Chem. Mater.

2007, 19, 3361-3363 3361

Solution-Processed Organic Field-Effect Transistors Scheme 1. Synthetic Route of the Polymers of PT-VTVTV2
Based on Polythiophene Derivatives with and PT-VTVTV4
Conjugated Bridges as Linking Chains

Ying Wang,†,‡ Erjun Zhou,†,‡ Yunqi Liu,*,† Hongxia Xi,†,‡

Shanghui Ye,†,‡ Weiping Wu,†,‡ Yunlong Guo,†,‡
Chong-an Di,†,‡ Yanming Sun,†,‡ Gui Yu,† and
Yongfang Li*,†
Beijing National Laboratory for Molecular Sciences,
Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100080, People’s Republic of China, and
Graduate School, Chinese Academy of Sciences,
Beijing 100064, People’s Republic of China

ReceiVed March 30, 2007

ReVised Manuscript ReceiVed May 25, 2007 Several methods have been used to obtain the polymers
with high hole mobility, including increasing molecular
Organic field-effect transistors (OFETs), the critical weight, decreasing polydispersity of polymers, and structural
components of future organic electronics, attract much design.5 Among them, structural design is more desirable
interest because of their attractive applications, such as radio and many functionally capable semiconductor polymers were
frequency identification tags, displays, and large-area sen- reported to give mobilities of higher than 0.1 cm2 V-1 s-1.6
sors.1 One of the most important aspects for OFETs is that Recently, Weder et al. found that the network structure of
they can be fabricated by easy patterning techniques at low cross-linked conjugated polymers can have significant ben-
cost and have good compatibility with flexible plastic efits for the carrier communication between chains7 and the
substrates.2 Thus the solution processable polymers are polythiophene derivatives (PTs) with conjugated bridges as
preferable to low molecular weight materials, which do not linking chains have been used to improve charge transport
allow efficient patterning and show great device sensitivity in polymer solar cells.8 However, these cross-linking poly-
to structure defects.3 Although considerable efforts have been mers used as the semiconductors of OFETs have not been
taken in the development of new polymer semiconductors, reported yet. Longer conjugated bridges, which avoids the
to date the known polymer semiconductors are still limited distortion of the polymer main chains and possesses better
and only a few can truly realize the high mobilities required conjugation, could lead to higher mobility of the polymers
for organic circuits that have adequate performance for with conjugated bridges as linking chains. Moreover, we
application such as active matrix displays or low-cost found that the PTs with bi(thienylene vinylene) as conjugated
intelligent labels when deposited in air.4 Therefore, design side chains showed the best photovoltaic properties among
and synthesis of new conjugated polymer semiconductors the PTs with conjugated side chains.9 Thus, in the current
are highly desirable. paper, we have synthesized two novel PTs, PT-VTVTV2
and PT-VTVTV4 (see Scheme 1), with vinylene-thie-
* To whom correspondence should be addressed. E-mail: liuyq@mail.iccas.ac.cn nylene-vinylene-thieneylene-vinylene (VTVTV) with con-
(Y. Liu), liyf@iccas.ac.cn (Y. Li).
† Institute of Chemistry.
‡ Graduate School. (5) (a) Miyakoshi, R.; Yokoyama, A.; Yokozawa, T. Macromol. Rapid
(1) (a) Baude, P. F.; Ender, D. A.; Haase, M. A.; Kelley, T. W.; Muyres, Commun. 2004, 25, 1663. (b) Schilinsky, P.; Asawapirom, U.; Scherf,
D. V.; Theiss, S. D. Appl. Phys. Lett. 2003, 82, 3964. (b) Sheraw, C. U.; Biele, M.; Brabec, C. J. Chem. Mater. 2005, 17, 2175. (c) Li, Y.;
D.; Zhou, L.; Huang, J.; Gundlach, D. J.; Jackson, T. N.; Kane, M. Wu, Y.; Liu, P.; Birau, M.; Pan, H.; Ong, B. S. AdV. Mater. 2006, 18,
G.; Hill, I. G.; Hammond, M. S.; Campi, J.; Greening, B. K.; Francl, 3029.
J.; West, J. Appl. Phys. Lett. 2002, 80, 1088. (c) Huitema, H. E. A.; (6) (a) Pan, H.; Li, Y.; Wu, Y.; Liu, P.; Ong, B. S.; Zhu, S.; Xu, G. Chem.
Gelinck, G. H.; van der Putten, J. B. P. H.; Kuijk, K. E.; Hart, C. M.; Mater. 2006, 18, 3237. (b) Mcculloch, I.; Heeney, M.; Bailey, C.;
Cantatore, E.; Herwig, P. T.; van Breemen, A. J. J. M.; de Leeuw, D. Genevicius, K.; Macdonald, I.; Shkunov, M.; Sparrowe, D.; Tierney,
M. Nature 2001, 414, 599. (d) Crone, B. K.; Dodabalapur, A.; S.; Wagner, R.; Zhang, W. M.; Chabinyc, M. L.; Kline, R. J.; Mcgehee,
Sarpeshkar, R.; Gelperin, A.; Katz, H. E.; Bao, Z. J. Appl. Phys. 2001, M. D.; Toney, M. F. Nat. Mater. 2006, 5, 328. (c) Nishide, J.;
91, 10140. Oyamada, T.; Akiyama, S.; Sasabe, H., Adachi, C. AdV. Mater. 2006,
(2) (a) Wisnieff, R. Nature 1998, 394, 225. (b) Dimitrakopoulos, C. D.; 18, 3120. (d) Murphy, A. R.; Liu, J.; Luscome, C.; Kavulak, D.;
Purushothaman, S.; Kymissis, J.; Callegari, A.; Shaw, J. M. Science Fréchét, J. M. J.; Kline, R. J.; McGehee, M. D. Chem. Mater. 2005,
1999, 283, 822. (c) Garnier, F.; Hajlaoui, R.; Yassar, A.; Srivastava, 17, 4892. (e) Heeney, M.; Bailey, C.; Genevicius, K.; Shkunov, M.;
P. Science 1994, 265, 1684. Sparrowe, D.; Tierney, S.; McCulloch, I. J. Am. Chem. Soc. 2005,
(3) (a) Sirringhaus, H. AdV. Mater. 2005, 17, 2411. (b) Katz, H. E. Chem. 127, 1078.
Mater. 2004, 16, 4748. (7) (a) Kokil, A.; Shiyanovskaya, I.; Singer, K. D.; Weder, C. J. Am. Chem.
(4) (a) Ong, B. S.; Wu, Y. L.; Liu, P.; Gardner, S. J. Am. Chem. Soc. Soc. 2002, 124, 9978. (b) Hittinger, E.; Kokil, A.; Weder, C. Angew.
2004, 126, 3378. (b) Hwang, D.-H.; Kim, S.-K.; Park, M.-J.; Lee, Chem., Int. Ed. 2004, 43, 1808. (c) Weder, C. Chem. Commun. 2005,
J.-H.; Koo, B.-W.; Kang, I.-N.; Kim, S.-H.; Zyung, T. Chem. Mater. 5378. (d) Huber, C.; Bangerter, F.; Caseri, W. R.; Weder, C. J. Am.
2004, 16, 1298. (c) Babel, A.; Jenekhe, S. A. J. Am. Chem. Soc. 2003, Chem. Soc. 2001, 123, 3857.
125, 13656. (d) Zhu, Y.; Babel, A.; Jenekhe, S. A. Macromolecules (8) (a) Zhou, E. J.; Tan, Z. A.; Yang, C. H.; Li, Y. F. Macromol. Rapid
2005, 38, 7983. (e) Heeney, M.; Bailey, C.; Giles, M.; Shkunov, M.; Commun. 2006, 27, 793. (b) Zhou, E.; Tan, Z.; Yang, Y.; Huo, L.;
Sparrowe, D.; Tierney, S.; Zhang, W.; McCulloch, I. Macromolecules Zou, Y.; Yang, C.; Li, Y. Macromolecules 2007, 40, 1831.
2004, 37, 5250. (f) Yamamoto, T.; Kokubo, H.; Kobashi, M.; Sakai, (9) Hou, J.; Tan, Z.; Yan, Y.; He, Y.; Yang, C.; Li, Y. J. Am. Chem. Soc.
Y. Chem. Mater. 2004, 16, 4616. 2006, 128, 4911.

10.1021/cm070884m CCC: $37.00 © 2007 American Chemical Society

Published on Web 06/16/2007
3362 Chem. Mater., Vol. 19, No. 14, 2007 Communications

Table 1. Optical and Electrochemical Properties of the PT-VTVTV2

and PT-VTVTV4
UV-vis absorption spectra CV
solution film HOMO LUMO EEC
g
polymer λmax (nm) λmax (nm) (eV) (eV) (eV)
PT-VTVTV2 460 493 -5.01 -2.77 2.24
PT-VTVTV4 457 473 -5.09 -2.88 2.21

jugated bridges as linking chains. Their optical properties,

thermal properties, and field-effect characteristics are studied.
The syntheses of PT-VTVTV2 and PT-VTVTV4 were Figure 1. TGA of PT-VTVTV2 and PT-VTVTV4.
achieved by Stille coupling reaction by adding different ratios
of the monomer A (2%, 4%) as seed as outlined in Scheme to those of most regioregular polythiophenes such as -5.0
1 (for details of the synthesis, see Supporting information). eV of P3HT and -5.1 eV of PQT.4a The HOMO levels of
The monomer A was synthesized by Wittig-Hornor reaction the polymers are comparable with the work function of Au,
(Scheme S1 in Supporting Information). The regioregularities indicating better carrier injection from the contact to the
of PT-VTVTV2 and PT-VTVTV4 are 70% and 69%, semiconductors of OFETs.11 The HOMO-lowest unoccupied
respectively, which are calculated from the ratio of the molecular orbital (LUMO) gaps of PT-VTVTV2 and PT-
integral area of the two peaks at 2.5-2.8 ppm in the 1H NMR VTVTV4 were obtained to be 2.24 and 2.21 eV, respectively,
spectra (Figure S2 in Supporting Information). Gel-perme- which is consistent with the result obtained from UV-vis
ation chromatography (GPC) analysis exhibited a number- spectra measurement.
average molecular weight (Mn) of 37 000 with a polydis- The thermal property of PT-VTVTV2 and PT-VTVTV4
persity of 1.98 and 26 000 with a polydispersity of 2.25 was evaluated by thermalgravimetric analysis (TGA, Figure
against polystyrene standards for PT-VTVTV2 and PT- 1) and differential scanning calorimetry (DSC). The DSC
VTVTV4, respectively. of PT-VTVTV2 and PT-VTVTV4 showed broad peaks at
The absorption spectral data of the two polymers are ∼215 and 225 °C, respectively (Figure S5 in Supporting
summarized in Table 1. The UV-vis absorption spectra Information), which are attributed to the melting of polymer
(Figure S3 in Supporting Information) of PT-VTVTV2 and backbones. The high rigidity of the backbone of PT-
PT-VTVTV4 in diluted chloroform solution exhibited a main VTVTV4 due to more conjugated bridges was responsible
absorption with λmax at 460 and 457 nm, respectively, while for its higher meltng points than that of PT-VTVTV2.6a
their thin films showed a strong absorption with λmax at 493 Excellent thermal stability of PT-VTVTV2 and PT-VTVTV4
and 473 nm, respectively. The two polymers showed a small was manifested in their TGA profile with decomposition
red-shift in absorption from solution to thin film (33 nm for temperatures of 419 and 410 °C, respectively, demonstrating
PT-VTVTV2 and 16 nm for PT-VTVTV4), and the small its thermal stability approaching that of poly(4,8-didodecyl-
red-shifts are in sharp contrast to those of regioregular benzo[1,2-b:4,5-b′]dithiophene).6a,12
polythiophenes such as head-to-tail poly(3-hexythiophene) The structure order and crystallization of PT-VTVTV2 and
(P3HT about 100 nm) and poly(didodecylquarterthiophene) PT-VTVTV4 were investigated by film X-ray diffraction
(PQT about 75 nm), suggesting that PT-VTVTV2 and PT- (XRD) and atomic force microscopy (AFM). The XRD
VTVTV4 might have a conformation with twisted thienylene measurements were carried out for the thin films, which were
units in the solid state.6d,10 In addition, the thin-film spectrum prepared on n-octadecyltrichlorosilane (OTS)-modified SiO2/
of PT-VTVTV2 showed larger bathochromic shifts over its Si substrates by drop-coating and then annealing at 150 °C
solution spectrum than that of PT-VTVTV4, revealing its for 30 min (Figure S6 in Supporting Information). The XRD
higher molecular orders in the solid state and different chain pattern of the PT-VTVTV2 film exhibited highly crystalline
conformaton from PT-VTVTV4 due to fewer linking bridges. patterns with a strong primary diffraction peak at 2θ ) 5.0°,
The optical band gaps of the polymers were determined from which arises from the ordered interlayer stacking of the
the absorption onset. The optical band gaps of PT-VTVTV2 polymers and corresponds to a interlayer d-spacing of 17.3
and PT-VTVTV4 were found to be 2.0 and 1.99 eV, Å.13 The XRD pattern of PT-VTVTV4 films exhibited
respectively. The band gaps of these polymer films were several sharp peaks from 20° to 25° with concomitant
found to decrease a little as the fraction of bridges increased. disappearance of interlayer stacking peaks. The sharp peaks
The electronic states of the films on the Pt electrode were in the XRD spectrum, which arise from π-π stacking order,
investigated by cyclic voltammetry (CV) to better understand supported the good crystalliity of PT-VTVTV4. Figure 2
charge injection processes in the new polymer semiconduc- shows the AFM topographic image of PT-VTVTV2 and PT-
tors and devices made from them. The two polymers showed VTVTV4 thin films on OTS-modified SiO2/Si substrates.
similar reversible oxidation and reduction peaks (Figure S4
in Supporting Information). All the electrochemical data are (11) (a) Brédas, J. L.; Silbey, R.; Boudreaux, D. S.; Chance, R. R. J. Am.
also summarized in Table 1. The highest occupied molecular Chem. Soc. 1983, 105, 6555. (b) Drolet, N.; Morin, J. -F.; Leclerc,
N.; Wakim, S.; Tao, Y.; Leclerc, M. AdV. Funct. Mater. 2005, 15,
orbital (HOMO) levels of PT-VTVTV2 and PT-VTVTV4 1671.
were -5.01 and -5.09 eV, respectively, which are similar (12) Sonntag, M.; Kreger, K.; Hanft, D.; Strohriegl, P.; Setayesh, S.; de
Leeuw, D. Chem. Mater. 2005, 17, 3031.
(13) Chen, T. A.; Wu, X. M.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117,
(10) Trznadel, M.; Pron, A.; Zagorska, M. Macromolecules 1998, 31, 5051. 233.
Communications Chem. Mater., Vol. 19, No. 14, 2007 3363

resistance can be observed, which is consistent with the

results above. The devices based on PT-VTVTV2 afforded
a best hole mobility of about 1.1 × 10-3 cm2 V-1 s-1 with
an on/off ratio of 105 and threshold voltage of about -10 V
in saturation regime, much larger than that of the polymer
without the conjugated bridge.14 With the increase of the
conjugated bridges, the devices based on PT-VTVTV4
showed higher mobility, affording a best hole mobility of
Figure 2. AFM images of films spin-coated onto OTS-modified SiO2/Si about 3.8 × 10-3 cm2 V-1 s-1 with an on/off ratio of 104
substrates: (a) for PT-VTVTV2 and (b) for PT-VTVTV4. and threshold voltage of about 24 V. These data indicate
that the conjugated bridges can strongly increase the carrier
mobility of the polymers with conjugated bridges as linking
chains, which is consistent with the results in literature.7
Though the carrier mobilities of PT-VTVTV2 and PT-
VTVTV4 are not as good as those of the best devices
previously reported, they are among the best performance
of the copolymers with low regioregularity for OFETs
reported. To improve their mobility, many ways, such as
the modification of the structure of PT-VTVTV2 and PT-
VTVTV4 by introducing different alkyl group end-cappers
and improving their regioregularity, are underway.
In summary, we have synthesized a new class of PTs with
conjugated bridges as linking chains, PT-VTVTV2 and PT-
VTVTV4. OFETs based on them provide better FET
performance in spite of their low regioregularity, affording
Figure 3. FET characteristics of an exemplary OFET with PT-VTVTV2 a hole mobility of about 3.8 × 10-3 cm2 V-1 s-1 with an
on OTS-modified substrate (channel length ) 60 µm, channel width )
3000 µm): (a) output curves at different gate voltages and (b) transfer curve on/off ratio of 104. These polymer semiconductors therefore
in saturated regime at constant source-drain voltage of -100 V and square represent a useful class of solution-processable semiconduc-
root of the absolute value of current as a function of gate voltage. tors for fabrication of OFET circuits for printed electronics.
Films of both PT-VTVTV2 and PT-VTVTV4 show homo- Acknowledgment. The present research was financially
geneous morphology with small granule crystallite. The supported by National Natural Science Foundation (20472089,
crystallite of the PT-VTVTV4 film exhibits a more ordered 90206049, 20421101, 20573115, 50633050, 60671047, 5073093),
arrangement than that of the PT-VTVTV2 film, resulting in the Major State Basic Research Development Program, and the
Chinese Academy of Sciences.
more defined grain boundaries and smoother surface and
facilitating the fabrication of high performance OFETs. Supporting Information Available: The synthesis, DSC,
To characterize the FET performance of PT-VTVTV2 and UV/vis absorption spectra, and CV of PT-VTVTV2 and PT-
PT-VTVTV4, OFETs were constructed on OTS-modified VTVTV4, the fabrication and characterization of OFETs based on
SiO2/Si substrates with top-contact configuration. The tran- the films of PT-VTVTV2 and PT-VTVTV4, and XRD of the thin
sistors based on PT-VTVTV2 and PT-VTVTV4 were found films (PDF). This material is available free of charge via the Internet
to exhibit typical p-type FETs characteristics. The output and at http://pubs.acs.org.
transfer characteristics of typical OFETs are shown in Figure CM070884M
3. The output behaviors conform well to the conventional
(14) Sirringhaus, H.; Brown, P. J.; Friend, R. H.; Nielsen, M. M.;
metal oxide semiconductor FET gradual-channel models in Bechgaard, K.; Langeveld-Voss, B. M. W.; Spiering, A. J. H.; Janssen,
both the linear and the saturated regime, and no contact R. A. J.; Meijer E. W. Synth. Met. 2000, 111-112, 129.