Diketopyrrolopyrrole polymers for use in organic semiconductor devices

1. A polymer comprising:

(i) one or more repeating unit(s) of the formula A-D and at least one repeating unit(s) which is selected from repeating units of the formula B-D , A-E , and B-E ,

wherein when the polymer comprises repeating units of the formula A-D and B-D , the polymer is a random copolymer,

(ii) a polymer comprising one or more repeating unit(s) of the formula

or

(iii) a polymer comprising repeating unit(s) of the formula

wherein

Ar 23 is a group of formula

Ar 30 is a group of formula

wherein

R 26 and R 26′ are independently of each other a C 4 -C 18 alkyl group,

A is a group of formula

a is 0, or an integer of 1, or 2,

b is 0, or an integer of 1, or 2,

p is 0, or an integer of 1, or 2,

y is 0, or 1,

q is 0, or an integer of 1, or 2,

s is 0, or 1,

u is an integer of 1, or 2,

t is 0, or 1,

v is an integer of 1, or 2,

w is 0, or 1,

Ar 21 , Ar 21′ , Ar 24 , Ar 24′ , Ar 25 , Ar 27 , Ar 29 , Ar 31 , Ar 31′ , Ar 38 , Ar 34 , Ar 36 , Ar 39 , Ar 1 and Ar 1′ are independently of each other a group of formula

Ar 3 and Ar 3′ independently of each other have the meaning of Ar 1 , or are a group of formula

Ar 2 , Ar 2′ , Ar 26 , Ar 28 , Ar 33 , Ar 35 , Ar 37 , Ar 32 , Ar 32′ , Ar 22 and Ar 22′ are independently of each other a group of formula

one of X 1 and X 2 is N and the other is CH,

one of X 3 and X 4 is N and the other is CR 3′ ,

R 1 , R 2 , R 24 and R 25 may be the same or different and are selected from hydrogen, a C 1 -C 100 alkyl group, a C 6 -C 24 aryl, which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 thioalkoxy, and/or C 1 -C 8 alkoxy, or pentafluorophenyl,

R 3 and R 3′ are independently of each other a C 1 -C 25 alkyl group, which may optionally be interrupted by one or more oxygen atoms,

B is a group of formula

wherein

X 1 and X 2 are as defined above,

R 1″ and R 2″ may be the same or different and are selected from hydrogen, a C 1 -C 36 alkyl group, a C 6 -C 24 aryl, which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 thioalkoxy, and/or C 1 -C 8 alkoxy, or pentafluorophenyl,

and

D and E are independently of each other a group of formula

or

formula I, with the proviso that in case D and E are a group of formula I, they are different from A, wherein

k is 1,

l is 0, or 1,

r is 0, or 1,

z is 0, or 1, and

Ar 4 , Ar 5 , Ar 6 and Ar 7 are independently of each other a group of formula

wherein

one of X 5 and X 6 is N and the other is CR 14 ,

c is an integer of 1, 2, or 3,

d is an integer of 1, 2, or 3,

Ar 8 and Ar 8′ are independently of each other a group of formula

X 1 , X 2 , R 1″ , and R 2″ are as defined above,

R 14 , R 14′ , R 17 and R 17′ are independently of each other H, or a C 1 -C 25 alkyl group, which may optionally be interrupted by one or more oxygen atoms,

wherein A, B, and D and E are different from each other.

2. The polymer according to claim 1 ,

wherein A is a group of formula

wherein

X 1 , X 2 , X 3 , X 4 , R 1 , R 2 and R 3 are as defined in claim 1 .

3. The polymer according to claim 1 , wherein D and E are independently of each other a group of formula

wherein

one of X 5′ and X 6′ is N and the other is CR 14 , or CH,

R 15 , R 15′ , R 17 and R 17′ are independently of each other H, or a C 1 -C 25 alkyl group, which may optionally be interrupted by one or more oxygen atoms, and R 14 is a C 1 -C 25 alkyl group, which may optionally be interrupted by one or more oxygen atoms.

4. A polymer comprising repeating units of the formula

wherein A is a group of formula

R 1 and R 2 are a C 8 -C 35 alkyl group,

R 3 is a C 4 -C 18 alkyl group, and

B is a group of formula

or a group of formula Ia, Ib, Ic, Id, Ie, If, or Ig, with the proviso that B is different from A,

R 1″ and R 2″ are a C 8 -C 35 alkyl group,

one of X 1 and X 2 is N and the other is CH,

D is a group of formula

or

and

x=0.995 to 0.005, y=0.005 to 0.995, and wherein x+y=1.

5. A polymer of formula

wherein

R 24 , R 1 and R 1″ are a C 8 -C 38 alkyl group,

R 15 , R 15′ , R 3 and R 26 are a C 1 -C 18 alkyl group,

R 1′ is C 8 -C 36 alkyl,

R 3′ is C 1 -C 18 alkyl, R 1 ≠R 1′ and/or R 3 ≠R 3′ ,

n is 4 to 1000,

x is 0.005 to 0.995,

y is 0.995 to 0.005, and

wherein m+n=1.

6. The polymer according to claim 1 wherein R 1 and R 2 are a (branched) C 8 -C 36 alkyl group.

7. An organic semiconductor material, layer or component, comprising the polymer according to claim 1 .

8. A semiconductor device, comprising the polymer according to claim 1 .

9. The semiconductor device according to claim 8 , which is an organic photovoltaic (PV) device, a photodiode, or an organic field effect transistor.

10. The PV device according to claim 9 , wherein the PV device comprises in this order:

(a) a cathode (electrode),

(b) optionally a transition layer,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode), and

(f) a substrate.

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

applying a solution and/or dispersion of the polymer according to claim 1 in an organic solvent to a suitable substrate; and

removing the solvent.

12. A method of using the polymer according to claim 1 comprising adding the polymer according to claim 1 in PV devices, photodiodes, or organic field effect transistors.

13. The polymer according to claim 5 ,

wherein n is 4 to 200.

14. The polymer according to claim 5 ,

wherein n is 5 to 100.

15. The PV device according to claim 10 ,

wherein the transition layer is an alkali halogenide.

16. The PV device according to claim 15 ,

wherein the alkali halogenide is lithium fluoride.