Diketopyrrolopyrrole polymers for use in organic semiconductor devices

Patent metadata

Field	Value
Publication number	US-10177313-B2
Application number	US-201615264183-A
Country	US
Kind code	B2
Filing date	Sep 13, 2016
Priority date	Mar 23, 2009
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula (I) which are characterized in that Ar 1 and Ar 1′ are independently of each other are an annulated (aromatic) heterocyclic ring system, containing at least one thiophene ring, which may be optionally substituted by one, or more groups, 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.

First claim

The invention claimed is:

1. An organic semiconductor material, layer or component, comprising a polymer comprising one or more (repeating) unit(s) of the formula

wherein a is 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; d is 0, 1, 2, or 3; d′ is 0, 1, 2, or 3; with the proviso that b′ is not 0, if a′ is 0;
R 1 and R 2 may be the same or different and are selected from hydrogen, a C 1 -C 100 alkyl group, —COOR 103 , a C 1 -C 100 alkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C 6 -C 18 aryl groups and/or interrupted by —O—, —COO—, —OCO—, or —S—; a C 7 -C 100 arylalkyl group, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; a carbamoyl group, C 5 -C 12 cycloalkyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; a C 6 -C 24 aryl group, 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, Ar 1 and Ar 1′ are independently of each other an annulated (aromatic) heterocyclic ring system, containing at least one thiophene ring, which may be optionally substituted by one, or more groups,
Ar 2 , Ar 2′ , Ar 3 , Ar 3′ , Ar 4 and Ar 4′ have the meaning of Ar 1 , or are independently of each other

wherein one of X 3 and X 4 is N and the other is CR 99 ,
R 99 , R 104 and R 104′ are independently of each other hydrogen, halogen, or a C 1 -C 25 alkyl group, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 arylalkyl, or a C 1 -C 25 alkoxy group, R 105 , R 105′ , R 106 and R 106′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms;
C 7 -C 25 arylalkyl, or C 1 -C 18 alkoxy,
R 107 is C 7 -C 25 arylalkyl, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; C 1 -C 18 alkyl which is interrupted by —O—, or —S—; or —COOR 103 ; R 103 is C 1 -C 50 alkyl;
R 108 and R 109 are independently of each other H, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or C 7 -C 25 aralkyl, or
R 108 and R 109 together form a group of formula ═CR 110 R 111 , wherein
R 110 and R 111 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, or C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G, or R 108 and R 109 together form a five or six membered ring, which optionally can be substituted by C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D,
C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or C 7 -C 25 aralkyl,
D is —CO—, —COO—, —S—, —O—, or —NR 112 —,
E is C 1 -C 8 thioalkoxy, C 1 -C 8 alkoxy, CN, —NR 112 R 113 , —CONR 112 R 113 , or halogen,
G is E, or C 1 -C 18 alkyl, and
R 112 and R 113 are independently of each other H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—.

2. The organic semiconductor material, layer or component comprising a polymer according to claim 1 , wherein the polymer comprises one or more (repeating) unit(s) of the formula

wherein
R 1 is a C 8 -C 36 alkyl group,
R 3 is hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;
R 4 , R 4′ , R 5 , R 5′ and R 6 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;
R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, or C 7 -C 25 aralkyl,
R 8 is C 7 -C 25 aralkyl, C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, and
R 12 and R 12′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, or

wherein R 13 is C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group.

3. The organic semiconductor material, layer or component according to claim 1 , wherein the polymer comprises (repeating) unit(s) of the formula

wherein
A is a repeating unit of formula (I), and
COM 1 - is a repeating unit, which is selected from a group of formula Ar 1 , such as, for example,

wherein
one of X 5 and X 6 is N and the other is CR 14
R 14 , R 14′ , R 17 and R 17′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;
R 18 and R 18′ independently of each other hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be 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 which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; or C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms;
R 20 and R 20′ are independently of each other hydrogen, C 7 -C 25 aralkyl, C 1 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, and Ar 1 is as defined in claim 1 .

4. The organic semiconductor material, layer or component according to claim 3 , wherein A is a repeating unit of formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (H), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu) or (Iv) as defined in claim 2 .

5. The organic semiconductor material, layer or component according to claim 3 , wherein the polymer comprises one or more (repeating) unit(s) of the formula

Assignees

• Basf Se

Inventors

• Hayoz Pascal
• Aebischer Olivier
• Duggeli Mathias
• Kirner Hans Jurg
• Turon Marta Fonrodona

Classifications

• H01L51/0036 Primary

  Electricity · mapped topic

• C08G2261/228

  Polymers, i.e. more than 10 repeat units · CPC title

• C08G2261/334

  containing heteroatoms · CPC title

• C09B69/109

  containing other specific dyes · CPC title

• C08G61/124

  with a five-membered ring containing one nitrogen atom in the ring · CPC title