ORGANIC SEMICONDUCTOR COMPOSITIONS

Abstract

The present invention relates to organic copolymers and organic semiconducting compositions comprising these materials, including layers and devices comprising such organic semiconductor compositions. The invention is also concerned with methods of preparing such organic semiconductor compositions and layers and uses thereof. The invention has application in the field of printed electronics and is particularly useful as a semiconducting material for use in formulations for organic thin film transistor (OTFT) backplanes for displays, integrated circuits, organic light emitting diodes (OLEDs), photodetectors, organic photovoltaic (OPV) cells, sensors, memory elements and logic circuits.

Claims

1. A Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) comprising a mixture of at least one BXBX monomer unit having the Formula (A) and at least one monomer unit having the Formula (B): ##STR00054## wherein Y.sup.1 and Y.sup.2 are independently S or Se; k and l are independently 0 or 1 wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, independently represents hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; a C.sub.2-C.sub.10 alkynyl group substituted with a SiH.sub.2R.sup.22 group, a C.sub.2-C.sub.10 alkynyl substituted with a SiHR.sup.22R.sup.23 group, or a C.sub.2-C.sub.10 alkynyl substituted with a Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z group; wherein each R.sup.22 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; each R.sup.23 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; R.sup.24 is independently selected from the group consisting of hydrogen, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group, a substituted C.sub.5-C.sub.20 aryl group, a substituted or unsubstituted C.sub.6-C.sub.20 arylalkylene group, an acetyl group, a substituted or unsubstituted C.sub.3-C.sub.20 heterocyclic ring comprising at least one of O, N, S and Se in the ring; wherein x=1 or 2; y=1 or 2; z=0 or 1; and (x+y+z)=3; wherein each of R.sup.15, R.sup.16, R.sup.18, R.sup.19 and R.sup.20 independently represent H or optionally substituted C.sub.1-C.sub.40 carbyl or hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.17 represents a halogen atom, H or optionally substituted C.sub.1-C.sub.40 carbyl or C.sub.1-C.sub.40 hydrocarbyl group optionally comprising one or more heteroatoms; wherein k and l are independently 0 or 1; wherein at least two of R.sup.1, R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.9, R.sup.10, and R.sup.12, are a bond, represented by *, to another monomer unit having the Formula (A) or (B); and wherein Ar.sub.1, Ar.sub.2 and Ar.sub.3, which may be the same or different, each represent, independently if in different repeat units, an optionally substituted C.sub.6-40 aromatic group (mononuclear or polynuclear), wherein preferably at least one of Ar.sub.1, Ar.sub.2 and Ar.sub.3 is substituted with at least one polar or polarising groups; and wherein the copolymer is a random copolymer.

2. A PAHC according to claim 1, comprising at least 20 to 40% of monomer (A) and at least 60 to 80% of monomer (B), based on the total of all monomer units (A) and (B) in the copolymer.

3. A PAHC according to claim 1, wherein monomer unit (B) having the, Ar.sub.1, Ar.sub.2 and Ar.sub.3, which may be the same or different, each representing, independently if in different repeat units, an optionally substituted C.sub.6-20 aromatic group (mononuclear or polynuclear), wherein at least one of Ar.sub.1, Ar.sub.2 and Ar.sub.3 is substituted with at least one or more polar or polarising group, and n=1 to 20.

4. A PAHC according to claim 3, wherein Ar.sub.1, Ar.sub.2 and Ar.sub.3 are all phenyl which may be independently substituted with 1 or 2 groups selected from methoxy, cyanomethyl, CN and mixtures thereof, and n=1 to 10.

5. A PAHC according to claim 1, further comprising one or more monomers (C), (D), (D) and/or (E): ##STR00055## wherein each R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, each of which may be the same or different, is selected from the same group as R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, as defined in claim 1; wherein n=1 to 3; and wherein monomer (A) is present in an amount of at least 20 wt. %; monomer (B) is present in an amount of at least 60 wt. % and the remainder is comprised of monomers (C), (D), (D) and/or (E), based on the total weight of all monomer units in the copolymer.

6. A Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) comprising a mixture of at least one BXBX monomer unit having the Formula (A) and at least one monomer unit having the Formula (K): ##STR00056## wherein Y.sup.1 and Y.sup.2 are independently S or Se; k and l are independently 0 or 1 wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12; which may be the same or different, independently represents hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; a C.sub.2-C.sub.10 alkynyl group substituted with a SiH.sub.2R.sup.22 group, a C.sub.2-C.sub.10 alkynyl substituted with a SiHR.sup.22R.sup.23 group, or a C.sub.2-C.sub.10 alkynyl substituted with a Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z group; wherein each R.sup.22 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; each R.sup.23 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; R.sup.24 is independently selected from the group consisting of hydrogen, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group, a substituted C.sub.5-C.sub.20 aryl group, a substituted or unsubstituted C.sub.6-C.sub.20 arylalkylene group, an acetyl group, a substituted or unsubstituted C.sub.3-C.sub.20 heterocyclic ring comprising at least one of O, N, S and Se in the ring; wherein x=1 or 2; y=1 or 2; z=0 or 1; and (x+y+z)=3; wherein each of R.sup.15, R.sup.16, R.sup.18, R.sup.19 and R.sup.20 independently represent H or optionally substituted C.sub.1-C.sub.40 carbyl or hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.17 represents a halogen atom, H or optionally substituted C.sub.1-C.sub.40 carbyl or C.sub.1-C.sub.40 hydrocarbyl group optionally comprising one or more heteroatoms; wherein k and l are independently 0 or 1; wherein at least two of R.sup.1, R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.9, R.sup.10, and R.sup.12, are a bond, represented by *, to another monomer unit having the Formula (A) or (K); and wherein each R.sup.1, R.sup.2, R.sup.3 and R.sup.4, each of which may be the same or different, is selected from the same group as R.sup.1, R.sup.2, R.sup.3, R.sup.4; and wherein preferably at least one of the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4 is a polar group or polarising group and for the monomer group (K), * represents a bond to another monomer unit having the Formula (A) or (K); and n=1 to 3.

7. A PAHC according to claim 6, comprising at least 20 to 40% of monomer (A) and at least 60 to 80% of monomer (K), based on the total of all monomer units (A) and (K) in the copolymer.

8. A PAHC according to claim 6, wherein at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4 is a polar group or polarising group, and n=1 to 20.

9. A PAHC according to claim 8, wherein one or 2 of the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected from methoxy, cyanomethyl, CN and mixtures thereof, and n=1 to 10.

10. A PAHC according to claim 6, further comprising one or more monomers (L), (M), (M) and/or (N): ##STR00057## wherein each R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, each of which may be the same or different, is selected from the same group as R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7, as defined in claim 1; wherein n=1 to 3; Ar.sub.1, Ar.sub.2 and Ar.sub.3, which may be the same or different, each represent, independently an optionally substituted C.sub.6-40 aromatic group (mononuclear or polynuclear); and wherein monomer (A) is present in an amount of at least 20 wt. %; monomer (K) is present in an amount of at least 60 wt. % and the remainder is comprised of monomers (L), (M), (M) and/or (N), based on the total weight of all monomer units in the copolymer.

11. A Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) comprising a mixture of at least one BXBX monomer unit having the Formula (A) and at least one monomer unit having the Formula (O/O): ##STR00058## Formula (O/O)-represents cis and/or trans-indenofluorene isomers wherein Y.sup.1 and Y.sup.2 are independently S or Se; k and l are independently 0 or 1; wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12; which may be the same or different, independently represents hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; a C.sub.2-C.sub.10 alkynyl group substituted with a SiH.sub.2R.sup.22 group, a C.sub.2-C.sub.10 alkynyl substituted with a SiHR.sup.22R.sup.23 group, or a C.sub.2-C.sub.10 alkynyl substituted with a Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z group; wherein each R.sup.22 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; each R.sup.23 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; R.sup.24 is independently selected from the group consisting of hydrogen, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group, a substituted C.sub.5-C.sub.20 aryl group, a substituted or unsubstituted C.sub.6-C.sub.20 arylalkylene group, an acetyl group, a substituted or unsubstituted C.sub.3-C.sub.20 heterocyclic ring comprising at least one of O, N, S and Se in the ring; wherein x=1 or 2; y=1 or 2; z=0 or 1; and (x+y+z)=3; wherein each of R.sup.15, R.sup.16, R.sup.18, R.sup.19 and R.sup.20 independently represent H or optionally substituted C.sub.1-C.sub.40 carbyl or hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.17 represents a halogen atom, H or optionally substituted C.sub.1-C.sub.40 carbyl or C.sub.1-C.sub.40 hydrocarbyl group optionally comprising one or more heteroatoms; wherein k and l are independently 0 or 1; wherein at least two of R.sup.1, R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.9, R.sup.10, and R.sup.12, are a bond, represented by *, to another monomer unit having the Formula (A) or (O); wherein monomer (O/O) is either the cis and/or trans-indenofluorene monomer and each R.sup.1, R.sup.2, R.sup.3 R.sup.4, R.sup.5, R.sup.6, R.sup.7, each of which may be the same or different, is selected from the same group as R.sup.1, R.sup.2, R.sup.3, R.sup.4 R.sup.6, R.sup.7 and wherein preferably at least one of the groups, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is a polar or polarising group and for the monomer group (O/O)* represents a bond to another monomer unit having the Formula (A) or (O/O); and n=1 to 3.

12. A PAHC according to claim 11, comprising at least 20 to 40% of monomer (A) and at least 60 to 80% of monomer (O), based on the total of all monomer units (A) and (O) in the copolymer.

13. A PAHC according to claim 11, wherein for the cis/trans-indenofluorene monomer (O/O), R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 which may be the same or different and at least one wherein preferably at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is substituted with at least one polar group or more polarising group, and n=1 to 20.

14. A PAHC according to claim 13, wherein one or 2 of the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are selected from methoxy, cyanomethyl, CN and mixtures thereof, and n=1 to 10.

15. A PAHC according to claim 11, further comprising one or more monomers (P), (Q) and/or (R): ##STR00059## wherein each R.sup.1, R.sup.2, R.sup.3 and R.sup.4, each of which may be the same or different, is selected from the same group as R.sup.1, R.sup.2, R.sup.3 and R.sup.4, already defined above; Ar.sub.1, Ar.sub.2 and Ar.sub.3, which may be the same or different, each represent, independently an optionally substituted C.sub.6-40 aromatic group (mononuclear or polynuclear). Preferably at least one of Ar.sub.1, Ar.sub.2 and Ar.sub.3 is substituted with at least one polar or more polarising group, and n=1 to 20, preferably 1 to 10 and more preferably 1 to 5. Preferably, at least one of Ar.sub.1, Ar.sub.2 and Ar.sub.3 is substituted with 1, 2, 3, or 4, more preferably 1, 2 or 3, more preferably 1 or 2, preferably 1 polar or more polarising group(s); n=1 to 3; and wherein monomer (A) is present in an amount of at least 20 wt. %; monomer (O) is present in an amount of at least 60 wt. % and the remainder is comprised of monomers (P), (Q) and/or (R), based on the total weight of all monomer units in the copolymer.

16. A PAHC according to claim 1, wherein R.sup.3?R.sup.10=a C.sub.1 to C.sub.14 alkyl group or optionally substituted C.sub.1 to C.sub.14 alkyl group.

17. A PAHC according to claim 1, wherein k=l=0 or 1.

18. (canceled)

19. A PAHC according to claim 1, wherein the copolymers have a number average molecular weight (Mn) of between 500 and 100,000.

20. A PAHC according to claim 1, wherein the copolymers are semiconducting copolymers having a permittivity at 1000 Hz of greater than 1.5, preferably between 3.4 and 8.

21. (canceled)

22. A PAHC according to claim 1, wherein at least one (and more preferably 2) of groups R.sup.1, R.sup.6, R.sup.7, and R.sup.12 are (tri-C.sub.1-20 hydrocarbylsilyl) C.sub.1-4 alkynyl groups, preferably (trihydrocarbylsilyl)ethynyl- groups. Preferably at least one pair of R.sup.1/R.sup.6 and/or R.sup.7/R.sup.12 are trihydrocarbylsilyl ethynyl groups.

23. A PAHC according to claim 1, wherein R.sup.1, R.sup.3, R.sup.6, R.sup.7, R.sup.9 and R.sup.12 are hydrogen.

24. A PAHC according to claim 1, wherein Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z is selected from the group consisting of trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylethylsilyl, diethylmethylsilyl, dimethylpropylsilyl, dimethylisopropylsilyl, dipropylmethylsilyl, diisopropylmethylsilyl, dipropylethylsilyl, diisopropylethylsilyl, diethylisopropylsilyl, triisopropylsilyl, trimethoxysilyl, triethoxysilyl, triphenylsilyl, diphenylisopropylsilyl, diisopropylphenylsilyl, diphenylethylsilyl, diethylphenylsilyl, diphenylmethylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

25. A PAHC according to claim 1, having the Formula (A1) or (A2) ##STR00060## wherein R.sup.25, R.sup.26 and R.sup.27 are independently selected from the group consisting of C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 alkenyl, preferably independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, 1-propenyl and 2-propenyl, more preferably ethyl, n-propyl and isopropyl;

26. A PAHC according to claim 3, wherein the one or more polar or polarising group(s) is independently selected from the group consisting of nitro group, nitrile group, C.sub.1-40 alkyl group substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; C.sub.1-40 alkoxy group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; C.sub.1-40 carboxylic acid group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; C.sub.2-40 carboxylic acid ester optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; sulfonic acid optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; sulfonic acid ester optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; cyanate group, isocyanate group, thiocyanate group, thioisocyanate group; and an amino group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; and combinations thereof.

27. An organic semiconductor composition comprising a PAHC according to claim 1 and a polyacene small molecule, wherein the PAHC has a permittivity at 1000 Hz of between 3.4 and 8.0 or between 3.4 and 4.5.

28. (canceled)

29. An organic semiconductor composition comprising a Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) according to claim 1, wherein the composition has a permittivity at 1000 Hz of between 3 and 6.5, between 3.4 and 8 or between 4 and 6.5.

30. (canceled)

31. An organic semiconductor composition according to claim 27 having a charge mobility value of at least 0.5 cm.sup.2V.sup.?1s.sup.?1, preferably between 2 and 5.0 cm.sup.2V.sup.?1s.sup.?1.

32. (canceled)

33. An organic semiconductor composition according to claim 27, wherein said composition is embedded in an electronic device.

34. An organic semiconductor composition according to claim 33, wherein the electronic device is selected from organic field effect transistors (OFETS), organic light emitting diodes (OLEDS), photodetectors, organic photovoltaic (OPV) cells, sensors, lasers, memory elements and logic circuits.

35. An ink comprising a PAHC according to claim 1.

36. A process for producing a Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) comprising copolymerising a composition containing at least one BXBX monomer unit selected from the structures (A) and at least one arylamine monomer (B): ##STR00061## wherein Y.sup.1 and Y.sup.2 are independently S or Se; k and l are independently 0 or 1 wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, independently represents hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; a C.sub.2-C.sub.10 alkynyl group substituted with a SiH.sub.2R.sup.22 group, a C.sub.2-C.sub.10 alkynyl substituted with a SiHR.sup.22R.sup.23 group, or a C.sub.2-C.sub.10 alkynyl substituted with a Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z group; wherein each R.sup.22 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; each R.sup.23 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; R.sup.24 is independently selected from the group consisting of hydrogen, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group, a substituted C.sub.5-C.sub.20 aryl group, a substituted or unsubstituted C.sub.6-C.sub.20 arylalkylene group, an acetyl group, a substituted or unsubstituted C.sub.3-C.sub.20 heterocyclic ring comprising at least one of O, N, S and Se in the ring; wherein x=1 or 2; y=1 or 2; z=0 or 1; and (x+y+z)=3; wherein each of R.sup.15, R.sup.16, R.sup.18, R.sup.19 and R.sup.20 independently represent H or optionally substituted C.sub.1-C.sub.40 carbyl or hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.17 represents a halogen atom, H or optionally substituted C.sub.1-C.sub.40 carbyl or C.sub.1-C.sub.40 hydrocarbyl group optionally comprising one or more heteroatoms; wherein Ar.sub.1, Ar.sub.2 and Ar.sub.3, which may be the same or different, each represent, independently if in different repeat units, an optionally substituted C.sub.6-40 aromatic group (mononuclear or polynuclear), wherein preferably at least one of Ar.sub.1, Ar.sub.2 and Ar.sub.3 is substituted with at least one polar or more polarising group; wherein X is a halogen atom or a cyclic borate group; and wherein Z is a halogen atom.

37. (canceled)

38. A process for producing a Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) comprising copolymerising a composition containing at least one monomer unit selected from the structures (A) and at least one monomer selected from the structure (K): ##STR00062## wherein Y.sup.1 and Y.sup.2 are independently S or Se; k and l are independently 0 or 1; wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, independently represents hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; a C.sub.2-C.sub.10 alkynyl group substituted with a SiH.sub.2R.sup.22 group, a C.sub.2-C.sub.10 alkynyl substituted with a SiHR.sup.22R.sup.23 group, or a C.sub.2-C.sub.10 alkynyl substituted with a Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z group; wherein each R.sup.22 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; each R.sup.23 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; R.sup.24 is independently selected from the group consisting of hydrogen, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group, a substituted C.sub.5-C.sub.20 aryl group, a substituted or unsubstituted C.sub.6-C.sub.20 arylalkylene group, an acetyl group, a substituted or unsubstituted C.sub.3-C.sub.20 heterocyclic ring comprising at least one of O, N, S and Se in the ring; wherein x=1 or 2; y=1 or 2; z=0 or 1; and (x+y+z)=3; wherein each of R.sup.15, R.sup.16, R.sup.18, R.sup.19 and R.sup.20 independently represent H or optionally substituted C.sub.1-C.sub.40 carbyl or hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.17 represents a halogen atom, H or optionally substituted C.sub.1-C.sub.40 carbyl or C.sub.1-C.sub.40 hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 which may be the same or different, independently each represent, hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; wherein preferably at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4 is substituted with at least one polar or more polarising group which is independently selected from the group consisting of nitro group, nitrile group, C.sub.1-40 alkyl group substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; a C.sub.1-40 alkoxy group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; a C.sub.1-40 carboxylic acid group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; a C.sub.2-40 carboxylic acid ester optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; sulfonic acid optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; sulfonic acid ester optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; cyanate group, isocyanate group, thiocyanate group, thioisocyanate group; and an amino group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; and combinations thereof; wherein at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4 groups is a polar or polarising group, and n=1 to 20; wherein X is a halogen atom or a cyclic borate group; and wherein Z is a halogen atom.

39. (canceled)

40. A process for producing a Polycyclic Aromatic Hydrocarbon Copolymer (PAHC) comprising copolymerising a composition containing at least one BXBX monomer unit selected from the structures (A) and at least one monomer (O): ##STR00063## wherein Y.sup.1 and Y.sup.2 are independently S or Se; k and l are independently 0 or 1 wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, independently represents hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; a C.sub.2-C.sub.10 alkynyl group substituted with a SiH.sub.2R.sup.22 group, a C.sub.2-C.sub.10 alkynyl substituted with a SiHR.sup.22R.sup.23 group, or a C.sub.2-C.sub.10 alkynyl substituted with a Si(R.sup.22).sub.x(R.sup.23).sub.y(R.sup.24).sub.z group; wherein each R.sup.22 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; each R.sup.23 group is independently selected from the group consisting of a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.10 alkyl group, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, and a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group; R.sup.24 is independently selected from the group consisting of hydrogen, a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.10 alkynyl group, a substituted or unsubstituted C.sub.2-C.sub.20 cycloalkyl group, a substituted or unsubstituted C.sub.6-C.sub.20 cycloalkylalkylene group, a substituted C.sub.5-C.sub.20 aryl group, a substituted or unsubstituted C.sub.6-C.sub.20 arylalkylene group, an acetyl group, a substituted or unsubstituted C.sub.3-C.sub.20 heterocyclic ring comprising at least one of O, N, S and Se in the ring; wherein x=1 or 2; y=1 or 2; z=0 or 1; and (x+y+z)=3; wherein each of R.sup.15, R.sup.16, R.sup.18, R.sup.19 and R.sup.20 independently represent H or optionally substituted C.sub.1-C.sub.40 carbyl or hydrocarbyl group optionally comprising one or more heteroatoms; wherein R.sup.17 represents a halogen atom, H or optionally substituted C.sub.1-C.sub.40 carbyl or C.sub.1-C.sub.40 hydrocarbyl group optionally comprising one or more heteroatoms; wherein k and l are independently 0 or 1; wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 which may be the same or different, independently each represent, hydrogen; a branched or unbranched, substituted or unsubstituted C.sub.1-C.sub.40 alkyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkenyl group; a branched or unbranched, substituted or unsubstituted C.sub.2-C.sub.40 alkynyl group; an optionally substituted C.sub.3-C.sub.40 cycloalkyl group; an optionally substituted C.sub.6-C.sub.40 aryl group; an optionally substituted C.sub.1-C.sub.40 heterocyclic group; an optionally substituted C.sub.1-C.sub.40 heteroaryl group; an optionally substituted C.sub.1-C.sub.40 alkoxy group; an optionally substituted C.sub.6-C.sub.40 aryloxy group; an optionally substituted C.sub.7-C.sub.40 alkylaryloxy group; an optionally substituted C.sub.2-C.sub.40 alkoxycarbonyl group; an optionally substituted C.sub.7-C.sub.40 aryloxycarbonyl group; a cyano group (CN); a carbamoyl group (C(?O)NR.sup.15R.sup.16); a carbonyl group (C(?O)R.sup.17); a carboxyl group (CO.sub.2R.sup.18) a cyanate group (OCN); an isocyano group (NC); an isocyanate group (NCO); a thiocyanate group (SCN) or a thioisocyanate group (NCS); an optionally substituted amino group; a hydroxy group; a nitro group; a CF.sub.3 group; a halo group (Cl, Br, F, I); SR.sup.19; SO.sub.3H; SO.sub.2R.sup.20; SF.sub.5; an optionally substituted silyl group; wherein preferably at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.7 is substituted with at least one polar or more polarising group which is independently selected from the group consisting of nitro group, nitrile group, C.sub.1-40 alkyl group substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; a C.sub.1-40 alkoxy group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; a C.sub.1-40 carboxylic acid group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; a C.sub.2-40 carboxylic acid ester optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; sulfonic acid optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; sulfonic acid ester optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; cyanate group, isocyanate group, thiocyanate group, thioisocyanate group; and an amino group optionally substituted with a nitro group, a nitrile group, a cyanate group, an isocyanate group, a thiocyanate group or a thioisocyanate group; and combinations thereof; wherein X is a halogen atom or a cyclic borate group; and wherein Z is a halogen atom.

41-42. (canceled)

43. An organic semiconductor composition according to claim 27, wherein said composition is embedded in an organic semiconductor layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0251] FIG. 1 is a representation of top contact/bottom gate organic thin film transistor (OTFT)

[0252] FIG. 2 is a representation of bottom contact/bottom gate (OTFT)

[0253] FIG. 3 is a representation of top contact/top gate (OTFT)

[0254] FIG. 4 is a representation of bottom contact/top gate (OTFT)

[0255] LabelsA: Substrate; B: Gate electrode; C: Dielectric layer; D: Semiconductor layer; E: Source electrode; F: Gate electrode

EXAMPLES OF THE PRESENT INVENTION

[0256] The following examples of the present invention are merely exemplary and should not be viewed as limiting the scope of the invention.

Measurement of the Capacitance of the Polymer Binder

[0257] The polymer binder was diluted with tetralin in order to lower its viscosity and make it possible to obtain a film thickness of ?1 micron when spin coated for the spin speed range 1000-2000 rpm/s. The polymer binder solution was spin coated at 500 rpm for 10 seconds, followed by 1500 rpm for 30 seconds, onto ITO coated and cleaned 1?1 inch glass substrates.

[0258] To clean the ITO coated substrates they were submerged in a 3% solution of DECon 90 and put in an ultrasonic bath (water temperature >65? C.), washed with deionised water, submerged in deionised water and put in an ultrasonic bath (water temperature >65? C.), washed a further time with deionised water, submerged in isopropyl alcohol and then put in an ultrasonic bath (water temperature >65? C.), and then spin dried.

[0259] After deposition of the polymer binder the substrate was annealed on a hotplate at 120? C. for 5 minutes.

[0260] The substrate was then covered with a capacitance shadow mask, and top electrodes were deposited by evaporation of gold using a thermal deposition method. In order to determine the exact thickness of the polymer binder layer, the thickness was measured using a Dektak 3030 profilometer (available from Veeco, Plainview N.Y.) at three different positions and averaged; these values were subsequently used to calculate the dielectric constants of the polymer binders.

[0261] Capacitance measurements were then carried out using impedance analyser Agilent 43961A and a probe station. In order to improve the electrical contact between the ITO back electrode and the external probe electrode, a conductive silver paste was applied. The sample being measured was placed in a metal box on the metal plate to ensure minimum influence from the external environment.

[0262] Before each set of measurements was obtained, the analyser was calibrated using the 43961A Impedance Test Kit as a compensation routine was carried out to account for internal capacitance of the analyser and test fixture. The measurement calibration was carried out with open and shorted circuit; the dielectric constant was calculated using the following equation:

C=???.sub.o?(A/d).

[0263] Wherein C is the capacitance (Farads), A is the area (m.sup.2), d is the coating thickness (m), ? is the dielectric constant (permittivity), and ?.sub.o is the permittivity of free space and is taken as 8.8854?10.sup.?12 F/m.

[0264] As a reference sample, a polystyrene sample (Mw?350,000) having a thickness of 1 ?m was tested. The measured and calculated dielectric constant of the polystyrene reference was ?=2.55 at 10,000 Hz, which is in good agreement with the reported value (??2.5), refer to J. R. Wunsch, Polystyrene-Synthesis, Production and Applications, Rapra Review Reports, 2000, Volume 10, No. 4, page 32.

OTFT Fabrication Method

[0265] A substrate (either glass or a polymer substrate such as PEN) is patterned with Au source drain electrodes either by a process of thermal evaporation through a shadow mask or by photolithography (an adhesion layer of either Cr or Ti is deposited on the substrate prior to deposition of Au). The Au electrodes can the optionally be cleaned using an O.sub.2 plasma cleaning process. A solution of organic semiconductor in binder is then applied by spin coating (the sample is flooded with the solution and the substrate is then spun at 500 rpm for 5 seconds then 1500 rpm for 1 minute). The coated substrate is then dried in air on a hot stage. The dielectric material, for example 3 wt % PTFE-AF 1600 (Sigma-Aldrich cat #469610) dissolved in FC-43) was then applied to the substrate by spin coating (sample flooded then spun at 500 rpm for 5 seconds then 1500 rpm for 30 seconds). The substrate was then dried in air on a hot stage (100? C. for 1 minute). A gate electrode (Au) is then defined over the channel area by evaporation through a shadow mask.

[0266] The mobility of the OTFT for the binders is characterised by placing on a manual probe station connected to a Keithley SCS 4200 semiconductor analyzer. The source drain voltage (V.sub.DS) is set at ?2V (linear) or ?40V (saturation) and the gate voltage (V.sub.G) scanned from +20V to ?60V. Drain current is measured and mobility calculated from the transconductance.

[0267] The mobility of the OTFT for the formulations is characterised by placing on a semi-auto probe station connected to a Keithley SCS 4200 semiconductor analyzer. The source drain voltage is set at ?2V and the gate voltage scanned from +20V to ?40V. Drain current is measured and mobility calculated from the transconductance.

[0268] In linear regime, when |V.sub.G|>|V.sub.DS|, the source-drain current varies linearly with V.sub.G. Thus the field effect mobility (?) can be calculated from the gradient (S) of I.sub.DS vs. V.sub.G given by equation 1 (where C.sub.i is the capacitance per unit area, W is the channel width and L is the channel length):

[00002]$\begin{array}{cc}.Math.S=\frac{\text{?}}{L}.Math..Math.\text{?}.Math.\text{indicates text missing or illegible when filed}& \mathrm{Equation}.Math..Math.1\end{array}$

[0269] In the saturation regime, the mobility is determined by finding the slope of IDs.sup.1/2 vs. V.sub.G and solving for the mobility (Equation 2)

[00003]$\begin{array}{cc}.Math.I.Math.\text{?}.Math.\frac{\text{?}}{\text{?}}.Math..Math.\text{?}.Math.\text{indicates text missing or illegible when filed}& \mathrm{Equation}.Math..Math.2\end{array}$

Examples of the Present Invention

[0270] The following examples are intended to explain the invention without restricting it. The methods, structures and properties described herein can also be applied to materials that are claimed in this invention but not explicitly described in the examples.

[0271] Particularly preferred PAHCs according to the present invention are shown in the following tables 1 to 3:

TABLE-US-00004 TABLE 1 Preferred PAHCs [00040] [00041] Case 1 Y.sup.1 = Y.sup.2 are S R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e = H R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.4 and R.sup.10 are C.sub.1 to C.sub.14 alkyl groups, most preferably n-octyl groups. R.sup.3 and, R.sup.9 are bonds to another unit of Monomer (A) or (B). Case 2 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.3 and R.sup.9 are C.sub.1 to C.sub.14 alkyl groups, most preferably n-octyl groups. R.sup.4 and R.sup.10 are bonds to another unit of Monomer (A) or (B). Case 3 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.4 and R.sup.10 are CF.sub.3 groups. R.sup.3 and R.sup.9 are bonds to another unit of Monomer (A) or (B). Case 4 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.3 and, R.sup.9 are CF.sub.3 groups. R.sup.4 and R.sup.10 are bonds to another unit of Monomer (A) or (B). Case 1 R.sup.b, R.sup.d, R.sup.e = H Case 2 R.sup.a and R.sup.c = C.sub.1 to C.sub.4 Case 3 alkyl Case 4 Case 1 R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 R.sup.a = C.sub.1 to C.sub.6 alkoxy Case 3 (i) R.sup.a = methoxy Case 4 (ii) R.sup.a = ethoxy Case 1 R.sup.a, R.sup.b, R.sup.d, R.sup.e = H Case 2 R.sup.c = C.sub.1 to C.sub.6 alkoxy Case 3 (i) R.sup.c = methoxy Case 4 (ii) R.sup.c = ethoxy Case 1 R.sup.a, R.sup.b, R.sup.c, R.sup.d = H Case 2 R.sup.e = C.sub.1 to C.sub.6 alkoxy Case 3 (i) R.sup.e = methoxy Case 4 (ii) R.sup.e = ethoxy Case 1 R.sup.b, R.sup.d, R.sup.e = H Case 2 R.sup.a = R.sup.c = C.sub.1 to C.sub.6 alkoxy Case 3 (i) R.sup.a = R.sup.c = methoxy Case 4 (ii) R.sup.a = R.sup.c = ethoxy Case 1 R.sup.b, R.sup.d = H Case 2 R.sup.a, R.sup.c, R.sup.e = C.sub.1 to C.sub.6 Case 3 alkoxy Case 4 (i) R.sup.a, R.sup.c, R.sup.e = methoxy (ii) R.sup.a, R.sup.c, R.sup.e = ethoxy Case 1 R.sup.b, R.sup.d = H Case 2 R.sup.b, R.sup.c, R.sup.d = C.sub.1 to C.sub.6 Case 3 alkoxy Case 4 (i) R.sup.b, R.sup.c, R.sup.d = methoxy (ii) R.sup.b, R.sup.c, R.sup.d = ethoxy Case 1 R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 R.sup.a = Cyano (CN) Case 3 Case 4 Case 1 R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 R.sup.a = Isopropylcyano Case 3 group Case 4 Monomer B: [00042] Case 1 R.sup.a, R.sup.b, R.sup.d, R.sup.e = H Case 2 R.sup.c = Isopropylcyano Case 3 group Case 4 Monomer B: [00043]

TABLE-US-00005 TABLE 2 Preferred PAHCs [00044] [00045] [00046] Case 1 Y.sup.1 = Y.sup.2 are S R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e = H R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. groups R.sup.4 and R.sup.10 are C.sub.1 to C.sub.14 alkyl groups, R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 most preferably n-octyl groups. alkoxy groups; or cyano groups; or isopropyl R.sup.3 and, R.sup.9 are bonds to another unit of Monomer cyano groups. (A) or (B). Case 2 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.3 and R.sup.9 are C.sub.1 to C.sub.14 alkyl groups, most preferably n-octyl groups. R.sup.4 and R.sup.10 are bonds to another unit of Monomer (A) or (B). Case 3 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.4 and R.sup.10 are CF.sub.3 groups. R.sup.3 and R.sup.9 are bonds to another unit of Monomer (A) or (B). Case 4 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.3 and, R.sup.9 are CF.sub.3 groups. R.sup.4 and R.sup.10 are bonds to another unit of Monomer (A) or (B). Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.d, R.sup.e = H Case 2 groups R.sup.a and R.sup.c = C.sub.1 to Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 C.sub.4 alkyl Case 4 alkoxy groups; or cyano groups; or isopropyl cyano groups. Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 groups R.sup.'a = C.sub.1 to C.sub.6 Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 alkoxy Case 4 alkoxy groups; or cyano groups; or isopropyl (i) R.sup.a = methoxy cyano groups. (ii) R.sup.a = ethoxy Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.a, R.sup.b, R.sup.d, R.sup.e = H Case 2 groups R.sup.c = C.sub.1 to C.sub.6 Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 alkoxy Case 4 alkoxy groups; or cyano groups; or isopropyl (i) R.sup.c = methoxy cyano groups. (ii) R.sup.c = ethoxy Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.a, R.sup.b, R.sup.c, R.sup.d = H Case 2 groups R.sup.e = C.sub.1 to C.sub.6 Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 alkoxy Case 4 alkoxy groups; or cyano groups; or isopropyl (i) R.sup.e = methoxy cyano groups. (ii) R.sup.e = ethoxy Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.d, R.sup.e = H Case 2 groups R.sup.a = R.sup.c = C.sub.1 to C.sub.6 Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 alkoxy Case 4 alkoxy groups; or cyano groups; or isopropyl (i) R.sup.a = R.sup.c = methoxy cyano groups. (ii) R.sup.a = R.sup.c = ethoxy Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.d = H Case 2 groups R.sup.a, R.sup.c, R.sup.e = C.sub.1 to Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 C.sub.6 alkoxy Case 4 alkoxy groups; or cyano groups; or isopropyl (i) R.sup.a, R.sup.c, R.sup.e = methoxy cyano groups. (ii) R.sup.a, R.sup.c, R.sup.e = ethoxy Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.d = H Case 2 groups R.sup.b, R.sup.c, R.sup.d = C.sub.1 to Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 C.sub.6 alkoxy Case 4 alkoxy groups; or cyano groups; or isopropyl (i) R.sup.b, R.sup.c, R.sup.d = methoxy cyano groups. (ii) R.sup.b, R.sup.c, R.sup.d = ethoxy Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 groups R.sup.a = Cyano (CN) Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 Case 4 alkoxy groups; or cyano groups; or isopropyl cyano groups. Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 groups R.sup.a = Isopropylcyano Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 group Case 4 alkoxy groups; or cyano groups; or isopropyl cyano groups. Monomer C: [00047] Case 1 R.sup.1 = R.sup.2 = C.sub.1 to C.sub.14 alkyl group, preferably n-octyl R.sup.a, R.sup.b, R.sup.d, R.sup.e = H Case 2 groups R.sup.c = lsopropylcyano Case 3 R.sup.3, R.sup.4 = H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 to C.sub.4 group Case 4 alkoxy groups; or cyano groups; or isopropyl cyano groups. Monomer C: [00048]

TABLE-US-00006 TABLE 3 Preferred PAHCs [00049] [00050] [00051] Case 1 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e = H R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. preferably n-octyl groups R.sup.4 and R.sup.10 are C.sub.1 to C.sub.14 alkyl groups, most preferably n-octyl R.sup.5, R.sup.6 and R.sup.7 are H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 groups. to C.sub.4 alkoxy groups; or cyano groups; or R.sup.3 and, R.sup.9 are bonds to another unit of Monomer isopropyl cyano groups. (A) or (B). Case 2 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.3 and R.sup.9 are C.sub.1 to C.sub.14 alkyl groups, most preferably n-octyl groups. R.sup.4 and R.sup.10 are bonds to another unit of Monomer (A) or (B). Case 3 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.4 and R.sup.10 are CF.sub.3 groups. R.sup.3 and R.sup.9 are bonds to another unit of Monomer (A) or (B). Case 4 Y.sup.1 = Y.sup.2 are S R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11, R.sup.12 are all H. R.sup.3 and, R.sup.9 are CF.sub.3 groups. R.sup.4 and R.sup.10 are bonds to another unit of Monomer (A) or (B). Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.b, R.sup.d, R.sup.e = H Case 2 preferably n-octyl groups R.sup.a and R.sup.c = C.sub.1 to Case 3 R.sup.5, R.sup.6 and R.sup.7 are H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 C.sub.4 alkyl Case 4 to C.sub.4 alkoxy groups; or cyano groups; or isopropyl cyano groups. Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 preferably n-octyl groups R.sup.a = C.sub.1 to C.sub.6 Case 3 R.sup.5, R.sup.6 and R.sup.7 are H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 alkoxy Case 4 to C.sub.4 alkoxy groups; or cyano groups; or (i) R.sup.a = methoxy isopropyl cyano groups. (ii) R.sup.a = ethoxy Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1t o C.sub.14 alkyl group, R.sup.a, R.sup.b, R.sup.d, R.sup.e = H Case 2 preferably n-octyl groups R.sup.c = C.sub.1 to C.sub.6 Case 3 R.sup.5, R.sup.6 and R.sup.7 are H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 alkoxy Case 4 to C.sub.4 alkoxy groups; or cyano groups; or (i) R.sup.c = methoxy isopropyl cyano groups. (ii) R.sup.c = ethoxy Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.a, R.sup.b, R.sup.c, R.sup.d = H Case 2 preferably n-octyl groups R.sup.e = C.sub.1 to C.sub.6 Case 3 alkoxy Case 4 (i) R.sup.e = methoxy (ii) R.sup.e = ethoxy Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.b, R.sup.d, R.sup.e = H Case 2 preferably n-octyl groups R.sup.a = R.sup.c = C.sub.1 to C.sub.6 Case 3 R.sup.5, R.sup.6 and R.sup.7 are H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 alkoxy Case 4 to C.sub.4 alkoxy groups; or cyano groups; or (i) R.sup.a = R.sup.c = methoxy isopropyl cyano groups. (ii) R.sup.a = R.sup.c = ethoxy Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.b, R.sup.d = H Case 2 preferably n-octyl groups R.sup.a, R.sup.c, R.sup.e = C.sub.1 to Case 3 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, C.sub.6 alkoxy Case 4 preferably n-octyl groups (i) R.sup.a, R.sup.c, R.sup.e = methoxy (ii) R.sup.a, R.sup.c, R.sup.e = ethoxy Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.a, R.sup.e = H Case 2 preferably n-octyl groups R.sup.b, R.sup.c, R.sup.d = C.sub.1 to Case 3 C.sub.6 alkoxy Case 4 (i) R.sup.b, R.sup.c, R.sup.d = methoxy (ii) R.sup.b, R.sup.c, R.sup.d = ethoxy Case 1 R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 R.sup.a = Cyano (CN) Case 3 Case 4 Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.b, R.sup.c, R.sup.d, R.sup.e = H Case 2 preferably n-octyl groups R.sup.a = Isopropylcyano Case 3 group Case 4 Monomer C: [00052] Case 1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are C.sub.1 to C.sub.14 alkyl group, R.sup.a, R.sup.b, R.sup.d, R.sup.e = H Case 2 preferably n-octyl groups R.sup.c = Isopropylcyano Case 3 R.sup.5, R.sup.6 and R.sup.7 are H or C.sub.1 to C.sub.4 alkyl groups; or C.sub.1 group Case 4 to C.sub.4 alkoxy groups; or cyano groups; or isopropyl cyano groups. Monomer C: [00053]

[0272] The organic semiconductors compounds specified in the table are particularly preferred as they combine the beneficial properties of high charge transport mobility (of the binders) with a polarity that is more compatible with benign, non-chlorinated solvents that will be desirable for use in large area printing. In addition, as these compounds are more polar once deposited as the OSC layer, or alternatively as a component in the OSC layer, they are expected to be resistant to being re-dissolved by the hydrophobic solvents used for the organic gate insulators (OGI) such as Cytop. Furthermore, it is expected that the polar binders are useful for both top gate and bottom gate OTFTs, particularly for bottom gate OTFTs.