11808 J. Am. Chem. Soc.

1998, 120, 11808-11809

Tuning Redox Behavior and Emissive Wavelength of while the di(1,3,4-oxadiazole) phenylenes, which are π-deficient,
Conjugated Polymers by p-n Diblock Structures act as n-dope type blocks. The variation of the length of the
oligothiophene block affords the possibility of tuning redox
Wang-Lin Yu, Hong Meng, Jian Pei, and Wei Huang* behavior (related to the HOMO and LUMO of polymers) and
emissive color of the resultant polymers. Actually, there are two
Institute of Materials Research and Engineering
National UniVersity of Singapore series in these seven polymers. One includes polymers B, C,
Singapore 119260, Republic of Singapore and D (series 1) with 1,4-bis(1,3,4-oxadiazolyl)-2,5-dioctoxy-
benzene as the n-dope type block. The other series comprises
ReceiVed July 20, 1998 polymers E, F, and G (series 2) with 2,6-bis(1,3,4-oxadiazolyl)-
Since the discovery of electroluminescence of poly(p-phenylene toluene as the n-dope type block. Polymer A was synthesized
vinylene) a conjugated polymer,1 polymer light-emitting diodes for comparison. All of these polymers show highly thermal
(PLEDs) have drawn special attention because of the potential stability with the starting decomposition temperatures higher than
applications in developing large area and flexible displays.2-4 The 300 °C in air according to the thermogravimetric analysis (TGA).
emission of PLEDs comes from the radiative decay of excitons Polymers C and F are completely soluble in chloroform, tetrahy-
resulting from the recombination of electrons and holes, which drofuran (THF), N,N-dimethylformamide (DMF), and xylene. The
are injected from the two opposite electrodes, in the emitting average molecular weights (Mw) were measured to be higher than
layer.3 Balanced injection and transport of electrons and holes 15,000 against polystyrene standards with polydispersity around
are therefore crucial for achieving high quantum efficiency. 1.8. The other five polymers are partially soluble in the above
Unfortunately, so far most of the electroluminescent polymers solvents, and the average molecular weights (Mw) of THF-soluble
have unipolar character, showing greater tendency for transporting parts were measured to be 4000-10000 against polystyrene
holes than for transporting electrons.5 To overcome the problem standards. All of the seven polymers are readily dissolved in
of the unbalanced charge injection, three approaches have been chloroform with a small amount of trifluoroacetylacetone (TFA)
developed. The first is adding an electron-transporting layer to give clear solutions. The synthesis of polymers A and F has
between the emitting layer and cathode to fabricate multilayer been published in our previous papers.10,11 The other syntheses
devices.6,7 However, in practical applications one has to face will be published elsewhere.
some serious technical difficulties in fabricating such multilayer Transparent thin films of the polymers on glass substrates
devices. The second is using metals with low work functions (microscopy slides or quartz plates) were prepared by spin coating
such as Ca and Mg as cathodes.8 The problem of this approach from the polymer solutions. The UV-vis absorption and
is that such metals are highly susceptible to atmospheric degrada- fluorescence spectra of series 1 polymer films are displayed in
tion and are difficult to encapsulate. The third approach is making Figure 2, and the optical data of all of the polymers are
the emissive layer polar in nature to eliminate the charge buildup summarized in Table 1. For both series 1 and 2, the absorption
at the electrode-polymer interfaces.9 Although this development and luminescence spectra of the polymers shift to longer
results in a more balanced charge injection, some issues such as wavelength with the increase of the length of the oligothiophene
the slow charging time and operating stability have to be addressed segments. The emissive colors are blue, green, and orange for
before it can be widely employed. Therefore, it would be the polymers with one, two, and three thiophene rings in the
interesting and meaningful to develop new electroluminescent oligothiphene segments, respectively. This indicates that the p-n
polymers with an intrinsically balanced tendency for injecting diblock structure is an effective approach for tuning the emissive
and transporting electrons and holes for the development of highly color of conjugated polymers. Comparison between the polymers
efficient and stable PLEDs. For this goal, the key is to develop with the same oligothiophene segments in series 1 and 2 shows
a synthetic methodology to effectively adjust and control the that the polymers in series 1 exhibit longer wavelength of
HOMO and LUMO of conjugated polymers. Here we present a absorption and fluorescence. This can be attributed to the
new molecular design and synthesis, i.e., p-n diblock conjugated electron-donating character of alkoxy groups and coplanarity in
copolymers, in which typical p-dope type and n-dope type 2,6-bis(1,3,4-oxadiazolyl)toluene lower than that in 1,4-bis(1,3,4-
segments are alternatively incorporated into one backbone of oxadiazolyl)-2,5-dioctoxybenzene, which can be demonstrated by
conjugated polymer, to adjust the HOMO and LUMO of the the spectral comparisons between polymers A and B and polymers
resulting polymers. A and E. These results suggest that the electronic properties of
Seven p-n diblock conjugated copolymers were synthesized, the p-n diblock conjugated copolymers can be finely tuned by
and their chemical structures are illustrated in Figure 1. The attaching different functional groups on the phenylene ring or by
oligothiophenes, which are π-excessive, act as p-dope type blocks, changing the steric configuration in the n-dope type segments.
The redox behavior of the polymers (as coated films on a 1
* Corresponding author. Tel/Fax: (65) 872-7455. E-mail: wei-huang@ cm2 Pt electrode) was studied by cyclic voltammetry in a CH3-
imre.org.sg.
(1) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; CN solution of n-Bu4NClO4 (0.1 M) using a Pt wire as counter
Mackay, K.; Friend, R. H.; Burn, P. L.; Holmes, A. B. Nature 1990, 347, electrode and a Ag/AgNO3 (0.1 M) electrode as reference
539. electrode. When scanning cathodically, all of these polymers
(2) Hide, F.; Dı́az-Garcı́a, M. A.; Schwartz, B. J.; Heeger, A. J. Acc. Chem.
Res. 1997, 30, 430. displayed reversible reduction peaks around -1.8 V (-1.86 to
(3) Greenham, N. C.; Friend, R. H. In Solid State Physics; Enhrenreich, -1.73 V) vs SCE, and the corresponding reoxidation peaks
H., Spaepen, F., Eds.; Academic Press: San Diego, CA, 1995; Vol. 49, pp appeared around -1.6 V (-1.75 to -1.53 V). Thus, the reduction
1-149.
(4) Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri, N.; potentials of the polymers can be determined to be ca. -1.7 V.
Heeger, A. J. Nature 1992, 357, 477. The detailed data are listed in Table 1 and the cyclic voltammo-
(5) Tamato, N.; Adachi, C.; Nagai, K. Chem. Mater. 1997, 9, 1077. grams of series 2 polymers are given in Figure 3. Generally, the
(6) Brown, A. D.; Bradley, D. D. C.; Burroughes, J. H.; Friend, R. H.; increase of the thiophene ring number in the oligothiophene blocks
Greenham, N. C.; Burn, P. L.; Holmes, A. B.; Kraft, A. Appl. Phys. Lett.
1992, 61, 2793. does not change the reduction potential of the polymers remark-
(7) Strukelj, M.; Papadimitrakopoulos, Miller, T. M.; Rothberg, L. J. Science
1995, 267, 1969. (10) Huang, W.; Meng, H.; Yu, W.-L.; Gao, J.; Heeger, A. J. AdV. Mater.
(8) Braun, D.; Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982. 1998, 10, 593.
(9) Pei, Q.; Yu, G.; Zhang, C.; Yang, Y.; Heeger, A. J. Science 1995, 269, (11) Yu, W.-L.; Meng, H.; Pei, J.; Huang, W.; Li, Y.; Heeger, A. J.
1086. Macromolecules 1998, 31, 4838.

10.1021/ja982561k CCC: $15.00 © 1998 American Chemical Society

Published on Web 10/30/1998
Communications to the Editor J. Am. Chem. Soc., Vol. 120, No. 45, 1998 11809

Figure 1. Chemical structures of the polymers.

transporting/hole-blocking materials, and other 1,3,4-oxadiazole-

containing materials,13,14 and are comparable with those of some
good electron-transporting materials.7 The reduction onset po-
tentials of the polymers were measured to be -1.2 to -1.4 V.
These values are comparable with that of poly(cyanoterephthaly-
idene) (CN-PPV) [-1.6 V vs Ag/Ag+ (0.1 M)],15 which shows
good electron-transporting ability in PLED devices.16 Cyclic
voltammetric reduction potential values can be used as a surrogate
for LUMO energy levels.7 Thus, the results suggest that the
LUMO energy levels of the polymers may be lower than those
of conventional p-dope type electroluminescent polymers and
PBD and may be comparable with that of CN-PPV. Such energy
levels may provide a closer match to the work function of Al
Figure 2. Absorption and fluorescence spectra of polymers A-D as
when they are used as active materials in PLEDs.
films at room temperature. On sweeping anodically, the polymers A, B, C, E, and F
showed irreversible oxidation with the half wave oxidation peaks
Table 1. Optical and Electrochemical Data of the Polymers at 1.96, 1.75, 1.70, 1.95, and 1.64 V vs SCE, respectively.
absorption fluorescence oxidative reductive
Polymers D and G exhibited a reversible oxidation process with
polymer λmaxa (nm) λmaxa (nm) Epa/Epcb (V) Epc/Epab (V) the oxidation peaks at 1.30 and 1.38 V and the corresponding
rereduction peaks at 1.20 and 1.24 V, respectively. Unlike their
A 393 (358, 416) 458 1.96/s -1.77/-1.62 reduction potentials, the oxidation potential of the polymers is
B 420 (360, 443) 489 1.75/s -1.83/-1.60
C 441 (419, 471) 530 1.70/s -1.82/-1.70 sensitive to the variation of the thiophene ring number in the
D 461 (439, 494) 580 1.30/1.20 -1.79/-1.70 oligothiophene segments. The oxidation peak potential is reduced
E 360 (388) 460 1.95/s -1.73/-1.53 by 0.45 V for series 1 and 0.57 V for series 2, respectively, with
F 380 (358, 416) 497 (526) 1.64/s -1.86/-1.75 increasing the thiophene ring number in the oligothiophene
G 430 (456, 470) 570 1.38/1.24 -1.76/-1.67 segments from 1 to 3. For polymers D and G, the oxidation
a Obtained from solid films, numbers in parentheses are the potentials are 1.25 and 1.31 V with the onset potentials of 1.00
wavelengths of subpeaks or shoulders. b Peak potential of anodic (Epa) and 1.04 V vs SCE, respectively. These values are lower than
and cathodic (Epc) peak, respectively (vs SCE) measured between that of PPV15 and are close to those of electroluminescent
neutral and oxidized (oxidative) or reduced (reductive) states on a square substituted polythiophenes,17 which are hole-injection favorable
platinum electrode (1.0 cm2) in 0.1 M Bu4NClO4 solution in acetonitrile electroluminescent materials. It is demonstrated that the HOMO
at a scan rate of 50 mV/s.
level of the p-n diblock copolymers can be effectively adjusted
by changing the thiophene ring number in the oilothiophene
segments and it can be lower than that of PPV and are comparable
with those of substituted polythiophenes.
In conclusion, the present idea of p-n diblock structure in
conjugated polymers has afforded an efficient approach of tuning
emissive color of conjugated polymers. According to the
electrochemical studies, it provides a promising synthetic route
to adjust the HOMO and LUMO of electroluminescent polymers
to balance the injections of electrons and holes from the opposite
contacts. Intensive studies on the charge transporting properties
of these polymers in PLED devices are in progress.
JA982561K
(12) Janietz, S.; Wedel, A. AdV. Mater. 1997, 9, 403.
(13) Li, X.-C.; Holmes, A. B.; Kraft, A.; Moratti, S. C.; Spencer, G. C.
W.; Cacialli, F.; Grüner, J.; Friend, R. H. J. Chem. Soc., Chem. Commun.
Figure 3. Cyclic voltammograms of polymers E-G as films on Pt 1995, 2211.
electrode in CH3CN solution of Bu4NClO4 (0.1 M) at a scan rate of 50 (14) Fink, R.; Frenz, C.; Thelakkat, M.; Schmidt, H.-W. Macromolecules
1997, 30, 8177.
mV/s. (15) Li, X.-C.; Kraft, A.; Cervini, R.; Spencer, G. C. W.; Cacialli, F.; Friend,
R. H.; Gruener, J.; Holmes, A. B.; De Mello, J. C.; Moratti, S. C. Mater. Res.
ably. This implies that the reduction properties of the polymers Soc. Symp. Proc. 1996, 413, 13.
are dominated by the 2,6-bis(1,3,4-oxadiazolyl)phenylene seg- (16) Greenham, N. C.; Moratti, S. C.; Bradley, D. D. C.; Friend, R. H.;
ments. These reduction potentials are lower than those of 2-(4- Holmes, A. B. Nature 1993, 365, 628.
(17) Andersson, A. R.; Berggren, M.; Inganäs, O.; Gustafsson, G.;
biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) (-1.95 Gustasson-Carlberg, J. C.; Selse, D.; Hjertberg, T.; Wennerström, O.
to -1.94 V vs SCE),7,12 one of the most widely used electron- Macromolecules 1995, 28, 7525.