Diketopyrrolopyrrole polymers for use in organic semiconductor devices

Patent metadata

Field	Value
Publication number	US-9478745-B2
Application number	US-201414308766-A
Country	US
Kind code	B2
Filing date	Jun 19, 2014
Priority date	Mar 23, 2009
Publication date	Oct 25, 2016
Grant date	Oct 25, 2016

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. A compound of formula (III) shown below:

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 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 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 or C 1 -C 8 alkoxy; a C 6 -C 24 aryl group, in particular phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 thioalkoxy, 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 are groups of formula

which may be optionally substituted by one, or more groups,
R 3 and R 3′ 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 25 alkoxy;
R 4 , R 4′ , R 5 , R 5′ , R 6 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 arylalkyl, or C 1 -C 25 alkoxy;
R 114 is C 1 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms,
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 arylalkyl,
R 8 and R 8′ are independently of each other hydrogen, 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; or C 7 -C 25 arylalkyl,
R 11 and R 11′ are independently of each other C 1 -C 25 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, which can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy;
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, C 7 -C 25 arylalkyl, or R 13 , wherein R 13 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,
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 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 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 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 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 or interrupted by D, or C 7 -C 25 aralkyl,
R 10 and R 10′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, or a group of one of the formulae IVa to IVi,

wherein R 22 to R 26 and R 29 to R 58 represent independently of each other H, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E 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, a C 4 -C 18 cycloalkyl group, a C 4 -C 18 cycloalkyl group, 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 or interrupted by D, C 7 -C 25 aralkyl, or C 7 -C 25 aralkyl, which is substituted by G,
R 27 and R 28 are independently of each other hydrogen, C 1 -C 25 alkyl, or C 7 -C 25 aralkyl, or R 27 and R 28 together represent alkylene or alkenylene which may be both bonded via oxygen or sulfur to the thienyl residue and which may both have up to 25 carbon atoms,
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—;

with the proviso that the following compound

is excluded.

2. An organic semiconductor material, layer or component, comprising a compound according to claim 1 .

3. A semiconductor device comprising a compound according to claim 1 .

4. The semiconductor device according to claim 3 is an organic photovoltaic device including a solar cell, a photodiode, or an organic field effect transistor.

5. A process for the preparation of an organic semiconductor device, which process comprises a

Assignees

• Basf Se

Inventors

• Hayoz Pascal
• Aebischer Olivier Frédéric
• Düggeli Mathias
• Kirner Hans Jürg
• Turon Marta Fonrodona

Classifications

• H10K85/113

  Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene · CPC title

• C07D487/04 Primary

  Ortho-condensed systems · CPC title

• H10D30/67

  Thin-film transistors [TFT] {(Stacked nanowire, nanosheet or nanoribbon FETs H10D30/501)} · CPC title

• H01L51/0036

  Electricity · mapped topic

• H01L51/0035

  Electricity · mapped topic