# US 9,435,021 B2 · Co-deposition methods for the fabrication of organic optoelectronic devices

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- Number: US 9,435,021 B2
- Document ID: US9435021B2
- Status: Granted
- Kind: B2
- Application number: 13/193,036
- Filed: 2011-07-28
- Published: 2012-02-23
- Granted: 2016-09-06
- Earliest claimed: 2010-07-29
- Assignees: University of Southern California
- Applicants: Mark E. Thompson; Zhiwei Liu; Chao Wu
- Inventors: Mark E. Thompson; Zhiwei Liu; Chao Wu
- Web page: https://patentgrep.com/patent/US9435021B2

## CPC

- C23C 14/12: Organic material
- C07F 1/005: {without C-Metal linkages}
- C09K 11/06: containing organic luminescent materials
- H10K 71/164: {using vacuum deposition}
- H10K 85/371: {Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver}
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1029: containing one nitrogen atom as the heteroatom
- C09K 2211/1048: with oxygen
- C09K 2211/188: of other metals not provided for in one of the previous groups
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 2101/10: Triplet emission
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

A method for fabricating an OLED by preparing phosphorescent metal complexes in situ is provided. In particular, the method simultaneously synthesizes and deposits copper (I) complexes in an organic light emitting device. Devices comprising such complexes may provide improved photoluminescent and electroluminescent properties.

## Claims

### Claim 1

A method, comprising:
co-depositing one or more metal complexes having the formula MXn and one or more ligands by thermal vacuum depositing from two different heating sources to form a film comprising a phosphorescent complex over a substrate,
wherein M is a transition metal or lanthanide;
wherein X is alkyl, aryl, F, Cl, Br, I, SCN, OCN, CN, OR, and SR or combinations thereof;
wherein ft is alkyl or aryl;
wherein n is 1-10;
wherein each ligand is independently a mono-, di-, tri- or polydentate ligand; and
wherein the co-depositing step forms in-situ a phosphorescent complex comprising two to six of the metal complexes having the formula MXn and the one or more ligands.

### Claim 2 (depends on 1)

The method of claim 1, wherein at least one ligand is a neutral ligand that is coordinated to the M through a C, N, O, P or S atom.

### Claim 3 (depends on 2)

The method of claim 2, wherein at least one ligand is a neutral ligand that is coordinated to the M through a N atom.

### Claim 4 (depends on 1)

The method of claim 1, wherein the phosphorescent complex is selected from the group consisting of:

### Claim 5 (depends on 1)

The method of claim 1, wherein the phosphorescent complex is homoleptic.

### Claim 6 (depends on 1)

The method of claim 1, wherein the phosphorescent complex is heteroleptic.

### Claim 7

A method, comprising:
co-depositing one or more metal complexes having the formula MXn and one or more ligand by thermal vacuum depositing from two different heating sources to form a film comprising a phosphorescent complex over a substrate,
wherein M is copper (I);
wherein X is alkyl, aryl, F, Cl, Br, I, SCN, OCN, CN, OR, and SR or combinations thereof;
wherein R is alkyl or aryl;
wherein n is 1-10;
wherein each ligand is independently a mono-, di-, tri- or polydentate ligand;
wherein one to six of the metal complexes having the formula MXn and the more than one ligands react in situ during the co-depositing step and form the phosphorescent complex.

### Claim 8 (depends on 7)

The method of claim 7, wherein the metal complex is CuI.

### Claim 9 (depends on 7)

The method of claim 7, wherein n is 1-3.

### Claim 10 (depends on 7)

The method of claim 7, wherein the phosphorescent complex includes 2 of the metal complexes.

### Claim 11 (depends on 7)

The method of claim 7, wherein each ligand is a neutral ligand that is coordinated to the copper (I) through a C, N, O, P or S atom.

### Claim 12 (depends on 11)

The method of claim 11, wherein each ligand is a neutral ligand that is coordinated to the copper (I) through a N atom.

### Claim 13 (depends on 7)

The method of claim 7, wherein at least one ligand is selected from the group consisting of:
wherein X is S, O, NR;
wherein R, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein the ligand is coordinated to the copper (I) via at least one atom of the ligand.

### Claim 14 (depends on 13)

The method of claim 13, wherein at least one ligand is selected from the group consisting of:
wherein R′ and R″ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

### Claim 15 (depends on 7)

The method of claim 7, wherein at least one ligand is a charged ligand having the formula:
wherein Y and X are independently selected from the group consisting of C, N, O, P and S.

### Claim 16 (depends on 15)

The method of claim 15, wherein
wherein A and B are each independently a 5 or 6-membered aromatic or heteroaromatic ring;
wherein A-B represents a bonded pair of aromatic or heteroaromatic rings coordinated to the metal via a nitrogen atom on ring A and an sp2 hybridized carbon atom on ring B;
wherein each of RA and RB may represent mono, di, tri, or tetra substituents;
wherein each of RA and RB substituents are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

### Claim 17 (depends on 7)

The method of claim 7, further comprising:
providing a first electrode disposed over the substrate before the co-depositing step; and
depositing a second electrode over the co-deposited film of phosphorescent complex.

### Claim 18 (depends on 17)

The method of claim 17, wherein the first electrode is an anode and the second electrode is a cathode.

### Claim 19 (depends on 7)

The method of claim 7, wherein the phosphorescent complex is homoleptic.

### Claim 20 (depends on 7)

The method of claim 7, wherein the phosphorescent complex is heteroleptic.