2004 International Conference on Solid Dielectrics, Toidorrse, France, h i f 5-9,

~ 2004

AC Electrical Breakdown and Conduction in PMMA Thin Films

and the Influence of LiC104 as an Ionic Impurity

Keiichi Miyairi and Eiji Itoh

Department of Electrical and Electronic Engineering, Shinshu University,
4-17-1, Wakasato, Nagana, Nagana Prefecture, 380-8553, JAPAN
E-mail : miyairi @ gipwcshinshu-u.ac.jp

Abstract: Poly(methy1 methacrylate) ( PMMA ) has
been widely used in electrical insulator and optical
device applications. It is known to be polar material,
especially above the glass transition temperature T,
(-110°C). In this work we have measured the
breakdown strength of PMMA thin films of 300nm
thickness between AI electrodes under alternating
voltage at frequencies between IOHz and 3Mz. Below
T,, the breakdown strength increases gradually from
2MV/cm to 3MVicm as the frequency is increased. On
the other hand, the breakdown strength decreases
drastically at a temperature near T,. Above T8, the
breakdown strength decreases with the frequency. The
decrease in the breakdown strength at high temperature
is considered in terms of heating due to the rotation of
polar side chains in PMMA. We have also investigated
the influence of the addition of ionic impurities
(LiCIO,) on the ac breakdown strength and also on the
electrical conduction in PMMA films. While the
breakdown strength decreases considerably with the
concentration of LiC104 at IOW temperature, it changes
little at high temperature although there is a
considerable increase in the conduction current.
INTRODUCTION
Recent advances in materials technology has provided
us with excellent electronic components, such as
integrated circuit elements, light emitting diodes, and
displays, in which dielectric films are widely used as
insulators. A diversity of organic materials developed
for these applications have been attracting a great deal
of attention since these new materials enable the
fabrication of new devices, such as electroluminescence
elements, organic field effect transistors, and memory
devices. Although many kinds of excellent insulating
films are produced today the mechanism of electrical
breakdown in them still remains unclear due to the
complexity of the phenomena 11-41, DC breakdown and
pulse breakdown in solid dielectrics have been
investigated extensively from a theoretical point of view,
and several theories have been proposed based on
charge multiplication and joule heating [ 1-71, However,
ac breakdown in solid dielectrics is more complex since
it is accompanied by dielectric loss heating, in addition
to charge multiplication and joule heating. Thin films
lend themselves very well to the study of dielectric
breakdown because of their self-healing nature, which
allows a large number of breakdown tests to be
perfonned on a single specimen [5]. As the PMMA
chain has dipolar side groups,'ii is a typical polymer for
the study of the effect of dipolar relaxation on the
breakdown. However, especially at temperature above
T, (-1 IOOC), the glass transition temperature for PMMA,
the polar groups may play a dominant role in the
conduction mechanism and might influence the
breakdown process. In addition, ionic impurity might be
present and become dominant especially above T,. In
this study, the ac breakdown and conduction in PMMA
thin films and the influence of LiCIOd as an ionic
dopant have been also investigated. LiCIO, has been
chosen as an ionic dopant because the lithium ion may
be expected to be very mobile, and it may be easy to
control the dopant dose in the film.
EXPERIMENTAL
Metal-Insulator-Metal (M-I-M) capacitors were
prepared by a three-step process: First, a bottom AI
electrode was evaporated on a glass slide that has been
cleaned under the ultra-sonication by water, acetone,
and hot alcohol. Thin films having thickness in the
range of 120-600 nm were then fabricated by
spin-coating on this electrode from chloroform solution.
For the film doped with LiCI04, the film was spin
coated from the mixture of chloroform and methanol
because LiCIO, was not soluble in chloroform but was
soluble in methanol. The thickness of a film was
calculated from the measured capacitance using the
known dielectric constant. Finally, a top AI electrode
was prepared by evaporation. The effective electrode
area was 25 mm2. All samples were placed in a vacuum
chamber and heat-treated at 90°C for 30 min to remove
residual water which might seriously influence the ionic
conductivity of the PMMA films. Real time
measurements were made automatically using a system
composed of a digital oscilloscope, controllable signal
generator and microcomputer.
RESULTS
The breakdown strength of PMMA
Since breakdown in the thin films was accompanied by
self-healing, multiple breakdown tests were possible on
each PMMA sample. The variation of the breakdown
voltage of PMMA with the test number was measured
after the sample preparation at IkHz. About 100

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 measurements were made on each sample. It was
observed that breakdown sites were scattered uniformly
across the sample surface and were all single holes. The
breakdown strength was found to increase for the first
20 or 30 tests and then reached a plateau. Breakdown
took place at the peak of the applied voltage and
suggests that the applied field strength played an
110- 120°C. For higher temperatures, the breakdown
strength again decreases with temperature. And the
breakdown strength of lwt% doped sample becomes
slightly higher than that of undoped sample at the
temperatures around T,.
E
Y

important role in the breakdown process.

The breakdown strength measured with ac voltages for

various frequencies between lOHz and 3kHz is shown
in Fig.1. The film thickness was 230nm. The breakdown
strength decreases with temperature for all frequencies.
The breakdown strength decreases steeply at
temperatures around 11 5OC which is very close to glass
transition temperature T,. The results manifest the
different dependencies on frequency on either side of T,.
The breakdown strength increases with frequency below
T, while it decreases with frequency above T,. It is
well known that the ac breakdown strength in
polyethylene is lower than the dc one, and it decreases
with frequency. In other words, the breakdown
mechanism changes at the glass transition temperature.
When dielectric loss due to dipolar relaxation is
Terrperature [ "c 1
predominant, it seems probable that the breakdown
strength decreases with frequency. As the PMMA Fig. 2 The temperature dependence of breakdown strength
molecule has polar side groups, the breakdown would as a function of LiC104 dopant dose (in wt%) at (a) IOHz and
be encouraged by heating due to the dielectric loss (b) 3"z.
especially above T,. At temperatures region below T,,
however. it is difficult to consider dielectric loss heating The conduction in PMMA
as a breakdown mechanism and further investigation
may he required to determine the mechanism in the low The breakdown strength of PMMA film might he
temperature region. associated with the conduction in PMMA since it
strongly depend on dopant dose below T,. Firstly we
investigated the dc conduction in PMMA at various
- 3 undoped PMMA temperatures to discuss the relationship between the
5
6 conduction and the breakdown strength in PMMA.
z Figure 3 shows the I-V characteristics of undoped
5c 2 PMMA films at various temperatures obtained IO
e seconds after application of the dc step voltage. The
tj film thickness was 320nm. The current is nearly
g 1 symmetric for positive and negative voltages and
s increases with temperature and voltage below T,. Above
-
? Tg, the current is much less dependent on voltage. Here,
- OL ' go ' '
Terrperature[%]
' '
' 100 ' ' ' '
' 150
the inset in Fig. 3 shows the temperature dependence of
the current at IMV/cm. The current increases drastically
with temperature at temperatures below T, and then
Fig.1 The temperature dependence of the breakdown
strength of undoped PMMA film at various frequencies. become independent of temperature above T,. Figure
4 shows the I-V characteristics of LiC10, doped (lwt%)
PMMA film of 280nm thickness. The current becomes
Figure 2 shows the temperature dependence of much larger than undoped film at the temperatures
breakdown strength as a function of LiC104 dopant dose helow T,, while the steady current becomes the same
in wt% at (a) IOHz and (h) 3Wr. The breakdown order of magnitude as undoped PMMA [Fig. 31 at high
strength decreases with dopant dose at temperatures temperatures above T,. From the inset in Fig. 4, the
below T, but seems to be independent of dopant dose at current increases drastically with temperature below
high temperatures above T,. The breakdown strength 90°C while it is much less dependent on voltage.
decreases monotonously for undoped samples. For
Iwt% and 2wt% doped samples, however, the
breakdown strength decreases with temperature below
9OoC and then increases again up by small amount to

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 Electnc Field I MVlcrn I
Voltage [ V ]
Fig. 3 I-V characteristics in non-doped PMMA films at
various temperatures. The inset is the current at IMVicm.
Figure 5 shows (a) voltage dependence of the I-t
characteristics at 110°C and (b) temperature dependence
of I-t characteristics at +25V in LiC104 doped PMMA
film ( 1 ~ 1 % )which is a same sample in Fig. 4. The
current increases with voltage within 5s after changing
the polarity of voltage and the time taken to reach
current peak decreases with voltage. The current then
decreases rapidly with time and becomes constant. It
should be noted here that the integration of the
measured current minus the constant current, i.e. the
total displacement charge, becomes constant above 15V.
The current peak also changes with temperature [Fig. 5
(b)] and the charge becomes constant again. The total
charge estimated to be 50-60 pC whereas the total
charge of Li' ions is estimated to be 250pC if all LiC104
molecules dissociate to Li' and C1Oi ions. In other
words, only about 20% of LiC104 molecules contribute
to ionic conduction in PMMA film.
Electric Field I MVlcm I
Voltage [ V 1
Fig. 4 I-V characteristics in LiCJO, doped PMMA films
[lwt%) at various temperatures. The inset is the current at
IMVicm.
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Time[S]
Fig. 5 [a) Voltages dependence of the I-t characteristics at
I I O T and (b) TempemNe dependence of at i25V in LiCIQ
doped PMMA film (1 w%).
Figure 6 shows oscillograms of applied voltage and
current in LiClO, doped PMMA film ( 2 ~ 1 %under
) ac
voltage at IOHz. The displacement current is dominant
at low temperatures below 90°C and a conductive
current which is in phase with the applied voltage
becomes predominant at high temperatures above T,.
On the other hand, the displacement current is
predominant for all temperatures in undoped PMMA
film which is presumably due to the much lower density
and mobility of residual ionic impurities in undoped
film. Since the total charge due to the conductive
current becomes much less than the total mobile charge
discussed in Fig. 5, the conductive current is
presumably due to the ionic conduction. The current
increase with temperature might be considered as an
increase of ionic mobility with temperature which is
able to follow the change in the voltage.
DISCUSSION
In principle, dielectric breakdown is achieved through
the following stages: (1) appearance of initial electrons,
( 2 ) charge multiplication, (3) current runaway. The
initial electrons come from the electrode or the bulk. To
determine the role of the electrode in providing initial
electrons, the influence of the electrode material on the
breakdown is key factor (not yet observed in PMMA
film). The injected current in PVK film which is known
as a hole conductive material was much larger for
positive biasing to Au electrode when the film was
sandwiched between Au and AI. However, there is no
difference in the breakdown phase between the positive
and negative polarity. That is, breakdown occurs at the
same rate in either polarity irrespective of the
asymmetric electrode system. The polarity
 independence shows that the work function of the dissipation, the breakdown strength of a thick sample is
electrode is not directly related with the initiation of the expected to be lower than that of a thin sample. The ac
breakdown, but rather with the build up during the breakdown strength of PMMA films at 1 kHz is
pre-breakdown stage. independent of film thickness between 120 and 600nm.
The anomalous frequency dependence of the breakdown
strength presented in this work is not explained by
40 theories of ordinary breakdown, such as avalanche or
thermal breakdown.
z 2o
$ 0 In the low temperature region below T,, it is probable
-
I
that there is an increase in the number of shallow levels
P -20 or density of free electrons i n y c hulk in LiC104 doped
-40 samples. And the large increase in current build up in
terms of the field enhancement due to hetero space
charges may lead to a lower breakdown strength. At
temperatures above T,, however, the ac breakdown
strength does not change even though there is an
outstanding increase in ac conductivity caused by
LiC104 doping. In other words, joule heating due to the
ac conduction does not contribute to ac breakdown
strength in the high temperature region.

0 0.05 0.1 0.15 REFERENCES

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Fig. 6 the oscillograms of applied voltage and current in
LiC104doped PMMA film (2wt%) at 10Hz.
In practical high polymer materials, charge carriers are
likely to be trapped in shallow localized electronic states,
and will contribute to ac conduction by inter-state
hopping. Consequently, a higher frequency should yield
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the present results do not meet this idea. It is probably
that the frequency dependence of the electric strength
shown here is not associated with an avalanche process,
since the formative time to the breakdown by avalanche
process is expected to he less than 1 ps in high
polymers.

PMMA films are typically amorphous, and electrons

trapped in shallow levels will move hack and forth
according to ac voltage cycles. Some energetic free
electrons will he produced from the shallow levels and
will lead to current build up. The build up of a critical
camer density and establishment of a conductive path
through the sample would be expected to require a
certain amount of time. Since a lower frequency voltage
serves to maintain a high electric field state for longer
times, the probability of current build up is higher at
low frequency, and results in a lower breakdown
voltage.

Several theories of solid breakdown predict that

breakdown strength is directly dependent on thickness.
It will be inherently dependent on thickness for an
avalanche breakdown. On the other hand, since thermal
breakdown caused by joule heating involves heat

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