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Polymer-Embedded Arylacetylene Semiconductors for Solution-Processed Organic Electronic Devices.

Assunta Marrocchi,1 Maria Laura Santarelli,2 Pascal Wolfer,3 Alessandra Broggi,2 Daniela Lanari,1 Paul Smith, 3 Natalie Stingelin-Stutzmann,3,4 and Luigi Vaccaro1 1 Dipartimento di Chimica, Laboratory of Green Synthetic Organic Chemistry, Universit degli Studi di Perugia, via Elce di Sotto 8, 06123 Perugia, I; e-mail: assunta@unipg.it 2 Dipartimento Ingegneria Chimica, Materiali Ambiente, University of Rome Sapienza, via Eudossiana 18, 00185 Roma, I. 3 Department of Materials, ETH Zrich, Wolfgang-Pauli Strasse 10, 8093 Zurich, CH. 4 Centre for Plastic Electronics, Imperial College London, London SW7 2AZ UK

Introduction Over the past three decades, the field of organic semiconductors has advanced rapidly, as these materials holds the promise of cost-efficient processing characteristics, lightweight, (semi)transparency, and mechanical flexibility. Most importantly they have the potential to be readily chemically tailored to fine-tune properties such as charge transport, light absorption, emission, etc., to address various application needs. Despite the latest impressive results, major drawbacks still exists, as organics often exhibit modest electrical performance, and vulnerability to ambient oxidants which requires costly vacuum- or inert atmosphere-based device fabrication steps, and encapsulation in barrier structures. All these constraints render organic-based devices less obvious as a viable alternative to more conventional electronics. As a consequence, there remains a persistent need for the development of semiconducting systems which exhibit high carrier mobility as well as environmental stability, and create the positive economy of scale conditions. Blending of organic semiconductors with insulating (semi-)crystalline polymers has been shown to be a useful strategy to address, among other things, these issues [1-4]. In addition, blending with properly selected commodity polymers to the semiconducting material(s) should enable control over melt- and solution viscosity, which may provide for instance, improved film-forming characteristics. Furthermore, excellent performance in organic field-effect transistors at remarkably low semiconductor contents combined with highly desirable mechanical properties may be featured by these two-component systems if tough insulating polymers such as polyethylene are utilized for this purpose. This has recently been demonstrated with poly(3-hexylthiophene) (P3HT):PE blends and diblock copolymers.[1,2] Besides these systems, that are comprised of two macromolecular species, oligothiophene:polyethylene (i.e. small-molecular:polymeric) binaries have also been studied [3], which provided additional insight into such crystalline:crystalline semiconducting:insulating organic blends. Small molecular species display well-defined conjugation length and provide simple model systems for elucidating relevant structure-property correlations, especially with respect to their electronic behavior. It was demonstrated that under judiciously chosen processing conditions, i.e. at elevated temperatures, the semiconducting characteristics of -quaterthiophene:polyethylene binaries were comparable to those found for the neat semiconducting compound provided that the oligothiophene content exceeds ~10 wt-%. Recently [5] we undertook extensive research into multi-component blends comprising semiconducting small-molecular arylacetylenes [6,7] and a range of insulating polymers (e.g. highdensity polyethylene, poly(vinylidene fluoride), and polybutene-1). A major advantage of arylacetylene systems is the possibility to access a broad range of molecules with specific geometries, that can be readily synthesized [8] from easily accessible precursors. Further, their production can easily be scaled up, and they can readily be isolated in high purity, thus reducing the risks concerning materials supply or costs. Here we report on the use of arylacetylenes 1-3 (Figure 1) in blending with the insulating poly(vinylidene fluoride) (PVDF). PVDF was selected as this polymer has been shown to allow film-processing at room temperature of, for instance, poly(3-

hexylthiophene) (P3HT) : PVDF binaries [9]. Arylacetylenes 1-3 have been designed bearing in mind that anthracene may enable large carrier mobilities, better solubility, and improved stability as compared to pentacene, [10] which has become a benchmark in the organic electronic field. For many manufacturing techniques, preparation of active layers at ambient conditions is preferable. Therefore, a number of solubilizing flexible hexyloxy-chains ranging from two to four (i.e. arylacetylene 2 and 3, respectively) is introduced at the terminal phenyl-ring systems to modulate the phase behavior resulting in a decrease of the semiconductors melting point and, hence, increasing its solubility features in most common organic solvents.

X C6H13O

X OC6H13

2: X= H 3: X= OC6H13

Figure 1. Structures of Arylacetylenes 1-3 Fine and homogeneous microstructures were obtained with room temperature processing blends of hexyloxy-substituted arylacetylenes:insulating polymer from homogeneous solutions. Semiconducting characteristics of field-effect transistors of blends thus produced were found to be comparable to those of devices comprising the unsubstituted arylacetylene 1 prepared at elevated temperatures. Further, it was possible to have arylacetylene concentrations as low as 30 wt% in the bulk but still have sufficient material to form a percolating network required for electronic transport. Discussion We found that 1:PVDF blends form homogenous solutions at elevated temperatures. In this systems, the semiconducting species exhibits a higher crystallization temperature than the polymeric insulator and, accordingly, crystallizes prior to the macromolecular component at all concentrations explored (Figure 1a). However, due to the relatively large gap between the solidus of the two components ( i.e. the significant difference in supercooling that is required for the semiconductor and insulator to solidify from solution), coarse, highly phase separated structures resulted when processing the blends at low solidification rates, i.e. at low deposition temperatures. The large incompatibility of 1 and the insulating matrix polymer employed is also reflected in the phase behavior of 1:PVDF binary. The non-equilibrium temperature/composition diagrams (Figure 1b) feature a classical monotectic behavior with an extremely large miscibility gap, resulting in an extended Li + S1 two-phase region. Consequently, only when processing such blends at increased solidification rates, i.e. at elevated temperatures, finer and more homogeneous microstructures can be obtained, as illustrated by optical micrographs in Figure 1c. These structural features previously were reported to be critical to yield high-mobility, low-percolation threshold systems. From a processing point of view, however, high-temperature operations are not particularly desirable, and, therefore we explored influencing the microstructure formation not by thermal means but by chemical modification of the semiconducting species. To this end, two flexible hexyloxy side-chains were introduced at the terminal phenyl-ring systems of 1 to give 9,10bis[3,4-(hexyloxy)phenylethynyl]anthracene (2). Indeed, addition of only two hexyloxy chains did not significantly modify the phase behavior of small molecule:polymer blends. Therefore, in a next step, we investigated compound 3 comprising four hexyloxy groups at the terminal phenyl rings. We found that this species crystallized prior to PVDF when solidification is performed in a temperature regime below approximately 35C (Figure 2a). Furthermore, when compared to the above described 1:PVDF binary, the difference in supercooling experienced by the two components

3 and PVDF is relatively small. Consequently, distinctly finer and more homogeneous distribution of the semiconductor was found for all compositions investigated when film drying was performed at room temperature (cf. Figure 2c).
a
220 200 180 160 140 Tc 120 ( 100 C) 80 60 40 20 0 20 40 0 1

300 Li 250 Li + Lii Lii

c)
25 C

PVDF

200

Li + S1
0.2 mm

Tm ( 150 C)
100 50 SPVDF + S1

100 C

T 20 40 60 80 100

T 0 20 40 60 80 100

cyclohexanon

wt-%

1 / PVD

PVD

wt-%

Figure 1. (a) Superimposed crystallization temperature/composition diagrams of 1:cyclohexanone and PVDF:cyclohexanone binary constructed with peak crystallization temperatures determined from DSC second cooling thermograms. The gray dashed lines indicate different processing routes applied for 1:PVDF binaries with solvent removal at 25 or 100 C, followed by cooling to room temperature. (b) Binary nonequilibrium temperature/composition diagram of 1:PVDF blend produced by co-dissolution in cyclohexanone, respectively, followed by solvent evaporation at ambient. The diagrams were constructed with peak temperatures recorded in DSC first heating thermograms (filled symbols) and polarized optical microscopy (open symbols). Li, Lii denote liquid phases and S1, SPVDF solid phases of compound 1 and PVDF, resp.; x indicates exceedingly minor endothermic transitions; e) Polarized optical micrographs of 1:PVDF 40:60 blends solidified at 25 C (top) and 100 C (bottom), respectively (polarizer/analyzer indicated with white arrows).
a
160 140 120 100 3 PVDF

180 160 140 120 Li Li + Lii SPVDF + Lii Lii

c)
25 C

Tc 80 ( 60 C)
40 20 0 -20 -40 0 20 40 60 T 80 100

Tm ( 100 C) 80
60 40 20 0 0

SPVDF + S3

0.2 mm

100 C

T 20 40 60 80 100

cyclohexanon

wt-%

3 / PVD

PVD

wt-%

Figure 2. (a) Superimposed crystallization temperature/composition diagrams of 3:cyclohexanone and PVDF:cyclohexanone as constructed with DSC peak crystallization temperatures in second cooling thermograms; (b) Binary non-equilibrium temperature/composition diagram of 3:PVDF blends. Li, Lii denote liquid phases and S3, SPVDF solid phases of compound 3 and PVDF, resp.; x indicates exceedingly minor endothermic transitions. (e) Polarized optical micrographs of 3:PVDF 40:60 blends solidified at 25 C (top) and 100 C (bottom), respectively (polarizer/analyzer indicated with white arrows).

From the 3:PVDF blends temperature/composition diagrams shown in Figure 2b, it is clear that also this systems feature a large incompatibility of the small-molecular semiconductor and the

insulating polymers. However, compared to the 1-based binary, here, the temperature range between the liquidus and solidus lines is significantly reduced, lowering the degree of phase separation occurring during blend fabrication. The favourable crystallization sequence found in 3: PVDF binaries combined with the small difference between the solidification temperatures of the two components seemed to offer an ideal platform to yield high-mobility, low-percolation threshold systems. Hence, electronic characteristics of binaries comprising 40 wt-% of 3 have been explored in bottom-gate bottom-contact field-effect transistors, allowing a detailed correlation of the phase behaviour with the electronic blend performance. Intriguingly, processing conditions applied, i.e. deposition temperatures selected, had only a minor influence on FET performance of 3:PVDF blends with an optimum casting temperature observed around 50 C. These observations can be correlated with the superimposed temperature/composition diagrams presented in Figure 2a. Arylacetylene 3 and PVDF solidify rapidly after each other, if not simultaneously, at all casting temperatures explored. Hence, the resulting finely phase-separated bi-component layers invariably lead to good device characteristics with a charge-carrier mobility FET ~5 x 10-4 cm2/Vs and an ONOFF ratio of ~103, comparable to those of the neat semiconductor [6]. Accordingly, these results demonstrate that simple binary crystallization temperature/composition diagrams of the individual component in the solvent selected are useful to understand solidification kinetics and to identify a suitable processing window, both with respect of selection of deposition temperatures and solution concentrations.

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