Organic semiconductors

Patent metadata

Field	Value
Publication number	US-12329024-B2
Application number	US-202017593352-A
Country	US
Kind code	B2
Filing date	Mar 17, 2020
Priority date	Mar 19, 2019
Publication date	Jun 10, 2025
Grant date	Jun 10, 2025

Abstract

The invention relates to novel organic semiconducting (OSC) random copolymers containing a halo-substituted 4,8-dithiophenyl-benzodithiophene unit and a benzodithiophene-dione unit, to methods for their preparation and educts or intermediates used therein, to compositions and formulations containing them, to the use of the copolymers and compositions as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photodetectors (OPD), organic field effect transistors (OFET) and organic light emitting diodes (OLED), and to OE devices comprising these copolymers or compositions.

First claim

The invention claimed is:

1. A conjugated copolymer comprising one or more units of formula I and one or more units of formula II that are distributed in random sequence along the polymer backbone

wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
Ar 1 is a group selected from the following formulae and their mirror images

Ar 2 is a group selected from the following formulae and their mirror images

X 1 , X 2 are H, F, Cl or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
W is S, O, Se, CR 1 R 2 or NR 1 ,
R 1-10 is H, F, Cl, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl or heteroarylalkyl, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
L is F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
Y 1 , Y 2 are H, F, Cl or CN,
X 0 halogen,
Z 1 S,
R 0 , R 00 are H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,
a, b are 1 or 2.

2. The conjugated polymer according to claim 1 , characterized in that in the units of formula I R 1 and R 2 are selected from the group consisting of straight-chain or branched alkyl, alkoxy or thioalkyl having 1 to 30 C atoms and being optionally fluorinated.

3. The conjugated polymer according to claim 1 , characterized in that in the units of formula II and its subformulae Ar 1 is selected from the following formulae and their mirror images

4. The conjugated polymer according to claim 1 , characterized in the units of formula I and II are selected from the following subformulae:

5. The conjugated polymer according to claim 1 , characterized in that the units of formula I and II are selected from the following subformulae:

6. The conjugated polymer according to claim 1 , characterized in that it is a random copolymer of formula III:

wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
A is a unit of the following formulae

B is a unit of the following formulae

x, y are >0 and <1, with x+y=1, and
n is an integer>1.

7. The conjugated polymer according to claim 6 , characterized in that it is selected from the following subformulae:

wherein
R, R′, R S have on each occurrence identically or differently denote H, F, Cl, straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 —═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl or heteroarylalkyl, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,
L is F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with with 1 to 30 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,
Y 1 , Y 2 are H, F, Cl or CN,
X 0 is halogen,
R 0 , R 00 are H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.

8. The conjugated polymer according to claim 1 , characterized in that it is selected of formula IV
R 21 -chain-R 22   IV

wherein “chain” denotes an oligomer or polymer chain selected from the following formulae,

and R 21 and R 22 have independently of each other one of the meanings of L, or denote, independently of each other, H, F, Br, Cl, I, —CH 2 Cl, —CHO, —CR a ═CR b 2 , —SiR a R b R c , —SiR a X a X b , —SiR a R b X a ,

Assignees

• Raynergy Tek Inc

Inventors

• Morse Graham
• Pron Agnieszka
• Kowalski Sebastian
• Tiwana Priti
• Snow Jonathan
• Tan Li Wei

Classifications

• H10K30/30

  comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K85/151

  Copolymers · CPC title

• H10K85/113 Primary

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

• C08G2261/514

  Electron transport · CPC title