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DOI: 10.1002/adma.200800557

Hydrouoroethers as Orthogonal Solvents for the Chemical Processing of Organic Electronic Materials**
By Alexander A. Zakhidov, Jin-Kyun Lee, Hon Hang Fong, John A. DeFranco, Margarita Chatzichristidi, Priscilla G. Taylor, Christopher K. Ober, and George G. Malliaras*
Organic electronics is a fast developing branch of modern science and technology that can complement conventional inorganic materials with lightweight, inexpensive, and mechanically exible organic semiconductors.[1] One of the key advantages of organic electronic materials lies in the low-temperature, high-throughput device fabrication they enable. The solution-based fabrication of a variety of devices such as organic light emitting diodes (OLEDs), organic thin lm transistors (OTFTs), organic solar cells, and sensors has been demonstrated using spin coating, ink-jet printing, and other wet printing techniques.[2,3] While substantial improvements in materials synthesis, purication and deposition techniques over the past two decades enhanced lm quality, uniformity, and environmental stability, the chemical processing of organic electronic materials remains one of the main challenges to be overcome. By chemical processing we mean any chemical treatment such as cleaning, depositing a second layer from solution to form multilayer devices, and depositing/developing resist layers for photolithographic patterning. A major challenge in chemical processing of organic electronic materials is the limited number of options regarding orthogonal solvents, i.e., solvents that do not dissolve or adversely damage an organic layer.[4] The main strategy to achieve solvent orthogonality is to use polar/non-polar solvents to process non-polar/polar active lms, respectively. For example, one can form a bilayer structure by using a polar solvent to deposit a (polar) lm on top of a non-polar lm. Accordingly, solvent orthogonality can be achieved either by carefully choosing proper organic material/solvent combinations[5,6] or by chemical modication of organic materials to achieve the desired polarity.[7] This strategy, however, offers limited latitude, since both types of solvents are often required for certain processes such as photolithography. Here we present a novel approach to chemical processing of organic electronic materials. The approach is based on the use of uorous solvents segregated hydrouoroethers (HFEs) in particular which we show to be completely benign to the majority of organic electronic materials (with the obvious exception of highly uorinated organic materials). We demonstrate that processing organic electronic lms using HFEs, even under extreme conditions such as boiling temperatures, does not cause any dissolution, cracking, delamination or other unfavorable physical or chemical damage. Moreover, we show that the use of uorous solvents enables straightforward photolithographic patterning of organic electronic materials. Fluorous solvents are peruorinated or very highly uorinated liquids, which are typically immiscible with organic solvents and water.[8] Therefore, they naturally extend our options for solvent orthogonality. We chose HFEs out of the variety of other available uorous solvents since they are well known to be highly environmentally friendly, green solvents.[9] HFEs are non-ammable, have zero ozonedepletion potential, low global warming potential and show very low toxicity to humans.[9] HFEs were introduced to industry in 1994 as third generation hydrouorocarbon liquids to be used as replacement of chlorouorocarbons and hydrochlorouorocarbon refrigerants. HFEs have also been demonstrated as environmental friendly cleaning solvents for electronics.[1012] Typical commercially available HFEs are isomeric mixtures of methyl nonauorobutyl ether and methyl nonauoroisobutyl ether (HFE 7100) and 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6dodecauoro-2-triuoromethylhexane (HFE 7500) shown in Scheme 1. We tested the impact of these solvents on well-characterized and commercially available organic electronic materials. The rst one was poly(3-hexylthiophene) (P3HT), a prototypical conjugated polymer which is soluble in common non-polar organic solvents such as chlorobenzene and is extensively used in OTFTs.[13] We therefore fabricated a nominally identical batch of P3HT OTFTs and tested them before and after a ve minute immersion into a beaker lled with solvent and held at room temperature. In addition to the HFEs listed above, we used representatives of polar protic (isopropyl alcohol IPA), polar aprotic (propylene glycol methyl ether acetate PGMEA), and non-polar ( p-xylene)

[*] Prof. G. G. Malliaras, Dr. A. A. Zakhidov, Dr. J.-K. Lee, Dr. H. H. Fong, J. A. DeFranco, Dr. M. Chatzichristidi, P. G. Taylor, Prof. C. K. Ober Department of Materials Science and Engineering, Cornell University Ithaca, NY 14853-1501 (USA) E-mail: ggm1@cornell.edu [**] A. A. Z., J.-K. L., and H. H. F. contributed equally to this work. We gratefully acknowledge support from National Science Foundation (Materials World Network DMR-0602821, and Center for NanoScale Systems EEC-0646547). The work was performed in part at the Cornell NanoScale Facility, a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation (Grant ECS-0335765). We would like to acknowledge 3M Company and particularly Mr. Erik Olson for fruitful discussions and extensive support of this work, and Prof. Hector Abruna (Cornell) for supplying the [Ru(bpy)3]2(PF6)2.

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Scheme 1. Chemical structures of HFEs solvents: a) HFE 7100 (mixture of two isomers, boilng point 61 8C) and b) HFE 7500 (boiling point 130 8C).

solvents. The second organic electronic material we tested was ruthenium(II) tris(bipyridine) with hexauorophosphate counter ions {[Ru(bpy)3]2(PF6)2}. This material is an ionic metal complex which is soluble in polar solvents such as acetonitrile and is used in electroluminescent devices.[14] We therefore fabricated a nominally identical batch of [Ru(bpy)3]2(PF6)2 electroluminescent devices and tested them after exposure to solvents according to the protocol discussed above. The details of device structure and fabrication are given in the experimental part. The results of solvent treatment on device performance are shown in Figure 1 and are summarized in Table 1. For the P3HT transistors, the transfer characteristics before and after solvent immersion are displayed in Figure 1a. The initial eld-effect hole mobility of the OTFTs was 1.0 103 cm2 V1 s1 with a device-to-device variation of 10%. As expected, the transistors fared reasonably well in IPA and PGMEA, showing only a minor decrease in performance. It should be noted that PGMEA, which is extensively used in photolithography, has been utilized in the photolithographic patterning of P3HT and a few other organic materials.[5,6] Immersion in the non-polar p-xylene, however, dissolved the P3HT lm and resulted in severe device damage. On the other hand, immersion in the HFEs did not cause any device degradation, indicating that HFEs are excellent orthogonal solvents for P3HT. Similar results were observed for the [Ru(bpy)3]2(PF6)2 electroluminescent devices. Figure 1b shows the results of solvent treatment in the emission characteristics of the devices. The emission shows the characteristic delay associated with the redistribution of the PF6 counter ions.[14] Table 1 shows the resulting loss in device external quantum efciency upon solvent treatment. As expected, immersion in p-xylene resulted in a rather small loss of performance, while IPA

Table 1. The results of solvent treatment on P3HT OTFTs and [Ru(bpy)3]2(PF6)2 electroluminescent devices. The data represent changes in the eld-effect hole mobility of the former and the quantum efciency of the latter after solvent treatment. Figure 1. a) P3HT OTFT gate sweep curves taken at a source-drain voltage of 100 V before and after solvent treatment. b) Temporal response of emission of [Ru(bpy)3]2(PF6)2 electroluminescent devices at 3 V applied bias before and after solvent treatment. c) Photograph of a [Ru(bpy)3]2(PF6)2 electroluminescent device operating in boiling HFE 7100.
Polar Protic IPA P3HT Ru(bpy)3(PF6)2 95% 45% Aprotic PGMEA 90% 0% Non-polar Fluorous HFE 7100 100% 100% HFE 7500 100% 100%

p-Xylene
0% 85%

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caused a substantial decrease in device efciency due to an increase in device current, and PGMEA lead to shorting of the devices and complete loss of electroluminescence. Once again, immersion in HFEs did not affect device performance. Therefore, HFEs are shown to be orthogonal solvents for two organic electronic materials with very different polarities, P3HT and [Ru(bpy)3]2(PF6)2.

To further demonstrate the orthogonality of HFEs we operated a [Ru(bpy)3]2(PF6)2 electroluminescent device in boiling HFE 7100 (61 8C) for one hour and did not observe any substantial change in its performance. Figure 1c shows the device operating in boiling HFE 7100. Similarly, immersion of a P3HT transistor in boiling HFE 7100 for one hour did not change the transistor characteristics. In addition to the above mentioned

Figure 2. a) Scheme illustrating the HFE-based lift-off patterning technique for organic materials. b) Scheme of imaging process of the photoresist employed in the HFE-based patterning. c) Optical micrograph of a patterned [Ru(bpy)3]2(PF6)2 lm.

device results, we performed optical and atomic force microscopy on a variety of polymeric electronic materials including poly(9,9-dioctyluorene), poly(9,9-didecyluorene-co-benzothiadiazole) (F8BT) and poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS), before and after immersion in boiling HFE 7100. No signicant change of morphology and no pinhole formation, cracking, or delamination was observed, conrming the orthogonality of HFEs even under extreme conditions. This new dimension in solvent orthogonality which is enabled by the use of HFEs offers unique opportunities for the chemical processing of organic electronic materials. One example is in the area of photolithographic processing: One can use a photoresist that is properly uorinated to be processable in HFEs[15] (similar photoresists have been developed for processing using supercritical CO2[16]). We have successfully demonstrated this approach to the patterning of [Ru(bpy)3]2(PF6)2 employing a resist formulation

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composed of a tert-butoxycarbonyl (t-Boc) protected resorcinarene[17] and a photoacid generator (PAG) by a lift-off technique (see Fig. 2). The details of the photoresist synthesis and the photolithographic patterning process are given elsewhere.[15] In brief, we synthesized an HFE-processable negative tone photoresist by appending four peruoroalkyl chains [(CH2)4(CF2)8F] and eight t-Boc groups to the resorcinarene molecule. The lithographic pattern of the photoresist is formed by turning it into an insoluble form upon acid-catalyzed deprotection reaction, in which the acid is liberated from the photoacid generator (PAG) by UV exposure. The developed resist solubility in HFEs is restored via 1,1,1,3,3,3-hexamethyldisilazane (HMDS) treatment at an elevated temperature.[18] A positive image of the active material is created by depositing an active material and subsequent resist lift off. The principal scheme of the technique is depicted in Figure 2a and b. A patterned [Ru(bpy)3]2(PF6)2 lm with featured down to the 2 mm scale is shown in Figure 2c. In conclusion, we show that HFEs represent a class of orthogonal solvents that are benign to a wide variety of organic electronic materials. HFEs offer a unique opportunity to move beyond the usual polar/non-polar axis in organic materials processing. Moreover, HFEs are environmentally friendly, green solvents, enabling chemical processing of organic electronic materials that can be readily adopted by industry. Coupled with uorous functional materials, they open new frontiers in materials processing, and have the potential to enable facile photolithographic patterning for organic electronics.

acetonitrile), followed by drying the lms in nitrogen atmosphere at 60 8C for 12h. After that 200 A Au electrodes were directly deposited on the ruthenium complex lm by thermal evaporation at a rate of 1 A s1. The OTFTs were prepared as follows: A P3HT solution (1% weight in 1,2,4-trichlorobenzene) was spin coated at 3000 rpm on a highly-doped silicon wafer with a thermally-grown 200 nm SiO2. The lm was then annealed at 100 8C for 1 h in nitrogen atmosphere. Source and drain electrodes 300 A Au electrodes were deposited onto the P3HT lm via the shadow mask by thermal evaporation at a rate of 1 A s1, dening channels of that were 100 mm long and 1.8 mm wide. Received: February 27, 2008 Revised: April 2, 2008 Published online: July 23, 2008

Experimental
Materials: The hydrouoroethers (HFE 7100 and HFE 7500) were obtained from 3M and used as received. Other solvents were purchased from Aldrich. Semiconducting polymer poly(3-hexylthiophene) with head-to-tail regioregularity >99% was obtained from Plextronics and used without further purication. [Ru(bpy)3]2(PF6)2 complex was synthesized according to known referenced procedures [14]. Device Fabrication: The electroluminescent devices were prepared as follows: 100 nm thick lms were deposited on clean ITO/glass substrate by spin-coating ltered solutions of Ru(bpy)3]2(PF6)2 (3 wt % in

[1] G. Malliaras, R. Friend, Phys. Today 2005, 58, 53. [2] E. Menard, M. A. Meitl, Y. G. Sun, J. U. Park, D. J. L. Shir, Y. S. Nam, S. Jeon, J. A. Rogers, Chem. Rev. 2007, 107, 1117. [3] Y.-L. Loo, AIChE J. 2007, 53, 1066. [4] K. Meerholz, Nature 2005, 437, 327. [5] J. Huang, R. Xia, Y. Kim, X. Wang, J. Dane, O. Hofmann, A. Mosley, A. J. de Mello, J. C. de Mello, D. D. C. Bradley, J. Mater. Chem. 2007, 17, 1043. [6] C. Balocco, L. A. Majewski, A. M. Song, Org. Electron. 2006, 7, 500. [7] X. Gong, S. Wang, D. Moses, G. C. Bazan, A. J. Heeger, Adv. Mater. 2005, 17, 2053. [8] I. T. Horvath, J. Rabai, Science 1991, 266, 72. [9] W.-T. Tsai, J. Hazard. Mater. 2005, 119, 69. [10] D. L. Cooper, T. P. Cunningham, N. L. Allan, A. McCulloch, Atmos. Environ. Part A 1993, 27, 117. [11] D. B. Bivens, B. H. Minor, Int. J. Refrig. 1998, 21, 567. [12] A. Sekiya, S. Misaki, J. Fluorine Chem. 2000, 101, 215. [13] H. Sirringhaus, N. Tessler, R. H. Friend, Science 1998, 280, 1741. [14] J. D. Slinker, J. Rivnay, J. S. Moskowitz, J. B. Parker, S. Bernhard, H. D. Abruna, G. G. Malliaras, J. Mater. Chem. 2007, 17, 2976. [15] J. K. Lee, M. Chatzichristidi, A. A. Zakhidov, J. A. DeFranco, P. G. Taylor, H. H. Fong, H. S. Hwang, A. B. Holmes, G. G. Malliaras, C. K. Ober, unpublished. [16] N. Sundararajan, S. Yang, K. Ogino, S. Valiyaveettil, J.-G. Wang, X. Zhou, C. K. Ober, S. K. Obendorf, R. D. Allen, Chem. Mater. 2000, 12, 41. [17] S. W. Chang, R. Ayothi, D. Bratton, D. Yang, N. Felix, H. B. Cao, H. Deng, C. K. Ober, J. Mater. Chem. 2006, 16, 1470. [18] V. Q. Pham, R. J. Ferris, A. Hamad, C. K. Ober, Chem. Mater. 2003, 15, 4893.

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