Indian

Vol. Joj,Jrnal of
33AJJune Chemistry
1994, pp, 524-539

Recent trends in conducting polymers: Problems and pro:mises

Sukumar Maiti

Materials Science Centre,Rd:eived

~ndian Institute of Technology,
19 November 1993 Kharagpur 721 302

Conducting polymers exhibit one of the most versatile behaviour of polymer materials. This re-
vi reports right from the synthesis t the applications of these new electronic materials and dis-
eu ses the associated challenges and sol tions. These polymers may be synthesized by conventional
eh 'n and step polymerization techniqu s as well as a few other special processes including electro-
ch mical synthesis. The problems of pol mer synthesis in general and synthesis of these el,ectroactive
po ymers in particular have been discus ed. The incorporation of oxidizing or reducing agents into
th se polymers, known as 'doping', type of doping agents used, the mechanism of doping and finally
th influence of the nature and level of opants incorporated on the conductivity and otht~rpropert-
ies of polymers have been discussed. T conductivity of these polymers also depends on a number
of actors, viz., technique of synthesis a d processing of polymers, their crystallinity and molecular
str cture, and temperature of the used nvironment. Since the dopants are small molecular weight
rn erials and are required in some cas s as high as 30-50% of the polymers, the macromolecular
pr perties are thus compromised by d ping. A new type of polymers known as narrow bandgap
po mers has therefore been developed which does not require any external dopants. This may bl
ac ieved by reducing the aromaticity or y increasing the content of quinoid form or by incorporation
of mpty p-orbitals in the polymer chai , Stability and processability problems of doped polymers
an various means to overcome these h ve also been discussed. By introducing ionizable groups in
the polymer chain, intrinsic conducting olymers may also be obtained which do not require exter-
nal dopants, Finally, some of the poten ial areas of applications of these new electronic materials
an their promises have been discussed.

Introdu
posed, purely from theoretical consideration, that
The versatility of polymers ha never properly substituted polyacetylene molecule
before en manifested so acutely as in th deve- would exhibit even superconducting behaviour at
lopment of conducting polymers, a class 0 mate- room temperature 1,
rials tha is traditionally well-known and widely While Natta and coworkers2 first prepared 1'0-
used as ·nsulators. Commodity as well as specia- lyacetylene as a dark coloured powder completely
lity poly ers are insulators because the at ms in insoluble in organic solvents, Hatano and cowork-
the poly er chain are covalently bonded. Metals ers3 reported for the first time the electrical con-
are con ucting due to the presence of etallic
ductivity of the order of 10 - 5 Sf em of their poly-
bonds, i which the valence electrons ar com-
acetylene sample. On exposure to air polya-
pletely elocalized and form an electron cloud
cetylene lost its conductivity, and colour of the
around e metal atoms. In the covalent onded
sample changed from greenish-black to pale-
molecul of saturated carbon compounds here is orange. It now appears that these workers had
no scop of dclocalization of the valenc elec-
prepared the trans-isomer of polyacetylene.
trons, a d consequently neither charge arriers
Subsequently, particularly in the seventies, vigo-
nor path for their movement are available Since
rous research activities led to the discovery of
in the onjugated molecule of a carbo com-
polysulphur nitride4, (SN)x' having metallic con-
pound, elocalization of electrons may occur ductivity and superconductivity5 at 0.24 K. This
through the interaction of .n-bonded ele trons, conducting polymer, known as synthetic metal,
such mo ecules may be conducting. Thus it was
however, remains an academic curiosity because
thought hat a long-chain conjugated m lecule, of its brittleness and explosive nature.
such as he polymer of acetylene,t-CH = Ht-n, Although Hatano and coworkers reported as
may pro e to be conducting. In fact, it wz s pro- early as 1961 the discovery of conducting polya.

I I
 MAITI: PROBLEMS & PROMISES OF CONDUCTING POLYMERS 525

cetylene, their product was powdery and insoluble

Table 1-cis-trans ratio of polyacetylene isomers obtained un-
in organic ~olvents, and therefore fabrication was der various conditions
extremely difficult. A decade later, Ikeda, Ito and
Shriakawa100·C
in Japan6-9
150°C dark - 78°C succeeded
condition in the synthesis
Polymerization 0-
Catalyst
"'iCV
MoCl/H20
Ti(O A1(C2Hsh
Ni(acetylacetonate
Ti( -n
- (1:~)
n - C4H9)1
n-
Co(N03h/NaBH4 2:0.5)
C4H9)1 0/80
98/2
24/76
0/100
59/41
50150 h C2Hs h
5195
(1cis/trans
A1(
A1(C2Hsh
A1(C2Hs)3
Toluene,
N-Heptane,O°C
Tetrahydrofuran, (1:4)
(1:4)
Toluene, 18°C
Ethanol, - 78°C n-Hexadecane,
Toluene, - 78°C
~
of free-standing polyacetylene films-one copper
coloured with room temperature conductivity of
1.7 x 10-9 S/cm, and the other, silver coloured
with a conductivity of 4.4 x lO-s S/cm.
The next significant milestone in conducting
polymer research was the observation that poly-
phenylacetylene, like polycyclic aromatic hydro-
carbons 10, on exposure to halogen vapours such
as bromide and iodine, showed an eight-fold in-
crease in conductivity 11. Similar observation was
reported earlier by Berets and Smith 12by expos-
ing polyacetylene pellets to vapours of BF3 and
BCI3. Following these earlier examples, Shiraka-
wa, McDiarmid, Heeger and coworkers exposed
the free-standing polyacetylene film to vapours of
chlorine, bromine, iodine, arsenic pentafluoride lene formed by this 'process depends on the cata-
and sodium, and reported an increase in conduc- lyst system and the polymerization conditions
tivity up to twelve orders of magnitude 13- 1S.In- used23 (Table 1).
creasing the conductivity of polyacetylene by
treatment with chemicals was termed as doping,
although the traditional doping method and the
n(CH == CH) Ziegler/Natt~
Catalyst
1- CH = CH -t"
concentration of dopant present in inorganic sem-
iconductors are quite different. Benzene and naphthalene have been polyme-
Very soon it was realized that polyacetylene, rized in arsenic trifluoride solvent using AsF s as
because of its processing difficulty and rapid fall catalyst24,2S.
in conductivity when exposed to air, has limited
commerdal applicability. In the late seventies
electrochemical synthesis offered a convenient n@ ~ Cat LI(5U-
~

route to obtain conducting polymers that are

stable to ambient environments16. Thus a few new
polymers have been added to the list of conduct-
ing polymers such as polypyrrole16, polythio-
phene17, polyparaphenylene18, polyphenylene sul-
o
n<8 Cot
A.F~ • ~O0 n

fide19, polyaniline20, polyphenylene vinylene21, pol-

yisothianaphthene22, etc. Similarly, acetylene derivatives have been po-
lymerized by chain polymerization process using
Synthesis of conducting polymers Ziegler type and other types of catalyst
Conducting polymers may be prepared by systems26-28 (Table 2).
chain or step polymerization process, electro- Heterocyclic monomers, viz., pyrrole and thio-
chemical synthesis, photochemical route and by phene have also been synthesized by chain po-
other methods. lymerization process using metal salts such as
perchlorates and chlorides of iron and
Chain polymerization process copper29 - 31.
Polyacetylene was prepared by polymerization
of acetylene by Ziegler-Natta catalysts. Free stand- Step polymerization process
ing films of polyacetylene prepared by the Shira- This process, unlike the chain polymerization
kawa process involves the passage of acetylene process, involves, in general, a condensation-type
gas over TiCVAl(C2Hsh catalyst solution in n- reaction between the reactive groups of two dif-
heptane at O°C, when the polymer is obtained as ferent molecules, although self-condensation is
a film on the surface of the catalyst solution. The not ruled out.
ratio of the two geometric isomers of polyacety- Polyphenylene sulfide is prepared by the poly-
526 INDIAN J CHEM, SEe. A, JUNE 1994

PolyparapheIl¥lene is synthesized by the poly-

condensation reaction between p-dibromobenzene
MonomerT1ble 2- Polymerization
Catalyst of acetylene derivativfs
Polymefuation
and magnesium in ether in the presence of nickel
system
chloride bipyridylcatalyst37.
Polyphenylene oxide has been synthesized by
CH3-C~CH
Monosl<~b*tuted acetylene
AlR/TICh
. Ullmann condensation of sodium salt of p-
Ziegler atta bromophenoP8.
Catalysts containing Homog neous
Pd, W, Mo, Ni, Co Modifi d-Ziegler
MoCI),Mo(Co)6' WCI) Homog neous ~:Y
n Br -('&-oNa ~(~. 0 )n
\- + NoBr
Modifi -Ziegler
BF) Cationi
Electrochemical Synthesis
(CH3hSi-C=CH MoCl), WCl) Modifie -Ziegler
C6HS -SjCECH Anionic
Electrochemical synthesis of conducting polym-
CICH2-- =CH Butyllithium
R-C=C
ers is similar to the electrddeposition of metal
Benzoyl peroxide, Free-ra ical
from an electrolytic bath; the polymer is deposit-
(R =, alkyl) .di-tert-butyl peroxide ed on the electrode surface and also in the in situ
y-radiation
doped form39,4o.
d acetylene Polypyrrole, poly thiophene and other polymers
CHl - C =Ic - nC)H7 MoCls, WCI6 have been prepared by this route:. For example,
TaBrs pyrrole in aqueous acetonitrile solvent containing
CHI - C =Ie - CoHs MOCIS' MoC16 tetraethylammonium tetrafluoroborate was .elec-
WCl6 tropolymerized in a two-electrode lelectrochemical
CFj7C '" q- CF3 y-ray ce1l16.The conducting polypyrrole containing BFi
ion (as dopant) was obtained as a film deposited
on the platinum electrode surface.
Similarly a copolymer of thiophene and pyr-
of para-dichlorobenzene wi~h sodi-
role has been prepared by electrochemical polym-
erization of 2,2'-thienylpyrrole41. Aniline42, ben-
zene, phenol43 and other aromatic hydrocarbons44
Cl+0 Na2S- *S*+20 NaCI have been electrochemically polymerized.

Photochemical synthesis
phene s lfide34 have been prepared by po ycond- Receritly pyrrole has been photopolymerized
Simila
ensation ly polyvinylene
between sulfide33
appropriate dichloroandcom
P~lythio-
ounds using a ruthenium (II) complex as photosensitiz-
and anh rous sodium sulfide. er45. Under photo-irradiation, Ru(II) is oxidized to
Ru(ill) and the polymerization is initiated by this
ethynyll ulfide, has been synthesized by a similar one-electron transfer oxidation process. Polypyr-
polycon ensation technique. The reacti n in- role (PPy) films may be obtained by photosensi- .....

volves
In thet polycondensation
author's laboratory abetween diiod acety-
new POlYme~ poly- tized polymerization of pyrrole using a copper
lene35 an sodium sulfide36. complex as the photosensitizer46. Photopolymeri-
zation of benzol C] thiophene has been carried out
NMP
n(1-- C =Ic- 1)+nNa
2
S----'
12Doc
in acetonitrile using CCL4 and tetrabutyl ammoni-
um bromide47.
-t-C=C-S-in +12n NaI
Miscellaneous processes
Conducting polymers have also been synthes-
first tim a phosphorus containing polyme which ized by other methods. Polyacetyllene has been
is solubl and semi-conducting in the virgO state. prepared by an indirect method, not involving the
TheMaiti
reac1nd
ion coworkers haveas also
may be shown reported lor the
follows35: acetylene monomer48 - 50. Polyvinyl chloride on
dehydrochlorination by a base in a polar solvent
THF
n(l--C= -I)+n(U - P- Li) yields polyacetylene.
I (i) 0-5°C
t-BuOK ~
C6H5
(ii) Room temp. -f- CH 2.- CH
t
----L
1
DMF/N2
-{CH=CH-li
CI
 MAITI: PROBLEMS & PROMISES OF CONDUCTING POLYMERS 527

Sometimes a precursor polymer was used to pre- lar chemicals. Thus inert and dry environments
pare the conducting polymer. For example, poly are required for polymerization. A slight variation
(2,5-thienyl vinylene) was prepared by heating the in the polymerization condition or in the compo-
precursor polymer5l• sition of the catalyst significantly alters the nature
of the polymer obtained. Some polymers undergo
isomerization reaction under light and/or heat.
Such polymers should be carefully stored in a
dark, cool and dry place.

Doping of polymers
The same polymer may be obtained from a dif- Doping in polymeric semiconductors is differ-
ferent precursor polymer52: ent from that in inorganic or traditional semicon-
ductors61. Inorganic semiconductors have a three-
dimensional crystal lattice and on incorporation
of specific dopants, n-type or p-type in ppm le-
vels, the lattice is only slightly distorted. The do-
High quality polyacetylene films have been pre- pant is distributed along specific crystal orient-
pared by the Durham route53,54. ations in specific sites on a repetitive basis. The
doping is usually quantitative and the carrier con-
centration is directly proportional to the dopant

1t
L-J-.:{"CFJ
CFJ
WCII/S:HI4~
CF'~:J
n
~
concentration.
Doping of conducting polymers involves

o CFJ +
LVcF, tv" WAIn
, ...J:.-.
random dispersion or aggregation
pants in molar concentrations in the disordered
of do-

structure of entangled chains and fibrils. The do-

pant concentration may be as high as 50% (ref.
The same film may also be obtained by the 62). Also incorporation of the dopant molecules
copolymerization route55. in the quasi one-dimensional polymer systems
considerably disturbs the chain order leading to
reorganisation of the polymer63. Thus the ultimate
conductivity in polymeric semiconductors de-
pends on many factors, viz., nature and concen-
tration of dopants, homogeneity of doping, carrier
mobility, crystallinity and morphology of polym-
ers.
Doping of inorganic semiconductors generates
Highly ordered polyacetylene may be synthes- either holes in the valence band or electrons in
ized by the template polymerization technique, the conduction band. On the other hand, polymer
viz., polymerization of acetylene within the pores doping leads to the formation of conjugational de-
of a membrane containing Ziegler-Natta catal- fects, viz., solitons, polarons, or bipolarons in the
yst56•57• Such ordered polymer exhibits higher polymer chain64• X-ray diffraction study on io-
conductivity . dine-doped polyacetylene shows that the C - C
Solid state polymerization has been used for the bond length of polyacetylene chain increases with
synthesis of conducting polymers such as polysul- donor doping but decreases on acceptor doping65•
fur nitride58,59 and polydiacetylene60•
Types of doping agents
Problems in polymer synthesis Doping agents or dopants are either strong re-
Polymerization reactions differ in many respects ducing agents or strong oxidizing agents66,67. They
from ordinary chemical syntheses. High purity of may be neutral molecules and compounds or in-
monomers (usually> 99.9%) and other chemicals, organic salts which can easily form ions. Thus do-
solvems, etc. is a prerequisite for obtaining high pants may be classified as (a) neutral dopants, (b)
polymers. The polymerization conditions should ionic dopants, (c) organic dopants and (d) polym-
be strictly controlled. Many catalyst systems, e.g., eric dopants (Table 3). Neutral dopants are con-
Ziegler-Natta catalysts and ionic catalysts, are verted into negative or positive ions with or with-
highly sensitive to moisture, oxygen and other po- out chemical modifications during the process of
528 INDIAm J CHEM, SEe. A, JUNE 1994

Doping techniques
Table 3-Dopants for polymers
Doping of polymers may be canied out by the
Dopant Active species Polymer" following methods: (a) gaseous doping, (b) solu-
for doping tion doping, (c) electrochemical doping, (d) self-
Neutrald
doping (e) radiation induced doping and (f) ion-
12 PA,PPS,PPP exchange doping.
Br2 PA(trans) Of these, the first three methods are widely
AsF2 PA,PPS,PPP used because of convenience and low cost. In the
Na PA gaseous doping process, polymers are exposed to
K PPP the vapours of the dopant under vacuum67• The
H2S PAn level of dopant concentration in polymers may be
FeCI3 FeCli PA easily controlled by temperature,.' vacuum, and
SnCI4 SnCli PA time of exposure. Solution doping involves the
Alel3 AlCl4 PP use of a solvent in which all the products of dop-
ing are soluble. Toluene. acetonitrile, tetrahydro-
Ionic do
furan, nitromethane, and other similar polar
ClO.;- PPY,PTh solvents are used as solvents. The polymer is
Na+ PA(trans) treated with the dopant solution.
CIOi PA, PPY, P3M' Simultaneous polymerization andl doping gener-
BFi PPY,PTh ally occurs in the electrochemical doping tech-
CF3SO) PPY,PTh nique68• But sometimes this method is used for
PF6 PPY,PTh doping polymers obtained by other methods also.
(CH3)4W PTh In this process only ionic type dopants are used
CIOi PA(cis) as the electrolyte in polar solvents such as ni-
AsF6 PA tromethane, acetonitrile, dichlorornethane, tetra-
hydrofuran, etc . •
Organic Self-doping does not require any external dop-
ing agent. In the polymer chain the ionizable
CF3S 3Na SO) PPY group, for example, sulfonate group of poly[3(2-
C~C$OH
JrCH C6H4S03H COO-
SO) PPY ethane sulfonate) thiophene] acts as the dopant
for the polymer69•
Polymer~ High energy radiations such as gamma-ray,
PVS SO) PPY,PAn electron beam and neutron radiation are used for
PPS SO) PPY,PAn doping of polymers by neutral dopants. For exam-
PS-Co~M'A COo- PPY ple, gamma-ray irradiation in the presence of SF6
gas 70 or neutron radiation in the presence of 12
(ref. 71) has been used to dope poly thiophene. It
PPP: Pol araphenylene,
'PA: Po1:ra%tylene,
phene,
PPY: Polypyrrole, PTh: Polythio-
PPS: Polyphenylene
P : Polyaniline, sulfide, thioPhJne).
P3MT: Poly( 3-methyl
is assumed that the neutral molecules, SF6 or 12, ..
first decompose to active dopant species under
high energy radiation70.

Mechanism of doping in polymers

doping. onic dopants are either oxidized or re- Since dopants are strong oxidizing or reducing
duced b an electron transfer with the olymer agents, on doping positive or negative charge car-
and the ounter ion remains with the pol mer to riers are developed in the polymers. This may be
make th system neutral. Another type f ionic represented by the following simplified scheme of
dopants . volves the anion derived from e dis- reaction66,67,72:
sociatio of the dopant molecule, which eutral-
Oxidation
izes thle ositive charge of the polymer du . g the Polymer + Dopant )(Doped polymer) +
electroc emical doping process. Organic opants
are anio .c dopants generally incorporat d into + Dopant-
polymer from aqueous electrolytes during anodic
deposili n of the polymer. Polymeric dop ts are Reduction
function . ed polymer electrolytes cont . Polymer + Dopant ~ (Doped polymer)-
phiphilic .ons.
+ Dopant +

Ii ,Ii 1111, I '11'14111.H.,~lllllllli

 MAITI: PROBLEMS & PROMISES OF CONDUCTING POLYMERS 529

Doping is not merely an oxidation or reduction ferent structures, processing of polymers, degree
reaction ..It was found that doping results in rear- of crystallinity, and temperature. It has been ob-
rangement of polymer chains and thereby new or- served that conductivity of cis-polyacetylene
dered structures are formed. The C - C bond doped with AsFs after connecting to electrode is
length of polyacetylene on doping decreases or 2-3 times higher than when the contacts are ap-
increases depending on the acceptor or donor plied after dopingll .
type of the dopant used.
In the doped polymers charged solitons are Influence of doping on conductivity
formed. These are charged defects with no spin. A The extent of enhancement of electric conduc-
reducing, i.e., donor type, dopant introduces an tivity of a polymer primarily depends on the
electron to the polymer chain which couples with chemical reactivity of the dopant with the polym-
a neutral defect resulting in a negative soliton er. The same dopant cannot be effective for dif-
with zero spin. Similarly an oxidizing (acceptor rerent polymers. Iodine, for example, enhances
type) dopant abstracts an electron from the po- the conductivity of polyacetylene by 10-12 orders
lymer chain and a positive spinless soliton is of magnitude, but it fails to dope polyphenylene
formed. This may be illustrated by the doping of sulfide or polyparaphenylene because of its weak
polyacetylene66• oxidizing ability. AsFs, being a stronger oxidizing
dopant, can successfully dope polyacetylene, poly-
phenylene sulfide or polyparaphenylene. Electric
trans .. POlYOCftyl.n. trons- Polyoc.tyl.n.
I Phon A·) IPhos. B )
conductivity of conducting polymers both in vir-
gin and doped conditions is shown in Table 4.

N.utrol soliton
Ta1Jle 4-Electrical conductivity of polymers in virgin and
doped state

Dopant L (Ace.ptor I Dopant 1(Donor) Polymer Dopant Composition of Conductivity

doped polymer (S/cm)
trn.ns- Polyace- None 4.4 x lO-s
tylene 12 [CHIld 1.6 X 102
Positi", soliton Nogoti •• sol iton
Br2 [CHBrO.23] 0.4
AsFs [CH(AsFs)O.I] 4x 102
The above sequence of electronic event occurs 80
Na-naph-!lCHNao28]
in the polymer chain at a very low doping level. thalide
But as the doping level is increased, formation of 1.7 X 10-9
cis-Polyace- None
a polaron is thought to take place: 5.5 X 102
tylene 12 [CHIo.3]
Doping
- AAAA @
AsFs [CH(AsFs)o.tl
Bu4NCI04 [CH(CI04)0.064]
1.1 X 103
9.7 X 102
Neutral soliton Polaron 10-12
Polyparapheny- None
Doping
• ~
G>
E& lene Ii
AsFs [C6H4(AsFs)0.4]
10-s
<5 X 102
K [C6H4Ko.6] 20
Bipotaron
AlCI3 [C6H4(AlCI4)0.23] 104

With increase in the doping level more and Polyphenylene None 10-16
more polarons interact to form bipolaron, which sulfide 12 lO-s
is a dication. Existence of bipolarons has been re- AsFs 5
ported in various doped highly conducting polym- Polyaniline None 10-10
ers such as polyparaphenylene, polypyrrole, poly- H2S04 1
thiophene, poly(3-methyl thiophene) (P3MT) and Polypyrrole None 10-8
in polyacetylene. These are regarded as the major CIOi [C4H3N(CI04b) 2 x 102
charge carriers in conducting polymers. BFi [C4H3N(BF4)0.nl 102
CF3C03 [C4H3N(CF3C03)0.121!12
Electrical behaviour Polythiophene None 10-7
Electrical conductivity of polymers, though pri- CIOi [C4H2S(CI04)0.3] 10-20
marily depends' on doping, is influenced by many BFi [C4H2S(BF4)0.3] 10-20
factors, viz., method of synthesis resulting in dif-

-----~-
530 INDIAN J CHEM, SEe. A, JUNE 1994

Cond ctivity of polymers depends dlr ctly on

Table 5-Influence of film thickness on tllle conductivity of
the do . g level. For vapour phase dop g, the
electrochemically prepared poly( 3-methyl thiophene)
doping evel increases with exposure tim of the
Film thickness Substrate surface Conductivity
polyme to the dopant vapour (Fig. 1). So etimes
(A) (S/cm)
a sharp rise in conductivity is observed fo a very
2,000 Irtdium-tin oxide 1,975
small i rement of the dopant level67. T s sharp
3,800 "" 1,470
increase may be due to the rapid increase in mo-
bility of the charge carriers, which in tu is due
to inter ain interaction. Table 6-Influence of stretching on the conductivity of po-
lymers
Polymer/Dopant Condition Condu(:tivity Ref.
Effect synthesis, processing and crystal~inity of system S/cm
polyme on conductivity
cis-PNAsFs Unstretched 1.1 x 103 77
Poly r conductivity also depends on th meth-
Stretched 3.0x 103 78
od of p lymer synthesis73,74, isolation an purifi-
Unoriented 1.6 X 102 79
cation t chniques, physical treatment of he po-
lymer, tc. Presence of oxygen and moi ture in Oriented 1 X 104 79
the: elec olytic medium affects the conduc 'vity of
the: dop d polymer75. Electrical conductivi also
valies th the film thickness of the doped polym-
er76 (Ta Ie 5). This is probably due to e fact simultaneous mechanical stretching and heat
that mo e ordered and defect-free polyme struc- treatment. It bas been reported that by stretching
ture is 0 tained in a thin film. polyacetylene film, higher order in chain structure
can be induced which in turn enhances the con-
ductivityn-79 (Table 6).
with the degree of crystallinity (Fig. 2). G nerally
degree f crystallinity may be induced in olym- Similarly, under the influence of magnetic field
ersElect cal conductivity
by echanical stretchingof orpolymers
in a better~' reases
ay by of 2-14 KG, high alignment of polyacetylene fi-
brils were obtained from nematic liquid crystals
of the polymer which showed very high electric
conductivity on doping with iodine 79(Table 6).
50·(
Influence of temperature on conductivity
One of the characteristic featun:s of semicon-
ducting materials is the increase in its electric
10'3 conductivity with increase in temperature. This
104
behaviour is in sharp contrast widl metallic and
ceramic materials. The influence of temperature
10'5
(T) on conductivity (a) in s€emiconducting materi-
0123456789
als including conducting polymers, doped or un-
doped, follows the relation:
Exposur ••• tim •••I h

Fig. 1-- nation of conductivity of PPS with level If doping

-a
time of exposure to AsFs vapours aoc e TI/(l +d)

I 5 where a is a constant and is proportional to elec-

~- -10 Virgin
tric activation energy, and d the dimension of.
space coordinates. The plot of In a versus T - 0.5.

! lJ1H'~'
i.e., when d = 1 or T-0.25 (i.e., when d = 3) shows

J- • -5
a linear relationship. This indicates the variable
range hopping of charge carriers in one or three
dimensions in space80•
Even in conducting doped polymt:rs with metal-
-15 lic conductivity (a> 103 S/cm), th'e temperature
O. 50 100
dependence of conductivity does not follow the
Crystallinity. % metallic behaviour. It has been neported81 that
Fig. 2-V~riation of conductivity of polyacetylene ~ith de- FeCl3 doped polyacetylene exhibits a small in-
gree of crystallinity crease in conductivity with decrease in tempera-

I I II t I!II~ , II' i II
 MAITI: PROBLEMS & PROMISES OF CONDUCflNG POLYMERS 531

ture up to - 53°C, but thereafter the conductivity gap with dissimilar energy, and hence two new
decreases gradually up to - 258°C. absorption peaks are produced (Fig. 3).
Attempts have been made to determine the op-
Optical behaviour tical band gap of polyvinylene sulfide33 using the
It is well-known that absorption of electromag- relation applicable to conventional amorphous
netic radiation particularly in the UV to near IR semiconductors84:
region of the spectrum provides important infor-
ahv oc (hv- Ellf-
mation about the energy bands of inorganic semi-
conductors. Optical absorption in conducting po- where J;,~ is the optical band gap, r a const~
lymers which are mostly amorphous or paracrys- ant, a optical absorption coefficient and
taIline may be due to the transition of charge car- h v the photon energy. The value of r is deter-
riers, through a forbidden energy gap, called 'opti- mined by the curve fitting method and is equal to
cal gap' or optical band gap. Doping introduces 1/2, 1 or 2. Maiti and coworkers have also used
additional energy bands in this forbidden gap, but the same eqution with r = 2 for determination of
it does not interfere with the principal energy the optical gap of amorphous polyethynyl
bands of the virgin polymers (Fig. 3). New ab- sulfide85 and poly(p-phenyl phosphoethynedi-
sorption peaks appear due to doping of polymers, yl)86.87.
but again the energy for absorption maximum
(Emax) does not depend on the nature of the do- Narrow band gap conducting polymers
pant82•83• The optical band gap controls the electronic
The number of new absorption peaks on dop- and optical properties of conducting polymers. A
ing depends on the virgin polymer. If the polymer reduction in the optical gap increases the conduc-
is a degenerate system, e.g. polyacetylene, both tivity of the polymers. Attempts have, therefore,
the resonating forms result in doped chains with been made to reduce the band gap in conducting
identical energy and hence only one new peak polymers by various techniques (Table 7). One
will appear on doping. Polyheterocyclics and poly- such method is the augmentation of the quinoid
phenylene sulfide are non-degenerate systems form in polythiophene by polymerization of iso-
having two different resonating structures, viz., thianaphthene, a benzoderivative of thiophene22•
benzenoid and quinoid, and on doping these two
forms produce new energy states in the optical
(Cl•••• k! lorml

Polythiophene (Eg=2.1 eV)

(A.omolie lorml I
(Clulnold I•••••

~
+- Polyisothianaphthene (Eg = 1.1 eV)
OIl
c:
QI
C
. ~. Thus the optical band gap (Eg) is reduced from
,,:.
u
Cl
'\
+-
.•
2.1 eV of polythiophene to 1.1"eV of polyisothia-
o0- II'", .. ; naphthene.
, ..•............••... ', Jenekhe synthesized a series of heteroaromatic
conjugated polymers containing alternating aro-
matic and quinoid structures in the main chain
o 1 2 3 4 5 having the followingrepeat unit8 8 •
Energy, eV
Fig. 3-Effect of d.oping on the optical ab~orption spectra of
(a) trans-polyacetylene, 'and (b) polypyrrole. Curves I and 11
refer to the corresponding virgin polymers and doped polym-
ers respectively.
 H 0
K
~,;>t- rl¥~1:
tion of Ref.
empty
141 orbitalsinteraction

&t
R
1.2 NR
R
JI CHEM,
I532 p-orlbitals
Planar SEe.
Increase
Strong of A,
quinoid
Introduction
ow bandgap 143
144
of 142
40
89
88
JUNE
22, INDIA
quinoid
quinoid
donor-acceptor (~_/tloO
1994polymers
conducting
Bandgap, Eg backbone
Reasons tals byEg
forstructure
small
Strong donor-acceptor incorporation of content
- ,1.1-0.75
Occupancy of tructure
frontier interaction and occu-
pancy of
empty {-a),
frontier orbi- lo95 orbitals
-k:2f:rx?-i
(~\

g'
by :incorpora- ~~

t
Rl = CH),
s
R2=n-C12
n
1125
0.5
R, 1.13
Table 7-N t 085

the b nd gap measured by the optical bsorp- poly( 4-oxo-4 H -cyclopenta[ 2, 1-b; 3,4-b']-dithio-
tion sp tra of the polymers having X sulfur, phene-2,6-cliyl with E g = 1.2 eV (ref. 48).
R =, phe yl and m = 1, n = 1, 2 or 3 in th above
stmctur shows gradual reduction in valu s from
1.1 eV 0 0.83 eV and finally to 0.75 e when
the fract on of the quinoid segments, i.e. (m + n)
was inc eased from 0.5 to 0.66 and . ally to
0.75. !
Incorporation of empty p-orbitals in the polym-
Anoth r approach for lowering of the optical er chain by effective variation in tht~ occupancy of
band ga in semiconducting polymers is b sed on frontier orbitals is another technique for lowering
the reclu tion of their aromaticity. Thus cy lopen- or band gap in conducting polymers such as po-
ta[2,1-b; 3,4-b']-dithiophene-4-one having he fol- ly(2,6-pyridinedicarbonylsulfide)89. This is due to
lowing t 0 resonating structures has a r ducecl the possibility of formation of canonical resonat-
aromatic ty in the polymerized form clue to the ing forms of the polymer:

"I
 MAITI: PROBLEMS & PROMISES OF CONDUCTING POLYMERS 533

in the oxidation and crosslinking of the chain

while heterocyclic polymers are not so reactive
with oxygen or air.
Stabilization of the conducting polymers has
been tried by two routes, viz., incorporation of
antioxidants such as benzoquinone and hindered
phenols or by using radical traps such as azobisi-
Stability and processability problems sobutyronitrlle. Another method is ion implanta-
Conducting polymers in general exhibit poor tion91.
thermal and environmental stability. Morevoer,
due to extended conjugated chain structure, these Thermal stability
polymers are insoluble and infusible and hence Thermal stability of most of the conducting po-
not easily processable. Polyacetylene, for example, lymers is poor excepting the heterocyclic polym-
shows electric conductivity in the semiconducting ers. The rate of thermal degradation is very much
range. But on exposure to atmosphere its conduc- dependent on the environment. Polyacetylene, for
tivity falls rapidly90,91. example, degrades at room temperature in air or
Conducting polymers, on doping, become more oxygen atmosphere, but in helium its degradation
unstable in environmental conditions. The rate of starts only at 320°C (ref. 97). Similarly, polythio-
reduction in conductivity of iodine-doped polya- phene and its derivatives are stable up to 200-
cetylene under room temperature is higher than 250°C in air, but do not decompose up to 700°C
that of its virgin state92. However, in dry oxygen, in inert atmosphere9J. Nature of the dopant also
iodine-doped polyacetylene loses its conductivity affects the thermal stability of the polymers. -Poly-
more slowly than its undoped state. Polypheny- pyridine, for example, doped with arylsulfonates
lene sulfide (PPS) which is stable in the virgin is only stable up to 80°C in humid environment,
state, is unstable in the presence of moisture in but when doped with BFi it retains its stability
the doped state80. But in dry air or oxygen, doped up to 150°C (ref. 98).
PPS is stable. Polyparaphenylene is very stable in Incorporation of heteroatoms having non-bond-
air in the presence of moisture but when doped ing electron-pairs in the conjugated chain struc-
with oxidizing dopants it is unstable in moisture93. ture augments thermal stability in conducting po-
But polythiophene and poly( 3-methyl thiophene) lymers. Polyethynyl sulfide85 is stable up to about
are stable both in the doped and undoped states 200°C and poly(P-phenylphosphoethynediyl)86 is
in the presence of moisture or air and oxygen94. stable up to 2·50°C.
The stability of these polymers is attributed to the
delocalization of electrons in the chain through Processability of conducting polymers
participation of the non-bonding pair of electrons Delocalization of electrons requires a conjugat-
of the sulfur atom. This principle of stabilization ed chain structure which in turn brings insolubil-
of conducting polymers has also received support ity and infusibility to the polymers. Conducting
from polyethynyl sulfide36,85 and poly(P- polymers such as polyacctylene, pulyparapheny-
phenylphosphoethynediyl)86,95. These two polym- lene, polypyridine, etc., possess therefore poor
ers do not show any reduction in conductivity processability. Polyacetylene could not be pro-
even after one year of storage in normal environ- cessed in the powder form until its free-standing
ment. film was obtained by the Shriakawa technique.
Some unusual solvent systems have been deve-
Influence of dopants on the stability of conducting loped for making films from conducting polymers,
polymers For example, molten arsenic trifluoride or molten
The nature of dopants plays an important role in iodine have been used as solvents for polypheny-
the stability of conducting polymers. For example, lene sulfide99,lOo.
perchloric acid doped polyacetylene is not sensitive A number of general techniques has been deve-
to water and oxygen. Similarly, electrochemical dop- loped for improving the process ability of the con-
ing of polyacetylene with sodium fluoride makes it ducting polymers. These include the following: (a)
more resistant to-oxygen96.When poly( 3-methyl thio- block copolymerization, (b) increase of cham fle-
phene) is doped with S03CFi it develops stability in xibility, (c) appropriate substitution in the chain,
atmospheric air94. (d) formation of polymer blends, and , (e) use of
It may be noted that conjugated chain polymers are processable precursor polymers. It may be noted
reactive to oxygen and atmospheric air resulting that all the above approaches to increase the pro-
534 INDIAN JICHEM, SEe. A, JUNE 1994

cessabili are achieved at the cost of cond cetylene has been deposited on carbon fiber to
of the pol ers. obtain a composite with high mechanical
Block copolymerization-The rigidity f the strength 108. Such blending or mixing of conductin,g
conjugat chain may be reduced and ther by its polymers with their nonconducting processable
processa ility improved by block copoly eriza- counterparts offers not only enhanced processa-
tion telc .que. A block copolymer of p lyiso- bility but also augments necessary mechanical
prene ~m polyacetylene with up to 20% of the strength, adhesion and environmental stabil-
latt(~r is oluble in common organic solv nts 101. ityI09,1l0.
Similarly, block copolymerization of 3-me lthio- Processable precursors-Use of soluble precur-
phene d methyl methacrylate produces poly- sor polymers for generation of high molecular
mers sol Ie in tetrahydrofuran 102. weight conducting polymers is an indirect way to
Increa in chain flexibility-Chain fle 'bility overcome the processability proble:m. This is a
can be mproved by incorporation of exible two-step process: first, a high molecular weight
centers flexible linkages in the chain. In rpor- soluble polymer is prepared and a film is cast
ation of rsenic atoms in the polyacetylene makes from solution; next the film is heated to convert it
the latte soluble in common organic sol ents24• into the final insoluble desired polymer. The de-
This is ssible by breaking the regular se uence hydrohalogeilation of polyvinyl chloride by treat-
of conju tion of polyacetylene by arsenic om in ment with a base48 - 50 and the metathesis polym-
the back one. erization of the Diels-Alder adduct by the Dur-
ham route to produce poly acetylene are two ex-
groups' the 3-position of thiophene m lecule amples of application of processable precursors
makes e substituted poly thiophene sol ble in for synthesis of insoluble conducting polym-
theAppro
mix: riate
re of substitution-Substitution
tetrahydrofuran, methylen01 ether
chlo- ers53,54.
rid(~and richloroethane (4:1:1 )103.

o . !A\ Intrinsic (self-doped) conducting polymers

R R

Since on doping charged species are formed in

S ~s~ the polymer chain it is logical to assume that if
R= -CH20(CH2hO(CH2hOCH3 ionizable groups are incorporated in the polymer
chain, the latter may not require dloping for en-
hancement of electric conductivity. These poly-
yields
Similarly I
<ll spluble
2-methoxy
and stable
aniline on pOlyme~zation
polymerlO4• mers containing ionizable species or groups are
called self-doped, or better termed as non-doped
or intrinsic conducting polymers. The ionizable
nrQ1
"Yl..OCHl • (rQr--T:-
~i;Hj
NH2 NH2 group generally introduced to various conducting
polymers is sulfonic acid group or its salts. Table
tion of long alkyl sulfonate grou 8 lists a few such intrinsic conducting polymers.
te position in thiophene molecul
ater-soluble polythiophene. Prospects of conducting polymers r '

Recent research and development activitles

__
SOiNo+
--l.~
iOf 'I ~
S n sOl N-1+
show that conducting polymers exhibit conducti-
vity from the semiconducting range (- 10 - 5
S/cm) right up to metallic conductivity (-104
S/cm). With this range of electric conductivity and
low density coupled with lower price, lower pro-
cessing energy requirement, and above all unique
in polar solvents such as DMF, DMAc, MSO, versatility of application and design flexibility, po-
etc.35•95.
poly(p-p imilarly,
en alkyl substitutionmakes
ylphosphoethynediyl) to theit soluble
3-posi- lymeric conductors pose a serious cfiallenge to
Thein
tion resence
e pyrroleof bulky phenylpoly(
ring makes SUbstitUlnts
3-oc 1 pyr- in the established inorganic semiconductor technol-
role) sol ble in common organic solvents105• ogy. New applications are emerging for these
Poly r blends-Blends of rigid conduc' g po- modem electronic materials.
lymers .th processable polymers are rep rted to Application of conducting polymers in the
have im roved processability. Blends of p lyacet- development of a rechargeable battery appears to
ylene d polyester have been formed 106. Blends be feasible and is at the threshold of commerciaii-
of poly ytrole and polyvinyl alcohol ha e also zation. A number of conducting polymers such
been pr pared by electro polymerization 107 Polya- as polyacetylene, polyaniline and oilier polyheter-

I " 'i", I II
 iOtn (C~)"~ /, 5 n
(S/cm)
3'-propylsulfonate)
HI
lrn
I
SO)
OJ n
NNso) n
Ref.
147
m-1,'
145
148
10-7
0.1
10-2
10-6
146
Conductivity
K+
MAm:
Fe2+,Fe3+
Na+ H+,Na+
H+ ¥~t
PROBlEMS & PROMISES
{@-Z~~* Counter
OF CONDUCTING ion 535
POLyMERS

Anode

r Palyaniline
{SUS mesh

![ Gasket

I----- Separator 20 mm .j
Fig. 4-Schematic representation of a rechargeable polymer
lithium battery.
Si02 Au Gate Ga- In Alloy
Fig. 5-Cross-sectional view of a plasticfield effect transistor
ocyclics has been used as electrode materials for. (FET)
rechargeable batteries. In fact, polyaniline-lithium
battery (Fig. 4) has already been marketed 111,112.
Vigorous research activities are being carried out vices the same polymer through control of dop-
to develop all polymeric solid-state batteriesll3 ing, or two different polymers-one polyhetero-
and also to use composite electrodes such as car- cyclics and the other polyaniline- have been
bon fiber-polyacetylene composite and alkali me- used. Plastic field effect transistor (PET), (Fig. 5)
tal a1loy~for better battery performance114• for example, has been fabricated with polythio-
A number of electronic devices such as Schott- phene as the semiconductor and [rtoluene sulfon-
ky diodes, plastics transistors, [rn junction, etc., ate doped polypyrrole as the source drain elec-
have been developed using semiconducting/con- trode115• Similarly a thin film [rn junction was
ducting polymers. For the fabrication of these de- made by depositing alternate layers of polypyrrole

J
536 INDIAN J CHEM, SEe. A, JUNE 1994

and pol thiophene on a platinum substr te with

contwll d electrochemical doping to m e the
polypyr ole layer Jrtype and polythiophe e layer
n-typell . Using chloroform soluble poly 3-hexyl
thiophe e) a 100-400 nm thick fIlm was cast on
indium-' oxide surface and then indi m was PI -

deposit on the surface by CVD techniq e to fa- Ag

Polypyrrole _
bricate'Schottky diode having room tern erature with Glucose
-Ket.- .. -
Glucose - .._-.- .. ~- -
rectifka ion property1l7,lls. Oxidase

by dep siting a fIlm of semiconducting olymer Fig. 7-A schematic diagram of a biosensor
such as poly[2-methoxy, 5-(2'-ethyl hexo )-1,4-
Light emitting
phenyle diodes
vinylene] on (LEDs) haveoxide
indium-tin beeRmade
coated
glass su ace1l9,120(Fig. 6). Si02
Since the electric conductivity of co ducting
polyme s varies in the presence of differe t chem-
ical sub tances, these are widely used as hemical
sensors or gas sensors. For example, thin fIlms of
polypyr ole show a decrease in conduc ivity in .. 13 N
4 .. -
_'-- -- -- - -. --
- .... -:::-- - -_I-
- --\..--- --
the pre ence of even 0.1% ammonia in ir, and '-5- -5 i ------
Water
--fI ..
-- .....
'
-\\- -
an iner ase in conductivity in 0.1% nitrog n diox- -----..--...-.......i ..".........,~_-+-.......,,--....r-....,..
ide and 0.1 % hydrogen sulfide. The sens' ivity of I I \
Gold Source Drain Gold
such g sensors is found to be 0.01% as con-
centrati n in airl21. These gas sensors a e oper- Fig. 8-Cross-sectional view of a 'moleculle based' transistor
using polyaniline. ..
able at mbient temperature .
Con cting polymers have been used to pre-
pare L ngmuir-Blodgett (LB) films. If it s possi- planted in vitro to obtain clinical information for
ble to c st a multilayered LB fIlm with th desired control of diseases like diabetes etc,13s(Fig. 7).
molec:u r architecture from soluble co ducting The most exciting prospect of conducting po-
poly me , the scope for miniaturization f elec- lymers has been envisaged in the development of
tronic: omponcnts such as micro circuit will be molecular electronics in which individual conduct-
remark bly extended. LB films with high olecu- ing polymer molecules will act as wires, diodes,
lair ord r have been cast from solutions of poly(al- transistors and other electronic devices139 (Fig. 8).
kyl thio hene)122and poly(alkyl pyrrole)123. It is expected that through LB t(~chnique highly
Som of the new fields for application of con- oriented molecular layers may be built up suc-
ducting polymers include gas separatio mem- cessively with desired polymers having controlled
brane 12, photo electrochemical celll25, op ical de- conductivity and predetermined sequence. This r •
vices126127, ion gates12S.129,memory sto age de- may perhaps be the right step to molecular elec-
vices 130131,non-linear circuit elements 132 etc. In tronics.
biologi al applications, conducting polym rs, viz., However, much work needs to be done before
polypy role are used as biosensors 133 a d con- some of these exciting ideas can be transformed
trolled release devices for pharmaceutic s134-136 into commercial products. Conducting polymers
Bioco patibility of the polymeric conduc ors is a having adequate mechanical strength and chemi-
plus pint for fabrication of artificial he rts con- cal/environmental durability as well as metallic
sisting of biological fuel cells and elect odes137. conductivity have not yet been synthesized. Al-
Condu ting polymer-based biosensors ma be im- though doping can enhance the conductivity to
very high orders of magnitude, the high level of
Wire to Front
Wire to ITO Electrode
doping required negates many of the desirable
properties of conducting polymers. Moreover,
complete control of the molecular architecture of
ITO- .~ I Meta conducting polymers still remains largely unattain-
'~
Polymer _J --Glass
able. However, these limitations would be over-
come in near future, and then a new generation of
Fig. 6-~chema\ic representation of a semiconduct~ngpolym- conducting polymers will offer the most versatile
er light emitting diode (lED) electronic materials for future technology.
 MAITI: PROBLEMS & PROMISES OF CONDUCTING POLYMERS 537

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28 Chien J C W, Wnek G E, Karasz F E & Hirsch J A,
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