# US 10,873,027 B2 · Process for the manufacture of a multilayer structure

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- Number: US 10,873,027 B2
- Document ID: US10873027B2
- Status: Granted
- Kind: B2
- Application number: 14/101,817
- Filed: 2013-12-10
- Published: 2014-06-12
- Granted: 2020-12-22
- Earliest claimed: 2012-12-11
- Assignees: Nissan Chemical Industries, Ltd.
- Applicants: Nissan Chemical Industries, Ltd.
- Inventors: Roland Martin
- Web page: https://patentgrep.com/patent/US10873027B2

## CPC

- H10K 71/12: using liquid deposition, e.g. spin coating
- H10K 71/15: characterised by the solvent used
- H10K 71/00: Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K 85/111: {comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene}
- H10K 85/631: {Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine}
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A process for the manufacture of a multilayer structure suitable for forming part of an organic electronic device having a cathode and an anode wherein liquid compositions with solvent systems comprising organic compounds with ionizable groups are deposited out of solution. Organic electronic devices can be made with use of the process including transistors, diodes, and photovoltaic devices, including organic light emitting diodes (OLEDs).

## Claims

### Claim 1

A process for the manufacture of a homojunction multilayer structure suitable for forming part of an organic electronic device having a cathode and an anode, comprising the steps of
a. depositing a nth layer Ln of the multilayer structure onto a substrate out of a liquid composition Cn comprising a solvent system Sn comprising at least one solvent and at least one organic compound Mi which comprises ionizable groups G which comprise at least one nitrogen atom capable of being reversibly protonated, mainly or totally in neutral (Gn) or mainly or totally in ionized (Gi) form, wherein the substrate is a previously deposited layer Ln−1 of the multilayer structure or is an element suitable for forming the cathode or the anode of the organic electronic device, and thereafter either
b1.1 evaporating the solvent system Sn to form the dry nth layer and, if the organic compound Mi comprises the group G mainly or totally in its ionized form Gi, converting partly or completely the groups Gi to the neutral form Gn, and
b1.2 thereafter depositing a (n+1)th layer Ln+1 of the multilayer structure onto the first layer Ln out of a liquid composition Cn+1 comprising a solvent system Sn+1, and organic compound M1 comprising the ionizable group G mainly or totally in ionized form Gi and thereafter
b1.3. evaporating the solvent system Sn+1 and converting the groups G1 to form the dry (n+1)th layer mainly or totally to the neutral form Gn or,
b2.1. evaporating the solvent system Sn to form the dry nth layer Ln comprising groups G mainly or totally in ionized form Gi and thereafter
b2.2. depositing the (n+1)th layer Ln+1 of the multilayer structure onto the dry nth layer Ln out of a liquid composition C(n+1), comprising a solvent system S(n+1), comprising organic compound M1 comprising ionizable groups G mainly or totally in the neutral form Gn and evaporating the solvent system S(n+1), to form a dry (n+1)th layer mainly or totally to the neutral form Gn and thereafter either
b3.1 depositing a (n+2)th layer out of a liquid composition C(n+2) comprising a solvent system S(n+2) comprising organic compound Mi comprising groups G mainly or totally in the ionized form Gi followed by converting the groups Gi in the dry nth and the dry (n+2)th layer mainly or totally to the neutral form, or
b3.2 directly converting the groups Gi in the nth layer mainly or totally to the neutral form Gn
wherein the solubility of organic compound Mi comprising groups G mainly or totally in ionized form Gi in solvent system Sn+1 and Sn+2, different or same, is at least three times as high as the solubility of organic compounds Mi comprising groups G mainly or totally in neutral form Gn in said solvent system Sn+1 and Sn+2, and
wherein the solubility of organic compounds Mi comprising groups G mainly or totally in neutral form Gn in solvent system S(n+1), is at least three times as high as the solubility of organic compound Mi comprising groups G mainly or totally in ionized form Gi in said solvent system S(n+1)′,
the solubility in all cases determined at 23° C. and atmospheric pressure,
wherein the total content of ionizable groups G of compound gin neutral form is at least 90% and less than 99.9%, based on the total amount of ionizable groups G present in the multilayer device, and
wherein organic compound Mi comprises a conjugated or non-conjugated polymer having a number average molecular weight of at least 5000 g/mol, and
wherein the ionizable groups G, which comprise at least one nitrogen atom capable of being reversibly protonated, of the organic compound Mi are part of the conjugated or non-conjugated polymer main chain.

### Claim 2 (depends on 1)

The process of claim 1 wherein organic compound Mi is protonated by one or more acids HaiAiai− selected from proton acids having a pKa of 5.5 or less and a boiling point under atmospheric pressure in the range of from 70 to 160° C. to form salts of general formula Mi(H+)ni (Aiai−)bi wherein ni represents the number of protons per compound Mi, A is a counter anion with negative charge ai and wherein ni=ai×bi.

### Claim 3 (depends on 2)

The process of claim 2 wherein ni is less to or equal to the total number of nitrogen atoms in organic compound Mi.

### Claim 4 (depends on 1)

The process of claim 1 wherein organic compound Mi comprises at least one group G selected from 5- or 6-membered heterocyclic rings comprising at least one nitrogen atom, arylamine and carbazole derivatives.

### Claim 5 (depends on 1)

The process of claim 1 wherein the groups G are selected from pyrrole, pyrazole, imidazole, oxazole, oxadiazole, triazole, indole, iso-indole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, quinoline, iso-quinoline and phenanthroline.

### Claim 6 (depends on 1)

The process of claim 1 wherein the solvent system for organic compound M comprising groups G mainly or totally in ionized form Gi comprises at least one proton acid HaiAiai, water and/or a C1-C3 alcohol or mixtures thereof.

### Claim 7 (depends on 6)

The process of claim 6 wherein the proton acids HaiAiai are carboxylic acids, preferably selected from formic acid, acetic acid, 2-propenoic acid, 2-propynoic acid, lactic acid, maleic acid, trifluoroacetic acid, trifluoropropanoic acid, trifluorobutanoic acid and mixtures thereof.

### Claim 8 (depends on 1)

The process of claim 1 wherein the conversion of groups G in ionized form Gi to the neutral form Gn is achieved by subjecting the layer comprising the groups Gi to elevated temperatures up to a maximum of 180° C.

### Claim 9 (depends on 2)

The process of claim 2 wherein the proton acids are evaporated and eliminated from the gas phase by applying reduced pressure or a carrier gas stream or a combination of both.

### Claim 10

An organic electronic device
which is prepared by a process comprising a process for the manufacture of a homojunction multilayer structure suitable for forming part of the organic electronic device having a cathode and an anode, comprising the steps of
a. depositing a nth layer Ln of the multilayer structure onto a substrate out of a liquid composition Cn comprising a solvent system Sn comprising at least one solvent and at least one organic compound Mi which comprises ionizable groups G which comprise at least one nitrogen atom capable of being reversibly protonated, mainly or totally in neutral (Gn) or mainly or totally in ionized (Gi) form, wherein the substrate is a previously deposited layer Ln−1 of the multilayer structure or is an element suitable for forming the cathode or the anode of the organic electronic device, and thereafter either
b1.1 evaporating the solvent system Sn to form the dry nth layer and, if the organic compound Mi comprises the group G mainly or totally in its ionized form Gi, converting partly or completely the groups Gi to the neutral form Gn, and
b1.2 thereafter depositing a (n+1)th layer Ln+1 of the multilayer structure onto the first layer Ln out of a liquid composition Cn+1 comprising a solvent system Sn+1, and organic compound Mi comprising the ionizable group G mainly or totally in ionized form Gi and thereafter
b1.3. evaporating the solvent system Sn+1 and converting the groups Gi to form the dry (n+1)th layer mainly or totally to the neutral form Gn or,
b2.1. evaporating the solvent system Sn to form the dry nth layer Ln comprising groups G mainly or totally in ionized form Gi and thereafter
b2.2. depositing the (n+1)th layer Ln+1 of the multilayer structure onto the dry nth layer Ln out of a liquid composition C(n+1), comprising a solvent system S(n+1), comprising organic compound Mi comprising ionizable groups G mainly or totally in the neutral form Gn and evaporating the solvent system S(n+1), to form a dry (n+1)th layer mainly or totally to the neutral form Gn and thereafter either
b3.1 depositing a (n+2)th layer out of a liquid composition C(n+2) comprising a solvent system S(n+2) comprising organic compound Mi comprising groups G mainly or totally in the ionized form Gi followed by converting the groups Gi in the dry nth and the dry (n+2)th layer mainly or totally to the neutral form, or
b3.2 directly converting the groups Gi in the nth layer mainly or totally to the neutral form Gn
wherein the solubility of organic compound Mi comprising groups G mainly or totally in ionized form Gi in solvent system Sn+1 and Sn+2, different or same, is at least three times as high as the solubility of organic compounds Mi comprising groups G mainly or totally in neutral form Gn in said solvent system Sn+1 and Sn+2, and
wherein the solubility of organic compounds Mi comprising groups G mainly or totally in neutral form Gn in solvent system S(n+1), is at least three times as high as the solubility of organic compound Mi comprising groups G mainly or totally in ionized form Gi in said solvent system S(n+1),
the solubility in all cases determined at 23° C. and atmospheric pressure,
wherein the total content of ionizable groups G of compound gin neutral form is at least 90% and less than 99.9%, based on the total amount of ionizable groups G present in the multilayer device, and
wherein organic compound Mi comprises a conjugated or non-conjugated polymer having a number average molecular weight of at least 5000 g/mol, and
wherein the ionizable groups G, which comprise at least one nitrogen atom capable of being reversibly protonated, of the organic compound Mi are part of the conjugated or non-conjugated polymer main chain.

### Claim 11 (depends on 10)

The organic electronic device of claim 10 which is a transistor, a diode or a photovoltaic device.

### Claim 12 (depends on 11)

The organic electronic device in accordance with claim 11 which is an organic light emitting diode (OLED).

### Claim 13 (depends on 10)

The organic electronic device in accordance with claim 10, wherein organic compound Mi is protonated by one or more acids HaiAiai− selected from proton acids having a pKa of 5.5 or less and a boiling point under atmospheric pressure in the range of from 70 to 160° C. to form salts of general formula Mi(H+)ni (Aiai−)bi wherein ni represents the number of protons per compound Mi, A is a counter anion with negative charge ai and wherein ni=ai×bi.

### Claim 14 (depends on 10)

The organic electronic device in accordance with claim 10, wherein organic compound Mi comprises at least one group G selected from 5- or 6-membered heterocyclic rings comprising at least one nitrogen atom, arylamine and carbazole derivatives.

### Claim 15 (depends on 10)

The organic electronic device in accordance with claim 10, wherein the groups G are selected from pyrrole, pyrazole, imidazole, oxazole, oxadiazole, triazole, indole, iso-indole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, quinoline, iso-quinoline and phenanthroline.