# US 11,028,277 B2 · Charge transport varnish

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- Number: US 11,028,277 B2
- Document ID: US11028277B2
- Status: Granted
- Kind: B2
- Application number: 16/074,991
- Filed: 2017-01-25
- Published: 2019-02-28
- Granted: 2021-06-08
- Earliest claimed: 2016-02-03
- Assignees: Nissan Chemical Corporation
- Applicants: Nissan Chemical Corporation
- Inventors: Juro Oshima; Takuji Yoshimoto
- Web page: https://patentgrep.com/patent/US11028277B2

## CPC

- C09D 11/52: Electrically conductive inks
- C09D 5/24: Electrically-conducting paints {(conductive materials H01B1/00)}
- H01B 1/127: {comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes}
- H01B 1/128: {comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes}
- H10K 30/20: comprising organic-organic junctions, e.g. donor-acceptor junctions
- H10K 71/15: characterised by the solvent used
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 85/215: {comprising substituents, e.g. PCBM}
- H10K 30/50: Photovoltaic [PV] devices
- H10K 30/82: Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K 50/155: comprising dopants
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- 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)
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- 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 charge transport varnish containing a charge transport substance, an electron-accepting dopant substance, and an organic solvent, wherein the electron-accepting dopant substance contains one or more types selected from naphthalene disulfonic acid, naphthalene trisulfonic acid, and naphthalene tetrasulfonic acid. This charge transport varnish is suitable for forming a hole collection layer that can be used to produce an organic photoelectric conversion element which exhibits high photoelectric conversion efficiency.

## Claims

### Claim 1

A charge-transporting varnish comprising a charge-transporting substance, an electron-accepting dopant substance and an organic solvent, wherein the electron-accepting dopant substance includes at least one compound selected from the group consisting of 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 1,3,5-naphthalenetrisulfonic acid, 1,3,6-naphthalenetrisulfonic acid; and 1,4,5,7-naphthalenetetrasulfonic acid, and
wherein the charge-transporting substance is a charge-transporting substance having a molecular weight of from 200 to 2,000.

### Claim 2

A charge-transporting varnish comprising a charge-transporting substance, an electron-accepting dopant substance and an organic solvent, wherein the electron-accepting dopant substance includes at least one compound selected from the group consisting of 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 1,3,5-naphthalenetrisulfonic acid, 1,3,6-naphthalenetrisulfonic acid; and 1,4,5,7-naphthalenetetrasulfonic acid, wherein the charge-transporting substance is at least one selected from the group consisting of aniline derivatives and thiophene derivatives of formulas (H2) to (H3) below,
in formula (H2), R7 to R10 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, an alkoxy group of 1 to 20 carbon atoms, thioalkoxy group of 1 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms or alkynyl group of 2 to 20 carbon atoms which may be substituted with Z1, an aryl group of 6 to 20 carbon atoms or aralkyl group of 7 to 20 carbon atoms which may be substituted with Z2, or an acyl group of 1 to 20 carbon atoms; R11 to R14 are each independently a hydrogen atom, a phenyl group, a naphthyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a furanyl group, a pyrrolyl group, a pyrazolyl group, a imidazolyl group or a thienyl group, which groups may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, an alkoxy group of 1 to 20 carbon atoms, a thioalkoxy group of 1 to 20 carbon atoms, an alkyl group of 1 to 20 carbon atoms, a haloalkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an acyl group of 1 to 20 carbon atoms, or a group of formula (H4), provided that at least one of R11 to R14 is a hydrogen atom; m is an integer from 2 to 5; and Z1 is a halogen atom, a nitro group, a cyano group, an amino group, or an aryl group of 6 to 20 carbon atoms or heteroaryl group of 2 to 20 carbon atoms which may be substituted with Z3; Z2 is a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms or alkynyl group of 2 to 20 carbon atoms which may be substituted with Z3; Z3 is a halogen atom, a nitro group, a cyano group, or an amino group,
in formula (H4), R15 to R18 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, an alkoxy group of 1 to 20 carbon atoms, thioalkoxy group of 1 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms or alkynyl group of 2 to 20 carbon atoms which may be substituted with Z1, an aryl group of 6 to 20 carbon atoms or aralkyl group of 7 to 20 carbon atoms which may be substituted with Z2, or an acyl group of 1 to 20 carbon atoms; R19 and R20 are each independently a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a furanyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group or a thienyl group, which groups may be bonded to each other to form a ring or may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, an alkoxy group of 1 to 20 carbon atoms, a thioalkoxy group of 1 to 20 carbon atoms, an alkyl group of 1 to 20 carbon atoms, a haloalkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an acyl group of 1 to 20 carbon atoms; and Z1 and Z2 are as defined above,
in formula (H3), R21 to R24 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a silanol group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group, an ester group, a thioester group, an amide group, a nitro group, an alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms or alkynyl group of 2 to 20 carbon atoms which may be substituted with Z1, an aryl group of 6 to 20 carbon atoms or aralkyl group of 7 to 20 carbon atoms which may be substituted with Z2, an acyl group of 1 to 20 carbon atoms, a sulfonic acid group, or a —NHY1, —NY2Y3, —OY4, —SY5 or —SiY6Y7Y8 group; Y1 to Y8 are each independently an alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms or alkynyl group of 2 to 20 carbon atoms which may be substituted with Z1, or an aryl group of 6 to 20 carbon atoms or heteroaryl group of 2 to 20 carbon atoms which may be substituted with Z2; X and Y are each independently a thiophene ring which may be substituted with Z2; the two sulfur atoms included on the dithiine ring may be each independently a SO group or a SO2 group; p, q and r are each independently 0 or an integer of 1 or more, these being numbers that together satisfy the condition p+q+r≤20; and Z1 and Z2 are as defined above.

### Claim 3 (depends on 2)

The charge-transporting varnish of claim 2, wherein the electron-accepting dopant substance includes at least one compound selected from the group consisting of 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 1,3,5-naphthalenetrisulfonic acid and 1,3,6-naphthalenetrisulfonic acid.

### Claim 4 (depends on 2, 3)

The charge-transporting varnish of claim 2 or 3, wherein the charge-transporting substance is a charge-transporting substance having a molecular weight of from 200 to 2,000.

### Claim 5 (depends on 2)

The charge-transporting varnish of claim 2 which is for use in forming a hole-collecting layer for an organic photoelectric conversion device.

### Claim 6 (depends on 5)

The charge-transporting varnish of claim 5, wherein the organic photoelectric conversion device is an organic thin-film solar cell or a photosensor.

### Claim 7 (depends on 5)

A hole-collecting layer produced from the charge-transporting varnish of claim 5.

### Claim 8 (depends on 7)

An organic photoelectric conversion device comprising the hole-collecting layer of claim 7 and an active layer provided so as to be in contact therewith.

### Claim 9 (depends on 8)

The organic photoelectric conversion device of claim 8, wherein the active layer includes a fullerene derivative.

### Claim 10 (depends on 8)

The organic photoelectric conversion device of claim 8, wherein the active layer includes a polymer having a thiophene skeleton on the main chain.

### Claim 11 (depends on 8)

The organic photoelectric conversion device of claim 8, wherein the active layer includes a fullerene derivative and a polymer having a thiophene skeleton on the main chain.

### Claim 12 (depends on 8, 9, 10, 11)

The organic photoelectric conversion device of any one of claims 8 to 11 which is an organic thin-film solar cell.

### Claim 13 (depends on 8, 9, 10, 11)

The organic photoelectric conversion device of any one of claims 8 to 11 which is a photosensor.

### Claim 14 (depends on 2)

A charge-transporting thin film produced from the charge-transporting varnish of claim 2.