Optical Materials 33 (2011) 14151418

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Flexible organic eld-effect transistors and complementary inverters based on a solution-processable quinoidal oligothiophene derivative
J.C. Ribierre a,b,, K. Takaishi a, T. Muto a, T. Aoyama a,
a b

Advanced Science Institute, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan Ewha Womans University, Department of Physics, Seoul 120-750, South Korea

a r t i c l e

i n f o

a b s t r a c t
We report on the fabrication and characterization of ambipolar organic eld-effect transistors based on the solution-processable quinoidal oligothiophene [QQT(CN)4] and using a new uorinated polymer (AL-X601) with a dielectric constant of 3.1 as dielectric material layer. As-prepared devices show ambipolar transport with hole and electron eld-effect mobilities of 6 102 and 5 103 cm2/V s respectively as well as an on and off state current ratio higher than 103. Inuence of a thermal annealing on the device performances was investigated and was found to lead to a majority carrier type conversion from a p-type to an n-type dominant behavior. QQT(CN)4 based eld-effect transistors and complementary inverters fabricated on exible substrates and using Al-X601 as gate dielectric material show high performance and good mechanical stability. 2011 Elsevier B.V. All rights reserved.

Article history: Received 30 November 2010 Received in revised form 6 March 2011 Accepted 7 March 2011 Available online 2 April 2011 Keywords: Organic eld-effect transistors Flexible organic inverter Quinoidal oligothiophene Solution-processable Polymer gate dielectric

1. Introduction Organic eld-effect transistors (OFETs) [13] have been the subject of intensive studies in the recent past due to their potential applications in low cost organic electronics including exible complementary logic circuits [4,5], switching devices for active matrixorganic light-emitting displays [6] and memory elements [7]. Despite outstanding progress in the development of organic semiconductors with high charge carrier mobilities, the realization of organic complementary circuits, which requires the integration of p-type and n-type OFETs on a single substrate is still challenging. For this purpose, the use of ambipolar OFETs, which can conduct simultaneously both holes and electrons, offers new alternative approaches in organic logic circuitry and can eliminate the need of patterning the p- and n-channels separately [8]. However, ambipolar OFETs generally show moderate charge carrier mobilities and high off-currents, leading to organic logic circuits with lower performance and higher power consumption than those based on a combination of p- and n-type OFETs. To overcome these drawbacks, the spatial and selective control of the ambipolar charge transport properties has been found to greatly improve the overall performance of the integrated circuits [9,10].

Dicyanomethylene-terminated quinoidal oligothiophene derivatives are now a well-known class of organic semiconducting materials for n-type and ambipolar OFETs [1115]. In particular, solution-processed top-contact OFETs based on the QQT(CN)4 molecule (chemical structure shown in Fig. 1a) have been found to show some unique and remarkable charge transport properties. It was reported that the charge transport properties of QQT(CN)4 thin lms can be converted and nely tune from p-type to n-type by either laser irradiation or thermal annealing [1618]. The selective and spatial control of the dominant carrier type by direct laser writing or thermal lithography provides a new effective method for patterning p- and n-type regions, making possible the fabrication of CMOS logic circuits and lateral pn diodes in thin lms made from a monolithic solution-processible organic semiconductor [19,20]. In this manuscript, we realized high performance solution-processed ambipolar top-contact QQT(CN)4 OFETs using a new gate dielectric uorinated polymer (AL-X601). The results also show that majority carrier type conversion can be achieved in these devices by a simple thermal treatment. This effect was used to fabricate both exible high mobility p-type and n-type dominant ambipolar QQT(CN)4 OFETs as well as complementary inverters with very good mechanical stability. 2. Experimental The QQT(CN)4 compound was synthesized following an improved method adapted from the literature [21]. As shown in Fig. 1a, bottom-gate top-contact QQT(CN)4 based OFETs were fabricated on indium tin oxide (ITO) glass substrates. These ITO

Corresponding authors. Addresses: Ewha Womans University, Department of

Physics, Seoul 120-750, South Korea . Tel.: +82 232774646 (J.C. Ribierre), Advanced Science Institute, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan. Tel.: +81 48 467 4571 (T. Aoyama). E-mail addresses: jcribierre@ewha.ac.kr (J.C. Ribierre), taoyama@riken.jp (T. Aoyama). 0925-3467/$ - see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.optmat.2011.03.015

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Fig. 1. (a) Schematic representation of an ambipolar gold top-contact QQT(CN)4 OFET using the uorinated polymer AL-X601 as gate dielectric. The chemical structure of QQT(CN)4 is also indicated. (b) Transfer characteristics of an asprepared QQT(CN)4 OFET with AL-X601, measured at Vd = 50 V. The channel was 45 lm long and 4000 lm wide.

substrates were sonicated in pure water, 2-propanol, acetone and chloroform baths followed by an UV-ozone surface treatment. An insulating uorinated polymer AL-X601 (Asahi Glass, Ltd.) with a dielectric constant of 3.1 and a breakdown voltage of 7.2 MV/cm was used as the gate dielectric material. This material presents a glass transition temperature higher than 150 C and is nearly transparent in the visible. A transmittance of 98% at 400 nm could be measured in an AL-X601 lm with a thickness of 3 lm. In addition, this polymer shows a strong resistance to most common solvents including 2-propanol, acetone, chloroform and propylene glycol monomethyl ether acetate (PGMEA). The 650 nm thick AL-X601 lms were spin-coated onto the ITO substrates from a PGMEA solution baked at 80 C for 90 s and then cured at 150 C for 60 min. QQT(CN)4 lms with a thickness of about 90 nm were deposited by spin-coating onto the AL-X601 layer from a 10 mg/ml chloroform solution. Gold source/drain electrodes were then thermally evaporated on top of the QQT(CN)4 lm through a shadow mask. Channel length and width was 45 lm and 4000 lm respectively. Concerning the thermal annealing of the devices, the treatment was carried out before the evaporation of the top gold electrodes using a hot plate at 180 C. Annealing time duration was about 15 s. Flexible QQT(CN)4 OFETs and complementary inverters using AL-X601 as gate dielectric were also fabricated, following a similar procedure as described above. In these devices, the ITO glass substrates were just replaced by patterned aluminum gate electrodes thermally evaporated onto exible polyethylenenaphtalate (PEN) lms (Q65FA; Teijin Dupont Films). Note that only the region of the device which needs to be thermally converted was placed onto the hotplate. The patterning of pn-regions in our samples using this approach can be achieved because of the low thermal conductivity of the PEN substrates. The electrical responses of the OFETs and logic circuits were carried out in air using a couple of picoammeter/voltage source units (Keithley, model 6487) and a source meter unit (Keithley, model 2400). 3. Results and discussion The transfer characteristics of an as-prepared QQT(CN)4 OFET with a 650 nm thick AL-X601 gate dielectric layer measured for a

drainsource voltage Vd of 50 V is displayed in Fig. 1b. The result shows that the on and off state current ratio is slightly higher than 103. The observed V-shape response indicates that this device is ambipolar, one arm at positive gate voltage Vg being associated to electron transport and one arm at negative Vg being related to hole conduction. This result suggests that no strong electron trapping occurs at the interface between the AL-X601 and QQT(CN)4 lms. This supports the idea that this new insulating uorinated polymer can be used as gate dielectric material in high performance n-type and ambipolar OFETs. The ambipolar charge transport properties taking place in QQT(CN)4 OFETs using AL-X601 as gate dielectric can be also seen in the output characteristics shown in Fig. 2 which were measured at different positive and negative Vg. These curves can be seen as the superposition of the standard saturated behavior for one charge carrier at high Vg and a superlinear dependence of the current at high Vd and low Vg which is associated to the injection of the opposite charge carrier. The hole and electron eld-effect mobilities were then calculated from the transfer characteristics in the saturation regime using the standard equation: Id = (W/2L)Cil(Vg VTh)2, where W is the channel width, L is the channel length, Ci is the insulator capacitance per unit area and VTh is the threshold voltage determined from the plot of the square root of the drain current versus the applied gate voltage as shown in the inset of Fig. 3a. We found that hole and electron eld-effect mobilities are about of 6 102 and 5 103 cm2/V s, respectively. These values are comparable with those measured in QQT(CN)4 OFETs with octadecyltrichlorosilane (OTS)-treated SiO2 gate dielectric layer [19] but signicantly higher than those measured in devices using either polyimide

Fig. 2. Output characteristics of an as-prepared ambipolar p-type dominant QQT(CN)4 OFET using the uorinated polymer AL-X601 as gate dielectric in (a) hole enhancement and (b) electron enhancement modes.

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mobilities, small hysteresis and can be converted from p-type dominant to n-type dominant by thermal treatment. Considering these attractive features, the next step in our present study was to fabricate and characterize the same type of devices prepared on exible PEN substrates, with the nal goal in mind of realizing high performance, mechanically stable, exible organic complementary inverters based on a monolithic solution-processable organic semiconductor. Fig. 4a displays the schematic representation of the exible QQT(CN)4 OFETs that were fabricated in this work. The transfer characteristics of the as-prepared and thermally treated exible devices measured at Vd = 50 V and various bending radii ranging from 5 to 35 mm are shown in Fig. 4b and c respectively. The results show that the eld-effect mobilities, threshold voltages and the on and off state current ratio are not signicantly modied in our devices for a bending radius up to 5 mm. The high stability of the electrical performances of these devices during the application of the bending stress shows the robustness and the potential of AL-X601 as gate dielectric material for exible organic electronics. To demonstrate this last statement, exible organic complementary inverter based on the combination of one as-prepared p-type ambipolar dominant QQT(CN)4 OFET and one thermally annealed n-type dominant QQT(CN)4 OFET

Fig. 3. (a) Transfer characteristics of as-prepared and thermally annealed QQT(CN)4 OFETs with an AL-X601 gate dielectric layer and measured at Vd = 50 V. The inset is a plot of the square root of the drain current versus the applied gate voltage. (b) Output characteristics of the n-channel in the annealed QQT(CN)4 OFET at different positive Vg. Annealing was performed at 180 C for 15 s.

[16] or poly-4-vinylphenol [22] as insulators. This suggests that AL-X601 is a very promising gate dielectric polymeric material for applications in exible organic electronics. Fig. 3a shows the transfer characteristics of as-prepared and annealed QQT(CN)4 OFETs measured at Vd = 50 V. The observed behavior is similar to that previously observed in QQT(CN)4 OFETs using either OTS-treated SiO2 or polyimide as gate dielectric [16,19]. While the n-conduction is not signicantly affected by the thermal treatment, hole current in the annealed device is strongly reduced by about two orders of magnitude. This large change is connected with both a decrease in hole eld-effect mobility and a signicant difference in threshold voltage. Such a majority carrier type conversion has been previously attributed to changes in lm morphology, which modify the charge transport and charge injection properties of the QQT(CN)4 OFETs [16,19]. Note that the large variations in threshold voltage upon thermal annealing strongly suggests some changes in the surface states at the dielectric/QQT(CN)4 interface. The other important information provided by Fig. 3a is the relatively small hysteresis in the transfer curves for both as-prepared and annealed devices, especially compared to that observed in the QQT(CN)4 OFETs with OTS-treated SiO2 [16]. It is also worth noting that Fig. 3b provides additional evidence that the majority carrier type conversion was achieved upon thermal treatment. It can be seen that the superlinearity observed in Fig. 2b which is associated with the presence of the two charge carrier types in the channel has vanished after the annealing. From our results, it appears that QQT(CN)4 OFETs using ALX601 as gate dielectric material shows high ambipolar eld-effect

Fig. 4. (a) Schematic representation of a gold top-contact QQT(CN)4 OFET using the uorinated polymer AL-X601 as gate dielectric and fabricated on top of patterned Al gate electrodes thermally evaporated onto a exible PEN substrate. Transfer characteristics of (b) as-prepared and (c) thermally annealed QQT(CN)4 OFETs measured at different bending radii and at Vd = 50 V.

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the future realization of high performance exible complementary logic gates. 4. Conclusion In summary, this work demonstrates the realization of exible high mobility ambipolar QQT(CN)4 OFETs using the uorinated gate dielectric polymer AL-X601. The low curing temperature of this insulating material makes it very promising for organic electronic applications. The majority carrier conversion in QQT(CN)4 thin lms upon thermal annealing was used to fabricate exible organic complementary inverters based on a monolithic organic semiconducting material and showing a very good mechanical stability. This work provides additional evidence that QQT(CN)4 and quinoidal oligothiophene derivatives are very promising candidates for applications in organic CMOS technology and optoelectronics. Acknowledgments The authors are grateful to Dr. Takafumi Sassa (RIKEN) as well as Dr. Masahiro Ito and Osamu Tagashira from AGC Chemicals for providing the uorinated polymer AL-X601. This work was supported by JSPS KAKENHI (No. 22350084). References
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Fig. 5. (a) Switching characteristics of a exible complementary inverter measured at VDD = 50 V in either the unbent state or for a bending radius of 5 mm. A schematic representation of the inverter is shown in the inset. The electronic logic circuit is composed of one as-prepared p-type dominant QQT(CN)4 OFET and one thermally annealed n-type dominant QQT(CN)4 OFET. The two transistors were fabricated on the same substrate and used AL-X601 as gate dielectric material. Their channel was 45 lm long and 4000 lm wide. (b) Corresponding gain measured at VDD = 50 V.

was fabricated. The two transistors used AL-X601 as polymer gate dielectric and were fabricated on the same substrate. A schematic representation of such an inverter is shown in the inset of Fig. 5a. This logic circuit shows a clear switching from an OFF state at high input voltage VIN to an ON state at low VIN as shown in Fig. 5a. At low VIN values, the output voltage VOUT is equal to the driving voltage VDD. In this regime, the p-type dominant OFET is on while the annealed n-type device is off. The switching of VOUT to low values then occurs when the n-type OFET is turned on at higher VIN. Note that VOUT does not reach zero in these logic circuits because the ptype dominant QQT(CN)4 OFET is never fully turned off and shows similar electron current as that in the n-type dominant device. It can be seen as well that the sweeping direction of VIN in this measurement does not affect signicantly the switching properties of the exible inverter, which is extremely important for practical electronic applications. Another important feature shown in Fig. 5a is the good mechanical stability of our logic circuit, which is consistent with the transfer characteristics of the QQT(CN)4 OFETs measured at different bending radii. Maximum gain of the organic inverter measured at VDD = 50 V was found to only decrease from 7.8 to 6.5 without any signicant shift in the switching response. Overall, this study demonstrates that exible QQT(CN)4 OFETs with AL-X601 gate dielectric have a strong potential for