Conductive film of fused porphyrins polymer and method of forming a coated substrate

Patent metadata

Field	Value
Publication number	US-2022010146-A1
Application number	US-201917289322-A
Country	US
Kind code	A1
Filing date	Nov 12, 2019
Priority date	Nov 13, 2018
Publication date	Jan 13, 2022
Grant date	—

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-β triply 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.

First 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 R 1 -R 8 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 2 and the monomers being the same or different.

2 . The conductive coating according to claim 1 , wherein n is superior to 50, preferentially superior to 100.

3 . The conductive coating according to claim 1 , wherein R 1 -R 8 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.

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.

5 . 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 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.

6 . 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.

7 . 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.

8 . 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.

9 . The method according to claim 4 , wherein the oxidant is selected from the group consisting of: FeCl 3 , CuCl 2 or Cu (ClO 4 ) 2 .

10 . 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.

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

12 . 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.

13 . 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.

14 . The method according to claim 4 , wherein the oxidant is FeCl 3 , sublimated between 100° C. and 200° C.

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

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

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 R 1 -R 8 are independently selected from the group:

Assignees

• Luxembourg Inst Science & Tech List

Inventors

• Boscher Nicolas
• Bengasi Giuseppe
• Baba Kamal

Classifications

• H01B1/124

  Intrinsically conductive polymers · CPC title

• B05D1/60

  Deposition of organic layers from vapour phase (vapour phase deposition in general C23C14/00, C23C16/00) · CPC title

• C08G12/26

  with heterocyclic compounds · CPC title

• H01B1/127

  comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes · CPC title

• H01B1/128

  comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes · CPC title