# US 12,110,418 B2 · Conductive film of fused porphyrins polymer and method of forming a coated substrate

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,110,418 B2
- Document ID: US12110418B2
- Status: Granted
- Kind: B2
- Application number: 17/289,322
- Filed: 2019-11-12
- Published: 2022-01-13
- Granted: 2024-10-08
- Earliest claimed: 2018-11-13
- Assignees: Luxembourg Institute of Science and Technology (List)
- Applicants: Luxembourg Institute of Science and Technology (List)
- Inventors: Nicolas Boscher; Giuseppe Bengasi; Kamal Baba
- Web page: https://patentgrep.com/patent/US12110418B2

## CPC

- C09D 5/24: Electrically-conducting paints {(conductive materials H01B1/00)}
- B05D 1/60: {Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00)}
- C08G 12/26: with heterocyclic compounds
- C09D 165/00: Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers
- H01B 1/124: {Intrinsically conductive polymers}
- 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 71/60: Forming conductive regions or layers, e.g. electrodes
- H10K 85/111: {comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene}
- 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)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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

## Abstract

A conductive coating comprising polymers of meso-meso, β-β doubly linked fused and/or meso-β, β-meso doubly linked fused and/or meso-meso, β-β, β-βtriply linked fused (poly)porphyrins. A method for forming on a substrate a thin conductive coating of polymers of meso-meso, β-β doubly and/or meso-β, β-meso doubly and/or meso- meso, β-β, β-β triply linked fused (poly)porphyrins, the method comprising the steps of providing a substrate in a vacuum chamber, performing on the substrate an oxidative chemical vapour deposition reaction with an oxidant and at least one porphyrin monomer.

## Claims

### Claim 1

A conductive coating comprising polymers of meso-meso, β-β doubly linked fused and/or meso-β, β-meso doubly linked fused and/or meso-meso, β-β, β-β triply linked fused (poly)porphyrins, said polymers being represented as:
wherein R1-R8 are independently selected from the group:
hydrogen, halogen, hydroxyl group, mercapto group, amino group, nitro group, carboxyl group, sulfonic acid group, substituted or non-substituted alkyl group, substituted or non-substituted aryl group, substituted or non-substituted alkoxy group, substituted or non-substituted aryloxy group, substituted or non-substituted alkylthio group, substituted or non-substituted arylthio group, alkylamino group, substituted or non-substituted arylamino group, substituted or non-substituted carboxylate group, substituted or non-substituted carboxylic acid, amino group, substituted or non-substituted sulfonate group, substituted or non-substituted sulfonamide group, substituted or non-substituted carbonyl group, substituted or non-substituted silyl group or substituted or non-substituted siloxy group;
wherein M is 2H or one metal atoms selected from the group of: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pd, In, Pt, Sc, Y, Eu, Er, Yb, Ti, V, Nb, Ta, U, Mo, W, Ru, Os, Rh, Ir, Ag, Au, Cd, Hg, Ti, Sn, Pb, As, Sb, and Bi,
wherein the polymers of general formula 1 comprises n monomers, n is superior to 50 and the monomers being the same or different.

### Claim 2 (depends on 1)

The conductive coating according to claim 1, wherein n is superior to 100.

### Claim 3 (depends on 1)

The conductive coating according to claim 1, wherein R1-R8 are independently selected from the group: H, phenyl, p-tolyl, mesityl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-di-octyloxyphenyl, 2,6-di-dodecyloxyphenyl, 3,4,5-tri-trimethoxyphenyl, 4-carboxyphenyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 3,5-di-hydroxyphenyl, 4-aminophenyl, 4-pyridyl, 4-bromophenyl, 4-chlorophenyl, 2,6-chlorophenyl, 4-fluorophenyl, 3,5-di-fluorophenyl, 2,6-di-fluorophenyl, pentafluorophenyl, 4-trifluoromethylphenyl and 3,5-di-trifluoromethylphenyl,
wherein M is 2H or one metal atoms selected from the group of: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pd, In and Pt.

### Claim 4

A method for forming on a substrate a thin conductive coating of polymers of meso-meso, β-β doubly and/or meso-β, β-meso doubly and/or meso-meso, β-β, β-β triply linked fused (poly)porphyrins, the method comprising the steps of:
providing a substrate in a vacuum chamber,
performing on said substrate an oxidative chemical vapour deposition reaction with an oxidant and at least one porphyrin monomer of general formula 2:
wherein at least two of R′1-R′4 are H, the others being respectively selected independently from the group consisting of: halogen, hydroxyl group, mercapto group, amino group, nitro group, carboxyl group, sulfonic acid group, substituted or non-substituted alkyl group, substituted or non-substituted aryl group, substituted or non-substituted alkoxy group, substituted or non-substituted aryloxy group, substituted or non-substituted alkylthio group, substituted or non-substituted arylthio group, alkylamino group, substituted or non-substituted arylamino group, substituted or non-substituted carboxylate group, substituted or non-substituted carboxylic acid, amino group, substituted or non-substituted sulfonate group, substituted or non-substituted sulfonamide group, substituted or non-substituted carbonyl group, substituted or non-substituted silyl group or substituted or non-substituted siloxy group,
wherein M is 2H or one metal atoms selected from the group of: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pd, In, Pt, Sc, Y, Eu, Er, Yb, Ti, V, Nb, Ta, U, Mo, W, Ru, Os, Rh, Ir, Ag, Au, Cd, Hg, Ti, Sn, Pb, As, Sb, and Bi.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the step of performing on said substrate an oxidative chemical vapour deposition reaction with an oxidant and at least one porphyrin monomer of general formula 2 comprises sublimating separately the oxidant and the at least one porphyrin monomer in said vacuum chamber to form gaseous phases respectively and delivering said gaseous phases on the substrate.

### Claim 6 (depends on 4)

The method according to claim 4, wherein the step performing on said substrate an oxidative chemical vapour deposition reaction with an oxidant and at least one porphyrin monomer of general formula 2 is further performing with at least one crosslinking monomer being a mono-meso-substituted porphyrin monomer and/or porphine monomer.

### Claim 7 (depends on 4)

The method according to claim 4, wherein at least two of R′1-R′4 are H, the others being respectively selected from the group consisting of: phenyl, p-tolyl, mesityl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-di-octyloxyphenyl, 2,6-di-dodecyloxyphenyl, 3,4,5-tri-trimethoxyphenyl, 4-carboxyphenyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 3,5-di-hydroxyphenyl, 4-aminophenyl, 4-pyridyl, 4-bromophenyl, 4-chlorophenyl, 2,6-chlorophenyl, 4-fluorophenyl, 3,5-di-fluorophenyl, 2,6-di-fluorophenyl, pentafluorophenyl, 4-trifluoromethylphenyl and 3,5-di-trifluoromethylphenyl.

### Claim 8 (depends on 4)

The method according to claim 4, wherein R′1 and R′3 are H and R′2 and R′4 are both selected from the group consisting of: phenyl, p-tolyl, mesityl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-di-octyloxyphenyl, 2,6-di-dodecyloxyphenyl, 3,4,5-tri-trimethoxyphenyl, 4-carboxyphenyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 3,5-di-hydroxyphenyl, 4-aminophenyl, 4-pyridyl, 4-bromophenyl, 4-chlorophenyl, 2,6-chlorophenyl, 4-fluorophenyl, 3,5-di-fluorophenyl, 2,6-di-fluorophenyl, pentafluorophenyl, 4-trifluoromethylphenyl and 3,5-di-trifluoromethylphenyl.

### Claim 9 (depends on 4)

The method according to claim 4, wherein the oxidant is selected from the group consisting of: FeCl3, CuCl2 or Cu (ClO4)2.

### Claim 10 (depends on 4)

The method according to claim 4, wherein the step of performing the oxidative chemical vapour deposition reaction is performed at a pressure comprised between 10−4 mbar to 10−2 mbar.

### Claim 11 (depends on 5)

The method according to claim 5, wherein the oxidant is sublimated at a temperature comprised between 100° C. and 350° C.

### Claim 12 (depends on 5)

The method according to claim 5, wherein the at least one porphyrin monomer of general formula 2 is sublimated at a temperature comprised between 200° C. and 300° C.

### Claim 13 (depends on 4)

The method according to claim 4, wherein the at least one porphyrin monomer of general formula 2 is a metalized 5,15-(diphenyl)porphyrin (MDPP), wherein M is one metal atoms selected from the group of: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pd, In, Pt.

### Claim 14 (depends on 4)

The method according to claim 4, wherein the oxidant is FeCl3, sublimated between 100° C. and 200° C.

### Claim 15 (depends on 4)

The method according to claim 4, wherein the substrate is a polymer, or paper.

### Claim 16 (depends on 4)

The method according to claim 4, wherein the substrate is an insulating substrate selecting from the group of: glass, polymer, or paper.

### Claim 17

A device comprising a substrate and a thin conductive coating of directly fused (poly)porphyrins, wherein said thin conductive coating comprises polymers of meso-meso, β-β doubly linked fused and/or meso-β, β-meso doubly linked fused and/or meso-meso, β-β, β-β triply linked fused (poly)porphyrins, said polymers being represented as:
wherein R1-R8 are independently selected from the group:
hydrogen, halogen, hydroxyl group, mercapto group, amino group, nitro group, carboxyl group, sulfonic acid group, substituted or non-substituted alkyl group, substituted or non-substituted aryl group, substituted or non-substituted alkoxy group, substituted or non-substituted aryloxy group, substituted or non-substituted alkylthio group, substituted or non-substituted arylthio group, alkylamino group, substituted or non-substituted arylamino group, substituted or non-substituted carboxylate group, substituted or non-substituted carboxylic acid, amino group, substituted or non-substituted sulfonate group, substituted or non-substituted sulfonamide group, substituted or non-substituted carbonyl group, substituted or non-substituted silyl group or substituted or non-substituted siloxy group;
wherein M is 2H or one metal atoms selected from the group of: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Pd, In, Pt, Sc, Y, Eu, Er, Yb, Ti, V, Nb, Ta, U, Mo, W, Ru, Os, Rh, Ir, Ag, Au, Cd, Hg, Ti, Sn, Pb, As, Sb, and Bi,
wherein the polymers of general formula 1 comprises n monomers, n is superior to 50 and the monomers being the same or different.

### Claim 18 (depends on 15)

the method according to claim 15, wherein the polymer is polyethylene naphthalate and the paper is printer paper sheet.