temperature. Unfortunately it is not possible to have a compound that will
cure in 20-40 s at 180°C and yet will not react at room temperature. Shelf
stability of epoxide moulding compounds is usually represented in terms of
spiral flow retention since, as the compound reacts, its spiral flow diminishes
until it will be too low to fill a mould. It is normal to store epoxide moulding
compounds at 4°C or below to increase their shelf-life and Fig. 5.11 shows
the loss of spiral flow with time for a typical epoxide stored at several
temperatures. At 4°C the flow retention is almost 100% even after 60 days.
At 25 and 35°C flow retention reduces significantly with time. There is
l00rr=====================~-'
~
1:1
:8
j SO 25"C
&!
~
3SOC
0
0 30 60
Storage Time/days
Fig. S.11. Loss of spiral flow with time at different temperatures.
TRA
L-..._ _ ___N_SF_E_R_M_O_U_L_D_IN_G_CO_M_P_O_U_ND_F_O_R_M_U_L_A_T_IO_N
___ -'I I 149
obviously a trade-off between reactivity and shelf-life and it is usually true

that the greater the reactivity of a compound the shorter its shelf-life will be.
This should be borne in mind when making catalyst selections for a
formulation. Ideally, a catalyst would be totally latent at room temperature,
only becoming reactive at the moulding temperature.
5.3.9 Raw Material Purity and Cost

The purity of materials used in the formulation is of the utmost importance
in determining device reliability since ionic impurities are known to cause
corrosion failures. The purity of the constituents used has been dramatically
improved over the last few years, but materials with increased purity usually
cost more than their less pure analogues. When formulating an epoxide
moulding compound, the purity requirements need to be taken into account
and considered against the likely cost penalties for improved purity. There is
no point in using the highest purity raw materials for a compound designed
to encapsulate reed relays or resistors, yet the utmost purity will be required
for materials to encapsulate small geometry semiconductor devices, where
sensitivity to impurities may cause corrosion or parametric failures (see also
section 5.5.7).
5.3.10 Reliability of Encapsulated Devices versus Flammability Rating

Traditionally, the semiconductor industry has required encapsulated devices
to meet local or international standards of flammability, either for the
individual device itself, or in a generic sense, by some certification
recognized world-wide on the plastic encapsulant selected for that device.
The most widely accepted test is in the latter category, that is, it defines
flammability rating of the epoxy, tested under laboratory conditions. This is
the UL94 test invented by and still carried out by Underwriters, Laboratory
in the USA. There are various categories in which the test results are
specified, the most rigorous of these, in non-burning terms, being the VO, for
a specified thickness of test specimen. Very often a supplier's data sheet will
say, under the flammability heading, that the material is VO. This means
virtually nothing unless the specimen thickness is mentioned. For example,
probably the most standard single flammability rating accepted in most
parts of the world is presently VO in 0.125 in. Other ratings for example VI,
or HB (horizontal burning) again need to be defined for a thickness of test
specimen. As their names suggest, these are lower FR ratings and not
generally relevant in this industry.
Flame retardancy is imparted to a moulding compound by incorporation
of two different species, each of which is a flame retardant, but which works
in synergy with the other such that the combined result is greater than the
sum of the two individual results. These species are:
1. Antimony oxides (trioxide or occasionally pentoxide).
2. Brominated resins.
It is particularly in regard to category 2 that we see a trade-off, since the
brominated resins are designed to break down above 200°C, when flame-
retarding gases are released. Unfortunately, these materials are not fully
stable at lower temperatures, and moisture test results in particular, and
high temperature storage test results, will frequently be impacted by the
presence of the brominated resin in combination with the other ingredients
of the resin system in a flame-retarded compound. It can be seen that there is
a trade-off in terms of ultimate device reliability and the FR rating of the
moulding compound. For some very critical applications, where for
commercial or other reasons it is essential to put a particular device into
plastic, it is known that some devices will only work in plastic, at least with
today's technology, if that plastic has the level of brominated resin reduced
(thus compromising the FR rating) or eliminated. Whether the market as a
whole will accept this, apart from in occasional special instances, remains to
be seen. However, work is in progress to identify superior flame-retardant
systems that do not have the disadvantage of reducing product reliability
and also to produce pure modern and conventional systems from which
most or all of the brominated resin has been eliminated.
5.3.11 Susceptibility to Alpha Particle Radiation versus Costs of Encapsulant

Transient device malfunctions can occur on devices with small geometries
because of random bombardment of the chip by alpha particles. Whilst such
blips are of short duration and cause no physical damage to the device, the
effects can be devastating, depending upon the function for which the
equipment containing the device is being used. This problem is not unique to
plastic encapsulated devices, but is one which the industry has been required
to address. One solution is to use a moulding compound made using filler
material with critically low levels of uranium and thorium to minimize the
rate of emission of alpha particles to a statistically calculated acceptable
level. The trade-off in this instance is that of a major price differential for the
modified encapsulant which is typically around four or five times the cost of
the original version. It is therefore not practicable to standardize on a low
alpha compound for all production and so devices requiring this protection
must be selectively encapsulated in the more expensive material.
Another approach in general use, which obviates the need for a more
costly moulding compound, requires adding two layers of a polyimide
conformal coating to the chip surface. This imparts acceptable protection
against alpha particles and is significantly cheaper. (However, the cost of
L-_C_O_M_M_O_N_M_O_U_L_D_I_N_G_P_R_O_B_L_E_M_S_A_N_D_H_O_W_T_O_A_V_O_ID_T_H_E_M_----li I 151
two additional process steps needs to be considered, as do possible

mechanical effects arising from the presence of a layer of material between
the chip and encapsulant.)
5.4 COMMON MOULDING PROBLEMS AND HOW TO AVOID

THEM
Whilst the encapsulation of semiconductor devices using a transfer

moulding technique is relatively straightforward, attention has to be given
to a large number of parameters in order that properly moulded parts are
obtained in acceptable yields. It is essential that the correct moulding
compound is selected for a particular application, since a compound that is
suitable for moulding diodes or transistors may be totally unacceptable for
moulding VLSI circuits in high pin count packages. The moulding
compound should be stored prior to use, in the correct manner as
recommended by the supplier. Normal storage procedures involve keeping
the unopened drums of material at 4°C or below then allowing them to
equilibrate with the ambient temperature prior to opening and use.
Incorrect storage may lead to partial curing, with an accompanying loss
of spiral flow and the possible inclusion of moisture. The use of a poorly
designed mould or one that is badly worn may also lead to poor quality
moulded parts with excessive flashing and voiding being common occur-
rences. Another important factor which directly influences the quality and
yields of moulded parts is the use of moulding operatives with little or no
training in the handling and moulding of the compounds.
Even if all the above has been taken into account, it is still possible that
moulding problems may be encountered from time to time. Some common
moulding problems are now reviewed.
5.4.1 Flashing and Resin Bleed

The term 'flashing' is applied to moulding compound that has flowed into
unwanted areas, usually in the parting line region, although with worn
knockout pins flashing may also form so-called 'chimneys' on a moulding.
Excessive flashing leads to parts which, at worst, are totally unacceptable or
in less severe cases require additional cleaning time. Cleaning will also be
required to remove flash remaining in the mould, since it may prevent the
mould closing properly during the next cycle, leading to a worsening of the
problem (see Fig. 5.12).
Resin bleed refers to the separation of the organic components (resins) of
the moulding compound from the inorganic components (fillers). It is
usually a precursor to flashing since material is flowing into areas where it is
Fig. 5.12. Flash on moulded devices.
not supposed to, the size of the gap along which flow occurs being too small
to allow the filler particles and pigment to migrate. Resin bleed adheres
tenaciously to the surfaces it comes into contact with leading to problems
with lead-framed devices in which the lead-frame has to be plated or
soldered in a later operation.
Flash is generally above 0.001 in thick and the colour of the moulding
compound whereas bleed is translucent, difficult to see and below 0.001 in
thick. There are a number of causes of flash and bleed, the principal ones being:
1. High transfer pressures. Excessively high transfer pressure may result in
flash and bleed along the parting line area. The transfer pressures
recommended by the moulding compound manufacturer should be used
and it is essential that the clamping pressure of the mould is sufficient
(e.g. five times the transfer pressure).
2. Worn moulds. As with most mechanical equipment, continued use leads
to wear and, in the case of a mould, the parting line area becomes worn
allowing flashing and bleeding to occur. As the wear increases it will be
necessary to replace or recondition the mould. It may be possible, as a
palliative measure, to prolong the use of worn moulds by using moulding
compounds with shorter spiral flows and/or increased melt viscosity.
This can be accepted for use with rigid, non-fragile inserts such as TAB
and bump chip type assemblies, but with standard wire-bonded lead-
frames, wire sweep will eventually become a problem giving reduced
yields (see section 5.4.4).
COMMON MOULDING PROBLEMS AND HOW TO AVOID THEM II 153
3. External release agents. Epoxide moulding compounds generally incor-

porate release agents and external release agents are largely unnecessary.
The regular use of external release agents on the mould surface may
eventually plasticize the moulding compound. This results in additional
flashing and, more particularly, bleeding of the resin. The use of external
release agents should be avoided, or at least kept to a minimum. It is also
possible that the internal and external release agents may be incompatible.
4. Out of specification inserts. If lead-frames or device leads are not
produced within a rigidly specified thickness range, flashing and bleeding
can be exacerbated. Parts thicker than an acceptable tolerance will
prevent the mould closing properly, with flash and bleed occurring
around the standard thickness parts. Conversely, thin parts will allow
flash and bleed around themselves, because, although the mould is closed
properly, there may be a gap between the mould and the thinner leads or
lead-frames.
5. Unsuitable moulding compound. A compound with an abnormally low
melt viscosity can give bleed problems and possibly flashing. Filler
particle size is also important because flash and bleed are dependent
upon the particle size distribution of the filler. These two parameters are
controlled by the moulding compound .supplier and with persistent
problems the manufacturer should be consulted for help with flash and
bleed control.
5.4.2 Knit Lines and Incomplete Fill

Knit lines and incomplete fill are said to occur when the mould cavity
remains only partially filled and/or the moulding is not homogeneous, with
grooves appearing in the parts. Knit lines are at best cosmetically
objectionable and at worst, sites for entrapment of moisture and ionic
contaminants that can lead to early corrosion failure of a device. A typical
example of non-filling is shown in Fig. 5.13.
Common causes of incomplete fill and knit lines are:
1. Insufficient or excessive amounts of moulding compound. In a normal
moulding operation preforms of the moulding compound are used
having a specific weight in order to completely fill all the cavities of the
mould, and to give a cull of suitable thickness to allow the pressure of the
ram to be transferred to the material at all times. Using less than the
required amount to fill the mould will obviously result in incomplete fill.
The usual reason for the inadvertent use of less than the ideal amount of
material is variation in preform weight, where the use of several preforms
of low weight will result in a significant loss of material. Less obviously,
the use of too much material may also lead to incomplete fill. This can
occur because the larger than normal mass of material does not liquefy
Fig. 5.13. Moulded leadframes showing examples of incomplete fill.
sufficiently, the melt viscosity not reaching the required minimum. By

paying attention to the cull thickness, it is easy to determine if too much
material is being used since the cull or biscuit should normally be
between 0.125 and 0.250 in thick. Excessive material will also lead to
waste and increased production costs.
2. Incorrect moulding pressure and temperature. Moulding temperatures and
transfer pressures should be maintained within the range set by the
moulding compound manufacturer. Whilst the maintenance of correct
temperatures and pressures is straightforward, low transfer pressure or
low temperature is often the cause of incomplete fill. On many machines,
the only accurate way of setting the transfer pressure is to use a force
gauge which the ram can act upon directly to give an exact value of the
transfer pressure. A low moulding temperature may be used inadver-
tently because of reliance upon inaccurate temperature gauges on a press
or because of inoperative heating elements within the mould that give
cool areas. A low moulding temperature will prevent the moulding
compound from achieving the minimum melt viscosity required for
complete mould filling. Conversely a high moulding temperature may
accelerate the reaction rate of the epoxide leading to premature gelation
of the compound before all the cavities are filled.
3. Transfer speed. The transfer speed or fill time is also very important in
determining whether complete fill of all the cavities is achieved. A rapid
transfer can cause heating of the compound in the restricted area of the
gates leading to premature gelation or gate blockage. A slow transfer will
mean that the compound gels before the transfer process is complete.
Both long and short transfer speeds can thus lead to incomplete fill . For
average size moulds, a transfer time of between 15 and 20 s would be
acceptable.
COMMON MOULDING PROBLEMS AND HOW TO AVOID THEM II 155
4. Preheating. Dielectric preheating of preforms is recommended to achieve

good quality moulded parts and to reduce overall cycle time. For any
given application and set of moulding parameters there will be a narrow
temperature range from which the preheated preform temperature
should not vary. Too Iowa temperature may lead to incomplete fill
because the melt viscosity will not achieve the required minimum
necessary to completely fill the cavities. Too high a preheat temperature
may lead to premature curing and gelation of the compound before all
the cavities are filled.
5. Incorrect or short flow. On any new moulding application the flow
requirements of the compound must be established within the limitations
imposed by the moulding operation and the supplier's specification. With
all the other important parameters fixed, an application requiring a
compound with a spiral flow of 35 in will have incomplete fill problems if
a compound with a spiral flow of 25 in is used. Where a material with the
correct spiral flow has been selected, there is still the possibility of
incomplete fill if the compound has been exposed to high temperatures
during shipping or storage that have reduced the spiral flow. It is
important that a good correlation has been achieved between the spiral
flows as determined by the customer and the supplier.
6. Inadequate venting. Although epoxide moulding compounds cure by an
addition reaction, without the evolution of volatile reaction products,
vents are still required in a mould to prevent entrapment of air, absorbed
moisture or any components evolving from the component to be
encapsulated. The vents are usually situated opposite the gates and
should be deep enough to allow the removal of air without the build-up
of a back pressure. Inadequate venting can lead to air entrapment,
incomplete fills and knit lines. Particular attention has to be given to
cleanliness in the vent areas since the build up of wax or resin bleed (both
often difficult to see) may lead to their partial or complete blockage.
7. Gate blockage. Incomplete fill is also sometimes caused when gates
become partially or completely blocked, preventing or impeding the flow
of the moulding compound into the cavity. Usual causes of gate blockage
are oversized filler particles and partially cured moulding compound.
The problem is particularly likely to occur in semiconductor applications
with small-outline (SO) type packages where gates less than 0.010 in deep
are common. The presence of partially cured particles of moulding
compound usually arises because of cleanliness problems in the mould or
in the preforming operation.
8. Worn equipment/insufficient clamping pressures. The use of worn moulds,
transfer pots and rams, or the use of insufficient clamping pressure can
lead to the excessive flashing of a compound into areas where material is
not required. Moulding compound consumed in flash is not available for
filling cavities and incomplete fill may again be the result.
5.4.3 BUsters and Voids
Blisters, as their name implies, appear as eruptions in the moulding surface,
and are due to the expansion of underlying trapped gases or volatiles when
the pressure is relieved. Voids occur as small irregular imperfections in the
surface of the moulding, although they also sometimes appear within the
bulk of the compound. The usual causes of blisters and voids are:
1. Excessive volatiles. Problems with volatiles are caused by an excessive
free moisture content within the moulding compound which is unable to
be vented during the moulding operation. Moisture finds its way into a
moulding compound through poor handling procedures. Moulding
compounds are typically stored at temperatures around 4°C and if a
drum is opened before equilibration with room temperature moisture is
likely to condense from the atmosphere onto the moulding compound.
This is particularly likely if the operating environment is one of relatively
high temperature and humidity. Correct storage procedures include
allowing the material to reach room temperature before the drum is
opened and avoiding excessive atmospheric exposure to any open drums.
Other causes can include contamination on the inserts, e.g. solder flux
not completely removed.
2. Rapid transfer. If the transfer speed is not adequately controlled a too
rapid transfer may occur, leading to turbulent or 'jet-like' flow of the
material into the mould cavities. This can cause vents to be blocked
before all the unwanted volatiles have escaped from the cavity. Too fast a
transfer may also lead to excessive heating of the compound and
premature gelation which can cause void formation and rapid gate
wear.
3. Inadequate venting. Just as inadequate venting can lead to non-filling of
cavities, a precursor to this situation may be the formation of voids and
blisters.
4. Excessive moulding temperature (blisters). Epoxide moulding com-
pounds are usually rigid enough at the end of a moulding cycle to
withstand any internal pressures caused by small amounts of trapped air
or volatiles. However, if an excessive moulding temperature is used, the
epoxide may become sufficiently elastic for more pressure relief to occur,
often resulting in blister formation on removal of parts from the mould.
At even higher temperatures thermolysis of the moulding compound
components can lead to further volatile evolution with subsequent blister
formation.
5. Melt viscosity (voids). The melt viscosity during a moulding operation is
one of the most important parameters influencing mouldability. An
abnormally low melt viscosity can give uncontrolled cavity filling leading
to the entrapment of volatiles and gases, with the subsequent formation
of internal or external voids.
COMMON MOULDING PROBLEMS AND HOW TO AVOID THEM II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _- " 157
5.4.4 Wire Sweep During Semiconductor Transfer Moulding

The flow of epoxy through the gate into the mould cavity during the fill part
of the cycle and the subsequent swirling around in the cavity during the time
that the cavity is filling can cause mechanical damage. In the case of an
integrated circuit, wires can be moved unacceptably close to one another or
in extreme cases can be lifted off bond pads or sheered close to the bond or
even made to touch each other whilst still connected to the appropriate
points on the lead frame and chip, causing a direct shortout.
Irrespective of the quality of the mechanical design of the chip or other
insert, which may prove to be vulnerable to the exact flow pattern of the
epoxy, there are basic guidelines to be observed that will minimize yield
losses in a high production IC plant and which will reduce damage to inserts
whether the item encapsulated is a semiconductor or other fragile
component.
A mistake often made is that moulders become confused between damage
caused by mould pressure (transfer pressure) and that caused by excessive
filling speed. In a transfer press, even if the pressure is set unnaturally high
(e.g. 1500 psi would be higher than the industry normally uses), that
pressure is not developed throughout the system until all the cavities in the
tool have filled, and back pressure is present throughout the system,
resulting in a situation where the ram passing on the pressure is no longer
moving, i.e. its speed is tending to zero. In this condition the pressure drop
though the transfer speed control valve tends to zero whereas when the ram
is moving, a pressure drop from the pump side of the speed control valve to
the ram actuating cylinder side can be as much as 80%, e.g. if 1500 psi is
applied on the high side, the actual pressure moving the ram during the main
part of the filling cycle could easily be as low as 200 psi. The reason that
transfer pressure itself rarely causes any mechanical damage, even to fragile
items such as glass reed inserts in a reed relay, is that when the full pressure
is applied, the cavity is full and the pressure developed is applied
symmetrically around the fragile part.
Damage caused during filling is most often caused by the sheer
momentum of the encapsulant entering the cavity through the gate. The
mass of the material is fixed and cannot be adjusted in the interests of
reducing damage. The moulder can, however, reduce the velocity by
ensuring that the transfer speed control is correctly set. In this way, the ram
velocity will be reduced and there is no need to adjust the transfer pressure
setting, since the transfer pressure determined by the pressure-setting valve
will only be reached in full when the ram has stopped moving and the fill is
complete.
For an integrated circuit, in the early days of transfer moulding, for
example, with 14/16 lead DIL devices, a general rule was that filling should
be completed within 10-25 seconds. However, some American IC producers
successfully worked on overall cycle times of 60 seconds or less with
conventional mould presses and conventional encapsulants, and the filling
part of the overall cycle was as low as 9 seconds. In the opinion of the
industry as a whole, this was too fast but, for example, at least one company
is known to have operated on this basis for many years in a number of
plants around the world and achieved yields in excess of 99%.
The introduction in the last five or six years of a wide range of more
sophisticated devices, with lead counts regularly above 100, has led to a
greater requirement to understand wire sweep, and a number of epoxy
manufacturers now supply some of their standard formulations in at least
two different versions. In terms of the viscosity of the compound, typically,
these can be called regular and 'low viscosity' versions, and Plaskon, for
example, on their S7 low stress compound do precisely that. The S7 low
viscosity version has identical final properties after moulding and post cure
as the standard version, but the viscosity during the important transfer part
of the cycle, at moulding tool temperature of around 175°C, is nearly half
that of the 'regular' version. It is important to note that when using a low
viscosity version of a material, no advantage will be gained unless the
transfer speed control is correctly set. For example, consider a moulder
using the regular version of the material, where filling takes place in 15
seconds and the filling is controlled not by the ram speed control setting but
by the viscosity of the moulding compound itself. In that situation, if no
alteration is made to press settings, and the low viscosity version of the
material is used, the ram will complete its fill in something like 6 seconds,
resulting in even more mechanical damage than was taking place with the
more viscous compound at the 15 second time. There is obviously here an
interaction between the viscosity properties of each moulding compound
and the optimum filling time for a given design, since the requirement is to
minimize damage to the insert (including wire sweep on an IC) and also to
ensure that all the cavities in the tool have completed their fill before the
epoxy has fully cured in some parts of the system. For example, if the ram
speed control is set so the filling would complete in say 60 seconds, many
epoxides would start to solidify in some cavities after perhaps 30--35 seconds
at a tool temperature of 170°C. Some fast cure compounds would already
have solidified after 18-20 seconds. Therefore a balance is required between
the requirement to avoid mechanical damage and the requirement within a
given moulding compound to achieve a 100% fill at a given tool
temperature.
There are other sophistications that can be introduced if a particularly
difficult cavity requires to be filled. Some cavities are inherently difficult such
as those where the cavity is divided into two halves by a large slab of foreign
material e.g. a ceramic substrate. It is often difficult to achieve a complete fill
here because of differential flow of epoxy along the top and bottom halves of
the cavity. This is not strictly a function of the main point under discussion
L--_C_O_M_M_O_N_M_O_U_L_D_IN_G_P_R_O_B_L_E_M_S_A_N_D_H_O_W_T_O_A_V_O_I_D_T_H_E_M_-----'I I 159
here, but links up to it in tenns of the design of the insert. For example, in
order to balance flow between the two halves of a cavity, a bent 'flap' is
sometimes introduced immediately inside the gate of the cavity to act as a
baffle and modify the flow characteristics. In the case of uneven filling, the
purpose of a baffle is to equalize the flow and to reduce turbulence
immediately inside the gate. It can also playa part in restricting the velocity
of the material, in effect steering it away from those wires nearest to the gate
which are often most likely to be damaged by the in-rush of material.
Finally, some transfer presses have been sold in the last 10 years which
attempt to address this problem in a rather sophisticated manner, including
the technique of altering the available pressure on the ram at different points
in its travel. At this time, however, it is not clear that this sort of
sophistication is necessary. The working of the restrictor valve in the
transfer speed control is a perfect example of a simple idea that works well
and covers every eventuality, but the important thing is that the transfer
speed control is often misunderstood or taken for granted, and yet it
remains, closely behind actual mould tool temperature settings, one of the
most important controls on a hydraulic press.
5.4.5 Staining of Moulds and Poor Cosmetic Appearance

Mould stain refers to discoloration of a mould surface by the deposition of
unwanted residues from the moulding compound. It is typically brown and
represents the colour of the residue or its oxidation product. Typical causes
of these residues are minute amounts of impurities within some of the
natural wax release agents used in older moulding compounds. Another
source of stain, on its own or in combination with the impurities from the
release system, is deposits consisting principally of uncured resin. The high
purity resins now used in semiconductor grade moulding compounds
contain certain low molecular weight fractions and whilst this is undesirable,
it is a fact of life that the industry has to tolerate. This low molecular weight
fraction of resin is less able to take part in the nonnal curing reaction and
remains within the matrix and at the interface with the mould tool as a
slightly sticky layer. Mould staining on materials manufactured during the
1970s was principally caused by deposits from the natural Carnauba Wax
release system, but in the 1990s the contribution from the release system is
now minimal. The main source of contamination is now from the resins used
in the fonnulation. There is an irony here in as much as the staining
propensity of many of the expensive and very pure semiconductor grade
moulding compounds is much greater than that of the related 'general
purpose' compounds, which in chemical tenns are not so clean but which in
nonnal use are less liable to build up a heavy stain so rapidly.
Staining is typically seen with epoxide novo lac-based moulding com-
pounds and continued staining or build-up of residues leads to cosmetically
objectionable parts which may exhibit markability problems. A cause of
staining and poor cosmetic appearance is excessive temperatures. The use of
excessive moulding temperatures leads to a decrease in the operating time
before the discoloration becomes unacceptable because of accelerated
oxidation of the waxes. By selecting a lower moulding temperature staining
can be reduced, although the cure time may need to be extended to avoid
undercure and sticking.
5.4.6 Sticking in the Mould

Mould sticking refers to the incomplete removal of parts from a mould due
to adhesion between the moulding compound and the metal surfaces of the
cavity. In less severe cases, a part may be released largely intact, but its
surface will have imperfections and there will be residual moulding
compound on the mould surfaces. More serious sticking can actually result
in parts being physically cracked or tom apart (see Fig. 5.14). In both cases,
extensive cleaning of the mould will be required between consecutive
moulding cycles, reducing productivity and yields. Causes of sticking are:
I. Undercure of the moulding compound. Undercured moulding compounds
adhere well to mould surfaces because they have not achieved the
crosslinking density, cure shrinkage and hot hardness of the fully cured
compound. The two main reasons for this are the use of low moulding
temperatures and short cure times. Each compound will have a specific
minimum mould cycle time/temperature relationship below which
problems can occur because of undercure. The moulding conditions
specified by the manufacturer usually allow a safety margin but if it is
Fig. 5.14. Parts cracked because of a sticking problem.

L -_ _ ---'1 I
E_PO_X_ID_E_-_B_A_SE_D_T_RA_N_S_F_E_R_M_O_U_LD_IN_G_C_O_M_p_O_U_ND_S_ _ 161
necessary to use a lower than recommended moulding temperature the

cycle time should be increased. Should mould cycle time be important, a
long cycle time can be reduced in stages until the point at which sticking
occurs is reached, and then increased slightly again to avoid the problem.
2. Incompatible release agent. Although moulding compounds contain an
internal mould release, additional external mould release is often used,
particularly when breaking in a new mould or when beginning work on a
little-used press. When it is necessary to use an external release agent,
effort should be made to ensure its compatibility with the moulding
compound in use since certain external releases may interfere with the
material's cure leading to sticking as in (1) above. The use of external
release agents should be kept to an absolute minimum and, where there is
any doubt regarding compatibility, the compound supplier should be
contacted.
3. Dry moulds. One case in which application of an external mould release
agent may be necessary to prevent sticking is when a mould has dried
out. With continued use, the mould release agent permeates into the
micropores of the mould, promoting a weak boundary layer between the
metal and the moulding compound. However, if a mould is left at
temperature for excessive periods without "being used, this film of release
agent will lose its effectiveness because of thermal degradation. Such a
dry mould will exhibit very bad sticking until the release film has been re-
deposited. To assist this process, small amounts of external release agent
can be sprayed into the cavities and runners, any excess being wiped off
with a lint-free rag. The external release should be the same as the
internal release. In addition, the first shot moulded should be given a
longer cycle time in order for the release from the compound to 'soak in'.
4. Poor mould design. Draft angles are machined into mould cavities and,
combined with the cure shrinkage of the compound, facilitate release
from the cavity. Sticking may occur in moulds with shallow or no draft
angles when compounds with low shrinkage are moulded and this is
particularly important with the latest generation of low stress com-
pounds, where draft angles of 8-120 are recommended. Good mould
design also dictates the use of knock-out pins in the runners and cavities
and their presence often makes the difference between sticking and good
release.
5.5 EVALUATION OF EPOXIDE-BASED TRANSFER

MOULDING COMPOUNDS
For a moulding compound to be suitable for semiconductor encapsulation,

it must have a number of special characteristics which need to be well
defined and controlled within certain critical limits. This section discusses
some important properties that affect mouldability of moulding compounds
and details evaluation methods.
5.5.1 Hot Plate Cure Time

The hot plate cure time of a moulding compound indicates how long a
compound takes to gel at a given temperature. It gives a good guide to
establishing the cycle time of a moulding operation and the time available to
transfer the liquefied epoxide from the pot into the individual cavities. As its
name suggests, the hot plate cure time is determined by placing a small
amount (2-3 g) of moulding compound onto a hot plate at the moulding
temperature and kneading it backwards and forwards with a wooden
spatula until it gels. The gel time can be determined with an accuracy of
better than ± 1 s.
5.5.2 Spiral Flow

The spiral flow is the distance a material flows in a specific type of mould
under a given set of conditions. It is important because it should always be
longer than the maximum distance the compound has to travel in the press.
If a compound is exposed to any temperature excursions or held at room
temperature for long periods its spiral flow will decrease and so this method
is a good way of ensuring that the material is within specified limits.
The test is performed with a transfer pressure of 1000 psi, which is
measured directly at the ram face with a Dillon type force gauge. Platens
should be set to the required temperature and controlled to within ± 5°F. A
typical temperature is 350°F (177°C). The material is moulded as a powder
and sufficient charge is used to give a cull thickness of between 0.12 and
0.14 in. Some trial shots will usually be required to establish the required
charge size to give a cull thickness within the specified limits. The spiral
flow is recorded to the nearest inch at the point of farthest flow where the
spiral is continuous, and a mean value of at least three consecutive shots,
which must agree to within ±2%, is reported. A typical cull and spiral is
shown in Fig. 5.15.
5.5.3 Viscosity and Mouldability

The viscosity versus time characteristics of a compound during the transfer
moulding operation are important factors in the achievement of successfully
moulded parts. The fluidity of the material under the effects of both
temperature and pressure must be controlled within well-defined limits, so
that stress-free parts are moulded, mould cavities fill properly and problems
such as wire sweep do not occur. There are various methods for the
quantitative determination of flow and viscosity of moulding compounds
---li I
L -_ _E_P_O_X_I_D_E_-B_A_S_E_D_T_RA_N_S_F_E_R_M_O_U_L_D_IN_G_C_O_M_PO_U_ND_S_ _ 163
Fig. 5.15. Typical cull and spiral from a spiral flow test.
but the principal three are the ram follower/spiral flow test, the Koka flow
test, and the torque rheometer (Brabender plastograph) test.
5.5.3.1 Ram Follower/Spiral Flow Test

This is one of the most common methods for evaluating flow and viscosity, and
utilizes the spiral flow mould mentioned above. This test measures the
movement of the transfer ram with time during a moulding cycle using the
spiral flow mould at a specified temperature and pressure (usually those
required for the spiral flow test). By recording the ram movement, the
displacement of the moulding compound is effectively monitored. It is possible
to obtain a direct read-out of ram travel against time if the ram is connected to
a chart recorder via the appropriate interfacing circuitry and the resulting
plots can be compared from compound to compound or batch to batch.
5.5.3.2 Koka Flow Test

This method utilizes an extrusion process, where the material under
investigation is forced through a nozzle to impinge upon a plunger. The
movement of the plunger is measured against time in a similar way to the
ram follower method and again the resultant curve yields information on the
gel time and viscosity of the material.
5.5.3.3 Torque Rheometer (Brabender Plastographj Test

This method utilizes a torque rheometer, such as the Brabender plastograph,
to monitor material viscosity against time. This is achieved by introducing
the compound into a heated mixing chamber where it interacts with two
activated rotors. These rotors are connected to a torque meter and the
changes in rotation torque are measured against time. Upon introduction,
600
O~ ________________________- - J
o 1 2
Time/mins
Fig. 5.16. Typical torque versus time curves for a moulding compound at different
temperatures.
the torque reading will be high, but as the compound heats up and melts its
viscosity drops and the torque reading falls. However, at the elevated
temperature of the chamber the curing reaction occurs and so the viscosity,
and thus the torque reading, begins to increase until the compound gels.
From this type of experiment the minimum melt viscosity, the reactivity and
the gel time of a compound can all be evaluated. Typical results for this type
of test performed at various temperatures are shown in Fig. 5.16.
With these three tests it should be remembered that the behaviour of the
compound will be different to that occurring in a moulding operation and
some allowances will need to be made, particularly since the flow of a
compound into mould cavities will be mould design dependent.
5.5.4 Hot Hardness

At the end of a moulding cycle the hot hardness of a moulding compound is
important because, if the surface hardness is insufficient, damage to parts
can occur during ejection. The hardness of a moulding compound represents
a collection of interrelated properties rather than a single physical property
of a material. The hot hardness test is usually performed on the cull from a
spiral flow test. A reading is taken on the cull as soon as the press opens
using a pre-calibrated Shore D durometer pressed onto the cull until it is
seated flat. The Shore D hardness number can then be read directly from the
durometer. By making measurements of hot hardness for various mould
cycle times it is possible to record the increasing hardness of a compound as
it becomes fully cured. A typical example is given below:
EPOXIDE-BASED TRANSFER MOULDING COMPOUNDS II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _- " 165
Mould cycle time (s)

60 75 90 lOS
Hot hardness at 180°C 74 77 80 85

Hot hardness at 160°C 48 50 69 76
5.5.5 Flash and Bleed Characteristics

The flash and bleed characteristics of a moulding compound can be
evaluated using a specially prepared flash mould. This consists of channels
of varying depths, emanating from a central cull area. The shallowest
channel would be as little as 5 pm deep and the other channels would have
increasing depths such as 10, 25, 50 and 100 /lm. Depths of 25 /lm or less
allow only resin bleed, whilst at depths greater than 25 /lm flashing can also
occur. Materials are evaluated by measuring the length that the flash or
bleed has travelled along a particular channel. For a given compound, the
flash and bleed characteristics will vary from moulding operation to
operation and will be dependent on a large number of factors. It is therefore
important to ensure that any material evaluations are performed on the
same mould under identical conditions.
5.5.6 Mould Release (see also 5.3.4)

There is no absolute method for quantitatively determining the mould
release of a compound and, in practice, measurements are often performed
using an arbitrary mould. A typical example would be to mould a tapered
slug of material and then measure the force required to free the taper from
the mould. The differences in the values obtained for various materials can
then be related to their release performance in an actual moulding
application. Experience with a mould under carefully controlled conditions
often allows a release force value to be determined below which release
performance on the application under investigation can be considered
acceptable.
5.5.7 Reliability of Plastic Encapsulated Devices and Assessment of

Reliability
The subject of device reliability is particularly important and one that has
been addressed in great detail by many workers over a considerable period.
In the space available here it is not possible to mention more than the basic
points to encourage further reading but it is worth noting that the previous
edition of this work contains a chapter on plastic encapsulated device
reliability to which the reader can refer.
Plastic encapsulated transistors and early microcircuits initially sold on a
strictly cost basis and for any application requiring predictable and
dependable functioning the hermetic equivalent would always be specified.
With advances in both wafer passivation and the purity of encapsulants it is
no longer valid to regard plastic encapsulated devices as inferior to their
hermetic equivalents and devices have been introduced in plastic in recent
years in outlines where no directly equivalent hermetic package is available.
The industry standard 85/85 accelerated test (devices conditioned in a
chamber at 85°C and 85%RH, sometimes with a bias voltage) remains valid
and well respected in terms of enabling a device to be suitably qualified for
service in relatively hostile conditions. Equally, if batches of the same chip
encapsulated in different package outlines, or with a different encapsulant,
are tested, then the test forms the basis of a meaningful comparison.
Unfortunately, current packages do not regularly provide failures until after
several thousand hours, in comparison with say 20 years ago when 500 to
1000 hours' exposure often gave significant failures. Consequently more
aggressive accelerated tests have been devised and these include:
1. The pressure cooker test which is normally carried out at 121°C and 15
psi. This has the advantage of inducing relatively early corrosion failures,
sometimes within 24-48 hours, although these periods have increased
with improved encapsulant technology. A disadvantage is that the results
obtained from pressure cooker testing do not always correlate with those
from 85°C/85%RH testing. Although the failure mode remains that of
corrosion, the actual mechanisms may be subtly different and not directly
extrapolateable to typical in service conditions.
2. HAST (highly accelerated stress testing) This type of accelerated test is
now in use at virtually all semiconductor houses and is based on the
principal that, within certain limits, it is valid to further increase
temperatures, pressures and relative humidities in order to produce rapid
failures, often in the manner of a coarse screening process, prior to
selecting the most promising candidates for more conventional testing
over an extended period. Very large acceleration factors are attained and
reliability testing can be completed in much shorter times.
Pioneering work on predicting lifetimes of plastic encapsulated devices in
defined environments was carried out in the 1970s by the British Post Office
Research Centre in conjunction with Ferranti Semiconductors. This work
culminated in the mid-1980s in the definitive edition of specification M 219
which essentially simplifies down to two measurements on an aqueous
extract from a cured sample of the encapsulant. These are the conductivity
of the aqueous extract and the pH. For optimum device lifetime the extract
should have low conductivity and a neutral pH. Low conductivity is an
indication of raw material purity and good manufacturing disciplines. The
pH is influenced by the chemistry used in the formulation. On a trade off
L-_ _ _ _ _C_H_A_L_L_E_N_G_E_S_I_NT_O_T_H_E_21_S_T_C_E_NT_U_R_y_ _ _ _ _ --ll I 167
basis a system having some major advantages but producing a far from ideal
pH can have the pH modified or buffered by the incorporation of an acidic
or alkaline additive that will have little or no other influence on the
formulation.
5.6 CHALLENGES INTO THE 21ST CENTURY
A number of predictions can be made with a high degree of confidence based

on the progress that has already been made since the inception of plastic
moulding of the first relatively straightforward transistors. These predic-
tions include:
That semiconductor devices will continue to get smaller and/or combine
more electronic functions on a given area of silicon and space will continue
to be at a premium. The result will be that devices will generate more heat
than in the past, meaning that the requirement for higher thermal
conductivity encapsulants will become more significant as a percentage of
the total market. Thus far the requirement for materials with a thermal
conductivity significantly greater than that possessed by a standard
compound has been relatively small, and relatively costly highly filled
materials with special filler systems to enhance conductivity have been used.
These are far from ideal for general applications and it is reasonable to
suggest that ways will be found of enhancing the thermal conductivity of
materials without recourse to unnecessarily abrasive additives in the filler
system and without necessarily having to compromise on other mechanical
parameters such as expansion coefficient mismatch.
We have already seen, particularly in the period from the mid-1980s
onwards, the introduction of devices with 100 or more leads, and whilst
many of these initially were in ceramic packaging, commercial dictates have
resulted in many now being offered in plastic in a variety of configurations.
The resulting small geometries around the chip will necessitate particular
care being taken in terms of the moulding operation because of the increased
likelihood of minor wire movement causing problems e.g. if the wires are
only a fraction of a millimetre apart on such a device, the movement
required to contact an adjacent wire is very small.
Combined with the increasing complexity of the chip, and the probability
of greater heat generation, the trend is towards smaller package outlines,
especially in terms of thickness, meaning that there is a thinner layer of
encapsulant present to provide protection. This not only highlights the need
for enhanced material properties, but could also lead to more difficult
moulding in terms of filling the mould cavities without entrapping
significant amounts of air, as discussed in section 5.4 on moulding faults.
The smaller device geometries will continue to place demands on the
moulding compound manufacturers in terms of the purity of the epoxy,
because of the correlation with failures caused by corrosion in moist
conditions, and in some instances by movement due to mechanical/thermal
stresses.
Whilst no material, at time of writing, has completely solved the
'popcorn' effect, sufficient evidence exists to suggest that it wiIl be worth
continuing to develop materials with lower moisture absorption in the cured
condition, and greater adhesion to the chip/lead-frame assembly, with a
view towards, ultimately, omitting the dry bagging operation.
The purity of epoxy encapsulants has improved dramatically since the
inception of transfer moulding of semiconductors. The latest resins are now
close to the purity of silicone moulding compounds, but can still vary from
batch to batch, and sources of the purest resins is limited (reference the scare
throughout the industry when a Japanese resin plant suffered an explosion
in July 1993). Another approach that has shown promise at various stages in
the last 20 years relates to the concept of 'adding purity' by using various
additives to neutralize impurities present in the raw materials. Work was
carried out by the editor of this book on behalf of the Plessey Company in
the early 1980s and the Morton Chemical Company was working along
similar lines. The materials then produced showed some promise, whilst not
finding general favour. It is known that work continues at most, if not all, of
the major manufacturers of epoxies for semiconductor encapsulation on this
concept, and many of today's moulding compounds incorporate at least one
additive performing the function of a 'getter' to block mobile ions in the
material and hence to simulate enhanced purity. Other additives can be
incorporated, for example, to neutralize the pH of the aqueous extract when
testing on the material is carried out according to the M 219 method
discussed above.
5.7 REFERENCE
1. European Semiconductor, 49, July/August 1996.
5.8 FURTHER READING
Goosey, M. (ed.) Plastics for Electronics, Elsevier Applied Science, London, 1985.
Manzione, L. T., Plastic Packaging of Microelectronic Devices, Van Nostrand
Reinhold, New York, 1990.
Seraphim, D. P., Lasky, R. C., and Li, C. Y., Principles of Electronic Packaging,
McGraw-Hill, New York, 1989.
Sinnadurai, N., Handbook of Microelectronics Packaging and Interconnect Technol-
ogy, Electrochemical Publications, Ayr, Scotland, 1985.
F_U_R_TH
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __E_R_R_E_A_D_I_N_G________________ ~I I 169
Sinnadurai, N., Plastic packing is highly reliable, IEEE Trans. on Reliability, June
1996.
Tummala, R. R., and Rymaszewski, E. J., Microelectronics Packaging Handbook,
Van Nostrand Reinhold, New York, 1989.
Materials for Advanced 6
Encapsulation
NIGEL HACKETT
Dexter Electronic Materials, Langley, England
6.1 INTRODUCTION
Early transistor and diode encapsulation was accomplished by dispensing a

small amount of silicone or flexible epoxy over the die and bond wires in a
process known as 'glob-top'. However, the drive for low-cost, high-volume
packaged semiconductor production soon initiated the introduction of
transfer and injection moulding methods (see Chapter 5 for more details of
transfer moulding materials and techniques). This move allowed polymeric
encapsulants to replace the traditional but more expensive ceramic and
metal packages in most areas except those requiring the highest reliability.
The standard packaging format through the 1970s was the ubiquitous dual
in-line plastic package and this really was the father of low-cost electronics
packaging. The 1980s brought revolutionary changes in electronics tech-
nology in general, and in plastic packaging in particular. The main change
from a packaging and assembly perspective was the move away from the use
of through hole leaded components to the use of surface mount technology
and the use of so-called surface mount devices (SMDs). These newer surface
mount devices were both cheaper and easier to assemble than their
predecessors and with leads on all four sides of the Ie packages, surface
mount technology initially offered opportunities for increased packaging
density. This change to SMD, although not requiring any radically different
package moulding techniques, did initiate a lot of work in the modification
and optimization of moulding compounds for these generally much smaller
172 I 1~_______M_A_T_E_R_lA__L_S_F_O_R_AD
___V_A_N_C_E_D_E_N
__CA
__PS_U_L_A_T_I_O_N______~
packages. Unfortunately, it soon became apparent that conventional plastic

quad leaded flat pack packages could not continue to accommodate the
increasing numbers of leads required of future devices without either
unacceptable increases in package area or moves to much finer pitches that
would be difficult to handle and assemble. There has thus been major
development of packaging techniques over the last few years, which in turn
have necessitated the development of many new materials.
From the late 1980s to the mid 1990s many new moulding materials,
primarily epoxies, were developed and adopted by manufacturers. Each new
generation of material offered something additional in terms of benefits such
as reduced cost, improved performance, productivity and reliability. These
improvements were brought about largely by iterative enhancements of
existing technologies; for example, the use of new additives helped to
improve the thermal conductivity, CTE (coefficient of thermal expansion),
adhesion, viscosity and stress.
The electronics industry is typically characterized by its ability to
incorporate improved performance, reduced cost and smaller size in each
successive generation of a particular electronic device. Good examples are
the mobile telephone, the hand-held camcorder and the personal computer.
This has been achieved by the development and production of ever more
sophisticated semiconductor devices with higher levels of integration and
much smaller features. Because of the need to reduce continuously the size
of electronics, the increased levels of integration have had to be achieved by
silicon feature size reductions on the chip, and even at the individual
electronic component level the driving need is to build more functionality
into each packaged device. This increased functionality at the chip level has
been accompanied by the general requirement to have larger numbers of
leads or connections to the chip. Twenty years ago a typical semiconductor
device would need perhaps 16 or 24 connections to the outside world and
this was easily accommodated with a dual in-line packaging approach. By
the year 2000 many of the more sophisticated semiconductor devices will
need hundreds and in some cases thousands of interconnections to be made,
in a package area not radically different in size from that of the traditional
dual in-line or quad flat pack packages.
These rapid developments in semiconductor technology have resulted in
major changes in the packaging of the devices and this in turn has brought
new challenges and increasingly demanding performance requirements to
the manufacturers of the encapsulants used in these applications. In
addition to the wide proliferation of new area array type packaging
approaches this miniaturization of components has resulted in increasing
demands on the polymers, especially in the areas of toughness, thermal
conductivity, high temperature performance and moisture resistance. Also,
the movement to surface mount assembly, from the use of leaded through
L -_________________ __R_O_D_U_C_T_I_O_N__________________~I
I_NT I 173
Fig. 6.1. Ball grid array substrate with encapsulated wire bonded and flip chip
attached devices.
Low Prollie Glob Top lor COB

~ Encap"ulated flip Chip Device
%
Tall Glob Top lor COB Potting V.",lon lor COB or Modul. .
(No potting dam)
Fig. 6.2. Various methods used for the encapsulation of wire bonded and flip chip
attached chip on board (COB) devices.
hole component mounting techniques, has meant that many new challenges
have been encountered.
Whilst the traditional packaging techniques still continue to evolve, the
emphasis in more recent years has been towards the use of new
alternatives. In particular, the natural progression towards new device
packaging methods such as chip scale packaging (CSP), where the package
174 I ~I________M_A_T_E_R_I_A_L_S_F_O_R_A_D__V_A_N_C_E_D_E_N__CAP
__S_U_L_A_T_I_O_N______~
Table 6.1 The market for encapsulants and die attach materials
Market segment 1997 ($m) 2004 ($m) %AAGR
Liquid encapsulants 40 120 17

Underfill encapsulants 9 85 38
Die attach 12 20 7
area is only fractionally larger than the silicon it encases (not more than 1.2
times), has demanded the design and development of new packaging and
assembly techniques. This in tum has changed both the application methods
and performance demands upon the polymeric encapsulants being used.
Interestingly, there has been a significant readoption of the so-called
'glob-top' approach (as once used in early plastic encapsulated transistor
production), albeit with much improved polymers on vastly different device
types. Currently, no one package type has emerged as the future industry
standard; indeed most forecasts still show the significant continuing use of
leaded packages, with newer packaging styles being adopted in addition.
What is very clear, however, is that the continuing evolution of package
and device types will require newer generations of encapsulants and
packaging materials to be produced. The current market size and forecast
for these encapsulants (and die) attach materials is shown in Table 6.1.
This chapter concentrates on the liquid materials that are finding wider use
as flip chip underfills and glob-top encapsulants in new electronics
packaging applications. These applications are shown schematically in
Figs 6.1 and 6.2.
6.2 MATERIAL CHOICES FOR ENCAPSULANTS
As a result of the wide range of alternative package types becoming

available (and indeed needed), many new materials have been introduced to
meet not just the changing needs of the packages themselves, but also the
more stringent reliability and performance requirements. The chemistries
used in these new materials are naturally diverse with the two major types of
encapsulants being silicone or epoxide based. Silicones are used both for
potting pre-moulded devices and as glob-top encapsulants but, as with the
moulding compounds, the predominant chemistry remains epoxide based.
The major difference between epoxide- and silicone-based materials is that
the silicones tend to be rubbery whilst the epoxides are hard rigid coatings.
This is because at typical operating temperatures the silicones are above
their glass transition temperatures whilst the epoxides are below. The choice
of specific types, however, is somewhat different from those used in more
traditional moulding compounds.
MATERIAL CHOICES FOR ENCAPSULANTS
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~
175
6.2.1 Basic Formulation

Generally, for example, an epoxide-based liquid encapsulant formulation
for micro-electronic applications will consist of the following ingredients:
• epoxide resin(s)
• hardener(s)
• catalyst(s)
• filler(s)
• elastomer(s)
• other additives
As indicated above, there may also be multiple blends of many of the
ingredients to achieve the desired properties. In some cases specific
components (such as elastomers) may be omitted, but generally all the
above families will be represented in an encapsulant formulation.
As can be seen, the number of possible combinations is virtually limitless.
For specialized applications, some unusual combinations will be used
although for relatively standard applications the general choice of materials
is somewhat more limited. This, however, still leaves many possibilities since
there is a wide range available in each of the individual ingredients used and
of course in the levels that can be used.
6.2.2 Specific Ingredients
6.2.2.1 Epoxide Resins

The types of epoxide resin used in advanced encapsulation applications and
their principal features are discussed below. A more detailed description of
epoxide chemistries and properties can be found in Chapter 4.
Aliphatic
Glob-top type coatings have the tendency to exhibit large thermal shrinkage
stresses due to their high thermal expansion coefficients and high moduli.
With high loadings of fillers the thermal expansion coefficients can be
significantly reduced to values typically around 40 ppm;oC. For this reason
the aliphatic resins generally used in these applications are those with low
viscosities that enable high filler contents to be used. They are also normally
required to be flexible so that they can be used at low temperatures. This
type of material often tends to have relatively high levels of chlorides due to
the manufacturing techniques used in their production and care must
therefore be taken when selecting a resin, particularly if it is likely to come
into contact with the aluminium metallization on a semiconductor surface.
Overall, the biggest weakness of these resins, however, when used in
microelectronics applications is their poor water resistance.
176 II MATERIALS FOR ADVANCED ENCAPSULATION
~------------------------------------------------------~
Cycloaliphatic
The cycloaliphatic epoxides used in glob-top applications are also generally
low viscosity materials, offering much lower viscosities than are typical with
the standard diglycidyl ether resins. They thus again find use where high
filler loadings are required. Their compact structures allow much higher
crosslink densities to be achieved but they lack flexibility due to the absence
of the ether linkage found in other systems. They do, however, give
inherently high Tgs when cured, allowing use at elevated temperatures. Due
to the use of an alternative manufacturing process, a much lower level of
chlorides is present than in the aliphatic epoxides, although they still have
relatively poor water resistance. Examples of cYcloaliphatic epoxides are
dicyclopentadiene dioxide and vinyl cYclohexane dioxide which are solid
and liquid at room temperature respectively. When fully cured the
cycloaliphatic resins give very high glass transition temperatures, lower
dissipation factors and good arc resistance.
Aromatic Glycidyl Ethers
These materials tend to exhibit moderately high viscosities and this limits
the amount of filler that can be used in conjunction with this type of resin.
Despite this limitation, the inherent high strength and good water resistant
properties make these epoxide resins a good choice, especially when used in
conjunction with others.
Epoxide-novolacs
Although widely used in transfer moulding encapsulant formulations, their
very high viscosities limit the use of these resin types to specialized
applications. They do, however, offer low moisture absorbance coupled with
high strength and high glass transition temperatures. They are used, for
example, in liquid encapsulants in small quantities to help raise the glass
transition temperature.
Speciality Structures
More and more speciality resins are becoming available based both on
epoxide chemistry and, for example, cyanate esters. By allowing effectively
tailored properties, these types of materials are best used in conjunction with
more standard resins. As with most new technology, the disadvantages
include high cost and possible compromises in more basic properties.
6.2.2.2 Hardeners
Anhydrides
Anhydride-based curing systems are the main choice of hardener for liquid
encapsulants used in microelectronic applications. Their low viscosities
coupled with high purities and high functionalities make them ideal for
many applications. In addition, the latent reactivity at low temperatures
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ensures extended pot life. Anhydrides are also relatively low-cost materials
and, unlike the aliphatic amines, they are not skin-sensitizing agents.
Amines
Amines have for many years been one of the mainstays of epoxy curing
technology and are still used in less critical areas, although they have largely
been replaced by anhydride technology for newer microelectronics applica-
tions. They are available in a wide range of forms, both aliphatic and
aromatic. The aromatic amines are less reactive than the aliphatic amines
and generally offer longer pot lives and higher glass transition temperatures.
Speciality
Many other materials are available, again with properties tailored to meet
specific application requirements. They are mainly employed in specific
formulations such as those used in the 'snap cure' products for smart cards
or flip chip underfills.
6.2.2.3 Catalysts
In the formulation of glob-top type encapsulants the catalysts used are often
defined as follows:
• Latent reaction. Latent catalysts are particularly important because they
allow longer pot life and longer flow times. They only induce significant
reaction above a certain temperature.
• Blocked reactivity. By using a catalyst that is chemically blocked it is
possible to achieve a much faster curing system while retaining a long pot
life and flow time.
• Chemically stable. Chemical stability is vital if an even cure is to be
achieved over the pot life and shelf life of the product.
For more details of the formulation of epoxide systems the reader should
refer to Chapter 4.
6.2.2.4 Fillers
A large number of fillers are used in the formulation of encapsulants for
electronics applications and they are typically used to lower thermal
expansion coefficients, improve thermal conductivities and reduce costs.
They also tend to improve the mechanical properties and modulus. Some
advantages and disadvantages of using fillers in encapsulant formulations
are shown in Table 6.2.
When formulating an encapsulant it is therefore vitally important that
careful consideration be given both to selection of the appropriate fillers for
178 1 1-1____M_A_T_ER_IA_L_S_F_O_R_A_D_V_A_N_C_E_D_E_N_C_AP_S_U_L_A_T_IO_N
_ _ _- - '
Table 6.2 Some advantages and disadvantages of using fillers in encapsulants
Advantages Disadvantages
Reduced cure shrinkage/stress Increase density

Reduced cost Increased dielectric constant
Reduced thermal expansion coefficient Loss of transparency (?)
Increased pot life Could introduce impurities
Improved thermal conductivity Reduced tensile strength
Improved thermal stability Reduced flexural strength
Impart flame retardancy
Improved arc resistance
Improved dielectric strength
Reduced moisture and gas permeability
Control curing (reduced exotherming)
a specific application and to the level to be used. Perhaps one of the most
important considerations when selecting fillers are the changes that they
could make on the electrical properties of the encapsulant. If good
insulating properties are required, as is typically the case with electronic
encapsulants, the condition and type of filler employed will be important
since ions, salts and moisture-soluble impurities may be adsorbed onto the
filler particles' surfaces which can degrade the final electrical properties.
Some of the key fillers used in encapsulant applications are as follows.
Calcium Carbonate (CaC0 3 )

This is the filler of choice for low-cost systems and, as it is non-abrasive, it is
ideal for machine dispensing. The main disadvantages are high levels of
ionic contaminants coupled with relatively high thermal expansion. It is
therefore primarily used in materials for low-end consumer products such as
in encapsulants for smart card manufacture.
Alumina Trihydrate (AI2 0 3 .3H2 0)

Hydrated alumina shares many of the same properties as calcium carbonate,
the main difference being that it can impart flame-retardant properties to
formulations in which it is used. Polymer combustion is retarded by a
dehydration reaction in which the hydrated alumina absorbs part of the heat
of combustion and, being in the solid phase, acts as a heat sink removing
energy from the combustion zone. The evolution of water vapour may also
be important in diluting combustion gases and reducing the availability of
gaseous oxygen. By incorporating this type of filler it is sometimes possible
to avoid the use of additional specific flame-retardant additives, although it
is not generally thought to exhibit any synergistic effects with other flame
retardants.
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Alumina (A 12°3)
Conventional alumina is also used in encapsulant formulations particularly
where high thermal conductivity is required, although it is very abrasive and
imparts poor mechanical strength. It also has a relatively high coefficient of
thermal expansion. Alumina is typically higher in cost than calcium
carbonate and still has the disadvantages of relatively high ionic impurity
levels and a high thermal expansion.
Silica (Si0 2 )
Silica is usually thought of as being simply Si02 but there are in fact over 20
distinct phase of silica, each one still chemically being Si02 . Several types of
silica find use as fillers in electronic encapsulant applications.
One of these phases is known as fused silica and it is the most important
type of silica used in glob-top type encapsulant formulations for microelec-
tronics applications. Fused silica is produced by subjecting high purity
crystalline quartz to very high temperatures such as those found in an arc
furnace. It has a relatively low thermal expansion coefficient of approx-
imately 9.54 ppmrC over the temperature range O-lOOO°C and a compar-
atively low density (2.15 g/cm3). Fused silica is also readily available in high
purity grades. It has the advantage of being available in many distinct
physical forms, including a spherical type. The disadvantages of fused silica
can include abrasiveness (although it is typically less abrasive than alumina)
and a lower thermal conductivity than some other inorganic fillers.
Another type of silica that finds use in some encapsulant applications,
although not usually in glob-top type formulations, is quartz. This has the
advantage of a higher thermal conductivity than fused silica and could be
considered for use in applications where an encapsulant was to be used with
power devices.
A third type of silica which finds widespread use in the formulation of
liquid encapsulant systems is the so-called fumed silica. This is an
amorphous form of silica that has a very large surface area. It can be
used in, for example, liquid epoxy encapsulant systems to provide
thixotropic and anti settling properties. The thickening effect of fumed silica
is brought about by the interaction of silanol (SiOH) groups on adjoining
particles, as well as between the silanol groups and the reactive groups of the
hardener system (such as amine groups). Fumed silica is also used as a
reinforcing agent to enhance mechanical properties in elastomeric materials,
such as the silicone-based encapsulants.
Boron and Aluminium Nitrides

Boron and aluminium nitrides represent two examples of the latest
generation of fillers offering a number of key property advantages over
conventional fillers, and they are specifically targeted at high thermal
180 I LI____M_A_T_E_R_IA_L_S_F_O_R_A_D_V_A_N_C_E_D_E_N_C_AP_S_U_L_A_T_IO_N_ _ _ -----..l
conductivity requirements. Boron nitride and aluminium nitride have

theoretical maximum thermal conductivities of 1300 and 320 W/mK
respectively compared with the 10-35 W/mK typically quoted for alumina.
Their current high costs and limited availabilities limit their use, but further
advances in this area are expected in the near future especially as thermal
management of components becomes an increasingly important issue and as
there is a greater need to remove and dissipate heat from devices.
Talc
Talc is the name given to hydrated magnesium silicate which has the
theoretical formula 3Mg0.4Si02.H20 and it occurs in several ores from
which talc products are made. The form most used in encapsulant
formulations is finely ground talc which consists of thin platelets. It
possesses a good degree of chemical resistance, being inert to most acids and
it is also a good insulator. The use of talc in epoxide encapsulant
applications leads to higher stiffness and improved creep resistance at both
room and elevated temperatures. Encapsulants loaded with talc have also
been shown to have increased lap shear strengths at their adhesive
interfaces; a property that is important in encapsulant applications because
the possibility of moisture ingress along interfaces must be avoided. In order
to obtain the full benefits from using talc it must be incorporated into an
encapsulant using the appropriate compounding techniques.
Carbon Black
Although not directly comparable to the other materials listed above as
fillers, the carbon blacks are sometimes used in encapsulant formulations at
relatively low levels in order to give the material a black appearance. They
are produced by the thermal decomposition of oil or gas and exist in a
number of forms such as lampblack, channel black and thermal black.
Carbon blacks are also good at imparting stability against ultra-violet light
exposure, as well as increasing modulus and tensile strength.
6.2.2.5 Elastomers
Low Viscosity
Low viscosity elastomeric polymers are used in encapsulant formulations to
enable higher filler loadings to be achieved where it is critical to reduce the
thermal expansion coefficient of the cured encapsulant. These are often
based on silicone chemistry.
High Purity Materials

Semiconductor device reliability is known to be compromised by ionic
impurities that can be found in some encapsulants. This is especially critical
in the materials used to encapsulate highly integrated devices, where
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impurity levels can be related directly to device performance and lifetimes to

failure. Device lifetimes are determined by accelerated life testing where high
temperatures and humidities are used to bring about failures in much
shorter periods than would occur naturally. A typical example of a
traditionally used set of conditions would be testing at 85°C and 85%
relative humidity. Because of the influence of impurities on device reliability
it is essential that only the highest purity raw materials are used in
encapsulants destined for use with semiconductor devices.
Heterophase
Heterophase additives in a formulation form discrete isolated areas within
the encapsulant during curing. It is possible to incorporate, for example,
rubber-like molecules into an encapsulant which can be clearly seen as
discrete structures using a microscope. By being effectively a separate part of
the material structure it is possible to maintain overall properties of the
system (such as high TJ despite using an elastomer.
Low Glass Transition Temperature (Tg ) Elastomers

Low glass transition temperature elastomers are important for applications
where the encapsulated device may be exposed to temperature cycling/
thermal shock. The lower Tg of the elastomer enables the encapsulant to
retain its flexibility at lower temperatures than is possible for more
conventional materials.
Hydrophobic
Hydrophobic elastomers have chemical structures that enable the encapsul-
ants in which they are used to minimize water absorption. This is
particularly critical in surface mount applications, where resistance to the
moisture-induced 'popcorn effect' may be a requisite.
6.2.2.6 Other Additives

Silanes
Silane coupling agents are a unique range of compounds which can
effectively overcome the interfacially related problems that occur when two
components of differing chemical nature and physical form come into
intimate contact. In encapsulants, the example is the interfacial region
between the organic components such as the epoxide resin and the inorganic
filler particles. Because of their unique molecular structures, silane coupling
agents are often able to eliminate effectively these interfaces by forming
bonds bridging the organic and inorganic components. As their name
implies, silanes are based upon silicon and they can be represented by the
general formula:
182 I L-I____M_A_T_ER_I_A_L_S_F_O_R_A_D_V_A_N_C_E_D_E_N_C_A_P_S_V_L_A_T_IO_N_ _ _---'
XRSi(OR'h
where X represents an organic functional group, R represents the chemical
linkage between the reactive functional group and the silicon and the
Si(OR'h part provides the capability to react with inorganic materials such
as filler particles. Typical examples used in epoxide-based formulations
include aminopropyl triethoxysilane and glycidoxy propyl trimethoxysilane.
Silane coupling agents are generally used to improve adhesion both
internally (between the resins and fillers) and externally (to the substrate).
The electrical properties of a silane treated material will also be better than
those of the untreated material with dielectric constants, dissipation factors
and volume resistivities all being stabilized.
Pigments
Pigments are often used to impart a particular colour to an encapsulant and
they are particularly important in encapsulants used with light-sensitive
devices where minimal optical transmission is required (see also carbon
blacks above). They also playa role in ensuring security and have even been
used to produce encapsulants with a characteristic company colour. Typical
pigments include titanium dioxide, cadmium sulphide, iron oxide and
barium sulphate, although it should be noted that not all of these are used in
electronic encapsulant applications.
Surfactants
A surfactant (or, more correctly, surface active agent) is a substance that,
when present at a relatively low concentration in a particular system has the
ability to adsorb onto the surfaces or interfaces of the system, thereby
altering to a significant extent the surface or interfacial free energies of those
surfaces or interfaces. Although there are many types of surfactants, they all
exhibit a characteristic molecular structure consisting of two different
structural groups known as lyophilic and lyophobic groups. This is known
as an amphipathic structure and it is because of this structure that
surfactants are able to have such a big influence on the nature of interfacial
interactions. Surfactants are therefore used in encapsulant applications to
modify the interfacial interactions and also help to reduce the possibility of
void formation.
Rheological Modifiers
Rheology modifiers are used to modify and tailor the flow and thixotropy
characteristics of an encapsulant. These could be used, for example, where it
is necessary to prevent flow through small holes in a package.
Ion Scavengers
As mentioned above, ionic impurities in an encapsulant can comprise
semiconductor reliability, and ion-scavenging additives are sometimes added
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EN__
C_A_P_SU
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___ S ________ ~I I 183
to encapsulants intended for use in high reliability applications or where the

device to be encapsulated may be particularly sensitive. These are typically
based on appropriate metal salts and by effectively capturing ionic impurities
and immobilizing them, the encapsulant's overall performance may be
enhanced, especially from an accelerated life testing perspective. Chloride
ions are one such ionic impurity that can be scavenged with these materials.
6.2.3 Combinations
As already mentioned the possible combinations of ingredients used for a
specific encapsulant formulation are virtually limitless. In order to give an
idea of the possible effect of just one of these combinations, Table 6.3 shows
the effect of using different resins with one version of the anhydride curing
system. The effect on coefficient of thermal expansion is dramatic, especially
when it is considered that this is in an unfilled system. Addition of a low
thermal expansion coefficient filler would further reduce the thermal
expansion, with similar differences.
Most systems used today are formulated with a combination of different
resins in order to obtain the necessary compromise in properties. Newer
resins are also now becoming available that are more tailor-made for a given
specific application. Whilst this can assist in the basic formulation, there is
usually a down side to be considered, not the least of which is the relatively
high cost and limited availability of these newer resins.
Similarly, multiple options of other ingredients are also often used. In a
case where improved reliability performance is required through the use of
materials such as ion scavengers, it may be necessary to combine several
types to compensate for the use of less pure resins with each scavenger being
specifically targeted at a single particular ionic impurity.
6.2.4 Limitations
There are of course specific limitations to what can be achieved by
combining the various formulation ingredients and whilst these limits are
constantly being extended, there are a number of areas where specific trade-
Table 6.3 The thermal expansion coefficients (CTE) of basic anhydride cured
encapsulants formulated with different epoxy resins
Epoxide resin CTE(ppmrC)
Aliphatic 80
Cyc10aliphatic 75
Aromatic glycidyl ether 60
Aromatic glycidyl novolac 55
Speciality resins 45-60
184 , ''--_ _ _M_A_T_E_R_IA_L_S_F_O_R_AD_V_A_N_C_E_D_E_N_C_AP_S_U_L_A_T_IO_N
_ _ _----'
offs do apply. Depending upon the actual application encapsulation

requirement, a choice will have to be made as to the compromise that is
most acceptable. The major trade-offs likely to be encountered when
considering encapsulant formulations include the following;
1. Modulus of elasticity v. thermal expansion coefficient (CTE). Generally a
lower modulus of elasticity tends to be preferred, as it will give better
performance in terms of low-stress characteristics. A low CTE, by
comparison, will however often be required to minimize the difference in
expansion coefficient between the encapsulant and the silicon/substrate.
Addition of a filler, especially one such as fused silica, will dramatically
reduce the CTE, but will also, unfortunately, increase the modulus. To
overcome this effect other options include the addition of heterophase
elastomers to the formulation or the use of a pre-coat layer prior to final
encapsulation.
2. Shrinkage v. cure speed. As a general statement, it is typically found that
the faster an encapsulant cures the higher will be its (chemical) shrinkage.
This may result in a compromise in productivity through the use of a
slower curing material in order to ensure that the optimum desired
shrinkage performance is achieved.
3. Moisture resistance v. glass transition temperature (Tg). Depending upon
the chemistry of the various epoxy resins and curing systems that can be
used in a formulation, it is known that the moisture resistance of an
encapsulant can vary significantly. It has been noted, for example, that
even resins with high Tgs can often also exhibit poor moisture
performance. Some compromise in performance can be achieved by
blending resins, or by the use of different hardeners.
4. Viscosity v. thermal expansion coefficient (CTE). This is considered to be
the classic compromise that affects almost all encapsulant applications.
In order to obtain the lowest thermal expansion possible, the level of
filler in a system needs to be maximized. However, despite the use of very
low viscosity resins, the need to achieve high filler loading levels results in
an increase in the overall viscosity of the resultant encapsulant. In some
applications the higher viscosity may not cause any problems whilst in
others (such as in underfill, or flip chip applications) any increase in
viscosity will result in an unusable material. As previously shown, one
way to minimize this effect is by careful selection of the resin types used.
6.2.5 Glob-Top Encapsulant Properties
The properties of an encapsulant both during the encapsulation process and

when cured are extremely important and must be optimized if the
encapsulated device performance is not to be compromised. Usually, it is
not possible to incorporate all of the desired properties into a single
__S________~I
M_A_T_E_R_I_A_L_C_H_O_I_C_E_S_F_O_R_E_N_C_A_P_S_U_L_A_NT
L -_ _ _ _ _ _ _ _ I 185
formulation and some compromise often has to be reached. For example,
the use of high loadings of inorganic fillers to reduce the thermal expansion
coefficient and increase the thermal conductivity of an encapsulant will also
have an impact on the flow and ease of dispensing of the material. It is also
not desirable to use solvents to improve the flow as these can lead to settling
of fillers and the possibility of void formation. The glass transition
temperature of an encapsulant should be as high as possible since the
thermal expansion coefficient above the Tg is usually much greater than
below the Tg with these types of material. The ultimate value of the Tg that
can be achieved will, however, be also determined by the maximum curing
temperature that can be used. Minimizing thermal expansion is a key to
reducing the stresses that can occur between dissimilar material subjected to
thermal excursions such as soldering.
In the latest generation of low-stress glob-top materials significant
improvements have been achieved compared to earlier materials. These low-
stress materials have become much more widely applicable because they
have thermal expansion coefficients that are much closer to the materials
they would typically come into contact with such as ceramic, copper, solder
and FR4 epoxy. These new low-stress materials also provide improved crack
resistance, reduced warpage of substrates and excellent protection of bond
wires in chip-on-board applications. The properties of a typical low-stress
glob-top material are shown in Table 6.4 and an example application is
shown in Fig. 6.3.
Fig. 6.3. Glob top encapsulant on a pin grid array package.

186 I ~I________M_A_T_E_RI__A_L_S_F_O_R_A_D__V_A_N_C_E_D__EN__C_A_P_SU_L_A_T_I_O_N______~
Table 6.4 Typical properties of a cured low-stress glob-top encapsulant
Thermal expansion coefficient 17-20 ppmrC
Glass transition temperature (Tg) > 150°C
Shore D hardness >95
Density 1.8 g/cm3
Volume resisitivity 6.34 x 1014 ohm·em
Dielectric constant 3.2 (105 Hz)
Dissipation factor 0.014 (105 Hz)
Thermal conductivity 5.9 X 10-3 W/mK
Ionic chloride <20 ppm
Epoxide-based encapsulants have in the past been found to contain

variable levels of chloride ions left from the epoxide resin manufacturing
process. These ions are known to be able to comprise the reliability of
encapsulated devices because in the presence of moisture they can cause
corrosion of the aluminium metallization, used to provide interconnection
and to form the bond pad areas on the semiconductor surface. Many studies
have been undertaken to characterize this effect and the result is that newer
materials have much lower levels of chloride ions than their predecessors.
6.3 HANDLING AND USE
Having selected the product to use in a specific application it is critical to

pay attention to the correct handling and use of the material. The
encapsulation process itself can playa major role in ensuring the final
acceptance of the components/devices being protected. Considerable pro-
gress has been made in recent years in the development of sophisticated
automatic and semi-automatic dispensing equipment. It is still, however,
necessary to pay attention to the handling and use of the material to ensure
a successful final outcome.
Several areas are key to the successful use of liquid encapsulants for
microelectronic applications. Whilst certainly not offering a definitive guide,
the following points have been found to be critical to the achievement of
successful encapsulation.
6.3.1 Material Form

Historically, many encapsulants were supplied as two-part systems. These
required the end user to mix, de-air and dispense them. The advantage of the
two-part systems was in their handling and shipping since each part was
generally stable at room temperature and there was no question of reaction
occurring before mixing. Whilst this mixing before use is relatively easy and
therefore quite acceptable with the older formulations, newer products now
HANDLING AND USE
L -____________________________________________________ ~
II 187
often require more intensive (largely high shear) mixing, usually under
vacuum and at an elevated temperature. For this reason most microelec-
tronic encapsulants are now typically premixed by the manufacturer.
Depending upon the specific formulation, the material will then be
packaged in some form of bulk container or in a syringe or cartridge. The
former are generally referred to as one-component systems and the
challenge for the formulator is to provide them with a reasonable room
temperature shelf life. The latter are normally referred to as premixed or
frozen products and usually require low temperature storage (e.g. -40°C) to
minimize pre-use reaction and thus to give good shelf lives e.g. in excess of
four months.
6.3.2 Packaging
The correct choice of packaging can also be crucial to ensuring quality and
productivity. Factors that should be taken into account include shelf life,
pot life, shipment, storage and handling. The type of packaging should be
optimized for both shipment and handling. The size will largely be
determined by the chemistry of the material and the dispensing equipment.
Too large a size will result in material being wasted, either at the end of a
production run, or as a result of increased viscosity as a material nears its
pot life. Too small a size and frequent replacement will be needed, thereby
adding unnecessary work for the user and affecting overall productivity.
In addition to the inner packaging, thought should be given to the outer
packaging. As an example, if material is to be shipped by air it is essential
that the outer packaging meets lATA regulations. In addition, the
packaging should be sufficiently robust to withstand the shipment and be
able to hold dry ice (in the case of frozen products) sufficient to maintain a
low temperature throughout the journey.
6.3.3 Storage
Specific storage requirements for each product should be provided by the
material supplier. Generally, frozen products should be kept at -40°C or
below since storage at a higher than recommended temperature will
adversely affect the material's ultimate performance. Too high a temperature
will generally result in a reduced pot life, increased viscosity or reduced flow.
Although it may still be possible to use material that has been incorrectly
stored, there is always a risk of incurring quality problems by doing so.
6.3.4 Thawing
Once removed from cold storage it is important that the material is allowed
to thaw properly prior to use. The time taken to thaw will depend upon the
188 11L _ _ _ _M_A_T_E_RIA_L_S_F_O_R_A_D_V_A_N_C_E_D_E_N_C_A_P_S_U_L_A_T_I_O_N_ _ _-...l
size of the packaging, the ambient temperature and the storage temperature.
Even thawing is best accomplished by leaving the material in a well-
ventilated area at room temperature (20--25°C). Although higher temper-
atures may accelerate the thawing process they may also create an uneven
temperature, especially for larger syringes and cartridges. A typical thaw
time for syringes in the 5-50 em3 range would be 30--40 minutes (from
-40°C), whilst a larger syringe (200--400 em3) might require somewhat more
than one hour.
Although it may be acceptable (dependent upon the material and
application) to start dispensing with the material a few degrees below the
ambient, it is critical to ensure that, at the very least, the material has
exceeded the dew point to avoid moisture condensation when dispensing.
For similar reasons the material should not be left exposed to the atmosphere
for any length of time, including after dispensing and prior to curing.
6.3.5 Preheating
In most applications preheating is a key factor in achieving good material
flow and wetting, whilst minimizing void formation. Generally, the substrate
to which the encapsulant is to be applied is heated although it is also
possible to use a needle heater if deemed essential. Syringe heating is not
recommended as it will in most cases lead to a reduction in the pot life of the
encapsulant.
For most applications, substrate temperatures in the region of 60--1 10°C
should be used. Reference to the supplier's literature showing viscosity and
onset of cure properties may be helpful in establishing initial operating limits
but for a specific application it is normally preferable to conduct a series of
trials to determine the optimum temperature. Dispensing onto a warmed
substrate will often aid bubble release although excessive warming will also
impair release if the epoxide gels too quickly.
6.3.6 Dispensing
Many different techniques can be used to dispense liquid encapsulants.
Historically, simple time/pressure dispense techniques have mostly been
employed. Whilst this is still an acceptable way to dispense materials for a
wide range of applications, newer developments in equipment have resulted
in better consistency. Use of a positive displacement valve ensures a
constant amount of material is delivered, regardless of variations in viscosity
that might occur due to changing temperature or pot life of the material.
For dispensing very small volumes, where the positive displacement valve
may not be sufficiently accurate, it is also possible to program a time/
pressure dispense system with the viscosity/temperature/time relationship of
a particular material thus ensuring consistent dispensing.
L -_ _ _ _ _ _ _ AP_P_L_I_C_A_Tl_O_N_T_E_C_H_NI_Q_V_E_S_ _ _ _ _ _-----l1 I 189
With larger dispensing areas becoming common, new techniques are

being developed. These include the use of showerhead dispensing or x-y
dispensing equipment. The latter being used to produce more complex
dispense patterns to ensure maximum coverage. In addition, latest dispens-
ing systems include two (or more) dispensing heads allowing a 'dam'
material and a low viscosity system to be dispensed sequentially on the same
equipment. Recently, the use of screen or stencil printing has been used with
limited success; additional material and process development is required in
this area.
6.3.7 Cure
Data supplied by the material manufacturer should also be used as a
starting point to establish the optimum cure schedule. Due to the wide range
of possible applications, these data should only be used as a guide. Factors
such as temperature limitations may mean an alternative cure schedule is
preferable. Whilst a longer time at a lower temperature can often be
substituted for a short time at a high temperature, it should be remembered
that most materials have an absolute minimum temperature that must be
reached to enable full curing to be achieved. This is especially true when
using a material with a latent or blocked catalyst. Generally, a lower
temperature cure will result in lower stress, whilst a higher temperature will
result in higher T g • Often a two (or more) step cure is used to help minimize
stress, with the final high temperature step being designed to ensure full
curing.
To ensure full curing has been achieved, the Tg and degree of cure should
be measured using thermo-mechanical analysis (TMA) and differential
scanning calorimetry (DSC) techniques. The variation in degree of cure with
time and temperature for a typical encapsulant is shown in Fig. 6.4.
6.4 APPLICATION TECHNIQUES
6.4.1 Dam and Fill Encapsulation

Growing numbers of electronic equipment manufacturers are using chip-on-
board and chip-on-flex approaches to achieve the increasingly higher
component densities needed. These devices can be very difficult to
encapsulate successfully, especially in high-density assemblies where it is
critical to control the flow of the encapsulant. It is also becoming common
to produce ball grid array (BGA) assemblies using a liquid encapsulant.
Known as plastic ball grid array (PBGA), these assemblies can be
encapsulated individually or in strips. In both cases a two-step dam and
fill encapsulation technique is the best solution for these processes.
190 I I~_______M_A_T_E_R_IA__LS__F_O_R_A_D__V_A_N_C_E_D_E_N_C_AP
__S_U_L_A_T_I_O_N______~
180C 165C 145C 130C
100
~ 80
~
~ 60
'0
~ 40
g» 20
c
o
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Time/Hours
Fig. 6.4. Variation of cure with time and temperature for a typical encapsulant
(Hysol FP4450).
The substrate is usually positioned using a conveyor to the dispensing

area and brought to the correct temperature. A two-head system, typically
equipped with two rotary positive displacement pumps, holds two en-
capsulants of different viscosities. One (the dam) will be high viscosity; the
other (the fill) will be low viscosity. Before dispensing, the encapsulants are
heated in the rotary pump to the recommended temperature, which is
typically around 40°C.
Firstly, using the high-viscosity encapsulant, a rectangular 'dam' is
dispensed around the die to be encapsulated. This effectively forms a barrier
around the die. Secondly, using the low-viscosity encapsulant, a spiral fill is
made. This starts just within the dam and progresses to the centre of the die.
The height of the dam material must be greater than the height of the wire
bonds, to ensure complete coverage and protection. The amount of material
used in this type of dam and fill operation varies depending upon the chip
configuration, but would typically be around 200-300 mg. Best results with
dam and fill applications are attained by dispensing the dam and fill before
curing and then co-curing the two materials; this ensures optimum adhesion
between the dam and fill.
6.4.2 Cavity Fill Encapsulation

This technique is mainly used for devices with a large number of
interconnects and in which the chip cavity serves as a boundary for the
encapsulant. The complexity of the application would normally preclude the
'----_ _ _ _ _ _ _A_P_P_L_IC_A_T_I_O_N_T_E_C_H_N_I_Q_V_E_S_ _ _ _ _ _ --,I 1 191
use of a single dispense technique which would cause void formation,

especially with multiple layers of wire bonds. The technique used is to
dispense two (or more) separate layers of low viscosity encapsulant. Each
layer of material must be applied accurately and carefully to avoid air
entrapment. Special small particle size fillers in the encapsulant may be
required if the wire spacing is very close.
As with dam and fill the substrate is typically positioned, using a
conveyor, to the dispensing area and brought to temperature. Only a
single dispense head is required, and this is connected to a rotary positive
displacement pump holding a very low viscosity material. (A dual head
system may be used to increase productivity but, unlike the dam and fill
technique, it is not essential.) At the start, the dispense needle is positioned
above the bond wire loop in the lower portion of the cavity. The first layer
of material is then dispensed around the die in a circular pattern. A
second dispense layer is then made following a spiral path, beginning at
the outer wire bonds and moving to the centre of the die. At each stage it
is vital that the material flows through and under the wire bonds to avoid
air entrapment. Further layers may be dispensed, if necessary, to build up
a thicker layer of encapsulant. The amount of material used in this cavity
fill technique would typically be 300-400 mg. The filling of a ball grid
array package with encapsulant is shown schematically in Fig. 6.5.
Accurate and uniform dispensing of a precisely controlled volume of
encapsulant in a complex pattern ensures complete filling of the cavity to a
precise height.
6.4.3 Smart Card Encapsulation

Smart cards were invented by Roland Moreno in 1974 and they are now in
everyday use around the world. The first smart cards consisted of a very
small die in such applications as telephone cards. Increased complexity,
including multifunctional cards, has resulted in larger and larger dies being
used in the production of the modules used in smart cards. The basic
functional component design of a smart card is shown in Fig. 6.6 where both
sides of the modules are clearly illustrated. Smart cards pose a unique
challenge to electronics assemblers because of strictly limited height and
diameter specifications. A typical smart card requires an encapSUlation with
a thickness of around 500 f.Lm. The area of the module is very restricted,
further limiting the encapsulant to a small perimeter around the die. The
dispensing process must therefore be closely controlled and must also
achieve a high degree of reproducibility.
Typically, the substrate is mounted on a tape which allows it to be
moved on a reel-to-reel carrier. In order to hold the tape in place the table
usually has a vacuum pump connected to it. The table itself is heated to
supply the necessary pre-heat. The substrate can be accurately positioned,
~----------------------------------------------------~
Mechanical Key Process

Dam Control Area
Die Attach Adhesive Aluminum Substrate
,--
.
.. • • .. • • .
I
. • • •• .. •.. • .. •• •. .. .,. • .
.. . • . • ~-- • • .... . .. ..
• • .. . ..
.. ..
.,. .. .. • ~~-:~ ffp"
.~
• •,. • •. .... ..
. e • .
. • ... • • . ~'.. ~....."';~~
,r,': _ .,..<~
.. • • ..
.. . • .. • • •
6
•••••.
• • • • • ..
....,, ~
.. • • . .
•
•.. .. • •• ,.
<:0'
• .. •.. .. • • • . .. •
..
.. ..• ... ..• .. •
~~
-1.:1{~: ~ ..5.f;
Fig. 6.5. Filling of a cavity in a ball grid array package.
using indexing holes in the tape carrier, into the correct dispensing
position.
The traditional method of dispensing involves use of a medium viscosity
encapsulant. The dispense needle follows a circular or rectangular outline
just beyond the outermost wire bond. The dispensing then continues in a
circular pattern towards the centre of the die. In order to maintain the
correct profile the substrate is then subjected to a post-heat stage. Control of
both the pre-heat and post-heat stages is critical to maintain the correct
thickness of encapsulant.
More recently alternative systems have been introduced using either a
shower head principle, or utilizing hot air levelling to 'flatten' the
encapsulant surface. Some early systems also used a grinding system to
remove the top of the glob but this technique has largely disappeared as it
relied upon the use of encapsulants with soft fillers which were poorly suited
to large die encapsulation.
L-_____________ A_P_P_L_IC_A_T_I_O_N_T_E_C_H_N_I_Q~U_E_S______________~I I 193
Fig. 6.6. Smart Card modules showing outside contact surface arrangement and
inside surface with glob top encapsulant covering the semiconductor device.
6.4.4 Flip Chip Underfill

As previously mentioned, the industry trend is toward smaller and smaller
packages, with higher and higher board densities. Chip scale packages (CSP)
are defined as packages that do not exceed l.20 times the die size or, more
generally, as packages which are slightly larger than the die. One way to
achieve this is by the use of flip chip technology, as shown in Fig. 6.7. As
with the smart card, the development of flip chip technology has resulted in
a parallel development of both materials and application techniques. The
properties of some typical encapsulants used in this type of application are
shown in Table 6.5.
194 I ~I________ M_A_T_E_R_I_A_L_S _F_O_R_ A
_D__
V_A_N_C_E_D__
EN__
C_A_P_S U
_L_A
_T_ I_O_N______~
~--.-y - I bat Semiconductor chip
Organic or c:enmk ~
Fig. 6.7. Schematic representation of flip chip assembly with polymeric underfill/
encapsulant.
The use of an underfill with flip chips reduces the thermal stress on
connections and adds environmental protection. The underfill plays a vital
role in lowering the thermal expansion mismatch between the flipped chip
and the substrate. This is essential for ensuring that the solder joint
interconnects are reliable. The use of an epoxide-based underfill with a
controlled thermal expansion coefficient has been shown to improve the
temperature resistance of flip chip devices by 5 to 10 times. Also, with the
use of an epoxy underfill, encapsulated flip chips on flexible circuitry have
been able to pass severe automotive temperature cycling requirements. By
Table 6.5 Properties of three flip chip underfill materials
Property 1 2 3
Filler content (%) 67 70 70

Gel time at 121°C (min) 6 12 9
Filler particle size (max) (JUIl) 35 10 30
Glass transition temperature eC) 182 188 160
Thermal expansion coefficient (ppmtC) 25 20 24
Hardness (Shore D) 97 98 97
Flex modulus at 25°C (GPa) 8.6 8.6 10.0
Moisture absorption (350 hours PCT) (%) 4.5 2.5 3.0
Cure schedule (hours;oC) 2/150 2/150 0.5/165
Pot Life at 25°C (hrs) 16 16 72
Die size (length of side) (mm) <10 >10 >10
Temperature cycling maximum (0C) 150 > 150 150
Minimum possible gap width (JUIl) 75 25 75
Chloride levels (ppm) 8 3 12
A_P_P_L_IC_A_T_I_O_N_T_E_C_H_N_I_Q_V_E_S____________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ I 195
eliminating the wire bonding stage, flip chip technology is considerably

lower-cost than conventional assembly techniques and it also offers the
benefit of more compact packaging.
After the flip chips are assembled onto the substrate, a dispenser is
required to apply underfill material along one or more sides of the chip, as
shown in Fig. 6.8. Generally, a three-stage dispense option is the best as it
results in minimal air entrapment. This does, however, depend upon the die
size and the pattern of bumps on the chip.
Actual process parameters for underfilling will greatly depend upon the
density of the bumps and the height between the substrate and the die. It is
vital to ensure that the filler particle size is smaller than the minimum gap. In
order to prevent blockage, the gap height should be two or three times the
maximum particle size of the fillers used.
To ensure maximum flow, the substrate is heated before, during and after
dispense. Temperatures up to 120°C may be used, depending upon the chip
configuration. A line or lines of material are spread along the edges of the
chip. The underfill material then spreads under the chip via capillary flow or
'wicking', helped by the heat. A final fillet may be dispensed after the flow is
complete to protect the last edge of the die. Due to variations between die
positioning and sizes it is essential to have some form of pattern recognition
system to align the fillet with the die edges. For a very large die it may be
Fig. 6.S. Vnderfilling of flip chips (a) flip chip on foil, (b) flip chip on a multichip
module.
~----------------------------------------------------~
necessary to repeat the dispensing along the edge of the die to completely
flow under the chip. Curing is then normally carried out in-line.
6.5 INDUSTRY TRENDS
Generally, the semiconductor market is now predominantly driven by the

consumer market. The main driving factors are as follows.
6.5.1 Improved Performance

Reliability requirements for semiconductors have increased in both com-
plexity and magnitude each year. Current test methods, however, bear little
or no relationship to any real world exposure. The movement away from
simpler tests, such as boiling water or high humidity exposure, towards
more complex tests such as highly accelerated stress testing (HAST) is a
move that will no doubt continue. Certainly it is necessary to differentiate
between different materials and methods for device encapsulation. The
difficulty is that as each new generation of materials surpasses the previous
generation in terms of reliability, new and tougher tests are needed to enable
the reliability performance of these encapsulants to be evaluated in a
reasonable period of time. There are currently some moves within the
industry away from this philosophy and back towards more real-world test
procedures in the interests of economy and productivity. The concern is
whether this severe testing is truly relevant to typical applications; i.e. how
relevant is it that a package will withstand 1000 or 1500 hours exposure to 5
atmospheres of steam at 150°C, when in typical service the package itself
will never be subjected to anything even approaching these conditions.
There are, however, two areas where reliability remains of paramount
importance and these are in board assembly and automotive applications. In
the first it is essential that parts withstand the JEDEC level testing, which
effectively simulates board mounting. In the second area, closer integration
of electronics in 'under-the-hood' applications will mean exposure to
conditions far more extreme than the older '85°Cf85%RH' type testing.
It seems likely that these more 'real-world' tests will become increasingly
important in the future, possibly at the cost of some of the more esoteric
procedures, especially if, as seems to be the case, a compromise solution
cannot be found.
6.5.2 Lower Product Cost

Widespread adoption of electronics in almost all areas of life has resulted in
continuing increases in volumes, but at ever reducing prices. New, more
complex devices are being introduced with minimal or no price premium.
The pressures on pricing have concentrated manufacturers' attention on
~________________I_ND
__U_S_T_RY __S________________~I
__T_R_E_ND I 197
topics such as productivity, yield improvement, cost reduction programmes
and time to market etc. This in tum has resulted in shorter product life times
and the need for more specialized materials.
Some movement is now being seen towards acceptance of lower
specification products and materials than would have been possible
previously, and this trend is being driven by the need to manufacture-to-
cost. It is too soon to tell whether this trend will continue, but it seems likely
that further pricing pressure will force manufacturers to at least consider
their options more critically.
6.5.3 Reduced Size

With increasing miniaturization and higher levels of integration, the drive
continues towards further reduction in device sizes. The move towards chip
scale packaging and direct chip attach will continue to escalate. In some
ways this move is helping in other areas, especially where new technology is
spurring reduced costs. Unfortunately, it also creates more difficulties with
even relatively low power devices generating heat (and the need to dissipate
it) when the size reduces. High thermal conductivity materials will,
therefore, become crucial to the next generation of device types.
6.5.4 Quicker Time to Market

There is now a need to bring new products to the market much more quickly
than ever before. With the increasing costs of development and rapidly
reducing prices, the only way to be sure of recouping the R&D costs is to be
first to the market. In addition to the cost aspect this may also help in
reducing the test requirements for new devices with only those truly relevant
tests being performed in advance of commercial introduction.
6.5.5 Reduced Product Life

Going hand in hand with quicker time to market it is also evident that the
life of many newer products is limited. As each generation of faster CPUs
reaches the consumer, another set of support chips is effectively made
obsolete. In all areas faster, smaller, lighter and better are the key words and
again this is having an impact on the formulation of encapsulants.
Encapsulants capable of providing the performance required for these
new devices will require reduced dielectric constants and loss factors,
improved thermal stabilities and better thermal conductivities.
198 I IL-___M_A_T_ER_IA_L_S_F_O_R_AD_V_A_N_C_E_D_E_N_C_AP_S_U_L_A_TI_O_N_ _ _ --l
6.5.6 Environmental Aspects

Gradually, the semiconductor business is moving, along with the rest of the
world, towards more environmentally friendly products. Until now this has
largely been through initiatives such as those aimed at removing CFCs and
reducing the usage of solvent-based washes within the manufacturing
processes. Whilst generally very successful in the manufacturing processes,
little emphasis has so far been put on the finished devices themselves. With
short product life becoming typical, the recycling of old components will
become an increasingly important issue. At the very least, making devices
'greener' so that disposal is simpler must be an aim.
One area that is being looked at from an environmental standpoint is that
of flame retardancy. Historically, most encapsulants have included some
form of halogenated resin, usually in conjunction with an antimony-based
compound, in order to achieve the required level of flame retardancy. For
transfer moulded packages, the flame retardancy was largely standardized
at a level equivalent to a package thickness of 1/8 inch or occasionally
1/16 inch. With packages becoming thinner, this level of flame retardancy
becomes considerably less relevant. In order to achieve a comparable level of
flame retardancy with the thinner sections, a much higher level of additives
would be needed. With the current state of the art this level would have a
considerable effect on the reliability of the devices. Many of the newer
packages are therefore being built with little or no flame retardancy
incorporated. For example, most flip chip and glob-top encapsulants are not
flame retarded. Whilst this may seem to be a dangerous move, the actual
amount of flammable material used on the smaller thinner packages is such
that very little 'fuel' is available.
Whether this move will spread to other device types remains to be seen. It
may well depend upon new, environmentally friendly, flame-retardant
systems being found; something that is not as yet available.
6.6 SUMMARY
The electronics industry continues to be driven forward by the inexorable

progress made by semiconductor device manufacturers and this is bringing
about a major change in the methods that can be used to package and
interconnect the newly emerging devices. The use of peripherally leaded
component packages will not be a viable solution for the increasingly
sophisticated devices that will have hundreds or even thousands of
connections. New packaging and interconnection technologies are therefore
evolving and with them has come the need for new materials. In particular,
there has been a growing trend towards area array-type packages such as the
ball grid array (BGA). For the future, packages will need to accommodate
ACKNOWLEDGEMENTS
~------------------------------------------------------~
II 199
the requirement for more and more I/Os within a diminishing packaging
area. Ultimately, the most likely scenario is that for advanced applications
the use of the flip chip approach i.e. the assembly of inverted unpackaged
devices directly onto a substrate will become widely adopted. This in turn is
driving the need for the new types of encapsulants and encapsulation
methods detailed above. There will also continue to be significant challenges
for encapsulant formulators such as the need for further increased thermal
conductivity and reduced dielectric constant materials. The future for
advanced encapsulants is both interesting and challenging but there is no
doubt it is also full of opportunity.
6.7 ACKNOWLEDGEMENTS
The author would like to extend his thanks to Maurice Edwards, Director of
Research and Development at Dexter Electronic Materials for many helpful
technical discussions and detailed background information.
Recent Developments in the 7
Chemistry of Lithography for
Electronics Production
DAVID MERRICKS
Shipley Company Inc, Marlborough, MA, USA
7.1 INTRODUCTION
The ever increasing integration and sophistication found in nearly all of the
electronic devices produced over the past decade has led to tremendous
advances in information technology. The production of the next generation
of components such as microprocessors is becoming increasingly demand-
ing and manufacturers need to produce ever more complex products using
finer featured printed circuit boards (PCBs) and discrete and integrated
circuits (lCs), with increasing circuit densities. This in turn requires the use
of highly efficient manufacturing processes and short product development
times.
Figure 7.1 shows the trend in feature size reduction for both ICs and
PCBs. As a general rule, the smaller the features used the more functionality
the device contains and the faster it will be able to operate.
Feature size reduction is expected to continue within semiconductor
manufacturing for the foreseeable future as new processing techniques such
as electron-beam and X-ray lithography allow the industry to find ways of
concentrating progressively more sophisticated interconnection systems into
smaller spaces. In the PCB industry, the reduction offeature size is expected
to come to a natural limit using conventional technology, as it becomes
202 I I CHEMISTRY OF LITHOGRAPHY FOR ELECTRONICS PRODUCTION
1250
i~ 250
~ 25
!
2.5
0.75
0.25 +---r-----r---r-"---r---r--~
1970 1975 1980 1985 1990 1995 2000
Year In Production
Fig. 7.1. Trend in feature size reduction of ICs and PCBs.
physically impractical for feature sizes to get much smaller using traditional
technology. Consequently, new technologies will also be required here.
For the past 40 or so years, polymers have been a key element in the
growth of both the IC and PCB industries. New synthetic procedures and a
greater understanding of the relationship between the molecular structure
and the mechanical, physical and thermal properties of polymers has led to
the supply of an ever-increasing variety of materials to meet the needs of
both industries.
The circuit structures of both ICs and PCBs are produced by a series of
steps incorporating lithographic processes which:
1. Delineate the circuit pattern in a thin film of radiation-sensitive polymer
(photoresist), and
2. Transfer the pattern produced onto the substrate using appropriate
etching or deposition techniques.
Figure 7.2 shows a schematic representation of the lithographic process,
using both positive-working and negative-working photoresists.
If a photoresist is negative-working, the exposed areas become insoluble
in the developing solution. If it is positive-working, the exposed areas
become soluble and are removed by the developing solution. The photo-
resists which are used to produce the circuit pattern normally have to be
removed before further processing can continue. However, some photo-
resists are used as permanent coatings, such as liquid photo-imageable
soldermasks (LPISMs) and photo-imageable dielectrics. These are used
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __R_O_D_U_C_T_I_O_N________________~I
INT I 203
Exposing Radiation
Ht Ht Mask
____ Photoresist
----Film to be Patterned
~ Substrate
~m~'
Positive Image Negative Image
~ Etching and Stripping ~
Fig. 7.2. The lithographic process.
mainly to protect and insulate the circuitry or to provide dielectric

separation between layers of conductors and again, because of the gradual
reduction in linewidth of circuit boards, new formulations with ever greater
resolution are continually required.
This review will concentrate on the polymers used in the various classes of
photoresist used by the electronics industry.
Figure 7.3 gives examples of the main polymer types used and these will
be covered in more detail in the following sections.
In the case of negative-working resists the crosslinking moiety which
forms the insoluble polymer network on exposure to light can either be
present in the formulation as a pendent group of the base polymer or be
present as a separate monomer containing unsaturated groups. In positive-
working resist formulations the photoactive moiety is almost always
separate from the polymer.
The remainder of this review comprises two sections, the first being
concerned with polymers used in photoresists for printed circuit board
(PCB) production and the second dealing with polymers used in photo resists
for IC production. The first section is split into two parts, the first part being
concerned with primary imaging (dry film, electrodepositable and liquid
Polymer Photoresist Type
R Rl
f CHz-J...lLCHZ-Jl
I Jx L I Jy
Negative-working Uquid,
ED or DF.
Positive-working ED.
COZRZ CO z R3 Positive e-beam, X-ray.
ACRYLIC
~'"+ CH 3
NOVOLAC
Positive-working liquid,
DF.
OH
~HCH2+-0-@+@-OCH2JHCH2+'O-@+@-OCIl2~\H2
EPOXY Negative-working LPISMI
Photodielectric
Positive-working
e-beam. X-ray.
POLYSULPHONE
Positive-/Negatlve-
working DUV resist.
POLY(HYDROXYSTYRENE)
ED - Electrodepositable. DF - Dry Film. DUV - Deep Ultra Violet.
Fig. 7.3. Typical polymers used in photoresists.
photoresists used as etch resists or plating resists) and the second part with
secondary imaging (LPISMs used as permanent dielectric coatings). The
second section progresses from the optical photoresists currently used in Ie
production, through potential future technologies such as deep ultra violet
(DUV), to electron beam and X-ray sensitive photoresists.
L-_P_H_O_T_O_RE_S_I_ST_S_F_O_R_P_R_INTE
__D_C_IR_C_U_I_T_B_O_A_R_D_P_R_O_D_U_C_T_IO_N_-----'I I 205
7.2 PHOTORESISTS FOR PRINTED CIRCUIT BOARD

PRODUCTION
7.2.1 Introduction
This section is mainly concerned with polymers used in the production of
PCBs, although the types of photoresists described here can also be used for
other applications, such as in the photochemical machining (PCM) industry
as print and etch resists or in the production of colour filters, where the resist
is permanently in place on the finished product. The first part of this section
is concerned with primary imaging which covers the use of polymers as print
and etch or plating resists on the inner and outer layers which comprise a
multilayer PCB, while the second part concentrates on secondary imaging,
describing polymer formulations used in solder masks.
7.2.2 Primary Imaging

In this section the three main types of primary imaging photoresists are
discussed, these being dry film, liquid and electrodepositable resists.
The so-called print and etch process uses a positive resist image to protect
the copper beneath the resist while the remaining unprotected copper is
etched away. When photoresists are used as plating resists they define the
image area on copper which will be electroplated. The electroplating then
serves as the etch resist after the photoresist is removed.
7.2.2.1 Dry Film Photoresists

Dry film resists are pre-dyed photosensitive systems containing additives
such as photo sensitizers and photoinitiators (which determine photospeed)
and which are primarily sensitive to ultra violet light such as the 365 om
actinic radiation emitted from mercury lamp sources.
The introduction of dry film resists, by Du Pont in 1968 as an alternative
to the conventional screen printing and liquid resists, revolutionized the
PCB fabrication process. The increased thickness of the dry film resist
structure compared to liquid resists, together with the better uniformity and
ease of application, was ideal in meeting customer specifications using a
pattern plating process. 1
Although often thought of as having resolution limitations for fine feature
applications, recent innovations in dry film imaging have led to improve-
ments in resolution capability. 35 ~m line widths can be achieved with ultra-
fine line resists which also eliminate the need for a polyester cover sheet as
an oxygen barrier during exposure. 2 These also offer increased adhesion and
conformance to the substrate surface with the use of wet lamination
techniques. Improvements in photospeed, sidewall profile and alkaline etch
resistance have also recently been realized.
A typical dry film photoresist structure consists of a photopolymer layer,
17 to 75 J.11ll thick, sandwiched between polyester (Mylar) and polyolefin
films.
The photoresist is normally applied to the board using heat and pressure
by a technique known as vacuum lamination. 1 The polyolefin separator
sheet is removed during the lamination step, whereas the polyester film
remains in place during exposure, providing a protective physical surface
and an oxygen barrier for the photopolymer. It is removed prior to
development. These layers are necessary to allow the photoresist films to be
wound into rolls without sticking to itself.
Both solvent and aqueous-developable/strippable dry film systems exist.
Disadvantages of the solvent-based systems include the necessity for more
costly process equipment, the toxicity of the (usually chlorinated) solvents
used and the cost of the solvent itself. However, these can be balanced by the
ability to recover the solvent by distillation, therefore greatly minimizing the
amount of waste and waste treatment costs. Semi-aqueous processable
resists are also available in which the developer contains up to 10% of an
organic solvent in an alkaline solution. This usually helps to improve image
quality or developing and stripping productivity.
The chemistry for formulating dry films has basically changed little in the
last 20 years and the key components are described below. Most dry film
photoresists are negative-working and contain the components also detailed
below, although there are some positive-working dry film resists in use.
• Polymer. This provides the physical strength of the photoresist film and
also determines the mode of developing and stripping.
• Monomer. This crosslinks on exposure by free-radical polymerization to
become insoluble in the developer.
• Photoinitiator. The source of free radicals during exposure. The choice of
photoinitiator depends on the principal wavelengths emitted from a
medium pressure mercury vapour lamp. The peak absorbance should be
on, or close to one of the major emission lines (usually 365 om).
Photoinitiators with absorbance wavelengths removed from those of the
lamp may also be used. In these cases photosensitizers, matched to the
principal lamp wavelengths are added which, after excitation, transfer
their energy to the photoinitiator.
• Plasticizers. These modify the physical and functional properties for a
given application.
• Dye. Normally a phototropic dye (usually blue or green) is incorporated,
which provides contrast between the exposed and unexposed areas. Dyes
are also used as anti-halation agents which prevent the undesired
reflection of UV light.
• Other additives. These can include adhesion promoters and thermal
polymerization inhibitors.
L-_PH_O_T_O_R_E_SI_S_T_S_F_O_R_P_R_INT_E_D_C_IR_C_U_IT_B_O_A_R_D_P_R_O_D_U_CT_IO_N_----'I I 207
Most dry films used today contain polymers formed from different types of
acrylate or methacrylate monomers. Figure 7.4 shows a variety of acrylates
used in negative-working dry film resists. The first two examples are aqueous
processable and also a crosslinking monomer is needed in the formulation
since there are no photopolymerizable groups present attached to the
backbone. The third example is a solvent processable resist and contains
pendent groups with unsaturation, which crosslink on exposure to form an
insoluble matrix.
Negative-working dry film systems based on polyfunctional alcohols with
acrylate end groups are also known 5 and a typical structure is shown in
Fig. 7.5.
Other additives are necessary in order for the above polymers to function
as dry film resists. Unsaturated monomers used are usually multiacrylates
and typical examples are shown in Fig. 7.5.
All negative-working photoresists contain a photoinitiator and also in
some cases a photosensitizer as well. The photoinitiator is a compound
which absorbs incident UV radiation of an appropriate wavelength from the
exposure lamp during the imaging step and splits into free radicals which
initiate polymerization of the unsaturated monomer (or unsaturated
polymer). Given an appropriate light source, efficient photoinitiation
Polymer Reference
2.
3.
fuz-iu-jfcuryu+ 5
C02CH2CHOH C0 2R
tH 20COCH=CH 2
R = Alkyl
Fig. 7.4. Acrylate dry film resists.
CH2-CHCO~OCH2CH2-r-O~O-+CH2CH20+-COCH=CH2
x ~ y
CHZ=CHCOZCHZCHZOCH2CH202CCH=CHZ
Diethylene glycol diacrylate
CH Z0 2 CCH=CH Z
CH1-CHCOZCHZ- C-CH2 CH3

I
I
CH Z0 1 CCH=CH2
Trimethylol propane triacrylate

Fig. 7.5. Acrylate compounds used in dry film photoresists.
'-----_PH_O_T_O_R_E_S_IS_T_S_F_O_R_P_R_IN_T_E_D_C_IR_C_U_IT_BO_A_R_D_P_R_O_D_U_C_T_IO_N_----'I I 209
depends on several factors, including suitable absorption coefficients and

wavelength sensitivities for the initiator molecule, initiation quantum yields
in the range 0.1 to 1.0, and the requirement that the initiator molecule or
any of its photofragments should not function as chain terminating agents.
Sometimes light of the appropriate wavelength, for initiating the above
reaction with a particular photoinitiator, is unavailable in sufficient intensity
from standard exposure units used. In these cases, another photoactive
compound is added with the photoinitiator, which is usually referred to as a
photosensitizer. The photosensitizer is chosen so that it absorbs the
appropriate wavelength of light and also is matched to the photoinitiator
in such a way that it can transfer the absorbed energy to the photoinitiator,
causing it to split into active radicals.
The choice of photosystem varies from one resist to another; however, it
must be compatible with both the other resist components and also the
spectral output of the light source. Examples of the more common
photoinitiators are benzophenone, Michler's ketone, isopropylthioxanthone
and butylanthraquinone. 3 Figure 7.6 shows absorbance spectra for a typical
photoinitiator-photosensitizer combination, isopropylthioxanthone (ITX)
and 2-methyl-I-[4-(methylthio)phenyl]-2-morpholinopropanone (MMMP),
with the major emissions from a mercury vapour lamp.6
Figure 7.7 shows the photosensitization and photoinitiation mechanism
in the ITX-MMMP system.
2.0 0.20 :00

f!-
~
"0
;;
.a
....
"0 '"'"
.
..,'0
'0 0.15 i
0
~0 1:1
5'
"
0
Q.
;
e
~
0.10
1.0
0.05
302313 334 365 405 435

Wavelength/nm
Fig. 7.6. UV absorption spectra of ITX and MMMP.

rgQgrbV>330n: l rgQgrJ*
-@-1-f-o/
I Me
rgQgr
+
Me
Polymer ·~-O
Me
Fig. 7.7. Mechanism of photosensitization and photoinitiation.
A non-photosensitive acrylate copolymer containing (meth)acrylic acid,

an example of which is shown in Fig. 7.8, may be converted into a water
soluble salt by reaction with an aqueous alkaline solution, provided that a
sufficient number of acid groups react to overcome the hydrophobic nature
of the (meth)acrylate ester groups in the polymer.
If a multifunctional acrylic monomer is included in the formulation, then
free-radical polymerization will result in a hydrophobic product which will
not be developed out after exposure and will therefore result in an image on
the substrate.
Positive-working dry film resists are also known and examples of two
different types are shown in Fig. 7.9. In these resists the exposed area is
developed away and therefore the mechanism is different to that of negative-
working resists. In both systems, acids are generated during exposure which
deprotect acid-labile groups present in the formulation and thus increase
solubility in alkaline developers in the exposed region. The first system
contains a novo lac resin and a hydrolysable moiety such as an orthoester
which reacts with the hydrochloric acid generated from exposure of the
polychloro-compound. 5
The second system contains an acrylic resin and a photoacid generator
which works by a chemical amplification mechanism (which will be
discussed in detail in section 7.3.2.2). In this system the t-butyl groups are
removed by the photogenerated Lewis acid to leave alkaline soluble
carboxylic acid groupS.7
L-_P_H_O_T_O_RE_S_I_ST_S_F_O_R_P_R_INT_E_D_C_IR_C_U_I_T_B_O_A_RD
__ P_R_O_D_U_C_T_IO_N_-...l1 I 211
O(CH2CH2OCOCH-C121
hv
Developed in
NazC03
Crosslinked Product
CH3 CH3
tCHz-t~CHz-t~t
COzNa b0 2cH3
+ C02 + H2 0
Fig. 7.8. Aqueous developable dry film resists.
Polymer
Polymer
PAG
PhZI+ SbF 6-
Fig. 7.9. Positive working dry film resists.
This latter type of system has also been used with visible laser direct
imaging, using an argon ion laser at 488 nm and 514 nm. Visible laser
imaging of normal negative-working resists has been attempted but these
systems suffer from the same limitations as UV sensitive formulations
including swelling in the developer and the need for an oxygen barrier
during exposure. The use of a chemically amplified resist here would
therefore have several advantages. These materials can be used as liquid
resists as well as in dry film applications.
7.2.2.2 Liquid Photoresists

Dry film photoresists have dominated primary imaging of PCBs for almost
30 years. Before that time liquid resists were used and were applied by a
variety of methods such as spray, roller and dip-coating. However, as
demand for finer resolution work grows, liquid photoresists are again
becoming a viable alternative to dry film. Although there are positive-
working liquid resists available, negative-working technology is the basis of
virtually all liquid resists as well as dry film resists.
Advantages of liquid resists over dry film resists include: less waste, since
dry film overhangs the board edges and the space in-between the boards and
cannot be recovered; and greater flexibility in coating thicknesses. Special-
ized resists and equipment such as collimated light sources, have enabled dry
films to resolve features of approximately the same thickness as the liquid
resists, but these methods are not yet suited to volume production work and,
although the exposure times of dry films are up to three times faster, they are
more susceptible to loss of resolution due to halation. A disadvantage of
liquid resists is that they cannot reliably protect circuit board plated through
holes, whereas dry films can do this by 'tenting' over the hole ends.
Although roller coating can produce uniform films of various thicknesses,
dip coating leads to non-uniformity, as the film at the top edge ofthe board
is thinner than at the bottom.
There are a number of negative-working liquid photoresists still in use
around the world in a wide range of applications and which have been used
for many years, such as water soluble resists based on polyvinyl alcohol or
casein and sensitized by chromium salts, 5 cyclized polyisoprenes sensitized
with bis-azides9 and systems based on vinyl cinnamates which work by
dimerization on exposure. 5
The cyclized polyisoprene resists were among the first negative-working
resists to be used in the production of integrated circuits. Solvent resist
systems containing acrylic copolymers, an example of which is shown below,
have been described. Io This family of resists which contain ionizable groups
such as acids or amines are normally used as electrodepositable resists (see
section 7.2.2.3) but have found use in spray and dip-coating (Fig. 7.10).
As in dry film resists, crosslinking monomers, photoinitiators, sensitizers,
dyes and other additives such as oxygen inhibitors are required for these
formulations to function effectively.
Similar formulations to the above system can be used to produce colour
filter arrays in active matrix liquid crystal display (AMLCD) colour filter
plates. 11 The resist, which is spin coated onto a glass substrate holding a
black matrix, is made up of an acrylic copolymer containing (meth)acrylic
L-_P_H_O_T_O_R_E_S_I_ST_S_F_O_R_P_R_INT_E_D_C_IR_C_U_I_T_B_O_A_R_D_P_R_O_D_U_CT_IO_N_----li I 213
+u,-t*u'-Htu,-p-
CH3 H 1H3
C02CH3 C02Et C02CH2CH2N(CH3l2
Fig. 7.10. Acrylate polymer used in dip-coated and ED photoresists.
acid as one of the monomers, a polyfunctional acrylate monomer, a

benzophenone-type initiator and a red, green or blue pigment dissolved in
cyclohexanone. The idea is to sequentially coat, expose and develop the
three differently coloured resists to produce the colour filter array.
Positive-working liquid resists based on novolac-diazo-naphthoquinone
chemistry (see section 7.3.2.1), which are applied by roller-coating tech-
niques, are also known.
A recent innovation has been the formulation of metal-ion free water
soluble resists containing no organic solvents. Systems in which the solvent
is water and the polymer is PVA or a natural colloid such as fish gelatin or
casein have been used for many years but, although they are quite cheap,
they must be sensitized by inorganic compounds usually containing toxic
ammonium dichromate. Systems based on radical 11a and chemically
amplified polymerization llb are also known. A typical radical initiator
system comprises a latex binder polymer having sufficient carboxylic acid
functionality to render it developable in aqueous alkaline solution, a
photopolymerizable monomer, a photoinitiator and a polyetber poly-
urethane thickener which supports an emulsion of the monomer fraction
in aqueous media. The polymers are made up of alpha, beta-unsaturated
compounds such as vinyl, acrylate or styrene monomers.
The chemically amplified resist systems are of low toxicity and have the
ability to be developed in water. A typical formulation containing a vinyl
acetal polymer and 4-N-phenylamino-I-methoxyphenyldiazonium hydro-
gen sulphate as the PAG is shown in Fig. 7.11.
7.2.2.3 Electrodepositable Photoresist/2

Electrodeposition is a process by which organic materials are coated from
aqueous suspension or solution onto a conductive substrate under the
influence of an electric field. The process utilizes direct current for depositing
resins so that predominantly electrophoretic processes operate. Electropho-
resis in this context means the migration of colloidal or suspended particles
(i.e. micelles) in an electric field. The particles migrate according to their
charge, to the anode (anaphoresis), or to the cathode (cataphoresis).
Electrodepositable photoresists are stable microemulsions from which a
film of organic photoresist may be deposited onto a circuit board or other
PAG
Polymer
Fig. 7.11. Chemically amplified waterborne resists.
conductive substrate. They are used primarily for high resolution selective
etching and pattern plating in the manufacture of PCBs (both inner and
outer layers), 3D moulded interconnect devices, multichip modules and
other interconnect level electronic devices.
These resists have the potential to displace solvent-based liquid resists as
well as dry film photoresists in most present-day applications over
conductive substrates, although ED resists are not yet that widely used.
The main advantages of ED resists over dry films are firstly, their superior
resolutions due to the ability to uniformly coat layers up to five times
thinner and secondly, their ability to conform to three-dimensional features.
Other advantages are the same as for liquid resists (see section 7.2.2.2).
A variety of electrodepositable film-forming resins are known, the most
often utilized to date being acrylates, epoxies and novo lacs, although the use
of polymers containing more diverse functionalities is gradually increasing.
In order for a polymer to be electrodepositable it must contain a distribution
of ionizable groups along its molecular chain. Polymers may be cationic,
containing basic sites such as amino groups, or they may be anionic
containing acidic sites such as carboxylic, sulphonic or phosphoric acid
groups. In some instances amphoteric polymers are known which have both
acidic and basic groups.
The polymer can also contain photosensitive functionalities such as sites
of unsaturation in the case of negative-working photoresists, or have
photo active groups such as diazonaphthoquinones (DNQ) attached, as in
positive-working photoresists. Although some polymers are formulated with
such functionalities present, in the most commonly used polymers such
L-_P_H_O_TO_R_E_SI_S_T_S_F_O_R_P_R_I_NT_E_D_C_IR_C_U_I_T_B_O_A_R_D_P_R_O_D_U_C_T_IO_N_----11 I 215
groups are absent and the main function of the polymer is as a carrier for the
other resist additives.
Another requirement of the polymer is that it must be able to form a
stable emulsion with suitable ionizers such as inorganic or organic acids
(which protonate the ionizable groups in cationic resins), or bases (which
deprotonate the ionizable groups in anionic resins) in the presence of other
resist additives such as photoinitiators, DNQ-photoactive compounds,
crosslinking agents and so on. Plasticizers are also added to control the
coating characteristics, to give good adhesion to the substrate and to ensure
that the coating is not brittle. The flexibility of ED resists is far superior to
that of dry film resists.
Negative-working and positive-working cataphoretic or anaphoretic resist
systems are known and examples of the resists used are shown in Fig. 7.12
and 7.13 (the numbers in parentheses indicate monomer parts by weight).
From Fig. 7.12 it can be seen that the polymers in examples 1,2 and 5 have
photosensitive groups along the polymer backbone, whereas crosslinking
monomers or photoactive compounps have to be added to the polymers in
examples 3, 4 and 6.
Resist additives such as monomers, dyes, photo initiators or photoactive
compounds are of the same basic types as those used in dry films (section
7.2.2.1) or DNQ photoresists (section 7.3.2.1).
Hydrophobic solvents, or plasticizers, are often added to electrodeposi-
table resists to lower the Tg of the polymer, enabling electrodeposition to
take place at lower temperatures and to control the film thickness more
easily. Plasticizers need to be chosen to maximize film coalescence and
flexibility and to minimize tack, which can sometimes be a problem during
contact exposure.
The coating mechanism, which is described briefly below, concentrates on
cataphoretic deposition for simplicity. The principles of anaphoretic coating
are basically the same, with only the charges on the micelles and the
electrodes being reversed.
In a cataphoretic emulsion, when an electric field is applied (approxi-
mately 10 volts/cm), micelles migrate by electrophoresis towards the cathode
at the rate of microns/second. In addition, all the water insoluble
components also migrate with the micelle. The conductivity of the solution
permits controlled electrolysis. Water decomposes to raise the pH at the
cathode and lower the pH at the anode, which is usually made of an inert
material such as stainless steel since, because it is the oxidizing electrode,
metal dissolution is otherwise possible.
When the micelles reach the cathode, their positive charge is neutralized
by hydroxide ions produced by the electrolysis of water. The micelles then
become destabilized and coalesce on the surface of the cathode to form a
self-limiting, insulating film that emerges nearly dry from the coating bath.
As the resistance of the film increases, the potential across the film increases
Type Polymer Reference
1. Negative!
I]
Anaphoretic
(Z) (Z) (1) (1.Z)
z. Positive!
Anaphoretlc 13
CH] CH] H f
-fCHz-jfCHz-j1fHz-j*HZ-,+
COZ COZDB" COZH
°~NCHZCHZ
NZ COZCH]
tllu I
o °z (5.8) (5) (4.3) (1)
]. Positive!
Anaphoretic 14
(1.85) (6.4) (1)
4. Negative!
Cataphoretic CH3 H 1H3 15
-fCHz-j1fHz-t*HZ-l+
COZDBu COZCHZCHZN(CH3)Z
COZCH3
(8.5) (3.4) (1)
5. Positive!
Cataphoretic 13
6. Amphoteric 16
CH] CH3 CH3 1H3

-fCHz-!ICHz-!1fHZ-!*HZ-,+
COZ
COZCH] 10ZH COZCHZCHZOH
CHI ZCHZN(CH3)z
Fig. 7.12. Acrylic resins for ED resists.
L--_PH_O_T_O_R_E_S_IS_T_S_F_O_R_P_R_INT_E_D_C_IR_C_U_IT_BO_A_R_D_P_R_O_D_U_C_T_IO_N_----'I I 217
Type Polymer Reference
1. Cataphoretlc/
Epoxy 17
?H OH OH
R2NCH2CHCH20~OCH2~HCH20~CH2~HCHZNR2
z. Cataphoretlc/ 18
Negative/Epoxy
OCOCH-CHZ
C~HCHZO~OCHZ!HCHZO~CH2~~HZ
MIXED WITH
~m N
tHzCHZCHZN(CH3)Z
3. Positive/
Anaphoretic/Novolac 19
4. Positive/
Cataphoretic/Novolac
16
~'"'~'"'t-
CHZ
I
tBu
N(CHZCHZOH)Z
Fig. 7.13. Epoxy and novolac resins for ED resists.

H20 - Ze- + ZH+ + 1/ Z0 2
HZO + e- - -OH + 112H Z
Fig. 7.14. Cell diagram for cataphoretic deposition.
causing water and occluded ions to be forced out of the coating by electro-
osmosis. Thus the combination of electrophoresis and electrolysis produces
a highly uniform and defect-free coating. The self-limiting nature of ED
coatings is mainly dependent on voltage, coating time and bath temperature
and conditions can be used which build up quite thick films. However, at
optimum conditions for thin coatings, film growth continues until film
resistance is so high that the electric field across the emulsion is too low to
induce delivery of the micelles, or the current flow drops low enough that the
cathodic pH is too low to induce coalescence. As a result, films should be
uniform even if they deposit at different rates across a part.
Meanwhile, the carboxylate anion, on reaching the anode, is neutralized
by hydrogen ions from the electrolysis of water. As resist solids are removed
from the bath at the cathode, there is a gradual build up of ionizer in the
bath. Therefore, to maintain bath chemistry, free acid must be removed by
ultrafiltration or by the use of semi-permeable membranes.
Figure 7.14 shows the cell diagram for cataphoretic deposition.
7.2.3 Secondary Imaging

In this section the main types of secondary imaging photoresists, usually
called soldermasks, are discussed. Liquid photo-imageable soldermasks
(LPISMs) are normally negative-working formulations which produce a
permanent coating on the circuit board in order to protect the copper
,-_P_H_O_T_O_R_E_S_I_ST_S_F_O_R_P_R_INT_E_D_C_IR_C_U_I_T_B_O_A_RD
__P_R_O_D_U_C_T_IO_N_------'I I 219
circuitry from physical and chemical damage as well as insulating the

circuitry to prevent short circuits. The areas of the board which are to be
soldered are not exposed and the mask in these areas is removed by a
developing solution. The mask therefore also provides a physical barrier to
solder bridging between conductors. A variety of techniques has been used
to apply soldermasks, such as screen printing, roller coating, electrostatic
spray and, more commonly these days, curtain coating. Dry film solder-
masks are also known which can be applied by vacuum lamination, similar
to dry films for primary imaging.
In the following sections, systems based on two-pack chemistry, cationic
polymerization and water-borne chemistry will be discussed.
7.2.3.1 Two-Pack Systems

Two-pack soldermasks have limited pot life, since they begin to react, by a
thermal crosslinking mechanism, as soon as they are mixed together prior to
coating.
LPISMs have been formulated containing epoxy oligomers with acrylic
monomers, which crosslink on exposure by a free radical mechanism.
Further crosslinking occurs, during thermal cure after development, by
opening of the epoxide rings with a nucleophile such as an amine compound
present in the formulation. The acrylate groups reduce exposure time by
binding the epoxy components well enough to withstand development.
These formulations can contain organic carrier solvents or they can be
100% solids, with the acrylic monomer acting as both the crosslinking
substance and carrier solvent for the polymer, dye, filler and photosystem.
LPISMs that are solvent based must be oven dried before they are imaged
and the solvent-free masks are imaged when still wet. 20
These formulations contain photoinitiators, monomers, polymers (acryl-
ates and epoxy-acrylates) and dyes that we have already met in previous
sections, along with thickening agents and fillers.
Another type of two-pack LPISM based on full-epoxy chemistry works
by dimerization during exposure,21 followed by thermal crosslinking
initiated by an amidine. The epoxy polymer and crosslinking mechanism
are shown in Fig. 7.15.
Figure 7.16 shows a schematic diagram of a typical soldermask process
using a screen print or curtain coat application.
7.2.3.2 Cationic Polymerization

Another class of LPISM is based on photo acid generation followed by
cationic polymerization.22 A typical formulation comprises a mixed cresol
novolac resin for improved thermal properties and aqueous developability, a
bisphenol A/epichlorohydrin epoxy resin for film strength, adhesion and
~~HCH2-fE- A -3f B -3;io@ CH-CHCo@OCH2~H2
z
?H
A= ~CH_CHCO~OCH2CHCH2
~ ,H
B= 0~OCH2CHCH2
-O@CH-CHCO-
2 - - o@CH-CHCO-
hv
~
I I
-O@CH-CHCO-
OH
I I
-O-CHz -CH-CHZ-N-~-R
+ L:::,.. N
~ I
R-C-NH Z
-OCH Z-
1
H - CH z
"
OH
NH
Fig. 7.15. Photodimerization and thermal curing of a full-epoxy LPISM.
dielectric properties, a triarylsulphonium salt which generates a Br0nsted

acid on exposure, hexamethoxymethylmelamine as thermal crosslinker, a
filler and other additives, including dyes and plasticizers dissolved in a
solvent such as propylene glycol methyl ether acetate. A major advantage of
this class of LPISM is the ability to resolve much finer features because of
the mechanism of crosslinking. The acid generated during exposure is
subjected to an additional thermal enhance step before development in
which the acid opens up the epoxide rings. Further crosslinking occurs
during the final cure step when the melamine compound reacts with free
hydroxyl groups. The mechanism is shown in Fig. 7.17.
Another advantage of this type of LPISM formulation is greater stability
and pot life. It is a single component photoresist and no thermal
crosslinking occurs before the thermal enhance stage. Also, these resin
systems can be developed in either solvent or aqueous solution.
L -_PHOTORESISTS
_ _ _ _ _ _ _ _ _ _ _FOR
_ _ _PRINTED
_______ CIRCUIT
_ _ _ _ _ _BOARD
_ _ _ _ _ PRODUCTION
___________ ~
II 221
Fig. 7.16. LPISM process.
7.2.3.3 Photo-imageable Dielectrics

The type of formulation described in the previous section can also be used in
modified form as a permanent photo-imageable dielectric in sequentially
built circuit boards. 22a As the trend in high density interconnection for PCBs
necessitates the move to thinner laminate, the photo-imageable dielectric
material provides a less expensive alternative. The trend toward PCBs with
higher layer counts and finer lines cannot continue at the present rate and
very high density interconnection will require a different strategy. One
solution is to focus on an intermediate substrate for bare chip mounting
which reduces the wiring density at the PCB level. This intermediate
package is referred to as a multi chip module or MCM?2b One type of
MCM construction (known as MCM-L) utilizes a PCB with an added layer
of deposited circuitry formed by using a photo-imageable dielectric.
These dielectric formulations show excellent adhesion, low dielectric
constants and also resistance to electroless plating chemistry. Other
advantages include the elimination of small-hole drilling, no lamination,
no registration of layers and the capability to photoform all the via holes
with one exposure (making it faster than laser drilling).
Both aqueous-developable22a and solvent-developable22c products have
been formulated.
Photolysis of Triarylsulphonium Salts
hv -- [ Ar3S+ X- ] *-----1~• Ar 2 S.+ X- + Ar.
~
Ar2S + z· + HX
Ring Opening of Epoxldes
Thermal Cure
R - Epoxy polymer
Fig. 7.17. Cationic polymerization of epoxy resins.
7.2.3.4 Water-borne LPISMs

A recent innovation has been the replacement of the organic carrier solvent
in LPISMs with water. 23 The driving forces are environmental consider-
ations, reducing the volatile organic content and reducing processing costs.
The soldermask is supplied as a single component product and it can be
applied using conventional application equipment, although some problems
due to excessive foaming can occur. The components necessary to produce a
photo-imageable soldermask are at present suspended in water as an
emulsion, rather than being in solution, as formulation difficulties can arise
with the latter. The biggest disadvantage is the difficulty in drying the mask
effectively after application. Since the presence of even minute quantities of
water in a soldermask can lead to performance failure, efficient drying is
critical. Water-borne coatings are generally more difficult to dry and it has
been found that insufficient drying can cause failure to image successfully
P_H_O_T_O_R_E_S_IS_T_S_F_O_R_INT_E_G_R_A_T_E_D_C_I_R_C_D_IT_P_R_O_D_D_C_T_I_O_N_----'I
L - ._ _ I 223
Polymer
Styrene/Acrylic copolymer
Monomer
Trimethylolpropane triacrylate
Photo!n! tia tor
Isopropylthioxanthone(ITX)
Fig. 7.18. Water-borne LPISM components.
and loss of exposed resist during developing. A combination of IR and

convection drying is therefore required to give consistent results.
The components of a typical water-borne LPISM are described in
reference 23 and Fig. 7.18 shows the polymer, monomer and photosystem
used in the formulation.
Being an acrylic polymer, the photospeed is very fast (around 120 mJI
cm 2); however to achieve the hardness necessary, a 4 J/cm 2 UV exposure is
necessary before the final thermal cure.
7.3 PHOTORESISTS FOR INTEGRATED CIRCUIT PRODUCTION
7.3.1 Introduction
This section concentrates on polymers which are currently used (or are
planned to be used in the future) in photoresists for integrated circuit (IC)
production.
The first part covers optical lithography, detailing near-UV systems which
utilize the g and i-line emissions of standard Hg-vapour sources and deep-
UV systems which operate at the 248 nm wavelength produced by an
excimer laser. The final part describes newer technologies, such as electron
beam and X-ray lithography, which will be necessary to produce the next
generation of IC devices.
The discussion here concentrates on single layer resists and multilevel
(bilayer and trilayer) systems are not covered.
A modem IC is a complex 3D structure of alternating patterned layers of
conductors, dielectrics and semiconductor films. The semiconducting
material is usually ultra-high purity silicon. The performance of the device
is, to a large degree, governed by the size of the individual circuit elements.
As a general rule, the smaller the elements, the faster the device and the
more operations it can perform. The device structure is produced by a series
of lithographic steps used to pattern each layer precisely.9
Forecasts of the future development of highly integrated silicon circuits
are focused on the dynamic random access memory (DRAM), which are the
devices with the highest complexity and integration density. DRAMs
currently represent the forefront of technology development.
Figure 7.19 shows the history of increasing complexity and simulta-
neously of decreasing smallest geometries on one chip.
It can be seen that dramatic advances are continually being made in
microelectronic device fabrication and especially in optical lithography, the
100
a!:l CONTACT PRINTING
......
..
~
::I
1\1
5.0
3.0 1:1 PROJECTION
J!
a
::I
2.0
a 5:1 PROJECTION
~ 1.0
0.5
0.3
0.2
0.1
o~----~----------~------------,-~
1978 1988 1998
Year
Fig. 7.19. Development trends of lithographic technology.
'--__
PH_O_TO_R_ES_I_ST_S_FO_R_I_NT_EG_RA_T_ED_C_I_R_CU_IT_P_R_O_D_U_C_T_IO_N_---'I I 225
technique that is used to generate the high resolution circuit elements

characteristic of today's integrated circuits.
However, optical lithography is now facing a serious problem due to the
limitation of wavelength, since the ultimate resolution of a printing
technique is governed, at the extreme, by the wavelength of light used to
form the image, with shorter wavelengths yielding higher resolution. The
minimum feature size of the most advanced devices, such as 64Mb DRAMs,
is around 0.3-0.4 ~, which is almost the same as the wavelength of the i-
line (365 om) light used for pattern transfer.
Around 15 years ago, the state-of-the-art device contained up to 8000
transistor elements and had ~ ~ minimum features. Today, devices with
several million transistor cells are commercially available and are fabricated
with minimum features of 0.3 ~ or smaller. Optical lithography (350-
450 om light range) has been used as the technology of choice and
incremental improvements in tool design (i.e. phase shift masks) and resist
performance (i.e. multilayer systems) have allowed the continued use of
350-450 nm light to produce ever smaller features. 24
However, as can be seen in Fig. 7.19, at the end of this decade the quarter
Gigabit memory device with smallest design rules of 0.25 ~ will be in
industrial mass production and prototypes of circuits with 0.15 ~ features
will be available. Concerning the lithography process, there will be a
competition between very advanced optical lithography such as DUV and
X-ray lithography using synchrotron radiation and particle projection using
either electrons or ions. 25
7.3.2 Optical Pbotoresists
7.3.2.1 G-line and I-line Resists

By far the most widely used lithographic system in the production ofICs is a
positive-working photoresist based on a combination of a novolac (phenol-
formaldehyde) resin with a diazonaphthoquinone photo active compound
(PAC)?6 These photoresists are designed to operate at the mercury g-line
(436 om) or i-line (365 nm). This type of system operates via a dissolution
inhibition mechanism. The novolac resin is alkali-soluble and is rendered
insoluble in aqueous alkaline solution through incorporation of a hydro-
phobic, radiation-sensitive material. Upon irradiation, the hydrophobic
moiety is converted to an alkali-soluble species, allowing selective removal
of the irradiated portion of the resist by an alkaline developer. The
development rate of the exposed resist is greatly accelerated relative to the
base resin. Figure 7.20 shows the reaction mechanism of a typical novolac-
DNQ system. The DNQ is the dissolution inhibitor, whereas the carboxylic
acid is the dissolution accelerator.
~2_hV_'"
80 2 R
DNQ
~2H
80 2 R
Indene carboxyUc acid
Fig. 7.20. Photochemistry of a novolac-DNQ system.
The group R attached to the photosensitive DNQ-sulphonyl moiety in

Fig. 7.20 is known as a ballast group which is usually (but not always) a
polyhydroxylated aromatic compound based on benzophenone.
Irradiation of the DNQ results in the loss of nitrogen and the formation
of a transient carbene intermediate, which rearranges to a ketene by a Wolff
rearrangement. The ketene then reacts with water in the film to produce a
carboxylic acid. Therefore control of humidity during exposure is important
since exclusion of water results in an entirely different series of reactions and
crosslinking occurs with the novolac resin. 26 It is thought that crosslinks are
produced between the resin and unreacted PAC in the unexposed region in
the presence of an alkaline developer, which leads to the dissolution
inhibition. This is shown in Fig. 7.21. This mechanism goes some way to
explaining the excellent contrast between exposed and unexposed regions
seen in novolac-DNQ resists.
The novolac matrix resins are usually of low molecular weight, typically
between 1000 and 2000, making them readily soluble in alkaline solutions.
These resins are also soluble in organic solvents, which make them easy to
spin-coat onto the silicon substrate. The novolac is rendered alkali-insoluble
by the addition of 10-20 weight% PAC.
PHOTORESISTS FOR INTEGRATED CIRCUIT PRODUCTION
~----------------------------------------------------~
II 227
Fig. 7.21. Proposed dissolution inhibition reaction.
All positive-working photoresists basically contain the same components.

However, the precise performance characteristics depend on the substitution
pattern of the resin and the PAC. It has been found that novolac molecular
weight, ortho-ortho substitution of the formaldehyde linkage, meta-/para-
cresol ratio of the resin and polydispersity (Mw/Mn) have the greatest effect
on resist photospeed, dissolution inhibition/enhancement, heat resistance,
contrast and exposure latitude. 27
Studies on the effect of novolac structure on the resist dissolution
characteristics have led to models that relate the dissolution rate to
intermolecular interactions and to new resist-developer systems?S
Since novolac resins have rather low glass transition temperatures (Tg) in
the range 70-120°C, a number of alternative phenolic resins have been
evaluated as replacements, such as poly(hydroxystyrene) and analogues?9
However, the performance of these alternatives has been found undesirable,
especially with respect to dissolution rates which are unacceptably high.
PAC structures have also been evaluated with respect to development
rates, resist image quality and overall performance. 3o It was shown that
multiple DNQ units per PAC molecule led to improved resist contrast and
image quality.
Figure 7.22 shows a number of different structures used as DNQ-PAC
backbones (ballast groupS)?6
W OH
[QrCt6(0H
OH
W OH
:)9t16(:
OH
Fig. 7.22. DNQ-PAC ballast groups.
The first two benzophenone analogues have non-vanishing absorptivities

at i-line, whereas the lower two non-benzophenone backbones are highly
transparent. Not all of the hydroxyl groups need to be esterified with DNQ-
sulphonyl chloride and the degree of esterification varies widely in different
resists. The degree of esterification and the proximity of hydroxyl groups
determine the absorption characteristics of the resist and its sensitivity to a
particular wavelength.
The position of attachment of the ballast group to the DNQ moiety also
affects the absorption wavelength. The 2,1,4-DNQ PACs are better suited
for exposure with i-line radiation, whereas 2,1,5-DNQ PACs yield a higher
light absorption and thus more efficient coupling of energy into the resist for
g-line radiation (Fig. 7.23).
A typical process flow for spin-coated photoresists used in semiconductor
manufacture is shown in Fig. 7.24.
7.3.2.2 Deep Ultra-Violet (DUV) Resist Systems

The ever-decreasing size of features on an IC requires reducing the
wavelength of light used to expose the photoresist and, as has already been
'----__P_H_O_T_O_R_E_S_IS_T_S_F_O_R_INT
__ EG_RA_T_E_D_C_I_R_C_v_I_T_P_R_o_D_v_c_T_I_o_N_----'l I 229
«x
o ~3
~
4
N2
Ballast-S02
2,I,S-PAC
«;~
o ~3
N2
5 4
S02-Ballast
2,1,4-PAC
Fig. 7.23. 2,1,5- and 2,1,4-DNQ PACs.
SILICON WAFER SPIN COAT

ADHESION PROMOTION PHOTORESIST
~-----1 SOFTBAKE
POST DEVELOP
BAKE
STRIP RESIST
Fig. 7.24. Photoresist process.

mentioned, optical lithography will eventually reach its limit. Alternative
lithographic technologies will then be needed which will also require new
resist chemistries. DNQ-based resists will be unsuitable for use with the new
technologies which will be used to resolve features much below 0.30 ~,
since the quantum yield is significantly less than 1.0 and the new
lithographic tools generally have low brightness sources. Therefore, highly
sensitive resists are required. Also, the non-bleachable absorption of
conventional photoresists is too high in the desired wavelength region to
allow uniform imaging through practical resist film thicknesses.
One way of improving sensitivity involves the concept of chemical
amplification. 31 This method employs the photogeneration of species,
usually acids, that catalyse many subsequent chemical events such as
deblocking of a protective group or crosslinking of a matrix resin, therefore
increasing the overall quantum efficiency. Chemically amplified resists
usually contain a matrix polymer, a photoacid generator (pAG) and a
moiety capable of being crosslinked or deblocked by the acid generated.
At the limit of optical technology is deep UV (DUV) photolithography,
and resist systems sensitive to krypton fluoride (KrF» or argon fluoride
(ArF) excimer laser radiation (248 nm and 193 nm respectively) can be
formulated based on the principle of chemical amplification. Laser sources
can provide narrow bandwidths with enough intensity to accommodate
resists that have sensitivities of 5~100 mJ/cm2.
DUV lithography at 248 nm has already been used for the fabrication of
prototype 64 Mbit DRAMs.32
In these resists, development immediately after exposure will not result in
a relief image in the resist and it is therefore necessary to have a thermal
enhancement step, in which the photogenerated acid either crosslinks
unsaturated functionalities or deprotects base-developable groups.
Chemically amplified resists can be placed in four main categories: 33 two-
component positive-tone; two-component negative-tone; three-component
positive-tone; and three-component negative-tone. Figure 7.25 shows two
mechanisms for a two-component positive-tone DUV resist. The first
example34 involves the acid-catalysed transformation of poly(t-butoxycar-
bonyl)styrene, which is insoluble in alkaline solution, to poly(hydroxysty-
rene), which is soluble. The second example35 involves a system which
combines a photoacid generator with a dissolution change agent in the same
molecule. The photoacid generated deprotects the t-BOC protected hy-
droxyl group which reacts with alkaline developers.
Figure 7.26 shows negative-tone imaging with two components, consist-
ing of a PAG and a self-crosslinking resin, comprised of p-vinylphenol and
vinylbenzyl acetate. 36 Benzyl cations formed during thermal enhancement
attack the phenolic groups to form links and regenerate the acid.
Crosslinking from one polymer chain to another greatly reduces the
solubility in alkaline developers.
PHOTORESISTS FOR INTEGRATED CIRCUIT PRODUCTION
L -____________________________________________________ ~II 231
_ fcH'Qi
+CH, Qi
+
OH
+ COl
+ CH1=C(CH3)1
OC01C(CH3)3 +
+H
Fig. 7.25. Two-component positive tone.
Positive-tone imaging with three components is shown in Fig. 7.27. The

system here is similar to the second example in Fig. 7.25, except the PAG
and dissolution inhibitor are separate components. A base soluble resin is
also used in this formulation. 37
Finally, negative-tone imaging with three components is shown in Fig.
7.28. Resists in this category38 consist of a crosslinkable resin, an acid, a
heat-activated crosslinking agent and a PAG. A phenolic polymer cross-
linking with a melamine derivative is shown.
It can be seen that most chemically amplified systems for 248 nm DUV
resists are based on phenolic polymers. Phenolics give good coating
qualities, requisite adhesion, high Tgs, good plasma etching resistance,
aqueous development without swelling and a variety of chemical reactivities
useful for dissolution rate manipulation. The absorption of the resin at
imaging wavelengths (248 nm) is at a minimum, whereas novolac resins
absorb strongly in this region.
Onium salts that produce Lewis acids on irradiation, such as aryl-
iodonium or arylsulphonium salts, are the most widely used PAGs. The salt
usually contains the hexatluorophosphate or hexatluoroantimonate anion.
/~ +CHZ OH
Fig. 7.26. Two-component negative tone.
HO--©-t-<Q>-OH
+ ZCOZ + ZCHZ-C(CH3>Z
Fig. 7.27. Three-component positive tone.

L-._ _P_H_O_T_O_R_E_S_IS_T_S_F_O_R_INT_E_G_RA_T_E_D_C_I_R_C_V_IT_P_R_O_D_V_C_T_I_O_N_----'! ! 233
RN(CH20-Ph- )2
Fig. 7.28. Three-component negative tone.
Other classes of PAG include o-nitrobenzyl esters of strong organic acids

such as sulphonic and fluorinated carboxylic acids 39 and halogenated
organic compounds. 40 The latter PAGs were developed for increased
thermal stability, to prevent any decomposition to acids in the unexposed
regions during the bake stages, since only very small amounts are needed to
catalyse the imaging reaction. Another resist for 248 nm imaging is based on
poly(dimethylglutarimide) which is a chemically stable aliphatic imide
polymer. On exposure, chain scission occurs which reduces molecular
weight and increases alkaline solubility.
DUV lithography at 248 nm is expected to be the preferred lithographic
technique for the next generation of ICs and is likely to be used for
producing geometries down to 0.18 !lm. However, there are still a number of
issues to be sorted out, one of the main ones being the instability of the
latent image between exposure and post-exposure bake. Clearly, a time-
dependent loss of catalyst or altered distribution could severely affect
photospeed and/or image quality. Excessive diffusion of the catalyst in
negative-working systems is known, leading to loss of image quality. In
positive-working systems, volatile basic substances present in the clean room
environment can neutralize sufficient amounts of the catalytic acid to
destroy the latent image at the top of the resist within minutes of exposure.
This can lead to dissolution inhibition and affect the image profile.
Photolithography at 193 nm is one of the main candidate technologies for
imaging devices with smaller dimensions than are possible with 248 om
radiation. Phenolic-based resists are unsuitable for use at this wavelength
because of their high absorbances. Polymers such as poly(methylmethacry-
late) have been used but their sensitivities are low. However, acrylic
copolymers have been incorporated into resists which are semi-transparent
at 193 nm and these lead to both high sensitivity (down to 10 mJ/cm2) and
high resolution (0.1 ~).41
These positive-working resists contain t-butylmethacrylate along with a
photo acid generator and work by a chemical amplification mechanism.
Iodonium salts are used as PAGs to generate a strong acid which cleaves the
t-butyl group freeing a carboxylic acid which dissolves in the developing
solution.
Other materials which appear to be popular candidates for 193 om resist
formulations include maleic anhydride alternating polymers that were
originally developed by Lucent Technologies (Bell Labs) and cyclic olefinic
polymers developed by the University of Texas.
Further details of recent progress in 193 om photoresists can be found in
the article by Allen. 51
7.3.3 X-ray and E-beam Lithography

It has been shown in the previous section that excimer lasers can be used to
image 0.25 micron features, but for even smaller features, new resists, masks
and optics will be needed. A great deal of progress is currently being made in
the fields of X-ray and electron beam lithography.
X-ray lithography 'shadow-prints' a mask image onto a substrate and the
shorter wavelengths used reduce diffraction effects to well below DUV
limits. Great constraints are being placed on mask fabrication since the
mask has the same dimensions as those desired on the chip pattern.
X-rays in the wavelength range 0.1-1.4 om can provide excellent
resolution, but as yet there is no lens that can adequately focus X-rays.
Another advantage is high resolution and in principle sub-0.1 micron
features can be imaged although various undesirable effects can conspire to
degrade performance. 42
Early work in X-ray lithography used electron beam bombardment
sources, but power was limited from such sources due to thermal effects.
Also, the distance between the mask and wafer needed to be relatively large
to minimize the penumbral shadowing that limits resolution. Because the
incident flux on the wafer was small, resists with sensitivities of less than
5 mJ/cm2 were required. This therefore limited the chemistry for resist
design. However, recent work directed towards step and repeat systems
using high intensity synchotron or laser-based radiation sources permits the
use of resists with sensitivities in the 50-100 mJ/cm2 range.
L -_ _P_H_O_T_O_RE_SI_S_T_S_F_O_R_I_NT_E_G_RA_T_E_D_C_I_R_C_U_IT_PR_O_D_U_C_T_IO_N--'I I
__ 235
The impact of X-rays with the resist generates electrons which have enough
energy to initiate chain scission (positive-working resist) or crosslinking
(negative-working). Therefore, most polymers that are sensitive to electron-
beam lithography are sensitive to X-rays. These materials will be described
later in this section after a brief description of electron beam lithography.
The resolution capability of e-beam systems is very high, since the size of a
focused electron beam can be as small as 10 nm. Also, due to the electron
size, there will be no diffraction effects occurring. The technique eliminates
the use of a mask, as the computer-generated beam, which is emitted by a
tungsten filament or lanthanum hexaboride source, is scanned over the
surface of the resist. However, the exposure time is longer than when using
optical lithography since electron beam writing is a sequential process and
because computer time is required to correct for 'proximity effects'.14
While virtually no scattering in organic materials occurs with X-rays, e-
beams show substantial forward scattering which causes the beam to expand
with its passage through the resist. With low energy electrons the
penetration depth into the resist is limited, whereas when high energy
electrons are used to minimize forward scattering, backscattering from the
resist and substrate becomes important. E-beam lithography is therefore
limited to direct-write applications of low volume logic chips and also to the
fabrication of high quality masks for optical lithography.
At high accelerating energies, polymer scission and crosslinking can
simultaneously occur, but materials can be chosen where one of the
mechanisms predominates to form negative or positive-working systems.
The response of the material to radiation is measured by the number of
chain scissions (Gs) or crosslinks (GJ that are produced per 100 eV of
absorbed energy and if the value for Gs is greater than that of Gx , scission
will predominate and the polymer will be a positive resist system. G is
determined by subjecting the polymer to cobalt-60 gamma radiation and
measuring the change in weight and dispersivity of the polymer. The Gs
values for positive-resist systems can range from 1.3 for polymethyl
methacrylate (PMMA), the benchmark for standard e-beam systems, to
10 for a polysulphone system and the Gx values for negative resists can range
from 0.1 for polyethylene to 10 for epoxy polymers. 24 The vast majority of
polymer systems will crosslink. DNQ-type systems are not suitable for use
as e-beam or X-ray resists since, because exposure is carried out in a
vacuum, there will be no water to react with the ketene to give an indene
carboxylic acid.
Figure 7.29 shows the mechanism of chain scission in PMMA, which
shows extremely high resolution (due to no swelling in developing solution),
ease of handling and gives excellent film forming characteristics, but is
relatively insensitive. The sensitivity ofPMMA can however, range from 50
to 200 mC/cm2 depending on the molecular weight. Structures with line
widths down to 10 nm have been created when using PMMA.43
CH3 CH 3
-fCH2-?-CH2-t~
yO {O n
OCH3 OCH3
+ co + C02 + CH3' + CH30'

Fig. 7.29. Chain scission in PMMA.
Figure 7.30 shows modified PMMA systems which have been developed
for use as more sensitive positive e-beam resists.
Poly(butene-I-sulphone) which is an alternating 1:1 polymer of sulphur
dioxide with an alkene is a more sensitive positive resist with a Gs value of 10
and a sensitivity of 10 mC/cm2 (10 kV).44 This material has a rather low
stability and the stability has been improved by combining the polysul-
phone, as a sensitizer, with novolac-type resins. The coating capability and
thermal plasma resistance is improved in this system, which has a sensitivity
of below 5 mC/cm 2 (20 kV).45
A positive-working resist for X-ray lithography has been developed46
based on a 2:1:1 polymer of 4-t-butoxycarbonyl styrene (TBS) and sulphur
dioxide (Gs = 3.6). This material undergoes main chain scission on
irradiation followed by deprotection of the hydroxyl group catalysed by
the sulphonic acid produced from the interaction of the released sulphur
dioxide with water. This combination of scission and deprotection leads to a
high sensitivity (10 mJ/cm2 using a laser source at 1.4 nm). Positive-working
systems based on an alkenyl silane-sulphone copolymer, i.e. allyltrimethyl-
silane-sulphur dioxide, which enhances resistance to an oxygen plasma
without adversely affecting sensitivity (1.5 mCjcm2 , 20 kV) have been
formulated. 47
L--_ _ PH_O_T_O_R_E_SI_S_T_S_F_O_R_I_NT_E_G_RA_T_E_D_C_I_R_C_U_IT_PR_O_D_U_C_T_IO_N
__ --'I I 237
Copolymer (15kV) Sensitlvlty Radiochemical

IIC/cm Z Gs value
PMMA 40 1.5
(X-CH3,Y-COZCH3)
X-CH3,Y-COZH 35 Z.O
X-CH3,Y-CN 14 3.5
X-H,Y-CN lZ 3.5
Fig. 7.30. Increasing sensitivity in acrylate resists.
Although there are more negative-working systems, they have been

limited in use by their tendency to swell in the developing solutions. The
initial molecular weight and polydispersity of these systems affects the
crosslinking density, exposure sensitivity and contrast.
Figure 7.31 shows the main types of negative-working e-beam resists in
use. The first two examples in the figure crosslink via chain reactions, but the
crosslinking can continue after irradiation due to the absence of oxygen to
terminate the reaction as well as the slow termination of radicals. 48 The
initiating species may be an anion, cation or radical. The process and
linewidth of the exposed image are difficult to control. The polystyrenes
shown in examples 3 and 4 are more thermally stable than epoxy-based
polymers and incorporation of a chlorine atom in the para-position of the
ring dramatically improves sensitivity.49 There is also no dark reaction with
these systems, however they do not suffer from swelling during develop-
ment.
The last example in Fig. 7.31 is an example of a non-swelling negative-
working e-beam resist, polystyrenetetrathiofulvalene (PSTTF).5o A three-
dimensional network is not generated in this case. The alteration of the
chemical nature of the side chain results in a large change in polarity and
therefore solubility characteristics of the material in the exposed areas.
Figure 7.32 shows a plot of e-beam v. X-ray sensitivity for a variety of
systems. A useful review of the current capabilities ofE-beam lithography is
given in reference 52. Another technique, ion-beam lithography, has been
238
I I CHEMISTRY OF LITHOGRAPHY FOR ELECTRONICS PRODUCTION
Sensitivity
1.
IH3
-l[cHZ-C CHZ---CHJ[- O.SpC/cm Z (lOkY)
10zcHzc6'~Hz !oz~
Z. IH3
-l[cHZ-Ct O.SpC/cm Z (lOkY)
L2;H2ciCO~HZ
-f·,-It
3.
20pC/cm Z (20kY)
©D
-{c·,-It
4.
< SpC/cm2
©D
C1
-f·,Jt
S.
©D, ,
(R)J: S>=<S)
Fig. 7.31. Negative working e-beam systems.
investigated to achieve high resolution. 41 This technique is similar to e-beam

lithography, but as ions scatter less than the smaller electrons, much higher
resolution is possible.
7.4 CONCLUSION
It appears certain that many exciting developments in electronics in the

future will result from the continual improvement in imaging techniques and
lithographic materials. The need to further decrease the size of features on
REFERENCES
I I 239
lOS
jH3
-+.J}
CH3
N
I
~
...,
"-
a fHZ-C---]f cHz-L
"-
0 10 4 I
COZCH3
I m
COZH I D
COZCH3
~:;
I
'"»"
f
,:,
...0 10 3 1"3 ~• •
::f: fHZ-Ct
Lze"HzciCO~HZ
""
Z
.. -+'-~'O'l
10
10
10-8
20k,V Electron Beam Sensitivity/ C/cm2
Fig. 7.32. E-beam v. X-ray sensitivity.
both PCBs and ICs will greatly increase the power of this technology. The
development of new, specialized polymeric materials will continue to feature
highly in this success.
7.5 REFERENCES
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2. Tilsley, G. M. and Roos, L., Circuit World, 13(1), 1986.
3. Sato, J., Netsu Kokasei Jushi, 1993, 14(2), 92-103.
4. DuPont, US Patent 3,469,982.
5. Allen, D. M., The Principles and Practice of Photochemical Machining and
Photoetching. Adam Hilger, Bristol, 1986.
6. Chang, C. H., Mar, A., Tiefenthaler, A. and Wostratzky, D., Photoinitiators:
mechanisms and applications. In Handbook of Coating Additives, ed. L.J. Calbo,
Dekker, New York, 1992, pp. 1-50.
7. IBM, US Patent 5,045,431 (1991).
8. Wallraff, G. M. et al., J. Imaging Sci. Technol., 36, 468, 1992.
9. Steppan, H., Buhr, G. and Vollmann, H., Angewandte Chemie Int. Ed. Engl., 21,
455, 1982.
10. Rohm and Haas, US Patent 4,592,816 (1986).
11. Sugiura, T., Journal of the SID, 1, 341, 1993. (a) Barr, R. K., Morton
International Inc., US Patent 5,364,737 (1994). (b) Shida, N., Ushirogouchi, T.
and Nakase, M., J. Photopolymer Sci. Technol., 1995,8, 173-178.
12. Merricks, D., Electrodepositable resists. In Special Polymers for Electronics and
Optoelectronics, ed. J. Chilton and M. T. Goosey, Chapman and Hall, London,
1995.
13. Kansai Paint Co. Ltd, U.S Patent 4,965,073 (1990).
14. Kansai Paint Co. Ltd, European Patent 0,383,223 (1990).
15. Rohm and Haas Co., US Patent 4,592,816 (1986).
16. Ciba-Geigy Co., US Patent 5,080,998 (1992).
17. Nippon Paint Co. Ltd, US Patent 5,055,374 (1991).
18. Nippon Oil Co. Ltd, European Patent 0,441,308 (1991).
19. Ciba-Geigy Co., US Patent 4,632,900 (1986).
20. Kurisu, V., PC Fabrication, 1990,66.
21. Rembold, K.-H., Polymerisable epoxy resins and their application in the field of
printed circuits. In Proc. 1st Printed Circuit World Convention, London, 1978.
22. Shipley Co. Ltd, European Patent 0,502,382 (1992). (a) Knudsen, P., Brainard,
R. and Schell, K., In Proc. Surface Mount International Conference and
Exposition, San Jose, 1993, pp. 203-216. (b) Clark, E., Transitioning to MCM
production, Printed Circuit Fabrication, 16(20), 69--73, 1993. (c) Enomoto, R.,
Asai, M., US Patent 5,055,321 (1991).
23. Morton International, Inc., European Patent 0,546,768 (1992).
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Polymers for Electronic and Photonic Applications, ed. C. P. Wong, Academic
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25. Heuberger, A., Lithography production techniques for the next generation of
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H. Henke, H. Homeyer and C. Petit-Jean-Genaz, Frontieres, Gif-sur-Yvette,
1992, pp. 192--6.
26. Dammel, R., Diazonaphthoquinone-based Resists, SPIE Optical Engineering
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27. Hanabata, M., Furuta, A. and Uemura, Y. Proc. SPIE Advances in Resist
Technology, 68, 76-82, 1986.
28. Templeton, M. K., Szmanda, C. R. and Zampini, A., Proc. SPIE 771, 1987,
136--47.
29. Reichmanis, E., The chemistry of polymers for microlithographic applications.
In Polymers for Electronic and Photonic Applications, ed. C. P. Wong, Academic
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30. Trefonas, P., Daniels, B. K. and Fischer, R. L., Solid State Techno/., 30, 131,
1987.
31. Reichmanis, E., Po/ym. Mater. Sci. Eng., 66,36-37, 1992.
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1991.
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34. Ito, H. and Wilson, C. G., Polymers in Electronics, ACS Symp. Ser. Vol. 242, ed.
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Ferroelectric Polymers 8
JOHN A. CHILTON
Bosworth College, Nazareth House, Barrack Road,
Northampton, UK
8.1 INTRODUCTION
The following chapter considers the science and application of electroactive

polymers. Within this area, polymers which are intrinsically 'active' will be
discussed along with polymers which themselves are inert, but have been
made active by the incorporation of a second (active) phase (usually a
ceramic material).
All crystalline materials may be categorized into one of 32 crystallo-
graphic point groups. Of the 21 which lack a centre of symmetry, 20 produce
an electric dipole (i.e. polarization) when mechanically stressed. These
materials are termed 'piezoelectric'. Ten of these classes possess a permanent
electric dipole and (using similar nomenclature as magnetic phenomena), are
called 'ferroelectric'. They also respond to changes in temperature and are
called 'pyroelectric'.
The generation of an electric dipole as a result of applied stress is known as
the piezoelectric effect. This was first recognized in the 1880s, but it was not
until the 1940s that major breakthroughs were made with the discovery that
certain ceramic materials (e.g. barium titanate and lead zirconate titanate
(PZT» were ferroelectric and could be rendered piezoelectric by application
of an electric field, a process known as 'poling' (described later). PZT has
been the preferred piezoceramic for many years and has been utilized in a
variety of piezoelectric transducers for in-air and underwater applications.
A full list of chemical acronyms and symbolism used in this chapter can
be found at the end of the chapter.
244 II FERROELECTRIC POLYMERS
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~
8.1.1 Ceramics
PZT is derived from the solid solution of two perovskite materials,
tetragonally distorted lead titanate (PbTi03) and rhombohedral lead
zirconate (pbZr0 3). The anisotropic nature of this material, especially at
the morphotropic boundary between the tetragonal and rhombohedral
phases, makes it a particularly strong piezoelectric.
The performance of PZT as a transducer material is none the less limited
by the conflicting nature of its piezoelectric and dielectric properties:
1. In hydrostatic mode, the induced electric polarization per unit strain (dh )
is determined by the tensor elements d33 and d31 • The piezoelectric strain
coefficient is given by
(8.1)
and the large negative value of d31 (-170 pCN- I ) almost completely
cancels d33 (450 pCW I ).
2. The piezoelectric voltage coefficient (gh) is given by
dh
gh=- (8.2)
Sollr
This gives the electric field produced in the material, per unit stress
and the large dielectric constant of the material (1800) produces a very
low gh.
Further, the brittleness, high density and fabrication problems have limited
the exploitation of ceramic materials. Similar electrical properties in a
polymeric material would give considerable practical advantages for many
applications. The search for a superior material has considered both pure
polymers and polymer composites, where an active filler is used to produce
the electrical properties.
8.1.2 Polymers
Investigations into piezoelectric polymers extend as far back as the 1920s
when it was discovered that certain organic materials such as rubber and
celluloid could be rendered piezoelectric by cooling in an electric field. I
Investigations have also found detectable piezoelectricity in wood, bone and
tendon, DNA, polysaccharides and the polypeptide, poly-y-methyl-L-gluta-
mate. Small, unstable piezoelectric effects in commercially available
synthetic polymers such as polystyrene, polypropylene and polymeth-
ylmethacrylate were reported in 1968. However, the major breakthrough
came in 1969 with the discovery by Kawai 2 that stretched and poled
INTRODUCfION II
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polyvinylidene fluoride (PVDF) exhibited the largest known piezoelectric

activity of all polymers investigated at that time. Since this discovery and the
detection of pyroelectric activity in PVDF in 1971, extensive research and
development has been conducted on this material, leading to a variety of
applications detailed later in this chapter.
Investigations in the 1970s were extended to include copolymers of
vinylidene fluoride (VDF) with related fluorinated vinyl monomers, vinyl
fluoride (VF), trifluoroethylene (TrFE) and tetrafluoroethylene (TeFE).3,4
The latter two copolymers were found to crystallize into a polar form
without the stretching stage required by PVDF. This facilitates easier
processing, offering a wider range of potential device structures. Research in
the 1980s and '90s has therefore focused on the ferroelectric behaviour and
piezoelectric activity of the vinylidene fluoride-trifluoroethylene copolymers.
Investigations into alternative piezoelectric polymers, both semicrystalline
and amorphous have continued, and two of the most significant discoveries
are worth a brief mention. Of semicrystalline materials, the odd-membered
polyamides (or nylons), particularly nylon-ll, were found to exhibit
reasonable piezoelectric activity especially when mechanically oriented. 5
The highest piezoelectricity in an amorphous polymer was discovered in
19806 in a copolymer of vinylidene cyanide and vinyl acetate.
Although PVDF and the associated copolymers have advantages over the
brittle ceramics, they are also subject to limitations however. A low value of
d33 (20 pCN-I) inhibits its use as an active device. Its large negative value of
d3I (-4.5 pCN- I) lowers the hydrostatic strain coefficient, dh , and finally, the
material's low Curie temperature makes for a strong temperature depen-
dence of the piezoelectric coefficients and problems with depoling at higher
temperatures.
8.1.3 Composites
Piezoceramic/polymer composite materials are a means of overcoming the
limitations of both ceramic and polymer materials to provide complemen-
tary properties which produce a superior piezoelectric device. The polymer
phase lowers the density of the material providing a better acoustic coupling
to water as well as a more easily adjusted buoyancy than that obtained for a
high density homogeneous ceramic. The low dielectric constant of the
polymer phase effectively increases the gh coefficients and the figure of merit.
The high elastic compliance of the polymer provides a better resistance to
mechanical shock and exhibits the high damping required for a good passive
device. The polymer's flexibility allows the composite to form to any
reasonable profile. Finally, the piezoelectric properties of the ceramic are
easily adjusted within the composite as they may be tailored via the
connectivity patterns (discussed later) to impart the maximum piezoelectric
response to the unit.
246 I LI______________F_E_R_R_O_E_L_E_C_T_R_I_C_P_O_L_y_M__E_R_S____________~
8.1.4 Overview
This chapter will initially be concerned with intrinsic ferroelectric polymers
and then move on to ferroelectric polymer composites. Texts are available
for a more detailed discussion of these and ceramic materials. 7 Material
preparation and properties are discussed along with a comparison of the
electroactive properties. After applications, a final brief section introduces
so-called smart materials. These have the potential to revolutionize both the
properties of devices we presently manufacture and the philosophy we use in
the design process.
8.2 ELECTROACTIVE POLYMERS
8.2.1 Polymer Synthesis

For ferroelectric use, the only practical polymers are PVDF, formed by the
linking together of simple VDF (l,l-difluoroethylene) molecules, and the
VDF-TrFE copolymer which consists of both VDF and TrFE molecules
linked together in the same chain.
The vinylidene fluoride monomer (CH2=CF2), is a relatively stable gas at
normal temperatures and pressures, boiling at -85°C. Commercially it is
produced by pyrolysis of more readily available precursors such as
trifluoroethane.
CF3 CH3 ----+) CH2=CF2 + HF
heat
Laboratory preparations are normally carried out in the liquid phase, a

typical route being the reaction of alcoholic potash with halogen substituted
ethane.
CHF2CH2Br + KOH (alcoholic) - - - + ) CH2-CF2 + KBr + H 20
heat
Trifluoroethylene, CHF=CF2. is also a gas at normal temperatures and

pressures, boiling at -52°C. It is slightly less stable than vinylidene fluoride
and a polymerization inhibitor is normally added to bulk quantities to
prevent premature reaction. Preparation is by routes analogous to those
used for vinylidene fluoride.
Polymers are prepared from the monomers by free radical polymerization
in suspension or emulsion, with water as the reaction medium. These two
routes are superficially similar but differ in the location of the organic
peroxide free-radical initiator and in the kinetics of the reactions. An
account of the reaction is given in most general texts on polymer
chemistry.8,9
It should be noted that the correct choice of initiator, and any other
additives necessary for efficient polymerization, is crucial to the preparation
L -_____________ E_L_E_CT __E_R_S____________~I
__R_O_A_C_T_I_V_E_P_O_L_y_M I 247
of material for use as a ferroelectric polymer. This is because of the essential

requirement to subject the polymer to very high electric fields to render it
electrically active (a process known as 'poling'). Any conductive residues in
the polymer can make poling very difficult, or in extreme cases impossible,
due to the high probability of dielectric breakdown. Because of this, details
of polymerization methods used to prepare commercially available, electri-
cally active material are not generally accessible.
Polymerization of the fluoro monomers is carried out at temperatures in
the range 20-60°C and at pressures up to 60 MPa. Even in the case of the
simple self-addition of vinyl fluoride molecules, the precise reaction
conditions have a significant effect on the detailed structure of the resulting
polymer. Because the molecules are not symmetrical they can link to each
other in the chain in three possible ways. These are the normal, and
energetically favourable 'head to tail' configuration (producing electrically
inactive material) or the so-called 'defect' combinations of 'head to head'
and 'tail to tail'.4 The effect of the low fraction of these defects present in the
poly (vinylidene fluoride) prepared by standard routes is small and the
polymer crystallizes from the melt in a non-polar form. In contrast to this,
the polymerization of a mixture of vinyl fluoride and trifluoroethylene
monomers results in many 'head to head' sequences, the effect of which
causes the polymer to crystallize in a potentially active form, a structure
only attainable in poly (vinylidene fluoride) by vigorous mechanical re-
orientation.
8.2.2 Polymer Structure

As stated in the previous section, there are three chain conformations of
PVDF. The two most common forms are described in this section. For a
more detailed explanation the reader is referred to the text by Lovinger.1O
Crystallization from the melt or solution produces the most common
polymorph of PVDF, the IX-phase (also known as form II). The chain
conformation, is trans gauche + trans gauche- (tg + tg-); see Figure 8.1(a).
Each chain conformation possesses a net dipole moment, originating from
the CF 2 bond, with a component perpendicular to the polymer chain. In the
case of the tg + tg- conformation the dipole components normal to the chain
axes are antiparallel and thus cancel each other. Therefore the IX-phase is
non-polar.
Transformation from the IX-phase to the polar p-phase (also known as
form I) is achieved by mechanically stretching or rolling at elevated
temperatures. This extends the polymer chains to the all-trans conformation
(Figure 8.1(b». As all the dipoles are normal to the chain axes, on a
microscopic scale, each crystallite has a net dipole and is piezoelectric.
However, on a macroscopic scale, there is zero polarization within the
polymer film due to random orientation of the crystallites. The final stage in
~----------------------------------------------------~
Key
® Carbon
® Hydrogen
® Fluorine
(a) (b)
Fig. 8.1. Schematic of the two most common chain conformations of PVDF: (a) IX-
phase (b) p-phase. Arrows indicate -CF2 dipole directions defined by the carbon
backbone.
rendering the PVDF film piezoelectric is known as poling and involves the
application of an electric field. This preferentially orients the crystallites in
the direction of the poling field, thus producing a net polarization.
In the copolymer of vinylidene fluoride and trifluoroethylene, the
increased number of comparatively large fluorine atoms prevents the
formation of the tg + tg~ conformation by replacing hydrogen atoms on
adjacent carbon atoms. This forces the molecular chains to crystallize
directly into the polar fJ-form. The copolymer film then undergoes a poling
stage similar to PVDF to make it fully piezoelectric.
8.2.3 Mechanical Processing and Fabrication
8.2.3.1 Introduction
Both PVDF and its copolymer with TrFE are thermoplastic and as such can
be easily processed in conventional thermoforming equipment. PVDF has a
combination of processability, mechanical strength and chemical resistance.
Because of this it has found a niche in the speciality polymers market
ELECTROACTIVE POLYMERS
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~ 249
unconnected with its unusual electrical properties."-13 The copolymer is a

similar material to PVDF and, whilst as yet no large commercial usage has
emerged, the same processing methods can be used.
The ease with which a plastics material such as PVDF can be formed into
large areas or complex shapes is one of the significant advantages that
polymer ferroelectric materials have over the conventional ceramic types.
8.2.3.2 Thin Films

Historically, nearly all the early investigations into the ferroelectric
properties of PVDF were carried out on thin ("" 25 jlm) films. This was
necessary to orient the material and develop an incipient ferroelectric
structure. This is most conveniently done by using conventional thin film
making equipment which stretches a pre-formed polymer strip in either one
or two in-plane directions. Additionally, very high fields (typically
100 kV mm- I ) must be applied to the oriented polymer during the poling
process to develop the ferroelectric properties. Practical considerations of
voltage availability and safety therefore set an upper limit on the thickness
of films which can be conventionally poled.
Uniaxial Film
The most straightforward method of mechanically producing a thin film is
to stretch it in one direction only. In the laboratory this can be done by
applying a load to one edge of a preformed sheet held at elevated
temperature. The load and the temperature are adjusted to produce
elongation, typically about four times the original length.
Commercial production methods involve passing a continuous band of
polymer through two pairs of rollers rotating at different speeds, in some
variants of this process the polymer strip passes over two single rollers. If the
second pair (or single) roller is rotating faster than the first then a stretching
force is applied to the polymer, the amount of stretch achieved depending on
the relative rotational speed of the two rollers. As with laboratory
stretching, the polymer is held at a suitable elevated temperature during
the operation. Material produced by stretching along one axis is termed
uniaxial. The polymer is oriented by this stretching and the mechanical
properties in the stretch direction are very different from those in the in-
plane direction perpendicular to it. Properties, especially tensile strength, are
enhanced in the stretch direction although this is accompanied by a
transverse strength reduction.
Biaxial Film
Film which is as strong as possible in both directions is often required. This
has led to the development of techniques for stretching in two mutually
perpendicular in-plane directions. Typically, a combination of longitudinal
250 I IL-_____________F_E_R_R_O_E_LE_C_T_R_I_C_P_O_L_YM
__E_R_S____________~
stretching using rollers followed by tentering where the edges of the film are
gripped in clamps running in divergent tracks is used. Specialized machines
have also been made which stretch film in two directions simultaneously.
Film produced by stretching in two directions at right angles is said to be
biaxially stretched. Strength is enhanced in all in-plane directions, although
not to the extent achieved in a single direction with uniaxial stretching.
The salient feature of these two methods of film production is that both
the uniaxial and the biaxial films are oriented in the way necessary to allow
the production of electrically active ferroelectric material by poling, so that
a single process not only produces a thin film, but one which is suitable for
conversion into an electrically active form.
Film Casting
Thin films can also be made by flowing a solution of a polymer onto a
smooth surface. After the solvent has evaporated the film is stripped from
the casting surface. Film thickness, can be controlled by adjusting the
viscosity of the polymer solution (by varying its concentration) and by
defining the depth of the deposited solution through the use of a roller or
sharp movable edge (,doctor blade'). Both PVDF and its copolymer with
TrFE can be successfully cast into thin films from ketone solutions. In the
case of PVDF, the resulting film is not oriented although it has been
reported that oriented material can be produced under some conditions
using specific solvents. 14 The copolymer film produced from ketone solution
is oriented and needs no stretching stage before poling. This is a
considerable practical advantage over PVDF.
8.2.3.3 Sheet Production

For some ferroelectric applications, polymer sheets of 1-2 mm thickness are
required. Commercially, this can be produced by extruding molten polymer
through a die of the appropriate cross-sectional shape and size. The hot
extrudate can be led over or through pairs of cooling rollers or into a
cooling liquid before it is cut into individual sheets or wound into a roll.
On a small scale, compression moulding, where the requisite quantity of
polymer pellets is introduced into a hot mould of the desired dimensions and
pressed into a homogeneous mould-sized sheet, has been found satisfactory.
Neither of these methods produces any significant orientation; this is
immaterial in the case of copolymer which is self-orienting but a further
stretching stage would be essential after sheet formation in the case of
PVDF.
8.2.3.4 Simple Three-dimension Structures

In the case of the PVDF-TrFE copolymer, advantage can be taken of its
self-orienting property to fabricate potentially electrically active structures.
POLING II
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~ 251
Attempts to thermally form oriented PVDF inevitably lead to loss of

orientation which is not easily recovered. Copolymer is more useful in this
respect as it reverts to the oriented form on cooling. Simple hemicylinders
can be formed from copolymer sheet by heating and bending round a
former. Shapes such as domes can be made by using heat and vacuum to
force the sheet to conform to a shaped master.
More complex shapes are possible by the use of injection moulding,
although the need to pole the active area with high fields must always be
considered, especially if the shape produces sharp edges or material thinning
(e.g. at corners).
8.3 POLING
The poling process is where the electric dipoles in a material are

preferentially aligned in one particular direction defined by the direction
of an applied electric field. This has to occur in electro active ceramics,
polymers and composites. Although this section is located in a discussion of
polymers, the comments equally apply to all three materials.
The conditions with which the ferroelectric material is poled are crucial in
determining its final electrical characteristics. The amount of net polariza-
tion produced as a result of poling is directly related to the level of
piezoelectricity. The higher the degree of polarization, the greater the
activity. There are two main poling techniques, conventional two-electrode
poling (commonly known as 'thermal' poling), and corona poling, each
requiring optimization of poling time, temperature and field to achieve
maximum polarization.
For thermal poling, the polymer film is first electroded on both sides. A
wide range of electrode materials can be employed e.g. painted-on silver
solutions, pressed-on metal foils and the more commonly used evaporated
or sputtered layers of chrome-gold or aluminium. A dc field is then applied
across the film thickness at an elevated temperature (typically 70-l00°C) for
a period of 15-120 minutes and then remains applied while the sample cools
to room temperature. The fields required to produce the maximum
polarization are just below the breakdown strength, typically 30-
120 kV mm- I . Figure 8.2 shows the piezoelectric strain coefficient as a
function of poling field for a 70:30 VDF:TrFE copolymer, illustrating that
saturation polarization occurs around 25 kV mm- I .
In corona poling, a corona discharge is produced by a needle electrode (or
an array of needles) at a high potential, a few centimetres above the top,
unelectroded surface of the polymer film. To provide a discharge path and
thus create a field across the sample, the opposite surface must be at ground
potential and is therefore metallized or in contact with a metal electrode. A
grid, at a lower potential, placed between the sample and the needle(s)
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~
40
~ :
..... ..
.-.. 38
-:
Z
U
~ 36
::l
•
"C
34
32
•
10 20 30 40
Poling Field (kVmm·')

Fig. 8.2. Piezoelectric strain coefficient d33 as a function of poling field for 70:30
VDF:TrFE copolymer. All film samples were poled at 100±2°C.
controls the intensity of the discharge, as illustrated in Fig. 8.3. Voltages of

typically 25--40 kV are applied to the needles with grid potentials of 5-
15 kV. The poling process can be completed at room temperature in a few
seconds, although higher and more thermally stable piezoelectricity has been
obtained at elevated temperatures. 15
PTFE FEI· + - - -- - - + - -t-- Needle
PC?lymer
Grounded
healable
plale
Fig. 8.3. Typical corona poling arrangement.

ELECTROACfIVE COMPOSITES
L -____________________________________________________~ II 253
Corona poling offers advantages over conventional thennal poling. The

absence of electrodes eliminates shorting problems during poling when there
is an electrical breakdown or defect in the polymer film. It is also more
adaptable to continuous production. However, success at achieving max-
imum polarization, particularly for thicker films ( > 40 J.lm) is more
dependent on experimental set-up than the thennal poling technique. It
should also be noted that if a material contains defects producing a
relatively high conduction path, neither technique will work, the sample
requiring either too much current or charge.
8.4 ELECTROACTIVE COMPOSITES
8.4.1 Composite Designs

Composite materials are so-called because they involve the mixing of two
different materials in order to improve on their individual limitations
without significantly reducing their advantages. Combining materials
involves not only choosing the correct components but also coupling them
in the optimum way. The type of phase coupling (or connectivity) is of
utmost importance because this controls the electric flux patterns which
exist within the sample as well as the mechanical properties. Symmetry is a
second important consideration since symmetry and properties are interre-
lated through tensor coefficients. In this regard there are several levels of
symmetry to be considered:
1. the crystallographic symmetry of each phase,
2. the phase symmetry after processing,
3. the combined symmetry of the composite,
4. the environmental influence on the total symmetry including electrodes
and clamps.
The physical and chemical properties of composites will depend on the
properties of the individual phases and may be conveniently classified as
either a sum, combination or product.
Sum Properties
A sum property is one where the composite coefficient depends on the
corresponding coefficients of the individual phases. For example, the
pennittivity (6) of a two-phase (or diphasic) composite is given by
ff' = VIe'! + V2e2 (8.3)
where £1 and £2 are the dielectric constants of the constituent phases and VI
and V2 are their volume fractions. The exponent (n) is + I for parallel mixing
and -1 for series mixing. For many composites, the geometric arrangement
is between these two extremes, in which case £ can often be described by a
logarithmic mixing rule for which n is non-integer.
254 I F_E_R_R_O_E_L_ECT
L I_ _ _ _ _ _ _ _ _ _ _ _ _ _ __RI __E_R_S____________~
__C_P_O_L_YM
Combinational Properties
A combinational property is one in which the composite coefficient depends
on two or more coefficients of the individual phases (which may average in
different ways). For example, the acoustic wave velocity determines the
resonant frequency for a piezoelectric device. The velocity is in tum
dependent on the Young's modulus and the density of the phases.
Product Property
A product property utilizes different properties in the two phases to produce
a third property through the interaction of the phases. For example, a
magnetoelectric composite can be made from a ferroelectric and a
ferromagnetic phase. When a magnetic field is applied to the composite,
the ferrite grains change shape (due to magnetostriction) and the strain is
passed onto the piezoelectric grains, resulting in an electrical polarization. 16
8.4.2 Connectivity
The physical properties of a composite can change by many orders of
magnitude depending on the way in which phase connections are made. As
such, connectivity is a major feature in property development for multiphase
composites. Each phase may be self-connected in zero, one, two or three
dimensions producing the ten diphasic connectivities (illustrated in Fig.
8.4): 0-0, 1-0,2-0,3-0, 1-1,2-1,3-1,2-2,3-2 and 3-3. For example, a 2-1
connectivity pattern has one phase self-connected in two-dimensional layers
while the other is self-connected in one-dimensional chains (or fibres). The
connectivity patterns are not geometrically unique. In the case of a 2-1
pattern the fibres of the second phase may be perpendicular to the layers of
the first phase (as in Fig. 8.4) or they may be parallel.
By convention, in electro active composites, the first number refers to the
active phase and the second, the inactive phase.
Some of the more important diphasic connectivities will now be discussed.
8.4.2.1 3-3 Connectivity

In a 3-3 composite, both phases are continuously connected in all three
dimensions to give two interlocking skeletons. This type of structure is seen
in certain polymer foams and by biological substances such as wood and
coral. Two basic designs are particularly noteworthy and described briefly
below.
I. Replamine composites. This process utilizes the three-dimensionally
connected structure of the calcium carbonate coral skeleton as a template
for a PZT replica. The structure has the characteristics of a narrow pore
size distribution, a pore volume approximately equal to the solid phase
L -_____________ E_L_E_C_TR
__ C_O_M_P_O_S_IT_E_S____________~I
O_A_C_T_IV_E__ I 255
•••
••••
Fig. 8.4. Connectivity patterns in diphasic composites.
volume and complete pore interconnectivity making every pore acces-

sible from all other pores. The dimensions of the pores vary from species
to species, but within one species the size range is quite narrow. Different
species of coral have different degrees of anisotropy in their structure
ranging from a 3-1 connectivity of nearly parallel tubes to highly
isotropic 3-3 structures. The replamine process involves shaping the
coral (which is easily machinable) to the desired geometry. The coral
template is then vacuum impregnated with a casting wax and the wax is
allowed to harden before the calcium carbonate coral skeleton is leached
away in hydrochloric acid leaving a wax negative of the original coral
template. The negative is reversed with a PZT slip containing PZT, water
and poly(vinyl alcohol). The wax negative is burned off leaving a coral-
type structure of PZT which is then sintered. The PZT replica is back
filled with a suitable polymer.
2. BURPS composites. The Burned-Out Plastic Spheres composites in-
volves a technique that proves to be a far simpler means of fabricating 3-
3 composites. PZT powder is mixed with volatile polymethyl methacry-
late (PMMA) spheres in a 30/70 volume ratio. The mixture is die-pressed
using poly(vinyl alcohol) as a binder and the PMMA spheres are
256 I LI______________F_E_R_R_O_E_L_ECT __E_R_S____________~
__R_I_C_P_O_L_YM
Replamine BURPS Perforated Perforated

(3-3) (3-3) (3-2) (3-1)
Rods Multi-layered Particles

(1-3) (2-2) (0-3)
Fig_ 8_5_ Composite formations.
volatilized out by very slowly heating the pressed pellet to 400°C. After
sintering, the cold highly porous pellets are vacuum impregnated with a
suitable polymer: either a flexible silicone rubber elastomer or a stiff
epoxy resin. The finished product contains PZT regions ranging from 20-
120 11m that are randomly interconnected within the composite.
Both these composite types and the ones discussed below are shown
schematically in Fig. 8.5.
8.4.2.2 3-2 and 3-1 Connectivity

Both 3-2 and 3-1 composites have a three-dimensionally connected ceramic
phase. The second (polymer) phase is one- or two-dimensionally connected
within the ceramic network. This tends to produce extremely rugged
composites.
Perforated PZT-polymer composites have been fabricated l7 by drilling
holes in sintered PZT blocks and filling with epoxy. In some cases the
perforation was left empty but capped with alumina plates and the whole
structure encapsulated in epoxy - referred to as perforated 3-2-0 or 3-1-0
composites. The maximum hydrostatic piezoelectric coefficients attained for
these composites are generally significantly greater than those associated
with solid PZT and values of dh.gh have been reported that are greater than
200 times the figure of merit for solid PZT.

The 1-3 composite consists of a one-dimensionally connected ceramic phase
contained within a three-dimensional polymer phase. The shape of the
E_L_E_C_T_R_O_A_C_T_IV_E__C_O_M_P_O_S_IT_E_S____________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ I 257
ceramic may be any that is continuous in one dimension between two
opposing composite surfaces. The following designs have been investigated
extensively:
1. PZT rod design. IS The rod shape was chosen to minimize the composite
density and lower the dielectric coefficient Sf by reducing the volume
percent of PZT. The composite is made by arranging the prepared rods
in disc-shaped racks and covering them with epoxy.
2. Diced design. 19 An alternative method of producing 1-3 composites is by
dicing a block of PZT and subsequently back filling the spaces between
the posts with the polymer phase.
One of the advantages of this connectivity design is that most of an applied
stress is taken across the ceramic phase thereby amplifying the piezoelectric
effect.

Piezoelectric composites with multilayer structures (2-2 connectivity) have
been fabricated to produce high stability electrical filters.
Tape-casting provides a convenient way of making thin composite
layers.z° Here, a ceramic powder is mixed with an organic binder to form a
slurry which is spread in a continuous layer onto a substrate. After drying,
the binder hardens to give a flexible plastic tape impregnated with the
ceramic. This tape can be cut in the normal way. To fabricate multilayer
composites, the component layers are stacked alternatively and pressed
together at about 50°C to obtain a firm bond before firing.

Composites with 0--3 connectivity consist of a three-dimensional polymer
matrix loaded with discrete ceramic particles. These are the simplest
composites to make and although they do not have the desirable stress
concentration factors found in other connectivity patterns, certain distinct
advantages make them extremely interesting.
One of the most attractive features of the 0--3 design is its versatility in
assuming a variety of forms, including thin sheets, extruded bars and fibres
and certain moulded shapes. This type of composite is also easy to fabricate
and amenable to mass production. By using the right kind of polymer, the
composite can be made flexible to conform to curved surfaces.
Early attempts created a flexible composite composed of 5-10 f.Lm ceramic
particles suspended in a polyurethane matrix. The d33 coefficient was
comparable with that of PVDF but the dh value was lower than those of
solid PZT and PVDF polymer.
An improved version of the 0--3 composite incorporated modified lead
titanate because of its greater piezoelectric anisotropy.21 The lead titanate
258 I LI______________F_E_R_R_O_E_LE_CT
__RI __E_R_S____________~
__C_P_O_L_YM
filler is produced by water quenching the ceramic to exploit the high strain in
the material (approximately 7%) to produce fine powders. The average
particle size was about 5 J.lID. To fabricate the composite bodies, the
piezoelectric powders and chloroprene rubber were mixed and rolled into
0.5 mm thick sheets at 40°C using a hot roller and then heated at 190°C
under pressure. The composites were poled at 60°C for 20 minutes in silicone
oil with a field of 10 MV m-1. This produced a piezoelectric response
comparable with, if not better than, that of homogeneous PZT samples. In
addition, the density of the composite was 50% lower than that of PZT.
Although 0-3 composites appear to be simple in structure, many factors
are involved in the choice of polymer and filler materials, fabrication and
poling procedures. A large research effort has been mounted to optimize
these factors and make better 0-3 composites.
8.5 PROPERTIES OF FERROELE~TRIC MATERIALS
Ferroelectric materials are characterized by a range of electrical, thermal

and mechanical properties. This section gives a brief description of the
characteristics unique to ferroelectric materials before detailing the prop-
erties that are important in assessing an active polymer's suitability for
transducer applications.
8.5.1 Ferroelectric Behaviour

Most electro active polymers and polymer composites are insulating mate-
rials and so a film with electrodes on its top and bottom surfaces forms a
parallel plate capacitor with a capacitance C where
C = BoSrA (8.4)
t
and Eo is the permittivity of free space, &r the permittivity of the material, A
the overlap area of the electrodes and t the film thickness. An applied
voltage (V) generates a charge Q given by
Q=CV (8.5)
The surface charge density is called the electric displacement D therefore,
D=2 (8.6)
A
Combining equations (8.4) and (8.5) gives
BoSrV
D=--= BoSrE (8.7)
t
In linear dielectrics, D is directly proportional to E, increasing and
decreasing linearly with E. In ferroelectric polymers, such as PVDF and
PROPERTIES OF FERROELECTRIC MATERIALS
~----------------------------------------------------~
II 259
-50 so
Fig. 8.6. Typical D-E hysteresis loop for an electroactive polymer.
the VDF:TrFE copolymers, the surface charge density increases with field in
a non-linear manner and exhibits a hysteresis when the field is decreased,
with a significant amount of surface charge remaining when the field is
completely removed. Subsequent applications and reversals of the electric
field produce the characteristic D-E hysteresis loops shown in Fig. 8.6.
The amount of surface charge density that remains is termed the remnant
polarization P r and is caused by a net alignment of dipoles within the
crystalline phase of the material. When the direction of the electric field is
reversed the charge rapidly decreases and changes sign. The field at which
the polarization passes through zero is termed the coercive field Ee and the
time taken to switch from positive to negative polarization is called the
switching time "s.
Measurement techniques are based on a circuit developed by Sawyer and
Tower in 1930?2 For PVDF and the VDF:TrFE copolymers, typical values
for Pr and Ee are in the region of 5 JlCm-2 and 50 kVmm-I respectively.
Furukawa et al. 23 have shown that for PVDF, switching times of a few
microseconds can be obtained at room temperature with an applied field of
a few hundred kV mm- I . Further investigations into VDF:TrFE24 have
found that for a 65:35 molar composition at 20°C, "s decreases from I ms to
100 ns as field strength increases from 80 to 400 kV mm-I .
8.5.2 Dielectric Properties
8.5.2.1 Dielectric Constant

The dielectric properties of a material are characterized by the permittivity e,
or more commonly by its relative permittivity (or dielectric constant) er
where
260 I IL______________F_E_R_R_O_E_LE_C_T_RI__C_P_O_L_y_M_E_R_S____________~
(8.8)
and Bo is the permittivity of free space, 8.85 x 10-12 Fm-l.

The value of B,. can be calculated from equation (8.8) after determining the
capacitance C of a sample with known area A and thickness t. Techniques
for obtaining C are described in many physics textbooks 25 with a large
number of capacitance bridges on the market based on these principles.
The values of B,. quoted for PVDF range from 10-12 at 1 kHz, depending
on the manufacturer. For VDF:TrFE copolymers, Br varies with molar
composition, reaching a maximum at 55:45 VDF:TrFE. This maximum
value at room temperature has been reported to be as high as 15,26 although
values nearer that of PVDF are normally observed. These values are over
two orders of magnitude lower than those of piezoelectric ceramics. This can
be seen as a disadvantage in some applications, such as long-range
hydrophones, which require materials with a high capacitance to allow
the signals produced to travel large lengths of cable with the minimum of
sensitivity loss due to cable impedance. Therefore, for piezoelectric polymer
devices, it is necessary to have an external pre-amplifier close to the
transducer to drive the cable.
8.5.2.2 Dielectric Loss

With alternating voltages, the charge stored on a dielectric has both real (in
phase) and imaginary (out of phase) components caused by resistive leakage
or dielectric absorption respectively. The dielectric permittivity is therefore a
complex quantity
B = i-jB" (8.9)
where s' is the real component and s" the imaginary part. The dielectric loss
or tan(be) is defined as
(8.l0)
A dielectric with capacitance C and dielectric loss tan(be) has an equivalent

conductance G at a frequency f where
G = wC tan(be) (8.11)
with w, the angular frequency equal to 2nf.
The noise voltage V0 produced by this conductance is given by the
expression for Johnson noise in a resistor
Vo= (8.12)
and the equivalent noise current i

P_R_O_P_ER_T_I_E_S_O_F_F_E_R_R_O_E_L_E_C_T_R_IC
L-_______ __M_A_T_E_R_IA
__ L_S______ ~I I 261
(8.13)
kB is Boltzmann's constant (1.38 x 10-23 J K-1) and T the absolute
temperature of the material. Thus the value of tan(c5e) quantifies the
amount of electrical energy dissipated into thermal energy. This is an
important consideration when designing and evaluating piezoelectric
transducers and normally needs to be as low as possible.
Values of tan(c5 e) can be calculated from conductance measurements or
obtained directly using modern capacitance bridges. Polymers are compar-
atively lossy dielectrics. Typical room temperature values of tan(c5e) for
PVDF range from 0.015 to 0.020 at 1 kHz and for VDF:TrFE from 0.015 to
0.025, compared with values of 10-4 for some ferroelectric ceramics such as
lithium tantalate and lead germanate. Composite materials tend to have
tan(c5e ) values somewhere between the values for the two pure phases.
8.5.2.3 Temperature Dependence

Unlike PVDF, the VDF:TrFE copolymers exhibit a distinct ferroelectric to
paraelectric phase transition when heated between room temperature and
the melting temperature. This transition can be seen in plots of Er as a
function of temperature, where &r shows a peak (dielectric anomaly) around
the Curie temperature, Tc. Figure 8.7 shows plots of Er and tan(c5e) vs
temperature for copolymers with molar ratios 56:44, 70:30 and 80:20
VDF:TrFE.
It can be seen that Tc increases with VDF content, ranging from 70°C for
the 56:44 composition to 121°C for the 80:20 VDF:TrFE. Phase transitions
for copolymers with VDF contents higher than 80 mol% are difficult to
detect as Tc is near the melting point. This offers an explanation to the fact
that a phase transition has not been observed in PVDF. The Tc of
copolymers rich in VDF show a large thermal hysteresis, as seen with the
70:30 and 80:20 compositions, with Tc much higher on heating than on
cooling. This hysteresis is also exhibited by tan(c5 e), however the peaks occur
at temperatures 5-lO°C lower than the peaks in Er. It is also interesting to
note that copolymers with VDF contents below 40 mol% show only a
modest dielectric anomaly,27 indicating it is the VDF content that is
responsible for the copolymer's ferroelectric behaviour.
8.5.3 Thermal Properties
8.5.3.1 Glass Transition

In common with most polymers that are completely or partly amorphous,
ferroelectric polymers experience a phase change at the glass transition
temperature Tg. Below Tg, the polymers are hard, rigid glasses. At Tg and
60 80
- - Dielectric CONtont - - Dielectric constant
.....M_. Dielectric 10.. 70 ........... Dielectric 10..
10
50
[ _ H••ting
10
60 _Heating
- Cooling - Cooling
50 t
56:44
VDF:TrFE g ~40
1! 70:30 g
::I VDF:TrFE ::
.2
i§ : [
.Il 20
.5! §.. 3D r
.. :5 :S 20
j j
.,~ .51 o
0
10 ! 10
60 80 100 20 40 60 80 100
20 40
Temperlture ('C) Temperature ('C)
50
- - Dielectric constant
.M........ Dielectric losl
16
.or- _Heltlng 14
12
~ 30
~j f-~~ 80:20 10 g
I 20
VDF:TrFE ~.' j
.j! / I :S
j ~"./ j!
'V 10 ........ .......! ..)",......................... .91
............ 0
20 40 60 80 100 120 140

Temperature ('C)
Fig. 8.7. Temperature dependences of Er and tan(b) for 56:44, 70:30 and 80:20 CDF:TrFE copolymers.
PROPERTIES OF FERROELECTRIC MATERIALS
L -____________________________________________________~ II 263
above, the polymers become flexible and elastomeric. Brittle, rigid polymers
have a Tg above room temperature, for example, polystyrene has a Tg of
100°C. Rubbery or elastomeric materials have a Tg below room tempera-
ture. This is the case for PVDF and the copolymers which have Tg in the
region of -40°c.
The mechanical properties of polymers show significant changes at
temperatures close to the glass transition. In some cases, this amounts to a
decrease in elastic modulus by a factor of over 1000 times. This effect on the
mechanical properties will be passed onto the piezoelectric properties of
PVDF and VDF:TrFE through the relationships described in later sections.
The glass transition temperature can be determined by measurement of
elastic constant as a function of temperature using dynamic mechanical
thermal analysis (DMT A).
8.5.3.2 Melting Behaviour

The melting points, Tm of PVDF and the copolymers can be ascertained
through conventional differential scanning calorimetry (DSC) or differential
thermal analysis (DTA) techniques. The single endothermic peak observed
for PVDF26 indicates a melting point at approximately 175°C. Copolymer-
ization is known to lower Tm due to shortening of the crystalline sequences.
Thus, the melting points of the VDF:TrFE copolymers with 70-80 mol%
VDF are close to 150°C, rising to around 160°C for the 50-55 mol% VDF,
before increasing with increasing TrFE content to a Tm of 200°C for
polytrifluoroethylene (pTrFE). A second, smaller endothermic peak was
observed for the copolymers with VDF molar compositions between 50-
80%, corresponding to the ferroelectric to paraelectric phase transition.
8.5.3.3 Heat Capacity

The heat capacity of a material is defined as the amount of heat required to
raise its temperature by I Kelvin. In pyroelectric applications, it is more
common to use the heat capacity per unit volume of material, also known as
the volume specific heat Hy. Values for PVDF and the copolymers are
shown in Table 8.1 and its importance in pyroelectric devices is discussed in
section 8.5.4.
8.5.3.4 Thermal Conductivity

As polymers have relatively loose molecular structures, their thermal
conductivities are lower than those of ceramics. This should be considered
when assessing materials for applications where heat conduction is
important, such as pyroelectric detectors. Values of thermal conductivity
obtained for uniaxially stretched PVDF show there is a much higher effect
Table 8.1 Comparison of pyroelectric properties
Material p s. F. FD Ref
(p.G m-1JCi) (MJ m-3 JCi) (m1 ~i) (fm 1 !Vi)
PVDuniaxial 27 2.43 0.1 0.88 (a)

VDF:TrFE 20 2.07 0.1 0.69 74
56:44
PZFNTU· 380 2.5 0.06 5.8 40
Values in ref (a) based on manufacturers' data.

·PZFNTU: doped lead zirconate, a typical pyroelectric ceramic - see reference 40.
parallel to the draw direction (5.5 mW em-I K- 1) compared to the value of

1.25 mW cm- I K- I for the transverse '2' direction. 28
8.5.4 Piezoelectric and Pyroelectric Properties

In general, there are two characteristics to be considered when conducting
an initial assessment of a material's suitability for a device; firstly the
appropriate piezoelectric or pyroelectric coefficients to determine the degree
of sensitivity and optimum mode of operation, e.g. thickness or hydrostatic;
and secondly the effect of temperature on these properties, thus defining the
maximum and minimum operating temperatures at which the material can
be used efficiently.
8.5.4.1 Piezoelectric Constants

Piezoelectric materials generate an electric charge in response to a
mechanical stress. This is known as the direct piezoelectric effect, where
the charge per unit area or electric displacement D is proportional to the
applied stress T. There is also a converse effect, as an applied electric field E
produces a proportional strain S in the material, resulting in either
expansion or contraction, depending on the field's polarity. For both effects,
the proportionality constant is termed the piezoelectric charge constant, d,
thus
d=!!.=~ (8.14)
T E
There are three additional piezoelectric constants; the g constant gives the
field produced by a stress and is useful in determining the voltage output of
a stressed material; the other constants, e which relates T to E and h which
relates S to E are only occasionally used. As T and S are related by the
elastic constants c of the material and E and D are related by the dielectric
constant, the piezoelectric constants are interrelated to one another.
Therefore
L-_______P_R_O_P_E_R_T_IE_S__
O_F_F_E_R_R_O_E_L_E_CT
__R_IC
__M_A_T_E_R_I_A_L_S______ ~I I 265
d e
- = - = BoBr (8.15)
9 h
e h
-=-=C (8.16)
d 9
The fonnal definition and derivation of these piezoelectric relationships may
be found in Berlincourt et al. 29
The piezoelectric constants are tensor quantities, hence it is necessary to
assign a coordinate system to produce a matrix of coefficients which relate to
the symmetry of the crystal axis.
Anisotropy is introduced into ferroelectric polymer films by the poling
process which aligns the dipoles in the direction of the poling field. By
convention, this axis is known as the '3' direction, as illustrated in Fig. 8.8.
For PVDF, an additional anisotropy is caused by the mechanical stretching
procedure as discussed in section 8.2.5. The 'I' axis is parallel to the stretch
direction and the '2' axis is perpendicular to this in the plane of the film.
Thus, for polymer films with symmetry type 2 mm (i.e. uniaxially stretched
PVDF) the components of the piezoelectric charge coefficient are:
J= 2 3 4 5 6
0 0 0 0 dl 5 0
dij = (8.17)
2 0 0 0 d24 0 0
3 d31 dn d33 0 0 0
J;
\O~
'0<:>
~~~~<t
~~J>~
#'...~
~2
Fig. 8.8. Conventional of axes for electrical and mechanical coefficients.
266 I LI______________F_E_R_R_O_E_L_EC_T_R_I_C_P_O_L_Y_M_E_R_S____________~
where the i subscript denotes the direction in which the charge is generated
and the j subscript denotes the direction of applied stress (1 to 3 for uniaxial
stresses and 4 to 6 for shear stresses). The matrix for ferroelectric polymers
with symmetry type 2 mm, for example VDF:TrFE copolymers and
biaxially stretched PVDF, is similar except the '1' axis is equivalent to the
'2' axis, thus d15 = d24 and d31 = d32 .
The coefficients diS and d24 associated with shear deformation are seldom
used as there is a lack of practical applications using the shear mode. The
most important piezoelectric coefficients for determining a material's
suitability for a particular device are the d3j and g3j components and the
hydrostatic coefficients dh and gh. The dh coefficient is a measure of the
charge generated due to application of a hydrostatic pressure. As the stresses
are uniform in all three directions dh is simply the sum of all d3j •
dh = d 31 + d 32 + d 33 (8.18)
The d33 coefficient describes the charge generated through the thickness of
the film ('3' direction) due to a stress applied along the '3' axis. As it is
difficult to stress a thin film in the thickness direction without contributions
from d31 and d32 , the calculation of d33 is often done using equation (8.18) and
measured values of d3h d32 and dh. However, it is possible to obtain d33 via the
converse piezoelectric effect by using optical techniques, e.g. interferometry30
to measure the minute changes in thickness (less than a micron).
The transverse coefficients d31 and d32 can be obtained using compara-
tively simple strain removal techniques, with generated charge passing
through a capacitor to allow the subsequent voltage to be measured on a
digital storage osciIIoscope. 31
The dh coefficient can be recorded by subjecting the sample to a
hydrostatic pressure. Methods of achieving this include enclosing the sample
in a uniform, low frequency (50 Hz 32 or 80 Hz 33) sound field and
application of a I atmosphere (0.1 MPa) pressure pulse by rapid air ingress
of an evacuated chamber. 31 In all cases, it is necessary to immerse the test
sample in silicone fluid or oil to stabilize the temperature and eliminate
compressional adiabatic heating effects. The gh coefficient, calculated using
equation (8.16), is important in comparing materials for hydrophones,
particularly in the hydrophone figure of merit product FOM h
FOMh = dhgh (8.19)
tan(be )
A comparison of piezoelectric coefficients between uniaxially and biaxially
stretched PVD F, the VDF:Tr FE copolymers and PZT 5 is shown in Table 8.2.
It is clear that the ceramic has very high piezoelectric charge coefficients
(d) when compared to the polymers, but as Er is over 100 times greater for
the ceramic (1700 compared to 12), g is an order of magnitude lower.
Therefore, ferroelectric polymers will produce a higher voltage output per
unit applied stress. However, this advantage is balanced out when figure of
Table 8.2 Comparison of piezoelectric properties
Material d3J d32 d33 dh g33 gh dhfb)

tan (j
(pC !VI) (mV-m !VI) (pm 2 !VI)
PVDFuniaxial(a) 23 3 -33 -7 -310 -66 23

PVDFbiaxial(a) 7 7 -20 -6 -188 -56 17
VDF:TrFE74 21 21 -51 -9 -524 -92 39
56:44
VDF:TrFE74 17 17 -40 -6 -422 -63 15
70:30
VDF:TrFE74 9 9 -24 -6 -263 -66 16
80:20
PZT-5(a) 160 160 -420 100 -28 -7 39
<al Manufacturers' data.

268 I LI______________F_E_R_R_O_E_L_EC_T_R_I_C_P_O_L_YM
__E_R_S____________~
merits are employed for particular applications, such as FOMh , as shown by
the values of ~(/h/tan(!5e).
The d values for the copolymers increase with increasing VDF content.
This correlates with results obtained by Japanese researchers,26,34 who
observed a maximum in piezoelectric constant at a VDF content of 55
mol%. It is also worth noting the d31 /d32 values of the copolymers are higher
than those ofbiaxially stretched PVDF, an additional advantage besides the
elimination of the stretching stage required by PVDF. However, the highest
d31 value, exhibited by uniaxially stretched PVDF, can be exploited in device
configurations that are based upon the application of stresses along one
transverse direction.
8.5.4.2 Electromechanical Coupling Factors

The electromechanical coupling factor k, quantifies the efficiency of a
piezoelectric material as a transducer, converting mechanical energy into
electrical energy and vice versa. Thus
12- = co~verted energy (8.20)
mput energy
It can be defined from measurements of dielectric permittivity under
different mechanical constraints, clamped (E8) or free (ET). It is therefore
dependent on the shape of the specimen and its vibrational mode.
Analogous to the piezoelectric coefficients, k31 is the coupling factor
related to the transverse vibration, perpendicular to the polarized direction
and k33 is related to the vibration of thick specimens parallel to the direction
of polarization. Thus:
k _ d31 (8.2Ia)
31 - [ T E] 1/2
e Su
k _ d33
(8.21b)
33 - [ T E] 1/2
e s33
where s is the compliance, i.e. the ratio of strain in the direction annotated
by the first subscript to stress in the direction shown by using the convention
in Fig. 8.8. The superscript E indicates this is the value under short circuit
(constant electric field) conditions.
There are also another two coupling factors, kp, for the radial vibration in
the plane of the sample, and k t for the vibration of thin specimens along the
polarized direction, where
2
kp = k31 1/2 (8.22a)
[1 - CTE]
L -_ _ _ _ -..l1 I
P_R_O_P_E_R_T_IE_S_O_F_F_E_R_R_O_E_L_E_CI'_R_IC_M_A_T_E_R_I_A_L_S_ _ _ 269
5
kt = h33 B~3 (8.22b)
c33
and (J is the Poisson's ratio under short circuit conditions, h33 is the
piezoelectric constant in equation (8.16) and C33 is the ratio of stress to strain
under open circuit (constant electric displacement) conditions.
Values of the coupling factors are determined by the piezoelectric
resonance method. This analyses the impedance Z of the material when it is
excited by a voltage source and uses the resonant frequency at which Z = 0
and the anti-resonant frequency for which Z is infinite, to calculate the
appropriate k.35 This method is satisfactory for ceramics, but large errors
occur when applied directly to the polymers because of their large
mechanical losses and subsequent high damping effects. It is necessary to
use equivalent circuit models to select the parameters that produce
resonance curves that are best fitted to observed ones. 36
The most practical coupling factor is kt> which is important in evaluating
a material for applications such as ultrasonic imaging that exploit the
converse piezoelectric effect to produce sound waves. The values of k t for
PVDF (0.2) and VDF:TrFE (0.3)37 are approximately half that of PZT
(0.55). Thus for the same driving voltage, the ceramic will be a superior
transmitting material. However, the peak driving voltage that can be
applied without damaging the material is 25 V pm-I for the polymers and
0.3 V pm-I for ceramics, almost 100 times greater. The smaller coupling
factor can therefore be compensated for by using a larger driving voltage,
although in some applications, high voltages are undesirable.
8.5.4.3 Pyroelectric Constants

A pyroelectric material generates an electric charge when subjected to a
change in temperature. It must be emphasized that at thermal equilibrium,
the surface charges due to the material's internal polarization are not
observable as they are dissipated by internal space charges or electrical
conduction. It is only when the temperature of the pyroelectric is altered
externally by heat conduction or incident radiation that a change in
polarization occurs, resulting in a detectable surface charge.
This is quantified by the pyroelectric constant p with temperature T
AP
p = AT (8.23)
Thus the charge Q produced by an electroded area A is given by
Q=pAAT (8.24)
A typical pyroelectric detector element with a capacitance of 10 pF produces
a charge of 10-16 Coulombs. It is necessary to use a low noise, high
impedance field effect transistor (FET) as a source follower amplifier to
enable these small charges to be detected.
270 I LI______________F_E_R_R_O_E_L_EC_T_R_I_C_P_O_L_Y_M_E_R_S____________~
To assess pyroelectric detector performance it is necessary to ascertain its
response to a changing source of radiation and compare this signal with the
noise signals inherent in the detector and amplifier. The figures of merit used
to compare pyroelectric materials are briefly explained below, however
more detailed accounts can be found elsewhere. 38 ,39
A simple detector consists of an electroded element of pyroelectric
material with area A, thickness t, capacitance CE and emissivity 11. The
element is exposed to a radiation of power W, which is modulated at a
frequency,! The temperature of the element will also be modulated at this
frequency by an amount dependent on the material's heat capacity Hand
thermal conductance to its surroundings G, with a thermal time constant 'rT
where
H
'rT=- (8.25)
G
The electrical time constant 'tE of the amplifier is given by
Ra (8.26)
(CE + CA )
'tE=~--""'"
where Ro is the gate resistance of the FET and CA is the amplifier's

capacitance. The frequency response of the detector is determined by these
two time constants.
The pyroelectric current i generated per Watt of input power is defined as
the current responsivity, Rj, thus
i
Ri = W (8.27)
Similarly for the voltage responsivity Rv

V
Rv=- (8.28)
W
At low modulation frequencies, i.e. ro < 'tTl, both R j and Rv are proportional
to frequency. For ro>'tT I
R. = 11 P (8.29)
I Hv t
where Hv is the specific heat capacity per unit volume. The voltage
responsivity Rv reaches a maximum at ro = ('rE 'rT)-1/2 at a value
pARa
RvCmax) = G( 're+'tT ) (8.30)
It is clear from equation (8.30) that Rv (max) is optimized by reducing the

element's thermal capacity by using a thin sample and also by minimizing G
by thermally isolating it from its surroundings.
The high frequency (ro> 'rEljro > 'rTI) dependence of Rv is calculated
from
L -_ _ _ _ _ _ ~P~R~O~P~E~R~T~IE~S__O~F~F~E~R~R~O~E~L~E~C~T~R~I~C~M~A~T~E~R~I~A~L~S______~I I 271
R - YIP (8.31 )
v - Hvt(CE + CA)W
If the capacitance of the element is larger than the amplifier's capacitance
(CE > CA ) then
(8.32)
Therefore, under these conditions, the response is proportional to a figure of

merit Fv
(8.33)
However, if CA > CE then a second figure of merit Fi is given by

Pi = .L (8.34)
Hv
Equations (8.33) and (8.34) clearly show that materials with a high
pyroelectric constant and small specific heat capacity are required. However,
the final choice of material is dependent on the capacitance of the amplifier
to be used and the size of the detector element.
Materials with a small dielectric constant, such as the ferroelectric
polymers, are best suited to large area elements and vice versa.
In evaluating a pyroelectric detector it is important to know the minimum
power of incident radiation that can be detected. This is obviously related to
the responsivity but the noise levels produced by the detector and amplifier
must also be considered.
The major noise sources for a typical pyroelectric detector are the
dielectric or Johnson noise, the amplifier current and voltage noise and the
thermal noise, caused by fluctuations in the power flow from the element to
its heat sink. Each of these has an equivalent voltage generated at the
amplifier input, V D (given by equation (8.12)), Vi, Va, Vr respectively, which
combine to give the total equivalent input noise Vn by the equation
~2 = VJ + V;2 + v,,2 + r;.2 (8.35)
The noise equivalent power (NEP) expresses the incident power required to
produce a signal equal to the rms noise voltage, thus
NEP = Vn (units W Hz- 1/ 2) (8.36)
Rv
The reciprocal ofNEP is defined as the detectivity D, thus giving a figure of
merit which increases, rather than decreases, with improved detector
performance. The specific detectivity D* defined as
*vA
D =NEP
(units mHzl/2 W- I ) (8.37)
allows a comparison of detectors with different areas when the dielectric
noise dominates, which is true for many devices. The D* will then become
272 I ~I______________F_E_R_R_O_E_L_EC_T_R_I_C_P_O_L_YM
__E_R_S____________~
D* =RvVA (8.38)
Vn
On substitution of Rv and Vo from equations (8.32) and (8.12) respectively,
a further figure of merit Fo is derived, showing that D* will be optimized by
maximizing Fo where
Fn= p (8.39)
BvVereo tan{be )
However, this does not apply for small detectors operating at very low or
very high frequencies, as other noise sources dominate. In this case, the
detectivity will be maximized by maximizing Fv in equation (8.33).
All pyroelectric materials are piezoelectric. Thermal expansion of the
ferroelectric polymer induces a small secondary pyroelectric effect due to the
piezoelectric coefficients coupling to the strains produced on expansion.
Another undesirable signal is generated when the pyroelectric detector
operates in an environment that is acoustically noisy or highly vibrational.
This microphonic signal can be significantly reduced by mounting the
detector in a rigid, mechanically isolated package.
A typical technique for obtaining values of p involves the use of a
chopped radiation source, such as a laser beam or an infra red lamp. The
measured charge is then compared with a known calibration sample.
Values of p, Bv and the figures of merit Fv and Fo for the ferroelectric
polymers are shown in Table 8.1 against values for a typical pyroelectric
ceramic based on doped lead zirconate. 40 The pyroelectric constants of the
polymers are at least an order of magnitude lower than the ceramic and the
smaller Fo indicates an inferior detector performance. However, in terms of
cost, the polymers offer an advantage as they are readily available in large
area, thin sheets, eliminating slicing, lapping and polishing required by the
ceramics. It is interesting to note that the increase in piezoelectric coefficients
exhibited by the copolymers does not manifest itself in the pyroelectric
properties, although a room temperature value of 90 p.C m-2 K- 1 has been
reported for Japanese 51:49 VDF:TrFE copolymer. 41
8.5.4.4 Temperature Dependence

For all device applications it is necessary to know the effects of temperature
on the piezoelectric and pyroelectric properties; firstly to ensure the material
has sufficient thermal stability to withstand elevated temperatures without
significant loss in activity and secondly to determine if the level of activity
varies with changes in operating temperature.
Thermal ageing studies are carried out by measuring the room temper-
ature activity after known periods of time at an elevated temperature.
Ageing curves for the VDF:TrFE copolymers are illustrated in Fig. 8.9. The
ageing temperature of 70°C is representative of the maximum temperature
L -_ _ _ _P_R_O_PE_R_T_I_E_S_O_F_F_E_R_R_O_E_L_E_C_T_R_IC_M_A_T_E_R_IA_L_S_ _ _ -----li I 273
28
24
20 - - - - - 80:20
---------- 70:30
---56:44
16
12
- ...... -- .............. -_ ............ -_ ......... -_ ............................. -_ ..............................
13 % loss
...
8 _______________________ _
13 % loss
6S % loss
2 6 10 14 18 22
Time at 70°C (hours)

Fig. 8.9. Ageing curves for VDF:TrFE copolymers.
most devices could be subjected to under extreme (but conceivable) storage

conditions, such as direct sunlight. The degree of thermal stability is directly
related to the Curie temperature of the ferroelectric polymer, as this is the
point where it experiences a permanent loss in ferroelectricity and hence
piezoelectricity. Therefore, the 56:44 VDF:TrFE copolymer with a Tc of
70°C depoles rapidly at this temperature, losing 65% of its activity after
1 hour. With increasing VDF content and thus increasing Teo losses in the
coefficient reduce to 23% and 13% after 24 hours for the 70:30 and 80:20
VDF:TrFE respectively. The 56:44 molar composition is clearly unsuitable
for most device applications and it appears that the 70:30 VDF:TrFE offers
the optimum combination of piezoelectric coefficient and thermal stability.
PVDF has a similar ageing curve, losing 10% activity after 24 hours at
70°C. Tests with a 100% relative humidity at 70°C result in a 20% loss and a
higher ageing temperature of 90°C produces a greater than 50% reduction. 42
However, it has been shown that after the initial loss in coefficient,
reductions in activity are insignificant with further periods of ageing. Thus
the use of pre-aged film is desirable in devices with stringent thermal
stability specifications.
Temperature dependence observations for PVDF36 and the copolymers27
found an increase in piezoelectric charge coefficient beginning at the glass
transition temperature. In the case of the copolymers, this rise reaches a
274 I I~______________F_E_R_R_O_E_L_E_C_T_R_I_C_P_O_L_Y_M__E_R_S____________~
maximum at a temperature Tmax,just below Tc (50°C for 55:45 VDF:TrFE,
100°C for 72:28), before undergoing a sharp fall. This confirms that the
temperature dependence is related to the ferroelectric to paraelectric phase
transition. Similar behaviour has been observed for the pyroelectric
constane l and the electromechanical coupling factor k3)' although it must
be noted that the value of k33 is independent of temperature. 36
Providing the temperature does not go above Tmax, this effect of
temperature on piezoelectric and pyroelectric properties is reversible,
particularly for pre-aged film. Rises in temperature from 20 to 50°C result
in approximately a 60% and 40% increase in d31 and d33 respectively.36
Similarly for 56:44 VDF:TrFE p is raised from 20 to 40 p.C m-2 K- 1.31 This
could be a disadvantage in many applications and electronic compensation
may be required.
8.5.5 Mechanical Properties
8.5.5.1 Elastic Compliance and Stiffness

It can be seen from the above sections that the mechanical properties of
ferroelectrics are closely related to the piezoelectric properties. The
compliance or elastic flexibility Sij is defined as
strain in direction i Si
(8.40)
Sij = stress in direction j = 1j
and the stiffness Cij is defined as
stress in direction i 1]
(8.41 )
Cij = strain in direction j = Sj
The subscripts i and j acquire a value 1 to 6 following the convention in Fig.
8.8, where T 1, T 2 , T3 are tension stresses parallel to the 1, 2 and 3 axes
respectively; T 4 , T 5 , T6 are the shear stresses around the axes 1, 2 and 3.
Similarly, S), S2, S3 are the relative tension strains and S4, S5, S6 the shear
strains. For more detailed information, the reader is directed to reference 20.
Techniques for obtaining these compliances have been developed and
values for PVDF are reported in the literature. 43
8.5.5.2 Young's Modulus

The Young's modulus (Y) describes the elastic compliance under tension.
(8.42)
This is the most common form of Young's modulus for polymers, as it is

comparatively straightforward to meet the required condition of a homo-
L -_ _ _ _P_R_O_PE_R_T_I_E_S_O_F_F_E_R_R_O_E_L_E_CT_R_IC_M_A_T_E_R_IA_L_S_ _ _ -----'I I 275
genous stress and strain. This condition is satisfied when the sample length is
much larger than its width and thickness.
The simplest technique for measuring Yll is to apply a tensile force F
parallel to the '1' axis to a specimen of areas A and length I. The Young's
modulus is proportional to the initial gradient of the resultant stress-strain
curve. Thus
F/A
Y= M/I (8.43)
where M is the incremental length in the .t, direction.

However, for most polymers under constant strain, Y will decrease with
time due to relaxation processes, or creep. Therefore, the value of Y is
dependent on the rate of strain and the speed of testing. More realistic
values are obtained under dynamic conditions, where the test sample is
subjected to sinusoidal vibrations. The applied force and resultant defor-
mations are detected by a combined load cell and strain gauge.
The Young's modulus of PVDF is typically 1.9-2.0 GPa, although this
varies with manufacturer. This is also true for the VDF:TrFE copolymers
where values of 1.84 and 1.15 GPa have been recorded for 70:30 VDF:TrFE
from different suppliers. 33 This difference becomes very important when
evaluating material for certain piezoelectric polymer device configurations,
such as those with rigidly supported membranes. 44 It has been shown for
these type of devices that the output or sensitivity Vo is proportional to the
product of piezoelectric coefficient, Y and thickness of membrane t, i.e.
(8.44)
Therefore, for the 70:30 VDF:TrFE with a Yof 1.15 GPa, which is almost
half that of PVDF, the effect of the doubled d31 value over biaxially
stretched PVDF is cancelled, assuming the film thickness is constant. In the
case of the copolymer with a Yof 1.84 GPa, the sensitivity is predicted to
double over an equivalent PVDF device.
8.5.5.3 Mechanical Loss

Dynamic measurements of elastic modulus will yield a complex quantity
defined as
Y= y' +iY" (8.45)
where Y is the complex Young's modulus, Y' the real part and Y" the
imaginary part, also called the loss modulus. The angle reflecting the time
lag between the applied stress and strain is 1I. Analogous to the dielectric loss
tangent, the mechanical loss tangent is
y"
tan(lIm ) = Y' (8.46)
276 I ~I______________F_E_R_R_O_E_L_ECT
__R_I_C_P_O_L_Y_M_E_R_S____________~
and the mechanical quality factor Qrn is equal to the reciprocal of tan(I5,J.
The tan(l5,J is a damping term and represents the ratio of energy dissipated
as heat to the maximum energy stored in the material during one oscillation
cycle.
The value of tan(l5,J for PVDF is typically 0.1. This is 10 times greater
than the values of 0.01 for ceramics (PZT 5). As discussed earlier, it is this
high mechanical loss or damping that prevents measurement of the
electromechanical coupling factors using piezoelectric resonance methods.
8.5.5.4 Poisson's ratio

Poisson's ratio (0-) is defined as the ratio of negative lateral strain to
longitudinal strain along the direction under tension. Thus:
(S.47a)
S31
0-31 =-- (S.47b)
Sl1
S32
0-32 =-- (S.47c)
S22
(Note that the negative is conventionally present to ensure a positive

Poisson's ratio.)
8.6 APPLICATIONS
8.6.1 Introduction
The discovery by Kawai 2 in 1969 of the strong piezoelectric effect in PVDF
and two years later by Wada45 and Bergman46 of a corresponding pyro-
electric response were important developments for the field of electrome-
chanical and pyroelectric transducers. The enormous potential for a light,
rugged, large area flexible material with piezo- and pyroelectric properties
was quickly realized and it inspired a world-wide effort on applications. The
low mass of these materials is particularly important in aerospace and space
applications, especially with the constraints placed on desigOers of satellites,
probes and a possible space station.
The need for a combination of desirable properties that often cannot be
obtained in single-phase materials has driven the development of composite
materials. For example, in an electromechanical transducer, one may wish
to maximize the piezoelectric voltage sensitivity, minimize the density (to
obtain good acoustic matching), and also make the transducer mechanically
flexible to conform to a curved surface. These properties are partially
conflicting in nature, and a single-phase material that simultaneously
'----_ _ _ _ _ _ _ _AP_P_L_IC_A_TI_O_N_S_ _ _ _ _ _ _ ----'I I 277
satisfies these requirements is virtually non-existent. Thus in many appli-

cations, one might optimize conflicting requirements by combining the most
useful properties of two or more phases that do not ordinarily appear
together in nature.
It should be noted that often the major difficulty has been that of ousting
entrenched, mature technologies rather than the shortcomings in piezoelec-
tric performance.
8.6.2 Sound Transducers in Air

Sensitivity and impedance considerations dictate that, overall, microphones
for converting sound to electrical energy are one of the most promising
applications for PVDF in acoustic transducers. A number of structures have
been reported in the literature,44,47--49 in most cases advantage is taken ofthe
fact that PVDF can be used as a combined diaphragm and transducer that
both collects the sound and converts it to an electrical signal without the
need for armatures, coils, magnets, etc., which increase both complexity and
cost. Typical structures take the form of self-supporting domes50 or
bimorphs consisting of two sheets of thin PVDF film (10-30 Jl.rrl) clamped
between two tlat plates. The domes or discs of PVDF are the active part of
the device, with the response frequency, and to some extent sensitivity,
governed by the mechanical dimensions of the active elements. Their low
mass contributes to the low level of inertially produced noise (a character-
istic of PVDF based units), which is especially important in portable
microphones. A unique advantage can be gained by using PVDF transducer
elements in so-called noise cancelling microphones, designed for use in noisy
environments. The great simplicity of the PVDF element permits the
construction of microphones that have a very symmetrical response to the
sound field, an essential requirement in this type of microphone.
The rather low sensitivity ofPVDF devices when used in sound producing
mode has limited the use of PVDF in this field to high audio frequency or
close coupled (e.g. headphone) devices. PVDF-based high frequency
tweeters were also incorporated in Pioneer speaker systems and enjoyed a
somewhat longer commercial life. Other sound producing devices have been
proposed, but none have achieved commercial application.
8.6.3 Sound Transducers in Water

A particular feature required of most underwater transducers is the need to
operate at significant depths, necessitating a transducer that will withstand a
considerable static over-pressure and yet will be sensitive to the very low
pressure tluctuations in sound waves.
Several approaches have been made to this difficult problem in devices
using thin PVDF film backed by air cavities,51-53 with varying degrees of
278 II
k ______________ F_E_R_R_O_E_LE_CT __E_R_S____________~
__R_I_C_P_O_L_YM
success. A more elegant use of PVDF underwater is in larger area
underwater microphones. These are fabricated from large
(150 mm x 150 mm) plates of PVDF and are used mounted flat against
the hull of a boat below the water line. The plates operate in a compression
mode and having no internal cavities will withstand high over-pressures.
The large-area plates are a cheaper option than the conventional approach
of using many small piezoceramic sensors.
A material of potentially even greater use underwater is the closely related
copolymer of vinylidene fluoride and trifluoroethylene. This material needs
no orientation before poling and can be formed using conventional plastics
processing methods into self-supporting shapes that only require activation
by poling. Such techniques are of use in the production of shaped PVDF-
TrFE underwater sensors.
Ferroelectric composites can also be used as an underwater transducer54
to detect (passive mode) and/or generate (active mode) sound. Transducers
made from ceramics have the disadvantage that their densities make it
difficult to obtain good impedance matching with water. One of the
problems with PVDF is its low permittivity which produces a low element
capacitance which loads the output. The equivalent circuit for a flank array
transducer linked to an amplifier via a cable is shown in Fig. 8.10. The open
circuit voltage sensitivity Moe is loaded by stray capacitance Cs, and/or cable
capacitance Ce. The end of cable sensitivity Mec is given by
(8.48)
where Ce is the element capacitance. If the element capacitance is much

greater than the combination of (Cs + Ce) then the sensor voltage output is
important and gh would be the appropriate device figure of merit. In the
reverse case, dh should be used and in general this would require amplifiers
to be in close proximity to each transducer unit, which would be an added
expense. Since composites have a better impedance matching (than
ceramics) to water and their permittivity can vary from 20 to 1000, they
would be an ideal choice for these transducers.
Dispersions of powders in polymers with 0-3 connectivity offer the
possibility of fabricating large area transducers at low cost. One of the major
Fig. 8.10. Equivalent circuit for a flank array transducer.

L -___________________ __S__________________~1
A_pp_L_I_C_A_T_IO_N I 279
underwater uses for hydrophones would be in hull-mounted flank arrays.

For good flow noise integration a large area must be covered. Ideally, the
hydrophones pick up sound generated by other bodies and this information
can be processed to detect and track the body. At present it is not certain
whether the large area required will be achieved with large-area, or an array
of small-area, tiles. Ting and Geil 55 have investigated array structures based
on PVDF and 0-3 composites. The major problems were due to coupling
effects between PVDF elements, which were not present for the composite
arrays.
The main sources of noise are:
1. Sea State Zero Noise (So), with this and its corresponding voltage (Vo)
given by
So ~ 0.0451- 0.8 (8.49)
Vo = ghhSo~ (8.50)
h = element thickness.
2. Amplifier Voltage Noise, which is component dependent.
3. Johnson Noise, with the voltage given by
Vi = ~ [ 4kB Th tan(b) ] 1/2 (8.51 )

weA(1 + tan 2 (b»
where
~= 1 (8.52)
1+ C,+Cc
Ce(l-jlan(b))
The predicted noise spectra for a hydrophone is chosen in Fig. 8.11. It can
be seen that the sea state zero noise dominates at low frequencies and the
amplifier noise dominates at high frequencies. So for most practical
applications gh is the best figure of merit.
8.6.4 Mechanical Applications

A number of applications have been suggested in the literature where an
applied force has been used to generate an electrical signal. One application
is in telephone keypads. 56 Other applications use the production of
movement by an applied field to activate cooling fans 5? or small information
displays. 58 None of these has progressed beyond a demonstration of
feasibility, probably because satisfactory commercially available devices
using other transducer techniques already exist. These devices do, however,
show the great breadth of applications possible with PVDF. Recently, a
range of sports practice equipment has been developed in the United States.
In one application, PVDF is used as a sensor in a device to measure the
power and accuracy of a baseball pitcher's throw, in another the reaction
280 I LI______________F_E_R_R_O_E_L_EC_T_R_I_C_P_O_L_YM ______________~
__E_RS
10-6
-7
10
10-8
~ ro
10 ~....1-L..L.LLI.I.Ir---1.--L.L.LLLLL,--..L...l....L.L.1.ICJJ.,. 01}
104
Frequency (Hz)
Fig_ 8.11. Predicted hydrophone noise spectra: (I) sea-state zero; (II) Johnson noise
of dielectric loss; (III), (IV) voltage noise of two existing pre-amplifiers. Materials
constants were as follows: Ilr = 44, tan(l5) = 0.032 + 0.47Vl + 1.4/- 1(f = 20 Hz-
10 kHz), dh = 13.8 pCN- 1 , gh = 0.035 V mM- 1 •
time and blocking power of football players is measured using PVDF

sensors embedded in a football and blocking pad. This application gives a
good illustration of the robustness of PVDF sensors.
8.6.5 Filter Bandwidth Modifications

A high frequency application of composites involves bandwidth modifica-
tion in electrical filters. Electrical circuits operating at high frequency
require some form of frequency control to limit the passband of frequencies.
This control can take the form of a piezoelectric component shaped so that
the frequency range of interest coincides with a resonant frequency of the
piezoelectric element. At resonance the piezoelectric filter has minimum
impedance, several orders of magnitude lower than its non-resonant
impedance. Consequently, the element readily passes signals at frequencies
close to its resonance, with the passband being defined by the mechanical Q
of the device as
(8.53)
Here, / is equal to the central frequency and !1/3dB is the 3 dB passband

which can be 0.1 % of the central frequency.
It is possible to reduce or widen the bandwidth of a piezoelectric material
by combining several active piezoelectric elements mechanically in series or
L -__________________ AP
__P_LI_C_A_T_IO_N
__S__________________~I I 281
parallel respectively. A reduction in bandwidth can be obtained by carefully

grinding several piezoelectric discs to the same thickness and binding them
together in a series configuration using an electrically conducting epoxy
resin. For the fundamental thickness mode of a single disc, the resonant
frequency is given by
1
A = 2L..jPs (8.54)
where p = sample density and s = elastic compliance.

The disc thickness L is equal to half the acoustic wavelength therefore,
since the sign of the stress changes every half wavelength, in order to
resonate in phase the polarity of adjacent discs must be reversed. Acoustic
wave transmission occurs only very close to fL and consequently the
bandwidth is reduced.
One problem associated with series multilayer transducer designs is the
extremely accurate dimensional tolerances which must be achieved if
constructive interference is to be achieved.
8.6.6 Biomedical Aplications

Work in this area has been carried out at the University of Padua (Italy) by
de Rossi and co-workers. They have identified many applications where the
tissue compatibility, easy conformability, good impedance matching to soft
tissues, low water absorption, lightness, large bandwidth and large area
make PVDF an ideal transducer. However, large scale applications are not
envisaged. Typical applications are non-invasive cardio-pulmonary sensors,
implantable transducers and sensors for prosthetics and rehabilitation
devices. 59,60 Forces available from piezo polymers in mechanical actuator
mode are very small, but a practical micro-injector making use of thin
PVDF tube working in radial contraction mode to dispense microlitre
quantities has been described. 61 An interesting medical use of piezopolymer
in the charge generation mode is in the stimulation of bone healing. The
charge generated by an implanted piezopolymer film around a long bone
fracture has been shown to accelerate healing. 62,63
Although narrow band pass filters are readily available for most
frequency ranges of interest, broadband filters, in which bandwidths up to
50% of the central frequency are required, are more difficult to produce.
Apart from electrical filters, broadband devices are being employed in
acoustic imaging, especially for non-invasive flaw detection. 64 Ultrasonic
imaging has an advantage over its optical counterpart of improving contrast
since it relies for contrast on elastic discontinuities which are generally of
greater magnitude than changes in refractive index, particularly in biological
tissue. In acoustic imaging the piezoelectric element acts as both source and
detector in a 'pulse-echo' operational mode. At present the image is built up
282 I ~I______________F_E_R_R_O_E_L_E_CT_RI__C_P_O_L_Y_M__ER_S______________~
by mechanically scanning a single transducer over the area of interest and
integrating its output to form a coherent picture.
The requirements for medical ultrasonic imaging transducers are met with
1-3 PZT-rod/polymer-matrix piezoelectric composites. The composites
provide a high electromechanical coupling and low impedance properties
superior to those of the conventional piezoceramics and piezopolymers.
Also, composite plates can be formed into complex shapes for beam
focusing and steering.
Medical ultrasonic imaging is an important diagnostic tool for physicians
as it provides images of the internal organs without subjecting the patient to
hazardous ionizing radiation. These images are formed by sending a short,
directed pulse of high frequency (2-20 MHz) sound into the body and
detecting the weak reflections from internal structures. Displaying the
intensity of the echo as a brightness and scanning the beam direction in a
plane yields remarkable tomographs of the soft tissue of the human body.
Since the speed of sound in tissue (= 1540 ms- I ) permits gathering of over
one hundred images in the time it takes for a standard television scan, real
time as well as static images can be formed. These views of the internal
organs provide substantial diagnostic information in cases ranging from
fetal examination through to cardiac assessment.
The key element in forming these pictures is the transducer which
generates the acoustic pulse and detects its weak echoes. At the heart of this
transducer lies a thin piezoelectric plate, a few hundred microns thick, that
accomplishes the energy conversions.
The requirements on this plate are:
1. It must be an efficient electromechanical energy converter, i.e. the
thickness mode electromechanical coupling coefficient k t should be as
large as possible.
2. It must efficiently couple acoustic energy into and out of the tissue, i.e. its
acoustic impedance must be close to that of tissue (1.5 Mrayl).
3. It must efficiently couple energy out of and into an electrical transmission
line, i.e. the dielectric constant should be adjustable over a wide range
from about 100 upwards.
4. Electrical and mechanical losses should be low, i.e. tan(t5) < 10%.
5. It should be readily formed into curved shapes and subdivided into
acoustically and electrically isolated subsections for focusing and steering
the acoustic beam.
Table 8.3 compares the above criteria for piezoceramics, piezopolymers and
1-3 piezocomposites. It can be seen that the mix of properties provides the
transducer designer with opportunities to enhance the performance of
existing designs.
AP
__
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _P_LI_C_A_T_IO_N
__S __________________~I I 283
Table 8.3 Comparison of important ultrasonic parameters
Parameter Ceramic Polymer Composite
Thickness mode electro- 40--50 20--30 S75

mechanical coupling (%)
Acoustic impedance (Mrayl) 20--30 4 6
Dielectric constant 100--2400 10 20--1000
Dielectric loss (%) S3 15 5
8.6.7 Capacitance Thermocompensation

Some ceramic single phases are used for specific applications with
apparently no need to resort to composite materials. For example, barium
titanate (BaTi03) is the dominant material used in capacitor manufacture.
However, electronic circuits are required to work under many conditions,
not least of which is a changing environment. In many situations it may be
possible to arrange a composite material so that the individual phase
parameters vary with external conditions in such a way that the overall
effect is to leave the composite parameter constant.
A thermocompensated capacitor should have its capacitance almost
independent of temperature. In general two methods are employed to attain
this stabilization:
1. A system of two or more capacitors are series or parallel connected so
that the temperature coefficients of capacitance have opposite signs (one
positive and the other negative).
2. One capacitor is made with a composite dielectric that is a mixture of two
dielectrics either having different signs of the temperature coefficient of
permittivity or making it in such a way as to eliminate the Curie peak so
that the permittivity is almost temperature independent.
The latter effect can be achieved with a composite made from BaTi03 and
PVDF.
The tetragonal distortion of BaTi03 is locked in below a particle size of
around 5 Jl1D because of a surface energy effect. 65 This locked-in deforma-
tion persists to temperatures far in excess of the usual Curie temperature.
This property may be used in making a composite of BaTi03 and PVDF.
The BaTi03 particles should be around 1 Jl1D in size and the above effect, in
conjunction with fluoride ions occupying oxygen deficient sites in the
BaTi03 lattice, will wash out the permittivity peak. This has been carried
out by Murali et al. where a BaTi03/PVDF (70%/30% weight) composite
was made. For frequencies higher than 100 Hz, the temperature dependence
of the permittivity was constant up to 190°C.
284 I LI______________F_E_R_R_O_E_LE_CT
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8.6.8 Pyroelectric Applications
Pyroelectric devices convert changing incident thermal radiation to an
electrical output and are now much used in intruder detectors and thermal
imaging systems. Conventionally, ceramics have been used in such appli-
cations; however, considering the desirable properties of large pyroelectric
coefficient, high volume resistivity, low dielectric constant and loss and low
specific heat, it can be seen that apart from the rather low value of
pyroelectric coefficient, polymeric materials are superior to ceramics in
several respects.
A number of experimental configurations have been described in the
literature,66-{;9 and one or two simple devices based on the use ofPVDF are
commercially available (Siemens, Microwatt Applications). The relatively
low pyroelectric coefficient of PVDF and, to some extent, the difficulty of
handling small pieces of the thinnest films seem to have inhibited its more
widespread adoption in practical devices. The availability of large active
areas does not of itself seem to have provided sufficient advantage to device
engineers.
8.7 SMART MATERIALS
This final section discusses what have been described for aerospace and
space applications as the most important emergent materials technology
area. SMART materials are more like a device than an intrinsic material.
The term 'SMART' comes from the fact that 'these materials sense some
effect and respond in some way as a result. In this way, they have both
'sensor' and 'actuator' properties. They are often modelled on biological
systems where the sensor/actuator/process parts are likened to the nervous
system/muscles/brain. This is a graphic analogy but not always very useful.
There is a suggestion that the 'brain' of the SMART structure is some form
of processing unit. Although this may be true, the most interesting area for
materials is where all three functions are performed intrinsically by the
material itself. Certainly, if a SMART structure consists of a sensor
connected to an actuator by some electronic processing unit, then the
structure is better described as a 'device' rather than a pur,e material.
Perhaps the simplest SMART materials can be used for vibration control.
This is very important in space applications where it is important to keep
satellite devices under tight control in order to work correctly. The SMART
structure can be a simple sensor adhered to a structure and electrically
connected to an actuator. The sensor could be a piece of 0--3 composite
(with lead titanate as the active material) and the actuator could be a PZT
disc. Any vibration produces an electrical signal in the composite and this is
fed to the sensor through an inverting amplifier circuit so that the PZT is
driven in antiphase. With the correct gain set, the vibration can be removed.
L -_ _ _ _ _ _ _ _ _ S_M_A_R_T_M_A_T_E_R_I_A_L_S_ _ _ _ _ _ _ _ -----'I I 285
Such a system as the one described above would have problems operating
over a wide range of frequencies because the composite, PZT and amplifier
circuit all have a frequency response and so the optimum gain would depend
on the type of frequencies expected for a particular operation.
The above principle is the basis of active vibration cancelling systems.
Such systems have been researched by many automotive companies for the
reduction of noise in the cavity (i.e. where the driver sits) and for the
production of a superior active suspension system.
One of the problems of such systems is that, the more complicated the
structure, the more care has to be taken to ensure that it is secure and
reliable over an extended period of time. For example, military specifica-
tions can often require 20-30 years in-service lifetimes. Reliability may
increase if the sensor, actuator and interface are intrinsically part of the
same piece of material. This could be achieved easily with 0-3 composite
material in the form of a disc. The central area would be the sensor (using a
lead titanate ceramic) and a ring of active material would surround this
(using a PZT ceramic). If the polymer matrix were the same for both
powders then the two regions of the material would be compatible and
integrity should therefore be high. Such a structure has been used to actively
cancel noise for underwater military applications. In such a system, the
tuning of the sensor and actuator parts would be carried out by controlling
the poling efficiency for the two different parts of the structure.
The above describes a basic form for SMART materials. A sensor and
actuator are coupled together either via electronics or through the material
itself. For the interested reader, there are many papers discussing specialized
materials incorporating different aspect of intelligence, most notably in
Japan and America. 70
Sensors can be based on acoustic waveguides,71 the piezoelectric effect72
or optical fibres. 73 The mechanism depends on the input to be sensed. The
actuator mechanisms fall within five areas:
1. Shape memory alloys. These are metals that revert to a predefined shape
above a certain temperature. In doing so, they can generate large forces
for actuation. The most prominent material is possibly nickel-titanium
alloys. The main drawback is the slow response of these materials. The
response depends on heating and cooling and so, the response depends
on how fast the temperature can shift.
2. The piezoelectric effect. These materials produce a much smaller stress
than shape memory alloys but they react much quicker. One of the
problems is that piezoelectric actuators are non-linear and hysteretic.
3. Electrostrictive materials. The electrostrictive effect is a result of the
quadratic dependence of the material permittivity with electric field. This
is typified by lead magnesium niobate - it is non-hysteretic but also non-
linear. No poling is required but a bias voltage may be necessary.
~----------------------------------------------------~
4. Magnetostriction. These are similar to piezoelectric materials except that

the response is to a magnetic field rather than an electric one. The
commonly known material is Terfenol-D - an alloy of terbium, dyspro-
sium and iron (z Tb.3DY.7Fe1.9).
5. Electro rhelogical fluids. These substances contain micron-sized particles
that form chains when placed in an electric field, resulting in increases in
the apparent viscosity by several orders of magnitude. The main
problems are abrasiveness and chemical instability.
Much of the present work on SMART materials is still in the research
stage. Potential applications may include control of aerodynamic, hydro-
dynamic and optical surfaces, stealth, robotics, damping/tuning of struc-
tures and vibration suppression. In the field of civil engineering, applications
are expected in the development of intelligent buildings and in bridge and
road monitoring.
The whole range of advanced composite materials is being considered as
possible hosts for SMART materials technology. But beyond the materials,
however, this area may have a significant influence on the philosophy used
for the design of structures. Engineers will not necessarily have to add mass
(and the associated cost) in order to ensure safety. The incorporation of
SMART materials will allow ongoing, continuous monitoring of a structure
and may even allow the structure to heal itself when damaged.
8.8 CONCLUSIONS
This chapter has provided the reader with an introduction to a unique class
of materials. From the discussions of properties and applications, it can be
concluded that electro active materials offer advantages over many alterna-
tive technologies, including flexibility, robustness and availability in large
areas, thin sheets or unusual geometries.
However, it is widely believed that these materials will become established
in applications that exploit their unique features, rather than through the
substitution of existing transducer materials. This requires an innovative
approach, which on examination of recent literature, appears to have
already begun and looks set to continue.
Table 8.4 gives some of the points to consider when designing a system
which will utilize an active material. It is observed that no one material is
suitable for all applications. Further, many disadvantages can be engineered
around with good system design.
The present position is such that technological and industrial advances
demand more versatile and responsive transducer devices. In the develop-
ment of such, a particular technology may well be used over others but each
individual application is considered on its own merits and in some cases, a
mixture of materials may well suit.
Table 8.4 Comparison of different electroactive materials
Electroactive material
Ceramics Polymers Composites
Very high active performance (d 33 ) Low d 33 produces a low active Reasonable acoustic coupling
performance
Very poor hydrostatic activity Large d 31 produces only a Adjustable buoyancy
reasonable hydrostatic
performance
Large e,. reduces gh Low T c leads to a strong Low Gr leads to a high gh
temperature dependence and
depoling problems
Brittle Low density leads to a good Good shock resistance
acoustic coupling
High density leads to poor Low Gr leads to a high gh Good formability (e.g. domes)
acoustic coupling
Fabrication problems Good shock resistance Piezoelectric properties are
easily adjusted
Shock resistance is very Very good formability - can be Reasonably low dielectric loss
dependent on microstructure formed into exotic shapes (e.g. (5%)
domes)
Only simple structures possible Stretching can be problematic er around 100-200 - good for
(e.g. discs) for PVDF many applications
Very low dielectric loss (~3%) Relatively high dielectric loss Interphase interactions and
(15%) defects can cause problems
High Gr leads to a high Low Gr (",10) which is bad for
capacitance - good for some applications
hydrophone applications
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8.9 ACRONYMS AND SYMBOLISM
8.9.1 Chemical acronyms used in tbis chapter
PZT = lead zirconate titanate PVDF = polyvinylidene fluoride

VF = vinyl fluoride VDF = vinylidene fluoride
TrFE = trifluoroethylene TeFE = tetrafluoroethylene
PMMA = polymethylmethacrylate PTFE = polytetrafluoroethylene
8.9.2 Symbolism
C = capacitance
8 = permittivity
8 0 = permittivity of free space
Q = charge
E = electric field strength
tan( c5e} = dielectric loss
w = angular frequency
kB = Boltzmann's constant
i = current
S = strain
c = modulus
s = elastic compliance
p = pyroelectric constant
t = time constant
R = resistance or responsivity
F = figure of merit or force
Y = Young's modulus
p = density
S = noise
A = surface area
8 r = relative permittivity
t = thickness
V = voltage
D = electric displacement or detectivity
G = conductance
f = frequency
T = absolute temperature or applied tress
g = piezoelectric voltage coefficient
d = piezoelectric strain coefficient
k = electromechanical coupling factor
(J' = Poisson's ratio
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P = polarization
H = heat capacity
W = power
'1 = emissivity
I = length
M = sensitivity
OJ . = volume flow rate
Note:
T is used for both absolute temperature and applied stress
R is used for both resistance and responsivity
F is used for both figure of merit and force
D is used for both electric displacement and detectivity
It is hoped that this will not confuse the reader.
8.10 REFERENCES
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8. Brydson, J. A., Plastics Materials, Butterworths, 1982.
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10. Lovinger, A. J., Science, 220 (4602), 1115, 1983.
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13. Stallings, J. P. and Howell, S. G., Poly. Sci. Eng., 11, 507, 1971.
14. Prest, W M. and Luca, D J., J. App. Phys., 49, 5042, 1978.
15. Bamji, S. S., Kao, K. J. and Perlman, M. M., J. Poly. Sci. (Phys.), 18, 1945,
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18. Harrison, W. B. Proc. Wkshop Sonar Mat., NRL 1976.
19. Savakus, H. et aI., Mat. Res. Bull., 16, 677, 1981.
20. Williams, J. C., Doctor-blade process, in Treatise on Materials Science &
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21. Yamashita, Y. et al., Jap. J. App. Phys., 20, 183, 1981.
22. Sawyer, C. B. and Tower, C. H., Phys. Rev., 35, 269, 1930.
23. Furukawa, T. and Johnson, G. E., App. Phys. Lett., 38, 1027, 1981.
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24. Tajitsu, Y., Masuda, T. and Furukawa, T., Jap. J. Appl. Phys., 26 (10), 1749,
1987.
25. Scaife, B. K. P., Complex Permittivity (ch 3), Hodder 1971.
26. Higashihata, Y., Sako, J. and Yagi, T., Ferroelectrics, 32, 85, 1981.
27. Yamada, T. and Kitayama, T., J. App. Phys., 52 (11), 6859, 1981.
28. Choy, C. L., Chen. F. C. and Luk, W. H., J. Poly. Sci. Poly. Phys., 18, 1187,
1980.
29. Berlincourt, D. A., Curran, D. R. and Jaffe, H., Physical Acoustics, Principles
and Methods, ed. Mason, W P., Academic Press, New York 1964.
30. Kepler, R G. and Anderson, R. A., J. App. Phys., 49, 4490, 1978.
31. Humphrey, K. J., Gamer, G. M., Shorrocks, N. M. and Whatmore, R. W., Proc.
6th IEEE Int. Sym. App. Ferr., 543, 1986.
32. Tancrell, R H., Wilson, D. T. and Rickett, D., IEEE utt. Sym., 624, 1985.
33. Humphrey, K. J., Gamer, G. M., Goosey, M. T., Whatmore, R W. and Ainger,
F. W., 1st Int. Con! Elec. Opt. Acoust. Prop. Poly., RAPRA, London, 1, 1988.
34. Yamada, T., J. App. Phys., 53(9), 6335, 1982.
35. IRE Standards on Piezoeletric Crystals, Proc. IRE,49, 1161, 1961.
36. Ohigashi, H., J. App. Phys., 47(3), 949, 1976.
37. Murayama, N. and Obara, H., Jap. J. App. Phys., 22 (22-3), 3, 1983.
38. Whatmore, R. W., Rep. Prog. Phys. (GB), 49 (12),1335,1986.
39. Porter, S. G., Ferroelectrics, 33, 193, 1981.
40. Whatmore, R. W. and Ainger, F. W., Proc. SPIE, 395, 261, 1983.
41. Yamazaki, R., Ohwaki, J., Yamada, T. and Kitayama, T., App. Phys. Lett., 39
(9), 772, 1981.
42. Gamer, G. M., Allen Clark Research Annual Review, 62,1975.
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Poly. Sci. (B) Poly. Phys., 26,141, 1988.
44. Lerch, R., J. Acoust. Soc. Am., 67, 1229, 1981.
45. Wada, Y. and Nakamura, K., J. Poly. Sci., A29, 161, 1971.
46. Bergman, J G., McFee, J H. and Crane, G R, App. Phys. Lett., 18, 203, 1971.
47. Tamura, M., Yamaguchi, T., Oyaba, T. and Oshimi, T. Y., J. Audio Eng. Soc.,
23,21 1975.
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49. Gamer, G. M., Systems Technology, 27, 22,1977.
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52. Holden, A. J., Parsons, A. D. and Wilson, A. E. J., J. Acoust. Soc. Am., 73, 1858,
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55. Ting, R. Y. et al., Proc. 10 Acoust., 9 (2), 153, 1987.
56. Pearman, G. T., Hokanson, J. L. and Meeker, T. R., Ferroelectrics, 28, 3111980.
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58. Toda, M., Fe"oeiectrics, 32, 127, 1981.
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Biological Eng. and Comp., 23 Suppl. Pt 1,420, 1985.
~_________________R_E_F_ER_E_N_C_E_S________________~I I 291
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4,239, 1986.
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C., Springfield 1981.
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and Lacabanne, C., Current Advances in Skeletogenesis, ed. Silberman, M. and
Sierkin, M. C., Exerpta Medica, Amsterdam, Int. Congr. Ser. 1982.
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66. Glass, A. M., McFee, J. H. and Bergman, J. G., J. App. Phys., 42, 5219, 1971.
67. Pfister, G. and Abkowitz, M. and Crystal, R. G., J. App. Phys., 44,2064,1973.
68. Burkard, H. and Pfister, G., J. App. Phys., 45, 3360, 1974.
69. Southgate, P. D., App. Phys. Lett., 28, 250, 1976.
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383, 1987
Polymers in Printed Circuit 9
Board (PCB) and Related
Advanced Interconnect
Applications
MARTIN GOOSEY
Shipley Europe Ltd, Coventry, England
9.1 INTRODUCTION
The first printed circuits were developed over 50 years ago in the United
States during the Second World War and were designed to reduce weight,
save space and increase reliability in military equipment. This new
technology replaced discrete wiring of electrical components which was
previously accomplished by the use of terminal boards and point-to-point
wiring and soldering. With the widespread commercialization of the
transistor from the 1950s onwards the demand for printed circuit boards
began to expand significantly. The world consumption of printed circuit
board laminate materials for 1998 has been estimated at around 225 million
square metres!
In recent years the term printed wiring has been used synonymously with
printed circuit and is technically more correct since a circuit also includes
various components and devices ('printed wiring board' is the term used in
the USA whilst in Europe 'printed circuit board' is preferred). A printed
circuit is a pattern of electrical conducting paths reproduced onto an
insulating medium designed to interconnect various devices (Fig. 9.1). There
Plastics for Electronics, 2nd edn. Edited by Martin Goosey_ Published in 1999 by Kluwer
294 I ~I__________P_o_L_Y_M_E_R_S__IN__P_R_INT__E_D__c_IR~C_U__IT__BO__A_R_D________~
Fig. 9.1(a). Printed circuit board for a mobile telephone application (courtesy
Nokia).
Fig. 9.1(b). An assembled printed circuit board with both through hole leaded and
surface mount components.
are many methods used for defining these conductive patterns but they all
involve the definition of a circuit pattern, usually in copper, on a dielectric
material such as glass fibre reinforced epoxide or paper-loaded phenolics. In
this chapter the basic approach to printed circuit board manufacture and
testing will be briefly outlined before details are given of the specific
polymeric substrates commonly used in current PCB manufacturing
operations around the world. The final part of the chapter will then address
L -________ P_RI
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__C_A_T_IO_N I 295
some of the new advanced interconnection methodologies that are begin-
ning to be forced into existence by the emergence of increasingly
sophisticated and highly integrated semiconductor devices. These new
routes are particularly interesting in the context of this book because they
involve polymeric materials throughout the fabrication process and as
substrates and inter-metal dielectrics.
9.2 PRINTED CIRCUIT BOARD FABRICATION
Printed circuit boards can vary in complexity from the most basic single-
sided boards used in low-cost consumer electronics to sophisticated fine
pitch multilayer boards sometimes containing up to 40 or more interconnect
layers. There are often many possible process variations for the fabrication
of the same board and the exact choice will be determined by numerous
factors such as cost limitations, production volumes, the manufacturing
facility and the specific application. The following text outlines a typical
route used but it is not intended to provide an exhaustive account. The
reader is therefore recommended to refer to more comprehensive texts on
printed circuit board processing such as that by Leonida J for a more
detailed description.
In the simplest case, a printed circuit board may have a single layer of
interconnection tracks defined on only one side of a suitable substrate. This
is known as a single-sided board and is typical of what would be found in
basic consumer electronics, for example, transistor radios and remote
control units. The circuit is defined in a thin layer of copper laminated onto
a suitable low-cost dielectric material such as a paper-filled phenolic using a
process known as print and etch. In this process, pieces of laminate that
have been cut to an appropriate size for processing are cleaned and coated
with an etch-resistant ink that will protect the areas where the copper tracks
are to remain. This resist can be screen printed onto the substrate or
alternatively a liquid or dry film photoresist could be used. Having cured the
ink or patterned the resist, the exposed copper is then etched away leaving a
pattern of copper under the protective resist. The organic resist is then
removed using a suitable solvent to expose the copper circuitry. In this case
the conductors are normally left as bare copper with no additional metal
plated on top. If there are special requirements for the board or if it needs to
have components reftow soldered onto it, an alternative method may be
used which allows the electrodeposition of a tin-lead based finish.
Additionally, after further cleaning of exposed copper in areas where there
will be components, a solderability preservative may be applied and the
holes, if required, for through hole leaded components, punched using a
suitable die. Although this is probably the most basic printed circuit
fabrication process, even here there are many process variables possible. For
296 I I~_________PO_L_YM
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__E_D__C_IR_C_U_I_T_B_O_A_R_D
example, there are options on when the holes are made, whether they are
punched or drilled and in the type and application methods of the final
solder mask protective coating and solderable finish, to name but a few.
The next type of board in terms of complexity is the double-sided board in
which the circuitry is confined to the outer surfaces of a single piece of
laminate (Fig. 9.2). In this process an additional procedure is normally
required to form interconnecting holes that connect the two sides of the
board. These are known as plated through holes (PTH) and are typically
provided by a combination of electroless copper followed by electroplated
copper to build up the required thickness. Plated through hole fabrication
involves drilling or punching the holes in the copper clad board at the
locations where the interconnections are required. This is followed by a
number of chemical processing stages that clean the hole walls and
condition them in preparation for metallization. Because the hole walls are
non-conducting they cannot be electroplated with copper directly and,
traditionally, an e1ectroless copper deposit is used to enable electroplating.
Recently, alternatives to electroless copper known as direct plate processes
have become popular and these employ a variety of conductive species such
as carbon and palladium sulphide to provide a conductive layer which then
facilitates direct electroplating of copper. Most double-sided boards have all
their conductors and hole walls made from copper with an additional thin
metallic solderable coating such as tin, tin-lead, nickel-gold or palladium.
Some of these coatings can also actually be used as etch resists in place of an
organic resist during manufacture.
Fig. 9.2. An actual section through a hole on a double·sided board. (Note the glass
fibre bundles in the central part of the section.)
L -_ _ _ _ -'I I
L_A_M_I_N_A_T_E_S_F_O_R_R_IG_I_D_P_R_I_NT_E_D_W_IR_I_N_G_ _ _ _ 297
After the double-sided board, the complexity increases significantly as the

boards become so-called multilayer in which, in addition to conductors on
the surface of the substrate, there are also additional conductor layers
sandwiched between alternating layers of dielectric in the bulk of the board
(Fig. 9.3). For most consumer electronics applications such as personal
computers and mobile telephones, the total number of layers would
typically be between 4 and 8. However, multilayer boards with many more
layers than this are routinely manufactured and some specialist companies
will produce boards with up to 40 layers or more. As with double-sided
boards there is a need to provide interconnections between all the layers of
metallization and this is usually achieved by providing connections through
the deposition of metal in the vias and holes which penetrate the board in
the same way as mentioned above for double-sided boards. The common
feature of all of these types of board is that they are made from materials
known as copper clad laminate and the following section discusses the
various types of laminate in use.
9.3 LAMINATES FOR RIGID PRINTED WIRING
Nearly all (rigid) printed wiring boards in current use are laminates made by
bonding together several sheets of fibrous reinforcing material which are
then surface clad with copper foil on one or both sides. The fibrous sheets
are usually in the form of woven fabric, mat or paper and made of glass,
often an electronic grade (E-glass), cellulose or synthetic polymers. These
are frequently referred to as base materials. The binding agents have
Fig. 9.3. Section showing a plated through hole in a multilayer board.

298 I ~I_________P_O_L_y_M__E_R_S_IN__P_R_UNT
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traditionally been thermosetting resins including epoxides, polyimides,
phenolics and polyesters. More recently, various new materials have been
introduced which have improved glass transition temperatures and enhanced
thermal properties. Fluorinated polymers such as polytetrafluoroethylene
(PTFE) and its derivatives are also used for high frequency applications.
9.3.1 Manufacturing Process

The manufacture of a laminate involves three basic steps: treating, laying up
and pressing. In the first operation the glass fabric material is passed
through a dip tank containing a solution of the resin. Mter saturation,
excess resin is removed by squeezing between rollers and the material is
dried in an oven to a partially cured state or B-stage. The semi-cured
material is known as a prepreg and is normally dry and tack-free. The exact
ratio of resin to base glass fabric material, and the degree and uniformity of
cure are all carefully controlled in the .treatment operation. For the lay-up or
build-up operation, copper foil is laid against a polished steel press-pan, and
a number of sheets of prepreg are laid on top to achieve the desired
thickness for the type of board. For two-sided boards a second sheet of
copper foil is placed on top of the stack which is capped with another press-
pan. The final operation takes place in a laminating press which may be
capable of laminating 100 or more sheets 1 m x 2 m x 1.5 mm thick. The
hydraulic presses can be operated at high pressure (2000-3000 psi). Each
press platen is uniformly heated and the pressure-temperature-cure cycle is
carefully controlled to minimize non-uniformities, undercure, void forma-
tion and excessive stress build-up. Some laminate manufacturers are now
using vacuum pressing methods to give quality advantages unattainable
with conventional pressing technology. Vacuum pressing is claimed to give
laminates with a higher degree of dimensional stability, more uniform
thickness and better surface topography.
The standard copper foil used in the preparation of laminates is called
electro-deposited (ED) copper and it is produced by plating onto a rotating
metal drum immersed in a copper electrolyte. The side of the foil in contact
with the drum is shiny and suitable for imaging of circuit patterns whilst the
other side is matte and rough and gives a good bond to the pre-preg to
which it is bonded. Depending upon the final thickness of the laminate
required, several layers of pre-preg will be sandwiched between the two
outer layers of copper. With the trend towards finer pitched interconnects
and higher circuit densities has come the need for much thinner copper foils.
These can be difficult to handle and so manufacturers have begun to
produce peelable copper foils where a thin copper foil is mounted on a
copper carrier foil approximately 70 pm thick. Typically, the structures
would have 5 or 9 pm of copper on a 70 /-lm copper carrier. The carrier is
not removed until drilling is completed and it therefore also serves to replace
L -_ _ _ _L_A_M_IN_A_T_E_S_F_O_R_R_IG_I_D_P_R_I_NT_E_D_Wl_R_IN_G_ _ _ _ --11 I 299
the use of a drill entry material. Another recent innovation in copper for
laminates is the production of so-called double-treated foils where both
sides of the foil have optimized morphologies. In these the shiny side of the
laminate is modified such that it is claimed to obviate the need for the
traditionally used oxide treatment which ensures good bond integrity. Other
recent innovations in copper for laminates include high ductility coppers
optimized for use in flex circuit applications and very low profile coppers
with improved elongation values and reduced roughness for fine inner layer
production (0.1 mm). In addition to the many different thicknesses of
copper available there is also a range of resin contents possible in the pre-
pregs used.
Multilayer boards are also assembled in a process very similar to that used
for making laminate where the individual layers of the board and prepreg
are heated under pressure in a press to give the final cured and bonded
assembly. In a recent development, the copper foil used in the board itself
has been employed to carry a high electrical current which causes heating in
the lay-up structure and curing of the assembly. Also, it is worth noting that
some companies use an autoclave, rather than a bonding press, to
manufacture multilayer boards. The vacuum autoclave offers a number of
advantages for certain specific applications. It is an isostatic vacuum press in
which nitrogen or carbon dioxide is used for both temperature and pressure
transmission.
9.3.2 Classification of Laminate Types and End Uses

Most of the laminates widely used for printed circuit boards are classified by
the standards such as those from the National Electrical Manufacturers
Association or NEMA (ASTM standards are identical). NEMA standards
are based on the combination of electrical, mechanical, thermal and
chemical properties which determine the suitability of a laminate for a
particular end use.
In the NEMA classification system, paper (cellulose) reinforced grades are
designated with the letter X, glass fabric grades with the letter G and flame
retardant grades with the letters FR. There is generally a flame retardant
equivalent for each of the X and G types which may differ only slightly in
specifications. In addition to NEMA standards there are military (MIL)
specifications which generally demand a higher level of performance.
However, most commercial glass-reinforced copper-clad laminates qualify
under both NEMA and MIL standards. Detailed descriptions and com-
parisons of these specifications can be obtained from the Institute for
Interconnecting and Packaging Electronic Circuits (IPC) which is based in
Northbrook, Illinois, USA. The most widely used NEMA grade printed
circuit board laminates are listed in Table 9.1 which also briefly describes
their composition, basic features and end uses.
Table 9.1 NEMA copper-clad laminates
NEMAgrade Resin Reinforcement Description Use
XXP Phenolic Paper Hot punching grade

XXXPC Phenolic Paper Room-temperature Inexpensive laminates mainly
punching grade used in low-cost consumer
items, e.g. calculators, watches
FR2 Phenolic Paper Flame retardant equivalent
of XXXPjXXXPC
CEMI Epoxy Paper + glass Punchable epoxy, properties Used extensively in consumer items,
between XXXPC and FR4 e.g. radios, smoke detectors; low-
cost substitute for FR4 in
single-sided wiring
GIO Epoxy Glass cloth General-purpose glass base; Widely used in demanding
excellent electrical applications, e.g. computers,
properties and water resistant telecommunications; relatively
expensive (approx. 2 x FR2)
FR4 Epoxy Glass cloth Similar to G 10, but
flame retardant
FR5 Epoxy Glass cloth Similar to FR4 but more Generally specified for
thermally stable military/aerospace applications
~________PR_O_P_E_R_T_I_E_S_A_ND
___T_ES_T_I_N_G_O_F__
LAM
___IN_ATE_S________~I
__ I 301
The epoxy glass-fabric grades possess superior electrical, mechanical and

chemical properties compared with the phenolic paper grades although the
latter grades are typically lower in cost. Flame retardant grade FR4 type
laminates account for the majority of all of the types produced and are
available in thicknesses ranging from 0.05 to 3 mm.
Although NEMA specifications provide a basic guide to properties, the
actual behaviour of laminates of the same grade may differ considerably
during the processing steps required to produce a printed circuit board.
Important factors that influence the detailed properties (apart from the resin
composition, which will be described in subsequent sections) are the
thickness and weave style of the glass fabric and the bonding or coupling
agent used to promote adhesion.
9.4 PROPERTIES AND TESTING OF LAMINATES
The general physical and chemical properties required of a printed circuit

board substrate are largely determined by the following factors:
I. Electrical
(a) excellent insulating properties retained under prolonged exposure to
humid environments and high circuit operating temperatures
(b) low dielectric loss
(c) uniform electrical properties
2. Mechanical/thermomechanical
(a) drillable or punchable
(b) dimensional changes induced by heat and/or chemical treatments
should be reversible, reproducible, uniform and small
(c) rigid substrates should have minimal warp and twist
(d) resistant to the effect of mechanical vibration
(e) resistant to thermal shock induced by soldering (e.g. 260-275°C for
5 s in wave soldering, 215-245°C for 20-60 s in vapour phase
soldering)
3. Chemical
(a) resistant to acids, alkalis and oxidants used in copper cleaning,
etching and plating
(b) resistant to organic solvents used in cleaning/vapour degreasing (e.g.
methylene chloride, trichloroethane).
(c) strong adhesion to copper retained under adverse environmental and
processing conditions.
Some of the desired properties such as the electrical performance are
relatively easy to measure and interpret. However, the thermomechanical
characteristics, such as dimensional stability and warp and twist, depend
upon a number of interacting complex physical and chemical properties
302 II~_________ P_O_L_y_M
__E_R_S_IN
__P_R_INT
__E_D
__ ________~
C_IR_C_U_I_T_B_O_A_R_D
including differential thermal expansion, swelling and stresses built in during

cure or lamination. They are therefore more difficult to predict or quantify
in a precise manner from simple measurements of basic properties. This is
especially true when considering a laminate which is anisotropic in nature,
i.e. the reinforcement acts in the XY plane but not significantly in the Z axis,
for which thermal expansion and mechanical properties are largely
determined by the resin.
Printed circuit board manufacturers rely heavily on a large number of
tests that are primarily designed to detect failures under conditions which
reproduce processing or extreme use. These procedures are covered
extensively by publications of studies instituted by the IPC. In the following,
the basic properties and test methods generally used to characterize
polymeric materials for printed wiring applications are briefly described.
Recommended ASTM testing standards are listed in Table 9.2. Additional
test methods and standards for printed wiring laminates are described in
IL-P-13949 and IPC-TM-650.
9.4.1 Test Conditioning

It is customary (and important) to define the environment in which tests are
performed on electrical and electronic grade materials. The conditioning
designations are:
1. condition A - as received; no special conditioning
2. condition C - humidity conditioning
Table 9.2 Standard test methods
Method ASTM
test no.
Electrical resistance D257

Dielectric breakdown voltage, electric strength Dl49
Dissipation factor and dielectric constant Dl50
Arc resistance D495
Flexural properties of plastics D790
Impact strength D256
Shear strength D732
Punchability D617
Warpage of sheet plastics Dll81
Thermal expansion D696
Deflection temperature under load D648
Thermal stress E2/125
Chemical resistance of plastics D543
Water absorption of plastics D570
Note: Flammability is normally tested according to Underwriters Laboratory Procedure UL 94.

PROPERTIES AND TESTING OF LAMINATES II
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303
3. condition D - immersion conditioning in distilled water

4. condition E - temperature conditioning
In designating specific test conditions the letter (C to E) is followed by three
numbers separated by obliques. The first represents the duration in hours,
the second is the conditioning temperature in degrees centigrade and the
third is the relative humidity, assuming humidity is controlled. For example,
C-96/35/90 which is a common conditioning for electrical resistance
measurements, indicates humidity conditioning for 96 h at 35°C and 90%
relative humidity.
9.4.2 Electrical Properties
9.4.2.1 Surface and Volume Resistivity

Resistivity measurements are obtained from resistance measurements using
electrode arrangements of defined geometries and are a measure of the
vitally important insulating characteristics of printed wiring board materi-
als. One commonly used electrode arrangement is the circular three
electrode pattern illustrated in Fig. 9.4 (ASTM D257). For surface
measurements the bottom electrode is the guard conductor which intercepts
stray (bulk) currents. Resistance measurements are usually made with an
applied potential of 500 V. Surface resistivity, Ps, is calculated from the
relationship:
R'P
PS=D
where R' is the surface resistance, P is the perimeter of the guarded electrode
and D is the distance between the inner and guard electrodes. The units
are expressed as a/square. Typical values for polymers lie in the range
Electrode 1 Electrode 2
Electrode 3
Fig. 9.4. Electrode arrangement for surface and volume resistivity measurements.
304 I ~I__________PO_L_YM
___E_RS__IN
__P_RI_NTE
___D __B_O_A_R_D________~
__C_IR_C_U_IT
107-108 n/square. Surface resistivity decreases with increasing humidity or

water absorption. The magnitude of this effect can be greatly increased if
ionic impurities are present on the surface which become conducting on
exposure to water. It is common practice to carry out measurements after
humidity conditioning (method C).
Volume resistivity is obtained from volume resistance using the arrange-
ment shown in Fig. 9.4 but with electrode 2 as the guard and with the DC
potential applied between 1 and 3. The resistivity is calculated from the
relationship:
RA
p=-
d
where R is the volume resistance, A is the effective area of electrode 1 and d
is the specimen thickness. Typical values for electrical grade polymers are of
the order of 10 15 n em at room temperature. Volume resistivity usually
exhibits an exponential decrease with increase in temperature and is also
significantly reduced by water absorption.
9.4.2.2 Dielectric Constant

The dielectric constant is the ratio of the capacitance formed by two parallel
plates with a material between them to the capacitance with air, or more
correctly, a vacuum as the dielectric. A uniform dielectric constant is
important for substrates used in high-frequency and microwave electronic
circuits.
A low dielectric constant is particularly desirable for double sided and
multilayer boards used for high-speed computer circuits or other high speed
applications where distributed capacitance is important. For the glass fabric
resin based systems such as FR4, this can be reduced by increasing the resin
to glass ratio since the E-glass has a dielectric constant of 6.1 compared with
approximately 3.5 for a typical epoxy resin. Figure 9.5 illustrates the effect
of resin content on dielectric constant.
The dielectric constants of most polymers are relatively low compared
with inorganic materials and lie in the range 2 to 4 (at 1 MHz) with a few
materials outside this range.
9.4.2.3 Dissipation Factor and Loss Factor

The dissipation factor is the ratio of the parallel reactance to parallel
resistance, i.e. the tangent of the loss angle (tan 0). The loss factor is the
product of tan ~ and the dielectric constant and is a measure of the total loss
of power occurring in the insulating material. Dissipation factors for most
plastics tend to decrease with increasing frequency and increase with
increasing temperature. For printed wiring applications values are usually
L -_ _ _ _ _ _ _ _P_R_O_P_E_R_T_I_E_S_A_N_D__
T_ES_T_I_N_G_O
__ F_L_A_M_I_N_A_T_E_S________~I I 305
7
N
6
== normal range
;§ for laminates
'iii
;:
!! 5
;!l
8
j
is 4
3 -L------r------r------r------.----~
o 20 40 60 80 100
Resin content (wi. %)
Fig. 9.5. Dielectric constant versus content for a glass-epoxy system.
reported at 1 MHz and at room temperatur!;! are in the range 3 x 10-2 to

3 X 10-4. A low dissipation factor is important especially for printed wiring
used in high-frequency electronic circuits.
9.4.2.4 Electric Strength

Electric strength (also referred to as dielectric strength) is the field strength
in volts per unit thickness of an oil-immersed sample, as shown in Fig.
9.6(a). The applied voltage is increased at a uniform rate smoothly or step-
wise. The magnitude of the electric strength depends upon the thickness of
material, the form and size of the electrodes, the frequency and waveform of
the applied voltage and the material properties. Hence, it is unwise to
compare dielectric strength data for different materials unless all test
conditions are standardized.
9.4.2.5 Dielectric Breakdown

Dielectric breakdown is a measurement of breakdown voltage which is
made parallel rather than perpendicular to the plane of a sample, as
illustrated in Fig. 9.6(b). In the standard test (D149) the electrodes are taper
pins inserted into the sample on 1 inch centres. The voltage is applied at a
controlled rate of increase with the sample immersed in oil. Dielectric
breakdown strength depends on both surface and bulk characteristics of a
material and is reduced by increases in humidity, water absorption and ionic
or other conducting contaminants. Typical values for polymeric materials
are in the range 10--50 kV.
306 I LI__________PO_L_y_M__E_R_S_IN__P_R_INT
__E_D__C_IR_C_V_I_T_B_O_A_R_D________~
a -E
b ......t - - - - - E -----t~
..
Fig. 9.6. Electrode arrangement for (a) dielectric strength (field perpendicular) and
(b) dielectric breadown measurements (field parallel).
9.4.3 Mechanical and Thermomechanical Properties
9.4.3.1 Flexural Strength and Modulus

Flexural strength is the force per unit area required to break a material in
bending. Flexural modulus is the ratio of the elastic limit of stress to
corresponding strain and relates to the stiffness of a material under load.
Load-defonnation measurements are obtained by applying a force to the
centre of a sample in the fonn of a beam or bar which is supported at both
ends as illustrated in Fig. 9.7. The flexural modulus (FM) is calculated from
LOAD
Fig. 9.7. Schematic illustration of flexural strength test.

___T_E_ST_I_N_G_O_F__L_A_M_I_N_A_T_E_S________~I
P_R_O_P_ER_T_I_E_S_A_ND
L -_ _ _ _ _ _ _ _ I 307
the slope of the steepest initial portion of the load deformation curve by the
equation
L3 m
FM = 4bd3
where L = span, b = width and d = depth of the beam under load.
Modulus values vary from 0.3 x 106 psi for thermoplastics to 5 x 106 psi
for reinforced laminates.
9.4.3.2 Deflection Temperature and Glass Transition Temperature

Deflection temperature, more commonly known as heat distortion temper-
ature, is a measure of the thermal stability of a plastic material. A widely
used procedure is ASTM D648, according to which the sample arrangement
is similar to that used for the measurement of flexural strength (Fig. 9.7). A
standard load (usually 264 psi) is applied to the centre of the sample which
is supported with a span of 4 inches. The temperature at which the sample
deflects 0.010 in upon heating at a rate of 2°C/min is reported as the
deflection temperature. The deflection temperature of a polymeric material
may approximate to the glass transition temperature (Tg) as determined, for
example, by thermomechanical analysis. The agreement is likely to be closer
for thermoplastic materials which soften reversibly above T g • For a
thermoset, however, the thermomechanical behaviour can be complicated
by the degree of cure. Thus under-cured materials may become more rigid
on heating and exhibit irreversible heat deflection behaviour. In the case of a
laminate, additional complications may arise due to stress relief.
In general, above the heat distortion or glass transition temperature most
fully cured thermosetting polymers lose their rigidity and hence Tg is an
indication of the upper limit of service temperature for rigid printed wiring
materials. In laminates the reinforcing effect may extend temperature
serviceability somewhat above the Tg , if dimensional stability is not deemed
to be too critical.
9.4.3.3 Thermal Expansion Coefficient and Dimensional Stability

The coefficient of thermal expansion is a measure of the dimensional
changes which occur on heating or cooling a sample. The values normally
measured are linear and reported at one particular temperature which, in the
ASTM D696 standard method, is 55°C. The coefficient is the change in
length per unit length per degree increase in temperature.
In general, polymers have larger coefficients of expansion than most of the
other materials used in electronic circuits. In addition, the thermal
expansion coefficients of polymers tend to increase above the glass transition
temperature. This effect is illustrated in Fig. 9.8. Since printed wiring boards
308 I L I_ _ _ _ _ _ _ _ _ _ P_O_L_y_M_E_R_S__
IN__
P_RI_NT
__E_D
__C_IR_C_U
__ IT__
BO A_R_D________~
__
.1r---------------------------------------~~
.08
.02
o~~~~----~----~----~~--~----~
20 40 60 80 100 120 140
Temperaturef'C
Fig. 9.8. Typical expansion curve for a DGEBA epoxy system.
may be subject to many thermal cycles, in order to minimize stresses, it is

desirable to minimize the difference in thermal expansion between the
copper foil and the laminate. This can be reasonably achieved in the case of
an epoxy-glass laminate since the expansion of copper (16.5 ppm OC- I ) lies
between that of E-glass (2.8 ppm OC- 1) and a typical epoxide resin (40-
50 ppm OC- I ) at room temperature. Thus values for the room temperature
expansion coefficient of an FR4 laminate are typically in the range 10-
15 ppm oC- 1 in the XY plane. However, in the Z axis the value is generally
in the range 40-50 ppm oC- 1 which is close to that of pure epoxide resin.
Figure 9.9 shows the Z axis thermal expansion coefficient of an FR4
300
U
]
,eo
a:>o 200
..
oW
1:1
.S:!
15
~
U 100
8
1
~
0
0 40 80 120 160 200
Temperaturef'C
Fig. 9.9. Z axis expansion coefficient versus temperature for a typical multilayer
epoxy laminate.
'--_ _ _P_O_L_y_M_E_R_S_U_SE_D_F_O_R_L_A_M_IN_A_T_E_M_A_NU_F_A_C_T_U_R_E_ _ _-'I I 309
laminate as a function of temperature. Here it can be seen that there is a

dramatic increase in the expansion in the Z axis above the glass transition
temperature. This phenomenon results from the increase in the thermal
expansion coefficient of the pure epoxide resin above Tg (Fig. 9.8), coupled
with the transfer of volume expansion to the Z axis due to the in-plane
confining action of the glass fabric.
This behaviour can result in severe problems due to cracking of plated
through holes for laminates exposed to temperatures close to or higher than
Tg • In addition, the copper foils in the inner layers of multilayer boards can
undergo similar cracking. Thus excellent dimensional stability in the XY
plane is achieved at the cost of low Z axis stability. This problem has
precipitated a considerable interest in the development of higher Tg epoxy
resins and the use of alternative polymers such as polyimides. Some of these
materials will be reviewed in the following section.
9.4.4 Water Absorption

High water absorption can result in a pronounced reduction in the
insulation resistance, dielectric breakdown, dissipation factor and mechan-
ical strength of a polymer. Water absorption is dependent upon the chemical
nature of the polymer as well as upon the presence of voids, which is
generally greater in composite materials such as laminates. In the fabrica-
tion of printed circuit substrates considerable care is taken to minimize void
formation. In the case of a laminate, this requires thorough impregnation of
the reinforcing material with the resin and complete removal of all volatile
materials.
9.5 POLYMERS USED FOR LAMINATE MANUFACTURE
Nearly all laminates suitable for printed circuit applications are based on
thermosetting polymer chemistry. Compared with the commonly available
thermoplastics, thermosets possess improved temperature performance and
chemical stability due to the crosslinking which occurs on curing to produce
a three-dimensional rigid chemical structure. The most important polymers
used for the fabrication of printed wiring laminates are now described.
9.5.1 Epoxide Resins

Epoxide (or epoxy) resins possess a combination of desirable properties
which have resulted in their widespread use for the fabrication of laminates.
The most important of these are: high adhesive strength; high mechanical
strength; good electrical insulation properties; low shrinkage; excellent
chemical resistance and thermal stability; ease of cure; and ready modifi-
310 I ~I_________P_O_L_Y_M__E_R_S_IN__P_R_INT
__E_D__C_IR_C_U_I_T_B_O_A_R_D________~
cation to optimize properties by blending and by use of different curing
agents.
Currently, the majority of thermosets used for printing circuit laminates
are epoxy-based. The resins which are employed almost exclusively are those
based on the diglycidyl ether of bisphenol A (DGEBA) and the tetrabromo
derivative which is used to provide flame-retardant properties. These
compounds are represented by the following formulae:
C6HCH20!X-OCH2&CH2-JX-OCH2C~H2
X= -50H
y
Y
Hc~~
0 : 0
H
Y
CH3
H Y
where Y = H or Br. A more detailed description of the chemistry of these
and related epoxy compounds is given in Chapter 4.
The choice of DGEBA resins for use in laminates is based on the higher
thermal and chemical stabilities which characterize aromatic systems,
coupled with the relatively low cost of raw materials. The resins are used
with n values in the range 0-2. A typical formulation would have an average
molecular weight of 900 (n = 2 for the non-brominated DGEBA) and a
solids content of 20% in a solution of acetone or cellusolve type solvent.
Aromatic polyamines are commonly used as curing agents, particularly,
metaphenylenediamine (MPDA), 4,4'-methylenedianiline (MDA) and di-
aminodiphenylsulphone (DADS), the formulae of which are as follows:
Melting point. 6O"C

MPDA
MDA Melting point. 17G-18O"C
Melting point, 207-209"C
The curing of these compounds with DGEBA is normally carried out in

two stages, typically 2 hours at 125°C followed by 2 hours at 160-200°C.
L -_ _ _ -'I I
P_O_L_y_M_E_R_S_V_SE_D_F_O_R_L_A_M_I_N_A_T_E_M_A_N_V_F_A_C_T_V_R_E_ _ _ 311
For FR4 grade laminates and prepregs, the most commonly used curing
agent is dicyandiamide (DICY).
fI2
H 2 N-C=N-C=.=N Melting point. 208"C
In the presence of a suitable accelerator, typically an imadazole (such as 2-

methyl imadazole) or benzyldimethylamine (BDMA), at concentrations of
2.5-3.5% by weight, laminated DGEBA and DICY cure in 1-1.5 hours at
170°C. This fast and relatively low temperature cure greatly facilitates
multilayer fabrication where higher temperatures are less desirable because
of increased dimensional changes. Furthermore, the B-stage material has
excellent long-term stability.
Typical physical and electrical properties of DGEBA cured with various
polyamines are shown in Table 9.3. It can be seen that the electrical and
mechanical properties are very similar. The main differences are in the heat
distortion temperatures which increase in the order DICY < MPDA <
MDA<DADS.
Recently, there has been considerable effort devoted to the development
of epoxy systems which possess all the desirable characteristics of an FR4
resin but that also exhibit improved dimensional stability, particularly for
multilayer fabrication. The approach generally pursued is to aim for a
system which has its glass transition temperature above the cure temper-
ature, thus ensuring that extensive thermal expansion does not occur during
fabrication.
Several proprietary laminating epoxy resin systems have been produced
with glass transition temperatures in excess of 170°C and with processing
conditions similar to those of the DGEBAjDICY system. For example, the
use of tetrafunctional epoxy chemistry in place of the conventional DGEBA
type resin systems has enabled Tgs to be increased from around 130°C to
170°C. These materials also possess improved chemical and thermal
stabilities combined with superior thermal expansion characteristics up to
soldering temperatures. An example of a range of tetrafunctional epoxy
laminate and prepregs is the FR406 series produced by Allied Signal.
This material is reported to have a Tg of 170°C, an x axis expansion of
13 ppmo <;-1 and a volume resistivity of 9 x 10 16 n em. Tetrafunctional
epoxy resins can also be used in laminates to aid in optical inspection
because they are inherently fluorescent. The fluorescent resin increases the
contrast between the copper and laminate when optical inspection is carried
out by the now preferred laser fluorescence method.
Even higher Tgs, in the region of 180-200°C, can be achieved by using a
combination of epoxide and bismaleimide triazine (BT) resins in a system
known as BT jepoxy. An example of a typical BT jepoxy glass laminate
system is the G200 series oflaminates produced by Allied Signal which has a
Tg in the region of 180°C, a dielectric constant of 4.0 and an x-axis
Table 9.3 Typical properties of laminating epoxy resin systems based on DGEBA
Property Curing agent' MPDA Brominated
+ 67% DGEBA
DICY MDA DADS MPDA glass fabric + MDA
Flexural strength
(psi x 10-3) 18 17 16 19 80-90 17
Flexural modulus
(psi x 10- 6 ) 0.44 0.39 0.42 0.46 3.8-4.2 0.41
Tensile strength
(psi x 10-3) 9 9.5 9 8 50-58 8.2
Deflection temperatureb
eC) (264 psi) 127 155 175 155 157
Dielectric constant
(25°C) 3.9 3.7 3.9 3.8 5.1 3.4
Dissipation factor
(1 kHz, 25°C) 0.012 0.017 0.013 0.Ql8 0.009
Dissipation factor
(1 MHz, 25°C) 0.021 0.035 0.027 0.035 0.019 0.033
Volume resistivity
Q cm x 10- 15) 10 2 0.1 10 0.2 10
Water absorption
(%) (24 h) 0.03 0.04 0.035 0.03 0.05--0.07 0.04
a Stoichiometric amounts used.

b Optimized cure cycle.
L-_ _ _P_O_L_y_M_E_R_S_V_SE_D_F_O_R_L_A_M_I_N_A_T_E_M_ANU
__F_A_C_T_V_R_E_ _ --,---.JI I 313
expansion of 13 ppm 0C- I . It should be noted, however, that as Tgs increase,

the ease of processing these more chemically stable materials through
standard electroless copper plating lines often becomes more difficult as the
resins are harder to texture prior to metallization.
9.5.2 Cyanate Ester

For Tgs above 200°C the chemistry of the resins used changes from the
epoxides and their derivatives and materials such as cyanate esters are
increasingly found to be useful. The term cyanate ester is used to define
organic resins which contain the cyanate ester functionality i.e. O-C=N.
The starting materials for their syntheses are, for example, the dicyanate
esters of substituted bisphenols such as bisphenol A. These then
cyclotrimerize upon heating to form substituted triazine rings that can
be further polymerized to give the polycyanurate thermosets used in
printed circuit board applications. The cyanate ester chemistry results in
high thermal performance when crosslinked and modifications to the basic
polymer backbone of the resin allow excellent dielectric properties to be
achieved. Cyanate ester laminate materials have been based upon both
thermosetting bisphenol-A dicyanate ester resins and cycloaliphatic struc-
tures (e.g. the dicyclopentadiene-based cyanate ester resins from Dow
Chemical). Unlike many epoxide materials, these systems do not contain
dicyandiamide. The resin systems are chemically modified to optimize
dielectric constant, adhesion, flame retardance and toughness. The cyanate
ester resins generally offer low dielectric constants coupled with Tgs in the
region of 240--260°C, whilst above this temperature polyimide chemistry is
the most popular. A typical example of these cyanate ester materials is
afforded by the N-SOOO range produced by Nelco which have Tgs of
around 250°C coupled with a dielectric constant of 3.5 and a dissipation
factor of 0.005. Cyanate esters have also been found to perform well as the
matrix resins for Aramid fibre reinforcements and as adhesives for
polyimide films. With base resin dielectric constants of around 2.S, the
cyanate ester resins offer significant advantages over other materials and
bridge the void between PTFE and standard multilayer materials. Some of
the properties of a typical cyanate ester are compared with an FR4
material in Table 9.4.
9.5.3 Polyimides
Polyimides were developed during the 1960s and early 1970s in response to
the demands of the military and aerospace industry for high temperature
performance polymers, as matrix materials for laminates and other
composites. Most aromatic/heterocyclic polymer systems that have a small
number of oxidizable C-H bonds per molecule exhibit excellent oxidative
314 I ~I__________PO_L_YM
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__E_D
__ ________~
C_IR_C_U_I_T_B_O_A_R_D
Table 9.4 Comparison of cyanate ester and FR4 laminate properties
Property FR4 Cyanate ester
Glass transition temperature (TgrC) 135 245
Thermal Expansion Coefficient (ppm 0C)
x- and y-axis 16 12
z-axis 80 45
Peel strength Obs/inch) 10 7
Moisture absorption (%) (0-24/23) 0.9 0.7
Dielectric constant @ 1 MHz 4.3 3.5
Dissipation factor @ I MHz 0.020 0.005
stability, but tend to be intractable and extremely difficult to process. In the

case of polyimides, however, this limitation has been largely overcome.
Some of the materials now in use for structural applications can withstand
continuous exposures in air to temperatures above 300°C.
_The characteristic structural featurl! of a polyimide is the presence of the
phthalimide grouping in the repeat unit, which is represented by the
formula
dl)- o
These units may be linked through alkyl or aryl groups to form the main
polymer chain, the latter generally giving higher temperature performance.
The most general method for the preparation of high temperature
polyimides is based on the reaction between an aromatic diamine and an
aromatic dianhydride or tetracarboxylic acid. This proceeds via the
formation of the intermediate polyamic acid which in further heating
undergoes a ring closure condensation reaction leading to imide formation.
The reaction is as follows:
o
II
HOOC C NHR-
NHRNH~H
o
Polyamic acid
L - -_ _ _ ------'I I
P_O_L_YM_E_R_S_U_S_E_D_F_O_R_L_A_M_I_N_A_T_E_M_A_NU_F_A_CT_U_R_E_ _ 315
The fact that water is eliminated during the final cure to produce a highly
condensed polymer with rapidly increasing viscosity (low flow) results in a
relatively high concentration of voids, removal of which requires heating
above Tg (typically > 290°C) under pressure for several hours. For this
reason, the condensation polyimides have not been successfully applied to
the fabrication of printed wiring and laminates, although polyimide films
prepared by this route are used in other electronic applications, including
flexible film substrates (as described in section 9.6).
In the late 1960s another class of polyimides was developed by Rhone
Poulenc in which the anhydride or acid is replaced by a bismaleimide and
the resulting polyimide is formed without elimination of water. The reaction
illustrated schematically below proceeds via amine addition about the
double bonds of bismaleimide to form a linear pre-polymer.
In the presence of excess bismaleimide and a free radical initiator, self-

addition can occur at the maleic double bond leading to crosslinking which
produces a polymer of high thermal stability.
Laminates based on Ciba's Keramid 601 polyimide resin are fabricated in
a conventional laminating press, and processed in a manner similar to that
used for epoxies but with an extended cure cycle or post-cure. The room-
temperature mechanical and electrical properties are similar to epoxy
laminates, as shown in Table 9.5. At elevated temperatures, the polyimides
exhibit exceptional stability. In particular, the thermal coefficient of
expansion in the Z aiis does not change significantly up to approximately
240°C, as shown in Fig. 9.10. Exhaustive tests have shown that polyimide-
based multilayer boards can withstand repetitive thermal cycling at elevated
temperatures (> 150°C) without cracking of plated through holes. Similar
excellent results were also obtained in solder shock tests (10 s at 288°C in
molten solder). The thermal stability of these materials is retained at
temperatures of approximately 200°C for continuous exposure in air, which
has qualified them for military applications.
Polyimides are also being used in conjunction with silica fabric (which has
a coefficient of expansion approximately one tenth that of E-glass) to
produce laminates with expansion coefficients in the XY plane which are as
low as 6--7 ppm, i.e. close to that of a ceramic chip carrier. This composite
satisfies the requirement for a substrate material for direct attachment of the
larger leadless chip carriers.
Table 9.5 Properties of printed circuit board laminates based on different polymers
Property Test FR4 Keramid 601 FR2 Teflon
epoxy polyimide phenolic glass-fabric
30-35% 22-25% 40-50%
resin resin resin
Flexural strength
(psi x 10- 3) 25°C A 80 71 20 15
299°C 30 57
Flexural modulus
(psi x 10-6 ) A 2.5 4.0 1.2
Interlaminar bond strength A 2.5 2.1 1.0 0.8
Dielectric constant
(l MHz, 25°C) D24/23 4.3 4.6 4.0 2.35
Dissipation factor
(l MHz, 25°C) D24/23 0.019 0.018 0.03 0.0005
Volume resistivity
(x 10- 15 n cm) C96/90/35 0.2 0.15 0.01 0.2
Electric strength
(kV/mm) A 22 20 25 28
Deflection temperature
eC) (264 psi) El/150 120 240 60 250
Thermal expansion
(XY plane, ppm;oC) El/150 12 11 18 20
Water absorption
(%) (24 h) D24/23 0.1 0.3 0.6 0.02
Maximum continuous
temperature eC) 150 250 105 250
POLYMERS USED FOR LAMINATE MANUFACTURE
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~
317
.30r-------------------------------r-----~
tJi! .20
§
"!
1i;I;l.10
o ~ __ ~~~ ______ ~ ______ ~ ______ ~ ____ ~
o 50 100 150 200 250

Temperaturef'C
Fig. 9.10. Z axis thermal expansion coefficient of a polyimide glass laminate
compared with FR4 epoxy.
An example of a polyimide-based copper clad laminate is the N-7205

series produced by Nelco. This material has a glass transition temperature of
270 e and excellent dimensional stability in the x-y plane.
0
Although polyimides are being employed increasingly in printed wiring

applications at the leading edge of the technology, they are four to five times
more costly than epoxy resins and are more difficult to process. Polyimides
account for only a small percentage of total laminate resin consumption.
However, despite the high cost, their use is expected to grow significantly.
9.5.4 Phenolic Resins

Phenolics were the first thermosets to be used for the fabrication of
electrically insulating substrates because of their ease of processing and
excellent chemical and heat resistances. Phenolic or phenol-formaldehyde
resins describe a variety of products made by the condensation of phenols
with formaldehyde. The first commercial processes for the manufacture of
phenolic resins were developed by Baekeland and Thuslow in the early 1900s
and the products were sold under the trade names of Bakelite and Novolac.
Two basic types of reaction occur between phenol and formaldehyde
depending upon the pH of the reaction medium. In the presence of an acid
catalyst, formaldehyde forms a carbonium ion, namely
which can add (electrophilically) to either of the two ortho or the para
positions of a phenol:
318 II POLYMERS IN PRINTED CIRCUIT BOARD
~----------------------------------------------------~
~
LQJ + CH2=O ~ LQJ
L C H2-OH
+ ¥
~
CH2 0H
Ortho Para
Since the linking of the phenolic groups may also occur at either the ortho
or the para positions, branching occurs as the polymerization proceeds:
f1: 11:
OH
rQr'CH'OH +© ~ ~,~
OH
The resulting novolac resins (prepolymers) generally have a value of n in the

range 6-12.
If the reaction is base catalysed and excess formaldehyde is present, the
6
condensation primarily occurs through formation of ether linkages:
~CH'--oH + + CH,O
~ r 1:1 H~
t OCH,
~ CH2 0H
The resulting resole resins can undergo further (thermal) reaction with
elimination of water to produce a highly crosslinked system. By contrast,
curing of the novo lac resins requires the addition of a curing agent capable
of forming additional methylene groups. Curing agents most commonly
used are resole resins or hexamethylene tetramine. In the case of the latter,
ammonia rather than water is liberated in the condensation reaction. Since
novo lacs require a second stage to fully cure, they are frequently referred to
as two-step phenolics, whereas the resoles are referred to as one-step
phenolics.
Phenolic resins used in lamination are primarily the one-step resoles,
although novolacs may be added to improve resistance to water. Further
improvements in water resistance and a reduction in brittleness are achieved
by using para-cresol in place of phenol. This inhibits branching since the
para position is blocked by the methyl group.
Phenolics are the lowest-cost resins used in printed wiring substrate
fabrication, but in the USA and Europe they account for only a relatively
small percentage of the volume due to their replacement by higher
--'I I
'--_ _ _P_O_L_y_M_E_R_S_V_S_E_D_F_O_R_L_A_M_I_N_A_T_E_M_A_NV_F_A_C_T_V_R_E_ _ 319
performance epoxies. In Japan and the Far East, phenolic resins represent a
significant proportion of laminate consumption in printed wiring manufac-
ture due to the wide acceptance of XXXP and FR2 grade laminates for
consumer electronics. The properties of typical materials are shown in Table
9.5.
The major disadvantage of phenolics is their low insulation resistance.
Phenolics generally exhibit greater water absorption and sensitivity of the
electrical properties to humid environments than epoxy resins, although
only the so-called low-loss grades are used for printed wiring substrates. For
these reasons, the use of phenolics in laminate fabrication has been
restricted to the lower cost paper-based reinforcements.
9.5.5 PolytetraOuoroethylene and Thermoplastic Polypbenyl Ether

The use of polytetrafluoroethylene or PTFE for printed wiring substrate
fabrication is a well-established practice brought about by the need for
improved high-frequency materials. The critical properties in this field of
application are a low dissipation factor, a uniform dielectric constant which
exhibits little variation with frequency over a wide bandwidth up to IS GHz,
combined with environmental and temperature stabilities. These properties
can be achieved in a number of teflon/glass or teflon/glass/ceramic
composites based on both fabrics and random glass. Their dissipation
factors at I MHz are typically more than 100 times lower than a normal
epoxy FR4, as shown in Table 9.5.
Polytetrafluoroethylene is the polymer resulting from the free radical
polymerization of tetrafluoroethylene CF2=CF2 . The reaction is usually
carried out in an aqueous emulsion which produces sub-micron particles of the
polymer, or in a suspension which gives rise to particles of 100 JLm or greater.
The polymer is processed from various resin grades, which differ in fineness, by
means of preforming followed by sintering as in powder metallurgy.
Typical examples of commercially available Teflon-based materials are
RT/duroid 5000 and 5880 which were first produced by the Rogers
Corporation in the 1960s. These contain random microfibre glass and have
dielectric constants of 2.33 and 2.20 respectively. PTFE materials are also
produced that contain a woven glass cloth impregnated with a ceramic
loaded thermoset resin. These have higher dielectric constants but give
thermally stable rigid laminates with electrical properties suitable for
microwave frequencies. In particular this type of material has mechanical
integrity similar to FR4 and can also be fabricated like FR4.
The major disadvantage of Teflon is its high cost (approximately 20 to 30
times greater than FR4 laminate). However, no material is currently
available which can compete with it for exacting microwave applications,
although some of the high temperature thermoplastics can be used in its
place for the fabrication of other high-frequency substrates.
320 I IL-________PO
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__E_D__C_IR_C_U_IT
Another material useful for high-frequency applications is based upon the
thermoplastic material polyphenyl ether (PPE). In this case the normally
thermoplastic material is modified to produce a crosslinkable thermosetting
material that can be used in a similar manner to the conventional epoxies to
produce base materials for high-frequency boards. Laminates produced
from this material have low loss values that make them interesting for high-
speed circuits operating in the Gigahertz region. They have glass transition
temperatures in the region of 190°C and commercial versions conform to the
UL94 v-o rating without the use of halogenated flame retardants. They
have been used in applications such as cellular phones, personal computers
and with ball grid array packages. The structural viscosity of the resin
permits close tolerances to be achieved during lamination and this makes
them attractive for the production of controlled impedance boards. An
example of this type of material is the GIGAVER 210 produced by Isola
AG using a PPE resin from Asahi Chemicals. PPE is also blended with
epoxy to produce GE's GETEK and Asahi produce an alkylated PPE which
can be thermosetting. Nelco has licensed this technology for its N6000 series
products.
9.6 POLYMERS FOR FLEXIBLE PRINTED WIRING
Flexible printed wiring is used primarily in electronic packaging applications

where low weight or volume is a prerequisite, or where excessive vibration is
likely to be encountered. The main advantage of flexible circuitry is its
ability to be shaped into more than one plane or conform to an irregular
shaped package.
The development of flexible printed wiring was made possible through the
availability of polymer films that possess high electrical insulation and good
chemical resistance, in particular polyester (e.g. polyethylene terephthalate)
and polyimide films which account for over 95% of the flexible film
consumption for printed wiring applications. The properties of the most
important of these polymers are discussed in the following sections.
9.6.1 Polyesters: Polyethylene Terepbtbalate (PET) and Polyethylene

Napbthalate (PEN)
Polyethylene terephthalate is the linear polycondensation product of
ethylene glycol and terephthalic acid:
L -_ _ _ _ P_O_L_y_M_E_R_S_F_O_R_F_L_EX_IB_L_E_P_R_I_NT_ED_W_I_R_IN_G_ _ _--,------II I 321
It was introduced commercially in fibre form in the 1950s. The polymer is

processed into film by melt extrusion followed by hot rolling and stretching
which results in molecular orientation accompanied by partial crystalliza-
tion. The deformation-induced orientation imparts high strength and
toughness to the film which is not a characteristic of the purely amorphous
phase. PET film is available in a number of grades for a variety of
applications including magnetic tapes, photographic substrates, packaging
and electrical insulation. Mylar® Type A from DuPont or equivalent grades
from ICI and Hoechst are normally used for flexible printed wiring and the
typical properties are shown in Table 9.6. The outstanding features of PET
are its high dielectric strength, low dissipation factor and excellent resistance
to chemicals and water. It also possesses a high tensile strength and does not
embrittle with ageing. PET based polyesters have melting points in the
region of 250--260°C and glass transition temperatures of 80°C, which limit
their usefulness where they are likely to encounter soldering temperatures
for any appreciable time. However, because of its low cost it is used
extensively in automotive dashboards where crimped terminations can be
used in place of soldered joints because of the small number of components
to be interconnected and the low interconnection density. It is also used
purely as a flexible harness in automotive and related applications.
Dielectric films have also been produced from polyethylenenaphthalate
(PEN), a polyester material similar to Mylar. The main advantage of PEN is
that it possesses better thermal properties than PET with a Tg approximately
1200 higher. In addition, it possesses good dimensional stability for a
polyester material and a relatively low dielectric constant. It is produced
commercially, for example, by ICI Americas, as Kaladex and as a series of
copper clad laminate materials (R/flex IPEN-L) by Rogers Corporation.
PEN offers a compromise in terms of performance and cost between PET
and polyimide.
9.6.2 Polyimide
For many years only one type of electrical grade polyimide was available in
film form and this was manufactured by DuPont under the trade name
Kapton®. Kapton polyimide is formed by the polycondensation of
pyromellitic dianhydride and 4,4'-diamino diphenylether. The reaction
proceeds via the intermediate formation of the polyamic acid as described in
section 9.5.3. More recently, however, other grades of polyimide have now
become available and these have trade names such as Apical, Novax, Upilex
and Espanex.
The polymer is melt-processed into the film form, the properties of which
are shown in Table 9.6. Polyimide films possess excellent dielectric and
insulation properties which remain constant over a wide range of temper-
ature and frequency. An outstanding feature of polyimides is their high
Table 9.6 Properties of high temperature thermoplastics
Property Polysulphone Udel Polyether Polyphenylene Polyetherimide Ultem + 20%
suIphone sulphide Ultem glass reinforced
Victrex Ryton
Flexural strength
(x 10-3 psi) 15.4 18.6 25 21 30
Flexural modulus
(x 10-6 psi) 0.39 0.37 1.7 0.48 0.9
Tensile strength
(x 10-3 psi) 10.2 12.2 16.2 15.2 20
Dielectric constant
(l MHz, 25°C) 3.03 3.45 3.8 3.1 3.5
Dissipation factor
(1 MHz, 25°C) 0 0.008 0.0014 0.006 0.0015a
Volume resistivity
(x 10- 15 n cm) 50 100 45 6.7 0.7
Electric strength
(kVjmm) 17 16 17.7 28 26.5
Deflection temperature
eC) (264 psi) 174 202 243 200 209
Thermal expansion coefficient
(ppmrC) 56 55 40 56 25
Water absorption
(%) (24 h) 0.3 0.4 0.05 0.25 0.26
Maximum continuous
temperature (0C) 160 170-200 170 170 170
a 1 kHz.
P_O_L_y_M
L -_ _ _ _ _ _ _ __E_R_S_F_O_R__F_L_EX
__ __IR_I_N_G________~I
IB_L_E_P_R_I_N_T_E_D_W I 323
thermal stability and ability to retain good physical properties over a wide
temperature range (-250 to + 300°C or even higher). The main disadvantage
of polyimide film is its relatively high water absorption which results in an
increase in the dielectric constant and dissipation factor and a reduction in
the resistivity and dielectric strength on exposure to high-humidity
environments. Moisture must be removed from Kapton films prior to
lamination with copper foil to avoid blistering and delamination.
Since polyimide film offers excellent dimensional stability, high tensile
strength and high temperature resistance, its use in more sophisticated
flexible circuit applications is growing rapidly. Polyimide film is also used
for the fabrication of a hybrid type of wiring board referred to as 'flex-rigid'
in which conventional rigid glass reinforced laminate wiring boards are
combined in a multilayer package with integral printed flexible cables that
are electrically connected by means of plated through holes. This type of
circuit board is used mainly for military and high reliability systems. A
major development in polyimide foils occurred in the last few years with the
introduction of adhesiveless flex materials (see below). These materials are
popular with producers because they offer better dimensional stability,
potential for higher layer counts, and a greater degree of flexibility due to
the absence of an adhesive layer. An example of this type of material is
Pyralux AP from DuPont which has a glass transition temperature of
220°C, a dielectric constant of 3.24 and an in-plane expansion coefficient of
40 ppm °C.- 1
9.6.3 Plastic Composites

Two composite materials which have also been used for low-cost flexible
wiring applications are Dacron-epoxy® and Nomex® by DuPont. Dacron-
epoxy consists of a non-woven polyester fibre mat embedded in an epoxy
resin. It possesses good chemical and moisture resistances, excellent
dimensional stability and, compared to other flexible film materials, has a
high folding endurance. It is also solderable and flame resistant and has a
cost similar to Kapton. Nomex is a low-priced nylon paper composite based
on an aromatic polyamide which possesses higher temperature resistance
than conventional polyamides. Nomex paper is composed of two different
forms of the same polymer, consisting of short fibres which provide high
tensile strength and sub-micron fibres which act as a binder.
Both Dacron-epoxy and Nomex are solderable and flame resistant.
Nomex, however, possesses much higher water absorption and is therefore
not generally used for applications involving humid environments. It is
considered that the use of Nomex and Dacron has diminished somewhat in
recent years.
324 I ~I__________PO_L_YM
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__P_R_nNT __________~
__E_D__C_IR_C_U_I_T_B_O_A_RD
9.6.4 Other Materials

Fluorinated polymers such as polytetrafluoroethylene (PTFE) and fluor-
inated ethylene-propylene copolymers (FEP) were some of the first materials
to be used in flexible circuit applications. As already mentioned above, these
materials have numerous properties such as low dielectric constants and
low moisture absorptions which make them of interest for this type of
application. However, their high costs and difficult processing have
encouraged the development of alternatives.
Polyetherimide (PEl) has also been introduced as a potential substrate
material for flexible circuits both as a base film and as an adhesive. Being a
high temperature thermoplastic with a cost somewhere between polyester
and polyimide, PEl would appear to be ideally suited to this type of
application. At the time of writing, however, the material has not yet found
wide application and this may in part be due to the high lamination
temperatures required.
9.6.5 Fabrication and Uses

Flexible film substrates are available as single- and double-sided copper-clad
laminates. Copper foil is generally laminated to the base material by means
of epoxy, polyimide, polyester, acrylic-based or several other types of
adhesives. Adhesiveless materials are also now available where the copper
metallization has been sputtered or evaporated onto polyimide. The
development of adhesiveless materials has been prompted because the
adhesives themselves can introduce several shortcomings. Overall perfor-
mance can be limited by the adhesives because they usually have lower
thermal stabilities than the polyimide core and because the added thickness
of the adhesive layer reduces heat dissipation through the circuit. Advan-
tages of adhesiveless materials also include better dimensional stability,
higher layer count capability and greater flexibility. (An example of this type
of material is produced by DuPont as Pyralux AP.)
Flexible printed wiring can be fabricated by means of either the additive
or the subtractive process as used for rigid substrates. An alternative method
which is growing in use because of its low cost is the screen printing of low
temperature curable conductive inks directly onto the base material (usually
Mylar). This additive technique is being used for the fabrication of single-
sided keyboards. Other low-cost consumer electronic applications for
flexible wiring include cameras, microwave ovens, video games, watches
and calculators. Flexible circuits are now used in under-bonnet applications
such as car engine management units and the Sojourner Mars Pathfinder
space vehicle also has flex circuits in it. For 1998 world-wide flexible
laminate consumption is estimated to have represented approximately 6%
of total laminate consumption by volume. For a more detailed description
'--_ _ _ _
INT_E_G_RA_T_E_D_C_A_PA_C_I_T_O_R_S_A_ND
__R_E_S_IS_T_O_R_S_ _ _ _ --'I I 325
of flexible circuit technology the reader is referred to the recent work by

Joseph Fjelstad?
9.7 INTEGRATED CAPACITORS AND RESISTORS
The relentless demand for more performance in smaller products is causing

major changes in the way printed circuit boards are made. One new method
involves the use of new so-called build-up techniques and these are detailed
below in section 9.8. Another method involves removing discrete compo-
nents from the surface of the substrate and actually integrating them into
the substrate itself. Discrete components such as resistors and decoupling
capacitors can often occupy a significant area of a board surface and this is
area that could either be removed to reduce the size of the board or which
could be used to incorporate additional functionality. Consequently, there is
growing interest in the replacement of surface mounted resistors and
capacitors with devices integrated during the substrate manufacturing
process.
By-pass capacitors can be fabricated by using the power and ground plane
layers of a printed circuit board. The capacitor layers are fabricated in the
same way as for conventional layers but using 50 Jlm thick FR4 with
specially prepared copper foils. Conventional copper foils have surface
treatments that give too coarse a morphology and so double-treated copper
foils with low profiles, i.e. relatively smooth surface treatment, are used. The
patterned capacitor layers can be tested prior to lamination and using this
approach it has been shown possible to eliminate 96% or in some cases even
100% of the by-pass capacitors. The so-formed capacitors also tend to
exhibit better performance at high frequencies than the discrete components
they replace. It should be noted, however, that the use of buried capacitors
will add additional layers to the board and that the process has been
patented as the ZBC 2000 technology by the American-based company
Zycon.
It is also possible to incorporate resistors into printed circuit boards by
screen printing carbon inks onto the inner layers. Suitable inks are available
commercially and these are capable of providing a wide range of resistance
values (e.g. I ohm to I Mohm). It is necessary to incorporate special
terminal ends which provide connection to the ink when the specific inner
layer to contain the resistors is being designed. When the resistors have been
printed, the ink is cured at temperatures of up to 180°C and they can then be
electrically tested prior to lamination. Tolerances achieved are typically in
the region of 20% which is acceptable for many applications. Better
tolerances can also be achieved if necessary, as in hybrid manufacturing, by
the use of laser trimming techniques.
326 I I~_________PO
__L_YM
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__E_D__C_IR_C_U_I_T_B_O_A_RD
9.8 POLYMERS IN ADVANCED INTERCONNECT APPLICATIONS
The electronics industry is characterized by the inexorable improvements it

makes possible in electronic apparatus and each generation of a product is
usually smaller, cheaper and better performing than its predecessor.
Obvious examples here include the personal computer, the camcorder and
the mobile telephone. These improvements have been made possible by the
relentless progress at the semiconductor level where feature sizes have
become smaller and devices have much more performance integrated into
them. Almost without exception it has been the semiconductor industry that
has led the way in terms of enabling these new products to be made. In order
to accommodate these changes, the conventional printed circuit board has
evolved significantly in the forty years or so since the concept first began to
be widely exploited. Boards have increased in sophistication both in terms of
the maximum number of layers that can be incorporated into a printed
circuit board and in the minimum feature sizes that can be defined on the
board. Until recently these incremental improvements in conventional
printed circuits were easily able to accommodate the new semiconductor
devices and indeed the new packages in which they were available.
Initially, the so-called traditional through hole leaded components gave
way to surface mount components where the devices were soldered directly
on to the surface of the board. Surface mount technology went some way to
enabling the component density on printed circuit boards to be increased
and it is now the predominant technology used in board assembly. However,
in order to accommodate the increasingly sophisticated semiconductor
devices being produced, further specific developments of the surface mount
package were necessary. Early surface mount devices typically had
interconnections (I/Os) emerging from just two sides of their packages.
This was perfectly acceptable when devices had only 16 or 24 leads but as
devices emerged with larger numbers of I/Os it was not possible to
accommodate these leads on just two sides of a package without the package
becoming unacceptably large. It was possible to pack more I/Os into a given
package footprint by reducing the size of the leads and hence the pitch
between them but package makers also started to utilize all four sides of a
package in the so-called quad flat-pack type package. More recently, the
requirement for additional I/Os has increased dramatically and some
commercial packages are available with hundreds or even more than a
thousand I/Os and this trend is set to continue. In order to be able to make
connection to a semiconductor device with such large numbers of
connections new packaging solutions had to be developed and the main
approach adopted was to utilize all of the package, rather than just the
periphery, to connect the device to the underlying interconnect on the
printed circuit board. This concept is known as area array packaging and
was first seen in devices known as pin grid arrays. These have largely been
L-_P_O_L_Y_M_E_R_S_IN_A_D_V_A_N_C_E_D_I_NT_E_R_C_O_NN_E_C_T_A_P_PL_I_c_A_T_Io_N_s_---l1 I 327
superseded by ball grid arrays in which the connections between the package
and the substrate are normally made by arrays of metal balls or bumps
covering a large part of the underside surface of the package. Further
evolution of this type of packaging involves the use of increasingly finer
pitches and reductions in the overall size of the package. The latest
manifestation of this type of packaging is represented by the so-called chip
scale package (CSP) where the package is only slightly larger than the device
it encapsulates. All predictions from the semiconductor industry indicate
that this inexorable increase in the number of l/Os on state-of-the-art silicon
devices will continue and therefore there will be increasing pressure to
continue the development of advanced packaging solutions incorporating
finer pitch area interconnects.
Printed circuit board makers have, up to now, been able to accommodate
these packaging innovations by making the features on their printed circuit
board smaller and by adding additional layers to their boards. However, the
industry is now reaching the limit of possible improvements that can be
made using conventional technology. For example, although leaded
components are usually no longer required, board makers still have to
provide holes in their boards which can be metallized to allow interconnec-
tion of the various layers of circuitry in a multilayer board. These holes are
traditionally mechanically drilled and it is desirable to make them as small
as possible. When hole diameters were 0.5 rom these could be routinely
drilled at high speed and with good accuracy but as the requirement for
much smaller holes has increased the difficulty of mechanically drilling them
has also increased. It is generally agreed that mechanical drilling of holes
with diameters below '"" 100 J.Lm is not practically possible for volume
production. Similarly, since the late 1960s the PCB industry has routinely
used dry film photoresist in the patterning process for making PCBs.
Although this is a somewhat contentious issue, it is generally acknowledged
that the volume production of fine line interconnects becomes increasingly
difficult below about 100 J.Lm using conventional dry film imaging technol-
ogy.
Consequently, there is a wide acceptance that in order to produce the sub-
100 J.Lm lines and spaces and small diameter via (holes) that will be needed to
provide acceptable interconnects for the high lead count area array packages
now beginning to be produced, an alternative method of making these
interconnects will be required. One popular route which has a number of
possible variants is the so-called sequential build-up (SBU) approach. This
method relies heavily on the use of polymeric dielectrics. In the sequential
build up route additional layers of fine line interconnects are built up on top
of a conventional substrate. The conventional substrate would typically be a
4--6 layer multilayer printed circuit board manufactured using conventional
processes. Extra layers of interconnect, typically one, two or three layers,
would then be added sequentially to both sides of the board. These
328 I ~I__________PO_L_y_M__E_R_S_IN__P_R_INT
__E_D__C_IR_C_V_I_T_B_O_A_R_D________~
additional layers would be sufficiently fine to enable chip scale packages to
be assembled and to provide the interconnect pathways required for the
large numbers ofl/Os. This is shown schematically in Fig. 9.11.
Many potential routes for providing this type of sequentially built-up
circuitry have been investigated and currently they can be divided into three
principal basic routes that have been introduced commercially. Of these
three routes, the first utilizes plasma etching in a mass via formation
method, a good example being the Dycostrate technology developed by the
Swiss company Dyconex. This method uses copper coated polyimides which
may ultimately be laminated on to an existing substrate. The copper is
patterned using conventional techniques and the via holes are then etched
through the polyimide using a mixed oxygen and fluorocarbon based
plasma. The organic layer cannot contain any glass reinforcement and base
materials containing Thermount reinforcement have been produced by the
company Isola for this type of process. Resin coated copper foil can also be
used to build up purely organic insulating layers and resin systems based on
epoxy and polyphenylene ether (PPE) have also been evaluated. Subsequent
conventional PCB metallization processes are then used to plate the vias
thereby forming the connection between the two levels of metallization. This
process is particularly elegant in that the vias are all formed in a single
plasma etching stage. There are a number of process variations on the basic
theme and boards produced in this way have found particular favour for
high reliability military and aerospace applications.
The other two SBU processes that are currently very popular use
alternative techniques to form vias in a suitable dielectric. One uses a
specially developed photo-imageable permanent dielectric and the other
Sequential
lamination
Conventional PCB
Technology
O ~'\5mm mechani.::al drilled vias: G.15mm mAr.hanical drillP-d viA!';
Fig.9.11. Typical application for sequential build-up technology with two additional
interconnect layers being deposited on to a conventional multilayer printed circuit
board.
,--_P_O_L_Y_M_E_R_S_IN_A_D_V_A_N_C_E_D_I_NT_E_R_C_O_NN_E_Cf
__ A_PP_L_I_C_A_T_IO_N_S-,-------'! I 329
uses a non-imageable dielectric in which the vias are 'drilled' using a

suitable laser. In the route using a photoimageable dielectric, the liquid
dielectric is coated onto the precleaned substrate using conventional curtain
coating techniques well established in the PCB industry. After drying, the
dielectric can be exposed through a mask, as with a conventional
photoresist, and the image developed. The residual dielectric is then given
a further exposure and final bake to impart the fully cured properties
required of a permanent dielectric. The patterned dielectric can then be
metallized using conventional PCB process chemistries and after subsequent
patterning the next layer of dielectric can be coated as required. Sections
through sequentially built structures produced with a dielectric are shown in
Fig. 9.12. A number of dielectric and ancillary process chemistries
(including dry film materials) are currently emerging in the market place
from the major chemical suppliers in this area.
The chemistry of the dielectrics tends to be based on types similar to those
employed in the liquid photoimageable solder masks that are already widely
used in the PCB industry. Typically, these include epoxide chemistry for
good chemical stability, high crosslink densities and the ability to withstand
subsequent processing chemistries. Epoxide based chemistries can also be
formulated to meet the demanding electrica:l property requirements of a
permanent dielectric i.e. low dielectric constant and loss and high volume
resistivity. A typical example is the Multiposit Photoimageable dielectric
made by Shipley. This dielectric contains epoxide and novo lac polymers as
well as a melamine for thermal curing and a flexibilized polymer component
to give the cured material a degree of compliance, low moisture absorption
and a low dielectric constant. The initial curing under UV exposure is
125JlIIl. via SOJlm dielectric
75JlIIl. via SOJlm dielectric
Fig. 9.12. Via structures produced in a photoimageable dielectric (courtesy Shipley).

330 II~_________PO
__L_YM
___E_R_S_IN
__P_RI_NT ________~
__E_D__C_IR_C_U_I_T_B_O_A_R_D
brought about by the use of an aryl phosphonium salt that generates an acid
group during exposure. This in tum is capable of catalysing the epoxide
curing reaction. Final curing is achieved thermally.
With these dielectrics one of the key requirements is good adhesion since
the dielectric will be in contact with a number of interfaces and different
materials. Any thermal expansion coefficient mismatch between these
materials can lead to reliability problems occurring during any thermal
excursions experienced in assembly or service. The dielectrics need to have
good adhesion to underlying copper and substrate material, typically FR4.
In addition, any subsequently deposited dielectric and copper metallization
must also adhere well to the previously deposited layer. Good adhesion of
these materials is usually achieved through the use of special formulation
additives such as flexibilizers and optimized surface modification stages
during the processing.
With the laser 'drilling' approach to via generation the dielectric does not
need to be photo-imageable and this enables a wider choice of chemistries to
be considered. The vias are 'drilled' (i.e. ablated) in the dielectric using either
a CO2 laser operating in the infrared (10.6 or 9.4 nm) or an excimer or Nd/
YAG laser with an output in the UV (248 and 355 nm respectively). Until
recently, UV lasers were preferred because of their ability to form better
quality via holes but the recent CO2 lasers have been much improved such
that they now can also produce good quality vias. Drilling rates of up to 280
holes per second, independent of hole diameter up to 0.35 mm, have been
achieved with a TEA CO2 laser. Unlike the photo-imageable dielectric
method where all vias are formed in one exposure, the laser method is a
sequential process and therefore the speed of the laser is particularly
important. The different lasers also have varying material drilling capabil-
ities, for example the Nd/YAG lasers are able to drill copper, glass and resin
whereas the excimer lasers cannot drill copper and glass. This means that
different approaches and materials have to be selected depending upon the
laser choice.
Laser drilling speeds have been increasing significantly over the last two
years and it is estimated that laser drilling now accounts for over 70% of
current commercial SBU board production as opposed to less than 30%
using a photo-imageable dielectric. The photo-imaging route is however
currently dominant in the production of advanced package substrates.
9.9 SUMMARY AND CONCLUSIONS
The most widely used polymeric materials in the printed circuit board
industry are epoxy resins based on bisphenol A. Epoxy-glass fabric
laminates account for the vast majority of the consumption of printed
circuit substrates. In particular, laminates with specifications equal to or
L -_ _ _ _ _ _ SD_M_M_A_R_y_A_ND
__C_O_N_C_L_D_S_IO_N_S_ _ _ _ _ _ ---'I I 331
better than NEMA grade GlOor FR4, which combine very good
dimensional stability with excellent electrical properties, are suitable for
the fabrication of high density wiring that is required for computers and
telecommunications equipment.
In much of the consumer electronics field where interconnection density is
generally low, cheaper substrates such as paper-based phenolic resins,
epoxy-glass mat composites and polyester or nylon-based flexible films are
employed. However, it is worth noting that with the increasing sophistica-
tion of consumer electronic goods such as mobile phones, camcorders and
palm top computers, the need for high density interconnects is growing
rapidly and these need higher quality substrate materials.
Polyimides which are available as both laminating resins and flexible films
are used in military and aerospace applications where high temperature
performance is critical. High temperature thermoplastics such as polysul-
phones and polyetherimides offer the potential for production of relatively
low-cost moulded substrates with excellent electrical characteristics and
thermal stability (see Chapter 11). The low dissipation factors characteristic
of these materials have generated considerable interest in their potential for
use in high-frequency circuits, as a substitute for the much more expensive
teflon-based substrates. Much of the demand for new or improved substrate
materials for printed wiring is generated by the ever-increasing density of
silicon microcircuits. As the chips become larger with more functionality the
number and density of interconnections increases. This requires the use of
finer traces, smaller pads and plated through holes, in conjunction with an
increasing employment of multilayer wiring. Consequently, substrates with
high dimensional stability are required to facilitate the precise registration of
circuit layers and to eliminate failures due to the cracking of plated through
holes. This latter problem results from excessive expansion and contraction
of the substrate that occurs during thermal cycling in processing steps such
as lamination and soldering. Furthermore, the higher current densities
associated with the current range of microprocessors gives rise to a greater
level of heat dissipation and hence thermal stress which add to the problems
of substrate thermomechanical stability.
Today, most of these problems are being resolved by the use of rigid
substrates based on high glass transition temperature resins such as
polyimides and modified epoxides. The reduced thermal expansion of these
materials at the normal processing or operating temperatures provides for
significant increases in dimensional stability compared with GIO or FR4
laminates. As device operating speeds increase, there is, however, still a need
for materials with reduced dielectric constants and improved loss factors.
In addition, composites are being developed in which the thermal
coefficients of expansion are matched more closely to those of the chip
substrates and copper foils to reduce thermal stress. Many of these
developments at the so-called leading edge of the technology are heralding
332 I ~I__________PO__L_YM__E_R_S__IN__P_RI_NT__E_D__C_IR_C_U__IT__B_O_A_RD__________~
the future for new approaches to providing advanced interconnect struc-
tures. The use of sequential build-up technology is one example of how a
radically different approach to providing interconnects is being utilized to
enable the increasingly sophisticated semiconductor packages with hundreds
or even thousands of I/Os to be accommodated. What is certain is that no
single polymeric material or composite will provide the necessary cost/
performance capability for all of the increasingly diverse interconnect needs
of the electronics industry.
9.10 ACKNOWLEDGEMENT
In the previous edition of this book the chapter detailing polymers used in
printed circuit board applications was written by Dr Rodney Hurditch.
Although there have been many significant new developments in the
materials used in this area much of the information presented in the original
chapter remains valid today and has. been included in this chapter. I would
therefore like to acknowledge the important contribution made to this
chapter by Dr Hurditch and to thank him for his valuable input.
9.11 REFERENCES
l. Leonida, G., Handbook of Printed Circuit Design, Manufacture, Components and

Assembly, Electrochemical Publications Ltd, 1981, Ayr, Scotland.
2. Fjelstad, J., An Engineer's Guide to Flexible Circuit Technology, Electrochemical
Publications Ltd, 1997.
New Polymers for Emerging 10
Interconnection Applications
JOHN EVERETT,* PHILIP GARROUt
and DAVID DALMANt
*Dow Deutschland Inc., IndustriestraBe I, D-77836
Rheinmiinster, Germany, tThe Dow Chemical Co., c/o MCNC
Research Triangle Park, NC 27709, USA and tThe Dow
Chemical Company, Midland, Michigan, MI 48674, USA
10.1 INTRODUCTION
The principal drivers for the development of new polymers for electronic
applications include:
• device, substrate and system miniaturization impacting operational speed
and product weight (e.g. portability),
• coefficient of thermal expansion (CTE) mismatch of semiconductor and
related packaging and interconnecting materials,
• increase in data signal processing speeds and need for dielectric constant
(&') and dielectric loss (&'') reduction,
• integration of low cost, production efficient, high performance materials
and enabling technologies into consumer products,
• improved product reliability.
With these considerations the global electronics business is continually
challenging the cost/performance balance of materials employed by the
industry. In order to get 'more-for-less' electronic designers, material
developers and manufacturers have spent considerable effort to investigate
the potential of new polymers, particularly ones that enable new technol-
334 !NEW POLYMERS FOR EMERGING INTERCONNECTION APPLICATION~
ogies to provide lower cost manufacturing. This chapter reviews several of

these new materials and is particularly focused upon emerging intercon-
nection methodologies.
10.2 PWB SUBSTRATES WITH ORGANIC REINFORCEMENTS
When manufacturing printed wiring board substrates (PWBs) a number of

choices in both selection of resin type and selection of resin reinforcement
are available. For example, in designing a substrate for high speed
transmission, it is critical to minimize the dielectric constant as this has a
direct impact upon signal propagation delays and crosstalk. Given that the
difference between the dielectric properties of resins (e.g. r.' = 4.0 for typical
epoxies and 2.0 for PTFE) is smaller than the reinforcement (r.' = 6.6 for E-
glass and 2.0 for PTFE) considerable interest has been paid in recent years
to the development of low dielectric constant organic reinforcement
materials. In particular, emphasis has been placed on new substrates
employing expanded-PTFE and aromatic polyamides, e.g. poly(para-
phenylene terephthalamide), PPTA. These are commercially known as
Teflon™ and Kevlar™, respectively. Table 10.1 compares the range of
related physical and mechanical properties of a number of glasses and
organic reinforcements. Although glass, especially in the form of quartz,
does have good electrical characteristics, it is very difficult to process
because it is so brittle. For example, significant difficulties are encountered
during weaving into the textile fabric form most suitable for PWB laminate
reinforcement, and also particularly during drilling operations. This later
point is highlighted in Table 10.1 where the relative drilling capability of
equivalent PWBs, manufactured from substrates containing the reinforce-
ments shown, are compared. Whereas for a typical E-glass FR4 PWB
laminate a drill will last well over 2000 hits before requiring sharpening or
replacement, quartz is nearly three orders or magnitude harder and thus
contributes to a considerable increase in fabrication costs.
Table 10.1 Properties of PWB reinforcements
Material E' E" Density x-CTE Modulus Relative

(J MHz, 23°C) (J MHz, 23°C) (g/cm3 ) (ppm/K) (GPa) drilling
E-glass 6.6 0.004 2.54 5.0 1.52 2000

S-glass 6.0 0.002 2.49 2.9 1.81 500
D-glass 4.6 0.0015 2.16 3.0 1.10 50
Quartz 3.7 0.0002 2.20 0.55 1.45 5
PPTA 3.8 0.020 1.44 -5.0 2.68 2000
e-PTFE 2.0 0.0002 2.21 60 0.19 2000
L -_ _ --'I I
P_W_B_SU_B_S_T_RA_T_E_S_W_I_T_H_O_R_G_A_N_IC_R_E_IN_F_O_R_C_E_M_E_NT_S_ _ 335
Laminates produced from organic reinforcements also enable the use of

laser and plasma ablation for the formation of PWB holes and vias,
Fig. 10.1 (a). Production of miniaturized structures with dimensions < 100
/.tIll is virtually impossible and currently not economical with mechanical
drilling methods. Further circuit densification gains can also be made since
the need for via routing around pads is avoided, see Fig. 10. 1(b). Via
reliability is also improved since it is often the pad delamination that causes
failure.
A Japanese company was the first to introduce materials based on
aromatic polyamide reinforcements I but since then two additional organic-
based reinforcing products have become commercially available, namely
laminates containing Thermount™ and those composed of Speedboard™
prepreg. Thermount is a non-woven paper-like fabric composed mainly of
Kevlar™ fibres, bound together with fibres of poly(meta-phenylene
isophthalamide), known as Nomex™, Fig.10.2. The mechanical and
dimensional stability of Thermount makes it well suited for fabricating
PWBs both when used alone or in sequentially built-up structures on FR4
laminate core,2 see Fig.IO.3 and Table 10.2. Several prepreg and laminate
vendors manufacture products with Thermount, usually impregnating the
fabric with epoxy, polyimide or cyanate ester resins.
Sequentially built-up circuitry is an increasingly popular way of facilitat-
ing PWB size reductions and enhanced interconnection densities (see
Chapter 9), the principle of which is further exploited when using the
Speedboard material since the dielectric constant of the material is even
lower, Table 10.2. Speedboard is an expanded poly tetrafluoroethylene
(ePTFE) material, better described as a matrix of PTFE nodes connected by
PTFE fibrils, see Fig. 10.4, and impregnated with resin. The exclusive
supplier, W.L. Gore and Associates, uses epoxy or cyanate ester resins as the
Conventional
Pad-Ies~ microvias
•
•
(a)
Fig. 1U.l.
336 fEW POLYMERS FOR EMERGING INTERCONNECTION APPLICATION~
H H-o- Hie
A.KEVLARTM B. NOME)(TM
NlCJN'
~-o-'\ ~-c
- II
o
'I
-
'\ c
II
0
I
I
-...::
~
c
II
0
I
~ c
0
II
n n
Fig. 10.2. Chemical structures of aromatic polyamides.
Fig. 10.3. Cross-section of a laminate using Thermount non-woven aramid fabric

(courtesy Mommers Print Service, Holland).
Table 10.2 General properties of Speedboard™ and Thermount™ containing

laminates
Property Speedboard N SpeedboardC Thermount Thermount

(epoxy) (cyanate ester) with epoxy with po/yi-
mide
Tg by DSC eC) 140 220 180 260

e' at I MHz, 23°C 3.1 2.6 3.9 3.9
e" at I MHz, 23°C 0.020 0.004 0.020 0.020
x,y,z-CTE (ppmrC) 60,60,60 60,60,60 8,8, 100 8,8,80
binder, and it is claimed that employing Speedboard can reduce the size of a
PWB by over 50%, and bring a gain of 20% in signal speed over standard
FR4 constructions. 3 Given that its dimensional stability is not as good as
laminates containing glass or aramid reinforcements, Gore promotes the use
of Speedboard via a so-called mixed dielectric concept, Fig. 10.4. The
Speedboard layers conform to the topography of the core dielectric, for
L -_ _ _ ---'I I
P_W_B_SV_B_S_T_RA_T_E_S_W_I_T_H_O_V_T_R_EI_N_F_O_R_C_E_M_E_NT_S_ _ _ 337
(a
Fig. 10.4. (a) Micrograph of ePTFE matrix; (b) cross-section of mixed dielectric
PWB (courtesy of W. L. Gore & Associates).
example FR-4, and also assume the core's improved thermal expansion
coefficient (CTE) characteristics.
10.3 PWB SUBSTRATES WImOUT REINFORCEMENTS
Films produced from polyimides have been used for over twenty years in
flexible PWB applications (see Chapter 9). More recently they, and films
containing epoxy, bismaleimide (BT) or poly(phenylene oxide) based resins,
have been used for the sequential build-up of circuitry on glass reinforced
substrate cores4 in so-called MCM-L technology. Indeed well over a dozen
different SBU methodologies, including DYCOstrate™ and the use of
photoimageable dielectric films, have been cited. 4 However, few of them
have sufficient dimensional stability to be employed in a solo form as a
substrate dielectric. Liquid crystalline polymers (LCPs), on the other hand,
possess a significant degree of molecular ordering and have correspondingly
low CTEs. Of the many main-chain thermotropic LCPs that have been
synthesized to dateS several have been commercialized.6 Far fewer, however,
have been utilized for electronic interconnect applications. Figure 10.5 and
Table 10.3 highlight the chemistry and properties of one such example.
Liquid crystal polymers offer additional advantages in that most of them
include inherent flame retardancy and recyclability. One of the regularly
quoted difficulties with LCP technology, i.e. the ability to produce a
dielectric film with uniform properties in the x- and y-directions, is claimed
to be avoided through the use of a counter-rotating die fabrication
process.? Further potential applications of LCPs in the electronics industry
that are currently being investigated include dimensionally stable fibres and
micro-foamed films with extremely low dielectric constants and losses.
y
Fig. 10.5. Chemical structure of Vectran™ LCP film.
Table 10.3 Some properties of Vectran™ LCP film
Property Vectran™
Melting point (OC) 320

Moisture adsorption ASTM 750 (%) 0.02
e' at 0.01/1/1000 MHz 3.7/3.2/2.7
e" at 0.01/1/1000 MHz 0.040/0.020/0.003
CTE in x-I y-/ z-directions (ppm/K) 20/80
Tensile modulus (MPa [Kpsi]) 520 [750]
Tensile strength (MPa [Kpsi]) 82 [12]
Another interesting form of self-reinforcing polymer is obtained from a

class of macromolecules referred to as rigid-rod polymers. One of the first
polymers of this type to be studied was poly-benzoxazole (PBO).8 Dow
Chemical's Polyimidebenzoxazole (PiBO) is a linear, rigid polyimide cast
into a film from the corresponding polyamic acid. Although it is not a liquid
crystalline polymer, many of the similar mechanical, thermal and electrical
properties are attributed to the highly aromatic and rigid structure of the
polymer, especially the benzoxazole moiety, see Fig. 10.6.
The thermal properties of such films produced from PiBO are outstand-
ing, with expansion coefficients of less than 0.005% (0.05 mil/in; 50 ppm).
This is 20 times better than typical FR4 type material, i.e. 1.5 mil movement
across the 30 inch diagonal of an 18 x 24 inch PWB panel verses 12 mil for
thin FR4. This drastically improved performance should allow smaller catch
pads for newer via technologies such as laser drilling. The properties of
PiBO are compiled in Table 10.4.
10.4 POLYMERS FOR mIN FILM MICROELECTRONICS

APPLICATIONS
Dielectrics for thin film microelectronic packaging can be either polymeric

or inorganic. Polymers, in general, are capable of forming thicker layers
POLYMERS FOR THIN FILM MICROELECTRONICS APPLICATIONS II 339
o
o~ ft II
:~<C}-Ar
C
II
o
-f > C
c
II
o
n
Fig. 10.6. Chemical structure of PiBO.
Table 10.4 Some properties of PiBO film
Property Value
Tg eC) >500
r/ at 1 MHz 2.6
E" at 1 MHz 0.004
Tensile strength (Mpa [Ksi)) 393 [57]
Tensile modulus (GPa [Msi]) 11 [\.6]
Water abs., 50% RH, 23°C (%) 1.3
Dielectric strength (V/mil) 8000
x,y-CTE (ppm/K) 3-5
with much lower stresses than the inorganics and can be applied by spin
coating rather than the typical chemical vapour deposition (CVO) route
required for materials such as Si02 and Si3N4 • The organic materials also
help to planarize topography rather than conformally coat as does deposited
Si02 • Some polymers also have lower dielectric constants, lower water
absorptions and are resistant to copper migration. On the other hand Si02
unquestionably offers better thermal conductivity, thermal stability and
chemical inertness.
The suitability of a specific polymeric material is highly dependent on the
intended application, the process chosen to fabricate the structure and the
environment that the device will be expected to operate in. Commercially
available materials are usually categorized by the via formation technique
that they are compatible with, i.e. dry etching (plasma, RIE or laser), wet
etching (usually aqueous base) or photosensitive (features created in a
process similar to negative working photoresists).
In general, polyimides (PIs) and benzocyclobutenes (BCBs) are the
polymeric materials being used commercially to fabricate polymeric thin
film devices for the applications detailed below. A variety of polymeric
materials are being examined for use as inner layer dielectrics on intergrated
circuits (ICs, see section 10.4.3.2). Generally, however, polymeric materials,
although possibly finding use in specific applications such as acrylics in flat

panel displays, do not yet meet all of the thermal, electrical, mechanical and/
or chemical resistance requirements for the broad range of applications
described below.
10.4.1 Polyimides (PIs)

PIs are available from several vendors, as shown in Table 10.5. Most
commercially available PIs are derived from the reaction of an aromatic
dianhydride with an aromatic diamine as shown in Fig. 10.7. Most products
are supplied as the soluble polyamic acid (PAA) intermediates, which evolve
water upon curing, to yield the final PI structure. Some, such as Olin
Probamide™ 400, are supplied as preimidized materials. The traditional
solvent used is n-methyl pyrrolidone (NMP). Most PIs are thermally
crosslinked thermoplastics. In order to obtain good film quality, high
molecular weight (Mw) PAAs are needed which tend to result in low
solubility, high viscosity systems. PAA solutions are stored at O°C. The
'curing' reaction typically requires temperatures of between 350 and 400°C,
or even higher, and results in about 50% shrinkage (sometimes more for
photosensitive materials). PIs show excellent thermal stablility up to
temperatures in excess of 400°C and they typically also exhibit excellent
mechanical properties. Polyamic acid derived PIs are, however, incompat-
ible with Cu metallurgies9 and generally need barrier metal such as
chromium or tantalum to protect the Cu from corrosion and migration.
More details on the chemistry of polyimides are available in references lO-
13; see also Chapter 9 for details of polyimides used in conventional printed
circuit board laminates.
PIs having rigid backbones fall into a special class of compounds which
reveal very high modulus and low biaxial (x-y, in plane) coefficient of
thermal expansion values. These CTE values, as well as other optical and
mechanical properties, are highly anisotropic, and thus Z axis CTEs are
reportedly significantly greater than 100 ppm. 14 'Low CTE' PI products are
exemplified by DuPont PyralinTM 2611, Hitachi PIQ-LlOO (IV), the Olin
Probamid™ 500 and Asahi PIMEL™ TL 530.
Although photosensitive materials are inherently more expensive to
manufacture, they are generally chosen to lower overall processing costs.
Several processing steps can be omitted when using photo-imageable
polymers as shown in Fig. 10.8.
Commercially available materials are limited to negative working systems.
Negative working photosensitive polyimides (PSPIs) can be further catego-
rized by the source of photoactivity. PIs that are not inherently photosen-
sitive are modified by 'covalent attachment' or 'ionic' attachment of
photosensitive groups to the parent PAA molecules. These are referred to as
ester type and salt type PSPIs respectively. The ester materials are similar to
Table 10.5 Properties of commercially available thin film PI and BCB dielectrics
Vendor Product Photo E' Tg (0C) CTE Tensile Elongation Water Stress Planar-
designation (ppm) strength (%) absorption (Mpa) izationt
(MPa) (%;*
Asahi Pimel + 3.3 40-50 150 30 40-50

TL-530 + 3.0 10-20 200 15 10-20
Ciba-Geigy Probamide
400 + 3.0 350 39 140 56 ca. 5.0 55
500 3.2 400 6-7 444 28 0.5 5-10 20
Dow Cyclotene
3022 2.65 >350 52 85 9 0.2 28-32 >90
4026 + 2.65 >350 52 85 9 0.2 28-32 >75
DuPont Pyralin
2540 3.5 400 26 160 60 2-3 40-50 30
2611 2.9 (x,y) 350 5 600 60 < 1.0 4-10 20
2730 + 2.9 (x,y) 350 15 170 25
Hitachi PIQ -13 3.4 290 50 116 10 2.3 30 25
- LlOO 3.2 360 3 320 22 5 25
Toray Photoneece + 3.3 280 45 145 30 1.1 45 25
UR-3800
• Water absorption values are reported under various humidity conditions, see ref. 2l.
t Planarization of an isolated 20--30 micron feature. See ref. 22.
o 0
o~o +
o
PMDA
0
! ODA
! -2HzO
tN~-&t Pol~.
o 0 n
Fig. 10.7. Generalized PI synthesis.
the polyamic acid structure except that the alcohol group (OH) has been
replaced by an ester group (OR) where the R group contains a photo cross-
linkable species. The salt-based materials are derived from the reaction of
polyamic acids with bases containing the photocrosslinking species. I 4-16
10.4.2 Beozocyclobutenes (BeBs)

Benzocyclobutenes, BCBs,l7commercialized by Dow Chemical under the
trade name Cyclotene®, are a family of thermoset resins. The chemical
structure of the commercial, siloxy containing, DVS-BCB is shown in
Fig. 10.9. The resins are supplied, 'B-staged' in mesitylene, to obtain
appropriate viscoelastic handling properties. They are available in both dry
etch and photosensitive formulations. Dry etchable BCB solutions are stable
at room temperature. The photosensitive BCBs are negative acting being
sensitive to I-line irradiation. 19 ,2o
Benzocyclobutenes have totally different chemical structures when com-
pared to PIs and therefore have significantly different physical, electrical and
processing characteristics. Curing typically takes place at 210 to 250°C and
can be carried out in less than 15 minutes on a belt fumace l8 or in a few
minutes on a hot plate under nitrogen, without the evolution of water or
DRY ETCH
POLYMER PHOTOPOLYMER
iIIIIIIIi
COAT DIELECTRIC
POLYMER
SUBSTRATE
~
RESIST
COAT & DRY
RESIST
-..
EXPOSE &
DEVELOP
RESISTOR
POLYMER
TRANSFER
PATTERN TO
POLYMER
~
STRIP
RESIST
~
CURE
POLYMER
Fig. 10.S. Comparison of dry etch and photosensitive fabrication of interconnect

vias.
other by-products. Shrinkage during cure is therefore extremely low « 5%).

BCBs show extremely low water pickup and excellent planarization. The
BCB/Cu interface is stable and does not require barrier metal
interfaces.9 BCBs are, however, less thermally stable than polyimides and
must be cured in an inert atmosphere. These materials are compared and
contrasted in Table 10.5.
10.4.3 On-chip Applications

Polymers have been used as chip overcoats (stress buffer) and multilevel
insulation since the 1980s when PIs were introduced for these applications.23
Fig. 10.9. Chemical structure of DVS-BCB (Cyclotene™).

344 /NEW POLYMERS FOR EMERGING INTERCONNECTION APPLICATION~
10.4.3.1 Stress Buffer for Silicon Devices

Large die such as Si DRAMs packaged using thermosetting transfer
moulding compound such as epoxides are often subject to significant
stresses. These stresses can cause cracking of the silicon or the protective
inorganic passivation (usually ShN4) and/or metal displacement. At-
tempting to avoid these problems, early practitioners used wet etchable
PIs as stress buffer layers. These required features to be defined in a layer of
photoresist followed by wet etching of the exposed PI to open the pad areas,
dry etching of the passivation and subsequent stripping of the photoresist.
More recently, photosensitive PIs and BCBs have been used to cut down the
number of process steps and improve on the wet etch PI resolution and side
wall profile. The increased resolution is needed to open the 'fuse links' that
are being built into today's chips to allow rerouting/repair. These fuse link
windows are typically 10 microns wide and are projected to get even smaller.
The current goal is to develop a one-mask process where the photodi-
electric is exposed and developed and the primary passivation (ShN4) dry
etched to open the pads and fuse links without photoresist protection. The
goal is for minimal dielectric to be removed when it is exposed to the
fluorinated Si3N4 etch gas.
10.4.3.2 Silicon Inner Layer Dielectric (ILD)

The combination of aluminium metallization, tungsten via fill (plugs) and
silica dielectric (deposited as conformal CVD Si02 or spin on glass
materials) has led the semiconductor industry to 0.25 pm feature manufac-
turing technology. It is clear, however, that progress towards the 2010 goal
of 0.10 pm features 24 is hindered by both the current dielectrics and the
metallization.
As features get smaller, so do the aluminium interconnect cross-sections
and thus the resistance of the conductor lines increases. Interconnect lengths
are not scaling relative to the other on-chip geometries since chips are
actually getting larger with time and some traces must still carry signals
across the full dimensions of the chip. This increase in conductor resistance
can therefore result in increasing RC time delays 26 at a time when device
operating speeds are moving to higher frequencies. It is felt that this
problem can be overcome by employing a lower resistance metallization
system based on copper interconnects and lower & (dielectric constant)
dielectrics. In fact, the Technology Roadmap24 calls out for planarizing
dielectrics with dielectric constants of less than 3.0 and low resistance
conductors as high priority requirements for 0.18 pm technology to evolve
by 2001.
Some manufacturers will replace the dielectric first, thus continuing to
require greater than 425°C thermal stability of the polymer dielectric in
I POLYMERS FOR THIN FILM MICROELECTRONICS APPLICATIONS I I 345
order to meet the aluminium annealling requirements. Others will replace

both the dielectric and the aluminium as they move to less than 0.25 micron
geometries.
Table lO.6 summarizes the desired E' for future Ie technologies.z4 It is
suggested that during 1998 polymers have begun to replace spin on glass
dielectrics in high end applications.
Polyimides were first proposed for interlayer dielectric applications in the
1980s25 and certain chips have been produced by IBM and Hitachi, through
the 1980s with a PI dielectric. In general, however, the industry has
standardized on aluminium metallization and silicon dioxide dielectric.
Ideal polymer requirements would include: E < 3.0, preferably < 2.5; spin
deposition; and planarizing rather than conformal coating to allow the
fabrication of four or more layers of interconnect; good gap fill;
compatibility with copper metallurgy; adhesion to aluminium, copper and
other interfaces; thermal stability under processing conditions; ability to
pass current reliability requirements and to be of ultra high purity. Table
10.7 summarizes vendors and the properties of some of the polymers being
considered for silicon-ILD applications, whilst Fig. lO.10 shows their
chemical structures.
Table 10.6 ILD trends in IC manufacture
Technology Year Dk Dielectric

(MFS in pm)
0.35 1996 3.9-3.0 Si02

0.25 1998 ~3 Polymer
0.18 2001 ~2 Polymer?
0.10 2007 ~2 Polymeric
aerogels
MFS = minimum feature size of structure in IC.
Table 10.7 Some properties of polymers examined for ILD applications
Material Vendor Application Tg (OC) &'

method
Flare Allied-Signal spin 378 2.5

Parylene-AF4 Alpha-Metals CVD 2.3
F-Polyimide DuPont spin 330 2.5
PFCB Dow spin 380 2.4
Cytop Asahi Chemical spin 100 2.2
Syntorg - PPQ Cemota spin 365 2.8
PIs various spin >350 2.9-3.6
BCB DOW spin 350 2.65
346 §EW POLYMERS FOR EMERGING INTERCONNECTION APPLICATION~
l.FLAMETM 2. Parylene-AF4
F F
{_R_O :
F
F F
:xx: txta:r~ t--0-9-.

F
n
. jt 1
3. F-polyimide (FPI- 136M from DuPont)
~III
o
r~
II
0
1-%
H
II
0
CJ'. CJ'.
II
0
%
OCJ'.
ocr
,
1-Y
--0--
Y
4.CYTOpTM 5. Polypbenylquinoxaline (PPQ)
n n
6.PFCB
F F F
F~O O>=<F
Fig. 10.10. Chemical structures of some polymers examined as ILDs.
Despite obstacles,27 there have been many reports on copper/polyimide

ULSI technology over the last five years 28 •29 which use barrier metal
protection of the copper (top, bottom and sides) and chemical mechanical
polishing to achieve planarization. Recently, processes based on copper and
benzocyclobutene have also been reported. 30,3)
10.4.3.3 Gallium Arsenide (GaAs) ILD

Figure 10.11 shows a scanning electron micrograph of a multilevel (four
metal layer) GaAs chip fabricated by the so-called Triquint QED2 process,32
where the BCB dielectric has been etched away to reveal the multilevel
metal. This four level metal structure could not be fabricated with
traditional air bridge technology.
10.4.4 Thin Film Multichip Module Packages (MCMs)

Multichip modules can be defined as the interconnection of two to several
dozen bare chips on a high density substrate. In some instances, such as with
some versions of the Pentium chip, the buyer is unaware that there are
multiple chips interconnected inside the package.
Thin film MCMs are used in electronic systems to reduce wiring induced
delays between chips, to reduce power dissipation or to reduce system size
and weight. Whether interconnect is constructed using only thin film
technology (MCM-D) where D stands for deposited dielectric or in
combination with ceramic (MCM-CD) or laminate (MCM-LD) technolo-
gies, the thin film is needed to deliver the fine dimensions necessary to
bridge, 'redistribute' or 'fan-out' high input/output (I/O) chips for inter-
connection. 33 ,34
Thin film MCM packaging has been implemented when traditional
interconnect cannot meet design requirements in application areas such as
mainframes,35-38 high end servers and desktops, avionics/ 9 telecommuni-
cation and other applications which require high I/O chips. Multilayer thin
Fig 10.11. Triquint QED2 multilevel metal GaAs process. 32

348 EEW POLYMERS FOR EMERGING INTERCONNECTION APPLICATlON~
Fig. 10.12. Miniaturization of avionics board with MCM packaging. 39
film technology consisting of Al or Cu/PI or BCB interconnect have been

implemented on silicon, alumina, glass ceramic and aluminium carriers. 34
Figure 10.12 shows the 4:1 size reduction that is achieved when an 82 chip
surface mount assembled avionics PWB board is replaced by its thin film
MCM equivalent on the left. 39
10.4.5 Bumping and On-Chip 1/0 Redistribution

Area array bonding technology delivers superior electrical performance,
reliability and reduced footprints.40,41 Tight peripheral bond pad pitches
caused by some of today's microprocessors and application-specific inte-
grated circuits (ASICs) require mating with a high density interconnect,
such as the MCMs described above or, alternatively, can be designed into
the chip to produce area array I/O. Chips produced with peripheral I/O can
be redistributed on the chip to an area array of bumps with looser pitch.
Redistribution is shown in Fig. 10.13 in cross section. Such redistribution
requires thin film polymers and techniques similar to those described above
for MCMs.
10.4.6 Optical Interconnect

The introduction of new types of interactive multimedia services is putting
increased demands on the existing telecommunications infrastructure. It has
been suggested that the required increase in transmission capacity and
__D_E_N_A_M_E_S________________~I
TRA
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 349
Bond Pad Active Circuits

Fig. 10.13. Redistribution of pads for area array bumping.4o
bandwidth will be impossible to achieve without the use of optical

transmission in switching, transport and access system equipment. 42 Low
cost polymeric optical waveguide technologies are projected to offer
breakthrough optical solutions in these areas.42,43
In addition, electrical buses in electronic systems are currently unable to
keep pace with on-chip clock speeds. Optical backplanes based on passive,
multimode polymer waveguides offer the promise of maintaining on chip
clock speeds across chip, package, board and cabinet boundaries. 44
The incentive for using polymer optical waveguides for short « 100 cm)
optical interconnects (PWB and backplane applications) is that the polymer
waveguide technology has the potential to become more cost effective when
compared to alternative glass or polymer fibre technologies.44 ,45
10.4.7 Flat Panel Displays

Flat panel displays for lap top computers, and soon televisions, has become
a multi-billion dollar industry. There are both passive and active matrix
technologies. 46 The schematic cross section of a passive matrix flat panel
display is shown in Fig. 10.14. Polyimide is universally used as the alignment
layer. PI is also being used as the matrix for some of the colour filter
pigments. 47 The glass 'barrier layers' (used to prevent sodium migration) are
currently of Si02 and the colour filter planarization layer is usually acrylic.
10.4.8 Sensors and Micromachining

Polymeric thin films have also gained acceptance in many sensor48 . and
micromachining49 applications.
10.5 TRADENAMES
Cyclotene™ is the trademark of the Dow Chemical Company.

CyctopTM is the trademark of the Asahi Chemical Company.
+-- Polarizer
+-- Top glass

~ Barrier layer
+-- Colour filter

planarization
+-- ITO electrode
~ Alignment layers
. ~
~~;~~~~;;~~;~~~~d~ ITO electrode

"""",',/~",,~,.r''''''''''''.''''''''''/'U''''''''v"'J'''''''' ~ Bottom glass
(not to scale)
Fig. 10.14. LCD cross-section.
Flare™ is the trademark of the Allied Signal Company.

Kevlar™ is the trademark of the DuPont de Nemours Company.
Speedboard™ is the trademark of W.L. Gore & Associates Incorporated.
Teflon™ is the trademark of the DuPont de Nemours Company.
Thermount™ is the trademark of the DuPont de Nemours Company.
Vectran™ is the trademark of the Hoechst Celanese Company.
10.6 REFERENCES
1. Hirakawa, T. and Kato, c., A new laminate for MCM-L, Proc. [SHM'93, p.l99,
1993.
2. Homan, G. E. and Powell, D. J., Fabricating PWBs and MCM-Ls with a new
nonwoven aramid reinforcement, 7th International SAMPE Electronics Confer-
ence, p.l77, 1994.
3. Haezebaert, G. and Durigon, A., Lower dielectric constant prepreg with
standard FR4 processing for high performance digital PWBs, Printed Circuit
Europe, July-August, 23,1996, and Snyder, W. W., A new low-dielectric material
for PCBs, Printed Circuit Fabrication, March, 41, 1990.
4. Novak, A., Lindahl, T. and Hellgren, E., Study of different techniques for
building MCM-L substrates, Proceedings PCWC VII, paper 20-1/7, Basel 1996,
and Aday, J., Tessier, T., Crews, H. and Rasul, J., A comparative analysis of high
density PWB technologies, [MAPS Journal, 19 (4), 404, 1996.
5. Perec, V. and Tomazos, D., in Comprehensive Polymer Science, ed. G. Allen,
First Supplement, pp. 300 and 701, 1992, and Weiss, R. A. and Ober, C. K.,
Liquid crystalline polymers, ACS Symposium Series, No. 435, 1990.
6. Editorial, High Performance Plastics, pp. 2 and 6, January, 1996.
R_EF_E_R_E_N_C_ES________________
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~I I 351
7. Jayaraj, K., Noll, T. E. and Blizard, K., Controlled thermal expansion PWBs
based on liquid crystal polymer dielectrics, Circuit World, 22 (2),1996, and Noll,
T. E., Jayaraj, K., Farrel, B. and Larmouth, R., Low cost. Near hermetic MCM
based on liquid crystal polymer dielectrics, IMAPS Journal, 19 (4),469, 1996.
8. Lisignea, R., Piche. J. and Mathisen, R., Ordered polymers for interconnection
substrates, ACS Symp. Series, No. 407, 446, 1989.
9. Adema, G., Hwang, L., Rinne, G. and Turlik, I., Passivation schemes for CuI
polymer thin film interconnections used in multichip modules, IEEE Trans.
CHMT, 16, 53,1993.
10. Ferger, C., Selection criteria for MCM dielectrics, in MCM Technologies and
Alternatives, eds D. Doane, and P. Franzone, Van Nostrand Reinhold, 1993, p.
311.
11. Ferger, C. et al., Polyimides: Materials, Chemistry and Characterization,
Elsevier, 1989.
12. Mittal, K. L. (ed.), Polyimides, Plenum Press, 1984.
13. Deutsch, A. et al., Measurement of Dielectric Anisotropy of BPDA-PDA PI in
Multilayer Thin Film Packages, IEEE Trans. CHMT, 17,486, 1994.
14. Volksen, W., Yoon, D. Y. and Hendrick, J., Polyamic alkyl esters: Versatile PI
precursors for improved dielectric coatings, Proc. ECTC, 572, 1991.
15. Rubner, R., Siemans Forsch-u. Entwicki-Ber., 5, 232, 1976.
16. Hiramoto, H., Photosensitive polyimides Proc. MRS, Advanced Electronic
Packaging Materials, 167, 87, 1990.
17. Kirchoff, R. and Bruza, K., Benzocyclobutenes in polymer synthesis, Progress in
Polymer Science, 18, 85, 1993.
18. Garrou, P. et al., Rapid thermal curing of BCB dielectric, IEEE Trans. CHMT,
16, 46, 1993.
19. Moyer, E. S. et al., Photodefinable BCB formulations for microelectronics
applications, part II, Proc. IEPS, 37, 1992.
20. Strandjord, A., Ida, Y., Rogers, B., Garrou, P., Cummings, S. and Kisting, S.,
Photo BCB, MCM-D processing and area array assembly, Int. J. Microcircuits
and Microelectronic Packaging, 19, 260, 1996.
21. Garrou, P. E., Polymer dielectrics for multichip module packaging, Proc. IEEE,
SO, 1942, 1992.
22. Beyne, E., Van Hoff, R., Pieters, F., Lenaerts, S. and Achen, A., The use ofBCB
and photo BCB dielectric in MCM-D for high speed digital and microwave
applications, Proc. Int Con! MCMs, 513, Denver, 1995.
23. Wilson, A., Use ofpolyimides in VLSI fabrication, in Polyimides, ed. K.L. Mitel,
Plenum Press, 715, 1984.
24. The National Technology Roadmap for Semiconductors, Semiconductor Industry
Association 1994.
25. Samuelson, G., Polyimide for multilevel VLSI, in Polymers for Electronic
Applications, ed. Feit and Wilkins, Amer. Chern. Soc. Symp. Series, 184, 93,
1982.
26. Bothra, S., Rogers, B., Kellam, M. and Osborn, C., Analysis of the effects of
scaling on interconnect delay in ULSI circuits, IEEE Trans. Electron Devices, 40,
591, 1993.
27. Gardner, D. et al., Encapsulated copper interconnection devices using sidewall

barriers, Proc. VMIC Con/., 99, 1991.
28. Kaanta, C. et al., Dual Damascene: a ULSI wiring technology, Proc. VMIC, 144,
1991.
29. Roehl, S. et al., High density Damascene wiring and borderless contacts for 64 M
DRAM, Proc. VMIC, 22, 1992.
30. Hayashi, Y. et al., A new two step metal-CMP technique for high performance
multilevel interconnects featured by AI and Cu in low E, organic film, IEEE 1995
Symposium on VLSI Technology - Digest of Technical Papers, 88, 1995.
31. Case, C., Komblit, A. and Sapjeta, J., Evaluation of Cyclotene 5021 as a low
dielectric constant ILD, Proc. VMIC Con/., 63, 1996.
32. Finchem, E., Mickanin, W. and Rosemeyer, C., A multilevel high density
interconnect process designed and developed for manufacturability, US Con! On
GaAs Manufacturing Technology (Man tech) Proc., 163, 1994.
33. Prasad, K. and Rerfecto, E., Multilevel thin film packaging: applications and
processes for high performance systems, IEEE Trans CHMT, Part B, 17, 38,
1994.
34. Garrou, P., MCM-D: thin film materials, processes and applications; Tummala,
R., Garrou, P., Knickerbocker, J. and Kumar, A., MCM-C materials, processes
and applications; Tessier, T. and Garrou, P., MCM-L: materials, processes and
applications, in Multichip Module Handbook, ed. P. Garrou and I. Turlik
McGraw Hill, 1997, in press.
35. Tummala, R., Potts, H. and Ahmed, S., Packaging technology for IBM's latest
mainframe computers (S/390/ES9000), Proc. ECTC, 682, 1991.
36. Akihiro, D., Toshihiko, W. and Hideki, N., Packaging technology for the NEC
SX-3/SX-X supercomputer, Proc. ECTC, 525, 1990.
37. Inoue, T., Matsuyama, H., Matsuzaki, E., Narizuka, Y., Ishino, M., Tanaka, M.
and Takenake, T., Microcarrier for LSI chip used in the HITAC M-880
processor group, IEEE Trans. CHMT, 15, 7, 1992.
38. Abbasi, S., The technology and manufacture of the VAX 9000 multichip unit in
MCM Technology: the Basics, ed. Doane and Franzione, Van Nostrand
Reinhold, 1993.
39. Hagge, J., State of the art MCMs for Avionics, IEEE Trans. CHMT, 15, 29,
1992.
40. Mis, D., Rinne, G., Deane, P. and Adema, G., Flip chip production experience,
Proc. ISHM, 291, 1996.
41. Simon, J., Topper, M., Reichl, H. and Chimel, G., A comparison offlip chip
technology with chip size packages, Proc. IEPS, 665, 1995.
42. Robertsson, M., Engberg, K., Eriksen, P., Hesselboom, H., Niburg, M. and
Palmkog, G., Optical interconnects in packaging for telecom applications, Proc.
10th European Microelectronics Con!, 581, 1995.
43. Palmkog, G., Arvidsson, G., Eriksen, P., Gustafsson, G., Hagel, 0., Hammar, J.
and Henriksson, P., Low cost single mode optical passive coupler devices with an
MT-interface based on polymeric waveguides in BCB, in press.
44. Bristow, J. et al., Optical polymer waveguide interconnect technology, Proc.
ISHM, 138, 1996.
R_E_F_E_R_E_N_C_E_S__________________~I
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I 353
45. Liu, Y. et al., Optoelectronic packaging and polymer waveguides for MCM and
board level optical interconnect applications, Proc. 45th ECTC, Las Vegas, 185,
1995.
46. O'Mara, W., Active matrix Bat panel displays, Solid State Technology, 34, (Dec),
65, 1991.
47. Latham, W., Hawley, D., Color filters from dyed polyimides, Solid State
Technology, 31, (May), 223, 1988.
48. Harsanyi, G., Polymeric films in microelectronic sensors, Proc. ISHM, 191, 1996.
49. Allen, M., PI processes for the fabrication of thick electroplated structures, Proc.
7th Int. Con/. On Solid State Sensors and Actuators, 60, 1993.
Moulded Interconnect Devices 11
(MIDs)
FRANK POHLAU and KLAUS FELDMANN
F APS, Lehrstuhl fur Fertigungsautomatisierung und
Produktionssystematik, University of Erlangen-Numberg,
Germany
11.1 INTRODUCTION
During this decade, the competitiveness of the electronics industry has been
determined by the following six aspects: cost reduction, miniaturization of
devices, function integration, product reliability, design freedom and
improved environmental compatibility.
11.1.1 MIDs Integrate Electronics and Mechanical Function

Some of these demands are met by continued electrical function integration
on silicon, and many others can be addressed by integration of mechanical
and electrical functions on the circuit carriers. A major trend in this respect
is the upcoming market for the so-called moulded interconnect devices
(MIDs). This has been supported by the continuing development and
commercialization of high temperature thermoplastic materials as well as
the development of techniques for their selective metal plating. Combined,
these have opened up new ways of circuit carrier design to the electronics
industry.
MIDs can basically be described as moulded polymer-based bodies
incorporating a functional metal plating on some areas of their surfaces,
thereby integrating electrical functionality into what is basically a mechan-
ical component as an additional benefit.
356 II MOULDED INTERCONNECT DEVICES (MIDs)
~----------------------------------------------------~
Fig. 11.1. Transition from conventional printed circuit board to moulded inter-
connect device.
11.1.2 Integration Potentials and Key Markets

MIDs can unite several important functions into a single unit such as, for
example, those of conventional printed circuit boards, casings, connectors,
heatsinks and cables. Some of them, especially those made in the Far East,
are also designed to be encapsulants for electronic components, e.g. light
emitting diodes. MIDs, however, must not be considered as simple
replacements for conventional assemblies, rather they complement them.
In Fig. 11.2, the most important integration potentials and markets for
MIDs are shown.
Currently, the key markets for MID technology are considered to be in
automotive electronics and telecommunications, especially for mobile
phones. These two market segments account for most of the applications
realized so far. Other important markets are office automation, consumer
electronics and system controls, e.g. programmable logic controls (PLCs). In
addition, MIDs are also eminently suitable for use in household appliances
and medical electronics. The market is currently showing an annual growth
rate of about 50%.
One . of the biggest challenges concerning the introduction of MID
technology is that of the simultaneous engineering requirements necessary to
incorporate the many possible advantages into a single product design. This
makes close cooperation of various departments in a company absolutely
essential for ultimate product success. Electrical and mechanical engineers
INTRODUCTION
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~ 357
Circuit Carrier Case Connector Cable
Molded
Interconnect
Devices
Household MultimediB
Appliances
Telecommunication
Passenger Comp. Office Automation
Engine Comp. Systems
TV, HiFi, Video Automation
Fig. 11.2. Integration potentials and key markets for MID.
must develop a good basic understanding of each of ·the complementary

disciplines, as well as additional knowledge in manufacturing and design
needs, MID development projects support, and need, teamwork.
11.1.3 Classification of MIDs

In order to classify MIDs according to their geometric complexity, a scheme
has been developed which is shown in Fig. 11.3. A 2-D MID corresponds to
the conventional printed circuit board. It basically means replacing the
conventional thermoset board material with a thermoplastic. The step
towards an MID in this case can be worth while if a very complex shape
needs to be milled or punched out of a conventional laminated type
material, causing high tooling or processing costs, or if a significant number
of holes for component leads need to be drilled. An MID comes out of the
mould in the required form and therefore does not need any additional
mechanical post-moulding processing.
2 Y2-D MIDs have one process plane, but are provided with additional
mechanical features situated either in the process plane or on the opposite
358 1 1-1____M_O_U_L_D_E_D_I_NT_E_R_C_O_NN_E_CT_D_E_VI_C_E_S_{M_ID_s_)_ _ _---'
Skatchof
Dimension "tYpe Features Applications
--
onsartlon process
2D 0
planar process
plane ..• conventional circuit
board
planar process
1A plane, 3D-elements
at the opposite side
U- - ffl simple casings
planar process
2"hD
18 plane, 3D-elements
at the opposite side
f1-u--Jl easy assembly,
modular structure
several parallel fixation of heavy

1C
process planes ~ components
several planar simple casings,

nx2D 2 process planes at an d~ miniature
circuit boards
angle
Regular surfaces, Telecom,

3D
3A
e.g. cylinders ~ Automotive
38 Freeform surfaces ~ Cameras
Fig. 11.3. Classification of MIDs.
side of it. Type IA MIDs are relatively widespread, because components can
be assembled onto them using conventional off-the-shelf onsertion equip-
ment, whilst still providing additional three-dimensional mechanical fea-
tures, e.g. fasteners, that help reduce assembly cost. Type IB and Ie MIDs
require modifications in the assembly equipment, at least an enlarged z-
stroke of the placement head. This limits their use in mass production. If no
components are necessary, and there are many examples of this situation,
MIDs with circuitry and mechanical features on the same side can be very
useful.
N-times 2-D MIDs have several process planes which are situated at an
angle to one another, whilst 3-D types have regular or even free-form
surfaces as process surfaces. These types increase the freedom of design
although they can also present further challenges for assembly equipment.
The more complex the type of MID, the more complicated the
downstream manufacturing processes such as assembly, connection and
test become. Therefore, any designer should try to keep the part as simple as
possible.
'--_ _K_E_y_A_D_V_A_NT_A_G_E_S_A_ND
__ -,I I
INT_R_O_D_V_CT_I_O_N_S_T_RA_T_E_G_I_E_S_ _ 359
11.2 KEY ADVANTAGES AND INTRODUCTION STRATEGmS
11.2.1 Advantages of MID Tecbnology

The advantages of MIDs can be summed up in three categories, techno-
logical, economical and ecological.
The main technological advantage of MIDs is that they integrate
electronic and mechanical elements onto circuit carriers in virtually any
geometric shape. In several cases they have enabled entirely new functions
and they usually help miniaturize electronic products by eliminating the
need for bulky planar circuit boards.
By integrating, and thus eliminating, some of the mechanical components,
substantial economic advantages can be achieved. The process chains are
shortened, especially in assembly, and reliability is increased by the reduced
number of connections, thus lowering quality cost. Miniaturization can also
lead to reduced consumption of raw materials, and integration slims down
inventories of components.
The substrate materials used, normally high temperature thermoplastics,
are inherently flame retardant, can easily be recycled after plastic and metal
separation and are thus ecologically less harmful than the conventional
materials they replace. A point that must not be omitted is that, despite the
fact that a new composite material is created by plating on plastics, the
number of different materials used in a product can usually be significantly
reduced.
Freedom of Design
o Integration
electronics - mechanics
o Miniaturization
New functions
Rationalization
o Less part count
o Shorter process chains
o Reduced use of material
o Increased reliability
Environmental Compatibility
Fig. 11.4. Main advantages of MIDs.

360 I LI____M_O_UL_D_E_D_I_NT_E_R_C_O_NN_E_C_T_D_E_V_I_C_E_S_(M_ID_s_)_ _ _ ----1
11.2.2 Function Integration

The most important functions that can be integrated into an MID are the
classical electrical and mechanical functions such as casing and circuitry.
However, there are also other new possibilities, e.g. incorporating position-
ing aids for the surface mounting of electronic components, contact pads for
switches or fastening elements for large components such as motors and
transformers, etc. One of the most interesting possibilities is the integration
of sockets, connectors and other contact elements. These components are
usually very expensive and by eliminating them as separate devices, the
potential for rationalization is considerably increased. Another very
interesting feature is integrated electromagnetic shielding that can simulta-
neously act as a stiffener or heat sink. Some of the functions that can be
integrated into an MID are depicted in Fig. 11.5 below.
11.2.3 Basic Introduction Decisions

The use of MID technology for a certain product can give maximum profit
if as many as possible of the above-mentioned advantages can be realized
and if as many functions as possible can be integrated into the MID part.
Some very important fundamental criteria need to be considered in order to
assist in making the decision to move to an MID based approach:
• Integration of mechanical and electrical functions. This is the core
requirement of an MID design; an assembly that does not include as
many functions as possible is not very likely to be a success.
• High number of components in the conventional solution. The more
components that can be integrated in an MID, the more efficiently the
technology can be put to use. Efficient integration maximizes the possible
increase in reliability and the possible savings in component cost.
electrical functions mechanical functions
Socket
Screw fastening eilllnents
Surface mounted THOs Casing
Snap fits
Shielding walls ---tf~~~'~~
Switches
Fig. 11.5. Integration potential of MIDs.

KEY ADVANTAGES AND INTRODUCTION STRATEGIES
L -__________________________________________________ ~~ II 361
• High assembly and logistics costs in the conventional solution. The

integration of functions leads to a reduction in part count and lowered
assembly and logistics costs. The more complex the conventional solution
is, the greater are the benefits that can be gained from the use of the MID
technology.
• Reduction of weight and miniaturization desired. Reducing the part
count by converting from conventional to MID technology yields
significant opportunities for both weight reduction and a reduction in
size of the final product. This is a major reason for using a moulded
interconnect device approach.
• Circuit structure maximum of two layers. With very few exceptions, MID
technology is currently limited to a maximum of two structured, current
carrying conductor layers.
• Few electronic components. Due to the complex three-dimensional
geometries of many MIDs, onsertion normally becomes more
complicated. Handling times during the onsertion process in an auto-
mated assembly line will therefore tend to increase considerably. The
fewer components there are, the less important this becomes, as necessary
periods for exchanging parts etc. then tend to dominate the cycle times.
• Use of surface mount devices (SMDs). The need to provide holes in a
substrate for leads of components results in additional tooling expenses
being incurred. Therefore, it is highly desirable to utilize surface mount
technology (SMD) components that can be placed on a normal surface.
However, MIDs do offer the possibility for the integration of receptacles
for the connection leads of leaded devices, thus enabling them to be
surface mounted. This helps to increase their potential spectrum of use
and also helps to cut logistics costs.
• Electromagnetic interference (EMI) shielding or heat dissipation is
necessary. A key step in MID manufacture is the ability to achieve
selective metal plating of the high temperature thermoplastics typically
used in these applications. In addition to providing conductors and
interconnections, it is also possible to utilize this metal layer for shielding
against electromagnetic interference (EMI) or as a heat sink for heat
dissipation, given that the amount of power is not too high.
• No glossy surfaces are necessary. As most of the MID manufacturing
methods involve the use of galvanic plating steps, use of MIDs as visible,
glossy components tends to be somewhat limited. However, this does not
apply to MIDs fabricated using fully additive plating processes, such as
the hot embossing or two-shot moulding techniques.
• Large production numbers. The frequent requirement for sophisticated
tooling usually makes the use of MID technology especially suitable for
applications where large production numbers are envisaged. There can be
and have been cases, however, when MID technology was used for very
small production numbers, e.g. because this approach was the only
362 I LI____M_O_V_L_D_ED_INT_E_R_C_O_NNE
__CT_D_EV_I_C_E_S_(M_ID_S_)_ _ _ ---l
conceivable way of manufacturing a part. Some other production

methods can have very high initial costs and thus, in these cases, the
use of MID technology may even be more economical for smaller
production runs.
11.2.4 Cost Considerations

One of the most important reasons for the introduction of a new technology
is, of course, the potential for a reduction in cost. The effective rational-
ization potential of an MID application over a conventional application
cannot always be readily calculated. It very much depends upon the specific
product, as all the process steps from classically separated disciplines,
including moulding, plating and assembly, need to be considered, especially
as they often influence one another.
As a rule of thumb, it can be said that MIDs tend to have higher initial
costs, when compared to conventional manufacturing methods, but lower
variable costs. This is due to the comparatively high tooling costs and
possibly also the large investment expenses, while assembly costs can be kept
to a minimum, thus saving on the variable side.
The most significant costs are tooling, especially in two-shot moulding
processes where two usually quite complex tools are needed for the
structuring of the circuit. Also, plating is an important cost factor due to the
amount of manual labour usually involved in the loading and unloading of
the part racks for the galvanic plating baths.
All cost statements are of course highly influenced by company specific
factors, such as depreciation models, labour calculation models and others.
It is also necessary to consider whether investment such as plating lines is
total cos1s
conventional
total costs MID
LIIIIII:==:::;;:2~~:::===== fixed costs MID

fixed costs
conventional
Break·Even-Point
production number
Fig. 11.6. Cost comparison between a typical MID and a conventional solution.
~_____________M_A_N_U_F_A_C_TU
__~__N_G_M
__E_TH
__O_D_S____________~I I 363
included in the cost calculation of a single part or whether investment is
calculated on a separate basis.
So far, cost savings of up to 40% have been achieved in MID products by
integration depending, of course, on the specific product, lot sizes and other
boundary conditions. In one project that achieved savings of 24% in total, it
should be noted that only about half of the total cost could be influenced by
the MID itself. In these areas, costs were reduced by 50-70%.
11.3 MANUFACTURING METHODS
After the basic decision to employ MID technology for a specific product
has been made, the manufacturing method and suitable materials need to be
selected. MIDs can be produced in a variety of ways. The most common
ones are explained below and they can be structured according to Fig. 11.7.
Basically, there is a distinction according to the moulding method
between one-shot, two-shot and insert moulding processes. After the
moulding, one-shot parts can either be metal plated by a hot embossing
process, in which the structure is formed by an engraved die, or can be
plated galvanically (in the following, the term 'galvanic' includes electro-
chemical as well as autocatalytic chemical plating processes). After galvanic
plating, the structuring is done by an imaging process, either by means of a
mask as in conventional circuit board manufacture or by direct laser
imaging.
In two-shot moulded parts, plating is always done galvanically, using the
different adhesion properties of the two plastic materials used for moulding
to achieve selective plating.
To achieve insert-moulded parts, a flexible foil carrying the circuitry is
inserted in the mould tool and subsequently over-moulded with a suitable
I MOULDED INTERCONNECT DEVICES I

MANUFACTURE OF 1-SHOT 2-SHOT
I
I
INSERT
CIRCUIT CARRIER MOULDING MOULDING MOULDING
MIrrALPLAnNG HOT GALVANIC SrRUC1URED
I
EMBOSSING GALVANIC FOIL
S'tRUClURING SHAPeD 30- lAsER

01. MASK DIRECT
Fig. 11.7. MID manufacturing methods.

364 I 1L-_______M_O_U_L_D_E_D__ThIT ___c_T_D_E_~
__E_R_c_O_NNE __ OM_I_D_s)________~
C_ES__
thermoplastic resin to obtain a stable plastic body with three-dimensional
circuitry. One variety of insert moulding is the already well-known outsert
moulding technology using punched metal parts as electrical conductors
which are over-moulded with an insulating resin to obtain e.g. a mains plug,
other connectors or electronic components. This technology will not be
further explained here.
In the following text, each manufacturing method is now described in
more detail. Not every method is suitable for every product and each
process will have certain advantages and disadvantages for a specific
application. Each process is characterized by key features that form the
basis of the decision on which process to use under a given set of boundary
conditions.
Of course, every process can be completed by a surface finish on the
circuit tracks. To simplify the graphics and proCess descriptions, this has
been omitted in the flow charts. Surfaces can be finished with traditional tin-
lead or nickel-gold metallizations or indeed virtually any of the other
surface finishes commonly used in conventional interconnect fabrication.
Some of the process chains described here are covered as a whole or in
part by one or several patents in various countries. The patent situation,
however, is not very transparent, so this publication only deals with the
technical flow of manufacturing methods.
11.3.1 Photo-imaging
The photo-imaging process is the oldest of all MID manufacturing
processes. It is quite similar to the traditional semi-additive process for
conventional printed circuit boards. Most adhesion promotion solutions for
thermoplastics were developed with this process in mind, and a compar-
atively large number of them are available for solderable thermoplastics
such as PEl and LCP.
Firstly, the surface of the plastic blank obtained by one-shot moulding is
activated using a chemical process suitable for the material used. The next
step is the application of a thin so-called flash layer of chemically deposited
copper. The thickness of this layer is usually no more than a few
micrometres.
There are then several ways of proceeding, the most common being a
semi-additive process. The part is covered in a photosensitive resist which is
then selectively exposed with UV radiation through a suitably patterned
mask, as in the conventional printed circuit board manufacturing process. A
planar film type mask, such as would be used on two-dimensional boards, of
course, has limitations when one is considering the imaging of three-
dimensional structures by omni-directionallight, as stray light will blur the
contours in recessed areas. This can sometimes be tolerated to a certain
extent depending on the application, but will usually have to be catered for
M_A
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N_U_F_A_C_T_U_R_I_N_G_M I 365
injection moulding
D
SUrfacDvation
electroless copper
D
apply photoresist
D
expose with 3-D mask
D
develop photoresist
D
electr
D copper
remove photoresist
D
etch away copper
Fig. 11.8. Photo-imaging process.
by using a three-dimensional mask. These masks are made of thermo-

formable PVC foil, the circuit structure being defined by laser scribing. The
mask is vacuum laminated to the part and this assembly introduced into an
exposure chamber equipped with several UV-Iamps.
The exposed resist is then developed and, depending upon whether a
positive or negative working resist system is used, either the exposed or
unexposed areas are stripped. The exposed flash copper areas are then built
up to the full desired copper thickness (usually around 35 /lm). Then, the
remaining photoresist is stripped and the underlying flash copper removed
by a differential etching step to reveal the insulating plastic surface.
The most important characteristics of the photo-imaging process are as
follows:
• one-shot moulding is used;
• structuring is similar to that used in printed circuit board manufacture,
i.e. it is a known and proven process;
366 I I~________M_O_U_L_D_E_D__INT
__E_R_C_O_NNE
___CT__D_E_V_I_C_ES__ __s)________~
(M_ID
• cost and time for layout changes is low;
• it is attractive for small lot sizes;
• through-hole contacts are easy to form.
Using one-shot moulding, the plastic substrates for mask-structured MIDs
are comparatively easy to manufacture. The process chain is similar to that
of conventional printed circuit board manufacturing, so the time for process
implementation is relatively short. The cost and time needed to carry out a
layout change are quite low, as only a new mask needs to be generated,
making design changes during product development easier than with some
other MID production methods. This, however, is restricted to changes in
the trace layout and the layout of SMD solder pads since, if holes for leaded
devices need to be relocated, tool changes will also become necessary. The
possibilities of quickly changing the layout make this process attractive for
small lot sizes, especially as the masks have a limited lifetime. Through-hole
contacts are easy to realize, as the whole surface of the substrate is plated in
the flash metallization process step.
Possible variations of the process are to apply the full desired copper
thickness to the plastic moulded body with a subsequent subtractive
structuring process using the photoresist as an etch resist, or to apply a
separate etch resist (e.g. tin) after application of the full copper thickness to
the later circuit traces, thus finally only etching away the unprotected flash
copper between the tracks.
11.3.2 Laser Imaging

Laser imaging has been successfully developed as an alternative imaging
method and the first steps of the process are very similar to those used in
photo-imaging. The first step after moulding is again adhesion promotion of
the plastic part surface. Next, a thin copper layer is applied. Again, two
different structuring methods can be applied. The more common method is
fully subtractive and is shown in Fig. 11.9. After electroplating the entire
moulded part to the desired full copper thickness of about 35 J.lITl, a final
layer of tin (Sn) is applied as an etch resist. The tin additionally functions as
a coupling medium for the laser, as the used wavelengths are normally not
very absorbable by copper. The tin is evaporated using a Nd-YAG laser,
exposing the underlying copper in what will subsequently become the
isolation channels. The exposed copper is subsequently etched away, leaving
tin-covered circuit traces and isolation areas very well suited as shielding
faces.
In another method applied in mass production, the metallic resist is
directly plated onto the flash copper layer. Then, it is partly sublimated by
laser. The exposed copper areas are built up to the desired final thickness
using an electroplating process. The resist is stripped, and the flash copper
L -_____________ M_AN
___U_F_A_CT __E_T_H_O_D_S____________~I
__U_R_I_N_G_M I 367
L--_--li
injection moulding
{} 1 - . 1_ - - '
surface activation
1....-------11 1.-1_----'
{}
electroless copper
L-_---.JIII-._--'
{}
full-build
electroplate copper
{}
plate etch resist 1 I iI
{} ~~.
laser structuring
of etch resist c=Jc:J
• •
" --
1electroplate copper
etch copper
1 differential etch
Fig. 11.9. Laser imaging process.
removed by a differential etching process. This variation is also shown in

Fig. 11.9.
The most important characteristics of the laser structuring process are as
follows:
• fine pitch features are possible (down to c. 80 /lm);
• only the isolation channel metallization needs to be removed;
• shielding and heat dissipation can easily be integrated;
• changes in track geometry are achieved simply by reprogramming the
laser.
As in the photo-imaging process, plastic substrates for laser imaging are
moulded in a single shot, making tooling no more complex than with a
conventional plastic part. A key advantage of laser structuring is the
possibility to realize track widths and isolation channels as narrow as about
80 /lm. As only the isolation channels are usually etched away, heat
dissipation problems and electromagnetic interference shielding of electronic
assemblies can be solved by the use of laser structured MIDs. Another
368 I L-I____M_O_V_L_D_E_D_I_NT_E_R_C_O_NN_E_C_T_D_E_V_I_C_E_S_(M_ID_s_)_ _ _ ---..J
advantage of this process in comparison to other MID manufacturing

methods is that a change of the track geometry requires no tool or other
hardware change. A change in the software programme of the computer
controlling the laser beam is sufficient, thus making this process very flexible
for small lot sizes.
There are several possible variations ofthe basic process. For example, an
organic etch resist can be used instead of tin. For some applications, it is
possible to directly structure the copper, using the laser as a milling tool to
form grooves in the surface where the isolation channels will be in a later
stage. Some plastics require that a thin copper layer remains at the bottom
of the grooves which is subsequently etched off to prevent short circuits
caused by carbonized organic material residues. Chemically different
thermoplastics allow the grooves to be cut right through all the metal,
down to the plastic.
11.3.3 Two-shot Moulding

The idea behind the various two-shot moulding processes is to utilize the
different adhesion properties of several grades of thermoplastics moulded
together in one body to achieve a selective plating of this body. One of the
shots accepts chemical plating with a metal whilst the other will not take any
metal. By its nature, two-shot moulding is the most geometrically versatile
of all known MID structuring processes.
There are also many variations of the two-shot moulding process and the
most common are shown in Fig. Il.lD.
One group of two-shot moulding processes utilizes an intrinsically
platable resin for one of the shots. The platability of the plastic resin is
normally determined by the fillers used in its formulation. Materials often
used for the platable shot are polyethersulfone (PES) and polyetherimide
(PEl); both are used glass filled and containing a catalyst of palladium to
injection mould
1. shot
D platable resin non-plat able resin

non catalytic resi n
~
catalyse
D 1~1M1JS I 1.-1 I 1fd!1b?51

injection mould ED_
·. [[]---I
{
2. shot
D I~I I m m I 12!!::!51
non-platable resin pial able resin non catalytic resin
m etal plate
Fig. 11.10. Two-shot moulding processes.

M_A
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N_U_F_A_C_T_U_R_I_N_G_M I 369
provide crystallization nuclei for the electro less metallization deposition.
Another common group of materials is polyamides whose plating properties
can also be controlled very efficiently by the filler type and content. With
both these material groups, the designer can choose which shot, platable or
not, is going to be moulded first, according in particular to the tooling
needs. If a precatalysed material is used, this process is called PCK (Printed
Circuit Kollmorgen). The plated metal is usually copper although some
processes and materials use nickel as the base coat. Once the flash metal is
on the plastic, subsequent layers can then be freely selected.
Another process, shown on the right in Fig. 11.10, uses non-catalytic
material for both shots. This requires that the first shot be transferred to a
chemical catalysing bath after moulding, with activation of the surface by
etching. Subsequently, the second shot is moulded to cover the later
isolation areas of the MID. This variation has two main advantages over the
PCK process. Firstly, cheaper, uncatalysed material can be used, and
secondly, the etching step after moulding the first shot increases adhesion
between the two shots. The drawbacks are the necessity for an additional
chemical process step between the two moulding operations and the
restriction that the platable material must be moulded first.
The key characteristics of two-shot moulding processes are:
• great freedom of design;
• high current carrying capacity;
• through-hole contacts are easy to form;
• structuring takes place during the moulding operation;
• a short process chain;
• low cost per piece for large production runs.
The design of two-shot moulded MIDs is very flexible. The position and
routing of the circuit traces is only limited by the tooling complexity. A very
interesting example of how maximum use of this freedom can be gained is
the use of elevated circuit tracks, whose sides can also be used for carrying
current, thus almost trebling current-carrying capacity on the same
footprint area of an assembly. Due to the fully additive chemical plating,
through-hole contacts are also quite simple to realize, given sufficient aspect
ratios. Even partial through-hole plating is possible. As the circuit is
structured during the moulding steps, no subsequent actions apart from
chemical metal plating are necessary, thus reducing the number of process
steps. This fact also contributes to a low cost per piece for large series, once
the high initial cost of the two-shot mould tool has been paid for.
11.3.4 Hot Embossing

Structuring of circuit traces by hot embossing is especially interesting when
comparatively simple circuitry needs to be applied to plastic parts. The
370 1 ,-I____M_O_U_L_D_E_D_I_NT_E_R_C_O_NN_E_CT_D_E_V_I_C_E_S_(M_ID_s_)_ _ _~
plastic substrate obtained by single-shot moulding is placed on a work piece
holder in a press. Then, the foil is placed onto it. Structuring itself is done by
a heated die carrying the later circuit track as protrusions. The die, usually
manufactured by engraving, is lowered to the substrate, punching out the
desired foil structure and activating the adhesive on the foil. After about a
second, the die is lifted back up to its initial position and the areas of the foil
not sticking to the substrate are removed.
An important consideration with hot embossing is the material of the foil,
which is usually an electrolytically obtained brittle copper with an easily
shearable crystal structure. The foil is coated on one side with a thermo-
activated adhesive and the other side can be plated with a variety of surface
finishes such as gold or tin/lead. The foil can be supplied to the press table
manually, although it will normally, however, be fed on a reel-to-reel basis.
The foil is fed from a supply-roll with a take-up roll collecting what remains
of the film to enable it to be sent back to the foil manufacturer for recycling.
Through-hole contacts are possible by embossing the foil into pre-formed
holes in the substrate, so that the walls of the holes are partly clad with the
foil. These holes are subsequently filled with conductive paste, connecting
the foil-clad portions of the hole and thus establishing the electrical link
between both sides of the substrate.
The key features of the hot embossing process are:
• structuring is by punching and glueing;
• there are few process steps;
• no chemical metal plating is required;
• suitable for glossy surfaces;
-
Mould plastic substrate L I_ _ 1t
- - JI -...J
D
Place substrate
and foil in press
lEis:
Through-hole contact
-: :E.
Emboss
galvanic plaUng (e.g. Sn)
Remove excess foil

~copperfOil
thermoactivated adhesive
Fig. 11.11. Hot embossing process.

M_A_N
L -_ _ _ _ _ _ _ _ _ _ _ _ _ __U_F_A_C_T_U_R_IN __E_T_H_O_D_S____________~I
__G_M I 371
• a large number of thermoplastics are platable;

• layout changes are inexpensive;
• low investment costs;
• it is an attractive method for small lot sizes.
As with several other MID processes, the substrate is obtained by a single-
shot moulding operation. A key advantage of the process is the 'dry' plating
by a structured die, leading to very few process steps and short cycle times.
Another advantage for an electronics manufacturer is that the introduction
of this process into a manufacturing plant makes it possible to produce
circuit carriers in-house without requiring any chemical equipment and the
respective waste disposal or water treatment facilities. The absence of
chemical plating steps to which the substrates are subject also makes it
possible to use hot-embossed MIDs as parts with glossy, visible surfaces.
Hot embossing is a very quick and clean plating process.
A further advantage is that the platability of the thermoplastic with good
adhesion does not depend on the chemical plating of the part, but only on
the adhesive used to coat the foil. It is much easier to develop an adapted
adhesive for a new material than it is to develop an adhesion promotion
process step for chemical plating. Therefore, the range of thermoplastics
available for plating by hot embossing is larger than that of any other MID
method. Furthermore, layout changes are comparatively inexpensive and
the general investment for a press is not very high either. This makes the
technology very suitable for small lot sizes.
11.3.5 In-mould Labelling

All variations of the in-mould labelling process comprise over-moulding a
pre-structured plastic film with a thermoplastic resin, thus stabilizing the
film and yielding a three-dimensional, stable circuit.
In most variants of the method, a process called capture decal is used. A
plastic film is manufactured and provided with the desired circuit traces in a
planar form. Then the foil is inserted into a mould tool. Sometimes, a prior
thermoforming step is necessary in order to make the film abut more closely
to the tool walls. After the film has been placed in the mould tool, a
thermoplastic resin is then injected.
The different in-mould labelling processes mainly vary in the way the film
is prepared and positioned in the tool. The most common method is shown
in Fig. 11.12. When the film is in the mould tool, the circuitry faces the tool
wall and the plastic film faces the tool cavity. Resin is then injected and,
because of slight melting of the film material, a good bond is formed. When
the part is ejected from the mould tool, the film forms the part's surface and
the circuit traces sit on top of it.
Besides the above process, there is a process, shown in Fig. 11.13, called
the transfer decal process. The circuit structure is provided on a carrier film
372 I M
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L I_ _ _ _ _ _ _ _ __E_R_C_O_NN
__E_CT __ID_s_)______~
__D_E_V_I_C_E_S_(M
manufacture
plastic film
film
structure film
thermoform film
overmould film
Fig. 11.12. Capture decal process.
Fig. 11.13. Transfer decal process.
that is inserted into the mould tool in a very similar manner to that
described above, but with the circuit film facing the tool wall and the traces
facing the cavity. When the resin has been injected and cooled down, the
part is removed from the cavity, with the carrier film covering the substrate
and the circuitry. The film is peeled off the part to uncover the circuit traces,
and disposed of.
Another variation of the in-mould technique developed in England by
AIT Ltd uses an aluminium--copper double layer foil. The copper layer is
structured before moulding and the aluminium foil inserted into the mould
tool in the same manner as with the transfer decal process. After moulding,
the aluminium layer is removed from the substrate by an etching step, rather
than by peeling. This method allows the use of polyphenylene sulphide
(PPS) as the substrate material and gives very good adhesion properties.
MANUFACTURING METHODS
L -____________________________________________________~ II 373
Aluminium foil ~
circuitry substrate
Fig. 11.14. Aluminium foil process.
Both the transfer decal and the AIT processes yield a completely level
surface, as the circuit traces are actually embedded in the moulded plastic
part. This can be advantageous when designing switches with sliding
elements or potentiometers etc.
The basic characteristics of the in-mould processes are as follows:
• there is planar structuring even before moulding;
• there are few process steps;
• there is a short cycle time;
• they are suitable for glossy surfaces;
• multilayers are possible.
The foil or film is structured in its planar state before moulding and addition
of the three-dimensionality.to the circuit structure. This makes it possible to
apply conventional structuring technology, such as photo-imaging and
screen printing of conductive paste, etc., without the need to purchase new
equipment and having to introduce unproven processes. The number of
process steps in the moulding itself is very limited, yielding short cycle times.
The fact that moulding is basically done after structuring leaves various
possibilities open for the type of surface quality required, thus, for example,
enabling in-mould labelled parts to be used for glossy surfaces. A last, but
very important advantage of the in-mould processes is the ability to
structure the foil or film in multiple layers, thus enabling the manufacture of
three-dimensional multi-layer circuitry.
11.3.6 Mechanical Structuring

In the following section, some less widespread, but nevertheless interesting,
methods for manufacturing MIDs will be described.
Mechanical structuring can be achieved in a number of ways. The basic
principle common to all of them is to break up a uniform metal layer on a
plastic substrate. This implies that the first steps are very similar to either
photo-imaging or laser structuring methods. Typically, this means first of all
that the substrate body is moulded by a one-shot process. Next, the surface
is activated with a suitable chemical treatment and metal (usually copper)
374 1 ,-I____M_O_U_L_D_E_D_I_NT_E_R_C_O_NN_E_CT_D_E_V_I_C_E_S_(M_ID_s_)_ _ _- - '
Injection Moulding
D
Metalplating [Lr1-IJ I I
Milling of Isolation Channels
~b
Fig. 11.15. Mechanical structuring processes.
applied by chemical plating. Finally, the copper may be reinforced by

electroplating as required.
As with laser structuring, only the isolation channels are then removed.
This can be effected either by engraving or similar milling techniques or by
moulding the part so that the later circuit traces lie in recesses, as shown on
the left in Fig. 11.15. The protrusions between the grooves are removed by
milling, grinding or another suitable method and leave isolated areas
between the current carrying tracks. This can also be used to provide
enhanced isolation properties compared to normal circuit boards.
The key advantage of mechanical structuring is its simplicity. On the other
hand, the methods used are usually sequential, thus requiring a considerable
amount of time for the structuring operation, especially when the circuitry
needs to be engraved. Mechanical structuring is well suited to applications
where few isolation channels are needed in a relatively flat surface.
11.3.7 Selectively Activated Catalyst

This process was initially proposed some time ago but it is only recently,
however, that chemicals have been developed which make it possible to
introduce the process into industrial mass production.
A catalytic lacquer is applied to the surface of the moulded substrate
either by spraying, immersion coating or another transfer method. Subse-
quently, the areas of the catalyst that are required to define the circuit traces
are selectively exposed to radiation, either by means of a laser as shown in
Fig. 11.16, or by flood exposure and the use of a mask. After exposure,
development of the catalytic lacquer enables the unexposed areas to be
washed off the substrate. The remaining areas then form the catalytic basis
for a fully additive chemical build-up of the circuitry.
M_ANU
L-_____________ ___F_A_CT
__U_RIN
___G_M
__E_TH
__O_D_S____________ ~I I 375
Injection Moulding
{}
Apply Catalyst
{}
Exposure by LASER
(or UV-Light and mask)
{} ==
Remove unexposed catalyst
{}
Electroless copper
....
Fig. 11.16. Selectively activated catalyst.
Advantages of this method over conventional structuring processes are

the much reduced number of process steps and the use of a single catalyst
for almost all thermoplastics, thus eliminating the need to provide individual
chemical pre-treatment processes for each type of polymer, as is necessary
with conventional chemical plating.
Due to the fact that laser imaging is the preferred exposure method for
this process, fine pitch structuring is possible, as with normal laser imaging
processes, making this method very versatile.
11.3.8 Screen Printing

Another simple process for producing circuit structures on plastic substrates
is screen printing, and the most common method uses a subtractive imaging
process. After moulding and surface pre-treatment of the circuit carrier,
electroless and/or electroplated metal (copper) is applied to the carrier
surface. Then, an organic, non-photosensitive etch resist is screen printed
onto the metal. The resist is cured, and the unprotected areas of the
metallization are removed by etching.
Advantages of this process are the use of well-known printing technology
and the absence of exposure and development processes which reduce the
amount of chemical process steps to a minimum. This process naturally has
its limitations in the width of tracks and spacings and especially in the
geometric freedom of the surfaces to be structured.
In a recently developed process, the adhesion promotion primer for the
electroless copper is printed directly onto the plastic surface. This combines
376 I ~I_________M_O_U_L_D_E_D_I_NT__E_R_C_O_NN__E_C_T_D__EV_I_C_E_S_(M__ID_s_)______~
Injection Moulding
Surface activation
Electroless copper
{}
Apply etch resist
Etch copper
Strip etch resist
Fig. 11.17. Screen printing of etch resist.
Injection Moulding
Print Primer
Electroless Copper =
Fig. 11.18. Screen printing of primer.
the advantages of the screen printing process and the selectively activated
catalyst, again drastically reducing process steps.
11.3.9 Technical Capability of MID Manufacturing Methods

In order to give an overview of the capabilities of the most common MID
manufacturing processes, some important technical data has been compiled
in Table 11.1 below.
ASSEMBLY AND CONNECTION TECHNOWGY
II 377
Table 11.1 Comparative. capabilities of MID manufacturing processes
Hot Photo-imaging Laser Two-shot In-mould

embossing direct moulding labelling
structuring
Platable •t 2500 400 t 75% of

surface, circuit
max. (cm2) carrier
surface
Z-extension 230 200 200 200
(mm)
Width of 0.2 0.125 0.08 0.25 0.1
conductors,
min (mm)
Width of 0.3 0.125 0.04 0.25 0.1
isolation
channels,
min (mm)
... Limited by available foils.

t Limited by size of galvanic bath.
t Limited by available embossing press.
As MID technology is still very new, all limitations are constantly being
altered. When considering a technology, it is highly recommendable to
discuss the specific requirements of the project in question. For example,
minimum track widths depend on the length in general and especially on the
parallel length of those tracks, and on the flow characteristics of the
thermoplastic used.
Not mentioned in the table are the possible thicknesses and compositions
of metallization layers. As a rule of thumb, every surface available for
conventional printed circuit boards is also feasible for moulded circuit
carriers. This includes gold for bonding, tin/lead for soldering and other
surface coatings such as nickel. Thicknesses are usually derived from those
common for planar interconnects, e.g. 18, 25, and 35 microns. These apply
for all methods and in some cases 70 IIDl thicknesses are also used. Hot
embossing foil is available in thicknesses up to 150 1IDl, thus enabling
relatively high currents to be carried. A survey showed that moulded
interconnect devices are at least equal and often even superior to
conventional circuit boards in current carrying capacity.
11.4 ASSEMBLY AND CONNECTION TECHNOLOGY
After manufacture of the circuit carrier, the next step usually is assembly. In
many cases, however, onsertion of components is not necessary to exploit
378 I I~________M__O_U_L_D_E_D_I_NT__E_R_C_O_NN__E_CT__D_E_V_I_C_E_S_(M__ID_s_)______~
the advantages of MID technology. Of 100 or so MID applications realized
so far, only about half are equipped with components in a conventional
way. The other half are used to fulfil important connection tasks such as
replacing connectors and wire harnesses.
11.4.1 Substrate Preparation and Component Onsertion

If assembly is necessary, it is usually structured in several steps as shown in
Fig. 11.19. MIDs are often more challenging to assemble than conventional
circuit boards, as they involve obstacles for the assembly line such as walls
and various protrusions etc.
In conventional circuit board assembly, solder paste or conductive
adhesive is screen or stencil printed onto the board, although this is not
possible for MIDs from type IB onwards (see above). These are provided
with walls and other dead zones on the process plane, have several process
planes or not even planar process surfaces, so that a stencil or printing
screen cannot be used to apply the paste or adhesive. Thus, dispensing is the
most common method of applying a connection means to an MID. The
dispensing angles, nozzle openings and other parameters, however, need to
be carefully controlled to achieve optimum results.
After preparing the MID by applying conductive adhesive or solder paste,
components are onserted. Also, MIDs from type 1B onwards cannot
normally be assembled using conventional component placement equip-
ment. Conventional pick-and-place machines are optimized to place as
many components as fast as possible and thus have minimized z-strokes of
the placement heads. This makes them unsuitable for placing components
next to walls, protrusions etc. Most of the placement heads, especially those
DIspensIng Assembly ' . Soldering
Fig. 11.19. Process chain for MID assembly.

'---_ _ _ _A_S_SE_M_B_L_y_A_ND
__C_O_NN_E_C_T_IO_N_T_E_C_H_N_O_L_O_G_y_ _ _ _ -'1 I 379
of very fast machines, are provided with multiple placement nozzles on a

revolving turret or similar kinematics and these are quite bulky and not
suitable for fine placement operations.
The geometric complexity of MIDs can require machines with improved
and more flexible kinematic capabilities. These have been developed recently
through the development and modification of existing machine designs.
Instead of the four degrees of freedom used in conventional machines, this
new design has a total of twelve degrees of freedom, distributed on two
placement heads working in parallel and a work-piece handling system. This
system contains a cardanic table, so that the process surface of the work-
piece can always be kept vertical.
The multiple degrees of freedom make it also possible to place
components on surfaces where an infinite 'placement normal', i.e. the
vector perpendicular to the placement surface, is not available. Normal
machines require a very long placement normal, as all equipment associated
with the onsertion head is positioned behind the pickup nozzle for
components.
Fig. 11.20. Cinematic simulation of component onsertion on MIDs.

380 I IL-____M_O_U_L_D_E_D_INTE
_ _R_C_O_NN_E_CT_D_E_V_I_C_E_S_(M_ID_s_)_ _ _ -----1
The entire system is more complex than a conventional pick and place
machine, as are the placement operations. In order to avoid collisions, a
cinematic simulation of the placement process has been introduced. As a
general rule, the process surfaces of an MID should be kept to a minimum,
as plain as possible and without too many surrounding walls.
11.4.2 Connection Technology

Onsertion is followed by establishing the connections between components
and substrate. Conventional solder procedures involve temperatures of up
to 300°C, and reflow soldering processes are gaining more and more
importance. For reflow soldering, the components are placed in solder paste
previously deposited on the substrate. The substrate is passed through an
oven with a number of infrared heaters which heat the solder paste until it
melts.
Infrared soldering processes comprise several phases. After a pre-heat
phase, the substrate is subjected to a peak phase, before a cool-down phase
finishes the process. In the peak phase, the temperature must be high enough
to ensure all solder joints are thoroughly reflowed. The infrared heaters
cause the temperatures at the substrate surface to rise well beyond the
melting temperature of solder, normally reaching about 265°C.
The temperatures involved require utilization of high temperature
thermoplastics, such as polyetherimide, polyethersulfone' or liquid crystal
polymers, if the reflow process needs to be adopted with unchanged
parameters. Other plastics can be infrared soldered if the process parameters
are adapted, which basically means that the peak temperatures are lowered
and soldering times shortened.
Special attention must be paid to walls protruding from the MID
substrate towards the infrared heaters. Even if the temperature at the
process surface is low enough not to harm the thermoplastic, the upper
edges of the wall may become so hot that they melt. On the other hand,
shading effects also need to be considered. If the temperature is sufficient at
top areas of the MID, secluded comers may not become warm enough to
ensure proper connection of solder joints located there. These problems can
only be avoided by careful design of the MID substrate.
The positioning of the electronic components is also very important.
Apart from general rules applied e.g. to avoid heat sinks, the possible
location of components on inclined or even vertical walls requires new
guidelines to be introduced. Due to their weight, components tend to
slide down from their proper positions when the viscosity of the solder
paste lowers during the reflow process. Not all components can thus be
placed on walls. Critical ones are quad flat packs (QFPs) and other large
devices. Small components such as so-called 0805s and 0603s etc. have
successfully been soldered on vertical walls. With melf and mini-melf
ASSEMBLY AND CONNECTION TECHNOLOGY
L -____________________________________________________ ~II 381
Fig. 11.21. MID with components placed on the side walls.
packaging, it is important to consider the orientation of the part to

prevent it rolling off. They should always be positioned with their
longitudinal axes vertical.
Thermoplastics not resistant to the temperatures involved in infrared
soldering can be processed using less aggressive methods. They have
moved into the focus of interest as the continuous cost reductions seen in
the electronics industry force the use of cheaper materials (naturally with
reduced temperature performance data). One of the soldering methods
suitable for these materials is vapour phase soldering, a batch process in
which a chamber is filled with the vapour of a soldering medium at
200°C to give a uniform temperature throughout the entire chamber. This
process is especially useful for soldering substrates with complex
geometry or large protrusions. The polymeric solder medium that used
to contain CFCs several years ago has been changed to a more
environmentally friendly formulation. The design of the circuit carrier
must allow the condensate building up on the process surface to be
discharged, thus it must not have pockets or similar features that could
trap the condensate.
Should the 200°C of vapour phase soldering also be too aggressive, which
is the case for many of the engineering and commodity thermoplastics,
382 II
L ____ M_O_U_L_D_E_D_I_NT_E_R_C_O_NN_E_Cf_D_E_V_I_C_E_S_(M_ID_s_)_ _ _----.J
selective soldering can be the solution. Selective soldering methods do not

heat the entire part, but concentrate the energy in one or several solder
points at a time, thus drastically reducing the heat stress to which the
substrate is subjected. In addition to the well-known laser soldering
techniques, microwave or fountain processes and light soldering are new
developments suitable for MID technology.
Conductive adhesives can help to further reduce heat transfer to a
substrate. Their curing depends on time and temperature and, if necessary,
they can be cured at room temperature, with accordingly longer curing time.
However, not all curing conditions yield the same results, with the strength
of joints generally improving with increasing curing temperature. Currently,
comprehensive studies on the use of conductive adhesives in MIDs are being
carried out.
Another connection method is wire bonding. MIDs are suited to
ultrasonic bonding of aluminium and gold wire, provided they have a
suitable surface coating, usually gold. If the thermoplastic can with-
stand higher temperatures, thermosonic bonding using gold wire is also
possible. For MIDs, wedge bonding is normally preferred to ball
bonding.
Press-fit assembly has also shown very reliable results in some applica-
tions. It can be used to connect several MIDs together by a bolt-fit approach
and connection to other assemblies can be done by integrated connector
pins. The counterpart· of the connector usually consists of conventional
metal and a research programme for replacing the metal springs by plastic
parts is currently being conducted.
MIDs require new approaches to connection technology, as most of the
materials used cannot withstand the conditions of regular infrared solder-
ing. However, suitable connection technologies have been developed.
11.4.3 Quality Assurance

Compared to conventional printed circuit boards, quality assurance
becomes more complex, as walls and the multitude of shapes of thermo-
plastic substrates make it more difficult to place all connections so that they
are clearly visible, i.e. inspectable. Similar methods to those required with
ball grid arrays (BGA) are necessary, e.g. X-ray inspection or other methods
suitable for inspecting hidden joints. Other procedures, such as climatic
testing, vibration and drop tests, can be carried out in exactly the same way
as for conventional technology.
It is worth noting that the integration of mechanical and electrical
functions can remove several connection points and thus also remove
potential failure sources. This compensates somewhat for the increased
effort necessary to inspect the remaining critical points.
~_________________M_A_T_E_R_IA_L_S__U_SE_D__________________~I I 383
11.5 MATERIALS USED
For MIDs, a wide variety of polymeric substrate materials is being used.

When selecting a material, the key properties to be considered are
processing and usage temperatures, required flammability rating, mechan-
ical and electrical properties, mouldability and platability as well as cost.
The list in Fig. 11.22 comprises the most common substrate materials. The
list does not claim to be complete, as processes to plate other materials with
high adhesion are constantly being developed.
The most common and longest used thermoplastics are polyetherimide
(PEl, available as 'Ultem' from G.E. Plastics), polyethersulfone (PES,
available as 'Radel' from Amoco) and liquid crystal polymer (available as
'Vectra' from Hoechst Celanese and as 'Zenite' from DuPont). The plating
processes developed for these material groups are thus the most mature and
well established. LCP is about twice as expensive as PEl and PES but has
superior flow characteristics.
Another group of polymers increasingly accepted for chemical plating are
the various types of polyamides. Although regarded as classical engineering
thermoplastics, some of them are temperature resistant enough to be
soldered.
Fig. 11.22. Materials used for MIDs.

384 I ~I_________M_O_V_L_D_E_D_I_NT__E_R_C_O_NN__E_C_T_D__EV_I_C_E_S_(M__ID_s_)______~
Materials important as the non-platable components in two-shot mould-
ing are other grades of LCP, PES and PEl as well as polyphenylenesulphide
(PPS), a generally non-platable material with excellent thermal stability, and
a polysulphone (PSU)jABS-blend.
In the processing of these thermoplastics, it is very important to optimize
the moulding parameters for plating, not necessarily for optimum through-
put in the moulding line. PEl, for example, needs to be moulded slowly, with
low injection pressure and high temperatures in order to form the surface
states required for successful plating.
11.6 EXAMPLE PRODUCT
An example for the integration of functions into a single moulded

interconnect is a thermometer developed by the Research Association
Three Dimensional Electronic Assemblies 3-D MID e.V as a technology
demonstrator.
The MID has been designed so that it can be manufactured by various
methods. So far, hot embossing, photo-imaging and laser structuring
Fig. 11.23. Thermometer as technology demonstrator.

L_I_T_ERA
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ___ T_U_R_E__________________~I I 385
methods have been utilized. The part comprises the functions of the circuit
board, display unit in the upper portion, battery holder and battery contacts
in the lower part as well as the function of a support to place the
thermometer on a table.
The components have been placed on the product using the above-
mentioned placement system and soldering was performed in an infrared
oven. The material used was PEl for the photo-imaged and laser structured
parts with polybutyleneterephthalate (PBT) used for the hot embossed
variation.
11.7 SUMMARY
Moulded interconnect device technology is beginning to mature as a

technology having been in existence since the mid 1980s. Industrial
production and applications experiences are now in place and it is widely
accepted that MIDs have a permanent position in the electronics industry.
MIDs have many advantages and offer an attractive way for the integration
of several traditional device functions into a single entity with the promise of
potential cost savings. Continued technical development by forward-looking
companies has turned MIDs into a commercial reality and they have found
wide application in many sectors of the electronics industry including
automotive, consumer, medical, aerospace and computer. Further applica-
tion depends upon the innovative capabilities of equipment designers and
their ability to realize the full advantage of the technical and economic
benefits provided by this interesting alternative circuit board technology.
11.8 LITERATURE
Burkner, G., Feldmann, K., Romer, M. and Franke, J. (eds), Proc. 1st International
Congress on Molded Interconnect Devices, MID 94, Meisenbach, Bamberg, 1994.
Burkner, G., Feldmann, K., Pohlau, F. and Romer, M. (eds), Proc. 2nd International
Congress on Molded Interconnect Devices, MID 96, Meisenbach, Bamberg, 1996
Franke, J., Integrated Product and Process Development for Three-Dimensional
Electronic Assemblies, Hanser, Munchen, 1995.
Hunter, P., MIDs-PCBs move into the third dimension, Electronic Production, June
1995.
Pohlau, F., Decision fundamentals for the introduction of MID technology. Proc.
VDI-ADB-Seminar Electronics Production, Munchen, 1995.
Index
Figure locations are indicated by bold type and tables by italic.
Acid anhydrides 99 Aluminium nitride, filler in encapsulants

Acrylics 51-2 179-80
applications 51 Amine-cured epoxides, resistivity 11
dry film photoresists 207-8 Amines, hardeners for encapsulants 177
electrodepositable resists 214, 216 2-Aminobenzylamine 98
photoresists 204, 207-8 Aminoethyl piperazine 96, 'TI
copolymers Aminopropyl triethoxysilane 182
monomers, use in liquid photo- Amplifier noise 280
imageable soldermasks 219 Anhydrides
solvent resist systems 212, 213 hardeners for encapsulants 176-7
water-borne liquid photo-imageable reactions 100
soldermasks 223 Antimony oxides 114-15, 150
properties 51-2 Arc resistance, definition 14
Acrylonitrile-butadiene--styrene 51 Arc testers 15
enclosures 69 Area array
light housings and armatures 75 bumping 346, 347
smart cards 78 packaging 325
wiring devices 69 Automated transfer moulding
Active matrix liquid crystal display machines 138-40
212-13
Acyclic aliphatic resins 92-3 Bakelite 2-3
Adhesives 20 Ball grid array 173, 189,191, 192, 198,
conductive 380 325
room temperature wlcanizing 41 Ball hardness test 68
silicone, see Silicones, adhesives Ball pressure test 67
Advanced interconnect applications, Barium titanate 243
polymers in 324-8 use in capacitors 283
epoxy resins 326 Benzocyclobutenes, use in thin film
polyimides 326 applications 337,339,340-2
polyphenylene ether 326 Benzophenone 209
Alkenyl silane--sulphone copolymer, use Benzyl-dimethylamine 100
in X-ray lithography 236 Biguanide 99
Alpha particle radiation, susceptibility of Biomedical applications of ferroelectric
transfer moulding compounds materials 281-3
to 150-1 Bismaleimide triazine resins
Alpha quartz, filler in transfer in laminate manufacture 312
moulding 143 in MCM-L technology 335
Alumina trihydrate 115-16 Blisters, in transfer moulding 156
filler in epoxide-based encapsulants Bone healing, use of piezopolymer
178, 179 film 281
388 II~__________________IN_D_E_X________________~
Boron nitride, filler in encapsulants Cured epoxy-based materials, recycling
179-80 of 123-4
Brabender plastograph test, see Torque Cure schedule, for materials used in
rheometer test encapsulation 189, 190
Breakdown voltage, definition 15-16 Cure speed, of material in encapsulants
Brominated resins 150 184
Bumping 346, 347 Curing agents
Burning process, mechanisms 112-13 for epoxide resins 93-106
Butanediol diglycidylether 118 aliphatic amines 11, 94, 95, 96
4-t-Butoxycarbonyl styrene, use in X-ray anhydrides 99-102
lithography 236 aromatic amines 97-8
Butyl glycidylether 118 catalytic 102-4
cationic photoinitiators 104-6
Calcium carbonate, filler in cycloaliphatic amines 96-7
epoxide-based encapsulants 178 4,4'-diaminodiphenyhnethane 97
Capacitors 4 4,4'-diaminodiphenylsulfone 97, 310
barium titanate used in 283 dicyanodiamide 99, 310
housings, use of thermoplastics in 74 diethylaminopropylamine 94
integrated 323 diethylene triamine 94
thermocompensated 283 3,3-dimethyl-5-methyl-l,6-diamino-
Carbon black 112, 180 hexane 94
Carboxyl-terminated butadiene ethylene diamine 94
acrylonitrile copolymers 120 metaphenylenediamine 310
Carnauba wax, mould release agent 144, 4,4' -methylenedianiline 310
159 novo lacs 102
Casein, use in liquid photoresists 212-13 photoinitiators 105
Catalysts 177, 372, 373 polyaminoamides 96
Cavity fill encapsulation 190-1, 192 polyether-polyamines 96
Charpy method 67 selection of 94
Chip tetraethylene pentamine 94
on board devices 173, 189 thermal initiators 105--{)
diode 43 toxicity 124
encapsulation 173, 189 triethylene tetramine 94
on flex devices 189 for phenolic resins
multichip module 221 hexamethylene tetramine 316
scale packaging 173-4, 193, 197,325-6 resole resins 316
Chlorendic anhydride 101, 102 Cyanamide 99
Circuit boards 3 Cyanate ester, used for laminate
see also Printed circuit boards manufacture 312, 313
Circuit breakers 71 Cyclized polyisoprenes, use in liquid
Clay 110-11 photoresists 212
Colour filters 205 Cycloaliphatic resins 92-3, 176
Commodity plastics, see Engineering Cyclotene@ 340, 341
thermoplastics
Comparative tracking index 15,66 Dacron-epoxy® 321-2
Conductivity, definition 12 Dam and fill encapsulation 189-90
Conformal coatings, silicone 32, 35-6, Deflection temperature 66, 307
39,40,41 Density of polymers 22
Connectors, use of thermoplastics in 72-3 1,2-Diaminocyclohexane 96, 97
Copper-clad silicone-glass laminates 45 4,4'-Diaminodiphenylmethane 97, 98
Creep, definition of 18 4,4'-Diaminodiphenylsulfone 97, 98, 310
Cresyl glycidylether 118 1,8-Diamino-p-methane 96, 97
L - -_ _ _ _ _ _ _ _ IN_D_E_X_ _ _ _ _ _ _ _-------'I I 389
2,6-Diaminopyridine 98 multiacrylates 207

2,4-Diaminotoluene 98 negative-working 207-10
Diazonaphthoquinones photoinitiator 206-7, 209
in electrodepositable resists 214 benzophenone 209
in optical resists 225, 226, 227-8, 229, isopropylthioxanthone 209
230 mechanism of action 210
Dibutyl-phthalate 117 2-methyl-l-[4-(methylthio)phenyl]-
Dicyanodiamide 99,310 2-morpholinopropanone 209
Dicyclopentadiene dioxide 176 Michler's ketone 209
Dielectric photosensitizer 207, 209
breakdown 305, 306 mechanism of action 210
constant 13-14 plasticizers 206
of ferroelectric materials 259-60 polymers 206-7
of laminates for printed circuit acrylate 207-8, 210
boards 304, 305 methacrylate 207
loss of ferroelectric materials 260-1 novolac resin 210
strength 15, 305, 306 polyolefin film 206
Dielectrics 327-8 positive-working 210, 211
epoxide-based 328 resolution 205
inner layer 342-5 solvent-based 206
photoimageable 202, 221, 327, 335 structure 206
Diethylaminopropylamine 94, 95 thermal polymerization inhibitors 206
2,2'-Diethyl-4,4'-diaminodiphenylmeth- visible laser direct imaging 211
ane 97, 98 see also Photo resists; Resists
Diethylene triamine 94, 95 Dry film soldermasks 219
Differential scanning calorimetry 189 DVS-BCB, structure 341
Diffusers, use of thermoplastics in 74-5 DYCOstrate™ 326, 335
Diglycidylether of bisphenol A 84, 87-8, Dynamic random access memory 224
96, 308, 310, 311
Diglycidylether of bisphenol F 88-9 Elastic compliance 274
Dihydroxychalconediglycidylether 91 Elasticity
Dimethyl-aminomethyl-phenoll00, 106 definition 16
3,3'-Dimethyl-4,4'-diaminodicyclohexyl- modulus of 184
methane 96, 97 Elastomers 175
3,3-Dimethyl-5-methyl-l,6-diamino- applications
hexane 94, 95 cables 46
Diode chips, protection with silicone connectors 72
paste 43 encapsulants 180-1
Direct chip attach 197 sleeving 45
Direct plate processes 3 wire and cables 70
Dispensing, materials used for glass transition temperature 181
encapsulation 188-9 silicone 32, 34, 35-6, 45-6
Dissipation factor 14, 304-5 thermoplastic 64, 70, 72
Dissolution inhibition 227 viscosity 180
Dodecenyl succinic anhydride 120 Electricity meters, use of thermoplastics
Draft angles of transfer moulds 137-8, in 71
161 Electric strength, see Dielectric strength
Dry film resists 205-12, 325 Electrodepositable resists 212-18
adhesion promoters 206 acrylates 214, 216
aqueous systems 206, 210 advantages 214
dye 206 cataphoretic deposition 218
monomer 206 coating mechanism 215, 218
390 I LI_________I_ND_E_X_ _ _ _ _ _ _ _ ---.l
Electrodepositable resists (cont'd) two-part systems 186

epoxide resins 214, 217 thermal conductivity 197
negative-working photoresists 214-15 see also Glob top
novolacs 214, 217 Encapsulation
photoactive compounds 215 advanced, materials for, see Encapsul-
photoinitiators 215 ants, materials for
plasticizers 215 cavity fill 190-1, 192
positive-working resists 215 of chip on board devices 173, 189
Electromagnetic compatibility 79 of chip on flex devices 189
Electromagnetic interference 79 dam and fill 189-90
shielding 359 flip chip underfill 193,194, 195-6
Electromechanical coupling factors 266, of semiconductors by transfer
268,269 moulding, see Transfer moulding
Electron-beam resists 237 smart card 191-2, 193
Emergency lights, use of Enclosures, use of thermoplastics for 69
thermoplastics in 77 Engineering thermoplastics
E-modulus 67 acrylics 51-2
Encapsulants acrylonitrile-butadiene-styrene 51
flame retardants in 198 applications
market size 175 capacitor housings 74
materials for circuit breakers 71
basic formulation 174-5 connectors 72-3
catalysts 177 electricity meters 71
combinations 183 enclosures 69
cure schedules 189, 190 fibre optic connectors 73
cure speed 184 installations 69-70
dispensing 188-9 insulation systems 73-4
elastomers 180---1 lamp holders 74, 75
epoxide resins, see Epoxide-based lighting 74-8
encapsulants moulded interconnect devices 73
fillers, see Epoxide-based relays 70
encapsulants smart cards 78
form 186-7 surface mount technology 73
glass transition temperatures 184, switchgears 70
185 wire and cables 70
handling 186-9 wiring devices 68-9
hardeners 176-7 elastomers 64, 70, 72
ion scavengers 182-3 electrical tests on 66
limitations to formulation 183-4 flammability 64-5
one-component systems 187 laser marking 79-80
packaging 187 liquid crystal polymers 52-3
pigments 182 mechanical tests on 67-8
preheating 188 metallization 79
requirements of 33 modified polyphenylene ether 53-5
rheological modifiers 182 painting 79
shelf-life 187 polyamideimide 60
shrinkage of 184 polyamides 55
silanes 181-2 polybutylene teraphthalate 56, 68
silicones, see Silicones, encapsulants polycarbonate 57, 58
storage 187 polycarbonate/acrylonitrile-but-
surfactants 182 adiene-styrene blends 58
thawing 187-8 polyesters 56
L -_ _ _ _ _ _ _ _IND_E_x_ _ _ _ _ _ _ ----..J1 I 391
Engineering thermoplastics (cont'd) storage of materials 187

polyetheretherketone 58 surfactants 182
polyetherimide 58-9, 60 thawing materials for 187
polyethylene terephthalate 56 two-part systems 186
polyoxymethylene/acetal 60-1 Epoxide novolacs, see Novolac resins
polyphenylene sulphide 61-2 Epoxide resins 83-125
polypropylene 62 aliphatic 92-3, 175--{)
polysulphones 62, 63 applications
polyvinyl chloride 63 advanced interconnect 326
post-treatment of 79-80 dielectrics 328
properties 320 electrodepositable resists 214, 217
recyclability 80 encapsulants, see Epoxide-based
thermal tests on 66-7 encapsulants
weathering tests 68 integrated circuits 4
see also named materials laminate manufacture, see
Environmental aspects of Laminates, epoxide resins
semiconductors 198 liquid photo-imageable solderrnasks
Epoxide-based encapsulants 219,220
aliphatic 175--{) MCM-L technology 335
aromatic glycidyl ethers 176 photoresists 204
basic formulation 174-5 printed circuit boards 298,301
catalysts 177 transfer moulding, see Transfer
chloride ion content 186 moulding, epoxides
combinations of ingredients 183 transistors 4
cure schedules for materials used in binder 85, 86
189 cationic polymerization of 222
cycloaliphatic 176 cured, properties 84-5
dispensing materials for 188 curing agents, see Curing agents, for
elastomers 180-1 epoxide resins
epoxide-novolacs, see Novolac resins cycloaliphatic 92-3, 176
epoxide resins 175--{) diglycidylether of bisphenol F 88-9
fillers 177-80 diglycidylethers, production 87-90
alumina 179 dihydroxychalconediglycidylether 91
alumina trihydrate 178 diluents 117, 118, 119
aluminium nitride 179-80 dry process 87
boron nitrides 179-80 extenders 106-12
calcium carbonate 178 advantages and disadvantages of
carbon black 180 J08
disadvantages 178 carbon black 112
silica 179 clay 110-11
talc 180 densities 109
hardeners 176-7 metallic fillers III
ion scavengers 182-3 requirements 107
limitations to formulations 18~ silica 108-9
one-component systems 187 talc 109-10
packaging 187 uses 106-7
pigments used in 182 Wollastonite 110
preheating materials for 188 filler 85, 86
rheological modifiers 182 first aid for contamination by 125
shelf-life 187 flame retardants 112-16
silane use in 181-2 alumina trihydrate 115-16
speciality structures 176 antimony oxides 114-15
392 I LI_________I_ND_E_X_ _ _ _ _ _ _ _ ----l
Epoxide resins (cont'd) comparison of 287

boron compounds 116 composites 253-5, 256, 257-8
decabromophenyleneoxide 116 connectivity 254-8
ethylene-bis-tetrabromophthalimide designs 253-4
116 properties 253-4
magnesia trihydrate 116 mechanical processing 248-51
phosphorus-based 116 biaxial film 249-50
trisbromostyrene 116 film casting 250
see also Flame retardants, in sheet production 250
transfer moulding thin films 249
flexibilizers 119-20 three-dimensional structures 25{}-1
general formulation considerations uniaxial film 249
121-3 poling 251-3
liquid process 87 properties 258-76
melt blending process 87 dielectric constant 259-60
melting points 89 dielectric loss 26{}-1
moulding materials 172 elastic compliance 274
plasticizers 117-18 electromechanical .coupling factors
properties 83, 86, 121-2 266, 268, 269
purity 9{}-1 ferroelectric behaviour 258, 259
relative permitivity 13 glass transition temperature 261,
safety precautions 124-5 263
solvent process 87 heat capacity 263
structure 83-4 mechanical loss 275-6
toughening agents 119-20 melting behaviour 263
toxicological properties 124 piezoelectric constants 264-6
world production of 84 piezoelectric properties 267
see also named materials Poisson's ratio 276
Epoxidized diene polymers 93 pyroelectric 264
Epoxidized glycol 119 pyroelectric constants 269-72
Epoxidized oils 93 stiffness 274
Etch resists 205 temperature dependence 261, 272-4
Ethylene diamine 94, 95 thermal ageing 272
2-Ethyl-4-methyl-imidazole 100, 106 thermal conductivity 263-4
Explosion-proof lighting, use of ultrasonic parameters 283
thermoplastics in 77 Young's modulus 274-5
Extenders for epoxide resins, see SMART materials 284-6
Epoxide resins, extenders structure 247-8
synthesis 246-7
Fatigue, definition 18 Fibre optic connectors, use of
Feedstock recycling 123 thermoplastics in 73
Ferroelectric polymers 243-87 Fillers
applications 276-84 in encapsulants, see Epoxide-based
biomedical 281-3 encapsulants
capacitance thermocompensation high thermal conductivity 22
282-3 in transfer moulding, alpha quartz 143
filter bandwidth modifications Fire resistance, silicones 29, 38, 4{}-1, 46
28{}-1 First Aid, for contamination by epoxide
pyroelectric 284 resin formulations 125
sound transducers in air 277 Flame retardants
sound transducers in water 277-9 action of 113
telephone keypads 279 in encapsulants 198
~_________________
IN_D_E_X________________~I I 393
Flame retardants (cont'd) catalysts in the formation of 177

in epoxy resins, see Epoxide resins, properties 184-5, 186
flame retardants materials 175-7, 179
in transfer moulding 149-50 process 171,174
Flammability, tests for 64-5, 149 Glow wire test 65
Flank array transducer, circuit 278 Glycidoxy propyl trimethoxysilane 182
Flashing of transfer moulding Glycidyl ethers 176
compounds 151, 152, 153, 165
Flat panel displays 347 Hardeners 176-7
Flexibilizing agents, effects on resistivity Hardness 67-8, 164, 165
of polymers 11 Heat capacity 263
Flexible printed wiring Heat deflection temperature 66
applications 323 Hexahydrophthalic acid-diglycidylester
fabrication 322 91
fluorinated ethylene-propylene Hexahydrophthalic anhydride 101, 102
copolymers 322 Hydrogen silesquioxane, use as a coating
plastic composites 321-2 44-5
polyetherimide 322, 329 Hydrophone noise 279, 280
polyethylene naphthalate 319
polyethylene terephthalate 319 Impact strength 67
polyimide 319, 321, 335 Installations, use of thermoplastics in
po1ytetrafluoroethy1ene 322 69-70
Flexural modulus, definition 306 Insulating tapes, silicone 46
Flexural strength 306 Insulation systems, use of thermoplastics
Flip chip in 73--4
devices 173 Integrated capacitors 323
technology 193, 199 Integrated circuits 4, 201, 224
underfills 174, 177, 193,194,195,196 size reduction 202
Fluorinated ethylene-propylene see also Lithography; Photoresists
copolymers, for flexible printed Integrated resistors 323--4
wiring 322 Interconnect vias, fabrication of 341
Fluoropolymers Ion scavengers, use in encapsulants 182-3
dielectric properties 14 Isophorone-diamine 96, 97
relative permitivity 13 Isopropylthioxanthone 209
FR4 epoxy laminate 24 UV absorption spectrum 209
Izod method 67
Gelatin, use in liquid photoresists 213
Glasscloth 26 Johnson noise 279, 280
Glass-epoxy resin, dielectric constant
304, 305 Kapton® 319
Glass fabric, properties 315 Kevlar ™ 332, 333
Glass fibres 26 Keypads, silicone rubber 46,47
Glass transition temperature 24, 66 Knit lines in transfer moulding 153-5
definition 23 Koda flow test 163
of elastomers used in encapsulants 181
of encapsulants 184, 185 Laminates
of ferroelectric materials 261, 263 copper-clad silicone glass 45
of laminates 307 cyanate ester 312, 313
of perspex 23 epoxide resins 309-18, 329
in transfer moulding 146, 147, 148 diglycidylether of bisphenol A
Glob-top 310-11
encapsulant 185 FR424
394 II
L-_ _ _ _ _ _ _ _ _ IND_E_X_ _ _ _ _ _ _ _---'
Laminates (cont'd) electromechanical coupling factors

glass transition temperature 310, 312 269
properties 309-10, 315, 316 mechanical loss 276
phenolic resins 316-17 piezoelectric 267
polyimides 313-16, 329 Lewis acids 103, 210
applications 314 boron trifluoride 103
preparation of 313 complexes 104
properties 314,315, 316 Lewis bases 103, 106
polytetrafluoroethylene 317-18 Lighting, use of thermoplastics in 74-8
printed circuit boards diffusers 74-5
classification 299, 300, 301 emergency lights 77
dielectric constant 304, 305 explosion-proof lights 77
manufacturing process 298-9 housings and armatures 75
testing of 302, 303 lamp holders 74
produced from organic reinforcements reflectors 77-8
333 spotlights 77
properties street lamps 75-6
deflection temperature 307 traffic lights, warning and hazard
dielectric breakdown 305 lights 76
dielectric constant 304 Limited oxygen index, definition 65
dissipation factor 304-5 Liquid crystal display
electric strength 305 active matrix 212-13
flexural modulus 306-7 cross-section 348
flexural strength 306 Liquid crystal polymers 52-3, 335
glass transition temperature 307 advantages of 335
loss factor 304 applications 53
resistivity 303-4 moulded interconnect devices 362,
thermal dimensional stability 308-9 378,381-2
thermal expansion coefficient surface mount technology 73
307-9,316 chemical structure 336
water absorption 309 production 52
rigid printed wiring 297-301 properties 52, 53, 336
classification of 299, 300, 301 Liquid photo-imageable soldermasks
manufacturing process 298-9 202,218-19,221
properties 301-2 water-borne 222, 223
testing of 302, 303 Liquid photoresists 212-13
thermoplastic polyphenol ether 317-18 advantages 212
Lamp holders, use of thermoplastics in chemically amplified 213, 214
74, 75 disadvantages 212
Laser metal-ion free water soluble 213
drilling of vias 328, 333 negative-working 212
imaging positive-working 213
of dry film photoresists 211 Liquid silicone rubbers 45-6
of moulded interconnect devices Lithography 201-39
364,365,366 deep UV 225, 228, 230-4
of thermoplastics 79-80 electron beam 201, 234-8, 239
lithography 230 poly(butene-l-sulphone) used in 236
soldering 380 polymethyl methacrylate used in
Lead zirconate titanate 243, 254-8 235-6
applications, SMART structures 284 resists, negative-working 237, 238
derivation of 244 laser 230
properties 244 optical, limitations 225
'--_ _ _ _ _ _ _ _ _I_N_D_EX
_________ --'I I 395
Lithography (cont'd) description 353

process 203 example product 382-3
production of integrated circuits 202 function integration 358
production of printed circuit boards integration potential 354, 355
202 introduction decisions 358--60
technology, development trends 224 key markets 354, 355
X-ray 225,234-8,239 manufacturing methods 361, 362-75
advantages 234 aluminium foil process 370, 371
resists 236 capture decal process 369, 370
Loss factor 14, 304 hot embossing 367, 368, 369
in-mould labelling 369-71
Magnesia trihydrate 116 insert moulding 361-2
MCM-L technology 335 laser imaging 364, 365, 366
Mechanical loss 275--(, mechanical structuring 371, 372
Melting point 23, 24, 89, 263 on-shot moulding 361
Metal complexes 103 photoimaging 362, 363, 364
Metallic fillers III screen printing 373, 374
Methacrylate monomers used in dry film selectively activated catalyst 372,373
resists 207 technical capability of 374, 375
4,4'-Methylenedianiline 310 transfer decal process 369, 370
I-Methyl-imidazole 106 two-shot moulding 361, 366, 367
2-Methyl-l-[4-(methylthio)phenyl]-2- materials 381, 382-3
morpholinopropanone 209 quality assurance 380
Michler's ketone 209 thermoplastic use in 73, 353
Microcircuits, use of high-purity silicone Moulding compound, hot hardness 164,
coatings in 44 165
Modified polyphenylene ether 53, 54, 55 Multichip module 221
Moisture resistance, of materials in en-
capsulants 184 National Electrical Manufacturers
Mould Association, classification system
finish, in transfer moulding 138 299, 300, 301
concentration versus adhesion 145--(, Needle flame test 65
release agents in transfer moulding Neopentllglycol diglycidylether 118
camauba wax 144, 159 NomexT 321-2, 333
releasability 144, 145 Novolac resins 89-90, 176
staining 144, 145, 159--69 curing 102, 315-16
sticking 160, 161 dry film resists 210
Moulded interconnect devices 354, 379 electrodepositable resists 214, 217
advantages of 357 encapsulants 176
applications 354 liquid photo-imageable soldermasks
thermometer 382, 383 219
assembly 375-78 optical photoresists 225, 226, 227
component onsertion 376, 377, 378 photo resists 204
process chain 376 positive-working liquid resists 213
substrate preparation 376 Nylon 55
classification 355, 356 applications
connection technology 378-80 circuit breakers 71
conductive adhesives 380 connectors 72
press-fit assembly 380 lamp holders 74
soldering 378-80 switch assemblies and relays 70
wire bonding 380 piezoelectric activity 245
cost considerations 360, 361 structure 8
396 I L-I_________IND_E_X_ _ _ _ _ _ _ _---'
On-chip I/O redistribution 346 negative-working 202, 203, 207, 214
Onium compounds 103-4, 105 optical, see Optical photoresists
Optical fibre cable materials 70 polymers used in 203, 204
Optical interconnect 346-7 positive-working 202,203, 210,
Optical photoresists 225-8 213-14, 225, 227
deep ultra-violet 228, 230-4 primary imaging 205-18
problems 233 see Dry film resists; Electrodeposi-
dissolution inhibition 227 table resists; Liquid photoresists
g-line 225 secondary imaging 218-23
i-line 225 cationic polymerization 219-21
novolac resin used in 225, 226, 227 photo-imageable dielectrics 221
photochemistry 226 two-pack systems 219
Organopolysiloxane 26 water-borne liquid photo-imageable
Oxirane group 83 soldermasks 222, 223
4,4'-Oxydianiline 97 spin-coated, process 229
water soluble 212
Packaging, of materials for encapsulants see also Resists
187 Photosensitization, mechanism 210
Parting line of transfer moulds 137 Photosensitizers 205-6, 209, 212, 214
Perspex, glass transition temperature 23 Phthalic anhydride 101
Phenolic resins Piezoelectric constants 264--6
curing agents for 316 Piezoelectric effect 243, 264
in deep UV photo resists 231, 234 Piezoelectric materials 243-5
in printed circuit boards 298, 301, composites 245, 253-8
316-17 copolymers 245
disadvantages 317 disadvantages of 245
formation of 316 mechanical processing 248-51
properties 315 polyamides 245
Phenylenediamine 97 structure 247-8
Phenyl glycidylether 118 synthesis 246-7
2-Phenyl-imidazole 106 see also Ferroelectric polymers; Lead
Photo-imageable dielectrics 202,221,327, zirconate titanate; Polyvinylidene
335 fluoride
Photoinitiation, mechanism 210 Pigments, used in encapsulation 182
Photoinitiators 104--5, 205-7, 209, 212, Pin grid arrays 325
215 Plasma ablation 326, 333
Photo resists 3-4, 234, 363 Plastic
chemically amplified 230 ball grid array 189
three-component negative tone 231, composites, for flexible printed wiring
233 321-2
three-component positive tone 231, definition I
232 encapsulated devices, reliability 165-7
two-component negative tone 230, Plasticizers
232 in dry film resists 206
two-component positive tone 230, in electrodepositable resists 215
231 effects on resistivity of polymers II
dry film, see Dry film resists Plated through holes 296
electrodepositable, see Electrodeposi- Poisson's ratio 276
table resists Poling 247, 251-3
for integrated circuit production corona 251, 252, 253
223-38 thermal 251
liquid, see Liquid photo resists Polyacrylonitrile, structure 7
INDEX
L -_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ II
~
397
Polyamideimide 59-60 wiring devices 69

Polyamides 55 blends 58
aromatic, structure 334 Polychlorotrifluoroethylene, structure 8
applications 55 Polyester
moulded interconnect devices 367, applications
381 connectors 72
hydrolysis of 19 flexible printed wiring 319
piezoelectric activity 245 insulation systems 74
properties 55 printed circuit boards 298
resistivity 11 reflectors 77
Polyaminoamide 96 switch assemblies and relays 70
Polyaniline, resistivity 11 traffic lights 76
Poly-benzoxazole 336 films, in capacitors 4
Poly(butene-l-sulphone), use in hydrolysis of 19
electron-beam lithography 236 materials, effect of humidity on 12
Polybutylene, structure 7 Polyetheretherketone 58
Polybutylene teraphthalate 56 in surface mount technology 73
applications Polyetherimide 58-60
capacitor housings 74 applications 59
circuit breakers 71 fibre optic connectors 73
connectors 72 flexible printed wiring 322, 329
enclosures 69 installations 70
lamp holders 74 insulation systems 74
light housings and armatures 75 light housings and armatures 75
moulded interconnect devices 383 moulded interconnect devices 362,
wiring devices 68 366, 378, 381-2
Polycarbonate 57, 58 reflectors 77-8
applications 57-8, 68 smart cards 78
capacitor housings 74 spotlights 77
connectors 72 surface mount technology 73
diffusers 74-5 properties 59, 60, 320
electricity meters 71 relative permitivity 13
emergency lights 77 structure 59
enclosures 69 Polyetherketoneketones 58
explosion-proof lights 77 Polyetherketones 58
light housings and armatures 75 Polyether-polyamine 96
reflectors 78 Polyethersulfone
smart cards 78 in moulded interconnect devices 366,
street lamps 76 378,381-2
switch assemblies and relays 70, 71 properties 320
traffic lights 76 structure 8
wiring devices 69 Polyethylene
properties 57 dielectric properties 14
structure 8, 57 glass transition temperature 24
Polycarbonate/acrylonitrile--butadiene-- melting point 24
styrene resistivity 11
applications structure 7
electricity meters 71 Polyethylene naphthalate, used in
emergency lights 77 flexible printed wiring 319
installations 70 Polyethylene terephthalate 8, 56
light housings and armatures 75 applications
smart cards 78 flexible printed wiring 319
398 I I'--________IND_E_X_ _ _ _ _ _ _ _---'
Polyethylene terephthalate (conl'd) machinability 19
lamp holders 74 resilience 16-17
properties 24 shrinkage 19
Poly(hydroxystyrene), use in stiffness 16-17
photoresists 204 strength 16-17, 19
Polyimidebenzoxazole 336 stress/strain characteristics 17-18
properties 337 toughness 16-17
structure 337 viscosi ty 19
Polyimides operating conditions 10
applications physical properties of 21-3
advanced interconnect applications density 22
326 glass transition temperature 23
flat panel displays 347 heat resistance 23
flexible printed wiring 319, 321, 335 melting point 23
laminate manufacture 313-16, 329 thermal conductivity 22
MCM-L technology 335 thermal expansion coefficient 22
printed circuit boards 298 thermal stability 23
thin film applications 337-40 properties required for emerging ap-
transfer moulding 132, 150 plications 331
relative permitivity 13 see also named materials and processes
Polyisoprenes, use in liquid photoresists Polymethyl methacrylate 51-2, 255
212 applications 52
Polyketones 58 diffusers 75
Polymers electron-beam lithography 235-7
applications of 2, 3, 4 street lamps 76
chemical properties of 20-1 chain scission 236
chemistry of 4-9 properties 24, 52
conductive, uses 12 structure 8
definition I Poly cr; methyl styrene, structure 8
degradation by moisture 12 Polyoxymethylene 60-1
density 22 Polyoxymethylene/acetal 60-1
electrical properties of 9-16 Poly(phenylene oxide)-based resins, use
arc resistance 14-15 in MCM-L technology 335
breakdown volatge 15-16 Polyphenylene sulphide 61-2
comparative tracking index 15 applications
conductivity 12-13 insulation systems 74
dielectric constant 13-14 light housings and armatures 75
dielectric strength 15-16 moulded interconnect devices 370,
dissipation factor 14 382
insulators 9-11, 13 reflectors 78
loss factor 14 spotlights 77
power factor 14 surface mount technology 73
relative permitivity 13-14 transfer moulding 132
resistance 10 properties 320
resistivity 10, 11, 12-13 structure 8-9
intrinsically conducting 3, 11-13 Poly(para-phenylene terephthalamide)
mechanical failure of 17-18 332
mechanical properties of 16-19 Polyphenyl ether 53, 54, 55
abrasion resistance 19 applications 54
elasticity 16-17 advanced interconnect applications
flexibility 19 326
hardness 19 capacitor housings 74
L -_ _ _ _ _ _ _ _ _IN_D_E_X_ _ _ _ _ _ _ _ ----'I I 399
Polyphenyl ether (cont'd) inert 19

connectors 72 materials produced from 318
electricity meters 71 resistivity II
enclosures 69 structure 8
installations 70 Polyvinyl acetate, structure 7
fibre optic connectors 73 Polyvinyl alcohol
light housings and armatures 75 in liquid photoresists 212-13
printed circuit boards 318 solubility 20
traffic lights 76 structure 7
wire and cables 70 Polyvinyl chloride 2, 63
wiring devices 68 applications
properties 53-4 installations 69
Polyphenyl ether/polyamide alloys, use in wire and cables 70
reflectors 77-8 properties 24
Polypropylene 62 structure 7
applications Polyvinylidene chloride, structure 7
capacitor housings 74 Polyvinylidene fluoride 244-5, 257
capacitors 4 applications
street lamps 76 pyroelectric devices 284
properties sensors 279-80
glass transition temperature 24 sound transducers in air 277
melting point 24 sound transducers in water 277-9
relative permitivity 13 mechanical processing 248-51
resistivity II biaxial film 249-50
structure 7 film casting 250
Polypyrrole, resistivity II sheet production 250
Polystyrene thin films 249
applications uniaxial film 249
diffusers 75 properties 258-9
electron beam resists 237 ageing curve 273
properties anisotropy 265
dielectric 14 dielectric constant 260
glass transition temperature 24 dielectric loss 261
melting point 24 electromechanical coupling factors
relative permitivity 13 269
resistivity II glass transition temperature 263
structure 6-7 mechanical loss 276
Polystyrenetetrathiofulvalene, use as an melting point 263
electron-beam resist 237 phase transition 261
Polysulphonejacrylonitrile-butadiene- piezoelectric constants 265--6
styrene blend, use in moulded piezoelectric properties 267
interconnect devices 382 pyroelectric 264
Polysulphones 62, 63 Young's modulus 275
applications structure 7, 247, 248
photoresists 204 synthesis 246
properties 62, 63, 320 Polyvinylidene fluoride-barium titanate,
structure 62 use in thermocompensated
Polytetrafiuoroethylene capacitors 283
applications Potting materials, silicone 34, 37
flexible printed wiring 322 Power factors, definition 14
printed circuit boards 298, 317-18 Power transistors, silicone protective
printed wiring boards 332-3, 335 coating 43-4, 45
400 I ~I__________________ IN_D_E_X________________~
Preheating, of materials used for encap- Relative thermal index 67, 77

sulants 188 Relays, use of thermoplastics in 70
Press-fit assembly 380 Reliability of plastic encapsulated de-
Printed circuit boards 201, 294 vices 165-7
binding agents 298 Replamine composites 254-5
double-sided 296 Resilience, definition of 16
fabrication 295-7 Resin bleed, of transfer moulding com-
double-sided 296 pounds 151-3, 165
multilayer 297 Resistance 10
single-sided 295 Resistivity 10-13
laminates used in, see Laminates, definition to
printed circuit boards factors affecting 11-12
lithographic processes in production of laminates 303-4
of 202 Resists, see Dry film resists;
multilayer 297 Electrodepositable resists;
photoresists for, see Photoresists Electron beam resists; Etch
polymers in 293-330 resists; Liquid photoresists;
see also named materials Optical photo resists; Photo resists;
size reduction 202 Print resists; Solvent
substrates with organic resist systems; Water
reinforcements 332-5 soluble resists
see also Printed wiring boards Rheological modifiers, use in encapsul-
Printed Circuit Kollmorgen 367 ants 182
Printed wiring boards Rigid-rod polymers 336
reinforcements 332-5 Rockwell hardness test 68
aromatic polyamide 333--4 Runner systems of transfer moulds 137,
expanded polytetrafluoroethylene 139
332-3,335
poly(para-phenylene terephthalami- Scanning acoustic microscopy 145
de) 332 Screen print application of soldermasks
properties 332 219
substrates without reinforcements Sealants, silicone 35-6, 41, 42, 43
335-6 Sea state zero noise 279, 280
see also Flexible printed wiring; Semiconductors 10, 11
Printed circuit boards encapsulation by transfer moulding,
Print resists 205 see Transfer moulding
Pyroelectric devices, use of ferroelectric industry trends 196-8
materials in 284 environmental aspects 198
Pyroelectric materials 243 improved performance 196
see also Ferroelectric polymers lower product cost 196-7
Pyromellithic dianhydride 101, 102 quicker time to market 197
reduced product life 197
reduced size 197
Quad flat packs 324, 378 tests for improved performance 196
Quartz, filler Sequential build-up approach 326, 327,
in encapsulants 179 335
in transfer moulding 143 circuitry 333
Shore D durometer 164
Ram follower/spiral flow test 163 Shore hardness test 68
Recycling, of cured epoxy-based Shrinkage
materials 123-4 of materials in encapsulants 184
Reflectors, use of thermoplastics in 77-8 in transfer moulding 137-8, 142
Relative permitivity 13 Silanes 181-2
'---_ _ _ _ _ _ _ _IN_D_EX
________ -------'I I 401
Silica 108, 143, 179 oxidative stability 27

Silicone-organic copolymers 47 polarity 27
Silicone oxides, applications products of combustion 29
thin films 337 surface tension 28
transfer moulding 132 temperature effects 28
Silicone rubber 33, 45--6 thennal stability 27, 33
glass transition temperature 23 toxicity 28-9, 34
keypads 46-7 water absorption 29
resistivity 11 release agents 47
Silicones 25-48 sealants 35-6, 41, 42, 43
adhesives 35-6, 41, 42, 43, 44, 47 structure 9, 25--6
applications 43 vacuum pump fluids 47
dispensing 43 Silicon inner layer dielectrics 342, 343,
high-purity 43-5 344
properties 42 Smart cards 78, 177-8, 191
thennally conductive 42-3 encapsulation 191-2, 193
ageing 34 SMART materials 284-6
applications 31, 33--47 actuator mechanisms 285--6
constructional materials 45-7 sensors 285
future developments 47-8 use in vibration control 284-5
insulating materials 45-7 Snap cure products 177
transfer moulding 132 Soldering
wires and cables 45-7 fountain 380
chemical purity 29 infrared 378
confonnal coatings 32, 35-6, 39, 40, laser 380
41 light 380
properties of 39--40 microwave 380
repairability 41 selective 379-80
curing reactions 30, 32-3 vapour phase 379
elastomers 32, 34, 35-6 Soldennasks 218
insulated cables 46 cationic polymerization 219-21
sleeving 45 advantages 220
electronic coatings curtain coat application 219
high-purity 43-5 dry film 219
encapsulants 33--4, 35-6, 37, 38-9,47, liquid photo-imageable 202, 218-19
174 water-borne 222, 223
gel 38 process 221
on-component elastomers 34, 35-6 two-pack 219, 220
self-priming 38 Solvent resist systems, acrylic copoly-
transparent 38 mers in 212
two-component elastomers 34, 35-6 Sound transducers
fluid molecule, model 27 in air 277
gels 32, 38, 39 in water 277-9
insulating tapes 4 Speedboard™ 333, 334
laminates 45 Spiral flow 141, 142, 148, 152, 162
polymerization reactions 30, 32, 33 Spotlights, use of thennoplastics in 77
potting materials 34, 37 Staining of moulds 159-60
product families 31 Stiffness, definition 16
production of 29-33 Storage
properties 27-9 of materials for encapsulants 187
elasticity 27, 34 of transfer moulding compounds 151,
fire resistance 29, 38, 40-1, 46 156
~2 I I~________________IND
__E_X________________~
Strain, definition 17 bumping 346, 347
Street lamps, use of thermoplastics in 75, flat panel displays 347
76 gallium arsenide inner layer dielectric
Strength, definition 16 345
Stress, definition 17 multichip module packages 345, 346
Stress relaxation, definition 18 on-chip applications 341-5
Stress/strain curve 17 optical interconnect 346-7
Stress testing, highly accelerated 166, polyimides 337-40
196 derivation 338
Surface mount devices 73, 171,324, 359 properties 338, 339
Surface resistivity, definition 12 silicon inner layer dielectric 343
Surfactants, used in encapsulation 182 stress buffer for silicon devices 342
Switchgear, use of thermoplastics in 70 synthesis 340
sensors and micromachining 347
Talc 109-10, 180 silicon inner layer dielectric 342, 343,
Teflon,rM see Polytetrafluoroethylene 344
Tensile elongation 67 Toluene 117
Tensile stress/strain relationships 67-8 Torque rheometer test 163, 164
Tetrabromobisphenol A 113, 114 Toughness, definition of 16
Tetrachlorobisphenol A 113, 114 Toxicity
Tetraethylene pentamine 94, 95 epoxide resins 124
Tetrafluoroethylene 245 silicones 28-9, 34
N,N,N',N'-Tetraglycidyl-4,4'-diamino- Traffic lights, use of thermoplastics in 76
diphenylmethane 91 Transfer moulding 131-8, 139, 140-68
Tetrahydrophthalic anhydride 101 definition 134
Thawing, of materials used for encapsul- design considerations 136
ants 187-8 epoxide novo lacs 176
Thermal ageing studies 272-3 epoxides 132, 140, 141, 142--6, 148,
Thermal conductivity 157-9, 161-7
coefficient, definition 22 advantages 132-4
encapsulants 185, 197 disadvantages 133
ferroelectric materials 263-4 evaluation 161-7
fillers 22, 143-4 flash and bleed characteristics 165
Thermal dimensional stability 308-9 hot hardness 164
Thermal expansion coefficient 42, 184 hot plate cure time 162
encapsulants 184-5 Koda flow test 163
epoxy resins 183 mouldability 162-4
filler content 142, 143 mould release 165
laminates 307-9, 316 properties 133-4
polyimidebenzoxazole 336 ram follower/spiral flow test 163
polymers 22 reliability 165-7
Thermal expansion curve 308 shelf stability 148
Thermal initiators 105-6 spiral flow 162
Thermal stability 23, 308-9 torque rheometer test 163-4
encapsulants 197 viscosity 162-4
Thermal tests on thermoplastics 66-7 equipment considerations 134-40
Thermo-mechanical analysis 189 automated moulding systems 138-
Thermoplastics, see Engineering thermo- 40
plastics draft angles 137-8, 161
Thermount™ 333,334 gate location 136, 139
Thin film applications 336-47 mould finish 138
benzocyclobutenes 337,339, 340-2 parting line 137
L - - ._ _ _ _ _ _ _ _ _ IN_D_E_X_ _ _ _ _ _ _ _ ---'I I 403
Transfer moulding (cont'd) rapid transfer 156

runner systems 137 resin bleed 151-3, 165
shrinkage 137-8 staining of moulds 159-60
venting 136--7 sticking in the mould 160, 161
external release agents 153, 161 transfer speed 154
flame retardants 149-50 undercure of moulding compound
formulation considerations 140-51 160-1
curing conditions 147, 148 viscosity of moulding compound 158
filler content 141, 142, 143, 144 voids 156
flammability 149-50 wire sweep 157-9
glass transition temperature 146, process 134
147,148 silicone-epoxides 132
mould release agents 144, 145, 146 silicones 132
raw material purity 149 storage of compounds 151, 156
resin viscosity effects 141, 142 stresses 146, 147
shelf stability 148-9 transfer speed 153
spiral flow 141, 142 Transistors 4
susceptibility to alpha particle radi- Triethylene tetramine 94, 95
ation 150-1 Trifluoroethylene 245
thermal conductivity 143, 144, 167 see also Vinylidene fluoride-
thermal expansion coefficient 142, trifluoroethylene copolymer
143 Triglycidyl-p-aminophenoI91
future trends 167-8 1,3,5-Triglycoidylisocyanurate 91-2
machines 135 Trimellithic anhydride 101
moulding pressure and temperature Tris-(dimethylaminomethyl)-phenol
153 (DMP 30) 100, 106
mould release agents 144
parting line 137 Ultem, properties 320
polyimides 132, 150 Ultrasonic imaging, use of ferroelectric
polyphenylene sulphide 132 materials in 281-2
preheating 154 Ultraviolet lithography 225, 228, 230-4
problems 151--61 Urea formaldehyde 2
blisters 156
dry moulds 161
excessive filling speed 157-8 Vacuum lamination 206, 219
excessive moulding temperature 156 Vectran™ 336
excessive volatiles 156 Venting transfer moulds 136--7
flashing 151-3 Vias
gate blockage 154-5 fabrication of 341
high transfer pressure 157 laser drilling of 328, 333
inadequate venting 154--6 Viny17
incompatible release agent 161 Vinyl acetate 245
incomplete fill 153, 154, 155 in chemically amplified resist systems
incorrect clamping pressures 155 213
incorrect flow 154-5 Vinyl cinnamates, use in liquid photore-
incorrect moulding pressure and sists 212
temperature 154 Vinyl cyclohexane dioxide 176
knit lines 153-5 Vinyl fluoride 245
melt viscosity 156 Vinylidene cyanide 245
poor cosmetic appearance 159--60 Vinylidene fluoride 245--6
poor mould design 161 Vinylidene fluoride-trifluoroethylene
preheating 155 copolymer 246
4M I I~_________________IND
__E_X________________~
Vinylidene fluoride--triftuoroethylene Voids
copolymer (cont'd) in encapsulation 185, 191
applications, sound transducer in transfer moulding 156
in water 278
mechanical processing 248-51 Wafer fabrication, use of high-purity
three-dimensional structures silicone coatings in 44-5
250-1 Water absorption of laminates 309
properties 259 Water-borne liquid photo-imageable
ageing curves 272, 273 soldermasks 222, 223
dielectric constant 260 Water soluble resists 212
dielectric loss 261 metal-ion free 213
electromechanical coupling factors Weathering of thermoplastics 68
269 Wire bonding 380
melting point 263 Wires and cables, use of thermoplastics
phase transition 261, 262 in 70
piezoelectric 267 Wire sweep·152, 157-9
piezoelectric constants 265-6 Wiring devices, use of thermoplastics
pyroelectric 264 68-9
Young's modulus 275 Wollastonite 110
structure 248
Vinylidene monomers, structure 7 X-ray lithography 225, 234-8, 239
Viscosity, advantages 234
evaluation resists 236
Koda flow test 163 Xylene 117
ram follower/spiral flow test 163 Xylylene diamine C)7
torque rheometer test 163-4
of materials in encapsulants 184 Young's modulus 27.4-5

Martin Goosey (Auth.), Martin Goosey (Eds.) - Plastics For Electronics-Springer Netherlands (1999)

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Martin Goosey (Auth.), Martin Goosey (Eds.) - Plastics For Electronics-Springer Netherlands (1999)

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Plastics for Electronics

Plastics for Electronics

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

ISBN 978-90-481-4018-3 ISBN 978-94-017-2700-6 (eBook)

Printed on acid-free paper

AII Rights Reserved

Chapter 1 Introduction to polymers and their important properties

Chapter 2 Silicone materials for electronic components

Chapter 3 Engineering thermoplastics 51

3.6 Design for recyclability 81

Chapter 4 Epoxide resins and their formulation 83

Chapter 5 Recent developments in the encapsulation

Chapter 6 Materials for advanced encapsulation 171

Chapter 7 Recent developments in the chemistry of lithography

Chapter 10 New polymers for emerging interconnect applications 333

Chapter 11 Moulded interconnect devices (MIDs) 355

Harry van Baal

The phenomenal and relentless progress in the development and commer-

excellent contributions from those authors whose first language is not

1.1 INTRODUCTION TO POLYMERS AND THEIR PROPERTIES

Table 1.1 Year of introduction and uses for various plastics

Year Material Application

1909 Phenol-formaldehyde Equipment cases

electronic components. Typical applications for polymers in the electronics

Use Suitable materials

Transfer moulding Epoxides, silicones, phenolics, polyimides.

called direct plate processes which enable electroplating of through holes in

1.2 CHEMISTRY OF POLYMERS

For simplicity, the benzene molecule is drawn as a hexagon with a circle

If one of the hydrogen atoms of an ethylene molecule is replaced by a

In addition to the substitution of one of the hydrogen atoms of ethylene

Substituent Resulting polymer

Substituent A Substituent B Resulting polymer

-C-O-CH3 Poly methyl methacrylate

to-st Polyphenylene sulphide

1<0>-1-<0)-01 Polyether sulphone

1.3 IMPORTANT ELECTRICAL PROPERTIES OF POLYMERS

1.3.1 Resistance and Resistivity

Table 1.4 Comparative electrical resistivities of materials

Resistivity Material Classification

and some fluorinated polymers have resistivities in excess of 1018 n em. It

1.3.2 Relative Permitivity (Dielectric Constant)

Table 1.5 Relative permittivities of various materials at 25°C

Material Relative permittivities

1.3.3 Dissipation, Power and Loss Factors

1.3.4 Arc Resistance

low-current arc is used to simulate the conditions likely to be found in

1.3.5 Comparative Tracking Index (CTI)

1.3.6 Dielectric Strength and Breakdown Voltage

1.4 IMPORTANT MECHANICAL, CHEMICAL AND PHYSICAL

In addition to having excellent electrical properties for electronic and

1.4.1 Mechanical Properties

All of these properties can be determined from the stress/strain charac-

Fig. 1.1. A typical stress/strain curve for a polymer.

In addition to mechanical failure under conditions of high stress, failure can

A number of other mechanical properties are also often considered

1.4.2 Chemical Properties

100% yields of the desired products and polymerization reactions are no

1.4.3 Physical Properties

The thermal stability or heat resistance of polymers is obviously of

Polyethylene -120 137

This chapter has given a brief introduction to polymers, their fundamental

2.1 DEFINITION AND HISTORY