Reliability of High-Voltage Tantalum Polymer Capacitors

Erik Reed, George Haddox

KEMET Electronics Corporation, 2835 KEMET Way, Simpsonville, SC 29681

ph6ns ; -6300, Fax : + I -864-228-4081
+ I -86 4-9 63
e-mail: erikreed@kemet.com

Abstract

Tantalum polymer capacitors provide lower ESR and frequently better reliability than conventional Mn02-
based tantatum .upucitors. Their lorvel ESR f'acilitates signiticant penett'ation into challenging low-voltage
applications such as CPU decoupling in laptop computers. Success in low-voltage applications was
tbrtunate because at first it proved dilllcult to fabricate leliable devices with ratings above roughly l6V-
Now, new tantalum polymer capacitors exist with ratings of 25y,35y, and higher that have reliability on
par with their lower-voltage siblings.

About seven years ago, time-to-failure data were presented at CARTS that demonstrated the good
reliability of 6V tantalum polymer capacitors of aggressive design. Also presented were models for voltage
and temperature acceleration that allow customers to estimate lit'etime at application conditions based on
Ii fetests performed at accelerated conditi ons'

The present work pertains to higher-voltage tantalum polymer capacitors with 25-50V ratings' A brief
desciiption of the iechnology that allows higher voltage opel'ation is provided. Time-to-failure data are
presented that were collected over a wide lange of voltages and temperatures. Trends in the data are
identifled and models fbr voltage and temperature acceleration are presented. Finally, typical lil'etimes at
rated conditions are estimated and are compared with the results originally presented for the 6V capacitors'

Introduction

The ilrst solid tantalum capacitors were manuf-actured using manganese dioxide (MnO:) as the cathode
layer. MnO2 decomposition at elevated temperatures provided a "self-healing" mechanism that allorvs
successful manut-acture of high-reliability capacitors even though the tantalum pentoxide (Ta2O5) dielectric
itself is impert'ect. The nature of the self healing is that localized heating at defect sites from concentrated
leakage cuirent renders the adjacent MnO2 only slightly conducting, eflbctively isolating the det-ective spot
in the dielectric from the rest ofthe capacitor.

MnOz-based solid tantalum capacitors have been unquestionably successtul, but they are not perfect' One
of their weaknesses results from the limited electrical conductivity of the MnO2 cathode material which
causes elevated equivalent series resistance (ESR) in the flnished capacitor.

Many applications, such as decoupling lorv-voltage microprocessors, require capacitors with very low
ESR]. The demand fbr lower ESR contributed to the development of higher conductivity cathode
materials, including conducting polymers. Tantalum capacitors made with conducting polymer have ESR
that is typically lower by a factor of 2 to 3 than similar capacitors made with Mnoz.

But with introduction of a new cathode material came questions regarding reliability. In response, a study
u,as perfbrmed to quantity the reliability of lou.voltage tantalum polymer capacitors of very aggressive
design made with poly(3,4-ethylenedioxythiophene) (PEDOT) polymer oxidized with iron (lll) toluene
sulf'onate. This process produces PEDOT doped rvith toluene sulfbnate and residual traces of iron.
Accelerated time-to-failure lifetests rvere performed on large samples of these capacitors at various
voltages and temperatures and the-resulting datawere analyzed to detetmine acceleration factors related to
changing r,oltage and temperature2.

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 These acceleration factors were fit to a pre-existing empirical model to predict median lifespan at any
temperature and voltage of interest, and it was found that the median life of these 6V tantalum polymer
capacitors might be as long as 1000 years at 85oC and rated voltage -- an entirely satisfactory result.
Subsequent work focused on fitting the original-data to a physics-based model and demonstrating similar
satisfactory performance of4V and 2.5V devicesr.

But, as always, there was a fly in the ointment. It proved reasonably straightforward to extend the initial
success to l0V devices, but it was somewhat harder to make reliable 16V devices. Reliable 25V devices
remained an elusive goal for many years and much effort rvas applied to understanding the limitations of
the technology.

A significant breakthrough occurred rvith the arrival of pre-polymerized PEDOT conductive polymer
dispersions doped with polystyrene sulfonate that can be used fbr some or all of the cathode layer in
tantalum capacitorsa. This new technology makes it possible to manuf'acture reliable tantalum capacitors
having much higher rated voltage.

Once again the problem is to prove that the devices are reliable, a problem that is the motivation fbr the
ra'ork presented here. The strategy employed here is essentially the same as was previously employed.
Large samples of capacitors are lifetested at many temperatures and voltages, and time-to-failure (TTF)
data are collected using an apparatus similar to that described previously. The TTF data are tlt to the same
empirical model previously used and median lit'etimes are extrapolated at 85"C and rated voltage.

But the data collected liom these capacitors difl'er in interesting ways flom the data previously presented.
Specifically, the distributions of failures in time display greater structure and complexity when compared
with the data reported for the low-voltage tantalum polymer capacitors. The shapes of the TTF plots
suggest the presence of more than one contributing degradation mechanism. These mechanisms ar.e
variously aflected by changing voltage and temperature, with individual mechanisms being dominant at
various voltages, temperatures, and times.

Representative data sets from 25V,35V, and 50V devices are presented to convey the general nature ofthe
collected data. Some educated guesses are made regarding what is going on inside ttre capacitors as they
fail at various voltages, temperatures, and times, and some conclusions are drawn regarding the overall
reliability one might expect from this new family of tantalum polymer capacitors.

Test Samples and Test Conditions

It was desired to explore a reasonably wide range of voltage ratings in this rvork. However, at the time the
experimental plan was conceived, there were very t'ew fixed designs in regular ploduction and there was
not always a "standard" design to copy tbr a given capacitance and rated voltage. For these reasons and the
desire to limit unnecessaty experimental variables, the test samples were created according to a simple
plan: (l) start with a single tantalum anode design, (2) create dielectric with 3 thickness.s .oughly
consistent with finished part ratings of 25V, 35V, and 50V, and (3) perform a single polymerization process
on all the anodes.

An obvious advantage ofthis strategy is that the number ofvariables to track is reduced to essentially one:
dielectric thickness. But a disadvantage is that these designs probably rvill not precisely match flnal
production designs which will likely employ tantalum powders of diff'erent surf'ace area per gram, slightly
diff'erent formation-to-rated voltage ratios, and small process variations intended to enhance perfbrmance in
specific designs. That is, the results of these tests may not precisely match the pertbrmance of the flnal
commercial product, but should be very similar.

The final experimental design for the investigation involved formation voltages of 70V, 100V, and l30V at
80"C for the capacitors called 25V, 35V, and 50V devices, respectively. The resulting capacitance values
were roughly 22uF, l5uF, and l0uF.

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The tbrmation-to-rated voltage ratio is not constant, but the values are genetally close to 2.8 to 1, with the
"50V" devices lagging behind at 2.6 to 1. l'o be consistent rvith the usual practice of using a higher
formation-to-rated ratio for higher lated voltage devices, the 50V parts should have been formed at 150V.
But this choice would be inconsistent with using the same anode design for each rated voltage since the
chosen tantalum porvder particle size limits the maximum allowed formation voltage. Nevertheless, the
final designs provide valuable information on the general impact of rated voltage on lifetest performance.

100 capacitors were tested at each set oftest conditions (rated voltage, test voltage. and test temperature)
and the resulting times-to-failure rvere detected and recorded rvith a computer-driven monitoring system.
Failure is defined as blowing a I ampere fuse. The test temperatures rvere limited to 85oC, 105"C, and
125"C. As much as possible, the same test voltages u'ere employed at each temperature tbr capacitors of
given rated voltage to facilitate direct observation ofacceleration due to temperature.

The range of test voltages u,as detelmined expelimentally to discover test conditions that would generate
some tailures in a reasonable time (rvithin a t'ew hours) while not taking an impractical time to approach
100% iailures (genetally not more than 3000 hours). It was not always possible to meet both objectives
simultaneously, and the test voltages that were finally chosen rypically fell into a fairly narrow range and
u,ere substantially higher than rated voltage (e.g., 1.8V, to 2.2Y, Ibr the "35V" samples). When test
voltages much lou,er than the bottom end of the chosen voltage range were attempted, there simply were no
tailures during the maximum allowed test period of 3000 hours, a fact that speaks well of the robustness of
these capacitors.

A practical comment is in order here. Weibull grading of high-reliability MnOz military capacitors per
MIL-PRF-55365 depends on generation of at least one failure within the first2.25 hours of testing at 85"C
using test voltages that cannot exceed 1.5 times rated voltage. Weibull grading as defined above would
not be practical for the 35V tantalum polymer samples because none of the capacitors would fail in the first
2.25 hours of testing at 1.5V, (an occasional early tailure is finally obset'ved when the test voltage is raised
to I .7V, which represents 60% of the tbrmation voltage - a very high voltage for a tantalum capacitor).

Typical Time-to-Failure Test Data

and tully discuss all of the collected data because of their volume.
It is impractical in this paper to present
Instead, l'epresentative samples of the data are presented and the larger trends are identified. The primary
focus is on the 35V samples, but the raw data for the 50V and25Y capacitors are subsequently introduced
and brielly discussed.
,l05"C
Figure 1 contains time-to-f'ailure (TTF) data collected at and test voltages ranging from 1.8V, to
2.2Y,for the samples fbrmed at l00V and called 35V rated samples. There are several distinct patterns that
can be identiiled in the resulting TTF distribution curves .

First, there are some initial faitures at the start of the test and the number of these initial failures increases
as the test voltage increases. The number of initial t-ailures is close to zero tbr test voltages less than l.SVr
(0.63V1). Second, l-ailures occur relatively gradually after the initial failures lbr a time period that depends
on the test voltage, with longer times at lower test voltages. Third, the capacitors start to wear out and
many tailures occur in a relatively short period of time. Finally, fbr the voltages where the onset of wear-
out takes a long time, eventually the capacitors stop wearing out and the TTF curve becomes more
horizontal again. These regions of the TTF culves are identitied in Figure l.

Some observations regarding these characteristics are in order. First, the concentration of failures at
roughly 0.02 hours occurs for a specific reason. The power supply voltage is ramped from 0V to the test
voltage in 60 seconds, and the iirst lailures do not occur until the voltage gets very close to the test voltage.
This tends to concentrate the initial failures into a tight distribution.

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 If the test voltage couldbe applied instantly, the power supply could provide enough current to blow many
I ampere fuses simultaneously, and the monitoring system could collect the failure information rapidly
enough, it is likely that the horizontal portion of the TTF curves would extend to shorter times u,'ithout
significant overlap of the curves. But to accommodate the timits of the power supply and the rest of the test
apparatus, a 60 second voltage ramp time was employed and it produced the best overall results.

99.99olo
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8 tov"
& 5oo/o

E 300/o

zi
zovo
1oo/o
5o/o

1o/o

0.1o/o
35V (Vf=100V) Capacitors Tested at 105C
0.01%
0.001 0.01 0.1 110 100 1000 10000

Time(hours) EKR, 01/31/2011

Figure l. Lognormal Plot of Failure Percentile versus Time-to-Failure at 1.8V,., l.gf,, 2.0V,., and 2.1V,
for Tests Performed at I05"C on l5uF, 35v Experimental rantalum Polymer capacitors.

The initial failures and flat part of each TTF distribution comprise a smaller percentage of the failures as
the test voltage is substantially reduced (they are <l 5o/o at I .8Vr). If the applied voltage had been rated
voltage or lower, it is easy to project from the trend of the curves that this percentage approaches zero.
Consequently, while interesting to observe and comment on, these regions of the failure distribution likety
provide no practical information regarding reliability at or below rated voltage. For this reason they u,ill be
ignored during estimation of voltage and temperature acceleration factors in subsequently lifetime
calculations, but they will receive mention'u,hen the potential underlying mechanisms are discussed.

Conversely, the near-vertical wear-out portion ofthe TTF distribution applies to an increasing percentage
ofthe capacitors as the test voltage approaches rated voltage (it is -68% at L8Vr). Consequently, this part
ofthe failure distribution is ofhigh interest as acceleration models are developed.

Finally, the portion of the TTF distribution that indicates cessation of wear out at long test times also
applies to a larger percentage ofthe capacitors as the test voltage is falls (-20% at l.8Vr). This region of
the failure distribution might influence lifetime calculations if under certain circumstances no parts could
fail because this mechanism became dominant before the onset of wear-out.

Voltage Acceleration Model

Itis clear that the data of Figure I suggest that the wear-out regions of the TTF cun/es generated at I 05"C
are sensitive to the test voltage. That is, wear-out occurs at shorter test times as the applied voltage
increases. Moreover, the relatively uniform spacing of the TTF culves - perhaps excluding the curve
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 as a power function.of voltage'
generated at 2.lV -- suggests that wear-out can be etTectively modeled
behavior to voltages lower than the test
Such a model should allo.-w reasonable extrapolation of wear-out
(Of course all extr.apolations are inherently risky, and other factors that could come into play at
""f,"g...
lower"test voltages must be considered rvhen evaluating the resulting
predictions')

the form of a power law:

For the pul.poses of this paper, the acceleration model is chosen to take
/ \ll
where Av is the voltage acceleration iactor and q is an empirically-derived exponent'
t, =(yr\,
A =t,
" \V,)
each TTF distribution on
The value of is determined by plotting the t50 times (or projected t50 times) of
11
a log-log plot of t50 versus voltage and determining the slope
of the resulting culve'

Furlher, t50 times lbr iiom the known data if a line having
lorver. applied voltages can be extrapolated
to loweruoltuges on the atblementioned plot. An illustration ol the
strategy tbr
slope:q is extended
ratio exponent and extrapolate to
processing the wear-out portion ofth-e data ofFigure 1, to find the voltage
where to place the parallel lines in
lower voltages, appears in Figures 2 and3. Note that when choosing
TTF distribution that most accurately represents only
Figure 2, an effort was made 6 nna ,n. portion of the
thJwear-out mechanism and avoids influence from other mechanisms'

99.990/o '

99.9olo

99%

9 5o/o
o 90o/o
80%
C)
(.) 70o/o
0)
0- 50%
E 300/o
E
20o/o
z 10%
5%

1o/o

0.1o/o

0.01o/o
0.001 0.01 0.1 1 10 100 1 000 1 0000

Time(hours) EKR,01/31/2011

Figure 2. Estimates oJ t511 Times of rhe wear-out.Phases of Timelo-Failure

Plots for 35V Experimental
Capacitors Testid at I05"C and Voltages l
from '8 to 2' lVr'
Tinralum Polymer

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Multiple of Rated Voltage EKR, 31Jan201 1

Figure 3. t5nTimes versus Test Voltage, Calculation of Voltage Ratio Exponent rl,
and Extt.apolation to
l,ower Test Voltagesfor 35V Experimental Tantalum i'olymei Capacitors
Testecl at 105"C and L,oltages
from 1.8 to 2.lVr.

This- graphical method provides an estimate of q=I8.5 fbr the voltage ratio exponent for the voltage
acceleration model. For comparison, the work done on 6V tantal-um polymer capacitors produced
estimates of q=14.5 al 125oC, 11=16.5 at l05oC, and 11=19.0 at 85oC. While not identical,
the q estimates
for the 35V samples appear to be in the right neighborhood in spite of the limitations of
the raw TTF data.

observe that the data point atZ.lYr does not fit the line in Figure 3. 2.lVr is abootT4yoof
the formation
voltage. Such a high test voltage has been observed in the past to stimulate at Ieast one additional
faiture
mechanism. In this case it is thought that the reduced t50 life time at 2. I Vr results from
the presence of a
second degradation mechanism and this data point was excluded from the estimation
of for this reason. 4
It is clear that the estimate of voltage acceleration created by the nrethod of Figures 2 and 3 is only
apploximate and is subject to some en'or. However, since it is impossible to execute the
lif'etests at low
enough voltage to discover something closer to the truth (at least in this investigator,s
lifetime), the method
described provides a useful means to make reasonable predictions in spite of the inherent
limitations.

TTFdatawerealsocollectedat85oCand l25"Ctbrthe35Vcapacitorsandatall threetemperaturesfbrthe

50V and 25V capacitors. The combined data appear in Figures 4, 5. and 6 for the 35V, 50V,
ana ziv
capacitors, respectively' While diflicult to soft out at tlrst, the combined plots make possible
it to discern
how the influence of the active regions of the failure distributions
linitiat taitures, t'lai region, wear-out
region, and anti-wear-out region) varies with voltage and temperature.

The reader is asked to fbrgive the strange order ofpresentation ofthe data tbr the various
rated voltages.
The chosen order -- 35V, 50V, and then 25V
- is thought to aid the description of the data. That is, the
35V samples behave in the most orderly and easill, described manner, followed by the 50V
,urpl..a dutu
that behave a little oddly at the lower voltages at 85oC, and finally the 25V samples, data
that might be hard
to understand at alI without seeing the 35V and 50V samples, daia first.

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99.9%

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95To
o) 90o/o
80%
0)
O 7lYo
0)
o- 50%o
G 30o/o
E
o 20%
z 10To
5Yo

1Yo

0.01o/o
0.001 0.0'l 0.1 1 10 1 00 1 000 1 0000

Time(hours) EKR, 01/30/2011

Figure l. Lognormal Plot of Failure PercentileversusTime-to-Failure at 1.8V,, 1.9V,,2.0V,, and2'lV,fot

fi,. f rrlaried at 85"C, 105"C, and 125"C on l5uF, j5V Experimental Tantalum Polymer Capacitors'

99 99%
99.9%

99o/o

95o/o
90%
80o/o
0) 70%
o
0)
& 5Oo/o
E 30Yo
E
o 20Yo
z 10%
5%

1%

0.|Yo
I 5OV 1Vt=130V) Cqpa.itors Iest"O at
o,o1%
0 001 001 01 1 10 100 1000 10000

Time(hours) EKR,01/30/2011

Lognormal Plot of Failure Percentile versus Time-to-Failure at l'1V,, l'5V,, l'6V",

1 7V,'' and
Figure 5.
l.EV,7or Teis PerJormerl it 85"C, 105"C, ancl 125"C on 10uF, 50V Experimental Tantalum Polymer
Capacitors.

more pronounced as
Observe in Figure 4 that the wear-out portion of the TTF distributions becomes
to but becomes muted as temperature talls to 85oC. Also observe that
temperature rises tiom 105"C 125"C,

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i" the next section
f''-1tiili:i"ff;1iffiil"*ila
rn contrast to the crear
temperarure sensitivitY"orth.e,il:i;H;,"liffi +if:[l[ffi],'l]
but harrorthe ttme
1-,]'i':,ll
iil;i,;;iJ;'rv tinte,tempeffi'ilLXHx;';?,lT"5ilfifi';i;; rower temperatures'
aoDears that fewer Parts
i"ri lo5oc than at 85oC'
"ii* ",
i:'"'-"J;t:i:?
in Figures
After observing simiar.patternsflat regions' 1'11u.,
but nt :i.'.:"J;,',:l;'ii'lJiil'fl?f;lt':'?tT
;,."-;';; l; made to describe the
il"i;*;; at-125"c in the
il;',-*. d"o**:t*.:"ff::fflJir;',','.',:'ffi,5:ilil';'

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voltages' e
more normal application
capacitors at

99.99o/o
r:*-*-rl 125C
2_2\lt ?.1
99.9Yo e.--V 105C
:,],n
(} ---o 85C
i' I :l'l./^
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antr-
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refl ects i
slowin of thetwear-out
lil",ur,r
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cotrditions'
iii:io;i;;;i""t under certain test
\^ ear-out regions
o"nt
for the 50v p{s l11"Iiii:',i,,iii"*:'T'1::"ffil 'Xli'i''lllllli;:XiJ:3
rhis same pattern appears Becau
6 for the 25v parts'
distinctively in Figure \r.\. .\rriri:,li,rr.
')ilt I t:('r\ tl::ltcttonii:s (irxrtpr--tre.ts'
\ii:}::'';,l': ttll';i''i'']"]""' ..:ir,*to.l
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application voltages, it is not presently knoltn whether the anti-wear-out region has special significance in
the estimation of long-term capacitor reliability or not. Further work must be done to better understand this
behavior.

100
1 00 1 .25 1.50 175 2.00

Multiple of Rated Voltage EKR, 3'lJan2011

Figure 7. t50 Times yersus Test l'oltage, Calculalion of Voltage Ratio Exponent 4, and Extrapolalion to
Liwer Test Voltages for j5V Experitientctl Tantalum Polymer Capacitors Tested at 85"C, 105"C, 125"C
and Voltages Ji'om 1.8 to 2.lVr.

Finally, to close out the subject ol voltage acceleration of the wear-out region of the TTF distributions,
plots oft50 versus test voltage, calculation ofthe voltage ratio exponent 1, and extrapolation ofexpected
i50s at lower test voltages are pertbrmed using the data of Figure 4 at all three temperatures. The results
are presented in Figure 7 lbr the 35V capacitors.

The estimate of q generated tiom the 125"C datais generally consistentwith the estimate generated from
the 105"C data. Also, the data point at 2. lVr is closef to the line (but still omitted fiom the calculation).
However at 85'C, substantial nonlinearity is evident in the data points. This provides additional evidence
that there is more than one mechanism at rvork'

Even ifone disregards the nonlinearity and other imperfections of the data, it is clear that the voltage
acceleration exponent n is temperature dependent. Subsequently we leam that the activation energy Ea
used in the Arrhenius model lbi temperatuie acceleration is voltage sensitive. This interaction of voltage
and temperature u'as also obser"red in the earlier rvolk with the 6V devices and was the motivation
for
exploring a physics-based model that simultaneously addressed voltage and temperature acceleration.

The physics-base model is inherently more elegant than the simple empirical model employed here.
go*.uer its form and the determination of the appropriate constants become burdensome if one wants to
accommodate the effects of multiple mechanisms in the data. For this reason. the simpler, but much less
elegant empirical model rvas used in spite of its limitations.

Graphical analysis ofthe data tbl the 50V and 25V capacitors proceeds similarly as for the 35V capacitors,
but is not shoq,n here. These data are even more contbunded by the interaction of the
various regions of
TTF distributions (i.e.. the various degradation mechanisms) and do not add anything meaningful to the

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discussion. However, they are generally consistent with the results for the 35V capacitors in regions where
the mechanisms operate independently.

Temperature Acceleration Model

As discussed above, the TTF plots in the wear-out region of the failure distributions are sensitive to the test
temperature. As is observed in Figures 4-6, capacitors wear out faster at higher temperatures and slower at
low temperatures. As was the case fbr changing test voltage, the wear-out distributions are f-airly
uniformly spaced with temperature which suggests that temperature acceleration of the wear-out region of
the TTF distribution can be predicted by a relatively simple formula.

ln(t rtl
In this study we use a simple Arrhenius model for temperature acceleration: , -t, _,1* la-aJJ , where
t2
At is temperature acceleration of time, k is Boltzmann's constant (8.628-5 eV,K), Ea is an empirically-
derived activation energy, and T is absolute Kelvin temperature.

10e

E3ooy;l
10'
o
l
o

3 10'
o
f
c6
E 10"
=

,,91,ffi
0.0026 0.0027 0.0028

lnverse Abs, Temp, [1/Tj (K'1) EKR, 31Jan20'1'1

Figure 8. t5s Times versus Inverse Absolute Temperature, Calculation of Ea, and Extrapolation of Results
to Lower Voltages for 35V Experimental Tantalum Polynter Capacitors Tested at 85"C, 105"C, and 125"C,
and Voltages from 1.8 to 2.lVr.

To determine the activation energy at each test voltage. the t50 time (or projected t50 time) of the n'ear-out
region ofeach TTF distribution is plotted on graph oflog-tinle versus jnverse absolute temperature graph.
Then the t50 times fbt a given test voltage and multiple test temperatures are connected with a best-fit line.
The slope of this line provides the activation energy at the test voltage. The results of this exercise appear
in Figure 8 where the equation ofeach best-fit line appears in the legend.

Observe that the activation energies are indeed sensitive to the test voltage, and increase as the applied
voltage falls. This was also seen in the previous work with 6V tantalum polymer capacitors.

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The activation energies in the present study lange from a little less than 1.0eV to about 1.4eV at the lowest
practical test voltagi of l.8Vr (lower voltages do not produce enough failures). In the previous work on
6V cupacito.s, tesivoltages that produced ii*ilu. t50 times at 105"C ranged from l.leV to l.4eV, so the
p..r.ni results for tempeiature aiceleration of the wear-out region of the TTF distributions are generally
consistent with the previous work.

A final exercise is pertbrmed in Figure 8 to extrapolate ft'om the experimental data to lorver test voltages.
This extrapolation was done by plicing X's on the graph above the fit lines with generally similar, but
slightlyincreasingspacingatinten,alsotO.tVr. Thisisaguessregardingwherethet50timeswouldhave
lallen had the test voltage been reduced at the test tempemtures.

While obviously not a highly precise exercise, it is gratilying to see that the X at rated voltage and l05oC
lands in the same g.n"ruir.ighborhood (2300 years) as was predicted by extrapolation ofthe 105oC
data
on the voltage acceleration gr.iph of Figure 7. Again, all extrapolations outside the range of the collected
data are inherently risky, ind other tactors that could come into play at lower test voltages must be
considered when evaluating the resulting predictions.

Mechanisms

It is clear that more than one mechanism is at work in the TTF distributions discussed in this paper. This is
in striking contrast to the T'lF distributions p|esented in the previous work concerning 6V tantalum
polymer iapacitors u,here the TTF distributions contained only one dominant mechanism, the wear-out
mechanism.

To this point in the discussion the various mechanisms have not been identified, but rather they have
been
qualitatively described based on how they afltct the appearance ofvarious t'egions ofthe TTF distribution.
ihe qualitatiye descriptions were (l) initial lailure region, (2) tlat region, (3) wear-out region, and (4) anti-
*,"u.-out region which ref-er to the shape of the TTF distribution from early time to later time.

Any meaninglul discussion of the underlying mechanisms must ret'erence our best understanding of the
conduction plysics of a tantalum polymer''capacitor. Since PEDOT is a P-fype semiconductor material, the
is the metal,
tantalum poiy.., capacitor is an Mf 3 (metal-insulator-semiconductor) device where tantalum
tantalum penioxide ii the insulator, and PEDOT is the semiconductora'

MIS devices have conduction behavior that is principally govemed by the energy levels found at the
plus
interf-ace of the insulator and the semiconductor (work tunctions of the insulator and semiconductor
at the intertace). These energy levels provide a barrier to conduction when
any electric charge located
insulator'
electric tields having direction consistent with the defined capacitor polarity are imposed on the
If the applied field &ceeds the barrier height. signiticant conduction occul's. If more than a small amount
of conduction occurs at high etectric field strength, signiticant heat is generated and dielectric breakdown
can occur due to thermui- .rnu*uy. The sutsequent discussion of mechanisms will start with
this
tbundation.

Freeman, et. al.a describe the breakclown voltage behavior (BDV) of capacitors made entirely
with in-situ
polymerized pEDOT versus entirely with ple-potymerized PEDOT. For the "in-situ-only" capacitors,
"pre-poly-only"
bDV in...ur.s with dielectric thickness and then saturates at about 40V, but fbr the
capacitors. breakdown voltage continues to rise with dielectric thickness.

capacitors is
They indicate that a likely;eason tbr saturation of the BDV characteristic of the "in-situ-only"
ut the interlace that "pins" the potential barrier such that it cannot rise as the electric field applied to
choige
the insulator rises. This intert'acial charge likely results ftom charge-bearing species
left behind during the
in-situ polymerization Process.

In contt.ast, the pre-polymerized dispersion of PEDOT particles employed.in the "pre-poly-only"

capacitors
species since the chemical reactions are complete and any
does not contain any residual charge-bearing

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residual charged particles are removed before the polymer dispersion is applied to the capacitor. In the
presence ofpristine dielectric and absence ofcharge to pin the potential barrier, the barrier is free to grow
with applied electric field and BDV is free to rise with dielectric thickness rvithout the saturation observed
in the "in-situ-only" capacitors.

The tantalum polymer capacitors described in this work are a hybrid of the two extremes described above.
That is, a few layers of in-situ PEDOT are deposited inside the tantalum anodes, thoroughly rvashed to
remove as much charged residue as possible, and then covered with pre-poll,merized PEDOT. It is
reasonable to expect that the behavior of the potential barrier in these devices will tall somewhere between
the two extremes described above.

The initial failures are almost certainly devices whose breakdorvn voltage is exceeded as the voltage is
ramped up to the final test voltage during the first 60 seconds of the test. Due to the hybrid nature of the
polymer cathode, it is not surprising that there is considerable spread in the observed breakdown voltages
(demonstrated by the non-vertical slope of the initiat tailure region of the TTF distribution), and that more
capacitors fail in this initial failure region as the test voltage rises.

For capacitors that survive the initial voltage ramp (analogous to a BDV test performed in 60 seconds), it is
hypothesized that a few more capacitors fbil over time as the potentiat barrier in the surviving capacitors
deteriorates slowly with time, perhaps because of accumulation of trace mobile negative charge at the
interf'ace.

This hypothesis is based on the assumption that the flat region in the TTF distributions is consistent with
behaviorofthebamier. Thisassumptionissupportedbytheverylowtemperaturesensitivityoffailuresin
this region and the f'act that the barier height and related electronic conduction is fbund to be largely
independent of temperaturea.

It is hypothesizedthat the wear-out region ofthe TTF distributions is caused by increased electric fleld in
the insulator as more oxygen is stolen from the dielectric in the neighborhood of the interface of the
tantalum and the dielectric. As oxygen is stolen fi'om the dielectric near the tantalum metal, the dielectric
there becomes more conductive. Growing conductivity of the dielectric near the metal causes the eflective
thickness of the remaining good dielectric to fall and the electric field strength to rise. Given enough time,
the electric field grovl's to the point where the potential barrier can no longer contain it and dielectr.ic
breakdown occurs.

Oxygen vacancy generation, migration, and absorption into the tantalum metal occur naturally over time
and are signifrcantly accelerated by temperature and the electric field. This degradation mechanism u,as
identified as the likely cause^of wear-out in the previous investigations of low-voltage tantalum polymer
capacitors referred to above.2'3

The remaining region of the TTF distributions is the anti-wear-out region where wear-out appears to slow
down or stop. It is hypothesized that with sufficient voltage, time, and temperature, de-doping of the
polymer occurs at the interface ofthe polymer and the dielectric. This process produces new insulator (de-
doped polymer) at the interface which reduces the electric field strength in the original dielectric.
counteracting the increasing field liom oxygen vacancy gener.ation.

Some suppott for this hypothesis comes flom the observation that BDV in "pre-poly-only" capacitors
sometimes exceeds the original formation voltage of the dielectric when the voltage is ramped up slowly.
Subsequent measurement ofdevices that were exposed to very high voltage, but did not break down, shorvs
reduced capacitance that is explained by introduction of additional insulation (de-doped polymer) between
the original dielectric and the remaining conductive polymer layer. If this hypothesis is valid, it is not
know whether this mechanism has any relevance to long-term life predictions at more normal operating
conditions.

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Part: li cl' l3
Summary and Conclusions

A brief history of tantalum capacitors shows that the use of conductive polymer as a replacement for MnO2
as the cathode layer was primarily driven by the need for lower ESR. But it rvas soon discovered that the
reliability of these tantalum polymer capacitors was quite good, often rivaling and sometimes exceeding
that of MnO: capacitots. Hou,ever. the rarrge of rated voltages initially available rvas limited because good
reliability was not possible at the higher rated voltages.

With rhe introduction of pre-polymerized PEDOT polymer dispersions, the existing voltage limit for
tantalum polymer capacitors is breached and reliable tantalum polymer capacitors with voltage ratings of
25V and higher can now be manufactured.

The natural need to assess the long-term reliability ofthese higher rated voltage devices lead to the present
reliability investigation. Here, highly accelerated lil'etesting is employed to establish voltage and
temperature acceleration models and predict lif'e at more normal application conditions.

TTF failure distributions wele collected on caretully prepared experimental capacitor designs at various
voltages and temperatures. The resulting tailure distributions are lbund to contain identifiable regions that
likely correspond u,ith separate degradation processes. These processes or f'ailure mechanisms are found to
be dominant at different tinies during the test. Moreover they are variously affected by voltage and
temperature, providing clues regarding the underlying physics.

The rvear-out regions of the TTF distributions were deemed to be of primary importance since the other
mechanisms are thought to either disappear or not impact dielectric failure under normal application
conditions. So, the behavior of the wear-out regions of the TTF distributions were graphically analyzed
and the results fit to simple empirical voltage and temperature acceleration models'

The lesulting models predict very long lif'e (median lif'e beyond 1000 years) under normal application
conditions. Even discounting tbl eally tailures and process variation, it is clear that these capacitors have
sufficient reliabiliry lbr all routine, and many high-reliability applications. They may even be more
reliable than their lower-voltage siblings.

The paper ends with discussion of the various likely failute mechanisms and their underlying physics.
Understanding of these complex devices is still in its inl'ancy. but much of the observed electrical behavior
can be understood if one accepts that these capacitors are MIS structures and behave according to MIS
theory.

References

rE.Reed and J. Marshall, "l8 Milliohms and Falling-New Ultra-Low ESR Tantalum Chip Capacitors,"
CARTS '99 Proceedings of the l9'h Capacitor and Resistor Technology Symposium, p. 133 (1999).

2
J. Paulsen. E. Reed, and J. Kelly. "Reliability of Tantalum Polymer Capacitors," CARTS'04 Proceedings
of the 24'h Capacitor and Resistor Technology Symposium, p. 114 (200a).

3
E. Reed. J. Kelly, and J. Paulsen. "Retiability of Low-Voltage Tantalum Polymer Capacitors," CARTS
usA 2005 Proceedings of the 25'i' Symposium fbr Passive components. p. 189 (2005).

t Y.
Freeman, W. Halrell, L Luzinov, B. Holman, andP. Lessner, "Electrical Characterization of Tantalum
Capacitors rvith Poly(3,4-ethylenedioxythiophene) Counter Electrodes," Joutnal of the Electrochemical
Society, p. G65 (2009).

201 I [(;\ t}:lleqtraries (..ourponerrrs. r\sscuihlrcs & l\'l*rerials Assriciation), Arhngton, VA

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