# US 10,870,771 B2 · Non-aqueous ink compositions containing transition metal complexes, and uses thereof in organic electronics

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- Number: US 10,870,771 B2
- Document ID: US10870771B2
- Status: Granted
- Kind: B2
- Application number: 16/070,038
- Filed: 2017-01-20
- Published: 2019-01-24
- Granted: 2020-12-22
- Earliest claimed: 2016-01-20
- Assignees: Nissan Chemical Industries, Ltd.
- Applicants: Nissan Chemical Industries, Ltd.
- Inventors: Robert Swisher; Elena Sheina; Sergey B. Li; Marc Sims
- Web page: https://patentgrep.com/patent/US10870771B2

## CPC

- C09D 11/52: Electrically conductive inks
- C09D 11/033: characterised by the solvent
- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D 11/36: based on non-aqueous solvents
- C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes
- H10K 71/15: characterised by the solvent used
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- C07F 11/00: Compounds containing elements of Groups 6 or 16 of the Periodic Table
- H10K 50/155: comprising dopants
- H10K 50/17: Carrier injection layers
- Y02E 10/549: Organic PV cells
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Described herein are non-aqueous ink compositions containing a polythiophene having a repeating unit complying with formula (I) described herein, a transition metal complex having at least one β-diketonate ligand, and a liquid carrier having one or more organic solvents. The present disclosure also concerns the uses of such non-aqueous ink compositions, for example, in organic electronic devices.

## Claims

### Claim 1

A non-aqueous ink composition for use in preparing a hole carrying film which is a hole injection layer (HIL) or a hole transport layer (HTL) and not for use in preparing an emission layer (EML) comprising:
(a) a polythiophene comprising a repeating unit complying with formula (I)
wherein R1 and R2 are each, independently, H, alkyl, fluoroalkyl, alkoxy, aryloxy, or —O—[Z—O]p—Re;
wherein
Z is an optionally halogenated hydrocarbylene group,
p is equal to or greater than 1, and
Re is H, alkyl, fluoroalkyl, or aryl;
(b) a transition metal complex having a ligand consisting essentially of one or more β-diketonate ligands, or consisting of one or more β-diketonate ligands and one or more ligands other than β-diketonate ligand, and the one or more ligands other than β-diketonate ligand are selected from the group consisting of inorganic ligands, cyanide (CN), carbonyl (CO), thiocyanato (SCN), aminoacids, iminoacetonates, ethylenediamines and amidinate; and
(c) a liquid carrier comprising one or more organic solvents, and
wherein the components of the composition including (a) the polythiophene, (b) the transition metal complex, and (c) the liquid carrier are selected to provide the hole carrying film which is a hole injection layer (HIL) or a hole transport layer (HTL) and not provide for the emission layer (EML).

### Claim 2 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein R1 and R2 are each, independently, H, fluoroalkyl, —O[C(RaRb)—C(RcRd)—O]p—Re, —ORf;
wherein
each occurrence of Ra, Rb, Rc, and Rd, is each, independently, H, halogen, alkyl, fluoroalkyl, or aryl;
Re is H, alkyl, fluoroalkyl, or aryl;
p is 1, 2, or 3; and
Rf is alkyl, fluoroalkyl, or aryl.

### Claim 3 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein R1 is H and R2 is other than H or wherein R1 and R2 are both other than H.

### Claim 4 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein the polythiophene comprises a repeating unit selected from the group consisting of
and combinations thereof.

### Claim 5 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein the polythiophene is sulfonated.

### Claim 6 (depends on 1)

The non-aqueous ink composition according to claim 1,
wherein the polythiophene comprises repeating units complying with formula (I) in an amount of greater than 50% by weight, based on the total weight of the repeating units.

### Claim 7 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein the transition metal of the transition metal complex is rhenium, vanadium, molybdenum, and/or tungsten.

### Claim 8 (depends on 7)

The non-aqueous ink composition according to claim 7, wherein the transition metal complex further comprises at least one oxo ligand.

### Claim 9 (depends on 1)

The non-aqueous ink composition according to claim 1,
wherein the liquid carrier comprises 1,3-butanediol, acetonitrile, ethylene glycol, 3-methoxypropionitrile, or a mixture thereof.

### Claim 10 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein the liquid carrier consists of (A) one or more glycol-based solvents.

### Claim 11 (depends on 10)

The non-aqueous ink composition according to claim 10, wherein the glycol-based solvent (A) is a glycol ether, glycol monoether or glycol.

### Claim 12 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein the liquid carrier is a liquid carrier consisting essentially of
(A) one or more glycol-based solvents and
(B) one or more organic solvents other than the glycol-based solvents.

### Claim 13 (depends on 12)

The non-aqueous ink composition according to claim 12, wherein the proportion by weight (wtA) of the glycol-based solvent (A) and the proportion by weight (wtB) of the organic solvent (B) satisfy the relationship represented by the following formula (1-1):
0.05≤wtB/(wtA+wtB)≤0.50 (1-1).

### Claim 14 (depends on 1)

The non-aqueous ink composition according to claim 1, further comprising metalloid nanoparticles.

### Claim 15 (depends on 1)

The non-aqueous ink composition according to claim 1, further comprising a synthetic polymer comprising one or more acidic groups.

### Claim 16 (depends on 1)

The non-aqueous ink composition according to claim 1, further comprising an amine compound.

### Claim 17 (depends on 1)

A process for forming a hole-carrying film, the process comprising:
1) coating a substrate with the non-aqueous ink composition according to claim 1; and
2) annealing the coating on the substrate, thereby forming the hole-carrying film.

### Claim 18 (depends on 17)

A device comprising the hole-carrying film formed by the process of claim 17,
wherein the device is an OLED, OPV, transistor, capacitor, sensor, transducer, drug release device, electrochromic device, or battery device.

### Claim 19 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein
the ligand
consists of one or more β-diketone ligands and one or more ligands other than β-diketone ligand, and
the one or more ligands other than β-diketonate ligand are selected from the group consisting of inorganic ligands, cyanide (CN), carbonyl (CO), thiocyanato (SCN), aminoacids, iminoacetonates, ethylenediamines and amidinate.

### Claim 20 (depends on 1)

The non-aqueous ink composition according to claim 1, wherein the ligand consists of one or more β-diketonate ligands.