Vacuum 69 (2003) 113118

Transport properties of selenium implanted polymer

composites
K. Krezhov
a,
*, K. Velitchkova
b
, S. Balabanov
c
a
Institute for Nuclear Physics and Nuclear Energy, Bulgarian Academy of Sciences, 72 Tzarigradsko Chauss! ee, BG-1784 Soa, Bulgaria
b
University of Mining and Geology, Darvenitsa, BG-1700, Soa, Bulgaria
c
Institute of Solid State Physics, 72 Tzarigradsko Chauss! ee, BG-1784 Soa, Bulgaria
Received 15 March 2002; received in revised form 1 April 2002
Abstract
Results on the temperature dependence of DC surface conductivity, s
S
; and currentvoltage characteristics for
polypropylene (PP), polymethylmetacrylate (PMMA) and Bi
12
SiO
20
lled ultra high molecular weight polyethylene
(UHMWPE) implanted by 90 keV Se ions at doses D
1
2:5 10
16
Se
+
cm
2
, D
2
7:5 10
16
Se
+
cm
2
, and D
3

1:5 10
17
Se
+
cm
2
are reported. The possible structures contributing to s
S
are addressed.
r 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Electron transport; Polymer; Polymer composites; Ion implantation; Clusters
1. Introduction
Ion implantation techniques have proved long
ago to be particularly valuable for modication of
material surface properties, especially the electrical
ones [1]. There is strong evidence that carbon
clusters that were formed via the ion implantation
into organic or element-organic polymers are
responsible for enhancement of the DC surface
electrical conductivity, s
S
[25].
Like carbon and silicon, selenium is also known
as a structuring element. It is expected that
implantation of Se into an insulating polymer
matrix such as the widely used ultra high
molecular weight polyethylene (UHMWPE), poly-
methylmetacrylate (PMMA), polypropylene (PP),
would affect the electrical and optical properties.
We report here results on the carrier transport
after Se implantation of these materials.
2. Experimental details
Two polymeric matrices, namely PP and
PMMA, and the polyethylene composite
(PEC)UHMWPE with 8 vol% ller were inves-
tigated. The samples were 2-mm thick disks with a
diameter of 15 mm. The PEC ller was milled
Bi
12
SiO
20
grown as single crystal [6].
Room temperature implantation of 90 keV
energy Se
+
ions (ILU-4 accelerator) was carried
out at implantation doses (D
Se
; Se
+
cm
2
): D
1

2:5 10
16
; D
2
7:5 10
16
and D
3
1:5 10
17
:
The ion projections, R
p
; of 83, 97 and 148 nm, and
*Corresponding author. Tel.: +359-2-743-1616; fax: +359-
2-975-3619.
E-mail address: krezhov@inrne.bas.bg (K. Krezhov).
0042-207X/03/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 2 - 2 0 7 X( 0 2 ) 0 0 3 1 7 - 2
straggling, DR
p
; of 17.5, 17 and 66 nm, for
PMMA, PP and PEC, respectively, were calcu-
lated using TRIM specialised software [7].
Two gold electrodes spaced 5 mm apart were
vacuum deposited on the implanted sample side.
Electrical measurements were performed by a
Terralin III electrometer. Temperature depen-
dences of s
S
were taken at 500 V bias voltage.
Currentvoltage characteristics were taken at
1051C and 451C called below high (HT) and
low (LT) temperature, respectively, and at
temperatures between them.
3. Results
Se
+
implantation caused a considerable increase
in s
S
: Depending on the Se
+
dose, temperature
range and polymer matrix itself the temperature
behaviour of s
S
was described by different models:
s
S
BT
m
; 1
s
S
s
0
exp
E
a
kT

; 2
s
S
A exp
T
0
T

1=n
; 3
s
S
C expaT: 4
Here s
0
; A; B and C are constants and E
a
is the
activation energy. T
m
(Eq. (1)) and expT
1=n

with n 124; (Eqs. (2) and (3)) describe different

known charge transport mechanisms [8,9]. The
expT
1
(Eq. (4)) law connected with an unspeci-
ed transport mechanism [3] was also valid for
some cases in a particular temperature range.
A change of slope sign is a common feature of
the curves s
S
f T; Fig. 1. Table 1 summarises
the results of least-squares analyses of the data in
terms of best w
2
which was accepted as a criterion.
The temperature activated hopping model ap-
plied only for PP to all temperature ranges and
doses, Fig. 1a. The activation energy, E
a
; and the
pre-exponential factor, s
0
; for the range 40851C
went through a minimum at D
2
: At D
2
another
interval could be separated also in the LT range
(50401C) with E
a
of about the same magnitude as
for D
1
and D
3
; and s
S
reaching its maximum of
0.128 O
1
cm
1
. The IV characteristics at both
HT and LT were tted by power functions, IBE
g
;
Fig. 1d. Dependence on applied electrical eld, E;
at LT was found only for D
1
; but at HT it took
place also for D
2
: The power exponent, g; was
between 1.2 and 1.53 and became higher (g 3:78)
only in the HT range of IV characteristics at D
1
:
With increasing Se amount g changed slightly for
the LT characteristics, its increase was higher for
the HT ones at higher E; Table 1. The magnitude
of g at low E was decreasing as with increase of
doses so with lowering of temperature.
For PEC the increase of s
S
with rising Se
content was most pronounced. Substantially dif-
ferent temperature behaviour depending solely on
ion dose was observed, Fig. 1b. The slope of s
S

f T at D
1
was positive in the HT range, then it
changed sign at 751C and s
S
BexpT
1
tted best
with E
a
0:122 eV and s
0
3:1 10
3
O
1
cm
1
.
The higher Se amount (D
2
) caused an s
S
rise
exceeding an order of magnitude. A change of
slope sign occurred at 651C, and s
S
BexpT
1

tted best. For D

3
s
S
reached the highest values.
No temperature dependence of s
S
was found for
D
3
in the range 115951C, but with T decreasing
to 401C s
S
went gradually down obeying
s
S
BexpT
1=2
: The power exponent g to the I
V characteristics, Fig. 1e, was in the range 1.22
1.36. Its value was almost independent of T; and
slightly decreased with increasing dose. Only for
LT IV characteristics at D
3
an electrical eld
dependence, characterised by a sublinear increase
of the current at low E; was observed but then it
Fig. 1. Charge transport in Se implanted polymer materials (a, d)PP, (b, e)Bi
12
SiO
20
lled UHMWPE (PEC), and (c, f)PMMA
at ion doses: K D
1
2:5 10
16
Se
+
cm
2
, ~ D
2
7:5 10
16
Se
+
cm
2
, m D
3
1:5 10
17
Se
+
cm
2
: (rightd, e, f): IA
characteristics at high (solid line) and low (dashed line) temperature; (lefta, b, c): DC temperature dependence of conductivity, s
S
:
The abscissa scale refers to the activation behaviour. The relationships describing the different behaviour of s
S
; in particular
temperature ranges (see text) are given in the legend to the panels and the lines are drawn just to guide the eye through the range of
relevant relationship applicability.
K. Krezhov et al. / Vacuum 69 (2003) 113118 114
2.6 2.8 3.0 3.2
1E-5
1E-4
1E-3
1E-2
(c)

s
= B.T
m

s
= C.exp(a.T)

s
=
0
.exp(-E
a
/ kT)
100 1000
1E-8
1E-7
1E-6
1E-5
1E-4
(f
2.6 2.8 3.0 3.2
1E-5
1E-4
1E-3
1E-2

s

[

1
c
m

1
]
(a)

s
=
0
.exp(-E
a
/ kT)
100 1000
1E-9
1E-8
1E-7
1E-6
1E-5
1E-4
I
,

[
A
]
(d)
2.6 2.8 3.0 3.2
1E-5
1E-4
1E-3
1E-2
(b)

s
=
0
.exp(-E
a
/ kT)

s
= C.exp(a.T)

s
=A.exp(-T
0
/ T)
1/2
100 1000
1E-9
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3
(e)
1000/ T, [K
1
]
E, [V.cm
1
]

s

[

1
c
m

1
]

s

[

1
c
m

1
]
I
,

[
A
]
I
,

[
A
]
)
K. Krezhov et al. / Vacuum 69 (2003) 113118 115
T
a
b
l
e
1
C
o
n
d
u
c
t
i
v
i
t
y
v
e
r
s
u
s
t
e
m
p
e
r
a
t
u
r
e
:

t
t
e
d
r
e
l
a
t
i
o
n
s
h
i
p
s
a
n
d
r
e
l
e
v
a
n
t
p
a
r
a
m
e
t
e
r
s
M
a
t
r
i
x
B
i
1
2
S
i
O
2
0

l
l
e
d
U
H
M
W
P
E
P
P
P
M
M
A
I
o
n
d
o
s
e
,
S
e
+
(
c
m

2
)
s
0
(
O

1
c
m

1
)
E
a
(
e
V
)
g
I

A
s
0
(
O

1
c
m

1
)
E
a
(
e
V
)
g
I

A
s
0
(
O

1
c
m

1
)
E
a
(
e
V
)
g
I

A
H
T
L
T
H
T
L
T
H
T
L
T
H
T
L
T
H
T
L
T
H
T
L
T
0
.
0
0
8
H
T
7
0
.
0
0
2
0
.
1
3
5
H
T
7
0
.
0
0
6
2
.
5

1
0
1
6
0
.
0
0
3
1
L
T
7
0
.
0
0
0
6
0
.
1
2
2
L
T
7
0
.
0
0
6
1
.
3
6
1
.
3
5
1
.
9
7

1
0

7
6
.
8
1

1
0

7
0
.
0
3
8
7
0
.
0
0
6
0
.
1
4
0
7
0
.
0
0
5
3
.
7
8
D

1
.
2
1
*
1
.
3
4
D

1
.
2
5
*
5
.
0
3

1
0

7
5
.
7
6

1
0

7
s
S
B
e
x
p

;
H
T
1
.
0
4
1
.
3
0
D

1
.
0
2
*
3
.
4
0

1
0

6
1
.
3
1

1
0

6
(
0
.
0
9
2
L
T
7
0
.
0
1
7
)
(
0
.
1
3
8
L
T
7
0
.
0
0
5
)
s
S
B
e
x
p

T
2
1

s
S
B
e
x
p

T
2
1

s
S
B
e
x
p

;
L
T
0
.
0
0
3
8
M
T
0
.
0
0
M
T
(
0
.
0
1
1
H
T
7
0
.
0
0
1
)
;
(
0
.
1
6
2
H
T
7
0
.
0
0
2
)
s
S
B
T
m
;
H
T
7
.
5

1
0
1
6
(
0
.
0
9
1
7
0
.
0
3
8
)
(
0
.
1
1
3
7
0
.
0
1
2
)
1
.
3
4
1
.
3
2
4
.
6
4

1
0

6
2
.
8
1

1
0

5
0
.
1
2
8
L
T
7
0
.
0
4
2
0
.
0
9
8
L
T
7
0
.
0
0
9
1
.
0
6
D

1
.
2
7
*
1
.
2
2
1
.
1
2

1
0

5
3
.
1
0

1
0

5
m

5
:
1
9
7
0
:
0
4
1
.
1
1
1
.
2
0
1
.
6
0

1
0

6
6
.
3
4

1
0

7
0
.
0
2
0
L
T
7
0
.
0
0
2
0
.
1
4
9
L
T
7
0
.
0
0
3
s
S
B
e
x
p

s
S
B
e
x
p

s
S
B
e
x
p

;
L
T
1
.
5

1
0
1
7
(
0
.
2
5
8
7
0
.
0
1
9
)
(
0
.
1
2
2
7
0
.
0
0
2
)
1
.
2
3
0
.
8
3
D

1
.
2
2
*
1
.
1
8

1
0

4
6
.
4
3

1
0

5
0
.
1
2
2
7
0
.
0
2
4
0
.
1
1
2
7
0
.
0
0
5
1
.
5
3
1
.
2
3
8
.
7
5

1
0

6
1
.
7
4

1
0

5
0
.
0
3
8
7
0
.
0
0
1
0
.
1
0
9
7
0
.
0
0
1
3
.
8
2
D

1
.
3
6
*
1
.
0
4
D

1
.
2
9
*
3
.
4
0

1
0

5
1
.
5
2

1
0

5
s
S
B
e
x
p

1
=
2

s
S
B
e
x
p

s
S
B
e
x
p

F
o
r
c
o
m
p
a
r
i
s
o
n
t
h
e
v
a
l
u
e
s
o
f
s
0
a
n
d
E
a
c
a
l
c
u
l
a
t
e
d
a
s
s
u
m
i
n
g
t
h
e
r
m
a
l
a
c
t
i
v
a
t
i
o
n
h
o
p
p
i
n
g
t
r
a
n
s
p
o
r
t
i
n
t
h
e
r
e
s
p
e
c
t
i
v
e
t
e
m
p
e
r
a
t
u
r
e
r
a
n
g
e
s
a
r
e
a
l
s
o
g
i
v
e
n
(
i
n
p
a
r
e
n
t
h
e
s
i
s
)
.
T
h
e
s
u
b
s
c
r
i
p
t
H
T
,
M
T
,
L
T
i
s
u
s
e
d
f
o
r
h
i
g
h
,
m
e
d
i
u
m
,
a
n
d
l
o
w
t
e
m
p
e
r
a
t
u
r
e
,
r
e
s
p
e
c
t
i
v
e
l
y
,
a
n
d
s
u
p
e
r
s
c
r
i
p
t
s
D
,
*
c
o
r
r
e
s
p
o
n
d
t
o
l
o
w
a
n
d
h
i
g
h
e
l
e
c
t
r
i
c
a
l

e
l
d
i
n
t
e
n
s
i
t
y
,
r
e
s
p
e
c
t
i
v
e
l
y
.
K. Krezhov et al. / Vacuum 69 (2003) 113118 116
had the same form at high E as that at HT,
Table 1.
In contrast, different mechanisms specic for a
given ion dose and a particular temperature range
seemed to govern s
S
f T of implanted PMMA,
Fig. 1c. At 701001C for D
1
; 40501C for D
2
; and
401001C for D
3
s
S
BexpT
1
tted the data. At
115601C for D
2
the best t was s
S
BT
m
as
found for amorphous carbon lms [8]. However,
for PMMA the power exponent, m 5:19; was
more than 3 times smaller than that for a-C:H
lms. For D
1
at 40651C s
S
BexpT
1
applied.
Prawer et al. [3] found for quartz implanted by
100 keV C
+
such a specic law the reason for
which is still not clear. Another peculiarity of
implanted PMMA is the jump in s
S
f T: It was
by about an order of magnitude for D
1
at 701C,
and by a factor of 2 for D
2
at 601C. Fig. 1c
illustrates that at 1151001C s
S
remained tem-
perature independent for D
1
and D
3
: As Table 1
shows the power exponent of the HT IV curve,
Fig. 1f, increased with dose. An electrical eld
dependence in this temperature range was found
only at D
3
; for which g at low E was 2.5 times
higher than g at high E: The electrical eld
intensity affected more strongly the LT IV
characteristics: at low Eg increased for D
1
and
decreased for D
3
:
4. Discussion
A reasonable explanation of the results can be
related to the ion implantation mechanisms. Se
ions come to and rest within the supercial region
wherein chain-like formations are seemingly built
due to the structuring ability of Se. On the other
hand, ion implantation in polymers is known to
cause segregation of knocked C atoms into clusters
[24,1012]. With increasing ion energy deposition
it evolution from chain structure through three-
dimensional carbon sp
3
network to amorphous
carbonaceous material was observed [11]. At some
stage, depending on the polymer matrix and
implantation conditions, the carbon cluster size
reaches saturation in its growth [13]. The increased
ion dose would lead then to an increasing
concentration of such clusters.
For D
Se
higher than D
1
s
S
of the three
implanted materials was spread over less than 3
orders of magnitude, 1 10
5
6 10
3
O
1
cm
1
,
which implies that the changes in the polymer
structure were already not so drastic and the
structures responsible for charge transport were
essentially formed. The conductivity supposedly
comes from the superposition of two mechanisms:
along Se chainstypical p-type [9] thermal activa-
tion conductivity and hopping conduction be-
tween conducting carbon grains (p-type below
1001C and n-type above 1001C [14]). The prevail-
ing contribution of the relevant mechanism should
determine the actual functional dependence ob-
served. The peculiar s
S
BexpT
1
and s
S
BT
m
relations might result from a comparable con-
tribution of both structures. Also, the extent of
macromolecule polarity of the polymer matrices is
seemingly reected by the specic effect of the
electrical eld as can be followed from the
behaviour of g from PEC through PP to PMMA.
This picture nds support from the evidence on
the inuence of the polymer matrix and on Se
content shown in Table 1.
For D
1
the conductivity exhibits thermal activa-
tion behaviour for all materials except PMMA at
low temperature, 60401C, where both mechan-
isms should operate. Assuming thermal activation
hopping one nds that E
a
to increases from the
densest PEC containing linear UHMWPE to the
branched PMMA and PP, with E
a
highest for PP.
PMMA and PP have shorter chains, more defects
and their molecules are more or less polar. The
pre-exponential factor s
0
does not change sig-
nicantly, but for PP it is maximum. Electrical
eld inuence is found prominent for polar
polymers. The power exponent, g; decreases from
PEC through PP to PMMA, and at LT and for a
weak eld g does not depend on polymer type. The
HT g for PP is an exception being more than 2
times higher than respective g for the other
materials. This fact reects the dependence of E
a
on polymer type.
Increased Se content (D
2
) in PP preserves the
transport mechanism but in PEC involves a second
kind of transport in all temperature ranges.
Concurrent action of both mechanisms is observed
for PMMA at LT, whereas at HT the major
K. Krezhov et al. / Vacuum 69 (2003) 113118 117
mechanism should be thermal activation hopping.
One nds that s
0
is maximum for PEC and
minimum for PMMA and this fact might be
associated with the polarity of different polymer
molecules, which probably affects the charge
mobility. E
a
is highest for PMMA, which is
consistent with the lowest DC current values at
both HT and LT. There is a eld effect for HT IV
characteristics only in the case of PP.
At the highest dose (D
3
) PP and PMMA showed
thermal activation transport (assumed to occur
predominantly along Se chains), while in PEC the
mechanism described by grain models should
prevail. The behaviour of s
0
is similar to that at
D
2
; but E
a
is minimum for PEC and maximum for
PMMA. Dependence of IA characteristics on the
electrical eld occurs for PMMA at both LT
and HT, for PEC only at LT, and there is not any
for PP.
5. Conclusion
Se implantation in different kinds of insulating
polymer material such as PP, PMMA, and PEC
was found to enhance drastically the DC con-
ductivity. Depending on temperature and polymer
molecule polarity an electrical eld dependence
was observed to take place predominantly for
polar polymers. The currentvoltage characteris-
tics are well described by a power law with power
exponent exceeding unity. The dependence of the
latter on polymer type, ion dose and temperature
was determined.
It is suggested that the charge transport
peculiarities are related to charge carrier transition
along selenium chains and/or between carbon
clusters, formed during the ion implantation
process. The s
S
BexpT
1
relationship was valid
in a particular temperature range and might be
associated with the competing contribution of
both conduction mechanisms: thermal hopping
along Se chains and hopping charge transport
between conducting carbon grains embedded in
the insulating material.
References
[1] Proceedings of the Fourth International Conference on
Radiation Effects in Insulators. Lyon, France 1987, Nucl
Instrum Methods B 1988; 32.
[2] Lee YS, Kim KW, Choi SC, Hong CE, Choi IS, Jeong K,
Whang CN. Nucl Instrum Methods B 1994;94:6672.
[3] Prawer S, Hoffman A, Petravic M, Kalish R. J Appl Phys
1993;73:38415.
[4] Velitchkova K, Krezhov K, Balabanov S. Vacuum
2000;58:5315.
[5] Iizuka M, Kuniyoshi S, Kudo K, Tanaka K. Nucl Instrum
Methods B 1993;80/81:10725.
[6] Gospodinov M. Dr Sci thesis, Institute of Solid State
Physics, Bulgarian Academy of Sciences, 2000.
[7] Ziegler JF, Biersack JP, Littmark U. The stopping and
range of ions in solids, 2nd ed. New York: Pergamon
Press, 1996.
[8] Shimakawa K, Miyake K. Phys Rev B 1989;39:757884.
[9] Mott NF, Davis EA. Electron processes in non-crystalline
materials, 2nd ed. Oxford: Claredon Press, 1979 [in
Russian: Moscow: Mir, 1982].
[10] Fink D, Ibel K, Goppelt P, Biersack JP, Wang L, Behar
M. Nucl Instrum Methods B 1990;46:3426.
[11] Calgano L, Compagnini G, Foti G. Nucl Instrum Methods
B 1992;65:41322.
[12] Pivin JC, Sendova-Vassileva M. Solid State Commun
1998;106:1338.
[13] Foti G, Reitano R. Nucl Instrum Methods B 1990;46:
3068.
[14] Robertson J. Adv Phys 1986;35:31774.
K. Krezhov et al. / Vacuum 69 (2003) 113118 118