A NEW,

ML - 1 CAPACITORS
TYPE
OF PLASTIC

MINIATURIZED
D.

CAPACITOR

J.

Valley
and J. S. Wagener
Kemet
Department
Linde
Division
Union
Carbide
Corporation
Parma
Research
Center
Parma,
Ohio

Introduction

FILM

In miniaturization
of electronic
components
and circuits,
a particular
problem
*
is encountered
with
capacitors
in the range
of
Since these capacitance
val0.1 pf and above
ues are too large
to be incorporated
directly
into an integrated
circuit,
they have to be added
the problem
remains
of
externally.
However,
developing
materials
and techniques
by which
these
capacitors
can be made as small
as possible in order
to avoid a multiplication
in size
of the circuit
to be produced.
The lower
range
of the capacitance
values
under
discussion
is covered
by plastic
when optimum
dielectric
propfilm
capacitors,
erties
at frequencies
up to the megacycle
range
Only two ways are open for minare desired.
iaturizing
these film
capacitors,
for which materials
such as polystyrene,
polyethylene
terephthalate
and polytetrafluoroethylene
are now
being used:
(1) raising
the dielectric
constant
Realizaand (2) reducing
the film
thickness.
tion of the first
of these alternatives
is a rather
remote
possibility
as long as organic
film materials
are employed.
As for the second
choice,
there
is a severe
limitation,
as long as the selfsupported
free films
now found in all commercial capacitors
have to be used,
because
of the
deterioration
of mechanical
strength
with decreasing
thickness.
On the other
hand,
a considerable
reduction
in film thickness
appears
possible
until electric
breakdown
becomes
a limiting
factor.
Present
materials
range
in minimum
film
thickness
from
0.15 to 1 mil,
and their
breakdown field
strengths
are of the order
of 5000
volts/mil.
Therefore,
with a safety
factor
of
250%, the minimum
usable
thickness
for an operating
voltage
of 100 volts
would be about
l/20
of a mil.
These
lower
thicknesses
can be obtained
if,
instead
of using a free film
to be inserted
between
two metal
foils,
serving
as the
electrodes,
the film
is deposited
onto these
foils.
The coating
process,
which has the best
potentia,
of yielding
very
thin films
of sufficient uniformity,
is vacuum
deposition,
and attempts
to utilize
this process
for deposition
of
organic
materials
have been made in the past.
However,
in all these
cases,
polymerization
of

the films
had to be stimulated
application
of either
glow dt;;charge,
diation
by ultraviolet
light,
or electron
bomdifficulties
were
enbardment,
4 and serious
countered
in obtaining
a uniform
and reproducible degree
of polymerization.
Preparation

of Polymeric

Films

A new polymeric
material
has been
discovered
by Union
Carbide
Corporations
Plastic
Division
that can be applied
in ultrathin
films
to aluminum
metal
foil for the manufacture
of high performoance
capacitors.
Dielectric
films
as thin as 100 A or less have been made but with
betteroresults
being
secured
at thicknesses
of
The polymer
remains
inert
to
1000 A or more.
practically
all environments
and furthermore
possesses
exceptional
dielectric
properties.
As
with any thin film
components,
uniformity
and
reproducibility
is critical
and has been achieved
to provide
pinhole-free
film for capacitor
applications.
Description

of Capacitors

Several
different
styles
of capacitors are possible
using the film
coated
substrate
A preferred
design
employs
two exapproach.
tended
coated
foils,
while
alternately
one coated
and one plain
foil can also be used.
Another
design
features
a coated
foil with a metallized
second
electrode
which permits
further
size reduction
and has lself-healingl
qualities
but
lacks
the stability
of the extended
foil designs.
Representations
of these designs
are shown in
The electrode
foil which
serves
as
Figure
1.
a substrate
for the vapor
deposited
polymer
is
capacitor
grade
aluminum,
0.15
or 0.25 mil
thick.
The added strength
imparted
by the dielectric
makes
possible
the use of 0.15 mil foil
in narrow
widths
even while
applying
high
tens ion during
winding.
After
winding,
the rolls
are terminated
in the standard
manner
by soldering
lead
wires
onto the flame
sprayed
ends.
The rolls
are then wrapped
with a high
temperature
dielectric
tape and placed
in metal
sleeves
to
which
glass-to-metal
end seals are attached
to

* U.S.

-205-

Patent

Applied

For

A final heat conditioncomplete

encapsulation.
ing at an elevated
temperature
causes
the internal
structu.re
to set, I minimizing
future
capacitance
shifts.
Properties

of ML-1

Capacitors

ML-1
capacitors*
can be summarily characterized
as having
excellent
electrical
properties
which
are stable
over a wide temperature
and frequency
range.
This is a result
of a well ordered
atomic
and highly
crystalline
molecuIar(polymer)
structure.
The melting
point of the polymer
is 400 C and while
it is
impractical
to make capacitors
for this high a
temperature,
tests have shown capacitors
for
continuous
service
at 265 C are possible.
Her metic
sealing
is necessary
for
service
above
125 C to prevent
oxidation
of the polymer.
ML-l
capacitors
have good radiation
resistance;
thephysical
and electrical
properties
are stable
to radiation
dose levels
of at least
IO8 rads
when protected
from
air.
ML-l
film
is also an exceptional
insulation
material
for use in cryogenic
applicaIts lplastic
nature
and high electrical
tions .
performance
even at temperatures
as low as
3.5 K make possible
the use of insulating
films,
less than 1000 x thick.
Such unprotected
films
can be rapidly
and repeatedly
cycled
from
room
air to liquid
helium
without
any deleterious
effects.

to capacitor

Electrical
applications

properties
most
are discussed

relevant
below:

Dielectric
Constant
of ML-l
film
is
Figure
2 inustrates
its con2.70 at 1000 cps.
stancy
over the range
from
60 cps to 1 mcps.
Similar
curves
are
shown
for polycarbonate
(PC) and polyethylene
terephthalate
(PETP).
Dissipation
Factor
is low,
typically
The value in0.00015
at 25C,
1000 cps.
creases
only slightly
over the frequency
range
of 60 cps to 1 mcps as shown
in Figure
3.
Dissipation
also
remains
very
low over
a wide
temperature
range
as shown in Figure
4.
Resistivity
of ML-l
film
is in excess of 1017 ohm-cm
which
is higher
than values
for other
commonly
used dielectrics
when measured in a similar
manner.
Insulation
Resistance of thin film
ML-l
capacitors
of 0.1 pf
rating
is about
lo6 megohm-microfarads
at
room
temperature
and drops
to 75 megohmComparative
IR -temmicrofarads
at 170 C.
perature
plots
are shown in Figure
5.

* U.S.

Patent

Applied

For

Capacitance-Temperature
change
is
illustrated
m Figure
6; the value
is predominantly
negative
and less than 100 ppm/C
over
the extreme
temperature
range
from
-185 to
+17OC.
Dielectric
Absorption
of ML-l
is
0.1% when measured
m accordance
with MIL-CCorresponding
values
for polycarbon19978B.
ate and polyethylene
terephthalate
when meas ured in the same
manner
are 0.2%
and 0.3%
respectively.
5
Dielectric
Strength
of ML-l
films,
determined
by applying
a potential
across
a
coated
foil,
using -a mercury
electrode,
is about
8000, volts per mil,
based
on a 2 micron
coating
However,
due to the roughness
of
thickness
.
the matte
side of the aluminum
foil,
which
is on
the same order
as the film thickness,
the high
dielectric
strength
of the film
cannot,
as yet,
be fully
realized
in a roll
capacitor.
Present
efforts
directed
at improving
the smoothness
of
the aluminum
foil are expected
to increase
the
dielectric
strength
of the finished
roll capacitor.
Working
Voltage
of current
ML-l
capacitors
is 50 volts
at 170 C.
ML-l
capacitors
can be operated
at higher
voltage
at lower
At 125 C a working
voltage
of
temperatures.
70 volts
is recommended;
suggested
working
voltages
for lower
temperatures
are indicated
in Figure
7.
Volumetric

Efficiency

The size of ML-l

capacitors,
using
the present
two-coated,
extended-foil
design,
is
less
than that of other
roll
capacitors
of extended-foil
design
employing
0.25 mil thick
dielectric
films.
A 0.47 d ML-l
capacitor,
with
metal
case,
hermetically
sealed
is compared
to
typical
capacitors
of similar
construction
in the
following
table:
The size difference
is considerable
in the case
where
high performance
is required,
especially
at temperatures
in excess
of 125C;
ML-I
capacitors
have a volume
of less than one-tenth
that of capacitors
made from
polytetrafluoroethylene
film.
Life

Testing

ML-I
capacitors
have been
life
tested
at temperatures
of 125 and 170C
and
voltages
of 50, 70, and 100 volts.
A failure
detection
system
is used which
automatically
indicates
time of failure
and panel identification.
This is done without
disturbanceto
other
units.
or interruption
of the test.
From
the panel identification
code,
test conditions
and elapsed
time
A schematic
of
to failure
can be determined.
the system
is shown in Figure
8.
A test panel
for one test condition,
i.e.,
50 volts,
17OC,

-206 -

has 45 test capacitor

positions
with series
diodes and a common
SCR triggering
circuit
which
By multiplexing
the
actuates
the clock printer.
six code characters
of the printer,
individual
identification
of more
than 50 panels
(2,250
PCS)
is possible.
The main objective
of the life testing
done to date has been the evaluation
of many material,
design
and processing
parameters
rather
than to establish
the failure
rate of a large
number of capacitors
of similar
genesis.
Although
the available
data do not permit
the statistical
determination
of specific
failure
rates,
it is sufficient
for some more
general
conclusions:
(1)

Capacitors
ous service

can be made for continuat 17OC,

50 volts.

(2)

Life performance
results
at 125 C,
70 volts are similar
to those at
170X,
50 volts.

(3)

wear
Apparent
detected
under
ditions
.

(4)

After
1000 hours
of life testing
at
125C,
50 volts,
there
is only a
slight
increase
in dissipation
(to
0.03%)
and less than 1% capacitance
increase.
There
is no significant
change
in insulation
resistance
or
temperature
coefficient
of capacitance.
For comparative
purposes,
the most applicable
military
specification
for life performance
(MILC-19978B-Char.
T) states
a change
in capacitance
of not more
than 5%
and for dissipation
not to exceed
0.10% after
250 hours.
Environmental

-out
has not been
the existing
test con-

1
2
3
4

-65
25
125
25

- C

Time

ML-l
capacitors
have demonstrated
excellence
in electrical.parameters
even at the
first
phase of development
and are expected
to
improve
with refinements
in production
techniques
and material
quality.
The overall
high performance
of
ML-l,
its low dissipation,
high insulation
resistance,
stable
temperature
and frequency
charis without
par among
modern
dielecacteristics,
Other
materials
which
offer
high pertries.
formance
in some characteristics
are notably
Such deficiencies
are,
for
deficient
in another.
temperature
range
of polyinstance
, the limited
styrene
and the large
size of polytetrafluoroethylene
film
capacitors.
ML-l
capacitors
can be used to best
advantage
where
stable
capacitance,
and high
and stable
Q are desired
over a wide temperature and frequency
range.
This provides
the design engineer
with a greater
flexibility
where
previously
temperature
restrictions
were required
for polystyrene
or size was sacrificed
for polytetrafluoroethylene
capacitors.
Furthermore,
in the l/100
p.f range
(10,000
pp.f) designers
can match
or exceed
characteristics
of
glass,
porcelain
and precision
ceramic
with considerable
space savings.
Aclmowledgments

sored by the
NObsr-89519.

(min)
30
15
30
15

This work in part has been sponBureau

of Ships under
Contract

References
1. J.

Testine

Temperature
Cycling
according
to
MIL-STD-202B,
Method
102A,
Test Condition
C,
for five cycles
as shown in the following
table
produced
an average
capacitance
change
of 0.1%
and no excessive
decrease
in terminal
to terminal insulation
resistance.

Temp.

Conclusions

Goodman,

2. A. Bradley
them.
Sot.

J.

Polymer

Sci.

and J. P. Hammes,
110, 15 (January,

-44, 551 (1960).

J. Electro1963).

3.

L. V. Gregor
on Electrical

and M. L.
Insulations,

McGee,
October,

Conference
1962.

4.

R. A. Fotland
and W. J.
Meeting
Electrochemical
Angeles,
March
7, 1962.

Burkhard,
Society,

121st
Los

5.

L. Adelson
Components
May,
1963.

and H. L.
Conference,

Rice,
Electronic
Washington,

6.

domponents
Electronics,

Selector,
Cornell-Dubilier
Class
206.

7.

Engineering
Inc.

Bulletin

Vibration
and Shock test to levels
beyond
those
specified
in MIL-STD-202B
produced
no
significant
change
in electrical
parameters.
Other
Environment
tests
such as humidsalt spray,
moisture
resistance,
etc. which
ity,
are more
a test of the hermetic
encapsulation
than the capacitor
structure,
have been satisfactorily
completed.

-207-

1001,

Film

D.

Capacitors,

C.,

I:I
\\\ QI
\\\
\\\
3 ca\.-

Dielectric

Constant

PC and PETP,

Ref.

as a Function
5.

-208-

of Frequency

at 25%;

Figure

Diaeipation
PC

as a Function

and PETP.

Ref.

of Frequency

50

IO0

PERATWRE
Figure

Diesipation
PC

and

as a Function
PETP,

Ref.

-209.

at 25-C;

5.

5.

150

PC)
of Temperature

at

1 KC;

Figure

Insulation

PC-l

Resistance
andPETP,

as a Function
Ref.

5;

I60

920
1C 1

80
TEMPERATURE

40

PC-Z,

of Temperature;
Ref.

7.

IO

PB PETP
-4

-50
Figure

I
I
50
TEMPERATURE (93

I
0

Capacitance
PC

and

Change
PETP,

Ref.

as
5.

-210-

a Function

of Temperature

I
100
at

I
150

1 KC;

Figure

Suggested

I
I00
TEMPERATURE
Working

Voltage

for

I
150

(C)

ML-l,

50 Volts

- 17OC.

---

UR-25
--L

2
____

3
____

7
_______

___---8

mYNt2c
C;- TEST CAPACITOR
F.-FUSE
Ds- DISCHARGE LIMITER

Figure

Failure

Ro;-GATE

RESISTOR

R. - RELAY COILS
R,SCR INTERRUPTER

Detection

System

RELAY

for

ML-l

I70

Roll

Capacitors

-.S-

TEST

TEST

YEL
-----

%
--

IO
--_---