Metal complexes as P-type dopants for organic electronic matrix materials

Patent metadata

Field	Value
Publication number	US-9929362-B2
Application number	US-201314406307-A
Country	US
Kind code	B2
Filing date	May 14, 2013
Priority date	Jun 6, 2012
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

A bi- or polynuclear metal complex of a metal of groups Vb/VIb/VIIb (IUPAC groups 5-7), has a ligand of the structure (a), wherein R1 and R2, independently of each other, can be oxygen, sulfur, selenium, NH, or NR4, wherein R4 is selected from alkyls and aryls and can be bonded to R3; and R3 is selected from alkyls, long-chain alkyls, alkoxys, long-chain alkoxys, cycloalkyls, haloalkyls, aryls, arylenes, haloaryls, heteroaryls, heteroarylenes, heterocycloalkylenes, heterocycloalkyls, haloheteroaryls, alkenyls, haloalkenyls, alkynyls, haloalkynyls, ketoaryls, haloketoaryls, ketoheteroaryls, ketoalkyls, haloketoalkyls, ketoalkenyls, haloketoalkenyls, where one or more non-adjacent CH2 groups can be replaced, independently, with (1) —O—, —S—, —NH—, —NR ∘ —, —SiR ∘ R ∘∘ —, —CO—, —COO—, —OCO—, —OCO—O—, —SO2-, —S—CO—, —CO—S—, —CY1=CY2, or —C≡O— in such a way that O and/or S atoms are not bonded directly to each other, or (2) aryls or heteroaryls containing 1 to 30 C atoms, as a p-type doping agent for matrix materials of electronic components.

First claim

The invention claimed is:

1. An organic electronic component comprising:
a matrix containing a p-dopant, the p-dopant being a bi- or polynuclear group metal complex containing at least two metal atoms selected from groups Vb/VIb/VIIb, IUPAC groups 5-7, which groups consist of vanadium, niobium, tantalum (group 5), chromium, molybdenum, tungsten (group 6), manganese, technetium, rhenium (group 7), and mixtures thereof, the metal complex having a neutral charge and containing at least one ligand L of the following structure:

where R 1 and R 2 each independently represents oxygen, sulfur, selenium, NH or NR 4 where R 4 is an alkyl or aryl group and may be bonded to R 3 ; and
where R 3 is selected from the group consisting of alkyl groups, long-chain alkyl groups, alkoxy groups, long-chain alkoxy groups, cycloalkyl groups, haloalkyl groups, aryl groups, arylenes, haloaryl groups, heteroaryl groups, heteroarylenes, heterocycloalkylenes, heterocycloalkyl groups, haloheteroaryl groups, alkenyl groups, haloalkenyl groups, alkynyl groups, haloalkynyl groups, ketoaryl groups, haloketoaryl groups, ketoheteroaryl groups, ketoalkyl groups, haloketoalkyl groups, ketoalkenyl groups, haloketoalkenyl groups, where one or more non-adjacent CH2 groups in suitable radicals may independently be replaced by:
—O—, —S—, —NH—, —NR ∘ —, —SiR ∘ R ∘∘ —, —CO—, —COO—, —OCO—, —OCO—O—, —SO 2 , —S—CO—, —CO—S, —CY1=CY2 or —C═C—, in such a way that no oxygen and/or sulfur atoms are bonded directly to one another, or
an aryl group or heteroaryl group containing 1 to 30 carbon atoms in which terminal CH 3 groups are regarded as CH 2 groups, CH 2 —H.

2. The component as claimed in claim 1 , wherein the metal atoms are selected from the group consisting of chromium, molybdenum, tungsten and mixtures of chromium, molybdenum and/or tungsten.

3. The component as claimed in claim 1 , wherein R3 is selected from the group consisting of haloalkyl groups, haloaryl groups, haloalkylaryl groups and haloheteroaryl groups.

4. The component as claimed in claim 1 , wherein R 3 is represented by the following formula:

where Y 1 -Y 5 are each independently selected from the group consisting of C—F, C—CF 3 , C—NO 2 , C—CN, C-halogen, C-pseudohalogen and N.

5. The component as claimed in claim 1 , wherein the metal complex further contains at least one ligand selected from the group consisting of the unsubstituted organic carboxylic acids, partially fluorinated organic carboxylic acids and perfluorinated organic carboxylic acids.

6. The component as claimed in claim 1 , wherein the metal complex further contains at least one ligand selected from the group consisting of unsubstituted acetic acid, partially fluorinated acetic acids and perfluorinated acetic acids.

7. The component as claimed in claim 1 , wherein the metal complex has a paddle wheel structure and contains chromium or molybdenum as the metal atoms and wherein R 1 and R 2 are oxygen.

8. The component as claimed in claim 1 , wherein the metal complex has a paddle wheel structure represented by the following formula:

where the metal atoms M are chromium or molybdenum and R 1 and R 2 are oxygen.

9. A method comprising:
using a matrix material as a component of an electronic device, the matrix material containing a p-dopant, the p-dopant being a bi- or polynuclear group metal complex containing at least two metal atoms selected from groups Vb/VIb/VIIb, IUPAC groups 5-7, which groups consist of vanadium, niobium, tantalum (group 5), chromium, molybdenum, tungsten (group 6), manganese, technetium, rhenium (group 7), and mixtures thereof, the metal complex having a neutral charge and containing at least one ligand L of the following structure:

where R 1 and R 2 each independently represents oxygen, sulfur, selenium, NH or NR 4 where R 4 is an alkyl or aryl group and may be bonded to R 3 ; and
where R 3 is selected from the group consisting of alkyl groups, long-chain alkyl groups, alkoxy groups, long-chain alkoxy groups, cycloalkyl groups, haloalkyl groups, aryl groups, arylenes, haloaryl groups, heteroaryl groups, heteroarylenes, heterocycloalkylenes, heterocycloalkyl groups, haloheteroaryl groups, alkenyl groups, haloalkenyl groups, alkynyl groups, haloalkynyl groups, ketoaryl groups, haloketoaryl groups, ketoheteroaryl groups, ketoalkyl groups, haloketoalkyl groups, ketoalkenyl groups, haloketoalkenyl groups, where one or more non-adjacent CH2 groups in suitable radicals may independently be replaced by:
—O—, —S—, —NH—, —NR ∘ —, —SiR ∘ R ∘∘ —, —CO—, —COO—, —OCO—, —OCO—O—, —SO 2 , —S—CO—, —CO—S, —CY1=CY2 or —C═C—, in such a way that no oxygen and/or sulfur atoms are bonded directly to one another, or
an aryl group or a heteroaryl group containing 1 to 30 carbon atoms in which terminal CH 3 groups are regarded as CH 2 groups, CH 2 —H.

10. The method as claimed in claim 9 , wherein the electronic device is an organic light emitting diode, and the matrix material is used as a hole transport layer in the organic light emitting diode.

11. The method as claimed in claim 9 , wherein the electronic device is a solar cell, and the matrix material is used as a p-doped layer in the solar cell.

12. The method as claimed in claim 9 , wherein the electronic device is an organic field effect transistor, and
the matrix material is used as an organic semiconductor layer in the organic field effect transistor.

13. A method comprising:
preparing a matrix material containing a p-dopant by a process including a vaporization step using an oxygen concentration of less than 2 ppm;
wherein the p-dopant is a bi- or polynuclear group metal complex containing at least two metal atoms selected from groups Vb/VIb/VIIb, IUPAC groups 5-7, which groups consist of vanadium, niobium, tantalum (group 5), chromium, molybdenum, tungsten (group 6), manganese, technetium, rhenium (group 7), and mixtures thereof, the metal complex containing at least one ligand L of the following structure:

where R 1 and R 2 each independently represents oxygen, sulfur, selenium, NH or NR 4 where R 4 is an alkyl or aryl group and may be bonded to R 3 ; and
where R 3 is selected from the group consisting of alkyl groups, long-chain alkyl groups, alkoxy groups, long-chain alkoxy groups, cycloalkyl groups, haloalkyl groups, aryl groups, arylenes, haloaryl groups, heteroaryl groups, heteroarylenes, heterocycloalkylenes, heterocycloalkyl groups, haloheteroaryl groups, alkenyl groups, haloalkenyl groups, alkynyl groups, haloalkynyl groups, ketoaryl groups, haloketoaryl groups, ketoheteroaryl groups, ketoalkyl groups, haloketoalkyl groups, ketoalkenyl groups, haloketoalkenyl groups, where one or more non-adjacent CH2 groups in suitable radicals may independently be replaced by:
—O—, —S—, —NH—, —NR ∘ —, —SiR ∘ R ∘∘ —, —CO—, —COO—, —OCO—, —OCO—O—, —SO 2 , —S—CO—, —CO—S, —CY1=CY2 or —C═C—, in such a way that no oxygen and/or sulfur atoms are bonded directly to one another, or
an aryl group or a heteroaryl group containing 1 to 30 carbon atoms in which termin

Assignees

• Siemens Ag
• Osram Oled Gmbh

Inventors

• Maltenberger Anna
• Pecqueur Sébastien
• Schmid Guenter
• Wemken Jan Hauke

Classifications

• H01L51/42

  Electricity · mapped topic

• Y02E10/549

  Organic PV cells · CPC title

• H01L51/009 Primary

  Electricity · mapped topic

• H01L51/506

  Electricity · mapped topic

• H10K30/50

  Photovoltaic [PV] devices · CPC title