POLYMERS

[1] This application claims the benefit of priority under 35 U.S. C. § 119 of U.S. Provisional Application Serial No. 62/516, 943 filed on June 8, 2017, the content of which is relied upon and incorporated herein by reference in its entirety.

Field

[2] The present invention relates generally to polymer blends containing an organic semiconducting polymer.

Background

[3] Organic semiconductors are used in variety of applications, including electronics, organic transistors, organic light-emitting diodes (OLEDs), organic integrated circuits, organic solar cells, and others. Enhancing the performance of organic semiconductors is of interest in numerous applications.

BRIEF SUMMARY

[4] One embodiment relates to a polymer blend comprising an organic semiconductor polymer blended with an isolating polymer. In some embodiments the organic semiconductor polymer is a diketopyrrolopyrrole fused thiophene polymeric material. In some embodiments the fused thiophene is beta-substituted. In some embodiments, the isolating polymer has a non-conjugated backbone. In some embodiments, the isolating polymer is selected from the group consisting of polyacrylonitrile, alkyl substituted polyacrylonitrile, polystyrene, polysulfonate, polycarbonate, an elastomer block copolymer, derivatives thereof, copolymers thereof and mixtures thereof.

[5] In some embodiments, the embodiments of any of the preceding paragraphs may further include the organic semiconductor polymer comprises the repeat unit of formula or 2' .

In some embodiments, in the structure and 2', m is an integer greater than or equal to one; n is 0, 1, or 2; Ri, R ₂ , R , R4, R5, R5, R7, and R ₈ , may be, independently, hydrogen, substituted or unsubstituted C4 or greater alkyl, substituted or unsubstituted C4 or greater alkenyl, substituted or unsubstituted C4 or greater alkynyl, or C5 or greater cycloalkyl; a, b, c, and d are independently, integers greater than or equal to 3; e and / are integers greater than or equal to zero; X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and A and B may be, independently, either S or O, with the provisos that: [6] i. at least one of Ri or R ₂ ; one of R or R4; one of R5 or R5; and one of R7 or R ₈ is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or cycloalkyl;

[7] ii. if any of Ri, R ₂ , R ₃ , or R4 is hydrogen, then none of R5, R5, R7, or R ₈ are hydrogen;

[8] iii. if any of R5, R5, R7, or R ₈ is hydrogen, then none of Ri, R ₂ , R , or R4 are hydrogen;

[9] iv. e and / cannot both be 0;

[10] v. if either e or/is 0, then c and d, independently, are integers greater than or equal to 5; and

[11] vi. the polymer having a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

[12] In some embodiments, the embodiments of any of the preceding paragraphs may further include the isolating polymer is polystyrene and derivatives thereof.

[13] In some embodiments, the embodiments of any of the preceding paragraphs may further include the polystyrene has a molecular weight of greater than 5,000.

[14] In some embodiments, the embodiments of any of the preceding paragraphs may further include the polystyrene has a molecular weight of greater than 10,000.

[15] In some embodiments, the embodiments of any of the preceding paragraphs may further include the isolating polymer forms an encapsulating layer between the organic semiconductor and an air interface.

[16] In some embodiments, the embodiments of any of the preceding paragraphs may further include the isolating polymer oxidizes preferentially to the organic semiconductor polymer.

[17] In some embodiments, the embodiments of any of the preceding paragraphs may further include the isolating polymer that oxidizes preferentially to the organic semiconductor polymer is polyacrylonitrile, alkyl substituted polyacrylonitrile, or copolymers thereof.

[18] In some embodiments, the embodiments of any of the preceding paragraphs may further include the weight ratio of organic semiconductor polymer to isolating polymer in the blend is between 95:5 and 5:95.

[19] In some embodiments, the embodiments of any of the preceding paragraphs may further include the weight ratio of organic semiconductor polymer to isolating polymer in the blend is between 80:20 and 40:60. [20] In some embodiments, the embodiments of any of the preceding paragraphs may further include wherein the weight ratio of organic semiconductor polymer to isolating polymer in the blend is between 55:45 and 65:35.

[21] Another embodiment relates to an organic semiconductor device comprising blending an organic semiconductor polymer with an isolating polymer in an organic solvent to create a polymer blend; and depositing a thin film of the polymer blend over a substrate. In some embodiments the organic semiconductor polymer is a diketopyrrolopyrrole fused thiophene polymeric material. In some embodiments the fused thiophene is beta-substituted. In some embodiments isolating polymer has a non-conjugated backbone. In some embodiments the non- conjugated polymer is selected from the group consisting of: polyacrylonitrile, alkyl substituted polyacrylonitrile, polystyrene, polysulfonate, polycarbonate, an elastomer block copolymer, derivatives thereof, copolymers thereof and mixtures thereof.

[22] In some embodiments, the embodiments of any of the preceding paragraphs may further include thermally annealing the thin film after the thin film is deposited over the substrate.

[23] In some embodiments, the embodiments of any of the preceding paragraphs may further include the annealing step is performed at a temperature of 100 °C to 180 °C.

[24] In some embodiments, the embodiments of any of the preceding paragraphs may further include the thin film is annealed in air.

[25] In some embodiments, the embodiments of any of the preceding paragraphs may further include the organic semiconductor polymer comprises the repeat unit of formula or 2' .

In some embodiments in the structure and 2', m is an integer greater than or equal to one; n is 0, 1, or 2; Ri, R ₂ , R , R4, R5, R5, R7, and R ₈ , may be, independently, hydrogen, substituted or unsubstituted C4 or greater alkyl, substituted or unsubstituted C4 or greater alkenyl, substituted or unsubstituted C4 or greater alkynyl, or C5 or greater cycloalkyl; a, b, c, and d are independently, integers greater than or equal to 3; e and / are integers greater than or equal to zero; X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and A and B may be, independently, either S or O, with the provisos that: [26] i. at least one of Ri or R ₂ ; one of R or R4; one of R5 or R5; and one of R7 or R ₈ is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or cycloalkyl;

[27] ii. if any of Ri, R ₂ , R ₃ , or R4 is hydrogen, then none of R5, R5, R7, or R ₈ are hydrogen;

[28] iii. if any of R5, R5, R7, or R ₈ is hydrogen, then none of Ri, R ₂ , R , or R4 are hydrogen;

[29] iv. e and / cannot both be 0;

[30] v. if either e or/is 0, then c and d, independently, are integers greater than or equal to 5; and

[31] vi. the polymer having a molecular weight, wherein the molecular weight of the polymer is greater than 10,000.

[32] In some embodiments, the embodiments of any of the preceding paragraphs may further include the isolating polymer is polystyrene and derivatives thereof.

[33] In some embodiments, the embodiments of any of the preceding paragraphs may further include the polystyrene has a molecular weight of greater than 5,000.

[34] In some embodiments, the embodiments of any of the preceding paragraphs may further include the polystyrene has a molecular weight of greater than 10,000.

[35] In some embodiments, the embodiments of any of the preceding paragraphs may further include the organic solvent is a non-halogenated solvent.

[36] In some embodiments, the embodiments of any of the preceding paragraphs may further include the non-halogenated solvent is selected from the group consisting of: w-xylene, o-xylene,

/^-xylene, toluene, tetralin, cis-decalin, trans-decalin, mesitylene, cyclooctane, and bicyclohexyl, and mixtures thereof.

[37] In some embodiments, the embodiments of any of the preceding paragraphs may further include blending an organic semiconductor polymer with an isolating polymer in an organic solvent to create a polymer blend is performed at a temperature greater than 70 °C.

[38] In some embodiments, the embodiments of any of the preceding paragraphs may further include the organic semiconductor polymer and the isolating polymer each have a solubility of 1 mg/mL or more in the non-halogenated solvent at room temperature. [39] Another embodiment relates to an organic semiconductor device, comprising a thin semiconducting film, the thin semiconducting film comprising a polymer blend. In some embodiments the polymer blend comprises an organic semiconductor polymer blended with an isolating polymer. In some embodiments the organic semiconductor polymer is a diketopyrrolopyrrole fused thiophene polymeric material. In some embodiments the fused thiophene is beta-substituted. In some embodiments the isolating polymer is selected from the group consisting of polyacrylonitrile, alkyl substituted polyacrylonitrile, polystyrene, polysulfonate, polycarbonate, an elastomer block copolymer, derivatives thereof, copolymers thereof and mixtures thereof.

BRIEF DESCRIPTION OF THE DBA WINGS/FIGURES

[40] FIG. 1 is a chart showing performance of the polymer of structure 4 after being thermally annealed in nitrogen or air.

[41] FIG. 2 shows a flow chart for an exemplary process of fabricating an organic semiconductor device.

DETAILED DESCRIPTION OF THE INVENTION

[42] Embodiments of the present disclosure will now be described in detail with reference to the accompanying drawings. References to "one embodiment", "an embodiment", "an exemplary embodiment", etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.

[43] The use of organic semiconductors (OSC) as functional materials has become a reality in a number of different applications for the electronics industry including, for example, printed electronics, organic transistors, including organic thin-film transistors (OTFTs) and organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic integrated circuits, organic solar cells, and disposable sensors. Organic transistors may be used in many applications, including smart cards, security tags, and the backplanes of flat panel displays. Organic semiconductors may substantially reduce cost compared to inorganic counterparts, such as silicon. Depositing the OSC from solution may enable fast, large-area fabrication routes such various printing methods and roll-to-roll processes.

[44] In some applications, annealing the OSC in air significantly reduces the cost of device production, compared to annealing in nitrogen or vacuum. However, in some applications, annealing in air can lead to reduced device performance. Thus, it is desirable to manufacture formulations that maintain device performance after annealing in air.

Organic semiconductor

[45] An organic semiconducting (OSC) polymer can be used to produce organic semiconductor devices. In some embodiments, the OSC polymer has a main backbone that is fully conjugated. In some embodiments, the organic semiconductor is a diketopyrrolopyrrole (DPP) fused thiophene polymeric material. In some embodiments, the fused thiophene is beta-substituted. This organic semiconductor may contain both fused thiophene and diketopyrrolopyrrole units. In some embodiments, the organic semiconductor is used in an organic thin-film transistor (OTFT) application. For example, as shown in structures 1 and 2, the OSC can have conjugated groups X and Y. In some embodiments, X and Y are conjugated groups that are connected to the DPP and fused thiophene moieties in such a way as to provide a continuous conjugated pathway along the polymer backbone. In some embodiments, Ri, R ₂ , R ₃ , and R4 are alkyl chains that impart solubility. In some embodiments, beta-substitution improves solubility. In some embodiments, the OSC has a solubility of 0.5 mg/mL, 1 mg/mL, 2 mg/mL, 3 mg/mL, 4 mg/mL, 5 mg/mL, or any range defined by any two of those endpoints. In some embodiments, the OSC has a solubility of 1 mg/mL or more at room temperature. In some embodiments, these polymers enable simple transistor fabrication at relatively low temperatures, which is particularly important for the realization of large-area, mechanically flexible electronics. A beta- substituted OSC polymer can also help to improve solubility.

[46] Generic structures of DPP fused thiophene polymers are shown in structures 1 and 2. The incorporation of fused thiophenes into polymers further containing DPP can result in more stable DPP conjugated copolymer structures, improved solubility of the copolymer due to the large alkyl-based R-groups on the fused thiophene moieties, and improved electronic and optical properties due to the larger conjugation units.

Structure 1 :

Ri

Structure 2:

[47] In some embodiments, the DPP fused thiophene polymeric material has the structure as shown in structure 3 or 4. In some embodiments, these DPP and fused thiophene polymers have hole mobilities of 1 cm^'s ^"1 , 2 cm^'s ^"1 , 3 cm^'s ^"1 , 4 cm^'s ^"1 , 5 cm^'s ^"1 , 10 cm ² V ^_1 s ^_1 , or any range defined by any two of those endpoints. The hole mobilities may be equal to or greater than any of these values. In one embodiments, the DPP and fused thiophene polymers have hole mobilities of 1 to 4 cm ² V ^_1 s ^_1 . In one embodiment, the DPP and fused thiophene polymers have hole mobilities of 2 cm ² V ^_1 s ^_1 . In some embodiments, the DPP and fused thiophene polymers have hole mobilities of 2 cm ² V ^_1 s ^_1 or more. [48] In some embodiments, the DPP and fused thiophene polymers have On/Off ratio of greater than 10 ⁵ . In some embodiments, the DPP and fused thiophene polymers have On/Off ratio of greater than 10 ⁶ .

[49] In some embodiments, the DPP and fused thiophene polymers have a threshold voltage in thin film transistor devices of 1 V, 2 V, 3 V, 4 V, 5 V, 10 V, or any range defined by any two of those endpoints. In one embodiment, the DPP and fused thiophene polymers have a threshold voltage of 1-3 V in thin film transistor devices. In one embodiment, the DPP and fused thiophene polymers have a threshold voltage of 2 V in thin film transistor devices.

Structure 3 :

Structure 4:

[50] In some embodiments, the organic semiconductor comprises the structure as shown in structures 5 and 6. In some embodiments, structures shown in structures 5 and 6 contain functional groups Ri, R ₂ , R ₃ , R4, R5, R5, R7, and R ₈ , repeat units m and n, and groups a, b, c, d, e, f, A, B, X, and Y. In some embodiments m is an integer greater than or equal to one; n is 0, 1, or 2; Ri, R ₂ , R , R4, R5, R5, R7, and R ₈ , may be, independently, hydrogen, substituted or unsubstituted C4 or greater alkyl, substituted or unsubstituted C4 or greater alkenyl, substituted or unsubstituted C4 or greater alkynyl, or C5 or greater cycloalkyl; a, b, c, and d are independently, integers greater than or equal to 3; e and / are integers greater than or equal to zero; X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and A and B may be, independently, either S or O.

[51] In some embodiments, at least one of Ri or R ₂ ; one of R or R4; one of R5 or R5; and one of R7 or R ₈ is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, or cycloalkyl. In some embodiments, if any of Ri, R ₂ , R ₃ , or R4 is hydrogen, then none of R5, R5, R7, or R ₈ are hydrogen. In some embodiments, if any of R5, R5, R7, or R ₈ is hydrogen, then none of Ri, R2, R ₃ , or R4 are hydrogen. In some embodiments, e and / cannot both be 0. In some embodiments, if either e or / is 0, then c and d, independently, are integers greater than or equal to 5. In some embodiments, the polymer has a molecular weight greater than 10,000.

Structure 5 :

Isolating polymer

[52] In some embodiments the OSC polymer is blended with an isolating polymer. In some embodiments, the isolating polymer is a non-conjugated polymer. In some embodiments, the isolating polymer has a non-conjugated backbone and conjugated side-chains. Blending with an isolating polymer that is non-conjugated or has a non-conjugated backbone avoids phase separation that can occur when the OSC is blended with a conjugated polymer. In some embodiments, the isolating polymer is not a semi-conducting polymer.

[53] In some embodiments an isolating polymer is blended with the OSC polymer to prevent oxidation of the OSC. In some embodiments, the isolating polymer is selected from polyacrylonitrile (PAN), alkyl substituted polyacrylonitrile (R-PAN), polyethylene (PE) and its copolymer, polystyrene, polystyrene-co-acrylonitrile, variants of polydimethylsiloxane (PDMS), polysulfonate, polyvinylacetate, polycarbonate, polypropylene, poly(methyl methacrylate), polyamide, polyphenylene sulfide, and elastomers such as a polymethylmethacylate-block- polybutylacrylate (PMMA-b-PBA). In some embodiments, the isolating polymer is polyacrylonitrile.

[54] In some embodiments, the isolating polymer is polystyrene, or derivatives of polystyrene.

The use of polystyrene as the isolating polymer may enable large-scale production of OSC devices. Further, polystyrene enables pre-aggregation and better alignment of the semiconductor.

[55] In some embodiments the isolating polymer has a molecular weight of 1,000, 2,000, 3,000, 4,000, 5,000, 10,000, 15,000, 20,000, 25,000, 35,000, 45,000, 50,000, 75,000, 100,000, 125,000, 150,000, 175,000, 200,000, 225,000, 250,000, or any range defined by any two of those endpoints. In some embodiments, the molecular weight of the isolating polymer is 5,000 or more. In some embodiments, the molecular weight of the isolating polymer is 10,000 or more. In some embodiments, the molecular weight of the isolating polymer is between 50,000 and 200,000.

Polymer blend

[56] In some embodiments, the performance of a device comprising the OSC polymer can be improved by blending the OSC polymer with another polymer. In some embodiments, the OSC polymer is blended with the isolating polymer in a solvent. Another advantage of the polymers such as those in structures 1-4 is that they can be processed easily in non-halogenated solvents. In some embodiments, the non-halogenated solvent is used to dissolve the mixture of OSC polymers with the isolating polymer. In some embodiments, the non-halogenated solvent is selected from w-xylene, o-xylene, ^-xylene, toluene, tetralin, cis-decalin, trans-decalin, mesitylene, cyclooctane, and bicyclohexyl. In some embodiments, a mixture of more than one solvent may be used.

[57] In some embodiments, the isolating polymer is polystyrene, and the polystyrene plus the non- halogenated solvent enables pre-aggregation and better alignment of the semiconductor.

[58] In some embodiments the weight ratio of the OSC polymer to the isolating polymer is 95:5, 90: 10, 85: 15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 60:40, 65:35, 70:30, 75:25, 80:20, 85: 15, 90: 10, 95:5, or any range defined by any two of those endpoints.

[59] In some embodiments, the blending of an isolating polymer with the OSC polymer can improve performance when the polymer is annealed in air and when the polymer is stored in air.

[60] FIG. 2 shows a flow chart for an exemplary method of fabricating an organic semiconductor device. At step 100, the organic semiconductor polymer is blended with the isolating polymer in an organic solvent. At step 200, a thin film of the blended polymer is deposited over a substrate. Optionally, at step 300, the thin film is thermally annealed. In some embodiments, the thermal annealing is performed at a temperature of 100 °C to 180 °C in air.

Mechanisms

[61] The performance of an OSC device is usually evaluated by several parameters, including charge carrier mobility, current On/Off ratio, threshold voltage, and the magnitude of the On current. In some applications, it is useful to achieve high parameters from a solution deposition process with a minimum number of processing steps. Such applications include preparing stable inks or formulations of the polymeric semiconducting materials. Besides intrinsic properties of OSC materials, several other factors can significantly affect the performance OSC materials in real applications. One of those is the possibility an unwanted decrease in device performance of OSC materials after thermal annealing. Thermal annealing is done to promote chain alignment and induce higher performance. However, annealing of some semi-conducting polymers in the presence of oxygen can cause a reduction in performance when compared to performance of devices annealed in nitrogen. The article "Enhancing Crystalline Structural Orders of Polymer Semiconductors for Efficient Charge Transport via Polymer-Matrix-Mediated Molecular Self- Assembly", Advanced Materials (Weinheim, Germany) (2016), 28(31), 6687-6694, proposes blending a low molecular weight donor-acceptor OSC polymer, such as PI (structure 7), with a non-conjugated polymer polyacrylonitrile (structure 8) in a 60/40 wt% ratio (PI/PAN). The resulting OTFT devices exhibited mobility of 16 cm ² V ^_1 s ^_1 and current On/Off ratio of greater than 10 ⁸ . This mobility is about one order of magnitude higher than that produced in devices made from the pure PI polymer. The article proposed a possible mechanism of enhancing crystalline structural order of this low molecular weight donor-acceptor OSC polymer PI by blending with PAN.

Structure 7: Structure 8:

[62] Despite the increase in mobility and On/Off ratio, the PAN used in the Advanced Materials article has a MW of 150,000 (Aldrich), and this high molecular weight PAN results in limited solubility in organic solvents, even in hot chloroform. This makes the real weight ratio of the OSC polymer to PAN in the OTFTs devices disclosed in the Advanced Materials article unreliable.

[63] It was found that the device performance, such as current On/Off ratio and the hole mobility, of the polymers having the structure shown in structures 3 and 4 decreased significantly after thermal annealing in air, as compared to similar devices that were thermally annealed under nitrogen (Tables 1 and 2, Figure 1).

[64] Various mechanisms are described herein that can be used to prevent air oxidation of OSC polymers. In some embodiments, a dielectric polymer is blended with organic semiconducting polymers. These mechanisms are applicable to devices made with any semiconducting polymer that is susceptible to performance degradation upon heating at elevated temperatures in air. The mechanisms described may work alone, or in combination with other mechanisms.

[65] In some embodiments, a first mechanism involves forming an encapsulating layer around the OSC to reduce air contact. In the first mechanism, an isolating polymer forms an encapsulating layer around the OSC materials to reduce the air contact, which in turn reduces the probability of oxidation of the OSC polymer. This mechanism provides localized encapsulation for the OSC polymer without creating OSC polymer micro-interfacial interactions or preventing continuous electronic pathways across each device.

[66] In some embodiments, a second mechanism involves blending a high-crystallinity polymer with the OSC polymer. This mechanism enhances crystalline structural order of the OSC polymers, which in turn increases packing alignment and facilitates better charge transport between chains and across domains. This mechanism allows the high-crystallinity polymers to help increase the thermal stability of the OSC polymer by blending.

[67] In some embodiments, a third mechanism involves sacrificial preferential oxidation of an isolating polymer. The sacrificial preferential oxidation reduces oxidation of the OSC materials. In some embodiments, the isolating polymer is polyacrylonitrile. In some embodiments, the isolating polymer is polystyrene. In some embodiments, the isolating polymer can be any polymer that oxidizes more readily than the semiconducting polymer and does not produce oxidation products that adversely affect charge transport. [68] In some embodiments, the oxidation products themselves may be conducting or semiconducting polymers. These may help bridge gaps and transport electrons between OSC polymer chains. In this mechanism, the isolating polymer can be oxidized to a conjugated structure to help increase the thermal stability of an OSC polymer by blending. In some embodiments, an oxidative-induction time (OIT) technique is used to determine which polymer will oxidize preferentially. Oxidative-induction time can be measured using differential scanning calorimetry (DSC) with continuous oxygen flow.

[69] In some embodiments, the isolating polymer is polyacrylonitrile. In some embodiments, blending PAN polymer with one of the OSC polymers shown in structures 3 or 4 produces high device performance. The high device performance is due to the prevention of oxidation of the OSC polymer by air using one of the two possible mechanistic routes for PAN oxidation

[70] Path one below shows one possible mechanism for the cyclization of PAN. In the mechanism of path one, the PAN is first cyclized then dehydrogenated. Path two shows another possible mechanism for the cyclization of PAN. In the mechanism of path two, the PAN is first dehydrogenated then cyclized.

DPAN

[71] IR data of PAN before and after heating at 200 °C for one hour indicate that most of the PAN is converted to this linear conjugated polymer DPAN. This IR data is consistent with solid ¾ NMR studies. [72] To further investigate the possible mechanism to prevent or reduce air oxidation of OSC polymers through blending with PAN, both a low molecular weight PAN (Mw = 80,000) and the Aldrich PAN (Mw = 150,000) were used. The lower molecular weight PAN improved solubility and enabled calculation of a more reliable weight ratio of the OSC polymer to the PAN polymer. This provides an accurate correlation of the weight ratio to the device performance.

[73] In one experiment, the PAN as shown in structures 9 and 10 were used to test the oxidation and cyclization mechanisms. Structure 9 is an alpha substituted PAN, in which R is an alkyl group. Structure 10 is a beta substituted PAN, in which R is an alkyl group. It was determined that both structures 9 and 10 are able to cyclize. Further, because alpha substituted PAN (structure 9) does not have a free hydrogen on the carbon backbones, only beta substituted PAN (structure 10) is able to dehydrogenate on the primary backbone.

Structure 9: Structure 10:

Experimental

[74] To investigate the possible mechanisms, PAN was blended with the OSC polymers shown in structures 3 and 4 in different ratios and the resulting solid mixtures were heated at different temperatures and time periods in air or under nitrogen protection. Solid state NMR, IR spectrometer, and thermogravimetric and differential scanning calorimetry (TG-DSC) studies on them were used to investigate the possible mechanism.

[75] In one experiment, a dialkylated tetrathienoacene copolymer with thiophene was deposited from a dichlorobenzene solution to yield ordered films with a short π-π distance of 3.76 A, with a field-effect hole mobility that exceeds 0.4 cm ² V ¹ s ¹ . An example of a dialkylated tetrathienoacene copolymer with thiophene is shown in Structure 1 1.

Structure 1 1 :

[76] In one experiment, the polymer shown in structure 3 was annealed in various atmospheres at 120 °C and 160°C. Table 1 shows OTFT device performance data for the polymer shown in structure 3. The polymer was cast from 10 mg/mL solution in tetrahydronaphthalene after thermal annealing in different atmospheres at 120 °C and 160 °C.

Table 1

[77] In another experiment, the polymer shown in structure 4 was annealed in various atmospheres at 120 °C and 160 °C. Table 2 shows OTFT device performance data for the polymer having the structure as shown in structure 4. The polymer was cast from 10 mg/mL solution in tetrahydronaphthalene after thermal annealing in different atmospheres at 120 °C and 160 °C.

Table 2

[78] In another experiment, the polymer shown in structure 3 was stored in ambient conditions and performance was monitored over time. Table 3 shows OTFT device performance data for the polymer having the structure as shown in structure 3. As shown in Table 3, there was a drop in average mobility over time. FIG. 1 shows a graphical representation of the device performance for the polymer shown in structure 3 after being thermally annealed in nitrogen or air.

Table 3

0.25 0.42 ~10 ⁶ -6.6

1 0.32 ~10 ⁶ 0.6

14 0.26 ~10 ⁶ -6.0

45 0.26 ~10 ⁶ -12.6

[79] In another experiment, the polymer shown in structure 4 was stored in ambient conditions and performance was monitored over time. Table 4 shows OTFT device performance data for the polymer having the structure as shown in structure 4. As shown in Table 4, there was a drop in average mobility over time.

Table 4

[80] In another experiment, polyacrylonitrile (PAN) was used as the isolating polymer.

Polyacrylonitrile was demonstrated to work with other OSC polymers. Table 5 shows device data for various blend ratios of the polymer according to structure 4 with polyacrylonitrile after thermal annealing in air at 160 °C for 10 min. As shown in Table 5, device data reaches a peak between 80:20 and 40:60. Higher ratios of polyacrylonitrile may dilute the semiconducting polymer and reduce the charge transport. Lower ratios of polyacrylonitrile result in device degradation in air at elevated temperatures. As shown in Table 5, at a ratio of 60:40, the OSC device exhibits a significant increase in On/Off ratio and hole mobility compared to a ratio of 100:0, which corresponds to a pure semiconducting polymer. The ratios in Table 5 are weight ratios.

Table 5

[81] In Tables 3-5, μ^ ^νε represents average charge carrier mobility in units of cm ² V ^"1 s ^"1 , μι ¹¹³ represents maximum charge carrier mobility in units of cm ² V ^"1 s ^"1 , I ₀ n/I ₀ ff ^ave represents average current On/Off ratio, and VTh ^ave represents threshold voltage in units of Volts.

[82] In another experiment, an organic thin-film transistor (OTFT) was formed with a bottom-gate top-contact configuration, with 100 nm thick gold used as drain/source electrodes. The device had a width of 1000 μπι and a length of μπι. The substrate comprised a 300 nm thermal grown SiC /Si with a spin-coated octadecyl-trimethoxylsiline (OTS) treatment. The polymer solution process used o-dichlorobenzene as a solvent at a concentration of 10 mg/mL. The solution was heated at 80 °C overnight. The solution was preheated to 80 °C before spin coating to prevent precipitation of polyacrylonitrile. The spin coating was done by flooding the surface for 1 minute prior to spinning at 1000 rpm for 1 minute. Following the spin coating, thermal annealing was done at a temperature of 120 °C to 160 °C for 10 minutes in experiment specific atmosphere (air, nitrogen, or vacuum). Measurements were taken using a Keithley 2634B two channel semiconductor measurement unit at room temperature and ambient conditions.

[83] As used herein, "polystyrene" includes any reasonable substitutes. "Polystyrene" may include compounds sold commercially as polystyrene, including copolymers and elastomers. Examples of polystyrene may include high impact polystyrene (HIPS), expended polystyrene (EPS), syndiotactic polystyrene (SPS), acrylonitrile-butadiene-styrene copolymers (ABS), styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene-butadiene-styrene block copolymers (SEBS), styrene-acrylonitrile copolymers (SAN), and methyl methacrylate- butadiene-styrene (MBS).

[84] Unless otherwise specified, molecular weights referred to herein are number average molecular weights (M _n ). The molecular weights referred to herein for organic semiconductor polymers are number average molecular weights determined by gel permeation chromatography (GPC) in 1,2,4-trichlorobenzene at 200 °C with a flow rate of 1 mL/min, and referenced to polystyrene standards. The molecular weights referred to herein for isolating polymers are obtained from packaging or data sheets from the polymer supplier, and may be number average molecular weights or weight average molecular weights (M _w ). The PDI (polydispersity index, M _w / Mn) for the isolating polymers is often close to 1, such that M _n is about equal to M _w . So, it is reasonable to refer to the molecular weights of the isolating polymers as number average.

[85] As used herein, a "derivative" of a compound is a similar compound derived from the compound by a chemical reaction.

[86] As used herein, the term "room temperature" is 20-25 °C.

[87] The term "alkyl" refers to a monoradical branched or unbranched saturated hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. This term is exemplified by groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-hexyl, n-decyl, tetradecyl, and the like.

[88] The term "substituted alkyl" refers to: (1) an alkyl group as defined above, having 1, 2, 3, 4 or 5 substituents, typically 1 to 3 substituents, selected from the group consisting of alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S0 ₂ -alkyl, SO2- aryl and -SC -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkyl group as defined above that is interrupted by 1-10 atoms independently chosen from oxygen, sulfur and Ra, where Ra is chosen from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and heterocyclyl. All substituents may be optionally further substituted by alkyl, alkoxy, halogen, CF ₃ , amino, substituted amino, cyano, or -S(0) _n Rso, in which Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (3) an alkyl group as defined above that has both 1, 2, 3, 4 or 5 substituents as defined above and is also interrupted by 1-10 atoms as defined above.

[89] The term "alkylene" refers to a diradical of a branched or unbranched saturated hydrocarbon chain, having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, typically 1-10 carbon atoms, more typically 1, 2, 3, 4, 5 or 6 carbon atoms. This term is exemplified by groups such as methylene (-CH2-), ethylene (-CH2CH2-), the propylene isomers (e.g., -CH2CH2CH2- and -CH(CH ₃ )CH ₂ -) and the like.

[90] The term "substituted alkylene" refers to: (1) an alkylene group as defined above having 1, 2, 3, 4, or 5 substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S02-alkyl, -S02-aryl and -S02-heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF ₃ , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or (2) an alkylene group as defined above that is interrupted by 1-20 atoms independently chosen from oxygen, sulfur and NRa- where Ra is chosen from hydrogen, optionally substituted alkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl and heterocyclyl, or groups selected from carbonyl, carboxyester, carboxyamide and sulfonyl; or (3) an alkylene group as defined above that has both 1, 2, 3, 4 or 5 substituents as defined above and is also interrupted by 1-20 atoms as defined above. Examples of substituted alkylenes are chloromethylene (-CH(Cl)-), aminoethylene (-CH(NH ₂ )CH ₂ -), methylaminoethylene (-CH( HMe)CH ₂ -), 2-carboxypropylene isomers (-CH ₂ CH(C0 ₂ H)CH ₂ - ), ethoxyethyl (-CH ₂ CH ₂ 0-CH ₂ CH ₂ -), ethylmethylaminoethyl (-CH ₂ CH ₂ N(CH )CH ₂ CH ₂ -), and the like.

[91] The term "aralkyl" refers to an aryl group covalently linked to an alkylene group, where aryl and alkylene are defined herein. "Optionally substituted aralkyl" refers to an optionally substituted aryl group covalently linked to an optionally substituted alkylene group. Such aralkyl groups are exemplified by benzyl, phenylethyl, 3-(4-methoxyphenyl)propyl, and the like.

[92] The term "alkoxy" refers to the group R-0-, where R is an optionally substituted alkyl or optionally substituted cycloalkyl, or R is a group -Y-Z, in which Y is optionally substituted alkylene and Z is optionally substituted alkenyl, optionally substituted alkynyl; or optionally substituted cycloalkenyl, where alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl are as defined herein. Typical alkoxy groups are optionally substituted alkyl-O- and include, by way of example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n- pentoxy, n-hexoxy, 1,2-dimethylbutoxy, trifluoromethoxy, and the like.

[93] The term "alkylthio" refers to the group Rs-S- where Rs is as defined for alkoxy.

[94] The term "alkenyl" refers to a monoradical of a branched or unbranched unsaturated hydrocarbon group typically having from 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms and having 1-6, typically 1, double bond (vinyl). Typical alkenyl groups include ethenyl or vinyl (-CH=CH ₂ ), 1 -propylene or allyl (- CH ₂ CH=CH ₂ ), isopropylene (-C(CH ₃ )=CH ₂ ), bicyclo[2.2.1]heptene, and the like. In the event that alkenyl is attached to nitrogen, the double bond cannot be alpha to the nitrogen.

[95] The term "substituted alkenyl" refers to an alkenyl group as defined above having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, aminocarbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S0 ₂ -alkyl, S0 ₂ - aryl and -S0 ₂ -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[96] The term "alkynyl" refers to a monoradical of an unsaturated hydrocarbon, typically having from 2 to 20 carbon atoms, more typically 2 to 10 carbon atoms and even more typically 2 to 6 carbon atoms and having at least 1 and typically from 1-6 sites of acetylene (triple bond) unsaturation. Typical alkynyl groups include ethynyl, (-C≡CH), propargyl (or prop-l-yn-3-yl, - CH ₂ C≡CH), and the like. In the event that alkynyl is attached to nitrogen, the triple bond cannot be alpha to the nitrogen.

[97] The term "substituted alkynyl" refers to an alkynyl group as defined above having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, aminocarbonylamino, hetero aryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -S0 ₂ -alkyl, S0 ₂ -aryl and -S0 ₂ -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF3, amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[98] The term "aminocarbonyl" refers to the group -C(0) RNRN where each RN is independently hydrogen, alkyl, aryl, heteroaryl, heterocyclyl or where both RN groups are joined to form a heterocyclic group (e.g., morpholino). Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[99] The term "acylamino" refers to the group - RNCOC(0)R where each RNCO is independently hydrogen, alkyl, aryl, heteroaryl, or heterocyclyl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[100] The term "acyloxy" refers to the groups -0(0)C-alkyl, -0(0)C-cycloalkyl, -0(0)C-aryl, - 0(0)C-heteroaryl, and -0(0)C-heterocyclyl. Unless otherwise constrained by the definition, all substituents may be optionally further substituted by alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[101] The term "aryl" refers to an aromatic carbocyclic group of 6 to 20 carbon atoms having a single ring (e.g., phenyl) or multiple rings (e.g., biphenyl), or multiple condensed (fused) rings (e.g., naphthyl or anthryl). Typical aryls include phenyl, naphthyl and the like.

[102] Unless otherwise constrained by the definition for the aryl substituent, such aryl groups can optionally be substituted with from 1 to 5 substituents, typically 1 to 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2- alkyl, SC -aryl and -SC -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[103] The term "aryloxy" refers to the group aiyl-O- wherein the aryl group is as defined above, and includes optionally substituted aryl groups as also defined above. The term "arylthio" refers to the group aryl-S-, where aryl is as defined as above.

[104] The term "amino" refers to the group -NH2. [105] The term "substituted amino" refers to the group - R _W R _W where each R _w is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, carboxyalkyl (for example, benzyloxycarbonyl), aryl, heteroaryl and heterocyclyl provided that both R _w groups are not hydrogen, or a group -Y-Z, in which Y is optionally substituted alkylene and Z is alkenyl, cycloalkenyl, or alkynyl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[106] The term "carboxyalkyl" refers to the groups -C(0)0-alkyl or -C(0)0-cycloalkyl, where alkyl and cycloalkyl, are as defined herein, and may be optionally further substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, in which Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[107] The term "cycloalkyl" refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings. Such cycloalkyl groups include, by way of example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and the like, or multiple ring structures such as adamantanyl, bicyclo[2.2.1]heptane, 1,3,3- trimethylbicyclo[2.2.1]hept-2-yl, (2,3,3-trimethylbicyclo[2.2.1]hept-2-yl), or carbocyclic groups to which is fused an aryl group, for example indane, and the like.

[108] The term "cycloalkenyl" refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings with at least one double bond in the ring structure.

[109] The terms "substituted cycloalkyl" or "substituted cycloalkenyl" refer to cycloalkyl or cycloalkenyl groups having 1, 2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO- heteroaryl, -SC -alkyl, SC -aryl and -SC -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1, 2, or 3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[110] The term "halogen" or "halo" refers to fluoro, bromo, chloro, and iodo.

[Ill] The term "acyl" denotes a group -C(0)Rco, in which Rco is hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclyl, optionally substituted aryl, and optionally substituted heteroaryl.

[112] The term "heteroaryl" refers to a radical derived from an aromatic cyclic group (i.e., fully unsaturated) having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms and 1, 2, 3 or 4 heteroatoms selected from oxygen, nitrogen and sulfur within at least one ring. Such heteroaryl groups can have a single ring (e.g., pyridyl or furyl) or multiple condensed rings (e.g., indolizinyl, benzothiazolyl, or benzothienyl). Examples of heteroaryls include, but are not limited to, [l,2,4]oxadiazole, [l,3,4]oxadiazole, [l,2,4]thiadiazole, [l,3,4]thiadiazole, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine, naphthylpyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, phenanthroline, isothiazole, phenazine, isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline, triazole, oxazole, thiazole, naphthyridine, and the like as well as N-oxide and N- alkoxy derivatives of nitrogen containing heteroaryl compounds, for example pyridine-N-oxide derivatives.

[113] Unless otherwise constrained by the definition for the heteroaryl substituent, such heteroaryl groups can be optionally substituted with 1 to 5 substituents, typically 1 to 3 substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, aminocarbonylamino, heteroaryl oxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO- heteroaryl, -SC -alkyl, SC -aryl and -SC -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[114] The term "heteroaralkyl" refers to a heteroaryl group covalently linked to an alkylene group, where heteroaryl and alkylene are defined herein. "Optionally substituted heteroaralkyl" refers to an optionally substituted heteroaryl group covalently linked to an optionally substituted alkylene group. Such heteroaralkyl groups are exemplified by 3-pyridylmethyl, quinolin-8-yl ethyl, 4- methoxythiazol-2-ylpropyl, and the like.

[115] The term "heteroaryloxy" refers to the group heteroaryl-O-

[116] The term "heterocyclyl" refers to a monoradical saturated or partially unsaturated group having a single ring or multiple condensed rings, having from 1 to 40 carbon atoms and from 1 to 10 hetero atoms, typically 1, 2, 3 or 4 heteroatoms, selected from nitrogen, sulfur, phosphorus, and/or oxygen within the ring. Heterocyclic groups can have a single ring or multiple condensed rings, and include tetrahydrofuranyl, morpholino, piperidinyl, piperazino, dihydropyridino, and the like.

[117] Unless otherwise constrained by the definition for the heterocyclyl substituent, such heterocyclyl groups can be optionally substituted with 1, 2, 3, 4 or 5, and typically 1, 2 or 3 substituents, selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy, heteroaryl, amino sulfonyl, aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, - SO-aryl, -SO-heteroaryl, -SC -alkyl, -SC -aryl and -SC -heteroaryl. Unless otherwise constrained by the definition, all substituents may optionally be further substituted by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF , amino, substituted amino, cyano, and -S(0) _n Rso, where Rso is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.

[118] The term "thiol" refers to the group -SH.

[119] The term "substituted alkylthio" refers to the group -S-substituted alkyl. [120] The term "heteroarylthiol" refers to the group -S-heteroaryl wherein the heteroaryl group is as defined above including optionally substituted heteroaryl groups as also defined above.

[121] The term "sulfoxide" refers to a group -S(0)Rso, in which Rso is alkyl, aryl, or heteroaryl.

"Substituted sulfoxide" refers to a group -S(0)Rso, in which Rso is substituted alkyl, substituted aryl, or substituted heteroaryl, as defined herein.

[122] The term "sulfone" refers to a group -S(0)2Rso, in which Rso is alkyl, aryl, or heteroaryl.

"Substituted sulfone" refers to a group - S(0)2Rso, in which Rso is substituted alkyl, substituted aryl, or substituted heteroaryl, as defined herein.

[123] The term "keto" refers to a group -C(O)-.

[124] The term "thiocarbonyl" refers to a group -C(S)-.

[125] The term "carboxy" refers to a group -C(0)OH.

[126] The term "conjugated group" is defined as a linear, branched or cyclic group, or combination thereof, in which p-orbitals of the atoms within the group are connected via derealization of electrons and wherein the structure can be described as containing alternating single and double or triple bonds and may further contain lone pairs, radicals, or carbenium ions. Conjugated cyclic groups may comprise both aromatic and non-aromatic groups, and may comprise polycyclic or heterocyclic groups, such as diketopyrrolopyrrole. Ideally, conjugated groups are bound in such a way as to continue the conjugation between the thiophene moieties they connect.

[127] The term "or," as used herein, is inclusive; more specifically, the phrase "A or B" means "A, B, or both A and B." Exclusive "or" is designated herein by terms such as "either A or B" and "one of A or B," for example. The indefinite articles "a" and "an" and the definite article "the" to describe an element or component means that one or at least one of these elements or components is present, unless otherwise stated in specific instances.

[128] Where a range of numerical values is recited herein, comprising upper and lower values, unless otherwise stated in specific circumstances, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the claims be limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed. Finally, when the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Regardless of whether a numerical value or end-point of a range recites "about," the numerical value or end-point of a range is intended to include two embodiments: one modified by "about," and one not modified by "about."

[129] As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. When the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Whether or not a numerical value or end-point of a range in the specification recites "about," the numerical value or end-point of a range is intended to include two embodiments: one modified by "about," and one not modified by "about."

[130] The term "wherein" is used as an open-ended transitional phrase, to introduce a recitation of a series of characteristics of the structure.

[131] As used herein, "comprising" is an open-ended transitional phrase. A list of elements following the transitional phrase "comprising" is a non-exclusive list, such that elements in addition to those specifically recited in the list may also be present.

[132] The present disclosure has been described above with the aid of functional building blocks illustrating the implementation of specified functions and relationships thereof. The boundaries of these functional building blocks have been arbitrarily defined herein for the convenience of the description. Alternate boundaries can be defined so long as the specified functions and relationships thereof are appropriately performed.

[133] The foregoing description of the specific embodiments will so fully reveal the general nature of the disclosure that others can, by applying knowledge within the skill of the art, readily modify and/or adapt for various applications such specific embodiments, without undue experimentation, without departing from the general concept of the present disclosure. Therefore, such adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. It is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation, such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of such teachings and guidance.

] The breadth and scope of the present disclosure should not be limited by any of the above- described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.