Diketopyrrolopyrrole polymers as organic semiconductors

Patent metadata

Field	Value
Publication number	US-10424737-B2
Application number	US-201514924060-A
Country	US
Kind code	B2
Filing date	Oct 27, 2015
Priority date	Jun 30, 2006
Publication date	Sep 24, 2019
Grant date	Sep 24, 2019

Abstract

The present invention relates to polymers comprising a repeating unit of the formula (I) and their use as organic semiconductor in organic devices, especially a diode, an organic field effect transistor and/or a solar cell, or a device containing a diode and/or an organic field effect transistor, and/or a solar cell. 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 semiconductor devices or organic photovoltaic (PV) devices (solar cells).

First claim

The invention claimed is:

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 e

Assignees

• Basf Se

Inventors

• Turbiez Mathieu G R
• Janssen Rene Albert Johan
• Wienk Martinus Maria
• Kirner Hans Juerg
• Dueggeli Mathias

Classifications

• C08G61/02

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• C08G61/126

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

• C07D487/04

  Ortho-condensed systems · CPC title

• C09B69/109

  containing other specific dyes · CPC title

• C08G61/122

  derived from five- or six-membered heterocyclic compounds, other than imides · CPC title