Synthetic Metals 123 (2001) 251±262

Polyaniline, a dynamic block copolymer: key to

attaining its intrinsic conductivity?$
James Y. Shimano, Alan G. MacDiarmid*
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323, USA
Received 15 September 2000; accepted 27 December 2000

Abstract

Photoluminescence studies of spun ®lms of polyaniline base (emeraldine oxidation state) show that ®lms prepared from NMP solution in
air having a relative humidity between 43  2 and 57  2% (218C) exhibit photoluminescence at 401 nm, which persists when the ®lms are
held in a dynamic vacuum. Films prepared from NMP solution containing water show similar behavior to those prepared in the above
humidity range. When protonated (``doped'') with HCl the above photoluminescence disappears and is replaced by a photoluminescence
peak at 467 nm. The reverse behavior occurs on deprotonation with NH3 vapor, the 467 nm peak disappearing and the 401 nm peak
reappearing. These results, together with photoluminescence studies on the phenyl/phenyl end-capped tetramer of aniline in both the
emeraldine and leucoemeraldine oxidation states, lead to the conclusion that in solution the emeraldine base is a dynamic block copolymer
in which reduced (benzenoid/amine) and oxidized (quinoid/imine) units are constantly interchanging positions via a tautomeric (hydrogen
migration) process between nitrogen atoms. This process is promoted by water. The resulting production of long sequences of the reduced
and oxidized units, which separate long sequences of the emeraldine base, persist when the NMP solvent is removed, resulting in
microphase segregation of these sequences in the solid ®lm. Since only the emeraldine base sequences can be doped by acids, the
conductivity of the doped ®lm is less than that of its predicted intrinsic conductivity. # 2001 Published by Elsevier Science B.V.

Keywords: Polyaniline and derivatives; Photoluminescence; Self-organization in macromolecules; Solution processing

1. Introduction by 1 y. It can exist in several oxidation states ranging from

Due to its ease of synthesis and processing, environmental
stability and low synthetic cost, polyaniline is probably the
most important industrial conducting polymer today. How-
ever, studies have shown that the experimentally achievable
conductivity of doped polyaniline may be much lower than
the intrinsic conductivity of the material [1]. It has been
reported that in the emeraldine salt form of polyaniline, less
than 1% of the available charge carriers actually contribute
to its observed conductivity [1]. If all the carriers contrib-
uted, the room temperature conductivity of the polymer
would be comparable to copper (105 S/cm) [1].
Polyaniline is a mixed oxidation state polymer composed
of reduced benzenoid units and oxidized quinoid units
(Scheme 1a), the average oxidation state which is given
$ The structural formula of polyaniline (emeraldine base
Presented as M.S. Dissertation by J.Y. Shimano at University of
Pennsylvania, Philadelphia, PA, 2000.
*
Corresponding author. Tel.: ‡1-215-898-8307; fax: ‡1-215-898-8378.
E-mail address: macdiarm@sas.upenn.edu (A.G. MacDiarmid).
the completely reduced leucoemeraldine base state (Scheme
1b), where 1 y ˆ 0, to the completely oxidized pernigrani-
line base state (Scheme 1c), where 1 y ˆ 1. The ``half''
oxidized (1 y ˆ 0:5) emeraldine base state (Scheme 1d) is
a semiconductor and is composed of an alternating sequence
of two benzenoid units and one quinoid unit. However,
emeraldine base can be non-redox doped with acid to yield
the conductive emeraldine salt state of polyaniline as shown
in Scheme 2. This non-redox doping process differs from
redox doping in that it does not involve the addition or
removal of electrons from the polymer backbone. Instead,
the imine nitrogen atoms of the polymer are protonated to
give a polaronic form where both spin and charge are
delocalized along the entire polymer backbone. This process
is reversible, as the conductive emeraldine salt state can be
converted back to the insulating emeraldine base state
through treatment with a base.
form) has always been written as a series of alternating two
benzenoid units and one quinoid unit, as shown in Scheme
1d. However, recent studies suggest that this representation

0379-6779/01/$ ± see front matter # 2001 Published by Elsevier Science B.V.

PII: S 0 3 7 9 - 6 7 7 9 ( 0 1 ) 0 0 2 9 3 - 4
252 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262

Scheme 1. Oxidation states of polyaniline.

may not be completely accurate. It has been observed that
there are signi®cant differences between the synthesized
powder of polyaniline (emeraldine base) and ®lms of this
powder cast from n-methylpyrrolidinone (NMP) [2]. When
conductivity relaxation time distribution measurements
are applied to the polyaniline powder, emeraldine base
exhibited only one relaxation peak. However, the ®lms
cast from NMP exhibited two peaks. Surprisingly these
two peaks correlated to the conductivity relaxation time
distribution peaks of the pernigraniline and leucoemeral-
dine base states of polyaniline, suggesting that these ®lms,
cast from polyaniline (emeraldine base) in NMP solutions,
contained regions similar to leucoemeraldine base and
pernigraniline base.
In addition, near-®eld scanning optical microscopy
images of ®lms of emeraldine base cast from NMP sug-
gested the presence of a two-phase structure in the ®lms [2].
These two phases corresponded to regions of the oxidized
quinoid repeat units and reduced benzenoid repeat units. The
®lm also contained intermediate phases that contained both
the oxidized quinoid and reduced benzenoid units.
Temperature dependent UV±VIS spectroscopy studies
demonstrated that the residual NMP that remained in the
polyaniline ®lm after casting was located in the region of the
reduced benzenoid repeat units (due to hydrogen-bonding
between the C=O groups in NMP and the N±H groups in the
benzenoid units). This led to the conclusion that the two-
phase structure observed in emeraldine base ®lms was a
result of the non-uniform distribution of NMP [2].
It was postulated that this ``phase separated'' structure
found in polyaniline ®lms cast from NMP leads to unex-
pected properties such as the emission of white light from
polyaniline when used as the emitting layer of a light
emitting diode [3]. The emission of light is observed in
polyaniline in both the emeraldine base and leucoemeraldine
base states. While this type of electroluminescence is
expected for the leucoemeraldine base state since it is known
to exhibit photoluminescence, it is unexpected for the
emeraldine base state since this state is not commonly
associated with photoluminescence. It was postulated that
for polyaniline (emeraldine base), electroluminescence
could only occur if the oxidized quinoid units and reduced

Scheme 2. Protonic acid doping of polyaniline (emeraldine base) to polyaniline (emeraldine salt).
 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
Scheme 3. Positional isomers of the phenyl/±NH2 end-capped tetramer of
aniline.
benzenoid units formed the phase separated structure dis-
cussed above [3].
Studies of oligomers of aniline suggest a possible differ-
ent cause for the above effects. For example, the phenyl/±
NH2 end-capped tetramer of aniline in the emeraldine base
oxidation state can in principle exist in three different
positional isomeric forms (Scheme 3). 1 H; 13 C and UV±
VIS studies of the phenyl/±NH2 end-capped tetramer of
aniline in d-chloroform (CDCl3) solution at 300 K have
shown that the solution consists primarily of isomer A with
smaller amounts of isomer B and no isomer C [4,5]. When
the tetramer is dissolved in d6-dimethylsulfoxide (d6-
DMSO), the solution consists of only positional isomer B
and no isomer A or C. UV±VIS spectroscopic studies
demonstrate that there is an instantaneous interconversion
of positional isomers A and B when the solvent is changed
to, for example, CHCl3.
In addition, each of the positional isomers of the phenyl/±
NH2 end-capped tetramer of aniline can exist in either a cis-
or trans-form [4,5]. NMR studies have shown that approxi-
mately equal amounts of the cis- and trans-isomer exist in
solution [4,5]. When the tetramer is cast in polycarbonate
®lms, photoisomerization between the cis- and trans-
isomers can be observed [6]. A circularly polarized laser
with a 523 nm wavelength oriented the tetramer of aniline in
the direction parallel to the light propagation vector [6]. This
orientation was a result of the cis-/trans-photoisomerization
of the tetramer [6].
The data collected on the positional isomers suggest that
tautomerism (intra- and/or interchain hydrogen migration)
occurs in the phenyl/±NH2 end-capped tetramer of aniline in
the emeraldine oxidation state (Scheme 4) [4,5]. This tau-
tomeric process interchanges the position of the benzenoid
and quinoid units, leading to the different positional isomers
of the oligomer in solution. In addition, NMR studies of the
positional isomers of the phenyl/phenyl end-capped tetramer
of aniline (emeraldine base) (Scheme 5a) also suggest that a
similar tautomeric process occurs [7]. It stands to reason that
the same type of tautomerization would probably occur in
polyaniline (emeraldine base) and, indeed, very recent pro-
ton studies of polyaniline (emeraldine base) in d6-DMSO/
NMP solution support this conclusion [7].
The fundamental purpose of this research was to attempt
to determine those factors which might be responsible for
253
Scheme 4. Tautomerization of the tetramer of aniline.
the reduction in conductivity of doped polyaniline from its
intrinsic value.
2. Experimental
2.1. Synthesis of polyaniline base
(emeraldine oxidation state) [8]1
The synthetic method used is based on, but modi®ed from,
our previously reported method [9]. An amount of 11.5 g
(0.0504 mol) ammonium peroxydisulfate (NH4)2S2O8, was
dissolved in 200 ml of 1 M HCl. An amount of 20.0 ml
(0.219 mol) aniline, previously distilled under nitrogen, was
dissolved in 300 ml of 1 M HCl. Both solutions were cooled
to 18C using an ice bath.
The (NH4)2S2O8 solution was then added to the aniline
solution, with constant stirring, over a period of 1 min. The
solution was stirred in an ice bath for 1.5 h, during which
the temperature of the reagents remained below 58C. Almost
immediately after the reactants were mixed, the solution
took on a purple tint. After 5 min, the solution took on a
green tint which progressed, as a precipitate formed, into a
dark green color with a coppery glint. The coppery glint was
less pronounced after 1 h.
After 1.5 h the solution was ®ltered using a Buchner
funnel (#1 Whatman ®lter paper). The precipitate was
washed with 750 ml of 1 M HCl. During the washing,
the washing solution always covered the entire precipitate.
This ensured no cracking of the ®lter cake, thus allowing it to
be washed adequately. The cake was dried for 10 min on the
Buchner funnel and then suspended in 1500 ml of 0.1 M
NH4OH overnight (16 h).
The solution was then ®ltered (Buchner funnel, #1 What-
man ®lter paper) and the ®lter cake was allowed to dry for an
additional 10 min. The cake was then placed in 50 ml of
0.1 M NH4OH and thoroughly mixed, creating a thick paste
1
The experimental method is given in full. A previous statement states
``. . . there are as many different types of polyaniline as there are people
who make it!''.
254 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
Scheme 5. Phenyl/phenyl end-capped tetramer of aniline in the (a) emeraldine base and (b) leucoemeraldine base states.
to which was then added 550 ml of 0.1 M NH4OH. It was
then stirred magnetically for 30 min. This process was
repeated an additional ®ve times.
This dispersion was then ®ltered and the ®lter cake dried
on the Buchner funnel for an additional 30 min. The ®lter
paper with ®lter cake was transferred to a petri dish and dried
under dynamic vacuum in a vacuum desiccator for 2 days.
The powder was then pulverized with a mortar and pestle
and placed in the vacuum desiccator and dried under
dynamic vacuum for an additional 2 days.
Approximately 25 mg of the dried powder was placed in a
small disposable vial and covered loosely with a cloth
followed by drying for an additional 12 h in a vacuum
desiccator to completely remove any trace amounts of water.
The vial was immediately sealed and submitted for ele-
mental analysis. The results of a typical elemental analysis
of the emeraldine base synthesized by the method described
above is shown in Table 1.
Table 1
Elemental analysis of polyaniline (emeraldine base)a
C (%) H (%) N (%)
Experimental 78.39 4.97 15.47
Calculated 79.53 5.02 15.45
a
University of Pennsylvania: in-house analytical laboratory.
Fig. 1. UV±VIS spectrum of polyaniline (emeraldine base) in NMP solution.
The UV±VIS spectrum of the emeraldine base was
measured in NMP solution (Fig. 1) by adding one drop of
a 0.8 wt.% emeraldine base/NMP solution to a cuvette
®lled with NMP. This spectrum is in good agreement
with previous (unpublished) results of the peak positions
(lmax ˆ 633, 327 nm) and previous relative intensities
(633 nm:382 nm ˆ 1:00:0.833) of polyaniline (emeraldine
base) in NMP [10]; this study 328 nm:623 nm ˆ 1:00:0.847.
2.2. Film casting
An amount of 0.8 wt.% emeraldine base/NMP solutions
were prepared by adding 0.040 g of polyaniline (emeraldine
base) over a period of 30 s to 5.0 ml of NMP under constant
stirring. The solution was sonicated for 10 min in a Branson
1200 Sonicator. The solution was then ®ltered through a
Whatman Puradisc 25TF ®lter (0.45 mm polytetra¯uor-
oethylene membrane).
Spun cast ®lms were prepared using a spinner from
Headway Research, Inc. A VWR Scienti®c Micro Cover
Glass was placed on the spinner. The spinner was turned on
and the spin rate set to 1000 rpm. The spinner was then
Total (%)
turned off and 1 ml of a 0.8 wt.% EB/NMP solution was
98.83 placed on the cover glass. The spinner was turned on and an
100.00
additional 1.5 ml of solution was added during the spin-
ning. After the sample had spun for 30 s, the spinning rate
 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262 255

Table 2
Emeraldine base spun film cast in controlled humidity

Sample Temperature (8C) Humidity (%)a Time exposed to airb Time after solutionc

1 21  1 9  4 6 min 38.38 s 46 min

2 21  1 26  4 7 min 1.30 s 1 h 56 min
3 21  1 35  2 6 min 44.78 s 4 h 34 min
4 21  1 43  2 7 min 38.59 s 6 h 37 min
5 21  1 50  2 6 min 41.75 s 15 h 37 min
6 21  1 57  2 6 min 17.56 s 20 h 55 min
10 21  1 45  2 6 min 45.02 s N/A
20 21  1 45  2 6 min 44.77 s N/A
a
Relative humidity as measured directly from the Fisherbrand Jumbo Thermo-Humidity Meter.
b
The elapsed time between the removal of the cover glass slide from the disposable petri dish and the placement of the slide back into the petri dish after
the film had been spun.
c
The elapsed time between the preparation of the EB/NMP solution to the time at which it was used to spin the film.

was increased to 3000 rpm for an additional 90 s for com-
plete evaporation of solvent.
Preparation of the 0.8 wt.% phenyl/phenyl end-capped
tetramer of aniline (emeraldine base) [11]2 (Scheme 5a) in
DMSO solution was similar to the preparation of the
0.8 wt.% emeraldine base/NMP solution. An amount of
0.040 g of phenyl/phenyl end-capped tetramer of aniline
(emeraldine base) was added over a period of 30 s to 5.0 ml
of DMSO under constant stirring. The solution was soni-
cated for 10 min in a Branson 1200 Sonicator. The resulting
solution was dark purple in color. The solution was then
®ltered through a Whatman Puradisc 25TF with a 0.45 mm
polytetra¯uoroethylene membrane.
In order to cast drop-cast ®lms, a VWR Scienti®c Micro
Cover Glass was placed in a vacuum desiccator. Approxi-
mately 1 ml of 0.8 wt.% phenyl/phenyl end-capped tetramer
of aniline in DMSO solution was placed on the cover glass
until it covered the entire surface of the glass. The solution
was dried under dynamic vacuum until the ®lm was dry and
no solution remained (16 h).
An amount of 0.8 wt.% polyaniline (emeraldine base) in
n-methylpyrrolidinone/water solutions were made by add-
ing the appropriate amount of deionized water drop-wise to a
2.5 ml solution of 0.8 wt.% emeraldine base/NMP solution
with constant stirring. The amount of water added ranged
from 0.1 to 2.5 ml.
In order to spin ®lms under controlled humidity, an I2R
Glove Bag Model X-37-37H was ®lled with dry air. The
spinning machine, seven 2.5 ml portions of 0.8 wt.% emer-
aldine base/NMP, VWR Scienti®c Micro Cover Glasses
sealed in disposable petri dishes, a Fisherbrand Jumbo
Thermo-Humidity Meter and other necessary supplies (pip-
ettes, spatula, paper tissue, etc.) were placed in the glove bag
under a slight ``over-pressure'' of dry air (Airco compressed
air cylinder). The bag was sealed and the humidity and
2
The oligomer used was in the emeraldine oxidation state as confirmed
by UV±VIS spectrometry, mass spectrometry and C, H, N elemental
analysis.
temperature were measured with the Thermo-Humidity
Meter. One cover glass was removed from its petri dish
and placed on the spinner. A ®lm was spun in the manner
previously described. After the ®lm was spun, it was placed
back in the petri dish and the dish was sealed. The time the
cover glass spent outside of the petri dish was recorded.
An apparatus was created to controllably raise the humid-
ity inside the glove bag. Four glass tubes, two feet in length
and two inches in diameter, were ®lled with glass wool that
had been soaked in deionized water overnight. Dry air
(Airco compressed air cylinder) was then passed through
the four wet glass wool tubes. Several more ®lms were spun
at measured relative humidities. The temperature and
humidity during the time of spinning, the elapsed time
between the removal of the cover glass slide from it dis-
posable petri dish and the placement of the slide back into
the petri dish after the ®lm had been spun (time exposed to
air) and the elapsed time between the preparation of the
emeraldine base/NMP solution to the time at which it
was used to spin the ®lm (time after solution) are listed
in Table 2. After photoluminescence spectra were been
measured, two of the ®lms (samples 1 and 2) were returned
to the glove bag, placed on the spinner again and spun
without the addition of more solution (samples 10 and 20 ) in
order to expose each one to the high humidity atmosphere in
the glove bag.
2.3. Photoluminescence measurements
Photoluminescence spectra were measured with a Photon
Technology International, Inc. Quanta Master Model C-60.
Since the photoluminescent structure in polyaniline is the
benzenoid unit [12], the excitation wavelength for measur-
ing polyaniline samples was set at 300 nm. This wavelength
falls inside the p±p absorption envelope of the benzenoid
units centered at 330 nm. The photoluminescence emis-
sion spectrum was measured between 330 and 550 nm.
Liquid samples were measured in a Photon Technology
International, Inc. 10 mm Suprasil Cuvette.
256 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
Fig. 2. UV±VIS spectrum of polyaniline (emeraldine base) (Ð), polyani-
line (emeraldine base) vapor doped to emeraldine salt (- - -) and
polyaniline (emeraldine salt) vapor dedoped to emeraldine base (± ± ±).
2.4. Chemical treatment of films
Spun ®lms of emeraldine base were vapor doped to the
emeraldine salt form by placing an emeraldine base ®lm
above 12 M HCl for 60 s. Films in the emeraldine salt state
were vapor dedoped by placing the sample above 14.8 M
NH4OH for 1 h (Fig. 2).
Step-wise vapor doping of emeraldine base to the emer-
aldine salt state was accomplished by placing a spun ®lm of
emeraldine base above a 6 M HCl solution for 5 s. This process
was repeated (approximately ®ve times) until no change in
the UV±VIS of the polyaniline could be detected (Fig. 3).
Step-wise vapor dedoping of emeraldine salt to the emer-
aldine base state was accomplished by placing an emeral-
dine salt ®lm above 14.8 M NH4OH for speci®c amounts of
time. In the ®rst step, the emeraldine salt sample was placed
over NH4OH for 5 s. However, the dedoping process
becomes more dif®cult as it progressed and the sample
was therefore held over the NH4OH for an increasing
amount of time with each step. For example, the sample
was placed over the NH4OH for 50 s during the second step,
5 min during the third, 10 min during the fourth and, if
necessary, 60 min during the ®fth step (Fig. 4).
Fig. 3. UV±VIS spectrum of spun film of emeraldine base step-wise vapor
doped with HCl.
Fig. 4. UV±VIS spectrum of vapor-doped emeraldine salt spun film step-
wise vapor dedoped with NH3.
Films of both polyaniline (emeraldine base) and phenyl/
phenyl tetramer of aniline (emeraldine base) were
reduced to polyaniline (leucoemeraldine base) and phe-
nyl/phenyl tetramer of aniline (leucoemeraldine base) in
an identical manner. Neat hydrazine was applied drop-
wise to the ®lms until the appropriate color change (blue
to clear for polyaniline and purple to clear for phenyl/
phenyl tetramer of aniline) was observed. The ®lm was
then dipped into deionized water in order to remove any
unreacted hydrazine, and placed under dynamic vacuum
in a vacuum desiccator for 1 h to dry. The UV±VIS
spectra for the samples were measured to con®rm that
the reduction had taken place (Fig. 5, polyaniline; Fig. 6,
phenyl/phenyl tetramer of aniline). The UV±VIS spectra
of both materials exhibited the loss of the peak associated
with quinoid units (666 nm for polyaniline and 624 nm
for the tetramer). It has been reported that the peak
associated with the quinoid units of polyaniline ®lms
can differ quite greatly from that of the solution depend-
ing on the method of sample preparation [13]. This is
consistent with the large deviation between the quinoid
peaks of polyaniline ®lms (666 nm) and its solutions
(633 nm).
Fig. 5. UV±VIS spectrum of polyaniline spun cast film in the emeraldine
base (Ð) and leucoemeraldine base (± ± ±) state.
 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
Fig. 6. UV±VIS spectrum of a drop cast film of the base form of the
phenyl/phenyl tetramer of aniline in the emeraldine oxidation state (Ð)
and leucoemeraldine oxidation state (± ± ±).
3. Results
3.1. Chromophore responsible for photoluminescence
Many electronic polymers exhibit photoluminescence
only in their fully reduced states [14]. Much like other
electronic polymers, the fully reduced leucoemeraldine base
state of polyaniline (Scheme 1b) exhibits photolumines-
cence in both the solid state [3,14,15] and in solution
[12,16]. However, polyaniline apparently differs from other
electronic polymers in that it has been reported that the
``half'' oxidized emeraldine base state (Scheme 1d) exhibits
photoluminescence in the solid state if cast into a ®lm from
solution [3,17,18]. However, as will be shown in this section,
this present study demonstrates that the presence of photo-
luminescence is not necessarily always the case. It has
previously been shown that the benzenoid units in polyani-
line demonstrate ¯uorescence, while the quinoid units
demonstrate no observable ¯uorescence [12]. In fact, intra-
chain energy migration can occur allowing the quinoid
groups to act as excitation traps and quench the photolumi-
nescence. Thus, the photoluminescence of polyaniline is
caused by the (reduced) benzenoid/amine groups and it is
quenched when such a group is adjacent to an (oxidized)
quinoid/imine group [12].
Results of this present study demonstrate that a solution of
the leucoemeraldine base state of polyaniline in NMP
exhibits a photoluminescence spectrum with lmax at
409 nm when it is excited with 300 nm light (Fig. 7). The
excitation wavelength of 300 nm was chosen so that it fell
within the range of the p±p absorption envelope of the
benzenoid units centered at 328 nm. These results are
similar to previous published studies which report a photo-
luminescence spectrum of polyaniline (leucoemeraldine
base) in NMP solution with lmax at 420 nm when it is
excited with 340 nm light [12]. Since polyaniline (leucoe-
meraldine base) consists only of reduced benzenoid units,
257
Fig. 7. Photoluminescence of polyaniline in NMP as it is oxidized from its
leucoemeraldine base state to its emeraldine base state.
the presence of a photoluminescence spectrum for polyani-
line (leucoemeraldine base) is also consistent with the
concept [12] that the photoluminescence of polyaniline is
a result of the reduced benzenoid units.
Our studies also demonstrate that when the polyaniline
(leucoemeraldine base)/NMP solution is oxidized (®rst by
air and then by a dilute solution of H2O2), the photolumi-
nescence intensity decreases until there is no measurable
signal when the polyaniline reaches its emeraldine base
oxidation state (Fig. 7). These results are also consistent
with previous published results in which air oxidation of a
polyaniline (leucoemeraldine base)/NMP solution leads to a
reduced photoluminescence intensity [12]. As the polyani-
line is oxidized from its fully reduced leucoemeraldine base
state to its ``half'' oxidized emeraldine base state, reduced
benzenoid units are converted to oxidized quinoid units. The
decrease in the photoluminescence spectrum can be attrib-
uted to the decreased concentration of photoluminescent
benzenoid units and/or the introduction of quenching qui-
noid units as previously reported [12]. While the decrease in
concentration of benzenoid units will certainly lead to a
decrease in photoluminescence, the formation of quinoid
units must quench the photoluminescence to some extent. If
the quinoid units did not quench photoluminescence, poly-
aniline (emeraldine base) in NMP solution would still be
expected to exhibit some sort of photoluminescence due to
the fact that it still has two benzenoid units per repeat unit of
polyaniline in its structure (Scheme 1d). Thus, our experi-
mental results are consistent with the previously reported
conclusion that the photoluminescence of polyaniline is
caused by the (reduced) benzenoid/amine groups and it is
quenched when such a group is adjacent to a (oxidized)
quinoid/imine group [12].
258 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
3.2. Phenyl/phenyl end-capped tetramer of aniline
In order to understand the photoluminescence spectrum of
polyaniline, it is helpful to study the oligomers of aniline.
The structure of the phenyl/phenyl end-capped tetramer of
aniline in its emeraldine base (Scheme 5a) and leucoemer-
aldine base (Scheme 5b) states is very similar to one repeat
unit of the emeraldine base and leucoemeraldine base states
of polyaniline (Scheme 1b and d). Thus, studying the
phenyl/phenyl end-capped tetramer of aniline can give
insight to the behavior of one isolated repeat unit of polyani-
line. The photoluminescence of the phenyl/phenyl end-
capped tetramer of aniline in its leucoemeraldine base state
is reported here for the ®rst time (Fig. 8). Like polyaniline,
the leucoemeraldine base state of the tetramer of aniline
consists only of reduced benzenoid units. Thus, the photo-
luminescence must be a result of the benzenoid units, which
is again consistent with previous reported results. It is
interesting to note the similarities between the photolumi-
nescence spectra of the leucoemeraldine base states of
solutions of polyaniline in NMP and ®lms of the tetramer
of aniline. Both exhibit similar lmax (408 nm in polyaniline
in NMP solution; 410 nm in tetramer of aniline ®lms). The
similarities can be explained by examining the nature of the
photoluminescence. In both the polymer and the oligomer
the luminescent species is the reduced benzenoid unit. The
photoluminescence begins with the p±p absorption of the
benzenoid units. Since the benzenoid units in both the
tetramer of aniline and polyaniline are identical, it is not
surprising that the photoluminescence of the two molecules
are similar. Thus, the number of adjacent benzenoid units in
a given molecule does not have an affect on the lmax of the
spectrum.
Our studies also demonstrated that when the phenyl/
phenyl end-capped tetramer of aniline was in its emeraldine
oxidation state, no photoluminescence was observed (Fig. 8).
Similar to the oxidation of polyaniline in NMP solution, the
Fig. 8. Photoluminescence of phenyl/phenyl tetramer of aniline film in the
emeraldine base oxidation state (Ð) and leucoemeraldine base oxidation
state (± ± ±).
disappearance of the photoluminescence spectrum can be
attributed to the decrease in concentration of photolumines-
cent benzenoid units and/or the introduction of quenching
quinoid units as previously reported [12]. Again, like poly-
aniline in NMP solution, the loss of luminescent benzenoid
units leads to a decrease in photoluminescence intensity;
however, the quinoid group must quench the photolumines-
cence to some extent. If the quinoid units did not quench
photoluminescence, ®lms of the phenyl/phenyl tetramer of
aniline (emeraldine base) would still exhibit some sort of
photoluminescence due to the fact that it still has two
benzenoid units in its structure (Scheme 5a). Thus, our
experimental results are consistent with the previously
reported concept that the photoluminescence of polyaniline
is caused by the (reduced) benzenoid/amine groups and it is
quenched when such a group is adjacent to an (oxidized)
quinoid/imine group [12]. These results also support the
postulate that more than two benzenoid units not adjacent to
a quinoid unit are needed for photoluminescence to be
observed.
3.3. Spinning of polyaniline (emeraldine base) film
The photoluminescence data collected on ®lms of the
phenyl/phenyl tetramer of aniline and the solutions of
polyaniline allow for the interpretation of photolumines-
cence spectra of ®lms of polyaniline. In our study, ®lms of
polyaniline in their leucoemeraldine base state demonstrate
a photoluminescence spectrum (Fig. 9) very similar to that
of ®lms of the tetramer and solutions of the leucoemeraldine
base (lmax ˆ 404, 410 and 408 nm, respectively). Since
®lms of leucoemeraldine base contain only reduced benze-
noid/amine groups, the photoluminescence is again due to
the benzenoid units consistent with previous reports [12].
However, photoluminescence spectra of ®lms of polyani-
line in the emeraldine base state are not consistent with
photoluminescent properties of either polyaniline in NMP
Fig. 9. Photoluminescence of polyaniline films in the emeraldine base
oxidation state (Ð) and leucoemeraldine oxidation state (± ± ±).
 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
solution or with the phenyl/phenyl end-capped tetramer of
aniline ®lms in their emeraldine base oxidation state. In our
study, some ®lms of emeraldine base exhibited no photo-
luminescent spectra, while ®lms prepared in a speci®c
manner always demonstrated photoluminescence. Fig. 9
illustrates an example where photoluminescence is observed
in polyaniline (emeraldine base) ®lms. The photolumines-
cence spectrum of polyaniline (emeraldine base) ®lms is
consistent with those previously reported [3,17,18] This
result is quite unexpected because the chemical molecular
structure of polyaniline in ®lms has been assumed to be
identical to that of polyaniline in solution and of the phenyl/
phenyl end-capped tetramer of aniline (Schemes 1d and 5a).
As stated earlier from the photoluminescence studies of the
tetramer of aniline, more than two repeat benzenoid units not
adjacent to a quinoid unit are necessary for the molecule to
demonstrate photoluminescence. Therefore, since emeral-
dine base ®lms of polyaniline exhibit photoluminescence,
they must contain more than two repeat benzenoid units not
adjacent to a quinoid unit.
As stated above, photoluminescence in polyaniline (emer-
aldine base) ®lms is only observed in the present study when
the ®lms are cast under speci®c conditions. Initial studies
suggested that photoluminescence could only be obtained
when the relative humidity, reported by local weather
reports, was above 50% during the casting of the ®lm!
These results are consistent with ®lms spun from emeraldine
base/NMP/water solutions. It should be noted that due to the
hydroscopic nature of NMP (label states: ``Hydroscopic-
Store Under Nitrogen''), all of the following solutions were
prepared with ``99.5% anhydrous'' NMP stored in its ori-
ginal Aldrich Sure/Seal bottle and removed from the bottle
using a syringe through the Sure/Seal cap. When small
amounts of liquid water are added to 0.8 wt.% emeraldine
base/NMP solutions (between 9 and 18 vol.%), ®lms spun
from these solutions consistently demonstrate a photolumi-
nescent spectrum (Fig. 10). However, ®lms spun with less
Fig. 10. The intensity of the lmax ˆ 400 nm photoluminescent emission
peak vs. the percentage of water added to 0.8 wt.% emeraldine base/NMP
solution.
259
Fig. 11. Photoluminescence of polyaniline (emeraldine base) films spun at
various relative humidities at 218C.
then 9 vol.% or more than 18 vol.% added water consistently
and did not demonstrate photoluminescence.
In order to more carefully examine the effects of humidity,
®lms were spun under controlled humidity. It is quite
remarkable to ®nd that photoluminescence is only observed
in ®lms of emeraldine base spun from NMP when the relative
humidity of the air surrounding the spinning apparatus falls
in the range of 43  2 to 57  2% at 218C (Fig. 11).
Several experiments demonstrate that the presence or
absence of water does not affect the photoluminescence
of polyaniline (emeraldine base) ®lm after the ®lm has been
cast. When the ®lms spun at 9  4 and 26  4% are placed
back into the glove bag (whose relative humidity was
measured at 45  2%) and are treated under similar condi-
tions to the ®lms that did show photoluminescence, they still
did not demonstrate photoluminescence. In addition, ®lms
of emeraldine base that did not demonstrate photolumines-
cence, still showed no photoluminescence even after being
treated with liquid water or exposed to water vapor. Simi-
larly, drying photoluminescent ®lms under dynamic vacuum
did not eliminate their photoluminescence.
It is our conclusion that published reports of photolumi-
nescence in ®lms of emeraldine base [3,17,18] must have
been measured on ®lms of emeraldine base that had been
spun in a relative humidity range of 43  2 to 57  2% at
218C or that had been cast from solutions of NMP that had
absorbed between 9 and 18 vol.% water (due to the hydro-
scopic nature of NMP).
In order for extended sequences of benzenoid and quinoid
groups to decrease the conductivity of the polyaniline, it
would appear that they must persist when the semiconduct-
ing emeraldine base state of polyaniline is doped to the
conducting emeraldine salt form. When a ®lm of emeraldine
260 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262

Fig. 12. Photoluminescence of polyaniline spun film in the emeraldine

base oxidation state (Ð), HCl vapor doped to the emeraldine salt oxidation
state (± ± ±) and NH3 vapor dedoped back to the emeraldine base oxidation
state (- - -).
Fig. 13. Photoluminescence of polyaniline spun film HCl-vapor-doped
step-wise from the emeraldine base state to the emeraldine salt state.
base that exhibits photoluminescence is doped with HCl
vapor, the photoluminescence spectrum remains. However,
the position of the peak is shifted from a lmax of 401 to completely disappears by the time the polyaniline reaches its
467 nm (Fig. 12). It is pleasing to note that this unexpected fully doped state, leaving only the 470 nm peak. This
phenomena has also been con®rmed in independent (as yet process is completely reversible, i.e. as the 470 nm peak
unpublished) observations reported at the conclusion of this disappears, the 400 nm peak reappears during the dedop-
study [18]. Since the photoluminescence spectrum is related ing of emeraldine salt ®lms with NH3 vapor.
to the HOMO/LUMO absorption transition [19], a change in The persistence of the leucoemeraldine base sequences
the HOMO/LUMO energy gap would lead to a change in the through HCl doping and NH3 dedoping cycles clearly
photoluminescence spectrum. When a ®lm of polyaniline is emphasizes the conclusion given in this section, viz. the
doped from its emeraldine base state to its emeraldine salt presence of such leucoemeraldine base sequences must
state, the HOMO/LUMO energy gap of the benzenoid p±p inhibit the conductivity of HCl-doped polyaniline since
transition decreases (as can be seen by the red shift of the
minimum from 445 to 523 nm associated with the benzenoid
p±p transition absorbance in the UV±VIS spectrum (Fig. 2)).
This change in the p±p absorption may be related to either
the doping of the emeraldine base sequences (whose change
is transmitted electronically to the leucoemeraldine units)
and/or to the protonation of the leucoemeraldine units. Thus,
the decrease in the energy gap leads to a decrease in energy
of the photoluminescence spectrum. This is consistent with
the red shift of the photoluminescence spectrum upon doping.
When the same ®lm is dedoped by NH3 vapor, both the UV±
VIS and photoluminescent spectra return to that of the original
emeraldine base ®lm. This is consistent with persistence of the
extended sequences of benzenoid units through both doping
and dedoping of a polyaniline ®lm.
The persistence of the extended benzenoid sequences
throughout the entire doping and dedoping cycle can be
clearly seen by the photoluminescence spectra of the step-
wise vapor doping (Fig. 13) and dedoping (Fig. 14) of
polyaniline ®lms. As the emeraldine base ®lm is doped with
HCl vapor, the 400 nm peak characteristic of emeraldine
base begins to disappear, and the 470 nm peak character- Fig. 14. Photoluminescence of polyaniline spun film NH3-vapor-dedoped
istic of the emeraldine salt appears. The 400 nm peak step-wise from the emeraldine salt state to the emeraldine base state.
 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
treatment of leucoemeraldine base does not lead to an
increase in conductivity. Furthermore, this observation
clearly shows that HCl doping does not promote the com-
bination of leucoemeraldine base and pernigraniline base
sequences to give dopable emeraldine base sequences.
4. Discussion
Based on the experimental data summarized below, we
propose that the most technologically important conducting
polymer, polyaniline, has a conductivity considerably less
than its proposed intrinsic conductivity because its mole-
cular structure is not that commonly believed and that it
contains defect sequences. The defect sequences result from
inter- and/or intrachain tautomeric processes (hydrogen
migration) in solution which is promoted by the presence
of water in the NMP or water absorbed by the NMP from the
air during ®lm formation. As the NMP solution evaporates
during the spinning process, the presence of water vapor
favors the formation of extended sequences of benzenoid/
amine groups (i.e. leucoemeraldine base) and quinoid/imine
groups (i.e. pernigraniline base) together with the alternating
benzenoid, quinoid groups (i.e. emeraldine base) along the
polymer backbone. This is consistent with the photolumi-
nescence data for the tetramer of aniline and polyaniline
®lms in their various oxidation states. The lmax for ®lms of
the tetramer of aniline in its leucoemeraldine base state
(410 nm), ®lms of polyaniline in its leucoemeraldine base
state (404 nm) and ®lms of polyaniline in its emeraldine
base state (401 nm), formed under speci®c conditions are all
in good agreement with each another. Thus, it is clearly
apparent that it is the common chromophore, i.e. the ben-
zenoid amine unit, in all of these species that gives rise to
photoluminescence. Since the phenyl/phenyl end-capped
Scheme 6. Tautomerization and phase segregation in polyaniline.
261
tetramer in its leucoemeraldine oxidation state (four adjoin-
ing benzenoid/amine groups) shows photoluminescence, but
not in its emeraldine state (two adjoining benzenoid/amine
groups), it is apparent that photoluminescence in ®lms of
emeraldine base formed in the presence of certain de®ned
concentration of water vapor (in air) or NMP containing
water must contain more than two adjacent benzenoid/amine
groups not adjacent to quinoid/imine groups. Thus, ®lms of
polyaniline in the emeraldine base state formed under the
above conditions do not have the molecular structure com-
monly believed.
We propose that in NMP solution, and also possibly in
other solvents, under certain conditions the relative positions
of the benzenoid and quinoid groups in emeraldine base can
interchange through the same type of tautomerization reac-
tion observed in the oligomers of aniline [4,5] (Scheme 6).
Thus, after evaporation of the solvent and casting of a ®lm, a
single molecule of polyaniline (emeraldine base) would
actually consist of extended sequences of benzenoid, qui-
noid and unchanged emeraldine base sequences rather than
containing only the alternating (2-benzenoid) (1-quinoid)
emeraldine base structure as depicted in Scheme 1d. These
extended sequences each constitute the molecular structure
of leucoemeraldine base, pernigraniline base and emeral-
dine base, respectively. Since there is no experimental
evidence that leucoemeraldine base and pernigraniline base
can be protonated (``doped'') to a highly conductive state,
like emeraldine base, such segments in a given polymer
chain will lead to reduced intramolecular conductivity. It has
also been shown that no interconversion of leucoemeraldine
base or pernigraniline base sequences occurs during proto-
nation. Thus, the extended sequences also persist in the
doped conducting form of polyaniline.
These extended sequences can be regarded as comprising
the chemical structure of a block copolymer. Hence, we
262 J.Y. Shimano, A.G. MacDiarmid / Synthetic Metals 123 (2001) 251±262
believe polyaniline in the emeraldine base state is a dynamic
block copolymer. Thus, polyaniline (emeraldine base) would
microphase segregate, as expected for a block copolymer
[20], when cast into a ®lm from solution (Scheme 6). The
resulting ®lm would not only contain domains of pure
emeraldine base, but also domains of leucoemeraldine base
and pernigraniline base. This phase segregation would
produce the two-phase structure described earlier [2]. These
domains would also have a great impact on the bulk con-
ductivity of the polyaniline ®lm. Phase segregated emeraldine
base domains will dope and will promote intermolecular
conductivity within the emeraldine base domain. However,
leucoemeraldine base and pernigraniline base domains will
not dope and will remain insulating. These undopable
domains will create regions in the polyaniline ®lm which
will not conduct and will decrease the bulk conductivity of the
®lm in relation to a ®lm that consisted, hypothetically, of
completely doped emeraldine base. The reduced intramole-
cular conductivity due to the extended sequences of undop-
able leucoemeraldine base and pernigraniline base and their
incorporation into phase segregated domains would lead to
the lower than expected conductivity of polyaniline.
We conclude that the above phenomena produces many
reduced and oxidized defect sequences in a polyaniline
molecule separating the (dopable) emeraldine state seque-
nces, resulting in a considerably smaller conductivity for
doped polyaniline than its predicted intrinsic conductivity.
Acknowledgements
The authors are especially grateful to Ms. Wei Wang for
donating the phenyl/phenyl end-capped tetramer of aniline
(emeraldine oxidation state) which she had synthesized and
completely characterized. This work was supported by
the US Of®ce of Naval Research under contract number
N0014-92-J-1369.
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