Organic semiconductors and their manufacture

A semiconductor device comprising a bis(substituted ethynyl) compound with a tri- or polycyclic aromatic hydrocarbon backbone with heteroatoms wherein the rings that constitute the backbone are annealed to each other via not more than two commonly shared ring atoms, respectively, and the number of the common atoms of the vicinal rings is twice the number of the common side areas, with the proviso that the backbone together with the ethynyl groups have a point symmetry selected from the group consisting of the C2h, the D2h and the Cs point symmetry group, which have the formula I

• wherein the ring labelled with A is an aromatic ring with 6 atoms, the ring marked B is a mono- or polycyclic unsaturated ring or ring system or annealed ferrocenobenzo of the subformula I(i)
• wherein the dotted bond marks the side of the benzo ring annealed to the central ring A in formula I, each annealed to ring A and the ring marked C is a mono- or polycyclic unsaturated ring or ring system or ferrocenobenzo of the subformula I(i) shown above, each annealed to ring A, each of rings or ring systems B and C may also carry a group ═S, ═O or ═C(NQ2)2, where “unsaturated” means having the maximum possible number of conjugated double bonds,
• and wherein in at least one of the rings or ring systems B and C at least one ring atom is a heteroatom selected from N, NQ, O and S, if the first ring forming or forming part of ring or ring system B and C directly annealed to ring A has six ring atoms in both rings or ring systems B and C;
• where the rings or ring systems marked B and C in the compound of the formula I each contain at least one heteroatom, where the heteroatom or heteroatoms are selected from N, NQ, S and O;
• and
• each of the rings B and C is selected from the group consisting of the following moieties where the dotted bond marks the side of the ring or ring system annealed to the rest of the molecule:
• or ring C is selected from the preceding moieties, while ring B is of the formula
• Q is, for each occurrence of Q and each ring independently of the other, hydrogen or an unsubstituted or substituted hydrocarbyl, unsubstituted or substituted hydrocarbylcarbonyl or heteroaryl as defined below for X or Z;
• or Q is selected from hydrogen, C6-C14-aryl, C6-C14-aryl-C1-C20alkyl, C1-C20-alkyl, and C1-C20-alkyl;
• Z* and Z** are independently of each other selected from the group consisting of H, unsubstituted or substituted C1-C20-alkyl, halogen substituted-C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C6-C14-aryl, unsubstituted or substituted heteroaryl with 5 to 14 ring atoms, unsubstituted or substituted C6-C14-aryl-C1-C20-alkyl, unsubstituted or substituted heteroaryl-C1-C20-alkyl, wherein the heteroaryl has 5 to 14 ring atoms, unsubstituted or substituted ferrocenyl, unsubstituted or substituted C1-C20-alkanoyl, perfluorinated C2-C10-alkanoyl, halo, unsubstituted or substituted C1-C20-alkoxy, C3-C20-alkenyloxy, C3-C20-alkynyloxy, unsubstituted or substituted C1-C20-alkylthio, C3-C20-alkenylthio, C3-C20-alkynylthio, carboxy, unsubstituted or substituted C1-C20-alkoxy-carbonyl, unsubstituted or substituted phenyl-C1-C20-alkoxy-carbonyl, amino, N-mono- or N,N-di-(C1-C20-alkyl, C1-C20-alkanoyl and/or phenyl-C1-C20-alkyl)-amino, cyano, carbamoyl, N-mono- or N,N-di-(C1-C20-alkyl, C1-C20-alkanoyl and/or phenyl-C1-C20-alkyl)-carbamoyl and sulfamoyl;
• two of the substitutents X, Y and Z present in formula I are substituted ethynyl wherein the substitutents are selected from the group consisting of unsubstituted or substituted hydrocarbyl with up to 40 carbon atoms, unsubstituted or substituted hydrocarbyloxy with up to 40 carbon atoms, hydrocarbylthio with up to 40 carbon atoms, unsubstituted or substituted heteroaryl, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted heteroarylthio, cyano, carbamoyl, substituted amino, halo-C1-C8-alkyl, trifluoromethyl, and substituted silyl;
• or two Y substituents, where each Y, independently of the other, or identically substituted, is selected from substituted ethynyl wherein the substituents are selected from unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, substituted silyl which is silyl substituted by two or three moieties selected from C1-C20-alkyl, C1-C20alkoxy, and phenyl- or naphthyl-C1-C20-alkyl;
• while the remaining substituents X, Y and/or Z, as far as present, are substitutents selected from the group consisting of unsubstituted or substituted C1-C20-alkyl, halogen substituted-C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl other than substituted ethynyl mentioned above, unsubstituted or substituted C6-C14-aryl, unsubstituted or substituted heteroaryl with 5 to 14 ring atoms, unsubstituted or substituted C6-C14-aryl-C1-C20-alkyl, unsubstituted or substituted heteroaryl-C1-C20-alkyl, wherein the heteroaryl has 5 to 14 ring atoms, unsubstituted or substituted ferrocenyl, unsubstituted or substituted C1-C20-alkanoyl, halo, unsubstituted or substituted C1-C20-alkoxy, C3-C20-alkenyloxy, C3-C20-alkynyloxy, unsubstituted or substituted C1-C20-alkylthio, C3-C20-alkenylthio, C3-C20-alkynylthio, carboxy, unsubstituted or substituted C1-C20-alkoxy-carbonyl, unsubstituted or substituted phenyl-C1-C20-alkoxy-carbonyl, amino, N-mono-(C1-C20-alkyl)amino, N,N-di-(C1-C20-alkyl)amino, C1-C20-alkanoylamino, phenyl-(C1-C20-alkyl)-amino, cyano, carbamoyl, N-mono-(C1-C20-alkyl)-carbamoyl, N,N-di-(C1-C20-alkyl)carbamoyl, C1-C20-alkanoyl-carbamoyl, phenyl-C1-C20-alkyl)-carbamoyl, sulfamoyl, N-mono-(C1-C20-alkyl)-sulfamoyl, N,N-di-(C1-C20-alkyl)sulfamoyl, C1-C20-alkanoyl-sulfamoyl, phenyl-C1-C20-alkyl)-sulfamoyl;
• and each of n and p is 0 to 4 and m is 0 to 2, with the proviso that the sum of m, n and p is at least 2;
• or the bis(substituted ethynyl) compound is a compound selected from those of the formulae V or VI
• or is a compound of the formula I* or I**,
• wherein each R′ independently is selected from C1-C20 alkyl, benzyl, C1-C12perfluoroalkyl, C1-C12perfluoroalkanoyl, fluorophenyl, and SiR3, where R independently is C1-C6alkoxy;
• R* is hydrogen or R′;
• and
• X and Z are substituted ethynyl as defined above.