Diketopyrrolopyrrole polymers for use in organic semiconductor devices
The present invention relates to polymers (I), or (II), and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.
1. A polymer of formula
wherein
x=0.70 to 0.99,
y=0.30 to 0.01, and wherein
x+y=1,
r+s=0.50 to 0.99, t+u=0.50 to 0.01, and wherein r+s+t+u=1,
A is a group of formula
wherein
R 1 and R 2 may be the same or different and are each independently hydrogen, a C 1 -C 38 alkyl group, a C 2 -C 38 alkenyl group, a C 3 -C 38 alkinyl group, each are optionally interrupted one or more times by —O—, —S— or COO, a C 7 -C 100 arylalkyl group, which can be substituted one to five times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, CF 3 and/or F; and a phenyl group optionally substituted one or more times by C 1 -C 25 alkyl, C 1 -C 8 alkoxy, halogen or cyano;
Ar 1 and Ar 2 are each independently
B is a group of formula III, which is different from A,
D is Ar 1 ,
R 204 and R 205 are each independently H, CN, COOR 206 or C 1 -C 8 alkyl;
R 206 is a C 1 -C 18 alkyl group;
E is a group of formula
which is different from D, wherein
k is 1,
l is 0, or 1,
v is 0, or 1,
z is 0, or 1,
a is an integer of 1 to 5,
Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently a group of formula
wherein one of X 5 and X 6 is N and the other is CR 14 ,
Ar 20 is an arylene group, or a heteroarylene group, each of which are optionally substituted,
R 12 and R 12′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one, or more oxygen or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R 13 is a C 1 -C 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 14 , R 14′ , R 15 , R 15′ , R 17 and R 17′ are each independently H, or a C 1 -C 25 alkyl group, optionally interrupted by one or more oxygen atoms;
R 18 and R 18′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;
R 19 is hydrogen, C 7 -C 25 aralkyl, C 6 -C 18 aryl; C 6 -C 18 aryl substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms;
R 20 and R 20′ are each independently hydrogen, C 7 -C 25 aralkyl, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms,
X 7 is —O—, —S—, —NR 115 —, —Si(R 117 )(R 117′ )—, —C(R 120 )(R 120′ )—, —C(═O)—,
X 8 is —O—, or —NR 115 —;
R 100 and R 100′ are each independently H, F, C 1 -C 18 alkyl, C 1 -C 18 alkyl interrupted by O, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy interrupted by O, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, C 2 -C 20 heteroaryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;
R 101 and R 101′ are each independently H, F, C 1 -C 18 alkyl, C 1 -C 18 alkyl interrupted by O, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy interrupted by O, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, C 2 -C 20 heteroaryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;
R 102 and R 102′ are each independently H, halogen, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;
R 103 and R 103′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms; C 6 -C 24 aryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 7 -C 25 arylalkyl, CN, or C 1 -C 25 alkoxy; or
R 103 and R 103′ together form a ring,
R 115 and R 115′ are each independently hydrogen, C 6 -C 18 aryl; C 6 -C 18 aryl substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 arylalkyl,
R 116 is hydrogen, C 7 -C 25 arylalkyl, C 6 -C 18 aryl; C 6 -C 18 aryl substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, or C 1 -C 18 alkoxy; C 1 -C 25 alkyl; C 1 -C 25 alkyl interrupted by —O—, or —S—; or —COOR 119 ; R 119 is C 1 -C 38 alkyl;
R 117 and R 117′ are each independently C 1 -C 35 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy,
R 120 and R 120′ are each independently hydrogen, C 1 -C 38 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 25 arylalkyl, and
R 121 is H, C 1 -C 18 alkyl, optionally interrupted by one or more oxygen or sulphur atoms, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 2 -C 20 heteroaryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; or CN.
2. The polymer of claim 1 , wherein Ar 1 and Ar 2 are each independently a group of formula
3. The polymer of claim 1 , wherein A is a group of formula
wherein R 1 and R 2 are each independently a C 1 -C 38 alkyl group.
4. The polymer of claim 1 , wherein D is a group of formula
5. The polymer of claim 1 , wherein E is a group of formula
wherein
R 100 and R 100′ are each independently H, F, C 1 -C 18 alkyl, C 1 -C 18 alkyl interrupted by O, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy interrupted by O, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, C 2 -C 20 heteroaryl, optionally substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;
R 102 and R 102′ are each independently H, halogen, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;
R 120 and R 120′ are each independently hydrogen, C 1 -C 38 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 25 arylalkyl;
Ar 20 is an arylene group, optionally substituted, or a heteroarylene group, optionally substituted,
R 12 and R 12′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R 13 is a C 1 -C 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 15 and R 15′ are each independently H, or a C 1 -C 25 alkyl group, optionally interrupted by one or more oxygen atoms,
R 18 and R 18′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy; and
R 20 and R 20′ are each independently hydrogen, C 7 -C 25 aralkyl, C 1 -C 25 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms.
6. The polymer of claim 1 , comprising repeating units of the formula
wherein
x=0.70 to 0.99, y=0.30 to 0.01, and wherein x+y=1,
A is a group of formula
wherein
R 1 is a C 1 -C 38 alkyl group,
D is a group of formula
E is a group of formula
wherein
R 12 and R 12′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R 13 is a C 1 -C 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group, and
R 120 and R 120′ are each independently hydrogen, or C 1 -C 38 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms.
7. The polymer of claim 1 , comprising repeating units of the formula
wherein
r+s=0.70 to 0.99, t+u=0.30 to 0.01, and wherein
r+s+t+u=1,
A is a group of formula
B is a group of formula
which is different from A, wherein
R 1 is a C 1 -C 38 alkyl group,
D is a group of formula
E is a group of formula
wherein
R 12 and R 12′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or
R 13 is a C 1 -C 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group, and
R 120 and R 120′ are each independently hydrogen, or C 1 -C 38 alkyl, optionally interrupted by one, or more oxygen, or sulphur atoms.
8. The polymer of claim 1 , which is a polymer of formula
wherein
x=0.70 to 0.99,
y=0.30 to 0.01, and wherein
x+y=1,
R 1 is a C 2 -C 24 alkyl group.
9. An organic semiconductor material, layer or component, comprising
(a) the polymer of claim 1 , and
(b) optionally at least another material.
10. The organic semiconductor material, layer or component of claim 9 , wherein the other material is a compound of formula
wherein
A 1 and A 2 are independently of each other a group of formula
a′ is 1, or 2;
b is 0, or 1;
c is 0, or 1;
R 1′ and R 2′ may be the same or different and are each independently hydrogen, a C 1 -C 38 alkyl group, a C 2 -C 38 alkenyl group, a C 3 -C 38 alkinyl group, each of which are optionally interrupted one or more times by —O—, —S— or COO, a C 7 -C 100 arylalkyl group, which can be substituted one to five times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, CF 3 and/or F; and a phenyl group optionally substituted one or more times by C 1 -C 25 alkyl, C 1 -C 8 alkoxy, halogen or cyano;
A 3 , A 4 and A 5 are each independently a bivalent group of formula
R 214 and R 214′ are each independently hydrogen, halogen, halogenated C 1 -C 25 alkyl, especially CF 3 , cyano, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;
R 3 is hydrogen, halogen, cyano, C 1 -C 25 alkyl,
, wherein
R 22 to R 25 and R 29 to R 33 are each independently H, halogen, cyano, or C 1 -C 25 alkyl, and
R 26 is H, halogen, cyano, phenyl, or C 1 -C 25 alkyl.
11. A semiconductor device, comprising the polymer of claim 1 .
12. The semiconductor device of claim 11 , wherein the semiconductor device is a device selected from the group consisting of an organic photovoltaic device, a photodiode, and an organic field effect transistor.
13. A process for the preparation of an organic semiconductor device, the process comprising:
applying a solution and/or dispersion of the polymer of claim 1 in an organic solvent to a suitable substrate; and
removing the solvent.
14. A photovoltaic device, a photodiode, or an organic field transistor comprising the polymer of claim 1 .
15. A process for the preparation of a polymer of formula
comprising reacting a dihalogenide comprising a formula X 11′ -A-X 11′ with diboronic acids, or diboronates comprising a formulae X 11 -D-X 11 and X 11 -E-X 11 in a solvent and in the presence of a catalyst; or
comprising reacting a diboronic acid, or a diboronate comprising a formula X 11 -A-X 11 with dihalogenides comprising a formulae X 11′ -D-X 11′ and X 11′ -E-X 11″ in a solvent and in the presence of a catalyst; or
a process for the preparation of a polymer of formula
comprising reacting dihalogenides corresponding to formulae X 11′ -A-X 11′ and X 11′ -B-X 11′ with diboronic acids, or diboronates comprising a formulae X 11 -D-X 11 and X 11 -E-X 11 ; or
comprising reacting diboronic acids, or diboronates comprising a formulae X 11 -A-X 11 and X 11 -B-X 11 with dihalogenides comprising a formulae X 11′ -D-X 11′ and X 11′ -E-X 11′ ;
x=0.70 to 0.99,
y=0.30 to 0.01, and wherein
x+y=1,
r+s=0.50 to 0.99,
t+u=0.50 to 0.01, and wherein
r+s+t+u=1,
A is a group of formula
wherein
R 1 and R 2 may be the same or different and are each independently hydrogen, a C 1 -C 38 alkyl group, a C 2 -C 38 alkenyl group, a C 3 -C 38 alkinyl group, each are optionally interrupted one or more times by —O—, —S— or COO, a C 7 -C 100 arylalkyl group, which can be substituted one to five times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, CF 3 and/or F; and a phenyl group optionally substituted one or more times by C 1 -C 25 alkyl, C 1 -C 8 alkoxy, halogen or cyano;
Ar 1 and Ar 2 are each independently
B is a group of formula III, which is different from A,
D is Ar 1 ,
R 204 and R 205 are each independently H, CN, COOR 206 or C 1 -C 8 alkyl;
R 206 is a C 1 -C 18 alkyl group;
E is a group of formula
which is different from D, wherein
k is 1,
l is 0, or 1,
v is 0, or 1,
z is 0, or 1,
a is an integer of 1 to 5,
Ar 4 , Ar 5 , Ar 6 and Ar 7 are each independently a group of formula
wherein one of X 5 and X 6 is N and the other is CR 14 ,
Ar 20 is an arylene group, or a heteroarylene group, each of which are optionally substituted,
R 12 and R 12′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one, or more oxygen or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or R 13 ,
R 13 is a C 1 -C 8 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
R 14 , R 14′ , R 15 , R 15′ , R 17 and R 17′ are each independently H, or a C 1 -C 25 alkyl group, optionally interrupted by one or more oxygen atoms;
R 18 and R 18′ are each independently hydrogen, halogen, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;
R 19 is hydrogen, C 7 -C 25 aralkyl, C 6 -C 18 aryl; C 6 -C 18 aryl substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms;
R 20 and R 20′ are each independently hydrogen, C 7 -C 25 aralkyl, C 1 -C 25 alkyl, optionally interrupted by one or more oxygen or sulphur atoms,
X 11′ is independently in each occurrence Cl, Br, or I,
X 11 is independently in each occurrence —B(OH) 2 , —B(OY 1 ) 2 ,
wherein Y 1 is independently in each occurrence a C 1 -C 10 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, and Y 13 and Y 14 are each independently hydrogen, or a C 1 -C 10 alkyl group.
16. An organic semiconductor device comprising the organic semiconductor material, layer, or component of claim 9 .
17. A photovoltaic device, a photodiode, or an organic field transistor comprising the organic semiconductor material, layer or component of claim 9 .