Diketopyrrolopyrrole polymers as organic semiconductors

1. A polymer comprising repeating unit(s) of the formula (I):

wherein

Ar 4 c Ar 3 b Ar 2 a —Ar 1 — and —Ar 1′ Ar 2′ d Ar 3′ e Ar 4′ f — may be the same or different, and are a group of formula:

wherein

▬ indicates the bond to the diketopyrrolopyrrole skeleton,

R 1 and R 2 are independently from each other C 1 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms, cyclohexyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or cyclohexyl, which can be condensed one or two times by phenyl, which can be substituted one to three times with C 1 -C 4 alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or —CR 5 R 6 —(CH 2 ) g —Ar 10 , wherein R 5 and R 6 are each hydrogen, Ar 10 is phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, and g is 0 or 1, and

R 4 and R 4′ are independently from each other C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms.

2. The polymer according to claim 1 , wherein the polymer is a co-polymer consisting of repeating units of formula:

* A *  (A)

and

* COM 1 *   (COM1),

wherein a molar amount of the repeating unit (A) is from 0.995 to 0.005 and a molar amount of the repeating unit (COM1) is from 0.005 to 0.995, with respect to a total of the repeating units included in the co-polymer,

a co-polymer consisting of repeating units of formula:

* A *  (A)

and

* COM 2 *   (COM2),

wherein a molar amount of the repeating unit (A) is from 0.995 to 0.005 and a molar amount of the repeating unit (COM2) is from 0.005 to 0.995, with respect to a total of repeating units included in the co-polymer,

a polymer consisting of repeating units of formula:

A-COM 1 , or

a polymer consisting of repeating units of formula:

A-COM 2 ,

wherein

A is a repeating unit of formula I,

—COM 1 - is a repeating unit of the formula:

R 7 and R 7′ are independently from each other C 6 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms,

R 44 and R 41 are independently from each other hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy,

R 45 is hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, wherein D is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, or —NR 25 —, R 25 is C 1 -C 12 alkyl, E is —OR 29 , —SR 29 , —NR 25′ R 25′ , —COR 28 , —COOR 27 , —CONR 25′ R 25′ , or —CN, and R 25′ , R 27 , R 28 and R 29 are each, independently, C 1 -C 12 alkyl or C 6 -C 14 aryl, and

—COM 2 - is a group of the formula

R 116 and R 117 are each, independently, hydrogen, C 1 -C 18 alkyl, which can optionally be interrupted by an oxygen atom, or C 1 -C 18 alkoxy, which can optionally be interrupted by an oxygen atom,

R 119 and R 120 are each, independently, hydrogen, C 1 -C 18 alkyl, which can optionally be interrupted by an oxygen atom, or

R 119 and R 120 together form a group of the formula ═CR 100 R 101 ,

R 100 and R 101 are each, independently, hydrogen, C 1 -C 18 alkyl, or

R 119 and R 120 together form a five or six membered ring, which optionally can be substituted by C 1 -C 18 alkyl.

3. The polymer according to claim 1 , wherein the polymer is a polymer consisting of repeating units of formula:

* A o COM 2 p *  (ACOM2), and optionally,

* COM 1 r COM 2 s   (COM12),

wherein the order of the unit * A * and the unit * COM 1 * is arbitrary in the repeating unit (ACOM2), and the order of the unit * COM 1 * and the unit * COM 2 * is arbitrary in the repeating unit (COM12),

o is 1,

p is 0 or 1,

r is 0 or 1,

s is 0 or 1,

a molar amount of the repeating unit (ACOM2) is from 0.005 to 1 and a molar amount of the repeating unit (COM12) is from 0.995 to 0, with respect to a total of repeating units included in the polymer,

A is a repeating unit of formula I,

—COM 1 - is a repeating unit of the formula:

R 7 and R 7′ are independently from each other C 6 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms,

R 44 and R 41 are independently from each other hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy,

R 45 is hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, wherein D is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, or —NR 25 —, R 25 is C 1 -C 12 alkyl, E is —OR 29 , —SR 29 , —NR 25′ R 25′ , —COR 28 , —COOR 27 , —CONR 25′ R 25′ , or —CN, and R 25′ , R 27 , R 28 and R 29 are each, independently, C 1 -C 12 alkyl or C 6 -C 14 aryl, and

—COM 2 - is a group of the formula

R 116 and R 117 are each, independently, hydrogen, C 1 -C 18 alkyl, which can optionally be interrupted by an oxygen atom, or C 1 -C 18 alkoxy, which can optionally be interrupted by an oxygen atom,

R 119 and R 120 are each, independently, hydrogen, C 1 -C 18 alkyl, which can optionally be interrupted by an oxygen atom, or

R 119 and R 120 together form a group of the formula ═CR 100 R 101 ,

R 100 and R 101 are each, independently, hydrogen, C 1 -C 18 alkyl, or

R 119 and R 120 together form a five or six membered ring, which optionally can be substituted by C 1 -C 18 alkyl.

4. A polymer consisting of repeating units of the formula:

wherein

R 1 and R 2 are each, independently, C 1 -C 25 alkyl,

R 3 and R 3′ are each, independently, C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms,

R 4 and R 4′ are each, independently, C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms, and

R 7 and R 7′ are each, independently, C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms.

5. The polymer according to claim 1 , consisting of repeating units of the formula:

wherein

R 1 and R 2 are each, independently, C 1 -C 25 alkyl, and

R 4 is C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atom.

6. A semiconductor device, comprising a polymer according to claim 1 .

7. The semiconductor device according to claim 6 , which is a diode, a photodiode, an organic field effect transistor and/or a solar cell, or a device containing a diode and/or a photodiode and/or an organic field effect transistor, and/or a solar cell.

8. The semiconductor device according to claim 6 , which is a solar cell, comprising in this order:

(a) a cathode,

(b) optionally, an electrically insulating transition layer,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode, and

(f) a substrate, wherein the photoactive layer comprises said polymer.

9. The semiconductor device according to claim 8 , which comprises the electrically insulating transition layer and the electrically insulating transition layer comprises an alkali halogenide.

10. The semiconductor device according to claim 9 , wherein the alkali halogenide is lithium fluoride.

11. The semiconductor device according to claim 6 , which is a thin film transistor device, comprising:

a plurality of electrically conducting gate electrodes disposed on a substrate;

a gate insulator layer disposed on said electrically conducting gate electrodes;

a plurality of sets of electrically conductive source and drain electrodes disposed on said insulator layer such that each of said sets is in alignment with each of said gate electrodes;

an organic semiconductor layer disposed in the channel between source and drain electrodes on said insulator layer substantially overlapping said gate electrodes, wherein said organic semiconductor layer comprises said polymer.

12. A process for the preparation of the organic semiconductor device according to claim 6 , comprising applying a solution and/or dispersion of the polymer in an organic solvent to a suitable substrate and removing the solvent.

13. A process for preparing a polymer consisting of repeating units of the formula:

A-COM 1 (VIId), or a polymer consisting of repeating units of the formula: A-COM 2 (VIIe), comprising reacting a dihalogenide of formula X-A-X, with an equimolar amount of a diboronic acid or diboronate corresponding to formula X 11 COM 1 X 11 , or X 11 COM 2 X 11 under the catalytic action of Pd and triphenylphosphine, wherein

X is halogen,

A is a group of formula:

wherein

Ar 4 c Ar 3 b Ar 2 a Ar 1 — and —Ar 1′ Ar 2′ d Ar 3′ e Ar 4′ f may be the same or different, and are a group of formula:

wherein

▬ indicates the bond to the diketopyrrolopyrrole skeleton,

R 1 and R 2 are independently from each other C 1 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms, cyclohexyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or cyclohexyl, which can be condensed one or two times by phenyl, which can be substituted one to three times with C 1 -C 4 alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or —CR 5 R 6 —(CH 2 ) g —Ar 10 , wherein R 5 and R 6 are each hydrogen, Ar 10 is phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, and g is 0 or 1, and

R 4 and R 4′ are independently from each other C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms,

—COM 1 - is a repeating unit of the formula:

R 7 and R 7′ are independently from each other C 6 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms,

R 44 and R 41 are independently from each other hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy,

R 45 is hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, wherein D is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, or —NR 25 —, R 25 is C 1 -C 12 alkyl, E is —OR 29 , —SR 29 , —NR 25′ R 25′ , —COR 28 , —COOR 27 , —CONR 25′ R 25′ , or —CN, and R 25′ , R 27 , R 28 and R 29 are each, independently, C 1 -C 12 alkyl or C 6 -C 14 aryl,

—COM 2 - is a group of the formula

R 116 and R 117 are each, independently, hydrogen, C 1 -C 18 alkyl, which can optionally be interrupted by an oxygen atom, or C 1 -C 18 alkoxy, which can optionally be interrupted by an oxygen atom,

R 119 and R 120 are each, independently, hydrogen, C 1 -C 18 alkyl, which can optionally be interrupted by an oxygen atom, or

R 119 and R 126 together form a group of the formula ═CR 100 R 101 ,

R 100 and R 101 are each, independently, hydrogen, C 1 -C 18 alkyl, or

R 119 and R 120 together form a five or six membered ring, which optionally can be substituted by C 1 -C 18 alkyl,

X 11 is independently in each occurrence —B(OH) 2 , —B(OY 1 ) 2 or

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.

14. The process of claim 13 , wherein Y 2 is independently in each occurrence —CY 34 —CY 5 Y 6 — or —CY 7 Y 8 —CY 9 Y 10 —CY 11 Y 12 —, wherein Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 are each, independently, hydrogen or a C 1 -C 10 alkyl group.

15. The process of claim 14 , wherein Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 and Y 12 are independently of each other hydrogen, —C(CH 3 ) 2 C(CH 3 ) 2 —, or —C(CH 3 ) 2 CH 2 C(CH 3 ) 2 —.

16. A monomer of formula X-A-X, wherein

A is a group of formula

X is halogen,

wherein Ar 4 c Ar 3 b Ar 2 a Ar 1 — and —Ar 1′ Ar 2′ d Ar 3′ e Ar 4′ f may be the same or different, and are a group of formula

wherein

▬ indicates the bond to the diketopyrrolopyrrole skeleton,

R 1 and R 2 are independently from each other C 1 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms, cyclohexyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or cyclohexyl, which can be condensed one or two times by phenyl, which can be substituted one to three times with C 1 -C 4 alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or —CR 5 R 6 —(CH 2 ) g —Ar 10 , wherein R 5 and R 6 are each hydrogen, Ar 10 is phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, and g is 0 or 1, and

R 4 and R 4′ are independently from each other C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms.

17. The monomer according to claim 16 , wherein A is a group of formula:

wherein

R 1 and R 2 are each, independently, C 1 -C 25 alkyl, and

R 4 and R 4′ are each, independently, is C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms.

18. A method of making a product, comprising incorporating the polymer of claim 1 into the product.

19. The method of claim 18 , wherein the product is selected from the group consisting of charge-transport material, semiconducting material, electroluminescent conducting material, photoconducting material, light emitting material, surface-modifying material, electrode materials in batteries, alignment layers, or in OFETs, ICs, TFTs, displays, RFITD tags, electro- or photoluminescent devices, backlights of displays, photovoltaic or sensor devices, charge injection layers, Schottky diodes, memory devices, planarising layers, antistatics, conductive substrates or patterns, photoconductors, and electrophotographic applications.

20. A polymer consisting of repeating unit(s) of the formula:

wherein

R 1 and R 2 are independently from each other C 1 -C 25 alkyl, which can optionally be interrupted by one or more oxygen atoms, cyclohexyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or cyclohexyl, which can be condensed one or two times by phenyl, which can be substituted one to three times with C 1 -C 4 alkyl, halogen, nitro or cyano, phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, or —CR 5 R 6 —(CH 2 ) g —Ar 10 , wherein R 5 and R 6 are each hydrogen, Ar 10 is phenyl or 1- or 2-naphthyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy, and g is 0 or 1, and

R 4 is C 6 -C 25 alkyl, which may optionally be interrupted by one or more oxygen atoms.

21. A polymer consisting of repeating units of the formula

wherein n is an integer of 2 or more.