Synthetic Metals, 55-57 (1993) 299-306

ALTERNATE DONOR-ACCEPTOR

299

SMALL-BAND-GAP SEMICONDUCTING POLYMERS;

POLYSQUARAINES AND POLYCROCONAINES

E.E.HAVINGA, W. ten HOEVE * and H. WYNBERG*

Philips Research Laboratories, PO Box 80 000, 5600 JA Eindhoven, The Netherlands
Syncom b.v., Nyenborgh 4, 9747AG Groningen, The Netherlands

ABSTRACT
The idea that conjugated polymers with alternate donor and acceptor moieties in the
main chain are characterized by a small band gap is proposed and explained. Experimental verification of this idea is reported in new classes of conjugated polymer semiconductors, polysquaraines and polycroconaines. These new materials show band gaps
down to 0.5 eV, conductivities around 10 .5 Slcm and are stable in air up 250 C or higher.

INTRODUCTION
Conjugated organic polymers are semiconductors. They are, generally, characterized
by rather large band gaps (1.5 to 4 eV [1] ). Smaller band gaps have been found for the
conjugated polymer poly(isothianaphthene) (about 1.2 eV) [2] and some chemically substituted polymers of the same class. Theoretical work on the explanation of this phenomenon [3] developed the basic idea that substituents and structures inducing quinoid
character in the ground state of the conjugated polymers tend to decrease the band gap.
However, the best experimental result obtained along this line is a semiconductor with a
band gap of 1 eV [4]. Polymers having much smaller band gaps are very important because they would show high intrinsic conductivity (i.e. without doping) and, possibly, a
good transparency in the visible spectrum and they might be useful as infrared
sensors/detectors. Moreover, they might give a clue for real intrinsically metallic organic
polymers.
Our approach to small-band-gap polymers is completely different. The idea is that a
regular alternation of conjugated donor- and acceptor-like moieties in a conjugated chain
will induce a small band gap. In this paper we will explain this concept and show experimentally that it works quite well. New polymers, polysquaraines and polycroconaines,
are synthesized by condensation of bifunctional donor moieties and acceptor-like
moieties squaric acid or croconic acid. The polymers are conjugated and show band gaps
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1993- Elsevier Sequoia. All fights reserved

300
down to 0.5 eV. There is an ample choice in donor moieties. Many of the polymers are,
moreover, very stable in air. Solubility in standard organic solvents can be obtained by
substitution with side chains, e.g. alkyl groups. The measured specific conductivity is of
the order expected for intrinsic conductivity and can be increased by doping in the usual
way. A preliminary account of this work has been published recently [5-1.
ALTERNATE DONOR-ACCEPTOR CONJUGATED CHAINS
The idea behind the new small-band-gap polymers is as follows. Visualize a conjugated
polymer formed by a regular alternation of donor- and acceptor-like moieties, possibly
separated by neutral parts. If the donor and acceptor regions are extended we have a
case similar to the inorganic n-i-p-i super lattice structures. It is known [6] that in such a
structure both the valence and conduction band are curved by space charge effects (see
Fig. 1). The band gap, E~o, has not changed at each place at itself, but a smaller band gap,
E~x, is found when the spatial alternation of the level of the bands is taken into account.

ET
n
I

x
I

Fig. 1. Band structure of a n-i-p-i quantum well structure (schematic).

The suggested polymer is a one-dimensional analogue of such a n-i-p-i structure. The
mechanism that causes the band curving will work equally well in this case. In order to
get strong curvature of the bands strong donors and acceptors are needed, such that already in the ground state of the system appreciable charge transfer from donor to
acceptor occurs. If the extension of the donor and acceptor regions is decreased the
curved band structure will not remain stable and a reshuffling of the bands will take place.
it is likely that at least some of the broadening of the energy bands will survive and that
the new valence and conduction bands will be broader than in the neutral case, leading
to a smaller band gap. In the limit of ultimate confinement of donor and acceptor regions,
viz. a regular alternation of atoms with different electronegativity, predictions on the basis
of the SSH model [7"1 give for small electronegativity differences no change in band gap.
However, the fact that the polymer (SN)~ is metallic and even a superconductor [8] is decisive experimental evidence that also in this limit a regular alternation of strong donor
and acceptor moieties can lead to small band gaps.

301

In the course of our study the synthesis of some alternate polymers has been reported.
The band gap of the polymer of (2-thiophene)pyridine was only slightly lower than that of
polythiophene [9]. In this polymer the difference in donor strength between pyridine and
thiophene is small. During the writing of this paper the synthesis and properties of an
alternate polymer of bithiophene and substituted silacyclopentadiene has been reported
[10]. This alternate donor/acceptor polymer shows a red shift of the absorption spectrum
in chloroform solution to 615 nm, more than 100 nm higher than in polythiophenes. The
conductivity of the undoped compacted solid was < 10-" S/cm, which increased upon
doping with iodine to 10 .3 S/cm. Although neither solid state spectra nor band gap were
reported, this example shows that the concept of alternate conjugated donor/acceptor
polymers as a means to obtain smaller band gaps works quite well.
However, in order to arrive at really small-band-gap conductors, strong donors and
acceptors are needed. Strong donor-like moieties are found in hetero ring systems with
N, O or S atoms. Many of them show a large amount of delocalization of the positive
charge in the rings. The main problem in realizing the alternate polymers lies in the
acceptor moieties. We have now realized that squaric acid (SA) and croconic acid (CA),
when incorporated in a polymer, are strong acceptors in which the negative charge is not
completely localized on the O-atoms attached to the ring, but significantly delocalized in
the chain. This follows from a comparison of the properties of cyanine dyes with those
of squaraine and croconaine dyes [11,12]. At equal length of the molecules the absorption of squaraine dyes is at about the same wavelength as that of the corresponding
cyanine dyes, and the croconaine dyes show even a marked red shift. The extinction coefficients are also of the same order of magnitude. An example is shown in Fig. 2.
If bifunctional donor moieties are combined with squaric acid or croconic acid new alternate polymers are formed, polysquaraines and polycroconaines, respectively. We will
show that their properties are in accordance with the idea sketched above.
1.00

400

500

600

700

8OO

9OO

Wavelength (nm)

Fig. 2. Comparison of the absorption spectra of corresponding cyanine, squaraine and

croconaine dyes. Data from solutions in acetonitrile (4.10 -e mol/I) [12].

302
PREPARATION
The synthesis of polysquaraines and polycroconaines is analoguous to that of the
squaric acid dyes and is performed by a simple 1:1 condensation reaction. The reaction
is very general. Both squaric acid and croconic acid condense easily with a large number
of donors bifunctionalized with active H-atoms such as in activated = CH2 or = CH- groups
or in aminogroups. Two representative examples are outlined in Fig. 3 (a,b). A number
of other donor moieties we used in such reactions are shown in Fig. 3 (c). Some donors
are well known from dye chemistry, others have been conceived by symmetric doubling
of monofunctional donors (D') in cyanine dyes. The unsubstituted polymers (R = H, CH3)
are rather intractable and insoluble because of the rigid conjugated main chains. Solubility has been increased by the introduction of alkyl, alkoxyl, etc. side chains, a well
known procedure for conjugated polymers. Details of the preparation will be published
elsewhere.

s.

I~

HO

H
I+

OH

O-

D1

SA

b.

O
N
+
R

D2

O
CA

F~1

D3

D2a: R = H
D2b: R = CH3
D2c: R = n-C4H9

D2d: R = n-CTH15
D2e: R = n-C,2H25
D2f: R = n-C18H37

D4

D3a: R1 = R2 = CH3
D3b: R1 = CH3,
R2 = n-C~2H25

D4a:R = H
D4b: R = OC,=H25
D4c: R = n-Ct2H25

Fig. 3. a. Condensation reaction of squaric acid (SA) with phenylenediamine (D1), b.ibid.
of croconic acid (CA) with benzo (1,2-4,5) di(1-alkyl 2-methylene 3,3-dimethyl pyrroline)
(D2), and c. a small selection of other donors giving similar reactions.

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The polymer (-SA-D1-) has been reported before 1,13], but no band gap and conductivity
data were given. We found a strong dependence of absorption and conductivity on the
pH. This is a general property of polysquaraines and polycroconaines prepared by reacting these acids with ammonia, alkylamines and aromatic diamines.
Probably
protonation/deprotonation of the N-atoms in the chain occurs, similarly as in polyanilines.
Their properties are under investigation and will be published later.
The best synthetic results are obtained by refluxing in a higher saturated alcohol with a
catalitic amount of either a mineral acid or a strong base and removing continuously the
water formed during the reaction. For polysquaraines 1-butanol and cyclohexanol proved
to be satisfactory, for polycroconaines 1-propanol was used because otherwise some
deterioration took place. In view of the instability of (D3) the reactions in this case were
carried out starting from the Stable HI salt.
CHARACTERIZATION
Spectra were recorded with the aid of a Philips X-ray automatic diffraction unit PW 1730
(CuK~ radiation, starting at ~ = 2 ) , a tH NMR Bruker NSL 300 spectrometer, a Bruker IFS
45 FTIR spectrometer (KBr pellets), a Beckman Acta M IV spectrometer (NIR-vis-UV)
and/or a Varian Superscan 3 UV-vis spectrometer. Solid state spectra were measured
either on thin layers deposited on glass from solution or from suspensions in nujol or
parafin oil. Conductivities were measured on pressed bars of about 20x5x(0.3 to 1) mm ~
using a four-probe method. DSC measurements were performed with a Perkin Elmer
DSC7, GPC with CHCI3 solutions in a Unicam PV 4100 chromatograph and PS-PVB mixedbed 3 #m columns, using polystyrene as a standard.
RESULTS
The FTIR spectra agree with expectations based on the spectra of the dyes (D'-A-D')
of the acids condensed with two monofunctional donors. The absence or near absence
of absorptions in the region 1680 - 1840 cm -~ in the SA polymers confirms that the
1,3-substitution scheme [12] is followed almost exclusively. However, in some cases
mixed 1,2- and 1,3-substitutions were found, particularly if DMSO was used in the reaction
medium. Such samples showed also lower wavelengths of maximum absorption. GPC of
(-SA-D2d-)~and (-SA-D2e-), gives molar masses corresponding to 15 and 25 units
(-SA-D2-), respectively. Although this is not a high molar mass, the length of the polymers
(or, if you like, oligomers) is sufficient for approaching the real polymer con(~uctive properties. Namely, these lengths correspond to 200 to 325 atoms in the conjugated chains and
from our previous work on oligothiophenes [13] it follows that some 30 to 50 atoms in the
conjugated chain are already sufficient to approach the band gap and conductivity after
doping of the polymers. The degree of polymerization of the other, less soluble, polymers
will probably be somewhat less, because the polymerization reaction is terminated when
the polymer precipitates from the reaction solution. 'H NMR data on the soluble polymers
agree with expectations (for dodecyl substituted squaraine (-SA-D2e-) & 0.88 tripl, end
-CH3, 1.26 with large tail to 1.72 middle-CH2-alkyl, 1.82 broad CH3 on rings, 4.0 very broad
NCH2, 6.0 very broad = CH- and 6.9 broad H-phenyl).

304

v
m
0
C

0
,D

<

0.00

0.50

1.00

1.50

2.00

2.50

Energy (eV)
Fig. 4. Absorption spectra of the polymer (-SA-D2c-) in CHCI3 solution and as solid layer,
compared with a corresponding dye. The absorption spectra are virtually independent
of the length of the alkyl group.
The vis-NIR absorption spectra of solutions of the polymers in chloroform are similar
to those of the dyes (D'-A-D') referred to above, except for a marked red shift and a slight
broadening. When measured as a solid, a small additional red shift is found and the
broadening is increased. An example of such spectra is given in Fig. 4.
Values of the energy of the absorption maximum as well as of the absorption cut-off
(band gap) of the solid state spectra are given in Table 1. It is seen that the smaller band
gaps E0 , down to 0.5 eV, are found for the CA polymers. This reflects the greater acceptor
strength of CA compared to that of SA [12] . Poly (CA-D2) shows an unexpected large
band gap, either because of steric crowding preventing planar configurations or because
of the low molar mass obtained (recall that the reaction temperature of polycroconaines
had to be chosen rather low to avoid deterioration).
The solid polymers are remarkably stable, the polysquaraines can be heated up to
300 C in air without degradation, some polycroconaines give DSC response above 250
C. Solutions in chloroform deteriorate upon standing in light. In the UV-vis spectra we
then find many peaks and shoulders at energies between the absorption maxima of the
polymer and that of the corresponding dye. Probably the acid formed by photoreaction
on chloroform splits the main chains into oligomers. This observation strengthens the interpretation of the NIR absorption maxima as due to band transitions rather than due to
polarons. X-ray data show that the polymers are partly crystalline, partly amorphous. No
clearcut relation between degree of crystallinity and composition could yet be found.

305

TABLE 1. Energy at solid state vis-NIR absorption maximum, E. . . . absorption cut-off or

band gap, E~, and specific conductivity, ~r, of some polysquaraines and some
polycroconaines. Question marks denote suspect for (bi)polaron absorption.

Acid

Donor

Em,x (eV)

Eg (eV)

cr (S/cm)

SA
SA
SA
SA
SA
SA
SA
SA
SA
SA
SA
CA
CA
CA
CA

D1
D2a
D2b
D2c
D2d
D2e
D2f
D3a
D3b
D4a
D4b
D2c
D2d
D3a
D3b

0.7 ?
1.35
1.3
1.3
1.35
1.3
1.3
1.3
1.2
1.5
1.9
1.35
1.3
0.9
0.9

0.4 ?
1.15
1.1
1.2
1.2
1.15
1.1
0.8
0.8
1.1
1.4
1.2
1.2
0.45
0.5

10-g_ 10-7
5.10 .7
10-7_ 10-5
10-6_ 10-s
5.10-s
4.10 -s
10 s - 3.10-s
10-7
5.10 ~
10-7_ 10-5
10-8
109
<10 9
10-5
10-5_ 10-4

The specific conductivities in Table 1 refer to virgin samples, This does not, however,
imply that the polymers are completely undoped. Namely, accidental doping either by
unintended impurities or by oxidation in air might very well occur. In fact, many samples
showed a gradual increase in conductivity upon standing in air. Ranges in #-values refer
to results on samples of different batches or at longer exposure to air. The lower values
are closer to intrinsic.
To verify whether these values are reasonable for intrinsic semiconductors with the
band gaps indicated we made a simple estimate of expected intrinsic conductivities # at
room temperature. In the standard equation # = n~.e./~ with n, = no exp ( --EJ2kT), we
assume a number of electronic states in the conduction band no = 1022cm3 and a mobility
p ~. 10 .5 cm2V-'s -' (actually the sum of electron and hole mobilities). The resulting values
for the intrinsic conductivity are ~r ~ 10-6, 8.10"9 and 6.10 -H S/cm for band-gap values of
0.50, 0.75 and 1.00 eV, respectively. It is, hence, very likely that, at least in Some of the
polymers, the measured conductivities are close to intrinsic values. The additional
extrinsic conductivity is p-type.
That the polymers are really through-conjugated pi-electron systems is further substantiated by measuring doped samples. Exposing pressed bars to the vapour of iodine
at 70 C immediately increases the conductivity. Ultimate values of ~ vary between 10.3
and 1 S/cm. For the soluble polymers similar conductivities were obtained after casting
films from solutions doped with DDQ (2,3-dichloro-5,6-dicyano-l,4-benzoquinone).
Whereas the iodine-doped samples increase their resistivity by orders of magnitude upon
standing in air, the DDQ-doped samples are rather stable under such conditions.
The ground state of the undoped polymers is degenerate, just like that of polyacetylene.
In lightly doped materials one would expect, therefore, soliton-like behaviour on the part
of the charge carriers.

306

CONCLUSIONS and PROSPECTS

From the results on polysquaraines and polycroconaines it is clear that the principle
of inducing smaller band gaps into conjugated polymers by a regular alternation of donor
and acceptor moieties works quite well. The band gap is smallest for a combination in
which the electronegativity difference between donor and acceptor is greatest. The
smallest gap measured so far is about 0.5 eV, leading to a probably intrinsic conductivity
of 10.5 S/cm.
Although the results obtained are already quite satisfying, one can think of many ways
to improve on them. Firstly, higher molar masses by carefull study of the synthesis conditions is called for. Combination of squaric acid and/or croconic acid with still stronger
donors looks promising, especially if these donors were conjugated to a greater extend
than those presently used. Investigations along these lines are underway. Furthermore,
we are testing some ideas about other strong acceptorlike units as building blocks.
Whether the limit of an intrinsic metallic conjugated polymer can actually be realized
along these lines is still an open question.

Acknowledgement. Thanks are due to A. Pomp for technical assistance.

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