Organic semiconductors

Patent metadata

Field	Value
Publication number	US-9761805-B2
Application number	US-201214234201-A
Country	US
Kind code	B2
Filing date	Jun 21, 2012
Priority date	Jul 19, 2011
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

The invention relates to novel organic semiconducting oligomers or polymers containing dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene units, methods for their preparation and educts or intermediates used therein, polymers, blends, mixtures and formulations containing them, the use of the oligomers, polymers, blends, mixtures and formulations as semiconductor in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these oligomers, polymers, blends, mixtures or formulations.

First claim

The invention claimed is:

1. An oligomer or polymer comprising divalent units of formula I

wherein
V 1 and V 2 are independently of each other O, S, Se or Te,
X 1 and X 2 are independently of each other CR 1 R 2 , C═CR 1 R 2 , SiR 1 R 2 or GeR 1 R 2 ,
R, R 1 and R 2 independently of each other, and on each occurrence identically or differently, denote H, F, Cl, Br, CN, straight-chain, branched or cyclic alkyl, with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —O—C(O)—O—, —C(S)—, —C(S)—O—, —O—C(S)—, —O—C(S)—O—, —C(O)—S—, —S—C(O)—, —O—C(O)—S—, —S—C(O)—O—, —S—C(O)—S—, —S—C(S)—S—, —O—C(S)—S—, —S—C(S)—O—, —C(S)—S—, —S—C(S)—, —NR 0 —, —SiR 0 R 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, or R 1 and R 2 , independently of each other, and on each occurrence identically or differently, denote aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted, or R 1 and R 2 together form an alicyclic group with 1 to 20 C atoms, which is optionally fluorinated or alkylated,
Y 1 and Y 2 are independently of each other H, F, Cl or CN,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl.

2. The polymer according to claim 1 , characterized in that it comprises one or more units of formula II
—[(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ]—  II

wherein
U is a unit of formula I as defined in claim 1 ,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, preferably has 5 to 30 ring atoms and is optionally substituted, preferably by one or more groups R S ,
R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerisable or crosslinkable group,
Sp is a spacer group or a single bond,
X 0 is halogen, preferably F, Cl or Br,
a, b, c are on each occurrence identically or differently 0, 1 or 2,
d is on each occurrence identically or differently 0 or an integer from 1 to 10,
wherein the polymer comprises at least one repeating unit of formula II wherein b is at least 1.

3. The polymer according to claim 1 , characterized in that it additionally comprises one or more repeating units selected of formula III
—[(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c —(Ar 3 ) d ]—  III

wherein
Ar 1 , Ar 2 , Ar 3 , are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, preferably has 5 to 30 ring atoms and is optionally substituted, preferably by one or more groups R S ,
a, b, c are on each occurrence identically or differently 0, 1 or 2,
d is on each occurrence identically or differently 0 or an integer from 1 to 10, and
A 1 is an aryl or heteroaryl group that is different from Formula I and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S , and is selected from aryl or heteroaryl groups having electron donor properties, wherein the polymer comprises at least one repeating unit of formula III wherein b is at least 1, and R S is on each occurrence identically or differently F, Br, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(O)NR 0 R 00 , —C(O)X 0 , —C(O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-.

4. The polymer according to claim 1 , of formula IV:

wherein
A is a unit of formula I as defined in claim 1 ,
B is a unit that is different from A and comprises one or more aryl or heteroaryl groups that are optionally substituted,
x is >0 and ≦1,
y is ≧0 and <1,
x+y is 1, and
n is an integer >1.

5. The polymer according to claim 2 , of the following formulae
*—[(Ar 1 -U-Ar 2 ) x —(Ar 3 ) y ] n —*  IVa

*—[(Ar 1 -U-Ar 2 ) x —(Ar 3 —Ar 3 ) y ] n —*  IVb

*—[(Ar 1 -U-Ar 2 ) x —(Ar 3 —Ar 3 —Ar 3 ) y ] n —*  IVc

*—[(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ] n —*  IVd

*—([(Ar 1 ) a -(U) b -(Ar 2 ) c —(Ar 3 ) d ] x —[(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c —(Ar 3 ) d ] y ) n —*   IVe

wherein these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe in at least one of the repeating units [(Ar 1 ) a -(U) b - (Ar 2 ) c —(Ar 3 ) d ] and in at least one of the repeating units [(Ar 1 ) a -(A 1 ) b -(Ar 2 ) c —(Ar 3 ) d ] b is at least 1.

6. The polymer according to claim 1 , of the following formulae

wherein R has on each occurrence identically or differently one of the meanings of R 1 as given in claim 1 .

7. The polymer according to claim 4 , of formula V
R 5 -chain-R 6   V

wherein “chain” is a polymer chain selected of formulae IV, and R 5 and R 6 denote independently of each other F, Br, Cl, H, —CH 2 Cl, —CHO, —CH═CH 2 , —SiR′R″R′″, —SnR′R″R′″, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , —ZnCl, —MgCl, —MgBr or P-Sp, R′, R″ and R″ have independently of each other one of the meanings of R 0 , and two of R′, R″ and R′″ may also form a ring together with the hetero atom to which they are attached.

8. The polymer according to claim 2 , wherein one or more of Ar 1 , Ar 2 and Ar 3 denote aryl or heteroaryl of the following formulae

wherein one of X 11 and X 12 is S and the other is Se, and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H or have one of the meanings of R 1 .

9. The polymer according to claim 3 , wherein one or more of the units Ar 3 and A

Assignees

• Wang Changsheng
• Tierney Steven
• D'Lavari Mansoor
• Nanason Lana
• Merck Patent Gmbh

Inventors

• Wang Changsheng
• Tierney Steven
• D'Lavari Mansoor
• Nanason Lana

Classifications

• C08G2261/95

  Use in organic luminescent diodes · CPC title

• C08G2261/92

  TFT applications · CPC title

• C08G2261/91

  Photovoltaic applications · CPC title

• C08G2261/3243

  containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene · CPC title

• C08G2261/124

  alternating · CPC title