Singlet harvesting with dual-core copper (I) complexes for optoelectronic devices

Patent metadata

Field	Value
Publication number	US-9537117-B2
Application number	US-201214236202-A
Country	US
Kind code	B2
Filing date	Aug 2, 2012
Priority date	Aug 2, 2011
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

The invention relates to dimeric copper(I) complexes according to formula A, in particular as emitters in optoelectronic devices such as organic light emitting diodes (OLEDs) and other devices

wherein:
Cu: Cu(I), X: Cl, Br, I, SCN, CN, and/or alkynyl and P∩N: a phosphine ligand substituted with a N-heterocycle.

First claim

The invention claimed is:

1. A copper(I) complex for the emission of light comprising a structure according to formula A:

wherein:
Cu is Cu(I);
X is selected from the group consisting of Cl, Br, I, SCN, CN, and alkynyl (R*—≡), wherein R*=R;
P∩N is a phosphine ligand substituted with an N-hetereocycle comprising a structure according to formula B:

wherein:
E is a carbon or a nitrogen atom;
E′ is a carbon or nitrogen atom, not substituted with a hydrogen atom;
dotted bond represents a single or double bond;
R is selected from the group consisting of a substituted or unsubstituted alkyl group [CH 3 —(CH 2 ) n -] (n is an integer from 0 to 20), a substituted or unsubstituted aryl group, and an unsaturated group selected from an alkenyl and an alkynyl group, wherein R is not a hydrogen atom;

R′, R″ are independently selected from the group consisting of a substituted or unsubstituted alkyl group [CH 3 —(CH 2 ) n -] (n is an integer from 0 to 20), a substituted or unsubstituted aryl group, and a heteroaryl group, wherein R′ and R″ are each directly bound to the phosphorous atom of the phosphine ligand; and wherein the N-heterocycle is an aromatic 6- or 5-membered ring selected from:

wherein
R1, R2, R3, are each selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group [CH 3 —(CH 2 ) n ] (n is an integer from 0 to 20), a substituted or unsubstituted aryl group, and an unsaturated group selected from an alkenyl and an alkynyl group; and
wherein the N-heterocycle is linked to the phosphorous atom at the positions marked with #.

2. The copper(I) complex of claim 1 , wherein R is an alkyl group [CH 3 —(CH 2 ) n -] (n is an integer from 0 to 20) substituted with halogens.

3. The copper(I) complex of claim 1 , wherein R is an aryl group substituted with an alkyl group, a halogen, a silane (—SiR* 3 ) wherein R* is the same as R1, or an ether group —OR** wherein R** is the same as R1.

4. The copper(I) complex of claim 1 , wherein R is an unsaturated group substituted with an alkyl group, a halogen, a silane (—SiR* 3 ) wherein R* is the same as R1, or an ether group —OR** wherein R** is the same as R1.

5. The copper(I) complex of claim 1 , wherein R′ and R″ are independently an alkyl group [CH 3 —(CH 2 ) n -] with n is an integer >6.

6. The copper(I) complex of claim 1 , wherein the aryl and heteroaryl groups are substituted with alkyl groups, halogens, silane (—SiR* 3 ) or ether groups —OR*, wherein R*is the same as R1.

7. The copper(I) complex of claim 1 , wherein R1, R2, and R3 are hydrogen atoms.

8. The copper(I) complex of claim 1 , wherein R, R1, R2, and R3 form annulated ring systems.

9. The copper(I) complex of claim 1 , wherein R, R1, R2, R3, R′ and R″ increase the solubility of the copper(I) complex in organic solvents.

10. The copper(I) complex of claim 1 further comprising:
a ΔE(S 1 −T 1 )-value between a lowest triplet state and a singlet state above the lowest triplet state of less than 2500 cm −1 ;
an emission quantum yield of greater than 20%; and
an emission lifetime of at most 20 μs.

11. The copper(I) complex of claim 1 , wherein the copper(I) complex is used for emission of light in an emitter layer in an optoelectronic device.

12. A method for manufacturing an optoelectronic device using the copper(I) complex of claim 1 , wherein the copper(I) complex is applied to a solid by using a wet-chemical process, a colloidal suspension process, or a sublimation process.

13. The method according to claim 12 , wherein the manufacturing is performed by using a wet-chemical process comprising:
depositing a first copper(I) complex that is dissolved in a first solvent onto a carrier; and
depositing a second copper(I) complex that is dissolved in a second solvent onto the carrier;
wherein the first copper(I) complex is not soluble in the second solvent and the second copper(I) complex is not soluble in the first solvent;
wherein the first copper(I) complex and the second copper(I) complex are each a copper(I) complex according to claim 1 .

14. The method of claim 13 further comprising:
depositing a third copper(I) complex that is dissolved in the first solvent or in a third solvent onto the carrier;
wherein the third copper(I) complex is a copper(I) complex according to claim 1 .

15. The method according to claim 14 , wherein the optoelectronic device is a white light-OLED, wherein the first copper(I) complex is a red light emitter, the second copper(I) complex is a green light emitter and the third copper(I) complex is a blue light emitter.

16. An optoelectronic device, comprising a copper(I) complex comprising a ΔE difference between a lowest triplet state and a singlet state above the lowest triplet state between 50 cm −1 and 2500 cm −1 .

17. The optoelectronic device of claim 16 , wherein the copper(I) complex is a copper(I) complex according to claim 1 used for emission of light in an emitter layer in the optoelectronic device.

18. The optoelectronic device of claim 17 , wherein a fraction of the copper(I) complex in the emitter layer is in the range of 2% to 100% by weight with respect to a total weight of the emitter layer.

19. The optoelectronic device of claim 18 , wherein the optoelectronic device is an organic light emitting diode (OLED).

20. The optoelectronic device of claim 17 , wherein the optoelectronic device is selected from the group consisting of an organic light emitting diode (OLED), a light-emitting electrochemical cell, an OLED-sensor, a gas or a vapor sensor that is not hermetically sealed from the outside, an optical temperature sensor, an organic solar cell (OSC), an organic field-effect transistor, an organic laser, an organic diode, an organic photo diode and a down conversion system.

Assignees

• Yersin Hartmut
• Monkowius Uwe
• Hofbeck Thomas
• Cynora Gmbh

Inventors

• Yersin Hartmut
• Monkowius Uwe
• Hofbeck Thomas

Classifications

• C09K11/06 Primary

  containing organic luminescent materials · CPC title

• C07F9/58

  Pyridine rings · CPC title

• C09K2211/188

  of other metals not provided for in one of the previous groups · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• H10K71/00

  Manufacture or treatment specially adapted for the organic devices covered by this subclass · CPC title