Nobel Prize in Chemistry 2000

Electrically Conductive Plastic

 The Nobel Foundation 2000

 REVIEWS

The Discovery of Polyacetylene Film: The Dawning of an Era

of Conducting Polymers (Nobel Lecture)**
Hideki Shirakawa*

This lecture is not directly related to
our discovery and development of
conducting polymers to which the
Nobel Prize in Chemistry 2000 was
awarded. However, I would like to
present my previous work that I had
carried out just before we reached the
discovery of chemical doping. I hope
that this will be of use and deepen your
understandings by learning what had
happened before and how we reached
the idea of chemical doping.
Keywords: chemical doping con-
ducting materials Nobel lecture
polyacetylene Ziegler Natta cata-
lysts

1. Prologue with increasing the number of repeating units in the con-

It has been recognized for many years that a very long
linear-conjugated polyene might have various interesting
properties, especially optical, electrical, and magnetic proper-
ties. The definition of the polyene is that an even number of
methyne (CH) groups is covalently bonded to form a linear
carbon chain bearing one p electron on each carbon atom.
Therefore, the chemical structure of the polyene is best
represented by a formula H(CHCH)nH, where n denotes the
number of repeating units. Recently polyacetylene has be-
come a more popular name than polyene because polyacety-
lene, synthesized by the polymerization of acetylene, has been
used extensively as specimens for various studies.
Pople and Walmsley described in their article in 1962[1] that
Although it is not possible to synthesize very long polyenes
(polyacetylene) at present, general interest in conjugated
polymers with related, but rather more complex, structures
makes a full study of the electronic states of this simple polymer
worthwhile. Although the first polymerization of acetylene
was reported in no later than 1958 by Natta and co-workers,[2]
who prepared polyacetylene that is structurally identical to
the very long conjugated polyene, the work was not accepted
widely in the field. Before that time interest in this compound
was limited, for chemists, to theoretical approaches to explain
a red-shift of absorption maximum (bathochromic effect) and
an increase in absorption coefficient (hyperchromic effect)
jugation, and to elucidate bond alternation in connection with
an electron phonon interaction for physicists. An accumu-
lation of experimental observations on relatively short poly-
enes[38] coupled with theoretical considerations such as the
free-electron model and simple Hckel molecular orbital
treatments strongly suggested that the difference between the
lengths of double and single bonds decreases with increasing
the conjugation and that all the bonds tend to be of equal
length in an infinitely long polyene. In other words, one would
expect that the infinitely long, one-dimensional arrangement
of p electrons forms a half-filled band, or that the highest
occupied (HO) and the lowest unoccupied (LU) p-electron
bands merge with each other, leading to metallic behav-
ior.[9, 10] In the 1950s, however, it became theoretically clear
that the polyene with bond alternation is energetically more
stable than that with bonds of equal length.[1, 1113] Since two
geometrical isomers, trans and cis, are possible for each
double bond, two isomeric forms, all-trans (1) and all-cis (2),
are expected as the two extremes of polyacetylene isomers.
Experimentally the carbon carbon bond lengths in poly-

[*] Prof. H. Shirakawa

University of Tsukuba
Tsukuba, Ibaraki 305-8577 (Japan)
Fax: ( 81) 45-971-1389
E-mail: hideki@ims.tsukuba.ac.jp
[**] Copyright The Nobel Foundation 2001. We thank the Nobel
Foundation, Stockholm, for permission to print this lecture.

Angew. Chem. Int. Ed. 2001, 40, 2574 2580  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 1433-7851/01/4014-2575 $ 17.50+.50/0 2575
REVIEWS H. Shirakawa

acetylene were directly measured by Yannoni and Clarke[14]
with use of the nutation NMR spectroscopy, 1.36 and 1.44
for the double and single bonds, respectively, in the trans form
and 1.37 for the double bond in the cis form.
Even after the first synthesis by Natta and co-workers,[2]
polyacetylene remained for some time a material of interest to
only a few organic [15, 16] and polymer chemists[1719] because
the product was obtained as insoluble and infusible powders.
double bond is cis as a result of favored orbital interaction
between the inserting acetylene and the active site of the
catalyst. Whether cyclic trimerization occurs to give benzene
or polymerization proceeds to give polyacetylene is deter-
mined by the conformation of the growing chain that takes
either cisoid or transoid structure in the vicinity of the active
site of the catalyst.[22] As no cis form had been known until
then, an important question remained: why is the mechanism
capable of yielding only a trans configuration of the double
bonds in polyacetylene?[2, 19]

2. trans or cis?

Among the few chemists working on polyacetylene, S.

Ikeda and co-workers had been studying a mechanism of
acetylene polymerization in connection with olefin polymer-
ization by various Ziegler Natta catalysts. They found that
the polymerization yields not only highly polymerized poly-
acetylene but also benzene, that is, a cyclic trimer of acetylene,
and that the ratio of these two products depends upon species
of Ziegler Natta catalyst used. They also found the forma-
tion of alkylbenzenes as a minor by-product of the acetylene
polymerization with a catalyst system composed of titanium
tetrachloride and trialkylaluminum. In a series of experiments
using carbon-14 and deuterium, they noted that a labeled
ethyl group is introduced in the ethylbenzene when triethyl-
aluminum labeled with carbon-14 or deuterium is used as the
co-catalyst.[20] In other experiments on the oxidation of
polyacetylene by alkaline potassium permanganate, they
observed the formation of propionic and acetic acids that
are derived from the alkyl groups in the trialkylaluminum
used as the co-catalyst.[20] From these results, they concluded
that polyacetylene and benzene could be formed from the
same active site of the catalyst system. Thus, the reaction
proceeds by cis-opening of the triple bond in acetylene
followed by a cis insertion into the titanium alkyl bond of the
catalyst. This mechanism fits the orbital interaction consid-
eration by Fukui and Inagaki,[21] for the role of the catalyst
according to which the initially formed configuration of the
3. Discovery of Film Synthesis
The conventional method of polymerization in the labo-
ratory is such that the catalyst solution is stirred thoroughly to
carry out the reaction under homogeneous conditions. The
acetylene polymerization has not been an exception: it was
customary for polymer chemists who synthesized polyacety-
lene to bubble acetylene gas into a stirred catalyst solution.
Unfortunately, the product was obtained as an intractable
black powder that is very difficult to make into samples of a
shape suitable for measurement of spectra and physical
properties because of its insolubility and infusibility.
In 1967, soon after I joined Ikedas group, we succeeded in
synthesizing polyacetylene directly in the form of a thin film[23]
by a fortuitous error. After a series of experiments to
reproduce the error, we noticed that we had used a concen-
tration of the Ziegler Natta catalyst nearly a thousand times
greater than that usually used. It is worth noting that the
insolubility of polyacetylene contributes to the formation of
the film. In addition, it was found that the film is composed of
entangled micro-fibers (called fibrils), this discovery was
made by transmission electron microscope observation of an
extremely thin film and by scanning electron microscope
observation of the surface of a thick film (Figure 1). The fibril
diameter is in the range of 20 100 nm depending upon the

Hideki Shirakawa was born in Tokyo, Japan on August 20, 1936. He received his B.S., M.S., and Ph.D. from the Tokyo
Institute of Technology. After completion of his Ph.D. in 1966, he joined Professor Sakuji Ikedas group at the Research
Laboratory for Resources Utilization, Tokyo Institute of Technology, where he investigated acetylene polymerization for
the elucidation of the polymerization mechanism by Ziegler Natta catalysts. In 1967, he noticed on formation of
polyacetylene in a form of a film with metallic luster following an unforeseeable experimental error by one of his co-
workers. By chance, this silvery film caught the eyes of Professor Alan G. MacDiarmid, he was
invited to work in University of Pennsylvania for one year during 1976 and 1977 where they
found the chemical doping of acetylene jointly with Professor Alan J. Heeger. In November
1979, he moved from the Tokyo Institute of Technology to the Institute of Materials Science,
University of Tsukuba, where he was appointed Associate Professor. In October 1982, he was
promoted to full professor and worked on polyacetylene and other conducting polymers. He
retired from the University of Tsukuba at the end of March 2000. He is currently a member of
Council for Science and Technology Policy, Cabinet Office. He received the Award of the Society
of Polymer Science, Japan in 1983, Award for Distinguished Service in Advancement of Polymer
Science, from the Society of Polymer Science, Japan in 2000, the Order of Culture in 2000 from
Japanese Government, and the Nobel Prize for Chemistry in 2000.

2576 Angew. Chem. Int. Ed. 2001, 40, 2574 2580

Polyacetylene Films REVIEWS
Table 1. The trans contents of polyacetylene prepared at different temper-
atures T.[a]
T [8C] trans Content [%] T [8C] trans Content [%]
150 100.0 0 21.4
100 92.5 18 4.6
50 67.6 78 1.9
18 40.7

[a] Catalyst: Ti(O-n-C4H9)4/(C2H5)3A1, Ti/Al 4, [Ti] 10 mmol L1.

the cis form is thermodynamically less stable than the trans

one. The observed cis-rich polyacetylene synthesized at lower
temperatures suggested the cis-opening of the triple bond of
the acetylene monomer consistent with the cis-opening
mechanism proposed by Ikeda.[22] In case of the polymer-
ization being carried out at higher temperatures, spontaneous
isomerization of the growing chain of cis double bonds occurs
to give trans ones, also consistent with the cis-opening
mechanism proposed by Ikeda.[22] The cis-opening mechanism
has been supported by the nutation NMR study[14] and by the
infrared study of copolymers of acetylene and [D2]acety-
lene.[24] In conclusion, the open problem why only trans
polyacetylene had been known was solved by the use of
films.

Figure 1. a) Transmission electron micrograph of an extremely thin film of

polyacetylene. b) Scanning electron micrograph of the surface of a thick 4. Electrical Properties of As-Prepared
polyacetylene film.
Polyacetylene Films

polymerization conditions. These inherent properties of The electrical resistivity of as-prepared (untreated) films
polyacetylene are absolutely necessary for the film formation with various cis/trans contents was measured by the conven-
even under the higher concentration of the catalyst. One more tional two-probe method under vacuum in a temperature
important factor that should be added
is that the catalyst used at that time,
Ti(O-n-C4H9)4/(C2H5)3Al, was quite
unique from the viewpoint of its good
solubility in organic solvents, such as
hexane or toluene, to give a homoge-
neous solution, and its high activity to
give exclusively high molecular weight
and crystalline polymers. On the con-
trary, most Ziegler Natta catalysts
form precipitates to give inhomogene-
ous solutions when a titanium com-
pound is mixed with alkylaluminum.
The use of the films enabled us to
obtain clear infrared spectra, as shown
in Figure 2,[24] and analysis of these
spectra indicated that the configura-
tion of the double bonds strongly
depends on the temperature of poly-
merization. The trans contents of poly-
acetylene prepared by the Ziegler
Natta catalysts decreases with decreas-
ing polymerization temperature (Ta-
ble 1). Thermal study[25] indicated that
the irreversible isomerization of the cis
form occurs at temperatures higher Figure 2. Infrared spectra of polyacetylene synthesized at a) 78 8C, b) 20 8C, and c) 150 8C. Cf.
than 145 8C to give the trans form. Thus ref. [24], Figure 4.

Angew. Chem. Int. Ed. 2001, 40, 2574 2580 2577

REVIEWS
range of 120 20 8C.[26] The resistivity and energy gap of
trans-rich polyacetylenes were 1.0  104 W cm and 0.56 eV,
respectively, whereas the values of a cis-rich (80 %) one were
2.4  108 W cm and 0.93 eV, respectively. Hatano et al.[17]
reported that the resistivity and energy gap measured on
compressed pellets of powder polyacetylene synthesized by
the same catalyst system are in the range of 1.4  104 and 4.2 
l05 W cm, and 0.46 eV, respectively, in good agreement with
those for trans-rich polyacetylene film. In conclusion, it
became apparent that the intrinsic electrical properties do
not change very much between powder and film.
5. Halogenation of the Polyacetylene Films
Since no improvement in electrical conductivity was
observed in film form, we tried to use the polyacetylene films
as a source of graphite films as the carbon content of the
polymer is as high as 92.3 %. Thermograms from differential
thermal analysis of cis-rich polymer revealed the existence of
two exothermic peaks at 145 and 325 8C and one endothermic
peak at 420 8C which were assigned to cis trans isomer-
ization, hydrogen migration accompanied with cross-linking
reaction, and thermal decomposition, respectively[25]
(Scheme 1). Thermogravimetric analysis showed that weight
loss reached 63 % at 420 8C. Therefore, pyrolysis of as-
prepared polyacetylene films is not suitable for the prepara-
tion of graphite films.
Electrophilic addition of halogens such as chlorine and
bromine to a carbon carbon double bond is a well-known
Scheme 1. Thermal characteristics of polyacetylene.
Scheme 2. Possible resonance structures for the intermediate during the chlorination of 1,3,5-hexatriene to give three chlorinated products.
2578
H. Shirakawa
reaction and proceeds with good yield and few side reactions.
Elimination of hydrogen halide from adjacent carbon atoms
in a halogenated hydrocarbon is also a well-known reaction to
introduce a carbon carbon double or triple bond. Since
polyacetylene reacts with chlorine and bromine under mild
conditions, we thought carbonization might be possible by
combining the both reactions. Thus, a polyacetylene film was
treated with chlorine at room temperature to give a chlori-
nated polyacetylene film, which was subsequently treated
with a basic reagent to eliminate hydrogen chloride to give a
carbon film in satisfactory yield. However, we found that the
carbon film was hardly graphitized even when heated at
2000 8C for several hours.
Fully chlorinated polyacetylene has a chemical structure of
(CHCl-CHCl)n, corresponding to a polymer of 1,2-di-
chloroethylene. It is known, however, that 1,2-disubstituted
ethylenes hardly ever polymerize. Therefore, the chlorination
of polyacetylene is the sole method to synthesize poly(1,2-
dichloroethylene). To investigate the chlorination process of
the polyacetylene film, in situ measurements were planned to
obtain infrared spectra during the chlorination of the poly-
acetylene film.
It is well known that chlorination of the simplest conjugated
polyene, 1,3-butadiene, gives two isomeric products, the 1,2-
addition product (3,4-dichloro-1-butene) and the 1,4-addition
product (1,4-dichloro-2-butene). Likewise, 1,3,5-hexatriene
gives three isomers, 1,2-, 1,4-, and 1,6-addition products. The
reason why the reaction gives various products is explained by
the existence of different resonance structures in the inter-
mediate (Scheme 2). The third isomer is thermodynamically
the most stable because the molecule has an inner conjugated
diene structure with the largest energy of resonance stabiliza-
tion.
The motivation for the study was to confirm that the 1,2n-
addition of chlorine might occur as the initial step of the
reaction as shown in Scheme 3. Since the longer inner polyene
structure has the larger energy of resonance stabilization, it is
anticipated that products of 1,2n-addition with larger n
predominate, rather than a 1,2-addition product at the initial
step of the reaction or in the partially chlorinated polyacetylene.
If such structures could be detected by infrared spectroscopy,
one might expect that the positive charge on the intermediate
carbocation is able to migrate far away from the reaction site
through the conjugated polyene structure.
Contrary to this expectation, the infrared spectrophoto-
meter recorded no spectrum but only a 100 % absorption line
in the full range of 4000 to 400 cm1 immediately after
addition of a trace amount of chlorine to the film. The
polyacetylene film changed into an opaque material because
Angew. Chem. Int. Ed. 2001, 40, 2574 2580
Polyacetylene Films
Scheme 3. Possible resonance structures for the intermediate in the chlorination of polyacetylene, the expected chemical structures of partially chlorinated
polyacetylene are also shown.
of some very strong absorptions. Upon continued reaction
with additional chlorine, the spectrum became clearer to give
that corresponding to a chlorinated polyacetylene.
6. Epilogue
Later, we know that the very strong absorption is the so-
called doping induced infrared band composed of three
bands at 1397, 1288, and 888 cm1,[2729] which have extremely
strong absorption coefficients compared with those of the as-
prepared polymer. The observed isotope shifts of these bands
in the spectra of poly([13C2]acetylene) and poly([D2]acety-
lene) demonstrated that these bands are of vibrational
origin[27] in the vicinity of the carbocation or positively
charged carbon atom in the conjugated polyene. At present,
the carbocation formed in long conjugated polyenes is widely
known as a positively charged soliton[30] that acts as a charge
carrier for the electrical conduction. At that time, to my
regret, I did not recognize that this carbocation could be a
charge carrier and thus polyacetylene could be the first
conducting polymer. To open an era of conducting polymers,
we had to wait until we intentionally carried out the doping
Angew. Chem. Int. Ed. 2001, 40, 2574 2580
REVIEWS
experiment with bromine at the University of Pennsylvania,
on Tuesday 23rd, of November 1976, and then later also
successively with iodine.[31, 32]
At the end of my lecture I want to express my heartfelt thanks
to the late Professor Sakuji Ikeda who gave me a chance to
work on the acetylene polymerization, to Professor Masahiro
Hatano who contributed to the semiconducting polymers and
encouraged me on my work, to the late Professor Shu Kambara
who organized our polymer research group and supported us
in our work even after his retirement, and to Dr. Hyung Chick
Pyun with whom I encountered the discovery of polyacetylene
film by the fortuitous error. Dr. Takeo Ito was the first graduate
student to work for me and who made a great contribution at
the initial stage of this work. My special thanks are to
Professors Shiro Maeda, Takehiko Shimanouchi, and Mitsuo
Tasumi for helpful discussion on the vibration analyses study. I
am indebted to Mr. Shigeru Ando for measurements of solid-
state properties and to Professor Yoshio Sakai for electrical
conductivity measurements. Throughout this period, our
research was partly supported by Grant-in-Aids for Scientific
Research from Ministry of Education, Culture and Science of
Japan.
Received: January 22, 2001 [A 445]
2579
REVIEWS
[1] J. A. Pople, S. H. Walmsley, Mol. Phys. 1962, 5, 15.
[2] G. Natta, G. Mazzanti, P. Corradini, Atti Accad. Naz. Lincei Cl. Sci.
Fis. Mat. Nat. Rend. 1958, 25, 3.
[3] R. Kuhn, Angew. Chem. 1937, 50, 703.
[4] J. H. C. Nayler, M. C. Whiting, J. Chem. Soc. 1965, 3037.
[5] F. Bohlmann, H. Manhardt, Chem. Ber. 1956, 89, 1307.
[6] F. Sondheimer, D. A. Ben-Efraim, R. Wolovsky, J. Am. Chem. Soc.
1961, 83, 1675.
[7] Y. Takeuchi, A. Yasuhara, S. Akiyama, M. Nakagawa, Bull. Chem.
Soc. Jpn. 1973, 46, 2822.
[8] K. Knoll, R. R. Schrock, J. Am. Chem. Soc. 1989, 111, 7989.
[9] N. S. Bayliss, J. Chem. Phys. 1948, 16, 287; N. S. Bayliss, Quart. Rev.
1952, 6, 319.
[10] H. Kuhn, Helv. Chim. Acta 1948, 31, 1441.
[11] Y. Ooshika, J. Phys. Soc. Jpn. 1957, 12, 1238; Y. Ooshika, J. Phys. Soc.
Jpn. 1957, 12, 1246.
[12] H. C. Longuet-Higgins, L. Salem, Proc. R. Soc. A 1959, 172.
[13] M. Tsuji, S. Fuzinaga, T. Hashino, Rev. Mod. Phys. 1960, 32, 425.
[14] C. S. Yannoni, T. C. Clarke, Phys. Rev. Lett. 1983, 51, 1191.
[15] L. B. Luttinger, J. Org. Chem. 1962, 27, 1591.
[16] W. E. Daniels, J. Org. Chem. 1964, 29, 2936.
[17] M. Hatano, S. Kambara, S. Okamoto, J. Polym. Sci. 1961, 51, 26.
2580
H. Shirakawa
[18] W. H. Watson, Jr., W. C. MeMordie, Jr., L. G. Lands, J. Polym. Sci.
1961, 55, 137.
[19] D. J. Berets, D. S. Smith, Trans. Faraday Soc. 1968, 823.
[20] S. Ikeda, A. Tamaki, J. Polym. Sci. Polym. Lett. Ed. 1966, 4, 605.
[21] K. Fukui, S. Inagaki, J. Am. Chem. Soc. 1975, 96, 4445.
[22] S. Ikeda, Kogyo Kagaku Zasshi 1967, 70, 1880.
[23] T. Ito, H. Shirakawa, S. Ikeda, J. Polym. Sci. Polym. Chem. Ed. 1974,
12, 11.
[24] H. Shirakawa, S. Ikeda, Polym. J. 1971, 2, 231.
[25] T. Ito, H. Shirakawa, S. Ikeda, J. Polym. Sci. Polym. Chem. Ed. 1975,
13, 1943.
[26] H. Shirakawa, T. Ito, S. Ikeda, Makromol. Chem. 1978, 179, 1565.
[27] I. Harada, Y. Furukawa, M. Tasumi, H. Shirakawa, S. Ikeda, J. Chem.
Phys. 1980, 73, 4746.
[28] J. F. Rabolt, T. C. Clarke, G. B. Street, J. Chem. Phys. 1979, 71, 4614.
[29] C. R. Fincher, Jr., M. Ozaki, A. J. Heeger, A. G. MacDiarmid, Phys.
Rev. B 1979, 19, 4140.
[30] W. P. Su, J. R. Sebrieffer, A. J. Heeger, Phys. Rev. Lett. 1979, 42, 1698.
[31] H. Shirakawa, F. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J.
Heeger, J. Chem. Soc. Chem. Commun. 1977, 578.
[32] C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H.
Shirakawa, B. J. Louis, S. C. Gau, A. G. MacDiarmid, Phys. Rev. Lett.
1977, 39, 1098.
Angew. Chem. Int. Ed. 2001, 40, 2574 2580
 REVIEWS

Semiconducting and Metallic Polymers:

The Fourth Generation of Polymeric Materials (Nobel Lecture)**
Alan J. Heeger*

When asked to explain the impor-
tance of the discovery of conduct-
ing polymers, I offer two basic answers:
first they did not (could not?) exist, and
second, that they offer a unique combi-
nation of properties not available from Keywords: conducting materials
any other known materials. The first doping Nobel lecture
expresses an intellectual challenge; the polyacetylene solid-state physics
second expresses a promise for utility in
a wide variety of applications.

1. Introduction * Finallyand perhaps most importantconducting poly-

In 1976, Alan MacDiarmid, Hideki Shirakawa, and I,
together with a talented group of graduate students and post-
doctoral researchers discovered conducting polymers and the
ability to dope these polymers over the full range from
insulator to metal.[1, 2] This was particularly exciting because it
created a new field of research on the boundary between
chemistry and condensed-matter physics, and because it
created a number of opportunities:
* Conducting polymers opened the way to progress in
understanding the fundamental chemistry and physics of
p-bonded macromolecules
* Conducting polymers provided an opportunity to address
questions that had been of fundamental interest to
quantum chemistry for decades:
Is there bond alternation in long-chain polyenes?
What is the relative importance of the electron electron
and the electron lattice interactions in p-bonded macro-
molecules?
* Conducting polymers provided an opportunity to address
fundamental issues of importance to condensed-matter
physics as well, including, for example, the metal insulator
transition as envisioned by Neville Mott and Philip
Anderson and the instability of one-dimensional metals
discovered by Rudolph Peierls (the Peierls Instability)
[*] A. J. Heeger
Department of Physics, Materials Department
Institute for Polymers and Organic Solids
University of California, Santa Barbara
Santa Barbara, CA, 93106 (USA)
Fax: ( 1) 805-893-4755
E-mail: AHeeger@Uniax.com
[**] Copyright The Nobel Foundation 2001. We thank the Nobel
Foundation, Stockholm, for permission to print this lecture.
mers offered the promise of achieving a new generation of
polymers: materials which exhibit the electrical and optical
properties of metals or semiconductors and which retain
the attractive mechanical properties and processing advan-
tages of polymers.
Conducting polymers are the most recent generation of
polymers.[3] Polymeric materials in the form of wood, bone,
skin, and fibers have been used by man since prehistoric time.
Although organic chemistry as a science dates back to the
eighteenth century, polymer science on a molecular basis is a
development of the twentieth century. Hermann Staudinger
developed the concept of macromolecules during the 1920s.
Staudingers proposal was openly opposed by leading scien-
tists, but the data eventually confirmed the existence of
macromolecules. Staudinger was awarded the Nobel Prize in
Chemistry in 1953 for his discoveries in the field of
macromolecular chemistry. While carrying out basic
research on polymerization reactions at the DuPont com-
pany, Wallace Carothers invented nylon in 1935. Carothers
research showed the great industrial potential of synthetic
polymers; a potential which became reality in a remarkably
short time. Today, synthetic polymers are used in larger
quantities than any other class of materials (larger by volume
and larger by weight, even though such polymers have
densities close to unity). Polymer synthesis in the 1950s was
dominated by Karl Ziegler and Giulio Natta whose discov-
eries of polymerization catalysts were of great importance for
the development of the modern plastics industry. Ziegler
and Natta were awarded the Nobel Prize in Chemistry in 1963
for their discoveries in the field of the chemistry and
technology of high polymers. Paul Flory was the next giant
of polymer chemistry; he created modern polymer science
through his experimental and theoretical studies of macro-
molecules.

Angew. Chem. Int. Ed. 2001, 40, 2591 2611  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 1433-7851/01/4014-2591 $ 17.50+.50/0 2591
REVIEWS A. J. Heeger

Biography, Reminiscence, and Thanks

Alan J. Heeger: I was born on a bitter cold morning ( 20 8F below zero) in Sioux City (Iowa)
on January 22, 1936. I was told that when my father went out in the cold that morning to go to
the hospital to visit his wife and newborn first son, his car would not start. Despite advice to the
contrary, he walked to the hospital; his ears were frostbitten on the way.
The Heeger family came to Sioux City (Iowa) from Russia as Jewish immigrants in 1904 when
my father was a small boy (age four). My mother was born in Omaha (Nebraska); she was a
first generation child of Jewish immigrants. My mother and father were married in the midst of
the Great Depression. My early years were spent in Akron (Iowa), a small midwestern
town of 1000 people, approximately 35 miles from Sioux City. I went to elementary
school in Akron and my brother, Gerald, was born in Akron. My father died when I was
nine years old, it was his 45th birthday. After my fathers death, we moved to Omaha, so my
mother could be closer to her family. She raised us as a single parent in a house that we shared with her sister and her sisters
children.
One of my earliest memories, is of my mother telling me of the importance of obtaining a university education. When she
graduated from high school, she received a scholarship to go on to university but went to work instead; she was needed by
her parents to help support the family. It was always clear to me that it was my responsibility to go to university; prior to my
generation no one on either side of my family had an education that went beyond high school. I and my brother were the
first in our family to receive the PhD degree.
My high school years were fun and frustrating, typical of the teen years. The most important accomplishment was meeting
my wife, Ruth. I have loved her for nearly fifty years, and she remains my best friend.
I was always a good student, but I do not remember science being especially easy. On the contrary, I recall that in high
school, physics was somewhat mysterious. I was impatient to get on with my education, to get on with more important
things, and therefore completed high school one year early.
My undergraduate years at the University of Nebraska were a special time in my life; the combination of partying and
intellectual awakening that is what the undergraduate years are supposed to be. I went to the University with the goal of
becoming an engineer; I had no concept that one could pursue science as a career. After one semester, I was convinced that
engineering was not for me, and I completed my undergraduate studies with a dual major in Physics and Mathematics. The
highlight was a course (in my senior year) in Modern Physics taught by Theodore Jorgensen. Professor Jorgensen
introduced me to quantum physics and twentieth century science. I was honored by the University of Nebraska in 1998 with
a Doctor of Science (h.c.) and had the pleasure of giving a Physics colloquium at that time. Ted Jorgensen came to the
lecture; he was 92 and working hard on revising his book on the Physics of Golf.
Again, I was impatient to get on with real physics. I started the path toward my PhD in Physics at University of
California, Berkeley while working part time for Lockheed Space and Missle Division in Palo Alto, CA. When I started at
Berkeley, my goal was to do a theoretical thesis under Charles Kittel. Thus, when the decision was made to go for my degree
on a full-time basis, I went first to Kittel and asked if I could work for him. Kittel had just returned from a trip to Moscow
where he met Landau, and he told me that Landau required that a prospective student had to pass a rigorous examination
before he would agree to take the student into his research group. Kittel indicated that I should take the PhD qualifier and
come back to him after I had done so. When I came back to discuss my future with him, Kittel told me that he would take me
on. He said, however, that although I could do a thesis under his direction in solid-state theory, he did not think I would be a
first-rate theorist. He recommended instead that I consider working with someone who does experimental work in close
interaction with theory. This was perhaps the best advice that anyone ever gave meand I followed his advice. I joined the
research group of Alan Portis.
I remember with clarity my first day in the laboratory. I was doing original research; at last I was involved with real
physics. After only one day of carrying out magnetic measurements on an insulating antiferromagnet, KMnF3 , I wrote a
theory of antiferroelectric antiferromagnets and presented it to Portis with great pride. He was patient with me then and
again a few days later when I apologized and told him my theory was nonsense. Through my interactions with Portis (I
recall spending many hours talking with him in his office), I learned how to think about physics; more important, I began to
learn about good taste in the choice of problems.
After completing my degree, I went directly to join the Physics Department at the University of Pennsylvania (PENN)
where I remained for over twenty years. It was an exciting period for condensed-matter physics at PENN. Eli Burstein had
made major progress in building the solid-state group; he convinced Robert Schrieffer to come to PENN, and he and
Schrieffer attracted an outstanding group of young people. Beginning with my experimental studies of magnetic impurities
in metals and the Kondo Effect, I learned many-body physics from Schrieffer.
Anthony Garito introduced me to tetracyanoquinodimethane (TCNQ); I brought him into my research group for post-
doctoral research. We worked together from 1970 through 1975 on the metal physics of TTF-TCNQ and on the discovery of

2592 Angew. Chem. Int. Ed. 2001, 40, 2591 2611

Conducting Polymers REVIEWS

the Peierls instability in quasi-one-dimensional p-stacked molecular crystals. Although the direct observation (with both
X-ray diffraction and neutron scattering) of the incommensurate Peierls distortion with wave number q 2 kF proved that
we were on the right track, this was a time of controversy and stress.
In 1975, the first papers on the novel metallic polymer, poly(sulfur-nitride), (SN)x appeared in the literature. I was intrigued
by this unusual quasi-1D metal and wanted to get into the game. I learned that Alan MacDiarmid, a professor in the
Chemistry Department at PENN, had a background in sulfur-nitride chemistry, and I made an appointment to see him with
the goal of convincing him to collaborate with me and to synthesize (SN)x. I recall that we met late in the afternoon of an
autumn day. After quite a long discussion during which I made little progress toward my goal, I realized that while I was
saying (SN)x, he was hearing (Sn)x. Needless to say, he was not impressed with my enthusiasm for (Sn)x being a metal;
any chemist knew that tin was a metal!
Once MacDiarmid and I got past this initial language problem, a true collaboration began. We realized that it was a long
reach across the Chemistry Physics boundary, and we were determined to learn from one another. Although we
collaborated during the week, we typically met on Saturday mornings with no agenda; just to try to learn from one another.
At that time, I was fascinated with the metal insulator transition as envisioned by Mott. I recall that I tried to convey my
interest in this problem to MacDiarmid by asking him to consider a linear chain of hydrogen atoms as a model system. He
balked right away; a linear chain of hydrogen atoms did not exist. After discussion, we focused in on the abstraction of a
chain of p-bonded CH units as an example of a system that would have one unpaired electron per repeat unit. Shortly
thereafter, MacDiarmid went to Japan for a visit. MacDiarmid is a very visual person. He loved the golden color of films
and crystals of (SN)x, and he showed samples and photos of this golden material during his lectures. After one such lecture,
a Japanese scientist came up to him during the coffee break and told MacDiarmid that he, too, had some shiny films. Thus,
MacDiarmid was introduced to Hidekei Shirakawa and to polyacteylene.
When MacDiarmid returned from Japan, he told me with great excitement about (CH)x . With the help of a small addition to
an ONR grant from the Program Officer, Kenneth Wynne, we were able to bring Hideki Shirakawa to PENN as a Visiting
Scientist. The initial discovery of the remarkable increase in electrical conductivity of (CH)x and the identification of that
increase as resulting from a transition from insulator (semiconductor) to metal followed in a very short time.
The soliton in polyacetylene was born with the observation of an electron spin resonance (ESR) signal in the pure material
where there should not have been one. Building on the earlier work by Michael Rice on phase-solitons, I realized that if one
drew a domain wall between the two identical forms with opposite bond alternation, one would have an unpaired spin and
postulated that the origin of the ESR signal might be a bond-alternation domain wall. Curt Fincher, then a graduate student
in my research group, had recently discovered the doping-enhanced infrared vibrational modes which became a signature
of the doping. In a luncheon seminar before the solid-state group at PENN, I argued that these doping-induced IR modes
might arise from the enhanced electric field at IR frequencies that would result if a charged bond-alternation domain wall
were to move back and forth driven by the external field of the incident IR radiation. Schrieffer listened closely and made
some comments about kinks at the end of my talk. A few days later he showed me how the mid-gap state would arise from
the formation of such a bond-alternation domain wall and how that mid-gap state would have a reversed spin/charge
relation relative to that of fermions. Wu-Pei Su then worked this out in detail, and the SSH papers were written.
I was drawn to Santa Barbara by the promise of a singular opportunity to build a special Physics Department, by the promise
of continuing my close collaboration with Bob Schrieffer, by the opportunity to work with Fred Wudl, andfranklyby
the lure of this beautiful place. Wudl, then a synthetic chemist at Bell Laboratories, and I were recruited to the University of
California, Santa Barbara (UCSB) together and enjoyed a close and productive collaboration over a period of 15 years.
Daniel Moses and I have worked together for 20 years, initially at PENN and then at UCSB. Dan dragged me into ultra-fast
pulsed-laser spectroscopy and into fast-transient photoconductivity as probes of the excited states of semiconducting
polymers. Dan continues in his efforts to resolve the remaining fundamental scientific issues in the field of semiconducting
polymers with creativity and with determination.
In 1986, in the process of building the Macromolecular division of our newly formed Materials Department, we convinced
Paul Smith to leave DuPont Central Research and come to UCSB. Whereas I and Alan MacDiarmid and most of the early
players in the conducting polymer field were amateurs in the field of polymer science, Paul was a professional. He quickly
hammered into my head the importance of making conducting polymers processible, and he had the annoying habit of
asking me embarrassing questions such as What is the intrinsic electrical conductivity of a conducting polymer?.
Anything I know about the processing and mechanical properties of polymers, I learned from Paul.
In 1990, Paul Smith and I decided that conducting polymers as materials had developed to a level of maturity that
commercial products were possible. With this as a goal, we founded UNIAX Corporation. Fortunately, on a trip to China in
1986, I met Yong Cao and immediately realized that he was a remarkable scientist. I was able to bring him to Santa Barbara
in 1987. Initially, he worked with Paul and with me at UCSB. When we founded UNIAX, Yong Cao was the first employee.
His creativity, determination and scientific strength were critical to our scientific progress and to the success of UNIAX.
During the 1990s, UNIAX played a leading role in developing the science and technology of conducting polymers with
many important contributions.

Angew. Chem. Int. Ed. 2001, 40, 2591 2611 2593

REVIEWS A. J. Heeger

The twenty-five years since the discovery of conducting polymers have taken me on a great ride; always on the frontier and
always with the challenge of exciting discoveries. In 1990, the discovery of polymer LEDs by Richard Friend and colleagues
at Cambridge gave the field a boost with the promise of important technology and with the excitement of an entirely new set
of phenomena to study. In 1992, while doing post-doctoral research in my group at UCSB, Serdar Saricifici discovered
ultrafast photo-induced electron transfer from semiconducting polymers to acceptors such as C60 . This discovery resulted in
the development of polymer photodetectors and photovoltaic cells that offer promise for use in a variety of applications. In
1996, the discovery of amplified spontaneous emission and lasing (simultaneously by our group, by Richard Friends group
at Cambridge and by Valy Vardenys group at Utah) opened yet another potentially important direction. And it goes on.
None of this could have been accomplished without the hard work, dedication and creativity of the students and post-docs
with whom I have had the pleasure of working over the past forty years. I thank them all.
I have enjoyed the life of a scientist while sharing both the exciting days and the disappointments with Ruth. She has filled
my life with love and surrounded me with beauty. She has also gallantly put up with my eccentricities for more than forty
years. We have succeeded in starting an academic dynasty; our two sons, Peter and David are both academics. Peter is a
professor and medical doctor who is doing research on immunology at Case Western Reserve University. David is a
professor and neuroscientist at Stanford University where he studies human vision. I have had the great pleasure of
collaborating and publishing articles (as co-author) with both of my sons. Now I am looking forward to the emergence of
my four grandchildren, Brett, Jordan, Julia, and Alice, as the next generation of the Heeger family. Of all the
congratulations that I have received as a result of the Nobel Prize, I took greatest pleasure from their pride in their
grandfather.

Florys insights and deep understanding of macromolecular
phenomena are summarized in his book, Principles of
Polymer Chemistry, published in 1953, and still useful (and
used) today. Flory was awarded the Nobel Prize in Chemistry
in 1974 for his fundamental achievements, both theoretical
and experimental, in the physical chemistry of macromole-
cules.
Because the saturated polymers studied by Staudinger,
Flory, Ziegler, and Natta are insulators, they were viewed as
uninteresting from the point of view of electronic materials.
Although this is true for saturated polymers (in which all of
the four valence electrons of carbon are used up in covalent
bonds), in conjugated polymers the electronic configuration is
fundamentally different. In conjugated polymers, the chem-
ical bonding leads to one unpaired electron (the p elecron)
per carbon atom. Moreover, p bonding, in which the carbon
orbitals are in the sp2pz configuration and in which the orbitals
of successive carbon atoms along the backbone overlap, leads
to electron delocalization along the backbone of the polymer.
This electronic delocalization provides the highway for
charge mobility along the backbone of the polymer chain.
As a result, therefore, the electronic structure in conducting
polymers is determined by the chain symmetry (i.e. the
number and kind of atoms within the repeat unit), with the
result that such polymers can exhibit semiconducting or even
metallic properties. In his lecture at the Nobel Symposium
(NS-81) in 1991, Professor Bengt Ranby designated electri-
cally conducting polymers as the fourth generation of
polymeric materials.[3]
The classic example is polyacetylene, (CH)n, in which each
carbon is s bonded to only two neighboring carbons and one
hydrogen atom with one p electron on each carbon. If the
carbon carbon bond lengths were equal, the chem-
ical formula, (CH)n with one unpaired electron per
formula unit would imply a metallic state. Alternati-
vely, if the electron electron interactions were too strong,
(CH)n would be an antiferromagnetic Mott insulator. The
easy conversion into the metallic state on doping[1, 2] together
with a variety of studies of the neutral polymer have
eliminated the antiferromagnetic Mott insulator as a possi-
bility.
In real polyacetylene, the structure is dimerized as a result
of the Peierls Instability with two carbon atoms in the repeat
unit, (CHCH)n. Thus, the p band is divided into p and
p* bands. Since each band can hold two electrons per atom
(spin up and spin down), the p band is filled and the p* band is
empty. The energy difference between the highest occupied
state in the p band and the lowest unoccupied state in the
p* band is the p p* energy gap, Eg . The bond-alternated
structure of polyacetylene is characteristic of conjugated
polymers (Scheme 1). Consequently, since there are no
partially filled bands conjugated polymers are typically semi-
conductors. Because Eg depends upon the molecular structure
of the repeat unit, synthetic chemists are provided with the
opportunity and the challenge to control the energy gap by
design at the molecular level.
Although initially built upon the foundations of quantum
chemistry and condensed-matter physics, it soon became clear
that entirely new concepts were involved in the science of
conducting polymers. The discovery of nonlinear excitations
in this class of polymers, solitons in systems in which the
ground state is degenerate, and confined soliton pairs (polar-
ons and bipolarons) in systems in which the ground state
degeneracy has been lifted by the molecular structure, opened
entirely new directions for the study of the interconnection of
chemical and electronic structure. The spin charge separa-
tion characteristic of solitons and the reversal of the spin
charge relationship (relative to that expected for electrons as
fermions) in polyacetylene challenged the foundations of
quantum physics. The study of solitons in polyacetylene,[4]
stimulated by the Su Schrieffer Heeger (SSH) papers[5, 6]
dominated the first half of the 1980s.

2594 Angew. Chem. Int. Ed. 2001, 40, 2591 2611

Conducting Polymers REVIEWS
charge carriers (through doping)
and from the ability of those charge
carriers to move along the p-bonded
highway. Consequently, doped
conjugated polymers are good con-
ductors for two reasons:
a) Doping introduces carriers into
the electronic structure. Since
every repeat unit is a potential
redox site, conjugated polymers
can be doped n-type (reduced)
or p-type (oxidized) to a rela-
tively high density of charge
carriers[7]
b) The attraction of an electron in
one repeat unit to the nuclei in
the neighboring units leads to
carrier delocalization along the
polymer chain and to charge-
carrier mobility, which is extend-
ed into three dimensions through
interchain electron transfer.
Disorder, however, limits the car-
rier mobility and, in the metallic
state, limits the electrical conductiv-
ity. Indeed, research directed to-
ward conjugated polymers with im-
proved structural order and hence
higher mobility is a focus of current
activity in the field.
Figure 1 shows the early results
on the conductivity of polyacetylene
as a function of the doping level;
even in these early studies the con-
ductivity increased by more than a
factor of 107 to a level approaching
that of a metal.[2]
The electrochemical doping of
conducting polymers was discov-
Scheme 1. Examples of a few conjugated polymers, note the bond-alternated structures. ered by the MacDiarmid Heeger
collaboration in 1980 and opened
yet another scientific direction.[8]
The electrochemistry of conducting
The opportunity to synthesize new conducting polymers polymers has developed into a field of its own with
with improved/desired properties began to attract the atten- applications that range from polymer batteries and electro-
tion of synthetic chemists in the 1980s. Although it would be chromic windows to light-emitting electrochemical cells.[9]
an overstatement to claim that chemists can now control the Although I have emphasized the processing advantages of
energy gap of semiconducting polymers through molecular polymers, even as late as 1990, there were no known examples
design, we certainly have come a long way toward that goal. of stable metallic polymers which could be processed in the
Reversible doping of conducting polymers, with associ- metallic form (a requirement for broad use in industrial
ated control of the electrical conductivity over the full range products). This major outstanding problem was first solved
from insulator to metal, can be accomplished either by with polyaniline (PANI). PANI has been investigated exten-
chemical doping or by electrochemical doping. Concurrent sively for over 100 years and attracted interest as a conducting
with the doping, the electrochemical potential (the Fermi material for several important reasons; the monomer is
level) is moved either by a redox reaction or an acid base inexpensive, the polymerization reaction is straightforward
reaction into a region of energy where there is a high density and proceeds with high yield, and PANI has excellent stability.
of electronic states; charge neutrality is maintained by the As shown by Alan MacDiarmid and his collaborators in the
introduction of counter ions. Metallic polymers are, therefore, mid-80s, polyaniline can be rendered conducting through two
salts. The electrical conductivity results from the existence of independent routes; oxidation (either chemically or electro-

Angew. Chem. Int. Ed. 2001, 40, 2591 2611 2595

REVIEWS
Figure 1. Electrical conductivity of trans-(CH)x as a function of (AsF5)
dopant concentration. The trans and cis polymer structures are shown in
the inset.
chemically) of the leuco-emeraldine base or protonation of
the emeraldine base through acid base chemistry.[10] Because
the insertion of counter ions is involved in both routes;
conducting polyaniline is a salt (a polycation with one anion
per repeat unit).
Processing high molecular weight polyaniline into useful
objects and devices proved to be a difficult problem. Yong
Cao, Paul Smith, and I made important progress in 1991 by
using functionalized protonic acids to both convert PANI into
the metallic form and, simultaneously, render the resulting
PANI complex soluble in common organic solvents.[11] The
functionalized counter ion acts like a surfactant in that the
charged head group is ionically bound to the oppositely
charged protonated PANI chain, and the tail is chosen to be
compatible with nonpolar or weakly polar organic liquids (in
the case of solutions) or the host polymer (in the case of
blends). The processibility of PANI induced by the surfac-
tant counter ions has enabled the fabrication of conducting
polymer blends with a variety of host polymers.[12] Since the
blends are melt-processible as well, the counter ion induced
processibility of polyaniline provides a route to conducting
polymer blends for use in industrial products. The surfac-
tant counter ions offer an unexpected advantage; they lead
to the formation of a self-assembled network morphology in
the PANI polyblends.[13] Because of these interpenetrating
networks, the threshold for the onset of electrical conductivity
in blends with traditional insulating host polymers is reduced
to volume fractions well below 1 %.[14] The PANI network is
sufficiently robust that it remains connected and conducting
even after the removal of the host polymer, thus opening
another new direction; the fabrication of novel electrodes for
2596
A. J. Heeger
use in electronic devices. The use of surfactant counter ions
was introduced with the goal of making PANI processible in
the conducting form. The self-assembly of phase-separated
networks was an unexpectedbut very welcomebonus.
Conducting polymers were initially attractive because of
the fundamental interest in the doping and the doping-
induced metal insulator transition. However, the chemistry
and physics of these polymers in their non-doped semi-
conducting state are of great interest because they provide a
route to plastic electronic devices. Although polymer
diodes were fabricated and characterized in the 1980s,[15] the
discovery of light-emitting diodes (LEDs) by Richard Friend
and colleagues at Cambridge in 1990[16] provided the stimulus
for a major push in this direction. The polymer light-emitting
diode is, however, only one of a larger class of devices in the
emerging class of plastic opto-electronic devices, including
lasers, high sensitivity plastic photodiodes (and photodiode
arrays) and photovoltaic cells, ultrafast image processors
(optical computers), thin-film transistors, and all-polymer
integrated circuits; in each case these sophisticated electronic
components are fabricated from semiconducting and metallic
polymers. All of these have a common structure: they are
thin-film devices in which the active layers are fabricated by
casting the semiconducting and/or metallic polymers from
solution (e.g. spin-casting or ink-jet printing).
2. Doping
Charge injection onto conjugated, semiconducting macro-
molecular chains, doping, leads to the wide variety of
interesting and important phenomena which define the field.
As summarized in Figure 2, reversible charge injection by
doping can be accomplished in a number of ways.
2.1. Chemical Doping by Charge Transfer
The initial discovery of the ability to dope conjugated
polymers involved charge-transfer redox chemistry; oxidation
(p-type doping), or reduction (n-type doping),[1, 2, 7] as illus-
trated with the following examples:
a) p-type doping [Eq. (1)]
(p-polymer)n 3/2 n y(I2) ! [(p-polymer)y(I3)y]n (1)
b) n-type doping [Eq. (2)]
(p-polymer)n [Na(C10H8) .]y !
(2)
[(Na)y(p-polymer)y]n (C10H8)0
When the doping level is sufficiently high, the electronic
structure evolves to that of a metal.
2.2. Electrochemical Doping
Although chemical (charge transfer) doping is an efficient
and straightforward process, it is typically difficult to control.
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
Conducting Polymers REVIEWS
copolymer. Upon protonation of the emer-
aldine base to the emeraldine salt, the
proton induced spin-unpairing mechanism
leads to a structural change with one un-
paired spin per repeat unit, but with no
change in the number of electrons.[17, 18] The
result is a half-filled band and, potentially, a
metallic state where there is a positive
charge in each repeat unit (from protona-
tion) and an associated counter ion (e.g. Cl,
HSO4, dodecylbenzenesulfonate (DBSA)
etc., the counter ion is not shown in
Scheme 2). This remarkable conversion
from semiconductor into metal has been
well-described, but it is not well understood
from the view of basic theory. There are no
calculations which show that the metallic
(emeraldine salt) final state is lower in
energy than the semiconductor and no de-
Figure 2. Doping mechanisms and related applications.
tailed understanding of the rearrangement
reactions sketched in Scheme 2.

Complete doping to the highest concentrations yields reason-

ably high-quality materials. However, attempts to obtain
intermediate doping levels often result in inhomogeneous
doping. Electrochemical doping was invented to solve this
problem.[8] In electrochemical doping, the electrode supplies
the redox charge to the conducting polymer, while ions diffuse
into (or out of) the polymer structure from the nearby
electrolyte to compensate the electronic charge. The doping
level is determined by the voltage between the conducting
polymer and the counter electrode; at electrochemical
equilibrium the doping level is precisely defined by that
voltage. Thus, doping at any level can be achieved by setting
the electrochemical cell at a fixed applied voltage and simply
waiting as long as necessary for the system to come to
electrochemical equilibrium (as indicated by the current
through the cell going to zero). Electrochemical doping is
illustrated by the following examples:
a) p-type doping [Eq. (3)]

(p-polymer)n [Li(BF4)]soln !
(3)
[(p-polymer)y(BF4)y]n Lielectrode

b) n-type doping [Eq. (4)] Scheme 2. Protonation induced spin unpairing in polyaniline, conversion
from insulator into metal with no change in the number of electrons. The
(p-polymer)n Lielectrode ! counter ion is not shown.
(4)
[(Li)y(p-polymer)y]n [Li(BF4)]soln

2.3. Doping of Polyaniline by Acid Base Chemistry 2.4. Photo-doping

Polyaniline provides the prototypical example of a chemi-
cally distinct doping mechanism.[10] Protonation by acid base
chemistry leads to an internal redox reaction and the
conversion from semiconductor (the emeraldine base) into
metal (the emeraldine salt). The doping mechanism is shown
in Scheme 2. The chemical structure of the semiconducting
emeraldine-base form of polyaniline is that of an alternating
The semiconducting polymer is locally oxidized and (near-
by) reduced by photo-absorption and charge separation
(electron hole pair creation and separation into free
carriers), Equation (5), where y is the number of electron
hole pairs (dependent upon the pump rate in competition
with the recombination rate).
(p-polymer)n hn ! [{p-polymer}y {p-polymer}y]n (5)

Angew. Chem. Int. Ed. 2001, 40, 2591 2611 2597

REVIEWS
The branching ratio between free carriers and bound
excitons (and the closely related issue of the magnitude of
the exciton binding energy) is a subject of continuing
discussion.[19]
Following photoexcitation from the ground state (1Ag in the
notation of molecular spectroscopy) to the lowest energy state
with proper symmetry (1Bu), recombination to the ground
state can be either radiative (luminescence) or nonradiative.
Some families of conjugated polymers exhibit high lumines-
cence quantum efficiencies (for example, poly(phenylene
vinylene) (PPV), and poly(paraphenylene) (PPP) and their
soluble derivatives); others do not (for example, polyacetyl-
ene and the polythiophenes). A number of mechanisms have
been identified that lead to low quantum efficiencies for
photoluminescence. Rapid bond relaxation in the excited
state and the formation of solitons with states at mid gap
prevent radiative recombination in polyacetlyene.[4] The
existence of an Ag state or a triplet excited state below the
1
Bu state will favor nonradiative recombination (in both cases,
direct radiative transitions to the ground state are forbidden).
Interchain interactions in the excited state (excimers) also
lead to nonradiative channels for decay.[2022]
2.5. Charge Injection at a Metal Semiconducting
Polymer Interface
Electrons and holes can be injected from metallic contacts
into the p* and p bands, respectively:
a) Hole injection into an otherwise filled p band [Eq. (6)]
(p-polymer)n y(e) ! [(p-polymer)y]n (6)
b) Electron injection into an empty p* band [Eq. (7)]
(p-polymer)n y(e) ! [(p-polymer)y]n (7) other materials. I focus on a few of these as illustrative
In the case of charge injection at a metal semiconducting
(MS) polymer interface, the polymer is oxidized or reduced
(electrons are added to the p* band or removed from the
p band). However, the polymer is not doped in the sense of
chemical or electrochemical doping, for there are no counter
ions. This distinction becomes particularly clear when com-
paring charge injection in the polymer light-emitting di-
ode[16, 23] (where there are no ions) with that in the polymer
light-emitting electrochemical cell where electrochemical
doping with associated redistribution of ions provides the
mechanism for charge injection.[9]
As indicated in Figure 2, each of the methods of charge-
injection doping leads to unique and important phenomena.
In the case of chemical and/or electrochemical doping, the
induced electrical conductivity is permanent, until the carriers
are chemically compensated or until the carriers are purpose-
ly removed by undoping. In the case of photo-excitation,
the photoconductivity is transient and lasts only until the
excitations are either trapped or decay back to the ground
state. In the case of charge injection at an MS interface,
electrons reside in the p* band and/or holes reside in the
p band only as long as the biasing voltage is applied.
2598
A. J. Heeger
Because of the self-localization associated with the forma-
tion of solitons, polarons, and bipolarons, charge injection
leads to the formation of localized structural distortions and
electronic states in the energy gap.[4] In the case of photo-
doping, the redistribution of oscillator strength associated
with the sub-gap infrared absorption and the corresponding
bleaching of the interband (p p*) transition provide a route
to nonlinear optical (NLO) response. Real occupation of low
energy excited states[4, 24] and virtual occupation of higher-
energy excited states (in the context of perturbation theory)[25]
lead to, respectively, resonant and nonresonant NLO re-
sponse.
By charge-injection doping at an MS interface, the polymer
semiconductor can be used as the active element in thin-film
diodes[15] and field-effect transistors (FETs).[2628] Tomozawa
et al.[15] demonstrated the first example of an electronic-
device component fabricated by casting the active polymer
directly from solution; even these early diodes exhibited
excellent current voltage characteristics. Dual-carrier injec-
tion in metal/polymer/metal structures provides the basis for
polymer light-emitting diodes (LEDs).[23] In polymer LEDs,
electrons and holes are injected from the cathode and anode,
respectively, into the undoped semiconducting polymer; light
is emitted when the injected electrons and holes meet in the
bulk of the polymer and recombine with the emission of
radiation.[16] Thus, as summarized in Figure 2, doping is a
common feature of conducting polymers; doping leads to a
remarkably wide-range of electronic phenomena.
3. Novel Properties Generate New Technology
As emphasized in the Introduction, conducting polymers
exhibit novel properties; properties not typically available in
examples:
a) Semiconducting and metallic polymers which are soluble
in and processible from common solvents
b) Transparent conductors
c) Semiconductors in which the Fermi energy can be con-
trolled and shifted over a relatively wide range.
In each case, the property is related to a fundamental
feature of the chemistry and/or physics of the class of
conducting polymers. These novel properties enable a number
of applications including polymer LEDs, conducting polymers
as electrochromic materials, polymer photodetectors, and
polymer photovoltaic cells.
3.1. Semiconducting and Metallic Polymers which are
Soluble in, and Processible from, Common Solvents
Because the interchain electron-transfer interactions of
conjugated polymers are relatively strong compared with the
van der Waals and hydrogen-bonding interchain interactions
typical of saturated polymers, conducting polymers tend to be
insoluble and infusible. Thus, there was serious doubt in the
early years following the discovery that p-conjugated poly-
mers could be doped to the metallic state as to whether or not
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
Conducting Polymers REVIEWS
processing methods could be developed. Significant progress styrene sulfonic acid complexes can be made with particle
has been made using four basic approaches: sizes less than 1 mm.[34] Transparent films with a specific
1. Side-chain functionalization; principally used for process- resistivity of 1 10 W cm can be cast from such dispersions.
ing semiconducting polymers from solution in organic Poly(ethylenedioxythiophene) polystyrene sulfonate (PE-
solvents or from water DOT PSS) can be prepared as a stable dispersion in
2. Precursor-route chemistry, principally used for processing water.[34, 35] Films of PEDOT PSS are semi-transparent and
polyacetylene and PPV into thin films can be spin-cast with a surface resistance of approximately
3. Counter-ion induced processing, principally used for 500 W cm2 and with 75 % transmission.
processing polyaniline in the metallic form from organic
solvents
4. Aqueous colloidal dispersions created by template syn-
thesis, principally used for processing polyaniline and
poly(ethylenedioxythiophene) (PEDOT). 3.2. Transparent Metallic Polymers
The addition of moderately long side chains onto the
monomer units resulted in derivatives of polythiophene, the Metals reflect light at frequencies below the plasma
poly(3-alkylthiophenes), or P3ATs; see Scheme 1. Since the frequency, wp , defined in Equation 8 where N is the number
side chains decrease the interchain coupling and increase the of electrons per unit volume, e is the electron charge, and m*
entropy, these derivatives can be processed either from is the effective mass (the optical mass) of the electrons in
solution or from the melt. Similarly, side-chain functionaliza- the solid.
tion of PPV (see Scheme 1) has progressed to the point where
a variety of semiconducting polymers and copolymers are w 2p 4pN e2/m* (8)
available with energy gaps that span the visible spectrum.[29]
Water solubility was achieved by incorporating polar groups At frequencies above the plasma frequency, metals are
such as (CH2)nSO3M (M metal) into the side chains (so- transparent.[36] For conventional metals (Na, Cu, Ag, etc.), N
called self-doped polymers).[30, 31] is of order 1023 per unit volume. As a result, the plasma
The ability to fabricate optical-quality thin films by spin- frequency is in the ultraviolet; therefore, conventional metals
casting from solution has proven to be an enabling step in the appear shiny and metallic-looking in the spectral range over
development of plastic electronic devices such as diodes, which the human eye is sensitive.
photodiodes, LEDs, LECs, optocouplers, and thin-film tran- Metallic polymers have a lower density of electrons; both
sistors.[32] the length of the repeat unit along the chain and the interchain
The counter-ion induced processibility of metallic poly- spacing are relatively large compared to the interatomic
aniline utilizes bifunctional counter ions such as DBSA to distances in conventional metals. Typically, therefore, for
render the polymer soluble.[11] The charge on the SO3 ion metallic polymers N is of order 2 5  1021 cm3. Thus, for
head group forms an ionic bond with the positive charge metallic polymers, the plasma frequency is at approximately
(proton) on the PANI chain; the hydrocarbon tail likes 1 eV.[37, 38] The reflectance of high quality, metallic polypyrrole
organic solvents. Processing PANI in the conducting form (PPy; doped with PF6) is shown in Figure 3. Metallic polymers
resulted in materials with improved homogeneity and crys-
tallinity, and with correspondingly improved electrical con-
ductivities;[33] the solubility of metallic PANI in organic
solvents has also enabled the fabrication of conducting blends
of PANI with a variety of insulating host polymers.[11, 12] These
polymer blends exhibit a remarkably low percolation thresh-
old as a result of the spontaneous formation of an inter-
penetrating-network morphology.[13]
Template-guided synthesis of conducting polymers was first
reported by S. C. Yang and colleagues.[34] The molecular
template, in most cases, polyacids such as polystyrene sulfonic
acid, binds the monomer, for example aniline, to form
molecular complexes which are dispersed in water as colloidal
particles. Upon polymerization, the aniline monomers form
polyaniline and remain attached to the template to form the
template polyaniline complex. By judicious choice of the
template molecule and the polymerization conditions, stable
submicron-size colloidal particles of polyaniline template
aggregate can be formed during polymerization. The stabili-
zation against coagulation arises from the Coulomb repulsion
between particles, which is a result of the surface charge
provided by the extra sulfonic acid groups in polystyrene Figure 3. Reflectance spectra of PPy-PF6 near the metal insulator
sulfonic acid. Very stable dispersions of polyaniline poly- transition; inset shows the low-energy spectra with expanded scale.

Angew. Chem. Int. Ed. 2001, 40, 2591 2611 2599

REVIEWS
exhibit high reflectance (and thus look shiny) in the
infrared, but they are semitransparent in the visible part
of the spectrum. The residual absorption above the
plasma frequency arises from interband (p p*) transitions
between the partially filled p band and the lowest energy
p* band.
Optical-quality thin films of metallic polymers are useful,
therefore, as transparent electrodes.[39] For example, polyani-
line,[40] polypyrrole,[41] and PEDOT[42] (Scheme 1) have been
used as transparent hole-injecting electrodes in polymer
LEDs (the initial demonstration of mechanically flexible
polymer LEDs utilized PANI as the anode[40] ). Transparent
conducting films can be used for a variety of purposes; for
example, as antistatic coatings, as electrodes in liquid-crystal
display cells or in polymer LEDs, or for fabricating electro-
chromic windows.
3.3. Semiconductors in which the Fermi Energy can be
Shifted across the Energy Gap
In comparison with traditional inorganic semiconductors,
semiconducting polymers cannot be considered materials with
ultra-high purity. As a result, although many device concepts
have been demonstrated using semiconducting polymers as
the active materials,[32] there was early skepticism that these
novel semiconductors could be used in commercial applica-
tions.
In some ways, however, semiconducting polymers are more
robust than their inorganic counterparts. In particular, where-
as pinning of the Fermi energy by surface states is a major
problem in conventional semiconductors, the Fermi energy
can be controlled and shifted all the way across the energy gap
in conjugated polymers. The absence of Fermi-level pinning
and the ability to shift the chemical potential all the way
across the energy gap are fundamentally important; these
novel features of semiconducting polymers underlie the
operation of polymer LEDs, polymer LECs, and polymer
photodiodes.
One might have expected chemical reactions between the
metal electrode and the polymer to lead to interface states
that pin the Fermi level, as in inorganic semiconductors.
Experiments have shown, however, that these interfacial
interactions do not lead to pinning of the Fermi level.
For example, electroabsorption measurements were used
to determine the built-in electric field in metal semi-
conductor metal (MSM) structures of the kind used
for polymer LEDs.[43] The results indicated that the maxi-
mum internal field is nearly equal to the single-particle
energy gap; the built-in field directly tracked the dif-
ference in work functions of the two metal electrodes,
as originally proposed by Parker.[23] Thus, the Fermi level
is not pinned by surface states. The absence of Fermi-
level pinning in semiconducting polymers is a major
advantage: conceptually, it greatly simplifies the device
physics, and technologically, it greatly simplifies the device
fabrication.
2600
A. J. Heeger
4. Semiconducting Polymers: Electronic Structure
and Bond Relaxation in Excited States
4.1. Band Structure, Electron Lattice Interaction,
Electron Electron Interaction, and Disorder
Although the linear and nonlinear optical properties of
conducting polymers have been investigated for over a
decade, there is still controversy over the description of the
elementary excitations. Are the lowest-energy elementary
excitations mobile charge carriers (charged polarons) either
injected at the contacts or created directly via inter-band
photoexcitation, or are the lowest-energy excitations bound
neutral excitons?[19] The answer is of obvious importance
from the perspective of our basic understanding of the physics
of conducting polymers. The answer is also important for
applications based on these materials.
The central issue relates to the strength of the electron
electron interactions relative to the bandwidth, relative to the
electron phonon interaction and relative to the strength of
the mean disorder potential. Strong electron electron inter-
actions (electron hole attraction) lead to the creation of
localized and strongly correlated negative and positive polar-
on pairs: neutral polaron excitons. Well screened electrons
and holes with associated lattice distortions (charged polar-
ons) on the other hand, are more appropriately described
using a band picture supplemented by the electron phonon
interaction. Molecular solids such as anthracene[44] are
examples of the former, where the absorption is dominated
by excitonic features; whereas inorganic semiconductors such
as Si and GaAs are examples of the latter (where rigid band
theory is a good approximation).
The electronic structure of conjugated polymers was
described by SSH[5, 6] in terms of a quasi-one-dimensional
tight-binding model in which the p electrons are coupled to
distortions in the polymer backbone by the electron phonon
interaction. In the SSH model, photoexcitation across the p
p* band gap creates the self-localized, nonlinear excitations of
conducting polymers; solitons (in degenerate ground state
systems), polarons, and bipolarons.[4] Direct photogeneration
of solitons and polarons is enabled by the Franck Condon
overlap between the uniform chain in the ground state and the
distorted chain in the excited state.[45, 46] When the ground
state is nondegenerate, as in the PPVs, charged polaron pairs
can either separate as mobile charged polarons or form bound
polaron excitons; that is, neutral bipolarons bound by a
combination their Coulomb attraction and their shared
distortion. Photoluminescence can be described in terms of
the radiative decay of polaron-excitons.
Conjugated polymers are p-bonded macromolecules, mol-
ecules in which the fundamental monomer unit is repeated
many, many times. Thus, N, the Staudinger index as in (CH)N,
is large. Since the end-points are not important when N is
large, the p-electron transfer integral (denoted as b in
molecular orbital theory,[47] and t in tight-binding theory)
tends to delocalize the electronic wavefunctions over the
entire macromolecular chain. This tendency toward delocal-
ization is limited by disorder (which tends to localize the
wavefunctions) and by the Coulomb interaction, which binds
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
Conducting Polymers REVIEWS
electrons when transferred to a nearby repeat unit to the
positive charge left behind; that is, to the hole.
In principle, disorder can be controlled. Chain extended
and chain aligned samples can be prepared. Indeed, by
utilizing the method of gel-processing of blends of conjugated
polymers in polyethylene,[48] a high degree of structural order
has been attained.[45, 46] Thus, as a starting point, it is useful to
consider idealized samples in which the macromolecular
chains are chain extended and chain aligned.
The relative importance of the Coulomb interaction versus
the band structure is a classic problem of the field. In tight-
binding theory, the p-electron band structure extends over a
band width, W 2 z t where z is the number of nearest
neighbors. Thus, for linear polymers with z 2 and t  2.5 eV,
W  10 eV.[4] Since the size of the monomer, typically 5 10
along the chain axis, is the smallest length in the problem, the
monomer length is the effective Bohr radius. Thus, on
general grounds, one expects the electron hole binding Scheme 3. Polyacetylene: a) undimerized structure, b) dimerized structure
energy to be reduced from 13.5 eV (the electron proton resulting from Peierls instability, c) cis-polyacatylene, d) degenerate A and
Coulomb binding energy in the H atom where the Bohr radius B phases in trans-polyacetylene, e) soliton in trans-polyacetylene, f) the
is 0.53 ) by a factor of 10 20 simply because of the change in soliton domain wall extending over a number of carbon atoms.

length scale. Dielectric screening provides an additional

reduction factor of e, where e  3 (typical of conjugated
polymers) is the dielectric constant for an electric field along
the chain. Thus, the binding energy is expected to be no more
than a few tenths of an eV. Since the typical band widths and
band gaps are all in the eV range, one can start with a one-
electron band approach and treat the Coulomb energy as a
perturbation. In this description, the electron hole bound
states are Wannier excitons which are delocalized over a
number of repeat units. There are obvious cases where this
argument breaks down. For example, one finds that in
structures containing benzene rings, specific sub-bands have
bandwidth near zero (nodes in the wavefunction reduce the
effective transfer integral to zero). When electrons and holes
occupy such narrow bands, the corresponding excitons are
easily localized by the Coulomb interaction onto a single
monomer. Thus, in general, one can expect both Wannier-
like excitons and Frenkel-like excitons for electrons and
holes originating from different bands in the same polymer.
determined by the magnitude of the Fermi wave-vector (kF).
Since kF p/2 a for the half-filled band of trans-(CH)x, the
Peierls distortion doubles the unit cell, converting trans-(CH)x
into trans-(HCCH)x, see Scheme 3 b where, schematically,
the dimerization is drawn as alternating single bonds and
double bonds (in reality, shorter and longer bonds). The
p band of (CH)x is split into two sub-bands, a fully occupied
p band (the valence band in semiconductor terminology) and
an empty p* band (the conduction band), each with a wide
bandwidth ( 5 eV) and significant dispersion. The resulting
band structure and associated density of states, shown in
Figure 4, results from the opening of the band gap that
originates from the doubling of the unit cell as a result of the
bond alternation caused by the Peierls instability of the 1D
metal.

4.2. Electronic Structure of Polyacetylene

Trans-polyacetylene (trans-(CH)x) was the first highly

conducting organic polymer.[1, 2] The simple chemical struc-
ture, CH units repeated (see Scheme 3 a), implies that each
carbon contributes a single pz electron to the p band. As a
result, the p band would be half-filled. Thus, based upon this
structure, an individual chain of neutral polyacetylene would
be a metal; since the electrons in this idealized metal could
move only along the chain, polyacetylene would be a one-
dimensional (1D) metal. However, experimental studies show
clearly that neutral polyacetylene is a semiconductor with an
energy gap of approximately 1.5 eV. Rudolf Peierls showed
many years ago[49] that 1D metals are unstable with respect to
a structural distortion which opens an energy gap at the Fermi
level, thus rendering them semiconductors. In the Peierls
instability, the periodicity (L p/kF) of the distortion is
Figure 4. Electronic structure of semiconducting polyacetylene; left: band
structure, right: density of states. The energy opens at k p/2a as a result of
Peierls distortion.
Shortly after the initial discovery of doping and the metal
insulator transition in polyacetylene, the SSH description of
the electronic structure was proposed.[5, 6] The construction of
the remarkably successful SSH Hamiltonian was based on two
assumptions:
1. the p-electronic structure can be treated in the tight-
binding approximation with a transfer integral t  2.5 eV

Angew. Chem. Int. Ed. 2001, 40, 2591 2611 2601

REVIEWS A. J. Heeger

2. the chain of carbon atoms is coupled to the local electron

density through the length of the chemical bonds [Eq. (9)]
where tn,n1 is the bond-length dependent hopping integral
from site n to n 1, and un is the displacement from
equilibrium of the nth carbon atom.

tn,n1 to a(un1 un) (9)

The first assumption defines the lowest order hopping

integral, to , in the tight-binding term that forms the basis of the
Hamiltonian. The second assumption provides the first-order Figure 5. Total energy of the dimerized polyacetylene chain; note the
correction to the hopping integral. This term couples the double minimum associated with the spontaneous symmetry breaking and
electronic states to the molecular geometry, giving the the two-fold degenerate ground state.
electron phonon (el ph) interaction where a is the el ph
coupling constant. The bond-length dependent hopping
integral is physically correct, as indicated by bond alternation 4.3. The Electronic Structure of Poly(phenylene vinylene)
observed in polyacetylene.[50, 51] The precise form of Equa-
tion (9), in which the dependence of the hopping integral on Poly(phenylene vinylene) (PPV) and its soluble derivatives
the CC distance is linearized for small deviations about to , is have emerged as the prototypical luminescent semiconduct-
the first term in a Taylor expansion. The resulting SSH ing polymers. Since PPV has a nondegenerate ground state,
Hamiltonian is then written as the sum of three terms[5, 6] structural relaxation in the excited state leads to the formation
[Eq. (10)] where pn are the nuclear momenta, un are the of polarons, bipolarons, and neutral excitons. Prior to treating
displacements from equilibrium, m is the carbon mass, and K the structural relaxation in the excited state, however, one
is an effective spring constant. The c n;s and cn,s are the fermion needs to develop a satisfactory description of the electronic
creation and annihilation operators for site n and spin s. excited states.
In PPV, with eight carbons in the main-chain repeat unit,
X the p band is split into eight sub-bands. Since each band can
H SSH t0 aun 1 un c n1;s cn ;s c n;s cn 1;s
n;s
X p 2n (10) hold precisely two electrons per repeat unit, the four p sub-
1 X 2
K un 1 un bands with the lowest energy are filled and the four p* sub-
n 2m 2 n
bands are empty. Thus, I begin with a description at the one-
electron level, that is, from the point of view of band theory.
The last two terms are, respectively, a harmonic spring Brazovskii, Kirova, and Bishop[52, 53] treated the band
constant term which represents the increase in potential structure of PPV with a tight-binding Hamiltonian, using
energy that results from displacement from the uniform bond standard values for the hopping integrals. The el ph coupling
lengths in (CH)x and a kinetic-energy term for the nuclear [Eq. (9)], can be included after defining the basic band
motion. structure of the semiconductor. From this simple ansatz, basis
The spontaneous symmetry breaking that results from the states which reflect the intrinsic symmetry of the phenyl ring
Peierls instability implies that for the ground state of a pristine and the dimer were calculated and used to expand the
chain, the total energy is minimized for j un j> 0. Thus, to wavefunction. The basis states hybridize as a result of ring-to-
describe the bond alternation in the ground state [Eq. (11)]. dimer hopping, thus yielding the 62 8 sub-bands in the
p system of PPV.
un ! huni ( 1)n uo (11) The resulting band structure (Figure 6) has a number of
important features. Six of the sub-bands (three occupied and
three unoccupied), labeled D and D* in Figure 6, are broad,
With this mean-field approximation, the value uo which
minimizes the energy of the system can be calculated as a
function of the other parameters in the Hamiltonian.[46]
Qualitatively, however, one sees that uo and uo both
minimize the energy for trans-polyacetylene since the bonds
all make the same angle with respect to the chain axis. Hence,
the energy as a function of u has a double minimum at  uo , as
shown in Figure 5. The corresponding structures of the two
degenerate ground states are shown in Scheme 3 d. The
double minimum of Figure 5 implies that nonlinear excita-
tions, solitons, will be important. In polymers with a non-
degenerate ground state, the degeneracy indicated in Figure 5
is lifted; for a nondegenerate ground state polymer, the
absolute minimum energy occurs at a single value of u. Figure 6. Electronic band structure of PPV.

2602 Angew. Chem. Int. Ed. 2001, 40, 2591 2611

Conducting Polymers
and the corresponding wavefunctions are delocalized along
the chain. The other two bands labeled L and L* (one
occupied and one unoccupied), are narrow and the corre-
sponding wavefunctions have amplitudes which are localized
on the ring. The L and L* sub-bands derive from the two ring
states whose wavefunctions have nodes at the para linkage
sites; as a result, these states do not participate in hopping and
the sub-bands do not acquire the resulting dispersion. On the
contrary, the delocalized D and D* sub-bands have relatively
high dispersion ( 1.7 eV), indicating good delocalization over
both ring and dimer states.
Starting from this simple yet physically robust model of the
band structure, the discussion of the electronic structure can
be extended to include the effect of the Coulomb interaction.
The delocalized nature of D1 and D1* implies that, for
electron correlation effects involving these sub-bands, it is
appropriate to compute an effective mass from the dispersion
curves and then compute the corresponding 1D hydrogenic
levels. From the k2-dependence of the dispersion near the
zone center, the effective masses in D1 and D1* are m*
0.067 me .
Using the well-known result for the binding energy of a
hydrogenic-like state in 1D, the exciton associated with the
lowest energy electronic transition (D1 !D1*) has a binding
energy and effective radii given by Equations (12 a):
Eb E *b ln2(ab/a?) ab a *b [ln(ab/a?)]1 (12 a)
where the terms are defined as in Equations (12 b) and e is the
dielectric susceptibility, h is Plancks constant, m* is the
electron effective mass at the zone center in k-space (for PPV,
m*  0.067 me), e is the electron charge and a?  2 (the
width of the chain).
m * e4 2 e
h
E *b 2
a b* (12 b)
e h
2
m * e2
From Equation (12 a), Eb  0.1 -0.2 eV (depending on the
value assumed for a?) and a radius of approximately 30 .
In addition to this weakly bound Wannier Mott exciton,
there are two other excitons in this model. The degenerate
D1 L1* and L1 D1* transitions are treated by assuming an
immobile (massive) carrier in the L or L* sub-band and a
mobile carrier in the D or D* sub-band. The resulting bound
state has a binding energy of  0.8 eV, and is a more tightly
bound (but still somewhat delocalized) exciton. Finally, the
L L* transition forms a very tightly bound Frenkel exciton,
localized on the phenyl ring.
With the electronic excitations established, they can be
compared to the data obtained from optical absorption
measurements. An unambiguous test of the agreement
between the proposed electronic structure (Figure 6) and
experiment requires data from chain-extended and chain-
oriented samples of macromolecular PPVs. With macromo-
lecular samples, chain-end boundary conditions are not
important; with oriented polymers, the polarization of the
various absorptions with respect to the chain axis can be
determined. Recent polarized absorption studies of highly
oriented PPV and PPP indicate that the one-electron model is
a good starting point.[54, 55]
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
REVIEWS
4.4. Solitons, Polarons, and Polaron Excitons: The
Elementary Excitations of Conducting Polymers
Although bond relaxation in the excited state is implicitly
allowed through the bond-length dependent hopping integral
in the SSH model, the effect of bond relaxation, and the
formation of solitons, polarons, and bipolarons, has not been
explicit in Section 4.3. These important concepts are summar-
ized in the following paragraphs. In the related experimental
studies, trans-polyacetylene and polythipohene were used as
the model systems for the degenerate ground-state polymer
and the nondegenerate ground-state polymer, respectively.[4]
4.4.1. Solitons
Charge storage on the polymer chain leads to structural
relaxation, which in turn localizes the charge. The simplest
example of the dramatic effect of this structural relaxation is
the soliton in trans-polyacetylene. The soliton is a domain
boundary between the two possible degenerate ground-state
configurations of trans-(CHCH)N, the A Phase and the
B Phase. For simplicity, we often draw the chemical
structure of the soliton as an abrupt change from A Phase
to B Phase, as shown in Scheme 3 e. In agreement with the
predictions of the SSH model,[4] however, the experimental
evidence indicates that the structural relaxation in the vicinity
of the domain boundary extends over approximately seven
carbon atoms, as illustrated in Scheme 3 f. The corresponding
spin and charge distributions are similarly delocalized.
The value of a picture like Scheme 3 e quickly becomes
evident when one tries to understand the quantum numbers of
the soliton and the reversed charge spin relationship that
characterizes the solitons of polyacetylene (see Figure 7 c).
Since the nonbonding, or mid-gap, state formed by the chain
relaxation can then be mapped to a specific atomic site, the
resulting distribution of charge and spin can be easily
addressed; if the state is unoccupied (doubly occupied), the
carbon atom at the boundary is left with a positive (negative)
charge, but there are no unpaired spins; the charged soliton is
positively (negatively) charged and spinless. Single occupa-
tion of the soliton state neutralizes the electronic charge of the
carbon nucleus, while introducing an unpaired spin onto the
chain. The localized electronic state associated with the
soliton is a nonbonding state at an energy which lies at the
middle of the p p* gap, between the bonding and antibond-
ing levels of the perfect chain. On the other hand, the defect is
both topological and mobile because of the translational
symmetry of the chain. Such a topological and mobile defect is
historically referred to as a soliton.[46] The term soliton (S)
refers simultaneously to all three types of solitons; the
quantum numbers for spin and charge enter only when
referring to a specific type (for example, neutral solitons
found as defects from the synthesis of undoped material or
charged solitons created by photoexcitation), and even then,
the spin is only implicit. Another feature of the soliton
terminology is the natural definition of an anti-soliton (AS)
as a reverse boundary from B Phase back to A Phase in
Scheme 3 e and 3 f. The anti-soliton allows for conservation of
soliton number upon doping or upon photoexcitation.
2603
REVIEWS A. J. Heeger

4.4.2. Polarons and Bipolarons
In cases such as poly(thiophene), PPV, PPP, and cis-
polyacetylene where the two possible bond-alternation pat-
terns are not energetically degenerate, confined soliton an-
tisoliton pairs, polarons, and bipolarons, are the stable non-
linear excitation and the stable charge-storage states.[56, 57] A
polaron can be thought of as a bound state of a charged soliton
and a neutral soliton whose mid-gap energy states hybridize to
form bonding and antibonding levels. The neutral soliton
contributes no charge and a single spin, as noted above, and
the charged soliton carries charge of  e and no spin; the
resulting polaron then has the usual charge spin relationship
of fermions; q  e and s 1/2. The polaron is illustrated
schematically for PPP in Figure 7 a and b. The positive
4.4.3. Solitons and Polarons in Conjugated Polymers:
Experimental Results
The models outlined above for solitons, polarons, and
bipolarons make concrete predictions of experimentally
observable phenomena, and indeed theoretical progress
would not have been possible without concurrent experimen-
tal investigation. Optical probes of the mid-gap electronic
states (see Figure 7 c) and magnetic measurements of spin
concentrations and spin distributions contributed greatly to
the refinement and verification of theoretical predictions. For
a detailed review of the experimental results, the reader is
referred to the Review of Modern Physics article on this
subject.[4]

5. Photoinduced Electron Transfer

The discovery of photoinduced electron transfer in compo-

sites of conducting polymers (as donors, D) and buckmin-
sterfullerene, C60 , and its derivatives (as acceptors, A) opened
a number of new opportunities for semiconducting poly-
mers.[58, 59] A schematic description of the photoinduced
electron transfer process is displayed in Scheme 4.

Figure 7. a) Schematic picture of a polaron in PPP, b) band diagram of an

electron polaron ; for a hole polaron the lower gap state is single occupied
and the upper gap state is empty, c) band diagrams for positive and negative
solitons with associated electronic transitions.

(negative) polaron is a radical cation (anion), a quasiparticle

consisting of a single electronic charge dressed with a local
geometrical relaxation of the bond lengths. Similarly, a
bipolaron is a bound state of two charged solitons of like
charge (or two polarons whose neutral solitons annihilate
each other) with two corre-
sponding mid-gap levels, as
illustrated in Figure 8 a and b.
Since each charged soliton
carries a single electronic
charge and no spin, the bipo-
laron has charge  2 e and
zero spin. The positive (neg-
ative) bipolaron is a spinless
dication (dianion); a doubly
Figure 8. Bipolarons in polymer charged bound state of two
with nondegenerate ground state, polarons bound together by
a) schematic picture of a negative the overlap of a common
bipolaron, b) bond diagram for a
negative bipolaron, for a positive
lattice distortion (enhanced
bipolaron, both gap states are geometrical relaxation of the
unoccupied. bond lengths).
Scheme 4. Photoinduced electron transfer from a conjugated semicon-
ducting polymer to C60 .
A broad range of studies has been carried out to fully
characterize this photoinduced charge transfer, culminating
with a study of the dynamics of photoinduced electron
transfer from semiconducting polymers to C60 using femto-
second time-resolved measurements.[60, 61] These studies dem-
onstrated that the charge transfer occurs within 50 femto-
seconds after photo-excitation. Since the charge-transfer rate
is more than 1000 times faster than any competing process
(the luminescence lifetime is greater than 300 picoseconds),
the quantum efficiency for charge separation approaches
UNITY! Moreover, the charge-transferred state is meta-
stable.[62, 63]
Semiconducting polymers are electron donors upon photo-
excitation (electrons promoted to the antibonding p* band).
The idea of using this property in conjunction with a
molecular electron acceptor to achieve long-lived charge
separation is based on the stability of the photoinduced

2604 Angew. Chem. Int. Ed. 2001, 40, 2591 2611

Conducting Polymers
nonlinear excitations (such as polarons) on the conjugated
polymer backbone. Buckminsterfullerene (C60) is an excellent
electron acceptor capable of taking on as many as six
electrons;[64] C60 , therefore, forms charge-transfer salts with
a variety of strong donors. It is reasonable, therefore to
consider electron transfer from photo-excited semiconducting
polymers to C60 . Figure 9 shows a schematic energy-level
Figure 9. Energy-band diagram for photoinduced electron transfer and
photoinduced hole transfer between semiconducting polymers and C60 .
diagram of the photoinduced electron (or hole) transfer
process, which can be described in terms of the following steps:
Step 1: D A ! 1,3D* A (excitation on D)
Step 2: 1,3D* A ! 1,3(D A)* (excitation delocalized on
D A complex)
Step 3: 1,3(D A)* ! 1,3(Dd Ad)* (charge transfer initi- electron transfer. The integrated LESR intensity shows two
ated)
Step 4: 1,3(Dd Ad)* ! 1,3(D . A .) (ion radical pair ence of the LESR signal intensity shows Arrhenius behavior
formed)
Step 5: 1,3(D . A .) !D . A . (charge separation) suggests a phonon assisted back-relaxation mechanism of the
where the donor (D) and acceptor (A) units are either
covalently bound (intramolecular), or spatially close but not
covalently bonded (intermolecular); steps 1 and 3 denote
singlet or triplet excited states, respectively.
Since the partial charge transfer at step 3 is strongly
dependent on the surrounding medium there is a continuous
range for the transfer rate, 0 < d < 1. At step 4, d 1, that is, a
whole electron is transferred. At each step, the D A system
can relax back to the ground state either by releasing energy
to the lattice (in the form of heat) or through light emission
(provided the radiative transition is allowed). The electron-
transfer step (step 4) describes the formation of an ion radical
pair; this does not occur unless ID* AA UC < 0, where ID* is
the ionization potential of the excited state (D*) of the donor,
AA is the electron affinity of the acceptor, and UC is the
Coulomb energy of the separated radicals (including polar-
ization effects). Stabilization of the charge separation (step 5)
can be enabled by carrier delocalization on the D (and/or
A) species and by structural relaxation. The symmetrical
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
REVIEWS
process of hole transfer from the photoexcited acceptor to the
donor is described in an analogous way, and can be driven by
photoabsorption in spectral regions where the acceptor can be
photoexcited but not the donor.
Even though the photoinduced electron-transfer reaction is
energetically favorable, energy must be conserved in the
process. In semiconducting polymers, the excess energy is
readily taken up by promoting the hole to a higher energy
state in the p* band. Ultimately, therefore, the ultrafast
nature of the photoinduced electron-transfer process results
from the delocalized nature of the p electrons. Once the
photoexcited electron is transferred to an acceptor unit, the
resulting cation radical (positive polaron) species on the
conjugated polymer backbone is relatively stable. Thus,
photoinduced electron transfer from the conjugated-polymer
donor onto an acceptor moiety can be viewed as photo-
doping (see Figure 2). The forward to reverse asymmetry of
the photoinduced charge separation in the conducting poly-
mer/C60 system is nevertheless remarkable; the asymmetry is
orders of magnitude greater than that observed in the
photosynthesis of green plants.
Definitive evidence of charge transfer and charge separa-
tion was obtained from light-induced ESR (LESR) experi-
ments.[58, 63, 65] Upon illuminating the conjugated polymer/C60
composites with light with hn > Ep-p* where Ep-p* is the energy
gap of the conjugated polymer (donor), two photoinduced
ESR signals can be resolved; one at g 2.00 and the other at
g 1.99.[58, 63] The higher g-value line is assigned to the
conjugated polymer cation (polaron) and the lower g-value
line to the C60 ion. The assignment of the lower g-value line
to C60 ion is unambiguous, for this low g-value was measured
earlier;[64] the higher g-value is typical of conjugated polymers.
The LESR signal vanishes above 200 K; this rules out
permanent photochemical changes as the origin of the ESR
signal and demonstrates the reversibility of the photoinduced
peaks with equivalent intensities. The temperature depend-
with activation energy of approximately 15 meV. This result
photoinduced charge-separated state.[63]
In MEH PPV/C60 composites, the strong photolumines-
cence of MEH PPV is quenched by a factor in excess of 103,
and the luminescence decay time is reduced from to 550 ps
to trad  60 ps (the instrumental resolution) indicating that
charge transfer has cut-off the radiative decay.[58, 62, 63] An
estimate of the transfer rate, 1/tct , can be obtained from the
quenching of the photoluminescence [Eq. (13)] where 1/to
and 1/trad are the radiative decay rates, Io and Icomp are the
integrated photoluminescence intensities of MEH PPV and
the MEH PPV/C60 composite, respectively.
1/tct  (1/trad)Io/Icomp (13)
The data imply, therefore, that 1/tct > 1012 ; that is, electron
transfer occurs on the sub-picosecond time scale. The ultrafast
charge-transfer process was subsequently time resolved;[60, 61]
the data directly confirm that charge transfer occurs within a
few hundred femtoseconds.
2605
REVIEWS
The photoinduced electron-transfer process serves to
sensitize the photoconductivity of the semiconducting poly-
mer.[66] Time-resolved transient photocurrent measurements
indicate that the addition of as little as 1 % of C60 into the
semiconducting polymer results in an increase of initial
photocurrent by an order of magnitude. This increase of the
photocarrier generation efficiency is accompanied by an
increase in lifetime of the photocarriers upon adding C60 .
Thus, the ultrafast photoinduced electron transfer from the
semiconducting polymer onto C60 not only enhances the
charge-carrier generation in the host polymer but also serves
to prevent recombination by separating the charges and
stabilizing the charge separation.
Conjugated polymers with higher electron affinities (e.g.
cyano-substituted PPV) function as the acceptor component
with MEH PPV as the donor.[67, 68] Through control of the
morphology of the phase separation into an interpenetrating
bicontinuous network of D and A phases, high interfacial area
was achieved within a bulk material: a bulk D/A hetero-
junction that yields efficient photoinduced charge separa-
tion.[6770] These all-polymer phase-separated blends were
successfully used in fabricating solar cells with efficiencies
that approach those fabricated from amorphous silicon.[69]
6. Metallic Polymers and the Metal Insulator
Transition
6.1. Metallic Polymers with High Performance Electrical
and Mechanical Properties
An early (and continuing) goal of the field of conducting
polymers was the creation of materials with high electrical
conductivity and with the excellent mechanical properties of
polymers. This goal has been achieved; more importantly the
conditions for realizing this combination of properties are
understood and can be applied to new materials.
Electrical conductivity results from the existence of charge
carriers and the ability of those carriers to move. In principle,
broad p-electron bandwidths (often several eV) can lead to
relatively high carrier mobilities.[4] As a result of the same
intrachain p bonding and the relatively strong interchain
electron-transfer interaction, the mechanical properties
(Youngs modulus and tensile strength) of conjugated polymers
are potentially superior to those of saturated polymers. Thus,
metallic polymers offer the promise of truly high performance;
high conductivity plus superior mechanical properties.
This combination of high electrical conductivity and out-
standing mechanical properties has been demonstrated for
doped polyacetylene.[7075]
6.2. Metal Insulator Transition in Doped Conducting
Polymers
6.2.1. The Role of Disorder
Ioffe and Regel[76] argued that as the extent of disorder
increased in a metallic system, there was a limit to metallic
2606
A. J. Heeger
behavior; when the mean free path becomes equal to the
interatomic spacing, coherent metallic transport would not be
possible. Thus, the Ioffe Regel criterion is defined in
Equation (14) where kF is the Fermi wave number and l is
the mean free path. The metallic regime corresponds to
kFl  1.
kF l  1 (14)
Based on the Ioffe Regel criterion, Mott proposed[77, 78]
that a metal insulator (M I) transition must occur when the
disorder is sufficiently large that kFl < 1. In recognition of
Andersons early work on disorder induced localization, Mott
called this M I transition the Anderson transition.[79] In the
limit where kFl  1 (i.e. where the strength of the random
disorder potential is large compared to the bandwidth), all
states become localized and the system is called a Fermi
glass.[80] A Fermi glass is an insulator with a continuous
density of localized states occupied according to Fermi
statistics. Although there is no energy gap, the behavior is
that of an insulator because the states at the Fermi energy are
spatially localized.
The scaling theory of localization demonstrated that the
disorder-induced M I transition was a true phase transition
with a well-defined critical point.[81] MacMillan[82] and Larkin
and Khmelnitskii,[83] showed that near the critical regime of
Anderson localization a power-law temperature dependence
is to be expected for the conductivity.
The M I transition in conducting polymers is particularly
interesting; critical behavior has been observed over a
relatively wide temperature range in a number of systems,
including polyacetylene, polypyrrole, poly(p-phenyleneviny-
lene), and polyaniline.[33] In each case, the metallic, critical,
and insulating regimes near the M I transition have been
identified. The critical regime is tunable in conducting
polymers by varying the extent of disorder (i.e. by studying
samples with different 1r  1(1.4 K)/1(300 K)), or by applying
external pressure and/or magnetic fields. The transitions from
metallic to critical behavior and from critical to insulating
behavior have been induced with a magnetic field, and from
insulating to critical and then to metallic behavior with
increasing external pressure.[33]
In the metallic regime, the zero temperature conductivity
remains finite with magnitude that depends on the extent of
the disorder. Metallic behavior has been demonstrated for
conducting polymers with s(T) remaining constant as T
approaches zero.[33] Well into the metallic regime where the
mean free path extends over many repeat units, the residual
resistivity will become small, as in a typical metal. However,
this truly metallic regime, with kFl  1 has not yet been
achieved.
6.2.2. Infrared Reflectance Studies of the Metallic State and
the Metal Insulator Transition
Infrared (IR) reflectance measurements have played an
important role in clarifying the metal physics of conducting
polymers. To clarify the nature of the metallic state, high
precision reflectance measurements were carried out over a
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
Conducting Polymers
wide spectral range on a series of PPy PF6 samples in the
insulating, critical, and metallic regimes near the M I
transition.[84] Since the reflectance in the infrared (IR) is
sensitive to the charge dynamics of carriers near the Fermi
energy (EF), such a systematic reflectance study can provide
information on the electronic states near EF and how those
states evolve as the system passes through the M I transition.
The data demonstrate that metallic PPy PF6 is a disordered
metal and that the M I transition is driven by disorder;
similar results were obtained for polyaniline.[37, 85]
Figure 10 shows s(w) for a series of PPy PF6 samples (A
F) as obtained from Kramers Kronig transformation of R(w)
at room temperature. For the most metallic samples, R(w)
exhibits metal-like features; a free-carrier plasma resonance
Figure 10. Frequency dependent conductivity s(w) for Ppy-PF6 . The inset
shows the far-IR data in greater detail.
as indicated by a minimum in R(w) near 1 eV and high R(w) in
the far IR. As PPy PF6 goes from the metallic to the
insulating regime via the critical regime (samples A through
F), s(w) is gradually suppressed in the IR. In the insulating
regime (F), s(w) remains well below that of the metallic
sample (A) throughout the IR range. The s(w) spectra are in
excellent correspondence with the transport results (this is
especially clear at low frequencies in Figure 10); the better the
quality of the sample, as defined by the higher sDC(300 K), the
higher R(w) in the IR.[84]
In the far-IR (below 100 cm1), the Hagen Rubens (H R)
approximation provides an excellent fit to R(w) [Eq. (15)],[36]
where sHR is the w-independent conductivity.
RHR(w) 1 (2w/psHR)1/2 (15)
The sHR values obtained from the Hagen Rubens fits are in
remarkably good agreement with the measured values of
sDC(300 K). The excellent fits and the agreement between
sH-R and sDC(300 K) imply a weak w dependence in the
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
REVIEWS
corresponding optical conductivity, s(w), for w < 100 cm1.
The s(w) data are fully consistent with the localization-
modified Drude model (LMD) [Eq. (16)][86] where kF is the
Fermi wave-number and l is the mean free path.
sLD(w) sDrude{1 C[1 (3tw)1/2]/(kFl)2} (16)
In this model, the zero-frequency limit determines the
constant C (precisely at the M I Transition, C 1) while a fit
to s(w) determines kFl. The suppressed s(w) as w approaches
zero arises from weak localization induced by disorder.[84] The
s(w) data from the various regimes were fit with the
functional dependence predicted by the LMD model; Fig-
ure 10 illustrates the excellent agreement of the fits to the data
with the parameters summarized in the inset. The phonon
features around 400 2000 cm1 are, of course, not included in
the LMD model. There are small deviations for w < 100 cm1
(more important in the less metallic samples), below which
phonon-assisted hopping makes a measurable contribution to
s(w) and to the DC (direct current) conductivity.
The parameters obtained from the fits are reasonable. The
screened plasma frequency, Wp wp/(e1)1/2 1.5  104 cm1, is
in good agreement with the frequency of the minimum in
R(w), and t is typical of disordered metals (t  1014 1015 s).
The quantity kFl is of particular interest for it characterizes the
extent of disorder and is often considered as an order
parameter in localization theory.[87, 88] For all four samples
represented in Figure 10, kFl  1, implying that all are close to
the M I transition. As the disorder increases and the system
moves from the metallic regime (sample A with kFl 1.38) to
the critical regime (sample E with kFl 1.01), kFl approaches
the Ioffe Regel limit,[76] precisely as would be expected. In
the insulating regime (sample F) kFl 0.94 < 1, consistent
with localization of the electronic states at EF. Thus, the IR
reflectance data obtained for metallic polymers indicate that
they are disordered metals near the disorder-induced M I
transition. There is remarkable consistency between the
conclusion obtained from transport studies and from IR
reflectance measurements.
6.3. Striving Toward More Perfect MaterialsChain
Extension, Chain Alignment, and Interchain Order
Experimental studies have established that for conducting
polymers, the electrical properties and the mechanical proper-
ties improve together, in a correlated manner, as the degree of
chain extension and chain alignment are improved. Polyace-
tylene remains the prototype example.
Figure 11 shows the correlation between the electrical
conductivity (s) and the draw ratio (l) for iodine-doped
polyacetylene films; the conductivity increases approximately
linearly with the draw ratio.[73] The slope of s versus l is
approximately a factor of two larger for the thinner films
(evidently the details of polymerization and/or doping result
in more homogeneous, higher quality material for the thinner
films). X-ray diffraction studies of these drawn films exhibited
2607
REVIEWS
Figure 11. Electrical conductivity of iodine-doped polyacetylene (parallel
to the draw axis) versus draw ratio; * thin films of thickness 3 5 mm,
* films of thickness 25 30 mm.
a high degree of structural order that improves with the draw
ratio; the structural-coherence length perpendicular to the
draw direction increases by about a factor of two as the films
are drawn, from 10 nm at l 4 to 20 nm at l 15.[73]
Consistent with the chain orientation and the improved
structural order, the anisotropy (sk/s?) in the electrical
conductivity increased with the draw ratio, approaching 250
as l !15 (although sk increased dramatically as a function of
l, s? remains essentially constant). These data set a lower
limit on the intrinsic anisotropy and demonstrate that heavily
doped polyacetylene is a highly anisotropic metal with
relatively weak interchain coupling.
Does the weak interchain coupling imply poor mechanical
properties? The answer is No; for films with l 15, Youngs
modulus reaches 50 GPa and the tensile strength approaches
1 GPa, mechanical properties which are characteristic of high-
performance materials. More importantly, the data demon-
strate a direct correlation between the electrical conductivity
and the mechanical properties. The linear relationship implies
that the increase in both the conductivity and the modulus (or
tensile strength) with draw ratio result from increased uniaxial
orientation, improved lateral packing, and enhanced inter-
chain interaction. The correlations between the electrical
conductivity and the mechanical properties observed for
polyacetylene are general. This correlation has been demon-
strated in every case studied,[31] and can be understood as a
general feature of conducting polymers.
Although the electrical conductivity is enhanced by the
relatively high mobility associated with intrachain transport,
one must have the possibility of interchain charge transfer to
avoid the localization inherent to systems with a 1D electronic
structure.[77] The electrical conductivity becomes three-dimen-
sional (3D; and thereby truly metallic) only if there is high
probability that an electron will have diffused to a neighbor-
ing chain prior to traveling between defects on a single chain.
For well-ordered crystalline material in which the chains have
precise phase order, the interchain diffusion is a coherent
process. In this limit, the condition for extended anisotropic
transport is given in Equation (17)[89] where L is the coher-
ence length, a is the length of the chain repeat unit, to is the
L/a  (to/t3d) (17)
2608
A. J. Heeger
intrachain p-electron transfer integral, and t3d is the interchain
p-electron transfer integral.
A precisely analogous argument can be constructed for
achieving the intrinsic strength of a polymer material; that is,
the strength of the main-chain covalent bonds. If Eo is the
energy required to break the covalent main-chain bond and
E3d is the weaker interchain bonding energy (from van der
Waals forces and hydrogen bonding), then the requirement is
coherence over a length L such that Equation (18) holds.[90]
L/a  Eo/E3d (18)
In this limit, the large number, L/a, of weak interchain
bonds add coherently such that the polymer fails by breaking
of the covalent bond. The direct analogy between Equa-
tions (17) and (18) is evident. When the interchain structural
order is nematic (i.e. without precise phase order), the
conditions become L/a  (to/t3d)2 and L/a  (Eo/E3d)2, respec-
tively.[89] Thus, the achievement of high-performance materi-
als with nematic order requires even greater longer-range
intrachain coherence.
In fact, for conjugated polymers, Eo results from a
combination of s and p bonds (the latter being equal to to)
and E3d is dominated by the interchain transfer integral, t3d .
Thus, the inequalities imply that, quite generally, the con-
ductivity and the mechanical properties will improve in a
correlated manner as the degree of chain alignment is
increased. This prediction is in excellent agreement with data
obtained from studies of the poly(3-alkylthiophenes), the
poly(phenylene vinylenes), poly(thienylene vinylene), and
polyacetylene.[31]
Assuming that the linear correlation persists to even higher
draw ratios, the extrapolated modulus of 300 GPa for poly-
acetylene would imply that the electrical conductivity of
perfectly oriented polyacetylene would be approximately 2 
105 S cm1.[91] However, this extrapolated value might still be
limited by structural defects (e.g. sp3 defects, etc.) rather than
by intrinsic phonon scattering.
A theoretical estimate of the intrinsic conductivity, limited
by phonon scattering, yields the Equation (19)[89] where sk is
the conductivity parallel to the chain, h is Planckss constant,
a is the strength of the electron phonon interaction, M is the
mass of the repeat unit of length a, and to is the transfer
integral (2 3 eV).
sk (e2/2 h a)n a3(2pMw0 t 20 /a2 h)exp[h@ ph/kB T] (19)
Using parameters obtained by experiment, Equation (19)
predicts sk 2  106 S cm1 at room temperature,[89] more than
an order of magnitude greater than that achieved to date. The
exponential dependence upon T arises from the fact that
backscattering must involve a high-energy phonon with wave
number near the zone boundary. The high conductivity values
and the exponential increase in conductivity on lowering the
temperature predicted by Equation (19) indicates that the
achievement of metallic polymers in which the macromole-
cules are chain extended and chain aligned is a major
opportunity.
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
Conducting Polymers
6.4. The Possibility of Superconductivity in Metallic
Polymers
Superconductivity has not yet been observed in doped
conjugated polymers. Might one expect superconductivity? If
so what are the materials requirements? There is every reason
to be optimistic that superconductivity will be discovered in
doped conjugated polymers:
a) They are metals
b) The coupling of the electronic structure to the molecular
structure is well known. Upon doping, the bond lengths
change such that charge is stored in solitons, polarons, and
bipolarons. Thus, the electron phonon interaction that is
responsible for superconductivity in conventional metals,
leads to important effects in metallic polymers. In this
context, doubly charged bipolarons can be thought of as
analogous to real-space Cooper pairs.
As shown above, however, currently available metallic
polymers are barely metallic; their electronic properties are
dominated by disorder with mean free paths close to the
Ioffe Regel criterion for disorder induced localization.
It is interesting to compare the transport properties of
available metallic polymers with those of the underdoped
high-Tc (critical temperature) superconductors at doping
levels where kFl  1. For example, when YBa2Cu3O7d is
underdoped to values of d such that the resistivity increases as
the temperature is lowered with 1r  1(1.4 K)/1(300 K)  2
(i.e. with temperature dependence similar to that found in the
best metallic polymers), the disorder associated with the
random occupation of the oxygen sites quenches the super-
conductivity.
The phase diagrams of MBa2Cu3O7d (where M Y, Dy,
etc.) have been thoroughly studied.[92] For large d,
MBa2Cu3O7d are antiferromagnetic insulators; increasing
the oxygen concentration introduces carriers into the CuO2
planes and results in a transition from the antiferromagnetic
insulating phase to the metallic and superconducting phase.
The changes in resistivity which occur during this evolution
from insulator to metal (and superconductor) have been
followed in detail in a continuous set of resistivity measure-
ments carried out on ultra-thin films.[93, 94] Thus, the proto-
typical high-Tc superconductors show behavior character-
istic of the disorder-induced metal insulator transition. Near
the metal insulator transition, the 1 versus T curves look
remarkably similar to those obtained from metallic poly-
aniline, polypyrrole, and PPV. At doping levels near the
metal insulator transition there is no sign whatever of the
fact that these copper-oxide systems exhibit superconductivity
with the highest known transition temperatures.
The point is quite clear. One cannot expect to make any
progress toward superconductivity in metallic polymers until
there is a major improvement in the quality of materials to the
point where the mean free path is much longer than the
characteristic monomer repeat units. When this has been
achieved, kFl  1 and the resistivity will be truly metal-like,
decreasing as the temperature decreases. The unresolved
question is how to realize the required improvements in
structural order? This remains as a major challenge to the
field.
Angew. Chem. Int. Ed. 2001, 40, 2591 2611
REVIEWS
Although the required structural order is lacking in
materials that are currently available, there is evidence that
in metallic polyaniline, the electronic states near the Fermi
energy interact strongly and selectively with a specific optical
phonon mode.[95] The 1598 cm1 Raman-active vibrational
mode (Ag symmetry) exhibits a distinct resonance enhance-
ment associated with the mid-IR absorption in metallic
polyaniline. Since the mid-IR oscillator strength results from
the intraband free-carrier Drude absorption, the resonant
enhancement suggests that the symmetry of the electronic
wavefunctions near EF matches the vibrational pattern of the
1598 cm1 normal mode. Quantum-chemical calculations of
the electronic wavefunctions and analysis of the normal
modes verified that this is in fact true.[95] Since the coupling of
the electronic states near EF to lattice vibrations is known to
lead to superconductivity in metals, the demonstration of
resonant coupling to a specific vibrational mode provides
some optimism; at least this is the kind of feature that one
would like to see.
The story of superconductivity in metallic polymers has not
yet begun. If and when superconductivity is discovered in this
class of materials, that discovery will create a new research
opportunity that will be exciting and potentially important.
7. Applications
Solid-state photonic devices are a class of devices in which
the quantum of light, the photon, plays a role. They function
by utilizing the electro-optical and/or opto-electronic effects
in solid-state materials. Because the interband optical tran-
sition (absorption and/or emission) is involved in photonic
phenomena and because photon energies from near infrared
(IR) to near ultraviolet (UV) are of interest, the relevant
materials are semiconductors with band gaps in the range
from 1 to 3 eV. Typical inorganic semiconductors used for
photonic devices are Si, Ge, GaAs, GaP, GaN, and SiC.
Photonic devices are often classified into three categories:
light sources (light-emitting diodes, diode lasers etc.), photo-
detectors (photoconductors, photodiodes etc.), and energy-
conversion devices (photovoltaic cells). All three are impor-
tant. Because photonic devices are utilized in a wide-range of
applications, they continue to provide a focus for research
laboratories all over the world.
Most of the photonic phenomena known in conventional
inorganic semiconductors have been observed in these semi-
conducting polymers.[32] The dream of using such materials in
high performance plastic photonic devices is rapidly
becoming reality: high-performance photonic devices fabri-
cated from conjugated polymers have been demonstrated,
including light-emitting diodes, light-emitting electrochemical
cells, photovoltaic cells, photodetectors, and optocouplers;
that is, all the categories which characterize the field of
photonic devices. These polymer-based devices have reached
performance levels comparable to or even better than their
inorganic counterparts.
This Nobel Lecture is, perhaps, not the proper place to
discuss in detail the many current and anticipated applications
of semiconducting and metallic polymers; there is simply
2609
REVIEWS A. J. Heeger

neither time in the presentation nor space in the written [12] Y. Cao, P. Smith, A. J. Heeger, US-A 5 232 631.
document to do justice to the subject. Suffice it to say here [13] C. Y. Yang, Y. Cao, P. Smith, A. J. Heeger, Synth. Met. 1992, 53, 293.
[14] M. Reghu, Y. Cao, D. Moses, A. J. Heeger, Phys. Rev. B 1993, 497, 1758.
that I am convinced that we are on the verge of a revolution in [15] H. Tomozawa, D. Braun, S. Philips, A. J. Heeger, H. Kroemer, Synth.
Plastic Electronics. I refer those interested to recent Met. 1987, 22, 63; H. Tomozawa, D. Braun, S. D. Philips, R. Worland,
reviews that focus on these important developments.[97] The A. J. Heeger, Synth. Met. 1989, 28, C687.
advances in printing technology, for example, high resolution [16] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, R. H.
Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347, 539.
ink-jet printing, to fabricate semiconductor devices by proc-
[17] A. G. MacDiarmid, A. J.Epstein in Conjugated Polymeric Materials:
essing the conducting polymer from solution has proven to be Opportunities in Electronics, Optical Electronics, Molecular Electron-
an enabling step in the development of plastic electronic ics (Eds.: J. L. Bredas, R. R. Chance), Kluwer Academic, Dordrecht,
devices such as diodes, photodiodes, LEDs, LECs, optocou- 1990, p. 53.
plers, and thin-film transistors.[32] [18] F. Wudl, R. O. Angus, F. L. Lu, P. M. Allemand, D. J. Vachon, M.
Nowak, Z. X. Liu, A. J. Heeger, J. Am. Chem. Soc. 1987, 109, 3677.
[19] N. S. Sariciftci, Primary Photoexcitations in Conjugated Polymers,
World Scientific, Singapore, 1998.
[20] S. A. Jenekhe, J. A. Osaheni, Science 1994, 265, 765.
8. Concluding Comments [21] J. Cornil, D. A. do Santos, X. Crispin, R. Silbey, J. L. Bredas, J. Am.
Chem. Soc. 1998, 120, 1289.
I am greatly honored to receive the Nobel Prize in [22] L. J. Rothberg, M. Yan, F. Papadimitrakopoulos, M. E. Galvin, E. W.
Kwock, T. M. Miller, Synth. Met. 1996, 80, 41.
Chemistry for the discovery and development of conducting [23] I. D. Parker, J. Appl. Phys. 1994, 75, 1656.
polymers. The science of semiconducting and metallic [24] E. S. Maniloff, D. Vacar, D. W. McBranch, H. Wang, B. R. Mattes, J.
polymers is inherently interdisciplinary; it falls at the inter- Gao, A. J. Heeger, Opt. Commun. 1997, 141, 243.
section of Chemistry and Physics. In creating and expanding [25] L. Y. Chiang, A. F. Garito, D. J. Sandman, Proceedings of the Materials
Research Society, Vol. 247, Materials Research Society, Pittsburgh,
this fourth generation of polymers, we attempted to under-
1992.
stand nature with sufficient depth that we could achieve [26] F. Garnier, R. Hajlaoui, A. Yasser, P. Svrivastava, Science 1994, 265,
materials with novel and unique properties; properties that 1684.
are not otherwise available. This was (and is) an elegant and [27] J. H. Burroughes, C. A. Jones, R. H. Friend, Nature 1988, 335, 137.
somewhat dangerous exercise; elegant because it required the [28] C. J. Drury, C. M. J. Mutsaers, C. M. Hart, M. Matters, D. M.
de Leeuw, Appl. Phys. Lett. 1998, 73, 108.
synthesis of knowledge from the two disciplines, and danger- [29] F. Hide, M. Diaz-Garcia. B. Schwartz, M. Andersson, Q.Pei, A. J.
ous because one is always pushing beyond the knowledge and Heeger, Science 1996, 73, 1833.
experience of his background. I started out as a physicist, [30] M. Kobayashi, N. Colaneri, M. Boysel, F. Wudl, A. J. Heeger, J. Chem.
however, I am what I have become. I have evolved, with the Phys. 1985, 83, 5717.
[31] A. J. Heeger, P. Smith in Conjugated Polymers (Eds.: J. L. Bredas, R.
help of many colleagues in the international scientific
Silbey), Kluwer Academic, Dordrecht, 1991.
community, into an interdisciplnary scientist. That my work [32] G. Yu, A. J. Heeger in The Physics of Semiconductors, Vol. 1 (Eds.: M.
and that of my colleagues Alan MacDiarmid and Hideki Schleffer, R. Zimmerman), World Scientific, Singapore, 1996.
Shirakawa has had sufficient impact on Chemistry to be [33] R. Menon, C. O. Yoon, D. Moses, A. J. Heeger in Handbook of
recognized by the Nobel Prize gives me, therefore, particular Conducting Polymers (Eds.: T. A. Skotheim, R. L. Elsenbaumer, J. R.
Reynolds), 2nd ed., Marcel Dekker, New York, 1998, p. 85.
satisfaction. [34] L. Sun, S. C. Yang, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem.
1992, 33, 379; G. Heywang, F. Jonas, Adv. Mater. 1992, 4, 116.
Received: February 13 , 2001 [A 451] [35] J. Friedrich, K. Werner, US-A 5 300 575.
[36] C. Kittel, Introduction to Solid State Physics, Wiley, New York, 1986.
[37] K. Lee, A. J. Heeger, Y. Cao, Phys. Rev. B 1993, 48, 14 884.
[38] K. Lee, R. Menon, C. O. Yoon, A. J. Heeger, Phys. Rev. B 1995, 52,
[1] H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J. 4779.
Heeger, Chem. Commun. 1977, 578. [39] Y. Cao, G. M. Treacy, P. Smith, A. J. Heeger, Appl. Phys. Lett. 1992, 60,
[2] C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H. 2711.
Shirakawa, E. J. Louis, Phys. Rev. Lett. 1977, 39, 1098. [40] G. Gustafsson, Y. Cao, G. M. Treacy, F. Klavetter, N. Colaneri, A. J.
[3] B. Ranby in Conjugated Polymers and Related Materials: The Heeger, Nature 1992, 357, 477.
Interconnectionof Chemical and Electronic Structures (Eds.: W. R. [41] J. Gao, A. J. Heeger, J. Y. Lee, C. Y. Kim, Synth. Met. 1996, 82, 221.
Salaneck, I. Lundstrm, B. Ranby), Oxford University Press, Oxford, [42] Y. Cao, G. Yu, C. Zhang, R. Menon, A. J. Heeger, Synth. Met. 1997, 87,
1993, chap. 3. 171.
[4] A. J. Heeger, S. Kivelson, J. R. Schrieffer, W. P. Su, Rev. Mod. Phys. [43] I. H. Campbell, T. W. Hagler, D. L. Smith, J. P. Ferraris, Phys. Rev.
1988, 60, 781. Lett. 1996, 76, 1900.
[5] W. P. Su, J. R. Schrieffer, A. J. Heeger, Phys. Rev. Lett. 1979, 42, 1698. [44] M. Pope, C. E. Swenberg, Electronic Processes in Organic Crystals,
[6] W. P. Su, J. R. Schrieffer, A. J. Heeger, Phys. Rev. B 1980, 22, 2099. Clarendon Press, Oxford, 1982.
[7] C. K. Chiang, S. C. Gau, C. R. Fincher, Jr., Y. W. Park, A. G. [45] T. W. Hagler, A. J. Heeger, Chem. Phys. Lett. 1992, 189, 333.
MacDiarmid, Appl. Phys. Lett. 1978, 33, 18. [46] T. W. Hagler, K. Pakbaz, K. Voss, A. J. Heeger, Phys. Rev. B 1991, 44,
[8] P. J.Nigrey, A. G. MacDiarmid, A. J. Heeger, J. Chem. Soc. Chem. 8652.
Commun. 1979, 594; C. Jones, P. M. Jordan, A. G. Chaudhry, M. [47] A. Streitweiser, Molecular Orbital Theory for Organic Chemists,
Akhtar, J. Chem. Soc. Chem. Commun. 1979, 96; R. D. Bach, D. H. Wiley, New York, 1961.
Lucast, J. Chem. Soc. Chem. Commun. 1979, 593. [48] P. Smith, P. J. Lemstra, J. P. L. Pijpers, A. M. Kile, Colloid, Polym. Sci.
[9] Q. Pei, G. Yu, C. Zhang, Y. Yang, A. J. Heeger, Science 1995, 269, 1981, 259, 1070.
1086. [49] R. E. Peierls, Quantum Theory of Solids, Clarendon Press, Oxford,
[10] W. R. Salaneck, I. Lundstrom, W. S. Haung, A. G. MacDiarmid, Synth. 1955.
Met. 1986, 13, 291. [50] C. R. Fincher, C. E. Chen, A. J. Heeger, A. G. MacDiarmid, J. B.
[11] Y. Cao, P. Smith, A. J. Heeger, Synth. Met. 1992, 48, 91. Hastings, Phys. Rev. Lett. 1982, 48, 100.

2610 Angew. Chem. Int. Ed. 2001, 40, 2591 2611

Conducting Polymers REVIEWS
[51] C. S. Yannoni, T. C. Clarke, Phys. Rev. Lett. 1983, 52 1191. [75] S. Tokito, P. Smith, A. J. Heeger, Polymer 1991, 32, 464.
[52] S. Brazovskii, N. Kirova, A. R. Bishop, Opt. Mater. 1998, 9, 465. [76] A. F. Ioffe, A. R. Regel, Prog. Semicond. 1960, 4, 237.
[53] N. Kirova, S. Brazovskii, A. R. Bishop, Synth. Met. 1999, 100, 29. [77] N. F. Mott, E. A. Davis, Electronic Processes in Noncrystalline
[54] E. K. Miller, D. Yoshida, C. Y. Yang, A. J. Heeger, Phys. Rev. B 1999, Matrials, Oxford University Press, Oxford, 1979.
59, 4661. [78] N. F. Mott, Metal-Insulator Transition, Taylor & Francis, London,
[55] E. K. Miller, C. Y. Yang, A. J. Heeger, Phys. Rev. B 2000, 62, 6889. 1990.
[56] K. Fesser, A. R. Bishop, D. Campbell, Phys. Rev. B 1983, 27, 4804. [79] P. W. Anderson, Phys. Rev. B 1958, 109, 1492.
[57] S. A. Brazovski, N. Kirova, Sov. Phys. JETP (Engl. Transl.) 1981, 33, 4. [80] P. W. Anderson, Comments Solid State Phys. 1970, 2, 193.
[58] N. S. Sariciftci, L. Smilowitz, A. J. Heeger, F. Wudl, Science 1992, 258, [81] E. Abrahams, P. W. Anderson, D. C. Licciardello, T. V. Ramakrishnan,
1474. Phys. Rev. Lett. 1979, 42, 695.
[59] S. Morita, A. A. Zakhidov, Y. Yoshino, Solid State Commun. 1992, 82, [82] W. L. McMillan, Phys. Rev. B 1981, 24, 2739.
249. [83] A. I. Larkin, D. E. khmelnitskii, Sov. Phys. JETP (Engl. Transl.) 1982,
[60] B. Kraabel, D. McBranch, N. S. Sariciftci, D. Moses, A. J. Heeger, Mol. 56, 647.
Cryst. Liq. Cryst. 1994, 256, 733; B. Kraabel, J. C. Hummelen, D. [84] K. Lee, E. K. Miller, A. N. Aleshin, R. Menon, A. J. Heeger, J. H.
Vacar, D. Moses, N. S. Sariciftci, A. J. Heeger, J. Chem. Phys. 1996, Kim, C. O. Yoon, H. Lee, Adv. Mater. 1998, 10, 456.
104, 4267. [85] K. Lee, A. J. Heeger, Y. Cao, Synth. Met. 1995, 69, 261.
[61] G. Lanzani, C. Zenz, G. Cerullo, W. Graupner, G. Leising, U. Scherf, S. [86] N. F. Mott, M. Kaveh, Adv. Phys. 1985, 34, 329.
De Silvestri, Synth. Met. 2000, 111 112, 493. [87] T. G. Castner in Hopping Transport in Solids (Eds.: M. Pollak, B. I.
[62] L. Smilowitz, N. S. Sariciftci, R. Wu, C. Gettinger, A. J. Heeger, F. Shlovskii), Elsevier Science, Amsterdam, 1991.
Wudl, Phys. Rev. B 1993, 47, 13 835. [88] P. A. Lee, T. V. Ramakrishnan, Rev. Mod. Phys. 1985, 57, 287.
[63] N. S. Sariciftci, A. J. Heeger, Int. J. Mod. Phys. B 1994, 8, 237. [89] S. Kivelson, A. J. Heeger, Synth. Met. 1987, 22, 371.
[64] P. M. Allemand, G. Srdanov, A. Koch, F. Wudl, J. Am. Chem. Soc. [90] A. J. Heeger, Faraday Discuss. Chem. Soc. 1989, 88, 1.
1991, 113, 1050. [91] S. Tokito, P. Smith, A. J. Heeger, Polymer 1991, 32, 464.
[65] K. Lee, R. Jansson, N. S. Sariciftci, A. J. Heeger, Phys. Rev. B 1994, 49, [92] J. M. Tranquada in Earlier and Recent Aspects of Superconductivity
5781. (Eds.: J. G. Bednorz, K. A. Mller), Springer, Berlin, 1990.
[66] C. H. Lee, G. Yu, D. Moses, K. Pakbaz, C. Zhang, N. S. Sariciftci, A. J. [93] T. Wang, K. M. Beauchamp, D. D. Berkley, B. R. Johnson, J. X. Liu, J.
Heeger, F. Wudl, Phys. Rev. B 1993, 48, 15 425. Zhang, A. M. Goldman, Phys. Rev. B 1991, 43, 8623.
[67] G. Yu, A. J. Heeger, J. Appl. Phys. 1995, 78, 4510. [94] G. Yu, C. H. Lee, A. J. Heeger, N. Herron, E. M. McCarron, L. Cong,
[68] J. J. M. Halls, C. M. Walsh, N. C. Greenham, E. A. Marseglia, R. H. G. C. Spalding, C. A. Nordman, A. M. Goldman, Phys. Rev. B 1992,
Friend, S. C. Moratti, A. B. Holmes, Nature 1995, 376, 498. 45, 4964.
[69] G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science 1995, [95] N. S. Sariciftci, A. J. Heeger, V. Krasevec, P. Venturini, D. Mihailovic,
270, 1789. Y. Cao, J. Libert, J. L. Bredas, Synth. Met. 1994, 62, 107.
[70] C. Y. Yang, A. J. Heeger, Synth. Met. 1996, 83, 85. [96] M. D. McGehee, E. K. Miller, D. Moses, A. J. Heeger in Advances in
[71] K. Akagi, M. Suezaki, H. Shirakawa, H. Kyotani, M. Shimamura, Y. Synthetic Metals: Twenty Years of Progress in Science and Technology
Tanabe, Synth. Met. 1989, 28, D1. (Eds.: P. Bernier, S. Lefrant, G. Bidan, Elsevier Science, Lausanne,
[72] J. Tsukomoto, Jpn. J. Appl. Phys. 1990, 29, 1. 1999.
[73] Y. Cao, P. Smith, A. J. Heeger, Polymer 1991, 32, 1210. [97] M. D. McGehee, A. J. Heeger, Adv. Mater., in press.
[74] T. Schimmel, W. Reiss, J. Gmeiner, M. Schworer, H. Naarmann, N.
Theophilou, Solid State Commun. 1998, 65, 1311.

Angew. Chem. Int. Ed. 2001, 40, 2591 2611 2611

 REVIEWS

Synthetic Metals: A Novel Role for Organic Polymers (Nobel Lecture)**

Alan G. MacDiarmid*

Since the initial discovery in 1977, that
polyacetylene (CH)x , now commonly
known as the prototype conducting
polymer, could be p- or n-doped either
chemically or electrochemically to the
metallic state, the development of the
field of conducting polymers has con-
tinued to accelerate at an unexpectedly
rapid rate and a variety of other
conducting polymers and their deriva-
tives have been discovered. Other
types of doping are also possible, such
as photo-doping and charge-injec-
tion doping in which no counter
dopant ion is involved. One exciting
challenge is the development of low-
cost disposable plastic/paper electronic
devices. Conventional inorganic con-
ductors, such as metals, and semicon-
ductors, such as silicon, commonly
require multiple etching and litho-
graphic steps in fabricating them for
use in electronic devices. The number
of processing and etching steps in-
volved limits the minimum price. On
the other hand, conducting polymers
combine many advantages of plastics,
for example, flexibility and processing
from solution, with the additional ad-
vantage of conductivity in the metallic
or semiconducting regimes; however,
the lack of simple methods to obtain
inexpensive conductive polymer
shapes/patterns limit many applica-
tions. Herein is described a novel,
simple, and cheap method to prepare
patterns of conducting polymers by a
process which we term, Line Pattern-
ing.
Keywords: conducting materials
liquid crystals nano-electronics
Nobel lecture polymers

Introduction increased by several orders of magnitude from the semi-

conductor regime are generally referred to as electronic
An organic polymer that possesses the electrical, electronic, polymers and have become of very great scientific and
magnetic, and optical properties of a metal while retaining the technological importance since 1990 because of their use in
mechanical properties, processibility, etc. commonly associ- light emitting diodes.[1] The emeraldine base form of polyani-
ated with a conventional polymer, is termed an intrinsically line and trans-(CH)x are shown in Figure 1 to illustrate the
conducting polymer (ICP) more commonly known as a increases in electrical conductivity of many orders of magni-
synthetic metal. Its properties are intrinsic to a doped
form of the polymer. This class of polymer is completely
different from conducting polymers which are merely a
physical mixture of a nonconductive polymer with a conduct-
ing material such as a metal or carbon powder distributed
throughout the material.

The Concept of Doping

Conjugated organic polymers are either electrical insula-

tors or semiconductors. Those that can have their conductivity
[*] Prof. A. G. MacDiarmid
Department of Chemistry
University of Pennsylvania
Philadelphia, PA 19104-6323 (USA)
Fax: ( 1) 215-898-8378
E-mail: macdiarm@sas.upenn.edu
[**] Copyright The Nobel Foundation 2001. We thank the Nobel Figure 1. Conductivity of electronic polymers. Conductivity increases with
Foundation, Stockholm, for permission to print this lecture. increased doping.

Angew. Chem. Int. Ed. 2001, 40, 2581 2590  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 1433-7851/01/4014-2581 $ 17.50+.50/0 2581
REVIEWS A. G. MacDiarmid

tude which can be obtained by doping. The conductivity
attainable by an electronic polymer has very recently been
increased an infinite number of times by the discovery of
superconductivity in regioregular poly(3-hexylthiophene).[2]
Although this phenomenon was present only in a very thin
layer of the polymer in a Field Effect (FET) configuration at a
very low temperature (ca. 2 K) it represents an historical
quantum leapsuperconductivity in an organic polymer!
Prior to the discovery of the novel protonic acid doping of
polyaniline, during which the number of electrons associated
with the polymer chain remain unchanged,[3] the doping of all
conducting polymers had previously been accomplished by
redox doping. This involves the partial addition (reduction) or
removal (oxidation) of electrons to or from the p system of
the polymer backbone.[46]
The concept of doping is the unique, central, underlying,
and unifying theme which distinguishes conducting polymers
from all other types of polymers.[7] During the doping process,
an organic polymer, either an insulator or semiconductor
having a small conductivity, typically in the range 1010 to
105 S cm1, is converted into a polymer which is in the
metallic conducting regime (ca. 1 to 104 S cm1). The
controlled addition of known, usually small ( 10 %) non-
stoichiometric quantities of chemical species results in
dramatic changes in the electronic, electrical, magnetic,
optical, and structural properties of the polymer. Doping is
reversible to produce the original polymer with little or no
degradation of the polymer backbone. Both doping and
undoping processes, involving dopant counterions which
stabilize the doped state, may be carried out chemically or
electrochemically.[6] Transitory doping by methods which
introduce no dopant ions are also known.[8]
By controllably adjusting the doping level, a conductivity
anywhere between that of the non-doped (insulating or
semiconducting) and that of the fully doped (highly conduct-
ing) form of the polymer can be easily obtained. Conducting
blends of a (doped) conducting polymer with a conventional
polymer (insulator), whose conductivity can be adjusted by
varying the relative proportions of each polymer, can be
made.[9] This permits the optimization of the best properties of
each type of polymer.
Since the initial discovery in 1977, that polyacetylene
(CH)x , now commonly known as the prototype conducting
polymer, could be p- or n-doped either chemically or electro-
chemically to the metallic state,[7, 10, 11] the development of the
field of conducting polymers has continued to accelerate at an
unexpectedly rapid rate and a variety of other conducting
polymers and their derivatives have been discovered.[5, 6] This
rapid growth rate has been stimulated by the fields funda-
mental synthetic novelty and importance to a cross-discipli-
nary section of investigatorschemists, electrochemists,
biochemists, experimental and theoretical physicists, and
electronic and electrical engineersand to important tech-
nological emerging applications of these materials.
In the doped state, the backbone of a conducting polymer
consists of a delocalized p system. In the undoped state, the
polymer may have a conjugated backbone such as in trans-
(CH)x which is retained in a modified form after doping, or it
may have a nonconjugated backbone, as in polyaniline
(leucoemeraldine base form), which becomes truly conjugat-
ed only after p-doping, or a nonconjugated structure as in the
emeraldine base form of polyaniline which becomes con-
jugated only after protonic acid doping.
Redox Doping
All conducting polymers (and most of their derivatives), for
example, poly-(para-phenylene) (1), poly(phenylenevinyl-
ene) (2), polypyrrole (3), polythiophene (4), polyfuran (5),
poly(heteroaromatic vinylenes) (6; where Y NH, NR, S, O);
polyaniline (7), etc., undergo either p- and/or n-redox doping

Alan MacDiarmid was born in New Zealand 74 years ago and after obtaining his higher education at the University of New
Zealand (M.Sc. 1950), University of Wisconsin (Ph.D. 1953), and Cambridge University (Ph.D. 1955), he joined the faculty
of the University of Pennsylvania in 1955, where he is currently Blanchard Professor of
Chemistry. During the past 24 years he has been involved exclusively with conducting polymers,
particularly the synthesis, chemistry, doping, electrochemistry, conductivity, magnetic and optical
properties, and processing of polyacetylene and polyaniline. He is the author/co-author of
approximately 600 research papers and 20 patents. He is the recipient of numerous awards and
honorary degrees both nationally and internationally. In 1973, he began research on (SN)x, an
unusual polymeric material with metallic conductivity. His interest in organic conducting
polymers began in 1975 when he was introduced to a new form of polyacetylene by Dr. Hideki
Shirakawa at the Tokyo Institute of Technology. The ensuing collaboration between
MacDiarmid, Shirakawa, and Alan Heeger (then at the Department of Physics at the University
of Pennsylvania) led to the historic discovery of metallic conductivity in an organic polymer, and
the award of the Nobel Prize for Chemisty, 2000.

2582 Angew. Chem. Int. Ed. 2001, 40, 2581 2590

Synthetic Metals
by chemical and/or electrochemical processes during which
the number of electrons associated with the polymer back-
bone changes.[5, 6] Selected examples of the different types of
doping are presented below.
Chemical and Electrochemical p-Doping
p-Doping, that is, partial oxidation of the p backbone of an
organic polymer, was first discovered by treating trans-(CH)x
with an oxidizing agent such as iodine,[7] [Eq. (1)]
trans-(CH)x 1.5xy I2 ! [CHy(I3)y]x (y  0.07) (1)
This process was accompanied by an increase in conduc-
tivity from ca. 105 S cm1 to ca. 103 S cm1. If the polymer is
stretch-oriented five- to six-fold before doping, conductivities
parallel to the direction of stretching up to around 105 S cm1
can be obtained.[5, 6]
Approximately 85 % of the positive charge is delocalized
over 15 CH units (depicted in Scheme 1 for simplicity over
only five units) to give a positive soliton.
Scheme 1.
p-Doping can also be accomplished by electrochemical
anodic oxidation by immersing a trans-(CH)x film in, for
example, a solution of LiClO4 dissolved in propylene carbo-
nate and attaching it to the positive terminal of a DC (direct
current) power source, the negative terminal being attached
to an electrode also immersed in the solution,[10] [Eq. (2)].
trans-(CH)x (xy) (ClO4) ! [(CHy(ClO4)y]x (xy)e (y  0.1) (2)
Chemical and Electrochemical n-Doping
n-Doping, that is, partial reduction of the backbone
p system of an organic polymer, was also discovered using
trans-(CH)x by treating it with a reducing agent such as liquid
sodium amalgam or preferably sodium naphthaline[7] [Eq. (3)
(Nphth naphthaline)].
trans-(CH)x (xy)Na(Nphth) ! [Nay(CH)y]x Nphth (y  0.1) (3)
The antibonding p system is partially populated by this
process which is accompanied by an increase in conductivity
of about 103 S cm1.
n-Doping can also be carried out by electrochemical
cathodic reduction[11] by immersing a trans-(CH)x film in, for
example, a solution of LiClO, dissolved in tetrahydrofuran
and attaching it to the negative terminal of a DC power
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
REVIEWS
source, the positive terminal being attached to an electrode
also immersed in the solution [Eq. (4)].
trans-(CH)x (xy)Li (xy)e ! [Liy(CH)y]x (y  0.1) (4)
In all chemical and electrochemical p- and n-doping
processes discovered for (CH)x and for the analogous
processes in other conducting polymers, counter dopant
ions are introduced which stabilize the charge on the polymer
backbone. In each case, spectroscopic signatures, for example,
those of solitons, polarons, bipolarons, etc., are obtained
characteristic of the given charged polymer. However, the
doping phenomena concept extends considerably beyond that
given above to doping processes where no counter dopant
ion is involved, that is, to doping processes in which transitory
doped species are produced, which have similar spectro-
scopic signatures to polymers containing dopant ions. This
type of doping can provide information not obtainable by
chemical or electrochemical doping. Examples of such types
of redox doping which can be termed photo-doping and
charge-injection doping are given below.
Doping Involving no Dopant Ions
Photo-Doping
When trans-(CH)x for example, is exposed to radiation of
energy greater than its band gap, electrons are promoted
across the gap and the polymer undergoes photo-doping.
Under appropriate experimental conditions, spectroscopic
signatures characteristic of, for example, solitons can be
observed[12] (Scheme 2). The positive and negative solitons
Scheme 2.
are here illustrated diagrammatically for simplicity as residing
only on one CH unit; they are actually delocalized over ca.
15 CH units. They disappear rapidly because of the recombi-
nation of electrons and holes when irradiation is discontinued.
If a potential is applied during irradiation, then the electrons
and holes separate and photoconductivity is observed.
Charge-Injection Doping
Charge-injection doping is most conveniently carried out
using a metal/insulator/semiconductor (MIS) configuration
involving a metal and a conducting polymer separated by a
thin layer of a high dielectric strength insulator. It was this
approach, which resulted in the observance of superconduc-
tivity in a polythiophene derivative, as described previously.
Application of an appropriate potential across the structure
2583
REVIEWS
can give rise, for example, to a surface charge layer, the
accumulation layer which has been extensively investigated
for conducting polymers.[8, 13] The resulting charges in the
polymer, for example, (CH)x or poly(3-hexylthiophene), are
present without any associated dopant ion. The spectroscopic
properties of the charged species so formed can therefore be
examined in the absence of dopant ion. Using this approach,
spectroscopic studies of (CH)x show the signatures character-
istic of solitons and the mid-gap absorption band observed in
the chemically and electrochemically doped polymer. How-
ever, coulombic interaction between charge on the chain and
dopant ion is a very strong interaction and one that can totally
alter the energetics of the system.
Non-Redox Doping
This type of doping differs from redox doping described
above in that the number of electrons associated with the
polymer backbone does not change during the doping process.
The energy levels are rearranged during doping. The emer-
aldine base form of polyaniline was the first example of the
doping of an organic polymer to a highly conducting regime
by a process of this type to produce an environmentally stable
polysemiquinone radical cation. This was accomplished by
treating emeraldine base with aqueous protonic acids
(Scheme 3) and is accompanied by a nine to ten order of
magnitude increase in conductivity (up to around 3 S cm1) to
produce the protonated emeraldine base.[1416] Protonic acid
doping has subsequently been extended to systems such as
poly(heteroaromatic vinylenes).[17]
Scheme 3.
The Polyanilines
The polyanilines refer to a very important class of
electronic/conducting polymers. They can be considered as
being derived from a polymer, the base form of which has the
generalized composition given in Scheme 4 a, and which
consists of alternating reduced, and oxidized, repeat units
(Scheme 4 a).[3, 14, 15] The average oxidation state can be varied
continuously from y 1 to give the completely reduced
polymer, to y 0.5 to give the half-oxidized polymer, to
y 0 to give the completely oxidized polymer (Scheme 4 b
d). The terms leucoemeraldine, emeraldine, and perni-
graniline refer to the different oxidation states of the
polymer where y 1, 0.5, and 0, respectively, either in the
base form, for example, emeraldine base, or in the protonated
salt form, for example, emeraldine hydrochloride.[3, 14, 15] In
principle, the imine nitrogen atoms can be protonated in
2584
A. G. MacDiarmid
Scheme 4. a) Generalized composition of polyanilines indicating the
reduced and oxidized repeat units, b) completely reduced polymer,
c) half-oxidized polymer, d) fully oxidized polymer.
whole or in part to give the corresponding salts, the degree of
protonation of the polymeric base depending on its oxidation
state and on the pH of the aqueous acid. Complete
protonation of the imine nitrogen atoms in emeraldine base
by aqueous HCl, for example, results in the formation of a
delocalized polysemiquinone radical cation[3, 15, 18] and is
accompanied by an increase in conductivity of about 1010.
The partly protonated emeraldine hydrochloride salt can be
synthesized easily either by the chemical or electrochemical
oxidative polymerization of aniline.[3, 14, 15] It can be deproto-
nated by aqueous ammonium hydroxide to give emeraldine
base powder (a semiconductor).
Allowed Oxidation States
As can be seen from the generalized formula of polyaniline
base (Scheme 4 a), the polymer could, in principle, exist in a
continuum of oxidation states ranging from the completely
reduced material in the leucoemeraldine oxidation state, y 1
to the completely oxidized material in the pernigraniline
oxidation state, y 0. However, we have shown[16] that at least
in N-methyl-2-pyrrolidinone (NMP) solution in the range
y 1 to y 0.5 (emeraldine oxidation state) only two
chromophores are present, characteristic of y 1, and y
0.5 species and that all intermediate oxidation states consist,
at the molecular level, only of mixtures of the chromophores
characteristic of these two states.
Since most of the properties of polyaniline of interest are
concerned with the solid state, we have carried out a series of
studies in the solid state which show that the same phenom-
enon is true in the y 1 to y 0.5 oxidation-state range and in
the y 0.5 to y 0 oxidation-state range. Within each of these
ranges all intermediate oxidation states consist, at the
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
Synthetic Metals
molecular level, only of mixtures of the chromophores
characteristic of the two states defining the beginning and
end of each range.[19, 20]
Doping
Polyaniline holds a special position amongst conducting
polymers in that its most highly conducting doped form can be
reached by two completely different processesprotonic acid
doping and oxidative doping. Protonic acid doping of
emeraldine base units with, for example 1m aqueous HCl
results in complete protonation of the imime nitrogen atoms
to give the fully protonated emeraldine hydrochloride
salt.[14, 15]
As shown in Figure 2, protonation is accompanied by a 9 to
10 order of magnitude increase in conductivity reaching
saturation in ca. 1m aqueous HCl.
Figure 2. Conductivity of emeraldine base as a function of the pH of the
HCl dopant solution as it undergoes protonic acid doping (* and &
represent two independent series of experiments).[14, 15]
The same doped polymer can be obtained by chemical
oxidation (p-doping) of leucoemeraldine base.[3] This actually
involves the oxidation of the s/p system rather than just the
p system of the polymer as is usually the case in p-type doping.
Its reaction with a solution of chlorine in carbon tetrachloride
proceeds to give emeraldine hydrochloride (Scheme 5).
Scheme 5.
Nanoelectronics
The basic purpose of this research is to blend the now well-
established field of electronic/conducting polymers with the
new, emerging field of nanoscience, by electrostatic fabrica-
tion (electrospinning) to produce nanoelectronicselec-
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
REVIEWS
tronic junctions and devices significantly smaller than the
diameter of a human hair (ca. 50 000 nm). It is commonly
accepted that a nanomaterial is defined as one consisting of a
substance or structure which exhibits at least one dimension
of less than 100 nm (0.1 mm).[21]
Our objectives were: 1) to develop a method by which
nanofibers (diameter < 100 nm) of organic polymers could be
controllably and reproducibly fabricated such that in one
given preparation, all fibers would have a diameter < 100 nm
and 2) to reproducibly and controllably fabricate, for the first
time, nanofibers of electronic polymers (in their semiconduct-
ing and metallic regimes) and/or their blends in conventional
organic polymers for the purpose of ascertaining their
applicability in the fabrication of nanoelectronic devices.
We have made substantial progress in achieving these
objectives by using a relatively little known, simple, conven-
ient, and inexpensive electrospinning method.[2227] We have
previously reported[23] fabrication of the first conducting
polymer fibers (diameter  950 nm to 2100 nm) of polyaniline
doped with rac-camphorsulfonic acid (PAn HCSA) as a
blend in poly(ethylene oxide) (PEO). We were surprised to
find that an electronic polymer, such as polyaniline, which
might have been expected to be more susceptible to
degradation than most conventional organic polymers, sur-
vived, without observable chemical or physical change,
following the 25 000 V electrospinning fabrication process in
air at room temperature.
Electrospinning
The electrospinning technique involves a simple, rapid,
inexpensive, electrostatic, nonmechanical method in which a
polymer solution in a variety of different possible common
solvents, including water, is placed in a hypodermic syringe or
in a glass pipette, at a fixed distance (5 30 cm) from a metal
cathode.[24] The positive (anode) terminal of a variable high
voltage transformer is attached to the metal tip of the
hypodermic syringe or to a wire inserted into the polymer
solution in the glass pipette, the negative terminal being
attached to the metal cathode. The tip of the syringe can be
placed vertically over the cathode or at any other convenient
angle to it. When the voltage applied between the anode and
cathode reaches a critical value, ca. 14 000 V at a ca. 20 cm
separation, the charge overcomes the surface tension of the
deformed drop of the polymer solution on the tip of the
syringe and a jet is produced. Since the polymer molecules all
bear the same (positive) charge, they repel each other while
traveling in air during a few milliseconds from the anode to
cathode and become separated.[25] At the same time, evapo-
ration of the solvent molecules occurs rapidly. Evaporation of
solvent is also enhanced because the similarly charged
(positive) solvent molecules repel each other. Under appro-
priate conditions, dry, meters-long fibers accumulate on the
surface of the cathode resulting in a nonwoven mesh of nano-
to micron-diameter fibers depending on experimental param-
eters (Figure 3).
2585
REVIEWS
Figure 3. 50 wt % Nanofiber blend of PAn HCSA fabricated from 2 wt %
PAn HCSA and 2 wt % PEO from chloroform solution at 25 000 V (anode/
cathode separation, 25 cm). Scale bar: 100 000 nm.
Nanofiber Fabrication
Since the submicron fibers (500 1600 nm) obtained in our
initial work[23] were not classifiable as true nanofibers, our
immediate objective was to break the nanotechnology
barrier and to consistently and reproducibly fabricate true
nanofibers (diameter < 100 nm) of an organic polymer. This
was accomplished (see Figure 4) using an 8 wt % solution of
Figure 4. Electrospun fibers of polystyrene (see text). Scale bar: 1000 nm.
The extended length of the fibers is clearly visible.
polystyrene (Mw 212 400) in tetrahydrofuran at a potential of
20 000 V between the anode and cathode which were sepa-
rated by 30 cm. The fibers were collected as a mat on an
aluminum target and were found to have diameter character-
istics: average: 43.1 nm, maximum: 55.0 nm, minimum:
26.9 nm. Other studies involving polystyrene gave fibers
whose diameters were consistently < 100 nm; average:
30.5 nm (maximum: 44.8 nm, minimum: 16.0 nm). It might
also be noted that the 16 nm fiber is only around 30
polystyrene molecules wide. It is also of interest to note that
a 16 nm fiber, such as the one mentioned above, lies well
within the ca. 4 30 nm diameter range of multiwalled carbon
nanotubes.[26]
Electronic Polymer Fibers
By using a previously applied method for producing
polyaniline fibers[27] we have prepared highly conducting
sulfuric acid doped polyaniline fibers (diameters, average:
139 nm, maximum: 275 nm, minimum: 96 nm) by placing a ca.
20 wt % solution of polyaniline in 98 % sulfuric acid in a glass
2586
A. G. MacDiarmid
pipette with the tip ca. 3 cm above the surface of a copper
cathode immersed in pure water at 5000 V potential differ-
ence. The fibers collect in or on the surface of the water. The
conductivity of a single fiber was ca. 0.1 S cm1, as expected
since partial fiber de-doping occurred in the water cathode.
The diameter and length of the fibers appear (Figure 5) to be
sensitive to the nature of the polyaniline used. No great
difficulty is foreseen in producing fibers < 100 nm diameter.
Figure 5. 100 % polyaniline fiber with an average diameter of 139 nm.
It is relatively easy to prepare conducting blends of
PAn.HCSA in a variety of different conventional polymers
such as polyethylene oxide, polystyrene, polyacrylonitrile, etc.
For example, ca. 20 wt % blends of PAn HCSA in polystyr-
ene (Mw 114 200) are obtained by electrospinning a chloro-
form solution; fiber diameter characteristics: average:
85.8 nm, maximum: 100.0 nm, minimum: 72.0 nm. These
fibers are sufficiently electrically conductive that their scan-
ning electron micrographs (SEMs) may be recorded without
the necessity of applying a gold coating.
Separate, individual nanofibers can be collected and
examined if so desired. An appropriate substrateglass slide,
silicon wafer, or loop of copper wire, etc.is held between the
anode and cathode at a position close to the cathode for a few
seconds to collect individual fibers (see Figure 6).
Figure 6. Polystyrene fibers collected on a bent copper wire (magnification
33  ) and subsequently coated with a thin layer of polypyrrole by in situ
deposition from aqueous solution. Scale bar: 1 mm.
Current/voltage (I/V) curves are given in Figure 7 for a
single 419 nm diameter fiber (Fiber 1) and for a ca. 600 nm
diameter fiber (Fiber 2) of a blend of 50 wt % PAn HCSA
and poly(ethylene oxide) collected on a silicon wafer coated
with a thin layer of SiO2 . Two gold electrodes separated by
60.3 mm are deposited on the fiber after its deposition on the
substrate.
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
Synthetic Metals
Figure 7. Current/voltage curves of 50 wt % PAn HCSA/PEO blend
nanofiber (see text).
Nanofibers as Substrates
The large surface to volume ratio offered by nanofibers
makes them excellent, potentially useful substrates for the
fabrication of coaxial nanofibers consisting of superimposed
layers of different materials. Catalysts and electronically
active materials can be deposited on them by chemical,
electrochemical, solvent, chemical vapor, or other means, for
use in nanoelectronic junctions and devices.
We have found, for example, that polyacrylonitrile nano-
fibers can be easily and evenly coated with a 20 25 nm layer
of conducting polypyrrole (Figure 8) by immersion in an
aqueous solution of polymerizing polypyrrole.[28] Analogous-
ly, we have found that electroless deposition of metals can also
be performed. Polyacrylonitrile fibers, for example, can be
evenly coated with gold by electroless deposition.[29]
Figure 8. Scanning electron micrograph of conducting polypyrrole-coated
polyacrylonitrile nanofibers. Scale bar: 1000 nm.
Carbon Nanofibers
As reported polyacrylonitrile fibers may be thermally
converted into carbon nanofibers with some shrinkage.[30]
We have similarly converted polyacrylonitrile nanofibers into
carbon nanofibers.
In summary, electronic polymers have been used for the
past 20 years to produce rectifying diodes by Schottky and p/n
junctions, transistors, light-emitting devices, photovoltaic
cells, rechargeable batteries, etc.[1] Now, the ability to fab-
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
REVIEWS
ricate nanofibers of electronic polymers which are only a few
molecules thick suggests the emergence of a field of nano-
electronics whereby the electronic properties of such nano-
fibers can be exploited for technological purposes.
Line Patterning of Conducting Polymers[30]
One of the exciting challenges of the first part of this
century will be the development of low-cost disposable
plastic/paper electronic devices.[3133] Conventional inorganic
conductors, such as metals, and semiconductors, such as
silicon, commonly require multiple etching and lithographic
steps in fabricating them for use in electronic devices. The
number of processing steps and chemical etching steps
involved limit the minimum price and therefore their applic-
ability in disposable electronics. On the other hand, conduct-
ing polymers combine many advantages of plastics, for
example, flexibility and processing from solution, with the
additional advantage of conductivity either in the metallic or
semiconducting regimes; however, the lack of simple methods
to obtain inexpensive conductive polymer shapes/patterns
limit many applications. We here describe a novel, simple, and
cheap method to prepare patterns of conducting polymers by
a process which we term, Line Patterning.
Line Patterning uses the difference in selected physical and/
or chemical properties between a substrate and insulating
lines which have been printed on it by a conventional copying
or printing process towards a fluid (or vapor) to which they
are both simultaneously exposed. The substrate and printed
lines react differently or at different rates with the fluid (or
vapor) to which they have been exposed. This results in a non-
uniform deposition on the substrate as compared to the
printed lines. If the fluid contains a conducting polymer, which
remains as a film after evaporation of the solvent, a pattern of
conducting polymer results. A pattern is first designed on a
computer and is then printed on, for example, an overhead
transparency using a standard, non-modified office laser
printer.
The printed (insulating) lines can be easily removed, if
necessary, in a few seconds by ultrasonic treatment in toluene,
dissolving the printed lines and leaving a clean pattern of
deposited material on the substrate whose shape was origi-
nally defined by the now nonexistent printed lines. Line
Patterning has the following advantages: no photolithography
is involved; no printing of conducting polymer is involved; it
uses only, for example, a standard office laser printer, which is
not modified in any way; commercially available flexible,
transparent plastic or paper substrates can be used; solutions
of commercially available conducting or nonconducting
polymers can be used from which the polymers may be
deposited on substrates, it is inexpensive; rapid development
of customized patterns (within hours) from a computer
designed pattern to product is routine.
We have exploited, for example, the observation that a
commercial dispersion of poly-3,4-ethylenedioxythiophene
(PEDOT, Baytron P, Bayer Corp.) wets commercial plastic
overhead transparency, but not the lines printed on it by a
standard office laser printer. A coating of PEDOT can be
2587
REVIEWS
applied by a roller and after evaporation of the solvent; the
printed lines can be easily and cleanly removed by sonication,
leaving only the conducting polymer on the transparency.
Two electrodes were prepared in this way, each containing
25 lines inch1. A drop of a standard commercial polymer
dispersed liquid crystal (PDLC) display[34] mixture containing
an optical adhesive and 15 mm spacer spheres was placed on
the center of each electrode. The second electrode was placed
on top at an angle of 908 to the first. This resulted in a (25 
25), that is, 625 pixels (square-inch matrix)1 (Figure 9).
Exposure to UV light for a few minutes resulted in polymer-
ization of the mixture to bind the two electrodes together and
to produce a free-standing working PDLC display device.
When an electrode pattern of 100 lines inch1 was used a
working 10 000 pixel square-inch1 display was produced.
Figure 9. Fabrication of a 625 pixel PDLC display (see text).
We have devised a novel way of separating conducting
polymer circuits from each other by making use of the height
(ca. 4 5 mm) of the printed toner lines, made by using a
standard office printer, above the substrate, for example, on
an overhead transparency. This is illustrated (Figures 10 and
11) by a push button switch to open and close a simple
electrical circuit. A combination of two patterned trans-
parencies where the two adjacent conductive areas are
electrically separated from each other by two ca. 4 5 mm
Figure 10. A simple electronic circuit (push button switch).
Figure 11. Push button switch.
2588
A. G. MacDiarmid
nonconductive printed toner lines is obtained by placing the
printed lines on top of each other as shown in Figures 11 and
12. Depression of the areas labeled PRESS causes the
upper transparency to bend. This electrically connects the
conducting PEDOT surfaces. When released, the transpar-
ency film returns back to its original position, thus breaking
the electrical circuit.
The two-dimensional conducting polymer circuits may be
readily converted into three-dimensional circuits by two
different methods as shown in Figure 12 simply by 1) stapling
two two-dimensional circuits together using a common office
stapler. The metal staple joins together electrically the
conducting polymer areas on two different substrates or
2) making a pinhole through the sheets, as shown, before
applying the PEDOT solution. Some of the solution enters the
pinhole and joins together electrically the conducting surfaces
on the two different circuits.
Figure 12. Three-dimensional connections; a) connected with staple,
b) connected by a coated hole; * connection to power supply.
We have recently observed a curious field effect which thin
films of PEDOT exhibit when exposed to a positive gate
potential in an FET configuration as shown in Figure 13. A
source/drain electrode and a gate electrode are prepared by
Line Patterning and are covered by a thin layer of PEDOT as
described above. A drop of the optical adhesive containing
spacer spheres described above is placed on the source/drain
Figure 13. Field-effect doped PEDOT. a) FET-type device, b) field-
effect configuration.
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
Synthetic Metals
electrode upon which the gate electrode is then placed at 908.
The two electrodes are manually squeezed together and the
optical adhesive is polymerized by exposure to UV light as
was done for the PDLC display described above. Several
thousand of these interconnected transistor-type devices
could be readily fabricated per square inch by the Line
Patterning process, if it were considered desirable. The free-
standing, flexible device shown in Figures 13 and 14 is
produced.
Figure 14. FET-type device.
The device exhibits the same general reversible features
commonly associated with a field effect transistor (FET) as
shown in Figure 15. The doped metallic PEDOT film (s 
2 S cm1 at room temperature) would not be expected to show
a change in conductivity by exposure to a field of this type
Figure 15. Field effect transistor characteristics. I source drain current;
U gate voltage.
under the configuration used. We believe this effect presents
an entirely new method for ascertaining the nature of highly
doped metallic conducting polymers. It has frequently been
postulated that a doped conducting polymer consists of
metallic islands surrounded by lowly conducting beaches
as shown in Figure 16. We postulate that in the effect we have
observed only the lowly conducting beaches and not the
metallic islands respond to the applied field. The applica-
tion of an electric field changes the conductivity of the
Angew. Chem. Int. Ed. 2001, 40, 2581 2590
REVIEWS
Figure 16. Percolation field effect in doped conducting polymers. Metallic
islands separated by beaches of non- or lowly conducting (semi-
conducting) polymer. The field changes the conductivity of the semi-
conducting beaches but not that of the metallic islandshence the
field changes the extent of electrical percolation between the metallic
islandsand therefore changes the bulk conductivity of the material.
beaches and hence the extent of electrical percolation in the
source/drain PEDOT electrode between the metallic is-
lands, hence changing the bulk conductivity of the material.
The response time for our device is much slower than for a
conventional field effect transistor. We therefore conjecture
that the chief changes in conductivity are probably caused by
slow diffusion of the dopant anions under influence of the
applied field. On removal of the field the system reverts to its
original state.
Preliminary studies show that the effect is also present in
polyaniline; it may therefore possibly be found in many other
conducting polymers and would thus represent a general
phenomenon characteristic of all conducting polymers, at
least within certain ranges of doping.
Summary
* Polyacetylene, (CH)x, the simplest organic polymer, can be
reversibly doped to the metallic regime by partial oxidation
or reduction either chemically or electrochemically.
* Polyaniline can be doped to the metallic regime by a simple
acid/base protonation.
* A large number of electronic conductive polymers are now
known.
* A variety of technological applications of electronic con-
ductive polymers, present and projected, are apparent.
This Nobel Prize has world-wide implications since it shows
the ever-increasing importance of interdisciplinary research
in this case collaborative research between a polymer chemist,
Hideki Shirakawa,[35] Alan Heeger,[36] a physicist, and myself,
an organometallic chemist. Each of us had the task of learning
the specialized scientific language of the other in order to
collectively focus on one specific scientific challenge, an
example of where 1 1 1 is more than 3!
The prize is also recognition of the good fortune that Alan,
Hideki, and I had in having each other as such excellent
colleagues and also in having such creative colleagues in each
of our respective individual research groupsthe work stem-
ming from a research group cannot be better than the persons
carrying it out. The prize is a recognition of them and their
work and also the work of countless others world-wide during
the past 23 years who put the flesh on the skeleton work
carried out by us in the 1970s at Penn (University of
2589
REVIEWS
Pennsylvania). If it were not for them there would be no prize
today in the field.
Research in an experimental science (and also in many other
fields) cannot be accomplished without financial support for
stipends, apparatus, supplies and the like. A funding organ-
ization and project officers within such an organization have
tremendous control over the future of science and technology in
any given country. In this respect Dr. Kenneth J. Wynne, my
contracting officer at the US Office of Naval Research for
many years, before his recent retirement, had the scientific
intuition and foresight to fund our first work on conducting
polymersthe first funding of work of this type anywhere in
the world. He funded it because of its scientific interest. The fact
that it now has great technological potential was not a
consideration at that time.
Of what use is a beautiful poem? It gives intellectual
stimulation and enjoyment. Similarly with research. If it has
some practical use, that is merely icing on the cake!
Early studies: Polyacetylene, (CH)x : Alan J. Heeger[36]
(formerly, Physics Department, University of Pennsylvania),
Hideki Shirakawa[35] (Tsukuba University), and many under-
graduate, graduate students, and post doctoral fellows. Finan-
cial support: Principally, US Office of Naval Research (Dr.
K. J. Wynne, Program Manager); University of Pennsylvania
Materials Science Laboratory.
Polyaniline: Arthur J. Epstein (Physics Dept., Ohio State
University) and many undergraduate, graduate students, and
post doctoral fellows. Financial support: Principally, US Office
of Naval Research (Dr. K. J. Wynne, Program Manager);
University of Pennsylvania Materials Science Laboratory.
Recent Studies: Nanofibers (Electrospinning): I. D. Nor-
ris, J. Gao, F. K. Ko, W. E. Jones, Jr., A. T. Johnson, Jr.
Financial support: US Office of Naval Research (Dr. K. J.
Wynne, Program Manager); Army Research OfficeMURI.
Line Patterning: D. Hohnholz, H. Okuzaki. Financial
support: Subcontract, Kent Displays, Inc. (ONR-SBIR Pro-
gram); US Office of Naval Research (Dr. K. J. Wynne,
Program Manager); Fellowship from Ministry of Education,
Science, Culture and Sports, Japan.
Received: May 2, 2001 [A 470]
[1] Handbook of Organic Conductive Materials and Polymers (Ed.: H. S.
Nalwa), Wiley, New York, 1997; Handbook of Conducting Polymers
(Eds.: T. A. Skotheim, R. L. Elsenbaumer, J. F. Reynolds), 2nd ed.,
Marcel Dekker, New York, 1998.
[2] J. H. Schon, A. Dodabalapur, Z. Bao, C. Kloc, O. Schenker, B.
Batlogg, Nature 2001, 410, 189.
[3] A. G. MacDiarmid, A. J. Epstein, Faraday Discuss. Chem. Soc. 1989,
88, 317, and refs therein.
[4] A. G. MacDiarmid, A. J. Heeger, Synth. Met. 1979/80, 1, 101, and refs
therein.
[5] Handbook of Conducting Polymers, Vol 1&2 (Ed.: T. A. Skotheim),
Marcel Dekker, New York, 1986.
[6] M. G. Kanatzidis, Chem. Eng. News 1990, 68(49), 36.
[7] C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H.
Shirakawa, E. J. Louis, A. G. MacDiarmid, Phys. Rev. Lett. 1977, 39,
2590
A. G. MacDiarmid
1098; C. K. Chiang, M. A. Druy, S. C. Gau, A. J. Heeger, E. J. Louis,
A. G. MacDiarmid, J. Am. Chem. Soc. 1978, 100, 1013.
[8] K. E. Ziemelis, A. T. Hussain, D. D. C. Bradley, R. H. Friend, J. Rilhe,
G. Wegner, Phys. Rev. Lett. 1991, 66, 2231.
[9] V. G. Kulkarni, W. R. Mathew, J. C. Campbell, C. J. Dinkins, P. J.
Durbin, 49th ANTEC Conference Proceedings (Montreal, Canada 5
9 May), Society of Plastic Engineers and Plastic Engineering, 1991,
p. 663; L. W. Shacklette, N. F. Colaneri, V. G. Kulkarni, B. Wessling, in
49th ANTEC Conference Proceedings (Montreal, Canada, 5 9 May),
Society of Plastic Engineers and Plastic Engineering, 1991, p. 665.
[10] P. J. Nigrey, A. G. MacDiarmid, A. J. Heeger, J. Chem. Soc. Chem.
Commun. 1979, 594.
[11] D. MacInnes, Jr., M. A. Druy, P. J. Nigrey, D. P. Nairns, A. G.
MacDiarmid, A. J. Heeger, J. Chem. Soc. Chem. Commun. 1981, 317.
[12] A. J. Heeger, S. Kivelson, J. R. Schrieffer, W.-P. Su, Rev. Mod. Phys.
1988, 60, 781, and refs therein.
[13] J. H. Burroughes, C. A. Jones, R. H. Friend, Nature 1988, 335, 137;
J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K.
Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, Nature 1990, 347,
539.
[14] J. C. Chiang, A. G. MacDiarmid, Synth. Met. 1986, 13, 193.
[15] A. G. MacDiarmid, J.-C. Chiang, A. F. Richter, A. J. Epstein, Synth.
Met. 1987, 18, 285.
[16] A. G. MacDiarmid, A. J. Epstein, Faraday Discuss. Chem. Soc. 1989,
88, 317, and refs therein; A. G. MacDiarmid, A. J. Epstein in Science
and Applications of Conducting Polymers (Eds.: W. R. Salaneck, D. T.
Clark, E. J. Samuelsen), Adam Hilger, Bristol, 1990, p. 117.
[17] C. C. Han, R. L. Elsenbaumer, Synth. Met. 1989, 30, 123.
[18] A. G. MacDiarmid, J.-C. Chiang, A. F. Richter, N. L. D. Somasiri, A. J.
Epstein in Conducting Polymers (Ed.: L. Alcacer), Reidel, Dordrecht,
1987, p. 105.
[19] F. L. Lu, F. Wudl, M. Nowak, A. J. Heeger, J. Am. Chem. Soc. 1986,
108, 8311.
[20] Y. Sun, A. G. MacDiarmid, A. J. Epstein, J. Chem. Soc. Chem.
Commun. 1990, 529.
[21] Nanotechnology: A Revolution in the MakingVision for R&D in
the Next Decade: Report of the Interagency Working Group on
Nanoscience, Engineering, and Technology, March 10, 1999.
[22] A. Formhals, US-A 1 975 504, 1934.
[23] I. D. Norris, M. M. Shaker, F. K. Ko, A. G. MacDiarmid, Synth. Met.
2000, 114, 109; A. G. MacDiarmid, W. E. Jones, Jr., I. D. Norris, J.
Gao, A. T. Johnson, Jr., N. J. Pinto, J. Hone, B. Han, F. K. Ko, H.
Okuzaki, M. Llagune, Synth. Met. 2001, 119, 27.
[24] J. Doshi, D. H. Reneker, J. Electrost. 1995, 35, 151; P. W. Gibson, H. L.
Schreuder-Gibson, D. Riven, AIChE J. 1999, 45, 190.
[25] D. H. Reneker, A. L. Yarin, H. Fong, S. Koombhongse, J. Appl. Phys.
2000, 87, 4531.
[26] S. Iijima, Nature 1991, 354, 56.
[27] D. H. Reneker, I. Chun, Nanotechnology 1996, 7, 216.
[28] Z. Huang, P.-C. Wang, A. G. MacDiarmid, Y. Xia, G. M. Whitesides,
Langmuir 1997, 13, 6480; R. V. Gregory, W. C. Kimbrell, H. H. Kuhn,
Synth. Met. 1989, 28, C823.
[29] A. M. Sullivan, P. A. Kohl, J. Electrochem. Soc. 1995, 142, 2250.
[30] I. Chun, D. H. Reneker, H. Fong, X. Fang, J. Deitzel, N. B. Tan, K.
Kearns, J. Adv. Mater. 1999, 31, 36; D. Hohnholz, A. G. MacDiarmid,
Synth. Met. 2001, 121, 1327.
[31] A. Dodabalapur, Z. Bao, A. Makhija, J. G. Laquindanum, V. R. Raju,
Y. Feng, H. E. Katz, J. Rogers, Appl. Phys. Lett. 1998, 73, 142, and refs
therein.
[32] C. J. Drury, C. M. J. Mutsaers, C. M. Hart, M. Matters, D. M.
de Leeuw, Appl. Phys. Lett. 1998, 73, 108, and refs therein.
[33] H. Okusaki, Y. Osada, J. Intell. Mater. Syst. Struct. 1993, 4, 50.
[34] Licristal E7 (Merck Corp., Germany), NOA-65 Optical Adhesive
(Norland Products, NH).
[35] H. Shirakawa, Angew. Chem. 2001, 113, 2642; Angew. Chem. Int. Ed.
2001, 40, 2574.
[36] A. J. Heeger, Angew. Chem. 2001, 113, 2660; Angew. Chem. Int. Ed.
2001, 40, 2591.
Angew. Chem. Int. Ed. 2001, 40, 2581 2590