Dyketopyrrolopyrrole polymers for use in organic semiconductor devices

A polymer comprising repeating units of formula (II) shown below:

• *A-DxB-Dy* (II), wherein
• x=0.995 to 0.005, y=0.005 to 0.995, and wherein x+y=1;
• A is a group of formula IVa, IVc, IVe, IVg, IVh, IVi, IVj, or IVk shown below
• R1 and R2 are a C1-C35alkyl group,
• R104 is a C1-C25alkyl group, which is optionally interrupted by one or more oxygen or sulphur atoms,
• B and D are independently of each other a group of formula Va, Vb, Vc, Ve, Vf, Vh, Vi, Vj, Vk, Vl, Vm, Vn, Vo, Vp, Vq, Vr, Vs, Vu, Vv, Vw, Vx, Vy, Vz, or Va′ shown below, with the proviso that at least one of (i) D in [A-D], (ii) D in [B-D], and (iii) B in [B-D]has the structure
• wherein
• a is an integer of 1 to 5,
• one of X1 and X2 is N and the other is CH,
• one of X5 and X6 is N and the other is CR14,
• R12 and R12′ are independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms, C1-C25alkoxy, C7-C25arylalkyl, or
• R13 is a C1-C10alkyl group, or a tri(C1-C8alkyl)silyl group,
• R14 is a C1-C25alkyl group, which is optionally interrupted by one or more oxygen atoms,
• R15 and R15′ are independently of each other H, or a C1-C25alkyl group, which is optionally interrupted by one or more oxygen atoms,
• R18 and R18′ independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C7-C25aralkyl, or C1-C25alkoxy,
• R19 is hydrogen, C7-C25aralkyl, C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy;
• or C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• and
• R20 and R20′ are independently of each other hydrogen, C7-C25aralkyl, C1-C25alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms,
• R116 is hydrogen, C7-C25arylalkyl, C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, C1-C18perfluoroalkyl, or C1-C18alkoxy;
• C1-C25alkyl;
• C1-C25alkyl which is interrupted by —O—, or —S—;
• or —COOR119,
• R101 and R101′ are independently of each other H, F, C1-C18alkyl, C1-C18alkyl which is interrupted by O, C1-C18alkoxy, C1-C18alkoxy which is interrupted by O, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy45, C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy,
• R102 and R102′ are independently of each other H, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25arylalkyl, or C1-C25alkoxy,
• R119 is C1-C25alkyl, C1-C25alkyl which is substituted by E′ and/or interrupted by D′, C7-C25arylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, or C7-C25aralkyl,
• D′ is —CO—, —COO—, —S—, —O—, or —NR112—,
• E′ is C1-C8thioalkoxy, C1-C8alkoxy, CN, —NR112R113, —CONR112R113, or halogen,
• R112 and R113 are independently of each other H;
• C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy;
• C1-C18alkyl;
• or C1-C18alkyl which is interrupted by —O—,
• X7 is —C(R120)(R120′)—,
• R120 and R120′ are independently of each other hydrogen, C1-C35alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms;
• or C7-C25arylalkyl,
• R103 and R103′ are independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• C7-C25arylalkyl, CN, or C1-C25alkoxy, or
• R103 and R103′ together form a ring,
• R303, R304, R305 and R306 are independently of each other H, F, C1-C18alkyl, C1-C18alkyl which is interrupted by O, C1-C18alkoxy, C1-C18alkoxy which is interrupted by 0, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, and
• R100 and R100′ are independently of each other H, F, C1-C18alkyl, C1-C18alkyl which is interrupted by O, C1-C18alkoxy, C1-C18alkoxy which is interrupted by O, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• or
• a polymer comprising repeating units of formula (II) shown below:
• *A-DxB-Dy* (II), wherein
• x=0.995 to 0.005, y=0.005 to 0.995, and wherein x+y=1;
• A is a group of formula IVa, IVc, IVe, IVg, IVh, IVi, IVj, or IVk as defined hereinabove,
• B is a group of formula
• R1 and R2 are a C1-C35alkyl group, and
• D is

A process for preparation of an organic semiconductor device, which process comprises:

• applying a solution and/or dispersion of a polymer in an organic solvent to a suitable substrate and removing the solvent,
• wherein the polymer comprises one or more (repeating) unit(s) of the formula *A-D* (I), or a polymer of formula *A-DxB-Dy* (II), or *A-DrB-DsA-EtB-Eu (III), wherein
• x=0.995 to 0.005, y=0.005 to 0.995, and
• wherein x+y=1.
• r=0.985 to 0.005, s=0.005 to 0.985, t=0.985 to 0.005, u=0.005 to 0.985, and
• wherein r+s+t+u=1.
• A is a group of formula
• wherein
• a′ is an integer of 1, or 2,
• b is an integer of 1, or 2,
• c is 0, or an integer of 1, or 2,
• d is 0, or an integer of 1, or 2,
• e is 0, or an integer of 1, or 2,
• f is 0, or an integer of 1, or 2,
• R1 and R2 are the same or different and are selected from hydrogen, a C1-C100alkyl group, —COOR203, a C1-C100alkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C6-C18aryl groups and/or interrupted by —O—, —COO—, —OCO—, or —S—;
• a C7-C100arylalkyl group, a carbamoyl group, a C5-C12cycloalkyl group, which is substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, a C6-C24aryl group, which is substituted one to three times with C1-C8alkyl, C1-C8thioalkoxy, and/or C1-C8alkoxy, or pentafluorophenyl, R203 is C1-C50alkyl;
• Ar1 and Ar1′ are independently of each other
• Ar2, Ar2′, Ar3 are independently of each other
• or have the meaning of Ar1, wherein one of X3 and X4 is N and the other CR99,
• R99, R104 and R104′ are independently of each other hydrogen, halogen, or a C1-C25alkyl group, which is optionally interrupted by one or more oxygen or sulphur atoms, C7-C25arylalkyl, or a C1-C25alkoxy group,
• R105, R105′, R106 and R106′ are independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25arylalkyl, or C1-C18alkoxy,
• R107 is C7-C25arylalkyl, C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, C1-C18perfluoroalkyl, or C1-C18alkoxy;
• C1-C25alkyl;
• C1-C25alkyl which is interrupted by —O—, or —S—;
• or —COOR119;
• R116 is hydrogen, C7-C25arylalkyl, C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, C1-C18perfluoroalkyl, or C1-C18alkoxy;
• C1-C25alkyl;
• C1-C25alkyl which is interrupted by —O—, or —S—;
• or —COOR119;
• R119 is C1-C25alkyl, C1-C25alkyl which is substituted by E′ and/or interrupted by D′, C7-C25arylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, or C7-C25aralkyl,
• R108 and R109 are independently of each other H, C1-C25alkyl, C1-C25alkyl which is substituted by E′ and/or interrupted by D′, C7-C25arylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C18alkenyl, C2-C18alkynyl, C1-C18alkoxy, C1-C18alkoxy which is substituted by E′ and/or interrupted by D′, or C7-C25aralkyl, or
• R108 and R109 together form a group of formula ═CR110R111, wherein
• R110 and R111 are independently of each other H, C1-C18alkyl, C1-C18alkyl which is substituted by E′ and/or interrupted by D′, C6-C24aryl, C6-C24aryl which is substituted by G, or C2-C20heteroaryl, or C2-C20heteroaryl which is substituted by G, or
• R108 and R109 together form a five or six membered ring, which optionally is substituted by C1-C18alkyl, C1-C18alkyl which is substituted by E′ and/or
• interrupted by D′, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C20heteroaryl, C2-C20heteroaryl which is substituted by G, C2-C18alkenyl, C2-C18alkynyl, C1-C18alkoxy, C1-C18alkoxy which is substituted by E′ and/or interrupted by D′, or C7-C25aralkyl,
• D′ is —CO—, —COO—, —S—, —O—, or —NR112—,
• E′ is C1-C8thioalkoxy, C1-C8alkoxy, CN, —NR112R113, —CONR112R113, or halogen,
• G is E′, or C1-C18alkyl, and
• R112 and R113 are independently of each other H;
• C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy;
• C1-C18alkyl;
• or C1-C18alkyl which is interrupted by —O—,
• B, D and E are independently of each other a group of the formulas shown below, with the proviso that at least one of (i) D in [A-D], (ii) D in [B-D], (iii) B in [B-D], (iv) E in [A-E], (v) B in [B-E], and (vi) E in [B-E] has the structure
• or formula IV, with the proviso that in case B, D and E are a group of formula IV, they are different from A, wherein
• k is 1,
• l is 0, or 1,
• r is 0, or 1,
• z is 0, or 1,
• a is an integer of 1, or 5,
• g is an integer of 1, or 2,
• h is an integer of 1, or 2,
• i is 0, or an integer of 1, or 2,
• j is 0, or an integer of 1, or 2,
• k is 0, or an integer of 1, or 2,
• l is 0, or an integer of 1, or 2,
• R1′ and R2′ have independently of each other the meaning of R1,
• Ar8, Ar8′, Ar9, Ar9′, Ar10 and Ar10′ have independently of each other the meaning of Ar2,
• Ar4, Ar5, Ar6 and Ar7 are independently of each other a group of formula
• wherein one of X5 and X6 is N and the other is CR14,
• Ar20 is an arylene group, or a heteroarylene group, each of which is optionally substituted,
• R118 has the meaning of R116,
• R12 and R12′ are independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms, C1-C25alkoxy, C7-C-25arylalkyl,
• or
• R13 is a C1-C10alkyl group, or a tri(C1-C8alkyl)silyl group,
• R14, R14′, R15, R15′, R17 and R17′ are independently of each other H, or a C1-C25alkyl group, which is optionally interrupted by one or more oxygen atoms;
• R18 and R18′ independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C7-C25aralkyl, or C1-C25alkoxy,
• R19 is hydrogen, C7-C25aralkyl, C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy;
• or C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• and
• R20 and R20′ are independently of each other hydrogen, C7-C25aralkyl, C1-C25alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms,
• X7 is —O—, —S—, —NR115—, —Si(R117)(R117′)—, —C(R120)(R120′)—, —C(═O)—,
• X8 is —O—, or —NR115—;
• R100 and R100′ are independently of each other H, F, C1-C18alkyl, C1-C18alkyl which is interrupted by O, C1-C18alkoxy, C1-C18alkoxy which is interrupted by O, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• R303 and R304, R305, and R306 are independently of each other H, F, C1-C18alkyl, C1-C18alkyl which is interrupted by O, C1-C18alkoxy, C1-C18alkoxy, which is interrupted by O, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• R307, R308 are independently of each other H, or a C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• R309, R310, R311, R312 are independently of each other H, or a C1-C25alkoxy, or C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• R101 and R101′ are independently of each other H, F, C1-C18alkyl which is interrupted by O, C1-C18alkoxy, C1-C18alkoxy, which is interrupted by O, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy, C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• R102 and R102′ are independently of each other H, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25arylalkyl, or C1-C25alkoxy;
• R103 and R103′ are independently of each other hydrogen, halogen, C1-C25alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• C7-C25arylalkyl, CN, or C1-C25alkoxy;
• or
• R103, R103′ together form a ring,
• R115 and R115′ are independently of each other hydrogen, C6-C18aryl;
• C6-C18aryl which is substituted by C1-C18alkyl, or C1-C18alkoxy;
• C1-C25alkyl;
• which is optionally interrupted by one or more oxygen or sulphur atoms;
• or C-7-C25arylalky,
• R117 and R117′ are independently of each other C1-C35alkyl group, C7-C25arylalkyl, or phenyl group, which optionally is substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy,
• R121 and R120′ are independently of each other hydrogen, C1-C35alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms;
• or C7-C25arylalkyl,
• R121 is H, C1-C18alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C1-C18perfluoroalkyl, C6-C24aryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• C2-C20heteroaryl, which is optionally substituted one to three times with C1-C8alkyl and/or C1-C8alkoxy;
• or CN,
• with the proviso that at least one of the groups Ar1, Ar1′, Ar2, Ar2′, Ar3 and Ar3′ is a group
• and/or at least one of the groups B, D and E contain a group

A polymer comprising repeating units of formula (I) shown below:

• wherein
• A is a group of formula IVc, IVe, IVg, IVh, IVi, IVj, or IVk shown below
• wherein R1 and R2 are independently of each other a C1-C36alkyl group,
• R104 is a C1-C25alkyl group, which is optionally interrupted by one or more oxygen or sulphur atoms;
• and
• D is