Conductivity spectroscopy in aromatic polyimide from 200 to 400 C

Sombel Diaham, Marie-Laure Locatelli, and Thierry Lebey

Citation: Applied Physics Letters 91, 122913 (2007); doi: 10.1063/1.2789288
View online: http://dx.doi.org/10.1063/1.2789288
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APPLIED PHYSICS LETTERS 91, 122913 2007

Conductivity spectroscopy in aromatic polyimide from 200 to 400 C

Sombel Diaham,a Marie-Laure Locatelli, and Thierry Lebey
LAPLACE [CNRS, INPT, UPS, Universit de Toulouse] Universit Paul Sabatier, Bt. 3R3,
118 Route de Narbonne, 31062 Toulouse Cedex 09, France

Received 20 July 2007; accepted 4 September 2007; published online 20 September 2007
Dielectric relaxation spectroscopy experiments have been performed in a polyimide PI in order to
measure its electrical conductivity from 200 to 400 C. The high temperature static dc
conductivity in PI appears as superimposed by electrode polarization due to the building up of thin
space-charge capacitor layers at the bulk-electrode interfaces of the metal-insulator-metal structure
making the conduction phenomenon difficult to identify in dielectric spectra. However, the dynamic
ac conductivity plot versus frequency allows for an approximation of the dc conductivity in PI
which was reported here up to 400 C with values reaching 106 1 m1 at 400 C. 2007
American Institute of Physics. DOI: 10.1063/1.2789288
The development of electronic devices operating under
high temperature stresses 300 C involves the use of appropriate dielectric materials for the packaging of components and their electrical insulation.13 Aromatic polymers
are often used to achieve the surface insulation of power
electronic dies, thanks to their good electrical properties and
easy processability.4 However, electrical properties of polymers above 200 C have not been studied enough up to now
to ensure their matching with high temperature applications,
although they seem to constitute one of the potential paths
for this kind of topic.3,5
Aromatic polyimides PIs are well-known for their
good thermal, electrical, and mechanical properties and appear also as potential candidates for high temperature power
electronic device insulation. Many studies have been led on
electrical properties in PI using metal-insulator-metal structures MIMSs by conduction current experiments,69 but
electrical conduction versus temperature has been rarely investigated by dielectric relaxation spectroscopy DRS despite recent improvements in the performance of rapid impedance bridges.10 DRS can also appear as a powerful and
quick tool for measuring the electrical conductivity versus
temperature of dielectric materials provided that one is accustomed to the physical background of polarization
phenomena.11,12 Therefore, the dc conductivity can be approached through the Ohmic conduction phenomenon appearing at low frequency and/or high temperature LF/HT.
Nevertheless, the dielectric spectra of MIMS, generally obtained at a high temperature, are often influenced by interfacial dielectric relaxations such as electrode polarization EP
due to the relaxation of thin space-charge capacitor layers
built up in the vicinity of the bulk-electrode interfaces of
MIMS.1317 Indeed, EP leads to superimposition of an extrinsic component, dependent on the metal nature of the electrodes, onto the intrinsic bulk properties. It also makes the
quantification of the dc conductivity in dielectric films difficult.
This letter presents the description of EP phenomenon
occurring in PI MIMS at LF/HT through DRS experiments
using a biphenyltetracarboxylic dianhydride acid pphenylene diamine PI as dielectric film layer. Then, measurements of the dc conductivity in PI obtained over a wide
a

Author to whom correspondence should be addressed. Electronic mail:

sombel.diaham@laplace.univ-tlse.fr

temperature range from 200 to 400 C and extracted from

the ac conductivity plot are presented. According to the literature, quantitative measurements of dc conductivity up to
400 C using DRS have never been carried out before for
any organic material. DRS results are plotted using the dielectric complex permittivity formalism * = i, where
and are the real and imaginary parts and i = 11/2.
Dielectric properties in PI have been studied using
MIMS where a film layer with thickness of 2 m has been
spin coated on a polished and cleaned stainless steel SS
substrate before curing at 400 C for 1 h under N2 atmosphere in order to remove solvent1822 and to achieve the PI
chemical structure.23,24 Gold circular upper electrodes of
5 mm in diameter were evaporated in vacuum onto the PI
surface in order to achieve the SSPIAu structures. Dielectric properties have been studied by DRS versus frequency
and temperature using an HP4194A impedance meter
coupled with an S-1060R probe station and a heating chuck
system. Dielectric properties have been investigated through
capacitance C P and loss factor tan measurements in a
frequency range from 100 Hz to 5 MHz, under an ac sinusoidal applied voltage of 500 mV rms, and in a wide temperature range from 200 to 400 C in air by step of 10 C
with a 5 C min1 heating slope between two consecutive
steps. The same results have also been obtained in N2 atmosphere and with other kinds of MIMS AuPIAu, AgPI
Ag, and AlPIAl.
Dielectric spectra versus frequency in PI MIMS exhibit
three relaxation phenomena in the range from 200 to 400 C
Fig. 1. One appears between 200 and 325 C and above
10 kHz. It could be ascribed to the Maxwell-Wagner-Sillars
relaxation present into PI which has been already investigated by thermally stimulated depolarization current experiments in the range of 170 200 C.2527 Such a polarization
process, noted as the relaxation, is usually attributed to a
space-charge building up within the PI bulk as a result of
microscopic and mesoscopic motions of charge carriers
trapped into internal interfacial sites acted by unsaturated
phenyl N C6H4 and carbonyl C v O groups.
The two other polarization phenomena appear respectively between 265 and 400 C and above 350 C. They are
referred here as the relaxation and the * relaxation, respectively. According to the literature, they have never been
observed previously due to usual temperature ranges of characterization 250 C of PI by DRS.28,29 They are charac-

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91, 122913-1
2007 American Institute of Physics
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122913-2

Appl. Phys. Lett. 91, 122913 2007

Diaham, Locatelli, and Lebey

FIG. 2. Schematic representation of the charge density distribution 0 of a

dielectric material of thickness d under an applied electric field. LD represents the Debye length of the space-charge built up.

FIG. 1. Frequency dependence of the real part a and imaginary part

b of the dielectric complex permittivity * and of the loss factor tan c
in polyimide between 200 and 400 C by step of 20 C.

EP appears as a result of macroscopic motions of charge

carriers electrons, holes, and ions within the bulk toward
interfaces with electrodes. Under the ac applied electric field
and at LF/HT, positively charge carriers respectively negatively have sufficient time to drift to the vicinity of the
negatively polarized electrode respectively positive in order to build up a space charge at the bulk-electrode
interface.32,33 Figure 2 shows a schematic representation of
the space-charge distribution versus the material length x
when an electric field is applied on a blocking electrode
system.33 Introducing the concept of the macroscopic dipole,
MacDonald and Coehlo have related the strong values of
at low frequency to the ac space-charge polarization. They
have also demonstrated and simulated that relaxations of
space-charge blocked at the bulk-electrode interfaces involve
a large dispersion of the real part of the complex permittivity
. In the present case, the occurrence of two high temperature relaxations is attributed to the presence of two spacecharge distributions in the PI bulk relaxing with different
activation energies. According to Coehlos model,33 the large
values of in PI would correspond to the formation of two
capacitance layers with respectively a Debye length LD
around 32% of the PI thickness for the relaxation and 5%
for the * relaxation.
Using the results of Fig. 1b, frequency and temperature
dependence of the ac conductivity ac = 0 in PI
can be obtained easily.17,30 For temperatures above 240 C,
ac is frequency independent at low frequency with the occurrence of a plateau Fig. 3. At high frequency, ac becomes linearly dependent with frequency exhibiting a slope
close to unity. The ac conductivity generally follows the
universal power law given by31

ac = dc + AN ,
1
teristic of the EP also called space-charge relaxation at the
bulk-electrode interfaces. In addition, it is possible to obwhere dc is the dc conductivity, A is a temperatureserve the f 1 dependences of and tan at low frequency
dependent parameter, and N is the exponent of the power law
from 200 C and their continuous shift toward higher fre0N 1. Above 240 C, the magnitude of the plateau region
quencies when increasing temperature. This change is asof ac corresponds to the dc conductivity for the related temcribed to the conduction phenomenon which is thermally acperature.
tivated and partially superimposed by EP see Figs. 1b,
When the temperature increases, it is possible to observe
1b, and 1c. Usually, the pure dc conduction is associthe progressive shift of the plateau region toward high freated to a frequency independence of at low frequency
quencies related to the increase of its magnitude. Such
related to an Ohmic behavior slope of 1 of .30 In Fig.
changes correspond, respectively, to the thermally activated
1a, the strong increase of at frequencies below 10 kHz
character of the ac conductivity and to the increase of the dc
represents the electrical signature of EP previously described
bulk conductivity in PI. An additional feature, which can be
by Jonscher as a consequence of the low frequency
observed at very high temperature and low frequency, apThis article is copyrighted
as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
dispersion.31
pears as a slight decrease of ac for frequencies below the
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122913-3

Appl. Phys. Lett. 91, 122913 2007

Diaham, Locatelli, and Lebey

FIG. 3. Frequency dependence of the ac conductivity ac in polyimide between 240 and 400 C.

plateau region. This decrease is ascribed to EP occurrence

which is also thermally activated and tends to superimpose to
dc.17
Figure 4 shows the evolution of dc vs temperature
which exhibits an Arrhenius-like behavior given by the following relation:

In summary, conductivity spectroscopy in PI films using

MIMS has been investigated by DRS in very high temperature up to 400 C. This represents a great theoretical and
experimental interest as an alternative method of classical
conduction current experiments under static polarization. In
the very high temperature range, the dc conductivity dc of
the material appears as partly masked by interfacial phenomena such as EP and is therefore rather difficult to extract.
Indeed, the building up of space-charge capacitor layers in
the vicinity of the bulk-electrode interfaces and its frequency
relaxation leads to an increase in the real part of the dielectric complex permittivity in PI at LF/HT of more than one
decade. Such a huge increase is due to the small thickness of
charge density distributions of space-charge capacitor layers
which confers a strong capacitance value to PI MIMS at low
frequency. However, by plotting the temperature dependence
of the ac conductivity, approximate values of dc in PI have
been extracted. An Arrhenius-like behavior of dc has been
brought to light up to 400 C with values reaching
106 1 m1 at 400 C.

R. Kirschman, High-Temperature Electronics IEEE, Piscataway, NJ,

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