Radiation Measurements, Vol. 25, Nos I--4, pp.

51-54, 1995
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CONDUCTIVITY OF AGED NON-OVERLAPPING AND

OVERLAPPING TRACKS IN ION IRRADIATED POLYIMIDE

D. FINK,* HUANWEN HU,*t R. KLETF,* M. MULLER,* J. ZHU,:~ CHANGLIN LI,§

YONME SUN,§ FENG MA and LIHONG WANG I

*Hahn-Meituer-Institute, Glienicker StraBe 100, 14109 Berlin, Germany;

tChinese Institute of Atomic Energy, P.O. Box 275, Beijing, China;
~:Shanghai Applied Radiation Institute, Shanghai University of Science and Technology,
Shanghai 201800, China;
§Institute of Modem Physics, Academia Sinica, No. 253 Nanchang Road, Lanzhou, China;
and
I Gesellschaft fur Schwerionenforschung, Planckstral3e 1, D-64291 Darmstadt, Germany

ABSTRACT

N o n - o v e r l a p p i n g as well as overlapping tracks of energtic ions

have been introduced into polyimide foils. After aging their
c o n d u c t i v i t y was measured. This - to our knowledge - first
systematic study shows that conductivity does not only result
from m u l t i p l e track overlapping, but can be found already in
single ion tracks. This conductivity is shown to be p r i m a r i l y a
c o n s e q u e n c e of electronic energy transfer. The c o n d u c t i v i t y of
single ion tracks is higher than that of typical insulators, but
still orders of magnitude lower than that of typical semiconduc-
tors. The conductivity is independent of the applied electric
field strength until at excessive voltages the electric current
increases nonlinearly up to complete breakthrough. The total
conductivity of an irradiated polyimide foil increases
p r o p o r t i o n a l l y with ion fluence for large ion track spacings,
and approaches saturation when the electronically active track
regimes begin to overlap. Above some thousand times track
o v e r l a p p i n g however, new chemical and structural changes in the
irradiated material lead to another strong increase in conducti-
vity.

KEYWORDS

Conductivity, nuclear tracks, polyimide, electronic energy

transfer, track radius

51
52 D. FINK et al.

CONDUCTIVITY OF SINGLE NUCLEAR TRACKS

By some slight modifications of the conventional measuring

t e c h n i q u e s (conductivity measurement across thin foils along the
perpendicular tracks, large area metallic contacts), the
accessible range of conductivities could be lowered by several
orders of magnitude. Thus conductivities of single, non-
o v e r l a p p i n g ion tracks in polyimide could be d e t e r m i n a t e d for
the first time.

We have limited our studies to aged tracks, i.e. to tracks which

have been exposed to atmosphere until equilibrium oxygen uptake
was obtained (after typically a few months), as these examina-
tions are more relevant for practical applications than in-situ
track examinations which are of academic value only. It turned
out that single ion tracks exhibit a small but n o n - n e g l i g i b l e
intrinsic conductivity in the order of 10 "16 to i0 13 ohm4cm -I (Fink
et al., 1994a). This radiation induced polymeric c o n d u c t i v i t y is
constant within a large interval of the applied electric field
strength, until at excessive voltages the electric current
increases n o n l i n e a r l y up to complete breakthrough.

The c o n d u c t i v i t y of a polymer with single n o n - o v e r l a p p i n g tracks

is anisotropic, insofar as it is high along the track d i r e c t i o n
and very low perpendicularly to the tracks. The m a g n i t u d e of
conductivity along the tracks is proportional to the local
electronic energy transfer, which implies that the c o n d u c t i v i t y
of single ion tracks is a consequence of electronic rather than
of collisional projectile/target interaction.

CONDUCTIVITY OF OVERLAPPING TRACKS

When the ion tracks start overlapping, the polymer c o n d u c t i v i t y

comes to saturation. From the corresponding ion fluences one can
estimate the radius of the conducting zones: 80 ~ for tracks of
low energy light ions (e.g. 2 MeV He+), and 180 ~ for tracks of
high energy heavy ions (e.g. 0.5 GeV In+). Thus the size of
c o n d u c t i n g zones along single ion tracks roughly coincides with
the size of the chemically modified regime.

For o v e r l a p p i n g ion tracks the overall polymeric c o n d u c t i v i t y

becomes isotropic. Its value remains unchanged with further
increase of the fluence up to about i000 times track
overlapping. At higher fluences ~ the conductivity a increases
proportional to #(8±i), until the conductivity of graphite is
nearly reached. Figure i shows that the conductivity scales
r e a s o n a b l y with the transferred electronic energy density (i.e.
fluence ~ x electronic energy loss Se) over many orders of
magnitude. A slightly better correlation is achieved by scaling
with ~ x Sex (i < x ~ 2), for a yet unknown reason.
The strong increase in conductivity of 103 to 105 times overlap-
ping tracks in polyimide by some 15 orders of m a g n i t u d e is
achieved within 2 orders of magnitude in fluence only. This
d r a m a t i c effect has been explained since long by hopping of
electrons between hypothetic nanoscopic conducting regions in an
else insulating matrix, the average distance of these conducting
clusters d i m i n i s h i n g with increasing ion fluence.
 TRACK CONDUCTIVITY 53

1015 _ 1013

I0 Iz _ 10 Io

10 9 _ 10 "l
7
E 10 6 _10 ~.
"T
1o 3 _101 .-..
- 10 "z 'E
>.- 10 0 4. 4, ÷ ~.
4./'÷~
~-- 10-3 - 10 -s 7
> e° ~ • ÷
10 -6 _ lO-e .-~
L_I

10-9 _10-11
C3
z 10_1Z _ 10 -1~.
CD
L.2

I0-1s Q _ 10-r7

10-1e I I I I I I I I I =- 10 -z°
10 -6 10 -s 10 -~, 10-3 10 -z 10 -1 10 0 101 10 z 10 3 10 ~,
DOSExENERI3Y LOSS [eV//~ 3]

Fig. i. Conductivity of ion irradiated p o l y i m i d e

as a function of the total t r a n s f e r r e d
electronic energy density (= ~ x S~). a)
Regime of single (i.e. non-overlapping)
ion track conductivity, b) regime of
saturation conductivity, c) regime of
strong conductivity increase, d) regime
of graphite-like conductivity. The
crosses denote our new high fluence
measurements, points refer to earlier
representative results from literature,
and the dashed zone limits the region
along which our new measured low fluence
data distribute.

CLUSTERS

In fact, the existence of these clusters could be verified by us

(Fink et al., 1990). Two cluster populations have been found
meanwhile. The size of the smaller ones is in the order of some
5 to 50 ~, depending on the examined system and the m e a s u r i n g
technique (SANS, SAXS, UV-Vis Spectroscopy). Both the SANS and
SAXS signals suggest that these conducting clusters are enriched
in carbon, in comparison with the surrounding matrix. An
u n a m b i g u o u s identification of the material of these c o n d u c t i n g
clusters has not yet been achieved. Recently we found hints that
they might consist of polybenzoids and/or polyquinoids, among
other matter rich in double bonds (Cardoso et al., 1994). The
large clusters, with sizes exceeding some i000 ~, appear to have
a fractal nature with sharp borders. Possibly they stem from
a g g l o m e r a t i o n of the smaller cluster population.

Our recent studies concerning the dependence of carbonaceous

cluster growth on the mean transferred electronic energy density
54 D. FINK et al.

(Fink et al., 1994b) have revealed that this cluster growth sets
in above a threshold of 10 .2 eV/~ 3. A comparison with Fig. l shows
that, as a consequence, the electronic hopping model of conduc-
tivity is not applicable to the conductivity of single ion
tracks - except for those stemming from GeV heavy ions -, as we
can u s u a l l y rule out the formation of clusters at these low
energy densities. We speculate that in this case, c o n d u c t i v i t y
stems from incorporated oxidized polymer destruction products.

CONCLUSIONS

Hitherto it was anticipated that conductivity of irradiated

polymers is exclusively a consequence of multiple ion track
overlapping. This work shows that also single, n o n - o v e r l a p p i n g
aged ion tracks exhibits some - though weak - conductivity. This
single ion track conductivity is a consequence of electronic
energy transfer and concentrates along the nuclear track core,
w i t h i n a radius between 80 and 180 ~. It is independent on the
ion track density as long as the tracks do not yet overlap.
Polymeric conductivity remains unchanged up to about i000 times
ion track overlapping. Only at higher degrees of overlapping,
the p o l y m e r i c conductivity increases dramatically due to strong
chemical and structural changes, until a graphite-like material
has been obtained.

The structural changes refer to the formation of carbonaceous

clusters. Two such cluster populations have been identified - a
small one of 5 to 50 ~ radius, which is probably p r o d u c e d within
the ion tracks, and a large one with dimensions exceeding i000
~, which might be interpreted as an agglomeration of smaller
ones. Though the emerging polymeric conductivity after high
fluence irradiation can be explained by the formation of these
clusters, they hardly can be made responsible for single ion
track conductivity.

REFERENCES

Cardoso, J., R. Montiel and H. Vazquez (1994). Personal

communication; to be published.
Fink,D., K. Ibel, P. Goppelt, J.P. Biersack, L. Wang and M.
Behar (1990). Ion beam induced carbon clusters in polymers.
Nucl. Instr. Meth. B46 342-346.
Fink, D. and R. Klett (1994a). Conductivity of single ion tracks
in polymers. Radiat. Elf. Def. Solids 25, 27-30.
Fink, D., W.H. Chung, R. Klett, A. Schmoldt, J. Cardoso, R.
Montiel, H. Vazquez, L. Wang, F. Hosoi, H. Omichi and P.
G o p p e l t - L a n g e r (1994b). Carbonaceous clusters in irradiated
p o l y m e r s as revealed by UV-Vis spectrometry, submitted to
Radiat. Elf. Def. Solids.