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Yuri Freeman

Tantalum and
Niobium-Based
Capacitors
Science, Technology, and Applications
Tantalum and Niobium-Based Capacitors
Yuri Freeman

Tantalum
and Niobium-Based
Capacitors
Science, Technology, and Applications
Yuri Freeman
Greer, SC, USA

ISBN 978-3-319-67869-6    ISBN 978-3-319-67870-2 (eBook)

DOI 10.1007/978-3-319-67870-2

Library of Congress Control Number: 2017953008

© Springer International Publishing AG 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,
broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology
now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, express or implied, with respect to the material contained herein or for any errors
or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims
in published maps and institutional affiliations.

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The registered company is Springer International Publishing AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
To my wife, Galina,
for all the good she brought into my life.
Acknowledgments

I would like to honor the memory of the great scientists whom I was privileged to
work alongside in my career: Prof. Lev Palatnik from Kharkiv Polytechnic Institute;
Dr. Ilia Skatkov from SCB ELITAN; Dr. Felix Zandman, founder of Vishay
Intertechnology; and Dr. Brian Melody from KEMET Electronics.
I would like to acknowledge Dr. Terry Tripp, whose papers and later collabora-
tion encouraged my work in the field.
I would like to thank my colleagues in the industry and academia who contrib-
uted to this book directly or through valuable conversations: KEMET’s Steve
Hussey, Dr. Phil Lessner, Jonathan Paulsen, Tony Kinard, Dr. James Chen, George
Haddox, Barry Reeves, Dr. Erik Reed, Dr. Javaid Qazi, Jeff Poltorak, Jim Fife, and
David Jacobs; Clemson University’s Dr. Rod Harrell, Dr. Igor Luzinov, and Dr.
Ruslan Burtovyy; and Tel Aviv University’s Dr. Alexander Gladkikh, Dr. Yuri
Rozenberg, and Dr. Alexander Palevski.
I would also like to acknowledge the engineers, technicians, and operators in the
manufacturing, analytical, and electrical labs and mechanical shops who helped
transform scientific ideas into advanced technologies and products.
I would like to thank KEMET CEO, Per Loof, for supporting research projects
even in challenging financial times and KEMET managers Ed Johns and Hal Perkins
for promoting novel tantalum capacitors into the most conservative military and
aerospace markets.
Special thanks to my children Anya and Daniel for their help with editing this
book.

vii
Contents

1 Major Degradation Mechanisms.............................................................. 1

1.1 Oxygen Migration............................................................................... 4
1.2 Field Crystallization............................................................................ 8
1.3 Thermal Crystallization....................................................................... 15
1.4 Interaction Between Oxygen Migration and Crystallization.............. 16
2 Basic Technology........................................................................................ 21
2.1 Anode Manufacturing......................................................................... 21
2.2 Ta2O5 Dielectric................................................................................... 28
2.3 Cathode............................................................................................... 32
2.4 External Layers, Encapsulating, and Testing...................................... 34
3 Applications................................................................................................ 41
3.1 High Charge and Energy Efficiency.................................................... 41
3.2 De-rating and High Reliability............................................................ 55
3.3 High-Voltage Polymer Tantalum Capacitors....................................... 68
3.4 Asymmetric Conduction and Stability................................................ 75
3.5 Anomalous Currents in Polymer Tantalum Capacitors....................... 89
3.6 High-Temperature Applications.......................................................... 98
3.7 Niobium and Niobium Oxide Capacitors............................................ 103
4 Conclusion.................................................................................................. 109

References......................................................................................................... 113

Index.................................................................................................................. 117

ix
About the Author

Yuri Freeman received his master’s degree as engineer-physicist from the renowned
school of thin solid films at the Kharkiv Polytechnic Institute in Ukraine. He gradu-
ated among the first in his class and hoped to continue his work in academia. However,
as it was still Soviet Union times and graduates were “distributed” often contrary to
their choices, Yuri was sent to work for SCB ELITAN, a developer and producer of
tantalum capacitors. At first Yuri thought sadly: “What could be more primitive than a
capacitor with two plates separated by a dielectric?” He realized only later that his
random assignment was an incredible opportunity for a scientist and an engineer!
The change started with his involvement in the development of niobium capacitors to
substitute tantalum capacitors, enforced by a shortage in tantalum in former Soviet
Union. Comparison of the degradation mechanisms in tantalum and niobium
capacitors became the topic of his Ph.D. in solid-state physics.
Shortly after the collapse of the Soviet Union, SCB ELITAN was closed and Yuri
started his work for Vishay Sprague, the original manufacturer of solid tantalum
capacitors. After several years with Vishay Sprague, where Yuri was promoted to
principal scientist, his facility in Sanford, Maine, USA, was closed, and manufactur-
ing moved overseas. While Yuri was looking for a new job, his Siberia-born wife fell
in love with sunny South Carolina, and that’s how Yuri ended up at KEMET
Electronics, a global producer of tantalum capacitors. This turned out to become the
best part of his career with the most challenging projects and the industry’s best team
to work with. Now, Yuri is a technical fellow/VP, director of Advanced Research and
Strategic Development at KEMET Electronics. He has more than 40 patents, more
than 30 peer-reviewed papers in prestigious scientific sources, and international
awards in the field of science and technology of tantalum and niobium-based
capacitors. As an adjunct professor, he is also teaching electronic components at
Clemson University.

xi
Introduction

According to Greek mythology, Tantalus was a Greek king who held the friendship
and favor of the gods until he challenged their will and was consigned to perpetual
thirst and hunger. The name Tantalum was given to the metal element with atomic
number 73 and symbol Ta by a Swedish chemist A. Ekeberg who discovered it in
1802 in minerals taken from Kimito, Finland, and Ytterby, Sweden. The custom of
the time was to dissolve new elements in mineral acids to investigate their chemical
properties. Yet this was tantalizingly difficult for Ekeberg to accomplish since tanta-
lum was exceptionally unaffected by mineral acids. Later research revealed that
tantalum owes its stability in aggressive environments to a thin film of native oxide
that covers tantalum surface when the metal is exposed to oxygen. In addition to
chemical stability, tantalum pentoxide (Ta2O5) thin films obtained by chemical
vapor deposition, thermal oxidation of sputtered layers of tantalum, or anodic oxi-
dation of tantalum in aqueous and nonaqueous solutions are among the best-known
dielectrics, combining high dielectric constant and electrical strength [1]. According
to the Tantalum-Niobium International Study Center (TIC), about a half of the tan-
talum produced globally is consumed in a wide variety of electronic components
and circuits, utilizing exceptional dielectric properties of the Ta2O5 films. In these
applications, Ta2O5 films are employed as dielectric layers for storage capacitors in
DRAM, gate oxides in field effect transistors, dielectrics in tantalum capacitors, etc.
Tantalum capacitors are broadly used in modern electronics due to their stability
in a wide range of temperatures and frequencies, long-term reliability, and record
high volumetric efficiency CV/cc (where C represents capacitance and V represents
applied voltage). These capacitors can be found in the most demanding applications
such as medical, aerospace, and military, as well as in numerous commercial appli-
cations such as automotive, telecommunications, and computers. Tantalum capaci-
tors are the essential component of cardio implants, which automatically sense
abnormal heart rhythms and deliver an electric countershock within seconds, saving
thousands of people from sudden cardiac death [2]. Figure 1 shows a Medtronic
cardio implant with tantalum capacitors as the key part of the therapy provided.
Tantalum capacitors consist of a tantalum anode made of tantalum powder sintered
in vacuum; an anodic oxide film of tantalum employed as a dielectric; and a cathode

xiii
xiv Introduction

Fig. 1 Medtronic cardio

implant with tantalum
capacitors

Fig. 2 Leaded (a) and chip (b) tantalum capacitors

which can be either a liquid electrolyte (wet tantalum capacitors), manganese dioxide
(solid MnO2 tantalum capacitors), or an inherently conductive polymer (polymer
tantalum capacitors). Depending on the type of assembly and encapsulation, these
capacitors can be either leaded, typically in hermetic metal cans, or surface-mount
chips typically in non-hermetic plastic casing. Some surface-mount chip configurations
with ceramic or plastic-over-metal casing can also be hermetic. Figure 2 illustrates
examples of the leaded and chip tantalum capacitors
Figure 2a presents leaded wet, MnO2, and polymer tantalum capacitors (from
the left to the right). Figure 2b presents a variety of chip MnO2 and polymer tantalum
capacitors
Tantalum capacitors are polar with positive polarity on tantalum anode. The bar
and/or sign “+” indicates positive termination on the marking of the capacitor.
Figure 3 shows an example of the marking on a chip tantalum capacitor
Introduction xv

Fig. 3 Marking on a chip

tantalum capacitor

This marking also shows the type of the capacitor (KM stands for T540 series
KEMET polymer tantalum capacitor), capacitance (337 stands for 330 μF),
working voltage (16 V), tolerance (K stands for +/− 10%), and date code (710
stands for year 2017, week 10).
The first wet tantalum capacitors were manufactured in the 1930s by Fansteel
Metallurgical Corporation, the largest producer of tantalum in the USA at that time
[3]. Early wet tantalum capacitors employed anodes made of tantalum foil, which
were later replaced with porous tantalum anodes sintered in vacuum with Ta powder.
These anodes had a considerably higher surface area per unit of volume in compari-
son to the surface area of the foil anodes, providing greater volumetric efficiency.
Porous anodes sintered in vacuum with capacitor-grade tantalum powder are now
used in all types of tantalum capacitors.
The disadvantage of wet tantalum capacitors is their high equivalent series resis-
tance (ESR), especially at low temperatures, which causes capacitance loss and
limits ripple current, operating frequencies, and the range of operating tempera-
tures. The major contributor to ESR in wet tantalum capacitors is the resistance of
the liquid electrolyte within the capacitor, typically an aqueous solution of sulfuric
acid. Current flow through the liquid electrolyte is provided by ions with much
lower mobility in comparison to mobility of current carriers in solid conductors. At
lower temperatures, viscosity of the electrolyte increases and mobility of ions
decreases. When ambient temperature approaches the freezing point of the electro-
lyte, ion mobility becomes negligible, causing extremely high ESR and total loss of
capacitance.
The invention of the solid transistor by J. Bardeen, W. Brattain, and W. Bradford
from Bell Telephone Laboratories, for which they received the Nobel Prize in
Physics in 1956, marked the beginning of modern electronics [4]. The replacement
of massive vacuum tube transistors with small semiconductor-based transistors
allowed for drastic decrease in size and increase in operating frequencies, thereby
improving the functionality of electronic devices.
xvi Introduction

To meet these challenges in the capacitor world, H. Haring, N. Summit, and R.

Taylor from Bell Telephone Laboratories invented the solid tantalum capacitor with
manganese dioxide (MnO2) cathode, initially named the “dry electrolytic device”
[5]. To produce MnO2 cathode according to this invention, tantalum anodes were
sintered in vacuum and anodized and then immersed in an aqueous solution of
manganese nitrate, followed by pyrolysis of manganese nitrate into solid manganese
dioxide and gaseous nitrogen oxide. Manganese dioxide covered the surface of the
dielectric inside and outside of the porous anode forming the cathode of tantalum
capacitor, while gaseous nitrogen oxide evaporated from the capacitor body.
Using this technology, Sprague Electric in the USA began mass manufacturing
solid MnO2 tantalum capacitors in the late 1950s. D. Smyth, G. Shirn, and T.
Tripp, three leading scientists at Sprague Electric, made significant contribution to
the science and technology of MnO2 tantalum capacitors [6–12].
The major advantage of solid MnO2 tantalum capacitors in comparison to wet
tantalum capacitors is their low ESR. This is because MnO2 is an n-type semiconductor
with electrons as majority current carriers having much higher mobility compared to
the mobility of ions in liquid electrolyte in wet tantalum capacitors. Next, MnO2 has
a narrow band gap, providing a significantly smaller temperature dependence of ESR
versus the temperature dependence of ESR in wet tantalum capacitors. Manganese
dioxide cathodes also provide solid tantalum capacitors with a strong self-healing
capability. This is because MnO2 is an oxidizer and a solid electrolyte, releasing
oxygen into the oxide dielectric to compensate oxygen vacancies there. Furthermore,
MnO2 can transform locally into lower manganese oxides such as Mn2O3, Mn3O4,
and MnO with considerably higher resistivity than resistivity of the MnO2 cathode.
This transformation occurs in defect areas of the dielectric, which have higher current
density and, thereby, higher temperatures. The low manganese oxides with high
resistivity block current flow through the defects in the dielectric, preventing thermal
runaway and capacitor failure.
Due to their high stability, reliability, and volumetric efficiency, MnO2 tantalum
capacitors have been broadly used for more than half a century in a wide range of
applications, including high-reliability applications in military and aerospace
electronics. With the large number of capacitors in use for a great period of time,
there have been instances of capacitor failures despite the low failure rate inherent
to these capacitors. The typical failure mode in solid MnO2 tantalum capacitors has
been a short, and in some instances, failed capacitors ignited. Typically, ignition
occurred in large, high capacitance and working voltage capacitors or capacitor
banks when a great amount of accumulated energy was rapidly released through a
small breakdown channel in the dielectric, causing rapid temperature increase and
release of oxygen from the MnO2 cathode. The burning of tantalum anode after igni-
tion was typically suppressed almost immediately due to the phase transformation
of MnO2 into low manganese oxides, which do not have active oxygen to support
burning. These low manganese oxides also prevent oxygen access from the ambient
atmosphere. Nevertheless, a possibility of ignition in case of failure as well as elevated
ESR in comparison to ESR in ceramic and film capacitors with metal electrodes
limited the applications of MnO2 tantalum capacitors.
Introduction xvii

The conductive polymer cathode was developed in the 1980s and 1990s by NEC
Corporation in Japan. Conductive polymer cathode was initially developed for
aluminum capacitors and later applied to tantalum capacitors to satisfy demand for
miniaturization and high operating frequencies by the fast-growing computer and
telecommunication industries [13]. NEC was also the first mass manufacturer of
polymer tantalum capacitors. Poly(3,4-ethylenedioxythiophene) (PEDOT) is
commonly used as the cathode material in polymer tantalum capacitors [14–16].
The major advantage of polymer tantalum capacitors in comparison to wet and
MnO2 tantalum capacitors is their low ESR with reduced dependence on tempera-
ture. This is because the conductivity of the inherently conductive polymer is in
the range of 100–1000 S/m, compared to the conductivity of the MnO2, which is
in the range of 0.1–1 S/cm. Another characteristic of polymer tantalum capacitors
is their non-ignition failure mode. These capacitors can avoid ignition because the
conductive polymer cathode does not contain active oxygen to ignite the tantalum
anode. The non-ignition failure mode is an important safety feature, especially in
low ESR circuits.
The history of tantalum capacitors reveals that the chief driving force in their
evolution from wet, to solid MnO2, to Polymer was ESR reduction. At the same
time, this evolution resulted in much lower working voltages in solid tantalum
capacitors in comparison to wet tantalum capacitors. Typically, the working volt-
ages achieve 125 V in wet tantalum capacitors and 63 V in solid MnO2 tantalum
capacitors. Until recently, the working voltages of polymer tantalum capacitors
have been limited to 25 V. Figure 4 shows typical ESR and maximum working
voltage in different types of tantalum capacitors.
The limited working voltage has made the applications of polymer tantalum
capacitors impossible in high-voltage, high-reliability circuits, where the combination
of low ESR and non-ignition failure mode is most critical. Traditionally, the working

Fig. 4 ESR and maximum working voltage in different types of tantalum capacitors
xviii Introduction

voltage of tantalum capacitors is increased through the use of higher formation

voltage during electrochemical oxidation of the tantalum anodes. Since the thickness
of the anodic oxide film of tantalum is directly proportional to the formation voltage,
a higher formation voltage results in a thicker Ta2O5 dielectric and, thereby, a greater
breakdown voltage (BDV) and working voltage for tantalum capacitors [17].
However, as the formation voltage increased in polymer tantalum capacitors with
PEDOT cathodes, the BDV increased to approximately 50 V and then leveled off,
even though the dielectric thickness continued to grow [16]. This “saturation” of the
BDV limited the ultimate working voltage of polymer tantalum capacitors to 25 V
since many years of testing and field application of different types of tantalum
capacitors established that a working voltage should be no larger than 50% of the
BDV to achieve long-term stability and reliability.
Another significant disadvantage of polymer tantalum capacitors was their high
direct current leakage (DCL), which was typically about ten times higher than DCL
in solid MnO2 tantalum capacitors and even more than that in comparison to DCL
in wet tantalum capacitors. Moreover, in many cases, DCL in polymer tantalum
capacitors continued to grow during life test and field applications, causing paramet-
ric and catastrophic failures of these capacitors. As a result of the combination of
low BDV and high DCL, polymer tantalum capacitors until recently were used only
in low-voltage commercial applications, which do not require long-term stability
and reliability. A deep understanding of the degradation and conduction ­mechanisms
in polymer tantalum capacitors and breakthroughs in their technology and screening
techniques was needed to overcome these limitations and develop high-­voltage and
low-leakage polymer tantalum capacitors for high-reliability applications.
Niobium (Nb) was an obvious choice to substitute tantalum as the anode material
in the electrolytic capacitors because the physical and chemical properties of
niobium and tantalum have so much in common that for some period of time they
were considered the same metal. The names of these two metals are also con-
nected. In Greek mythology, Niobe is Tantalus’s daughter. The first niobium capaci-
tors were developed in Leningrad (now St. Petersburg) in former USSR where sources
of tantalum were limited, while niobium was plentifully available. Mass manufactur-
ing of niobium capacitors was launched in the 1960s. Later, a joint team of engineers
and scientists from SCB ELITAN and Kharkiv Polytechnic Institute in Ukraine made
significant contributions to the science and technology of niobium capacitors
[19, 20]. OJSC ELECOND in Russia continues mass manufacturing of MnO2
niobium capacitors for commercial and special applications.
In the West, interest in niobium capacitors was fueled by the shortage of tantalum
in the early 2000s due to the vast consumption of solid MnO2 tantalum capacitors
in the fast-growing telecommunication industry. Besides niobium, niobium mon-
oxide (NbO) with a metallic-type conductivity was introduced by J. Fife as anode
material for electrolytic capacitors [21]. Mass manufacturing of the niobium oxide
capacitors with NbO anodes and MnO2 cathodes was launched by the AVX
Corporation in 2003 [22].
Niobium-based capacitors consist of porous anodes sintered in vacuum with
niobium or niobium oxide powders; anodic oxide film Nb2O5 as a dielectric; and
Introduction xix

MnO2 cathodes. The advantage of niobium-based capacitors in comparison to tantalum

capacitors is their lower cost per CV caused by larger availability and lower cost of
niobium in comparison to tantalum. Niobium oxide capacitors also demonstrate safety
features such as no ignition and no short failure mode [22, 23]. Despite of these
advantages, applications of niobium and niobium oxide capacitors in modern
electronics are very limited due to their lower volumetric efficiency and working
voltages in comparison to tantalum capacitors. Furthermore, DCL in niobium-based
capacitors is typically higher than DCL in tantalum capacitors and often increases
with time during the capacitor testing and field application, causing parametric and
catastrophic failures. In some early hermetic niobium capacitors developed in the
USSR, DCL was increasing with time during storage even without voltage applied;
however, when the seal was opened, DCL quickly fell back to its initial level.
The initial hypothesis was that a sort of “evil spirit” was created inside the hermetic
can during storage and then escaped from the can when the seal was opened. The “evil
spirit” was the official name of this type of failures in niobium capacitors even after it
was discovered that the real reason for the reversible DCL increase was redistribution
of moisture inside the hermetic can and that adding a controlled amount of humidity
to the can will help stabilize DCL in hermetic MnO2 niobium capacitors.
Surprisingly, the Greek myth about king Tantalus and his daughter Niobe played
a role in improvements in technology of niobium capacitors. As princess Niobe
was a delicate and sensitive offspring of her sturdy father, the niobium capacitor
technology, which was initially practically identical to the tantalum capacitor
technology, was adjusted to be more gentle, with less thermal and mechanical
shocks and additional healing steps to support the Nb2O5 dielectric. However,
major improvements in performance and reliability of tantalum and niobium-based
capacitors were achieved as a result of the deep understanding of the degradation
mechanism in these capacitors.
Chapter 1
Major Degradation Mechanisms

The basic bilayer of all types of tantalum capacitors, tantalum anode, and anodic
oxide film of tantalum as a dielectric is not a thermodynamically stable system. This
is demonstrated by the tantalum-oxygen equilibrium diagram that does not contain
two-phase equilibrium areas for pure tantalum and tantalum pentoxide (Fig. 1.1)
[24, 25]. Relaxation of the Ta-Ta2O5 system into the thermodynamically stable state
occurs through oxygen migration from Ta2O5 to Ta, resulting in a solid solution of
oxygen in tantalum anode and oxygen vacancies in the tantalum oxide dielectric.
Conductivity of the dielectric and, thereby, DCL of tantalum capacitor increase
exponentially with the concentration x of oxygen vacancies in the depleted with
oxygen Ta2O5–x [6, 8, 11]. Tantalum capacitors with thinner dielectrics are more
sensitive to oxygen migration since the thickness of the depleted with oxygen por-
tion of dielectric near the Ta-Ta2O5 interface is comparable with the total thickness
of the dielectric.
Another reason for the thermodynamic instability of tantalum capacitors is the
amorphous structure of the anodic oxide film of tantalum formed on crystalline
tantalum. The image of the Ta-Ta2O5 bilayer on Fig. 1.2 obtained by super high-­
resolution transmission electron microscopy (TEM) demonstrates the differences
between the amorphous structure of the anodic oxide film of tantalum and crystal-
line structure of tantalum [26].
One can see from Fig. 1.2 that atoms in the anodic oxide film of tantalum are
disordered and do not have any preferable orientation, which is inherent to amor-
phous structures, while atoms in the tantalum metal are ordered in a crystalline lat-
tice. This amorphous structure of the anodic oxide film of tantalum employed as a
dielectric in tantalum capacitors is of paramount importance to performance and
reliability of these capacitors. Typically, the dielectrics in the tantalum capacitors
are very thin (from 0.02 μm to 0.6 μm depending on the formation voltage). As a
result of the low thickness, the electrical field in the dielectric film at rated voltage
is on the order of several million V/cm. The disordered arrangement of atoms in the
amorphous dielectric results in a high density of electron traps for the electric cur-
rent carriers. Due to these traps, the mobility of electric current carriers stays low in

© Springer International Publishing AG 2018 1

Y. Freeman, Tantalum and Niobium-Based Capacitors,
DOI 10.1007/978-3-319-67870-2_1
2 1 Major Degradation Mechanisms

Fig. 1.1 Tantalum-oxygen equilibrium diagram [24]

Fig. 1.2 TEM image of

the amorphous anodic
oxide film formed on
crystalline tantalum (the
white spots represent
individual atoms)
1 Major Degradation Mechanisms 3

the high electrical field, preventing accumulation of critical energy that otherwise
might cause an electric avalanche and the breakdown of the dielectric.
On the other hand, the disordered structure of the amorphous dielectrics increases
the internal energy in the dielectric, making these dielectrics thermodynamically
unstable. Amorphous dielectrics trend to ordering and crystallization spontaneously
to reduce their internal energy. Growth of crystalline inclusions in amorphous
matrix of the anodic oxide film induces mechanical stress in the film due to a differ-
ence between specific volume of the amorphous and crystalline phases. Mechanical
stress associated with field-induced crystallization was detected experimentally
using in situ measurements on anodic oxide film of tantalum deposited on quartz
substrate [27]. Eventually this mechanical stress results in a disruption of the dielec-
tric and, thereby, in the failure of the capacitor. The rate of crystallization process is
a principal factor governing the performance and reliability of tantalum capacitors.
The rate of the crystallization process in anodic oxide films on tantalum depends
on many factors such as purity and morphology of the anode surface, type and tem-
perature of formation electrolyte, conditions of post-formation thermal treatment,
etc. In all cases, the crystallization rate increases with increasing thickness of the
anodic oxide film. The effect of the dielectric thickness on the rate of crystallization
can be explained by contributions to the internal energy of the dielectric by the bulk
of the anodic oxide film and the interface between the anodic oxide film and anode.
An amorphous film doesn’t need misfit dislocations on the interface with the crys-
talline anode in order to adjust its structure to the crystalline lattice of the anode.
Since these misfit dislocations increase internal energy, the amorphous film adjacent
to the crystalline substrate allows lower internal energy than a similar crystalline
film would be. This helps stabilize the amorphous state of the dielectric. On the
other hand, the disordering of atoms in the bulk of the amorphous dielectric increases
internal energy of the dielectric. The balance in internal energy of the dielectric and
therefore the balance between the tendency of the dielectric to remain amorphous or
to crystallize depend on the ratio between the surface and bulk of the dielectric. The
greater is the thickness of the amorphous dielectric, the larger is the contribution of
the bulk to the internal energy that makes thicker amorphous dielectrics more prone
to crystallization.
Despite the inherent thermodynamic instability, tantalum capacitors can be man-
ufactured with exceptional stability and reliability. Such high stability and reliabil-
ity can be achieved because kinetics of the degradation processes, oxygen migration
and crystallization, can be reduced by technological means to such a negligible level
that no degradation takes place during any practical duration of the testing and field
application, even at the highest possible operation temperatures and voltages.
Oxygen migration and crystallization processes also take place in niobium-based
capacitors, causing parametric and catastrophic failures of these capacitors. The
pace of the degradation processes in niobium-based capacitors at given dielectric
thickness, temperature, and applied voltage is significantly higher than that in tanta-
lum capacitors with the same dielectric thickness, temperature, and voltage.
Nevertheless, improvements in the stability and reliability of niobium-based capaci-
tors have been also achieved by the technological means slowing down degradation
processes in these capacitors.
4 1 Major Degradation Mechanisms

1.1 Oxygen Migration

Comprehensive investigation of oxygen migration in tantalum capacitors was con-

ducted during the early stages of manufacturing of solid MnO2 tantalum capacitors
[6–12]. The manufacturing includes multiple pyrolysis of liquid manganese nitrite
impregnating porous tantalum anodes to produce a solid MnO2 cathode. Thermal
treatment associated with this process, typically performed in the range of tempera-
tures 250–350 °C, resulted in an increase in DCL, dissipation factor (DF), and
capacitance, as well as in a large capacitance dependence on bias, frequency, and
temperature. Only at very low temperatures, there were practically no capacitance
dependence on bias and frequency as a result of the thermal treatment.
To explain the effects of the thermal treatment on capacitance behavior of tanta-
lum capacitors, a conductivity profile model was developed based on a gradient of
oxygen vacancies in the oxide dielectric [6–8]. The conductivity profile develops
during the thermal treatment as a result of oxygen migration from the tantalum
oxide to the tantalum, leaving oxygen vacancies in the oxide dielectric. This trans-
formation can be presented as:

Ta + Ta 2 O5 → Ta ( O )x + Ta 2 O5 − x + xVo ,

where Ta(O)x is a solid solution of oxygen in tantalum and x is a concentration of

oxygen in tantalum and concentration of oxygen vacancies Vo in tantalum oxide.
When the oxygen deficiency reaches the oxide-air interface, oxygen begins to
­diffuse through the oxide ultimately producing a gradient of oxygen vacancies each
with two trapped electrons. This oxygen vacancy gradient is associated with a gradi-
ent of conductivity since electrons trapped in the oxygen vacancies can be emitted
under applied voltage, increasing conductivity of the oxide dielectric. The point of
highest oxygen vacancy concentration and associated conductivity is located at the
metal-oxide interface, after which the level of conductivity decreases exponentially
across the dielectric.
The key to the model is a concept of a critical conductivity, defined as the level
of conductivity, which distinguishes conducting from nonconducting oxide. During
the thermal treatment, a portion of the oxide dielectric next to the tantalum interface
acquires a conductivity greater than critical conductivity and can thus be considered
a part of the electrode. This causes the effective dielectric thickness to decrease and
the capacitance to increase. When bias voltage is applied to the dielectric, the elec-
trons trapped in oxygen vacancies are emitted and withdrawn to the Ta electrode.
This reduces conductivity in such a way to move the intersection of the conductivity
profile with the critical conductivity toward the tantalum interface, thereby increas-
ing the effective dielectric thickness and reducing the capacitance. A similar effect
takes place when temperature is decreasing. In this case, the conductivity profile
shifts to lower magnitudes while simultaneously shifting its intersection with the
critical conductivity toward the tantalum surface. Consequently, the change in
capacitance arises not only from a small change in the dielectric constant with tem-
perature but also from the increase in the effective thickness of the dielectric.
1.1 Oxygen Migration 5

Reformation of the dielectric at the same voltage and temperature as the initial
formation eliminates oxygen vacancies in the oxide dielectric and reduces capaci-
tance dependence on bias, temperature, and frequency to these before the thermal
treatment. The magnitude of the capacitance after the reformation is equal to or
slightly higher than initial capacitance before the thermal treatment. The “extra”
capacitance depends on the temperature and duration of the thermal treatment and
was attributed to a change in the dielectric constant of the oxide dielectric due to the
structural transformations such as low-scale ordering, which takes place during the
thermal treatment [9, 28, 29].
Kinetics of oxygen migration in tantalum capacitors strongly depend on the pres-
ence of dopants in the oxide dielectric. It is well known that the material from the
formation electrolyte is incorporated into the outer portion of the oxide film during
the anodizing process [30, 31]. Both tantalum and oxygen move across the oxide
film during anodizing to form a duplex film that has a material of the electrolyte
incorporated in the outer layer at a concentration that increases proportional to the
concentration of the electrolyte. During thermal treatment typically performed on
tantalum anodes after the initial formation, a dopant can redistribute within the tan-
talum oxide making it more homogenous [7]. When the formation solution is phos-
phoric acid, the incorporated phosphorus has a profound effect on the capacitor
properties, including capacitance behavior as a result of the thermal treatment [32–
34]. Particularly, a much smaller capacitance dependence on temperature was
detected in the case of thermal treatment of a tantalum foil anodized in concentrated
phosphoric acid in comparison with the formation in dilute phosphoric acid or other
electrolyte solutions like H2SO4. This evidences about a slower pace of oxygen
migration in doped with phosphorus tantalum oxide.
A slower pace of oxygen migration was also detected in anodized tantalum
enriched with nitrogen [35–38]. Anodic oxide films produced on this tantalum have
a nitrogen-doped layer at the metal side of the film. Thermal treatment in air at
350 °C for 1 h resulted in significantly smaller capacitance increase in anodized
tantalum with greater than 10 atomic percent of nitrogen in comparison with anod-
ized tantalum without nitrogen doping. It was proposed that the presence of intersti-
tial nitrogen in crystalline lattice of tantalum greatly retards the extraction of oxygen
from the anodic oxide film, and this reduces the concentration of oxygen vacancies
and, thereby, conductivity of the oxide dielectric. When conductive tantalum nitride,
TaN, was used as anode material for tantalum capacitors, no degradation of the
anodic oxide film occurred as a result of the heat treatment at 350 °C for 1 h [39,
40]. This was indicated by no change in the capacitance and no capacitance depen-
dence on the bias, temperature, and frequency as a result of the heat treatment.
Increase in oxygen content in tantalum anodes also reduces the pace of oxygen
migration from the tantalum oxide dielectric to the tantalum anode. Oxygen content
in tantalum anodes increases during the thermal treatment after the initial formation
of the oxide dielectric. Reformation following the thermal treatment restores oxy-
gen content in the dielectric; however, it doesn’t affect oxygen distribution in tanta-
lum anodes since the formation and reformation temperatures are much lower than
the thermal treatment temperature. Thermal treatment of the formed tantalum
anodes is usually performed in air; however, the treatment can also be performed in
6 1 Major Degradation Mechanisms

a vacuum or an inert atmosphere to prevent ignition when the anodes are made with
fine high CV tantalum powder and have thin oxide dielectric. When there is no oxy-
gen in an ambient atmosphere to replace oxygen which migrated from the oxide
dielectric to the tantalum anode, a high concentration of oxygen vacancies develops
across the oxide dielectric, and a large portion of the dielectric becomes conductive
[3, 28, 42, 44].
Oxygen content in the bulk of tantalum anodes increases spontaneously during
the sintering of tantalum powders due to dissolving of oxygen from the native oxide
on the surface of tantalum particles prior to their sintering. This occurs at sintering
temperatures equal to or below 1870 °C, which are typically used for middle and
high CV tantalum powders [24]. Above 1870 °C, oxygen evaporates from tantalum
to vacuum chamber during the powder sintering; however, only very coarse tanta-
lum powders can be sintered at such high temperatures without a significant loss in
surface area. Despite the fact that increased oxygen content in the bulk of tantalum
anodes slows down further oxygen migration from the oxide dielectric, it can also
activate the crystallization processes in the amorphous matrix of the dielectric. The
effect of the bulk oxygen in tantalum anodes on the crystallization processes in
anodic oxide films of tantalum formed on the surface of these anodes will be dis-
cussed in the following chapter of the book.
Experiments on anodized niobium foil revealed that the Nb-Nb2O5 bilayer is
significantly more sensitive to thermal treatment than the Ta-Ta2O5 bilayer [9]. The
effects of thermal treatment on capacitance and capacitance dependence on bias,
temperature, and frequency observed in Ta-Ta2O5 system after heating in the 300–
400 °C range occur in Nb-Nb2O5 system after heating only in the 200–300 °C range.
Stronger effects of thermal treatment on anodized niobium were attributed to a
greater thermodynamic instability of the Nb-Nb2O5 bilayer relative to the Ta-Ta2O5
bilayer and also to the existence of the two lower niobium oxide phases: NbO2 with
semiconductor-type conductivity and NbO with metallic-type conductivity (Fig.
1.3).
A comparison of the degradation mechanisms in solid tantalum and solid nio-
bium capacitors with MnO2 cathodes was presented in [19, 20]. During thermal
treatment of these capacitors, two redox reactions take place: one at the Me-Me2O5
interface (Me: Ta or Nb) where Me anode extracts oxygen from Me2O5 dielectric
and the other at the MnO2-Me2O5 interface where MnO2 cathode compensates oxy-
gen in the depleted Me2O5 dielectric when oxygen vacancies reach this interface.
These two redox reactions correspond to each other by the conduction of oxygen
ions through the Me2O5 dielectric. Thus, under heating tantalum and niobium
capacitors with MnO2 cathodes display the properties of the galvanic cell generating
electric current in the external circuit. The short circuit current (Isc) generated by
these capacitors at high temperatures is equal to the current of oxygen ions through
the Me2O5 dielectric. Figure 1.4 presents Isc dependence on inverse temperature in
solid MnO2 tantalum and niobium capacitors [20].
As one can see in Fig. 1.4, the Isc and, thereby, the current of oxygen ions are high
in the Nb2O5 dielectric of the niobium capacitors at relatively low temperatures
1.1 Oxygen Migration 7

Fig. 1.3 Niobium-oxygen equilibrium diagram [24]

when the current of oxygen ions in the Ta2O5 dielectric of the tantalum capacitors is
still negligibly low. Higher current of oxygen ions in the Nb2O5 dielectric in nio-
bium capacitors in comparison with the current of oxygen ions in the Ta2O5 dielec-
tric in tantalum capacitors corresponds to lower activation energy (Ea) of oxygen
migration in these capacitors. These activation energies, calculated from Isc(T) data
using Arrhenius equation, were Ea = 1.64 eV for Nb/MnO2 capacitors and
Ea = 1.82 eV for Ta/MnO2 capacitors (Fig. 1.4).
A significant oxygen migration in niobium capacitors occurs in the temperature
range typically used in manufacturing of these capacitors for pyrolysis of manga-
nese nitrite to form MnO2 cathode. At these conditions, the MnO2 cathode becomes
exhausted with active oxygen and loses the ability to compensate oxygen vacancies
in the Nb2O5 dielectric, resulting in an increased DC leakage and DC leakage insta-
bility during testing and field application. Furthermore, at equal temperatures and
dielectric thicknesses, the pace of the crystallization process in the amorphous
matrix of the dielectric is also higher in the Nb2O5 dielectric in niobium capacitors
compared to the Ta2O5 dielectric in tantalum capacitors.
8 1 Major Degradation Mechanisms

Fig. 1.4 Short circuit current Isc dependence on inverse temperature in solid MnO2 tantalum and
niobium capacitors

1.2 Field Crystallization

The crystallization of the amorphous dielectric in tantalum capacitors can occur

during the formation of the anodic oxide film on the surface of tantalum anode (field
crystallization) and as a result of post-formation thermal treatment (thermal crystal-
lization). D. Vermilyea investigated crystallization process during formation of
anodic oxide film on tantalum foils and sputtered tantalum films [27, 28]. He showed
that crystallization occurs at nucleation sites on the metal-oxide interface. These
sites were attributed to the inclusion of a high impurity content in the metal. Due to
the uniform impurity distribution during tantalum sputtering, the crystallization rate
was much lower with sputtered tantalum films than that with tantalum foil. Vermilyea
detected an incubation period for the appearance of crystalline areas in the anodic
oxide film. This incubation period was associated with the time required for a crys-
tal growing underneath the amorphous matrix to reach a critical size when a disrup-
tion of the matrix occurs due to the critical mechanical stress. That provided a direct
access of the electrolyte to the tantalum surface, speeding up the crystal growth.
N. Jackson investigated the effect of formation conditions on the crystallization
rate in anodic oxide films on tantalum [45]. He showed that the critical parameters
controlling crystal growth are the type and temperature of the formation electrolyte.
The most dramatic effect in suppressing the crystallization process was achieved
with phosphoric acid. The effect of formation electrolyte, particularly the incorpora-
tion of phosphorus into the anodic oxide film during its formation in phosphoric acid,
was also shown in [17, 46, 47]. B. Melody, T. Kinard, and P. Lessner demonstrated
non-thickness limited anodizing under special formation conditions when anodic
oxide films may be grown to practically any thickness at a constant formation voltage
[48]. Obviously, these special formation conditions might provide suppression of the
crystallization to grow thick anodic oxide films with amorphous structure.
Carbon and transition metals like iron, nickel, and chromium are among the
impurities having the strongest effect on the density of nucleation sites for the crys-
1.2 Field Crystallization 9

Fig. 1.5 Craters in anodic

oxide film enriched with
carbon tantalum anode

tallization [45, 49]. These impurities can come to the tantalum and niobium anodes
from the metal powders or from materials and tooling used for powder pressing and
sintering (organic binder, metallic dies, etc.). High carbon content may result in
precipitation of tantalum and niobium carbides in anodes during powder sintering.
The precipitates of carbide phase work as nuclei for the crystallization and also
result in local thinning of the anodic oxide film [28]. The latter is due to poor anod-
izing of the carbide phase having strong bonds between tantalum and carbon atoms.
A strong electrical field in the thinning defects can cause breakdown of the dielec-
tric even at low applied voltage. As an example, Fig. 1.5 shows craters in anodic
oxide film enriched with carbon tantalum anode [50].
Oxygen in tantalum and niobium also plays an important role in crystallization
of the anodic oxide films on these metals. M. Tierman and R. Millard detected criti-
cal oxygen content in tantalum anodes that resulted in a sharp increase in direct
current leakage (DCL) in a liquid cell (wet test) [51]. This critical oxygen content
was attributed to the saturation of tantalum with oxygen when small oxide crystals
precipitate in tantalum anode and speed up the crystallization process. The major
contributor to the oxygen content in high CV anodes was a natural surface oxide
that dissolved in powder particles during the powder sintering in vacuum.
Critical oxygen content in tantalum anodes associated with the sharp DCL
increase in tantalum capacitors was investigated by X-ray diffraction analysis
(XRD) [52]. Tantalum atoms form cubic crystalline lattice, while oxygen dissolving
in tantalum as interstitial impurity occupies the center of the cube. Increasing oxy-
gen content in tantalum causes expansion of the cubic structure and thereby
increases in the period of the crystalline lattice of tantalum. This change in the
period of the crystalline lattice can be identified by the XRD analysis by the shift in
position of the peaks on the diffraction pattern. As an example, Fig. 1.6 shows (211)
diffraction peak for three oxygen contents in tantalum anodes with specific charge
50,000 μC/g and effective primary particle radius r = 2.1 μm.
According to Fig. 1.6, (211) diffraction peak is shifting left to the smaller diffrac-
tion angles and broadening with increase of oxygen content in tantalum anode. This
shift in position and shape of the diffraction peak indicates increase in the lattice
10 1 Major Degradation Mechanisms

Fig. 1.6 Tantalum (211) diffraction peak obtained for anodes with effective particle radius
r = 2.1 μm and oxygen content (…..) 3000 ppm, (----) 3400 ppm, and (___) 3600 ppm

100 0.3320
Direct current (A/FV×10 )
−4

Lattice parameter (nm)

0.3315

10
0.3310

0.3305
1
0.3300

Coc
0.1 0.3295
2 3 4 5
Oxygen content (p.p.m×104)

Fig. 1.7 Dependences of the DCL at 50 V formation and lattice parameter versus oxygen content
in the tantalum anodes with effective particle radius of 2.1 μm

parameter at higher oxygen contents in tantalum. Lattice parameter reaches its

­maximum value at the critical oxygen content Coc when DCL increases sharply,
while further increase in oxygen content does not affect the lattice parameter
(Fig. 1.7).
Flattening lattice parameter with increase of oxygen content above Coc indicates
that solid solution of oxygen in tantalum reached solubility limit. Further increase
1.2 Field Crystallization 11

Fig. 1.8 Cracks from a

crystal growing in anodic
oxide film on tantalum
anode with critical oxygen
content

of oxygen in tantalum causes formation of an oxide of tantalum with different crys-

talline lattices and much higher oxygen content than solubility limit of oxygen in
tantalum.
During tantalum powder sintering in vacuum, oxygen from the native oxide can
either evaporate into the vacuum chamber or dissolve into the bulk of the tantalum
particles. Oxygen evaporates from tantalum at temperatures equal to or above
1880 °C [24, 25] used for sintering of the coarsest tantalum powders with CV/g
equal to or below 5000 μC/g. At lower sintering temperatures used for sintering of
the higher CV/g tantalum powders, oxygen from the native oxide dissolves into the
tantalum particles, increasing the bulk oxygen content in sintered tantalum anodes.
When the specific charge CV/g of the tantalum powder increases due to decrease in
effective particle radius, the ratio between the particle surface and volume becomes
larger. This increase of the surface-to-volume ratio results in the larger contribution
of oxygen in native surface oxide to the total oxygen content in the tantalum powder
and tantalum anodes sintered with this powder. At the same time, lattice parameter
of tantalum at critical oxygen content remains practically unchanged with increase
of the CV/g of the tantalum powder. This evidences that the major reason of the
sharp DCL increase at critical oxygen content is saturation of oxygen content in
solid solution of oxygen in tantalum and precipitation of crystalline oxide phase in
the bulk of tantalum particles. The XRD analysis allows to distinguish between the
total oxygen content in sintered anodes and the bulk oxygen content in the powder
particles, which is primarily responsible for the sharp DCL increase at critical oxy-
gen content.
Characteristic cracks from growing crystals can be easily detected on the surface
of anodic oxide film on tantalum anodes with critical content (Fig. 1.8) [50].
At the same time, the small precipitates of the crystalline oxide particles appear
in the anodic oxide film even when oxygen content in the anode is much below the
critical content [50]. In this case, the surface of the anodic oxide film is typically
smooth with some scattered bumps and pits reflecting morphology of the underly-
ing tantalum substrate (Fig. 1.9a). After removal of the amorphous film by etching
12 1 Major Degradation Mechanisms

Fig. 1.9 Top (a) and bottom (b) of the anodic oxide film on tantalum with 50% of oxygen vs.
saturation

Fig. 1.10 Crystallization appearing in the anodic Ta2O5 film grown on tantalum with 3 nm (left)
and 30 nm (right) surface oxide

it down to the metal substrate in diluted hydrofluoric acid, one can see peaks of dif-
ferent sizes on the metal surface (Fig. 1.9b).
Electron diffraction analysis confirmed that these peaks are Ta2O5 crystals stand-
ing on the tantalum surface and hidden in the amorphous matrix before etching. The
density and size of these crystalline inclusions on the oxide-metal interface become
larger with increasing of oxygen content in the base metal.
The oxide film, which always exists on the surface of tantalum and niobium
anodes prior to anodizing, can also contribute to the growth of crystalline inclusions
in amorphous matrix of the anodic oxide film [50]. The native surface oxide has
amorphous structure and is only 2–3 nm thick [53]. This native oxide incorporates
into the anodic oxide film during its formation and practically does not influence the
crystallization process. In some cases, low-density initial crystalline inclusions on
tantalum surface with thin native oxide can grow through the whole thickness of the
anodic oxide film without causing mechanical damage. Figure 1.10a shows a crystal
that appears on the surface of the anodic oxide and remains tightly incorporated into
the amorphous matrix. When surface oxide is relatively thick, which is typically due
1.2 Field Crystallization 13

Fig. 1.11 TEM image of

the thermal oxide film on
tantalum and electron
diffraction pattern of the
crystalline inclusions in the
thermal oxide

to the heat release during exothermic passivation process when anodes are exposed
to air after their sintering in vacuum, crystal growth always results in cracking and
disruption of the anodic oxide film (Fig. 1.10b).
The higher the temperature the anodes were exposed in air prior to anodizing, the
thicker is the thermal oxide and the quicker crystallization and disruption of the
anodic oxide film appear. The reason for such intense crystallization of the anodic
oxide film formed on the relatively thick thermal oxide layer is that the thermal
oxide contains small particles of the crystalline phase scattered in the amorphous
matrix (Fig. 1.11) [50]. These microcrystals serve as numerous centers for crystal-
lization of the anodic oxide film. The thicker the thermal oxide is, the greater is the
portion of the crystalline phase. During anodizing, the thermal oxide incorporates
into the growing anodic oxide film forcing up its crystallization.
At given temperature and time, the thickness of the thermal oxide that forms on
the surface of tantalum during annealing in air increases with increasing the bulk
oxygen content in tantalum [50]. This effect was demonstrated by measuring the
oxygen depth profiles annealed in air tantalum foils with different oxygen contents.
Similarly, the thickness of the thermal oxide that forms on the surface of the porous
tantalum anodes when they are exposed to air after sintering in vacuum increases
with increasing the bulk oxygen content in the tantalum particles. As an example,
Fig. 1.12 shows second ion mass spectrometry (SIMS) oxygen depth profiles for the
surface of tantalum anodes sintered with 12,000 μC/g tantalum powder and having
different bulk oxygen content after the sintering.
As one can see in Fig. 1.12, the thermal oxide is thicker on tantalum anodes with
higher bulk oxygen content after sintering, which is indicated by higher and broader
SIMS peak of the surface oxide. The formation of the thick thermal oxide layer was
caused by oxygen’s inability to penetrate the saturated tantalum bulk upon reaching
the tantalum surface. The oxygen stayed on the tantalum surface forming the thick
thermal oxide layer. The characteristic morphology of the thick thermal oxide was
detected by scanning electron microscopy (SEM) on the surface of the tantalum
14 1 Major Degradation Mechanisms

Fig. 1.12 SIMS oxygen

depth profiles on the
sintered tantalum anodes
with 12,000 μC/g tantalum
powder with different bulk
oxygen contents

Fig. 1.13 SEM images of the surface of the sintered tantalum anodes with 12,000 μC/g tantalum
powder with high (a) and low (b) bulk oxygen content

anodes with high bulk oxygen content, while no similar features were detected on
the surface of the tantalum anodes with low bulk oxygen content (Fig. 1.13).
Results presented in Figs. 1.12 and 1.13 indicate importance of the procedures
used for deoxidizing the tantalum anodes and controlled passivation when the
anodes are exposed to air after sintering in vacuum. These processes allow to avoid
forming thick thermal oxide on the anode surface and, thereby, suppress field crys-
tallization of the anodic oxide film on tantalum anodes.
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