SVflTHUII[

llg|TRLS
ELSEVIER Synthetic Metals 65 (1994) 167-171

Tuning through the critical regime of the metal-insulator

transition in conducting polymers by pressure and magnetic field
M. Reghu, K. Vakiparta 1, C.O. Yoon, Y. Cao 2, D. Moses, A.J. Heeger
Institute for Polymers and Organic Solids, University of California at Santa Barbara, Santa Barbara, CA 93106, USA
Received 4 November 1993; accepted 27 January 1994

Abstract

In the critical regime of the disorder-induced metal-insulator ( M - I ) transition, the temperature dependence of conductivity
follows a power law, or(T)ot T °, and the reduced activation energy function, W = - T { A ( I n p)/AT}, is temperature independent
(W=/3). We have observed transport in the critical regime for four conducting polymer systems: potassium-doped polyacetylene
(K-(CH)~), iodine-doped polyacetylene (I-(CH)~), phosphorous hexafluoride-doped polypyrrole (PPy-PF6) and camphor sulfonic
acid-doped polyaniline (PANI--CSA). For oriented polyacetylene doped with either potassium or iodine and for PPy-PF6, W
is temperature independent over a wide temperature range at ambient pressure; while, at high pressures (8-10 kbar), W has
a positive temperature coefficient, indicating a pressure-induced crossover to the metallic regime. The enhanced interchain
transport at high pressures causes the crossover from the critical regime to metallic behaviour. Application of a magnetic
field (8 T) leads to a negative temperature coefficient of W for K-(CH)x, PPy-PF6 and PANI-CSA, indicating a crossover
from the critical regime to the insulating regime. Magnetic field-induced localization causes the crossover from the critical
regime to insulating behavior. Thus, the electrical properties of conducting polymers can be tuned through the disorder-
induced critical regime of the M-I transition into the metallic or insulating regimes by pressure and magnetic field, respectively.

Keywords: Metal-insulator transition; Magnetic field; Pressure

I. Introduction The electrical conductivity is, however, particularly

Although electrical conductivities of the order of 105
S/cm have been achieved in conducting polymers [1],
the intrinsic metallic transport properties have not been
determined. Since the metal-insulator (M-I) transition
in heavily doped conducting polymers is caused by
disorder-induced localization, improvements in struc-
tural order are critically important for achieving high
performance electrical (and mechanical) properties [2].
The quasi-linear temperature dependence of the ther-
mopower and the temperature-independent Pauli sus-
ceptibility observed in a number of conducting polymers
are indicative of an electronic structure with a finite
density of states at the Fermi level, like that of a metal
[3].
1Present address: Corporate R&D, Neste OY, POB 310, SF-06101
Porvoo, Finland.
2Present address: UNIAX Corporation, 5375 Overpass Road, Santa
Barbara, CA 93111, USA.
sensitive to microscopic disorder. Disorder is an inherent
feature of polymeric systems which are typically only
partially crystalline and which often exhibit complex
morphologies. The extent of disorder in conducting
polymers can be controlled to some degree by details
of sample preparation and processing [2]. Moreover,
order can be enhanced by tensile drawing to achieve
chain extension, chain orientation and interchain order
[2]. However, the disorder introduced during the doping
process can be substantial [4,5].
For a three-dimensional conductor very close to the
disorder-induced M - I transition, the correlation length
(Lc) is large and has a power law dependence on
6=[(Ev-Ec)/Ec]<I, Lc=a8 -1/~, where a is a micro-
scopic length, ~7 is the critical exponent, EF is the Fermi
energy and E¢ is the mobility edge. In this critical
region, Larkin and Khmelnitskii [6] found that the
resistivity follows a power law as a function of tem-
perature:

0379-6779/94/$07.00 © 1994 Elsevier Science S.A. All rights reserved

SSDI 0379-6779(94)02152-0
168 M. Reghu et al. / Synthetic Metals 65 (1994) 167-171
p(T) = (eZpv/hZ)(kB T/EF)- '/~ (1)
where PF is the Fermi momentum, e is the electron
charge and 1 < r/< 3. This power law is universal and
requires only that the disordered system be close to
the M-I transition, i.e., in the critical region where
6 << 1. A value of r/> 3 indicates that the system is just
entering into the metallic side of the M-I transition
from the critical regime. Although r/> 3 is above the
theoretical limit for the power law dependence, values
for r/ as large as 4.5 have been reported for n-doped
germanium in the critical regime of M-I transition [7].
The critical regime can be identified from the tem-
perature dependence of the reduced activation energy
function W(T) [7]:
W(T) = - T{A(ln p)/AT} (2)
In the critical regime, W is temperature independent
(see Eq. (1)); W=/3 [7,8]. The critical regime has been
studied in detail for PANI-CSA [8].
In previous studies of inorganic semiconductors, the
critical behavior near the M-I transition was observed
by tuning the interaction length by magnetic field and
the critical carrier density by uniaxial pressure [9,10].
In 'soft', anisotropic, doped conducting polymers with
relatively weak interchain interactions, the critical be-
havior near the M-I transition can be controlled by
tuning the interchain overlap of the ~--electron wave-
functions centered on polyconjugated chains by applying
high pressure and by tuning the position of the mobility
edge with respect to the Fermi energy by applying a
high magnetic field [8].
We summarize and compare the results of mea-
surements of the temperature dependence of the elec-
trical conductivity of four different heavily doped con-
ducting polymers: oriented polyacetylene doped p-type
with iodine (I-(CH)x), oriented polyacetylene doped n-
type with potassium (K-(CH)x), polypyrrole doped with
PF6 (PPy-PF6) and polyaniline doped with camphor
sulfonic acid (PANI-CSA). In order to probe more
deeply into the transition, we have investigated the
effects of high pressure and high magnetic fields on
the temperature dependence of conductivity. For each
of the four conducting polymers studied, the temper-
ature dependence of the resistivity (p) exhibits a power
law temperature dependence, p(T)czT -t~ (and W=/3)
over a significant temperature range [11]. We have
found that crossover from the critical regime to the
metallic or to the insulating regimes can be induced
by pressure and magnetic field, respectively.
2. Experimental
The details of the sample preparations of (CH)x and
PANI-CSA have been described in previous publica-
tions [8,11]. The conducting PPy films were prepared
by in situ electrochemical polymerization and simul-
taneous doping with P F 6 at - 40 °C in an electrochemical
cell [12].
High pressure conductivity measurements were car-
ried out in self-clamped beryllium--copper pressure cell
[11,13,14]. After pressurizing, the cell was clamped at
room temperature and then cooled to 1.2 K in a cryostat
containing a superconducting magnet (0-10 T). High-
purity hexane or 3M Fluorinet T M (3M Co.) was used
as the pressure-transmitting medium [11]. Four-probe
d.c. conductivity and magnetoresistance (MR) mea-
surements were carried out by using a computer-con-
trolled data acquisition system [8]. The temperature
was measured with a calibrated platinum resister (300
to 40 K) and a calibrated carbon-glass resister (40 to
1.2 I,:).
At least three samples were measured for each of
the four systems; all aspects of the data (for example,
magnetic field dependence and pressure dependence,
etc.) were reproducible from sample to sample.
3. Results and discussion
The room temperature conductivities (trR.r) of ori-
ented I-(CH)x and K-(CH)x in the direction parallel
to the chain axis are approximately 12 000 and 4000
S/cm, respectively [11,15]. In both K-(CH)~ and I-(CH)x,
the conductivity parallel to the chain axis is much higher
than that typically found for systems near the M-I
transition. However, since the anisotropy of the con-
ductivity (parallel versus perpendicular to the draw axis,
o-,/tr±) is nearly 100, the conductivity perpendicular to
the draw axis is comparable to that of other known
systems near the M-I transition [16].
The room temperature conductivity of K-(CH)x in-
creases from approximately 4000 S/cm at ambient pres-
sure to 8000 S/cm at 10 kbar [11]. The resistivity ratios
( P r = p(1.3K)/p(300 K)) for K-(CH)~ at ambient pressure
and 10 kbar are approximately 25 and 9, respectively
[11]. Thus, application of high pressure causes the
system to become more nearly metallic. The critical
regime can be conveniently identified from a log-log
plot of Wversus temperature. Log-log plots of Wversus
T for K-(CH)x are shown in Fig. 1, including data
obtained at ambient pressure, data obtained at 10 kbar
(H= 0) and data obtained at H = 8 T with the sample
at ambient pressure (with magnetic field parallel to
both chain axis and current directions). The pressure
dependence of conductivity is shown in the inset of
Fig. 1.
At ambient pressure (and in zero magnetic field),
W is essentially constant from 300 to 1.2 K, indicating
that the oriented K-(CH)x samples are in the critical
regime. However, at 10 kbar, the positive temperature
coefficient of W(T) indicates that the system has crossed
 M. Reghu et al. / Synthetic Metals 65 (1994) 167-171
2 r T .
..~
.// ~6
°
P (kbar)
1 i I" o.o1
1 10 100
T (K)
Fig. 1. Log-log plots of the reduced activation energy function
W = - T{A(In p)/AT} vs. T for K-(CH)~: ( 0 ) ambient pressure, H = 0;
( • ) 10 kbar, H = 0; (11) ambient pressure, H = 8 T. The inset shows
the pressure dependence of conductivity. The lines are drawn to
guide the eye.
over into the metallic regime. Under pressure, the
enhancement of the interchain transfer integral, which
results from the increased overlap of the 7r-electron
wavefunctions centered on different chains, increases
the conductivity in both parallel and perpendicular
directions to the chain axis. The pressure-induced cross-
over from the critical regime to the metallic regime
clearly shows that charge transport perpendicular to
the chain axis is an important factor in the M-I transition
in quasi-one-dimensional conducting polymers, in agree-
ment with theoretical predictions [17].
The negative temperature coefficient of W(T) at H = 8
T (see Fig. 1) implies a magnetic field-induced crossover
from the critical regime to the insulating regime (the
large positive magnetoresistance in K-(CH)~ is consis-
tent with the presence of strong disorder [11]). The
magnetic field-induced transition from the critical re-
gime to the insulating regime in K-(CH)~ is a direct
indication of the importance of interchain transport;
an ideal one-dimensional system would not be sensitive
to the magnetic field. Although Khmelnitskii and Larkin
[18] have presented a scaling argument which indicates
that the mobility edge can be shifted with respect to
the Fermi energy by a magnetic field, there is no
detailed theory available for describing the effect of a
magnetic field on the M-I transition, particularly in a
highly anisotropic (quasi-one-dimensional) system.
The log-log plots of W versus T for I-(CH)~ for
conductivity in the direction parallel to the chain axis
are shown in Fig. 2. The pressure dependence of
conductivity is shown in the inset of Fig. 2. The room
temperature conductivities (parallel to the chain axis)
at ambient pressure ( 0 ) and at 8 kbar ( • ) are
CrRT= 11 000 and crRv-- 9300 S/cm, respectively [15]. Note
that or(P) goes through a maximum at approximately
4 kbar. Although the conductivity at 8 kbar is lower
169
. . . . . . . I . . . . . . . . i
.~ e e oo • , • oo
." "
os ~ P (~)~o
"
. . . . . . . . I . . . . . . . . I
10 100
T (K)
Fig. 2. Log-log plots of the reduced activation energy function
W = -T{A(In p)/AT} vs. T for I-(CH)x: ( 0 ) ambient pressure, H = 0,
0r ~ 3, trRr ~ 11 000 S/cm; ( • ) 8 kbar, H = 0, )Or= 2, trRT= 9500 S/cm;
(11) ambient pressure, H=O, Or=9, trRT=7000 S/cm; (A) ambient
pressure, H = 0, 0r = 17, ~RT = 3500 S/cm; ( + ) ambient pressure, H = 0,
9r=32, trRv=2450 S/cm. The inset shows the pressure dependence
of conductivity for sample (O). The lines are drawn to guide the
eye.
than that at ambient pressure, the temperature de-
pendence of conductivity is weaker (more nearly 'me-
tallic') at the highest pressures. The values of Pr for
I-(CH)x at ambient pressure ( 0 ) and 8 kbar ( • ) are
approximately 3 and 2, respectively. The conductivity
in the direction perpendicular to the chain axis is lower
by two orders of magnitude [15]. At 8 kbar, the enhanced
interchain transport has reduced the anisotropy by a
factor of about 1.6 (for example, from or, Ar± = 105 at
1 bar to ~rll/~r± =66 at 8 kbar) [15]. Over the limited
temperature range from 180 to 60 K, W(T) is tem-
perature independent at ambient pressure (O), as shown
in Fig. 2. However, as Pr is gradually increased (either
by application of a magnetic field or by using a sample
with lower room temperature conductivity) the critical
regime is extended down to temperatures below 10 K.
Finally with pr = 32, a crossover to the negative tem-
perature coefficient (insulating regime, ( + )) is observed.
At T<60 K, W(T) shows a weak positive temperature
coefficient for the samples having pr = 3 (O), indicating
that the system is close to the metallic 'boundary'. At
8 kbar ( 0 ) , for samples having p~=3, W(T) exhibits
a strong positive temperature coefficient in the tem-
perature range from 180 to 1.2 K: again, by improving
the interchain transport, it is possible to crossover into
the metallic regime. The magnetic field dependence of
the conductivity in I-(CH)x is more complex than in
K-(CH)x due to the interplay of weak localization,
electron-electron interactions and anisotropic diffusion
coefficient contributions to the magnetoconductance
I15,191.
Log-log plots of W versus T for P P y - P F 6 a r e shown
in Fig. 3. The room temperature conductivities of
170 M. Reghu et al. / Synthetic Metals 65 (1994) 167-171

. . . . . . . . n . . . . . . . . ;

1 8T
0 kbar
OT ¢ee~'°ee° °°oooe~ uaeqp°eabe~j'° eej~e' eeRelpeooemmemnoooenge .

0.1 [,-,
•.."" ~='= 150r

•*"",~-
f"
"
." ~"
,40[
I • •
- - " " " ~ 130~ • "
-., . . . . - . - o o - - - ~ 'bV...%g%o
,2.' /

00, ".;2 II
ell
l." 11o~ . . . .
0 2 4 6 8 I0 0.1
P (kb&)
0.001 ........ ' ........ '
10 100
, l a i a lull I I I I a lull
T (K)
10 100
Fig. 3. Log-log plots of the reduced activation energy function
W = - T{A(In p)/AT} vs. T for PPy-PF6: (O) ambient pressure, H = 0 , z (K)
p r ~ l l ; ( 4 ' ) 4 kbar, H = 0 , pr~2.6; ( I ) 10 kbar, H = 0 , pr~2; (A) Fig. 4. Log-log plots of the reduced activation energy function
ambient pressure, H = 8 T ( T < 4 . 2 K only). All four data sets were W = -T{A(In o)/AT} vs. T for PANI-CSA: (O) ambient pressure,
obtained with the same sample. The inset shows the pressure de- H = 0 ; (A) ambient pressure, H = 8 T. The lines are drawn to guide
pendence of conductivity. the eye.

PPy-PF6samples in the critical regime are about 100-200

S/cm; Pr varies from 4 to 12. The pressure dependence of the critical exponent (r/) in the power law temperature
of conductivity, at room temperature, is shown in the dependence of conductivity correlates with Pr; samples
inset of Fig. 3. At 4 kbar, the positive temperature with smaller (larger) Pr give smaller (larger) values of
coefficient of W(T) suggests a crossover from the critical r/. The temperature range over which the dependence
to the metallic regime; however, the change in slope is a power law is wider for samples with smaller values
below 4 K shows that it is marginally metallic. At 10 of "0 [8]. For the data in Fig. 4, Pr = 3 and r/= 3.8. The
kbar, the temperature coefficient of W(T) remains pos- power law regime extends from 1.4 to 25 K as shown
itive to 10 K; below 10 K, W actually change sign from in Fig. 4 by the temperature independence of W(T) at
positive to negative, typical of a metal (i.e., the resistivity ambient pressure.
decreases with decreasing temperature). Thus, the in- The large positive magnetoresistance for nonoriented
terplay of critical and metallic regimes can be fine- films of PPy-PF6 and PANI-CSA [8] in the critical
tuned in PPy by pressure. The negative temperature regime results from the magnetic field-induced crossover
coefficient of W(T) at 8 T (at ambient pressure), similar to the insulating regime. In both materials, the magne-
to that observed in the case of K-(CH)x, indicates the toresistance (Ap/p) is isotropic [8], i.e., for both parallel
crossover from the critical to the insulating regime. and perpendicular directions of current with respect
These aspects of the transport data on both sides of to the magnetic field. The negative temperature coef-
the critical regime of the M-I transition, depending ficient of W(T) for PANI-CSA films at 8 T field is
upon pressure and magnetic field, are typical of heavily shown in Fig. 4. This field-induced crossover into the
doped conjugated polymers.
variable range hopping regime is consistent with a field-
The log-log plots of Wversus T for PANI-CSA (non-
induced shift of the mobility edge with respect to the
oriented, cast from solution [8]) are shown in Fig. 4.
Fermi level (with the Fermi level in the region of
The room temperature conductivities of PANI-CSA
localized states), when the localization length and mag-
samples are typically 200-350 S/cm. Even though the
netic length ((hc/eH) l/z) become comparable [8]. The
room temperature conductivities and resistivity ratios
are nearly identical for PPy-PF6 and PANI-CSA, the localization length for PANI-CSA in the critical regime
detailed variation of the conductivities with temperature is 100-160/~, i.e., comparable to the magnetic length,
are different. The conductivity of PANI-CSA [8] shows which is 128/~ at H = 4 T [8]. The pressure dependence
a stronger temperature dependence at low temperatures of conductivity of PANI-CSA is more complicated than
than that of PPy-PF6; whereas, at high temperatures that of doped (CH)x and PPy [20]. In PANI-CSA, the
the converse is true. The value of Pr for PANI-CSA conductivity decreases above 2 kbar and the temperature
depends on the extent of disorder present in the material dependence of conductivity is enhanced at high pres-
[8]. For the PANI-CSA samples in the critical regime, sures, both of which might be associated with pressure-
Pr varies from 2.5 to 5. The sample-to-sample variation induced changes in microstructure [20].
 M. Reghu et al. / Synthetic Metals 65 (1994) 167-171
4. Conclusions
The disorder-induced critical regime of the M-I
transition has been observed in K-(CH)x, I-(CH),,
PPy-PF6 and PANI-CSA. The critical regime can be
precisely identified from the log-log plots of W versus
T. In the critical regime W(T) is temperature inde-
pendent and the temperature dependence of conduc-
tivity follows a power law, p(T) =cT-~; W=~. For each
of the four heavily doped conducting polymer systems,
the positive temperature coefficient of W(T), observed
at high pressures, indicates the crossover to the metallic
regime. For K-(CH)x, PPy-PF6 and PANI-CSA, at 8
T, the negative temperature coefficient of W(T) indicates
crossover from the critical region to the insulating
regime. Thus, in heavily doped conducting polymers
the transport can be fine-tuned from the critical regime
into the metallic or insulating regimes by pressure and
magnetic field, respectively.
Acknowledgements
This work was partially supported by the MRL Pro-
gram of the National Science Foundation under Award
No. DMR-9123048, and partially supported by a re-
search grant from the Electric Power Research Institute
(EPRI). We thank M. Andersson for assistance in the
earlier stages of this work. K.V. was supported by a
grant from Neste OY, Finland. C.Y. was supported by
the Korean Science and Engineering Foundation (KO-
SEF). The PANI-CSA materials were supplied by
UNIAX Corporation.
References
[1] T. Ishiguro, H. Kaneko, Y. Nogami, H. Ishimoto, H. Ni-
shiyama, J. Tsukamoto, A. Takahashi, M. Yamamura, T.
Hagiwara and K. Sato, Phys. Rev. Lett., 69 (1992) 660.
171
[2] A.J. Heeger and P. Smith, in J.L. Br6das and R.R. Chance
(eds.), Conjugated Materials: Opportunities in Electronics,
Optoelectronics and Molecular Electronics, Kluwer, Dordrecht,
1990, p. 141.
[3] J. Tsukamoto, Adv. Phys., 41 (1992) 509 and refs. therein.
[4] M.J. Winokur, J. Maron, Yong Cao and A.J. Heeger, Phys.
Rev. B, 45 (1992) 9656.
[5] Y. Wada, in H. Aoki, M. Tsukada, M. Schluter and F.
Levy (eds.), Physics and Chemistry of Materials with Low-
Dimensional Structures, Kluwer, Dordrecht, 1992.
[6] A.I. Larkin and D.E. Khmelnitskii, Zh. Eksp. Teor. Fiz., 83
(1982) 1140 (Soy. Phys. JETP, 56 (1982) 647).
[7] A.G. Zabrodskii and K.N. Zeninova, Zh. Eksp. Teor. Fiz.,
86 (1984) 727 (Sov. Phys. JETP, 59 (1984) 425).
[8] M. Reghu, Y. Cao, D. Moses and A.J. Heeger, Phys. Rev.
B, 47 (1993) 1758; M. Reghu, C.O. Yoon, Y. Cao, D. Moses
and A.J. Heeger, Phys. Rev. B, 48 (1993) 17 685; Y. Cao,
P. Smith and A.J. Heeger, Synth. Met., 48 (1992) 91.
[9] T.G. Castner, in M. Pollak and B. Shklovshii (eds.), Hopping
Conduction in Solids, North-Holland, Amsterdam, 1991, and
refs. therein.
[10] D.J. Newson and M. Pepper, J. Phys. C: Solid State Phys.,
19 (1986) 3983; G. Biskupskii, A. E1 Kaaouachi and A.
Briggs, J. Phys. Condens. Matter, 3 (1991) 8417.
[11] K. Vakiparta, M. Reghu, M.R. Andersson, Y. Cao, D. Moses
and A.J. Heeger, Phys. Rev. 13, 47 (1993) 9977.
[12] K. Sato, M. Yamaura, T. Hagiwara, K. Murata and M.
Tokumoto, Synth. Met., 40 (1991) 35.
[13] A. Jayaraman, A.R. Huston, J.H. McFee, A.S. Coriell and
R.C. Maines, Rev. Sci. Instrum., 38 (1967) 44.
[14] H. Fujiwara, H. Kadomatsu and K. Tohma, Rev. Sci. Instrum.,
51 (1980) 1345.
[15] M. Reghu, K. Vakiparta, Y. Cao and D. Moses, Phys. Rev.
B, in press.
[16] N.F. Mott, Metal-Insulator Transitions, Taylor and Francis,
London, 2nd edn., 1990.
[17] S. Kivelson and A.J. Heeger, Synth. Met., 22 (1988) 371.
[18] D.E. Khmelnitskii and A.I. Larkin, Solid State Commun.,
39 (1981) 1069.
[19] Y. Nogami, H. Kaneko, H. Ito, T. Ishiguro, T. Sasaki, N.
Toyota, A. Takahashi and J. Tsukamoto, Phys. Rev. B, 43
(1991) 11 829.
[20] M. Reghu et al., unpublished results.