WO2024050387A2 - Compositions d'encre au platine et procédés de revêtement conducteur à basse température - Google Patents

Compositions d'encre au platine et procédés de revêtement conducteur à basse température Download PDF

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Publication number
WO2024050387A2
WO2024050387A2 PCT/US2023/073121 US2023073121W WO2024050387A2 WO 2024050387 A2 WO2024050387 A2 WO 2024050387A2 US 2023073121 W US2023073121 W US 2023073121W WO 2024050387 A2 WO2024050387 A2 WO 2024050387A2
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Prior art keywords
ink composition
particle
conductive ink
weight percent
free conductive
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PCT/US2023/073121
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English (en)
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WO2024050387A3 (fr
Inventor
S. Brett WALKER
Ayan MAITY
Maxwell Jacob TOLCHIN
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Electroninks Incorporated
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Publication of WO2024050387A2 publication Critical patent/WO2024050387A2/fr
Publication of WO2024050387A3 publication Critical patent/WO2024050387A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present disclosure relates generally to novel ink compositions comprising platinum and their methods of preparation and use. More particularly, the present disclosure relates to metal-organic decomposition (MOD) platinum ink compositions that are suitable for use on low temperature substrates. The disclosure also describes methods of forming dense conductive platinum films by applying the disclosed platinum ink compositions onto substrates of choice for electronic applications and conductive platinum films formed by such methods.
  • MOD metal-organic decomposition
  • a particle-free conductive ink composition including: a platinum metal; a first bidentate complexing agent; and a solvent; wherein the composition forms a conductive metallic film by curing at no more than 250 °C.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the platinum metal is a platinum (II) metal ion.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the first bidentate complexing agent is an amine- containing organic complexing agent.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the amine-containing organic complexing agent is a Ca-Cs amino ether ligand.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the amine-containing organic complexing agent is a primary amino ether ligand.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the amine-containing organic complexing agent is a primary C3-C8 amino ether ligand. [0013] Tn some aspects, the techniques described herein relate to a particle-free conductive ink composition, wherein the amine-containing organic complexing agent is 2- methoxy-ethylamine.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the solvent includes a terpene, a terpenoid, or a combination thereof.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the terpene is a purified terpene or the terpenoid is a purified terpenoid.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the terpene is a pinene or a limonene.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the terpenoid is a terpineol.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the solvent includes water.
  • the techniques described herein relate to a particle-free conductive ink composition, further including a second bidentate complexing agent.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the second bidentate complexing agent is a [>- diketone.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the [3-diketone is acetylacetonate.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the first bidentate complexing agent is 2-methoxy- ethylamine and the solvent includes a terpineol.
  • the techniques described herein relate to a particle-free conductive ink composition, further including a reducing ligand.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the reducing ligand is formic acid.
  • the techniques described herein relate to a particle-free conductive ink composition, further including a second bidentate complexing agent. [0026] Tn some aspects, the techniques described herein relate to a particle-free conductive ink composition, wherein the second bidentate complexing agent is a P- diketone.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the P-diketone is acetylacetonate.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the first bidentate complexing agent is 2-methoxy- ethylamine and the solvent includes a terpineol.
  • the techniques described herein relate to a particle-free conductive ink composition, further including a glycol.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the glycol is 1 ,2-propylene glycol, 1,3-propylene glycol, or a combination thereof.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the first bidentate complexing agent is 2-methoxy- ethylamine and the solvent includes water.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the composition forms a conductive metallic film by curing at no more than 250 °C.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the composition forms a conductive metallic film by curing at no more than 200 °C.
  • the techniques described herein relate to a particle-free conductive ink composition, wherein the conductive metallic film displays a conductivity of at least 1% bulk metal conductivity.
  • the techniques described herein relate to a method of applying the above compositions to a substrate and curing the composition at an elevated temperature to form a conductive film.
  • the techniques described herein relate to a method, wherein the applying step includes printing.
  • the techniques described herein relate to a method, wherein the printing is jet printing. [0038] Tn some aspects, the techniques described herein relate to a method, wherein the jet printing is aerosol jet printing.
  • the techniques described herein relate to a method, wherein the curing step is at no more than 250 °C.
  • the techniques described herein relate to a method, wherein the curing step is at no more than 200 °C.
  • the techniques described herein relate to a conductive film formed by applying the particle-free conductive ink composition to a substrate and curing the composition at no more than 250 °C to form the conductive film.
  • FIGs. 1A-1C show coating and imaging using a platinum ink composition of the disclosure.
  • complex-based, particle free ink compositions comprising platinum. These ink compositions can be applied and cured at low temperatures in order to meet the needs of the current conductive printing industry.
  • the particle-free conductive ink compositions are stable formulations that can deposit pure platinum metal on a variety of substrates at temperatures as low as 150 °C, or even lower.
  • the vast majority of commercially produced conductive inks are specifically designed for inkjet, screen-printing, or roll-to-roll processing methods in order to process large areas with fine-scale features in short time periods. These inks have disparate viscosities and synthesis parameters.
  • Particle-based inks are based on conductive metal particles, which are typically synthesized separately and then incorporated into an ink formulation. The resulting ink is then tuned for specific particle process.
  • the platinum ink formulations can comprise a platinum acetylacetonate as a precursor chelated by an amine ligand.
  • the platinum ink formulations can comprise a platinum complex in combination with formic acid.
  • particle-free conductive ink compositions comprising a platinum metal, a first bidentate complexing agent, and a solvent.
  • the particle-free conductive ink compositions preferably form a conductive metallic film by curing at no more than 250 °C.
  • the platinum metal is a platinum (II) metal ion.
  • a bidentate complexing agent is a ligand that contains two donor groups capable of binding to a central metal atom in a coordination complex.
  • the central metal atom is a platinum metal atom
  • the first bidentate complexing agent comprises at least two heteroatoms.
  • the at least two heteroatoms of the first bidentate complexing agent are at least two nitrogen atoms, at least two oxygen atoms, or at least a nitrogen atom and at least an oxygen atom.
  • the first bidentate complexing agent of the instant particle-free conductive ink compositions is an amine-containing organic complexing agent.
  • the amine-containing organic complexing agent can be a C3-C8 alkylamine ligand.
  • the amine-containing organic complexing agent can be a primary amino ether ligand.
  • the amine-containing organic complexing agent can be a primary C3-C8 amino ether ligand.
  • the amine-containing organic complexing agent can be 2- methoxy-ethylamine.
  • the solvent used in the instant conductive ink compositions is ideally suitable for use at an industrial scale in mass production.
  • aromatic hydrocarbons such as xylene, toluene, mesitylene, and the like, are highly regulated in most industrial countries. The use alternatives to these solvents can therefore be advantageous.
  • conductive inks formulated from aromatic hydrocarbons can have flash points that are lower than 60°C and that are therefore not typically acceptable in mass production environments.
  • the solvent of the instant conductive ink compositions does not comprise an aromatic hydrocarbon, although in other embodiments, the solvent can comprise an aromatic solvent such as anisole, xylene, toluene or the like.
  • the solvent comprises a polar, aprotic solvent. More specifically, the solvent can comprise a cyclic or acyclic ether solvent.
  • the cyclic ether solvent can be a furan, such as tetrahyrofuran.
  • the acyclic ether solvent can be a glycol ether, a dialkyl ether, or an ester.
  • the glycol ether can be ethylene glycol monomethyl ether (2- methoxyelhanol, CH3OCH2CH2OH), ethylene glycol monoethyl ether (2-ethoxyethanol, CH3CH2OCH2CH2OH), ethylene glycol monopropyl ether (2-propoxyethanol, CH3CH2CH2OCH2CH2OH), ethylene glycol monoisopropyl ether (2-isopropoxyethanol, (CFF CHOCFFCFfcOH), ethylene glycol monobutyl ether (2-butoxyethanol, CH3CH2CH2CH2OCH2CH2OH), ethylene glycol monophenyl ether (2-phenoxyethanol, C6H5OCH2CH2OH), ethylene glycol monobenzyl ether (2-benzyloxyethanol, C6H5CH2OCH2CH2OH), propylene glycol methyl ether (l-methoxy-2-propanol, CH3OCH2CH(OH)CH3), di
  • the dialkyl ether can be ethylene glycol dimethyl ether (dimethoxyethane, CH3OCH2CH2OCH3), ethylene glycol diethyl ether (diethoxyethane, CH3CH2OCH2CH2OCH2CH3), or ethylene glycol dibutyl ether (dibutoxyethane, CH3CH2CH2CH2OCH2CH2OCH2CH2CH2CH3.
  • the ester can be ethylene glycol methyl ether acetate (2- methoxyethyl acetate, CH3OCH2CH2OCOCH3), ethylene glycol monoethyl ether acetate (2-ethoxyethyl acetate, CH3CH2OCH2CH2OCOCH3), ethylene glycol monobutyl ether acetate (2-butoxyethyl acetate, CH3CH2CH2CH2OCH2CH2OCOCH3), or propylene glycol methyl ether acetate (l-methoxy-2-propanol acetate).
  • Other glycols suitable for inclusion in the instant particle-free conductive ink compositions include 1,2-propylene glycol, 1,3-propylene glycol, or a combination thereof.
  • the solvent comprises water.
  • the solvent comprises a terpene, a terpenoid, or a combination thereof.
  • the solvent comprises a pinene, a limonene, in particular a D-limonene, a terpineol, or a combination thereof.
  • the solvent comprises limonene.
  • the solvent comprises terpineol.
  • the solvent comprises a combination of limonene and terpineol.
  • the instant solvent does not comprise alpha-terpinene, gamma-terpinene, terpinolene, or terpene-4-ol.
  • the solvent it can be advantageous for the solvent to be a purified form of the solvent.
  • the solvent is a purified terpineol, a purified limonene, or a combination of a purified terpineol and a purified limonene.
  • a purified solvent is understood to be at least 95% pure, at least 97% pure, at least 98% pure, at least 99% pure, or even more pure.
  • the conductive ink compositions further comprise a second bidentate complexing agent.
  • the second bidentate complexing agent comprises at least two heteroatoms.
  • the at least two heteroatoms of the second bidentate complexing agent are at least two nitrogen atoms, at least two oxygen atoms, or at least a nitrogen atom and at least an oxygen atom.
  • the second bidentate complexing agent comprises a ketone.
  • the second bidentate complexing agent is a P-diketone. Even more specifically, the P-diketone is acetylacetonate.
  • the conductive ink compositions further comprise a reducing ligand.
  • the reducing ligand can be an organic acid such as formic acid.
  • the conductive ink compositions may possess low viscosity so that they are compatible with a broad range of patterning techniques, including slot die coating, spin coating, roll-to-roll printing, including gravure, flexography, rotary screen printing, screen-printing, aerosol jet printing, inkjet printing, airbrushing, Mayer rod coating, flood coating, 3D printing, and electrohydrodynamic printing.
  • the inks are compatible with inkjet printing, dip coating, and spray coating.
  • the patterned features can be highly conductive at room temperature and can achieve bulk conductivity upon decomposing at mild temperatures (e.g., in some cases at less than about 100 °C).
  • the ink compositions can remain stable at room temperature for months without particle precipitation.
  • conductive ink compositions also referred to as “conductive inks” or “inks”
  • conductive inks can be stable, particle-free, and suitable for a wide range of patterning techniques.
  • a “particle-free” ink is one that does not include any particles at a diameter of greater than about 10 nm.
  • a “particle- free” ink is one that has less than about 1% particles, preferably less than about 0.1% particles.
  • Platinum salts are employed in the inks as a precursor material, which ultimately yields the platinum in the platinum coatings, lines, or patterns of the structure formed in the printing process.
  • the particle-free platinum ink composition is configured for application to a substrate.
  • the particle-free platinum ink composition can be converted to a conductive platinum structure at a temperature of about 250 °C or less.
  • the particle-free platinum ink composition can be converted to a conductive platinum structure at a temperature of about 100 °C or less.
  • the particle-free platinum ink composition can be converted to a conductive platinum structure at a temperature of about 220 °C or less, of about 210 °C or less, of about 190 °C or less, of about 180 °C or less, of about 170 °C or less, of about 160 °C or less, of about 150 °C or less, of about 140 °C or less, of about 130 °C or less, of about 120 °C or less, of about 110 °C or less, of about 90 °C or less, of about 80 °C or less, of about 70 °C or less, of about 60 °C or less, or even of about 50 °C or less.
  • the particle-free platinum conductive ink composition has a concentration of about 1 to about 50 weight percent platinum of the conductive ink composition. In some embodiments, the particle-free platinum conductive ink composition has a concentration of about 1 to about 40 weight percent platinum of the conductive ink composition. Tn some embodiments, the particle-free platinum conductive ink composition has a concentration of about 1 to about 30 weight percent platinum of the conductive ink composition. In some embodiments, the particle-free platinum conductive ink composition has a concentration of about 1 to about 20 weight percent platinum of the conductive ink composition. In some embodiments, the particle-free platinum conductive ink composition has a concentration of about 1 to about 10 weight percent platinum of the conductive ink composition.
  • the particle-free platinum conductive ink composition has a concentration of about 5 to about 15 weight percent platinum of the conductive ink composition. In some embodiments, the particle-free platinum conductive ink composition has a concentration of about 1 weight percent, about 2 weight percent, about 3 weight percent, about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, about 11 weight percent, about 12 weight percent, about 13 weight percent, about 14 weight percent, about 15 weight percent, about 16 weight percent, about 17 weight percent, about 18 weight percent, about 19 weight percent, about 20 weight percent, about 21 weight percent, about 22 weight percent, about 23 weight percent, about 24 weight percent, about 25 weight percent, about 26 weight percent, about 27 weight percent, about 28 weight percent, about 29 weight percent, about 30 weight percent, about 31 weight percent, about 32 weight percent, about 33 weight percent, about 34 weight percent, about 35 weight percent, about 36 weight percent, about 37 weight percent, about 38 weight percent, about 39 weight percent, about 40 weight percent
  • the particle-free platinum conductive ink compositions of the instant disclosure have a desired viscosity.
  • the desired viscosity is obtained using a micro VISC viscometer.
  • the viscosity is measured at room temperature, such as at, or about, 22 °C.
  • the conductive ink composition has a viscosity from about 50 centipoise to about 1000 centipoise.
  • the conductive ink composition has a viscosity from about 0.5 centipoise to about 50 centipoise.
  • the conductive ink composition has a viscosity from about 1 .0 centipoise to about 40 centipoise. Tn some embodiments, the conductive ink composition has a viscosity from about 2 centipoise to about 30 centipoise. In some embodiments, the conductive ink composition has a viscosity from about 0.5 centipoise to about 10 centipoise. In some embodiments, the conductive ink composition has a viscosity of about 1.0, about 2.0, or about 3.0 centipoise.
  • the conductive ink composition has a viscosity of at least about 0.5 centipoise, about 1.0 centipoise, about 2.0 centipoise, about 3.0 centipoise, about 4.0 centipoise, about 5.0 centipoise, about 6.0 centipoise, about 7.0 centipoise, about 8.0 centipoise, about 9.0 centipoise, about 10.0 centipoise, about 20.0 centipoise, about 30.0 centipoise, about 40.0 centipoise, about 50.0 centipoise, about 60.0 centipoise, about 70.0 centipoise, about 80.0 centipoise, or about 90.0 centipoise.
  • the conductive ink composition has a viscosity of at most about 100.0 centipoise, about 90.0 centipoise, about 80.0 centipoise, about 70.0 centipoise, about 60.0 centipoise, about 50.0 centipoise, about 40.0 centipoise, about 30.0 centipoise, about 20.0 centipoise, about 10.0 centipoise, about 9.0 centipoise, about 8.0 centipoise, about 7.0 centipoise, about 6.0 centipoise, about 5.0 centipoise, about 4.0 centipoise, about 3.0 centipoise, about 2.0 centipoise, or about 1.0 centipoise.
  • the conductive ink composition has a viscosity of 0.8 - 1.3 centipoise at 22 °C.
  • the methods include the step of applying any of the above-described conductive ink compositions to a substrate. In some embodiments, the methods include the step of heating the conductive ink composition on the substrate at a decomposition temperature of about 250 °C or less to form the conductive structure.
  • the methods include the step of heating the conductive ink composition on the substrate at a decomposition temperature of about 220 °C or less, of about 200 °C or less, of about 190 °C, of about 180 °C or less, of about 170 °C or less, of about 160 °C, of about 150 °C or less, of about 140 °C or less, of about 130 °C or less, of about 120 °C or less, of about 110 °C or less, of about 90 °C or less, of about 80 °C or less, of about 70 °C or less, of about 60 °C or less, or of about 50 °C or less to form the conductive structure.
  • the conductive ink composition is heated with a heat source. Examples of heat sources include an TR lamp, oven, or a heated substrate.
  • the electrical conductivity of the conductive structure formed from the conductive ink composition is measured. In some embodiments, the electrical conductivity of the conductive structure is from about 2xl0 -6 Ohm-cm to about IxlO -5 Ohm-cm. In some embodiments, the electrical conductivity of the conductive structure is from about 3xl0 -6 Ohm-cm to about 6xl0 -6 Ohm-cm.
  • the electrical conductivity of the conductive structure is at least about 2xl0 -6 Ohm-cm, about 3xl0 -6 Ohm-cm, about 4xl0 -6 Ohm -cm, about 5xl0 -6 Ohm-cm, about 6xl0 -6 Ohm- cm, about 7xl0 -6 Ohm-cm, about 8xl0 -6 Ohm-cm, or about 9xl 0 -6 Ohm-cm.
  • the electrical conductivity of the conductive structure is at most about IxlO -5 Ohm-cm, about 9xl0 -6 Ohm-cm, about 8xl0 -6 Ohm-cm, about 7xl0 -6 Ohm-cm, about 6x10 6 Ohm-cm, about 5x10 6 Ohm-cm, about 4x10 6 Ohm-cm, or about 3x10 6 Ohm-cm.
  • the electrical conductivity of the conductive structure can in some embodiments be expressed in terms of sheet resistance (i.e., bulk resistivity divided by thickness) in units of ohms per square (also referred to as ohms/square or OPS).
  • the resistance of the conductive structure is no more than 5 ohms per square, no more than 2 ohms per square, no more than 1 ohm per square, no more than 0.5 ohms per square, or even lower.
  • the resistance of the conductive structure is no more than 1 ohm per square.
  • the conductive ink compositions of the instant disclosure can be used to form conductive structures having high levels of bulk platinum.
  • the conductive structure has a bulk platinum content of at least 1%.
  • the conductive structure has a bulk platinum content of at least 2%, at least 5%, at least 10%, at least 15%, at least 20%, or even higher.
  • the conductive ink compositions of the instant disclosure can be used in various printing applications, including slot die coating, spin coating, roll-to-roll printing, including gravure, flexography, rotary screen printing, screen printing, aerosol jet printing, inkjet printing, airbrushing, Mayer rod coating, flood coating, 3D printing, dispenser, and electrohydrodynamic printing.
  • the inks can be used in inkjet printing, dip coating, and spray coating.
  • patterns can be created using photolithography to create a mask to etch silver from certain areas, thereby creating high-fidelity features. Both positive and negative patterning processes may be used to create the patterns.
  • the particle-free platinum conductive ink composition is applied to a polymer substrate. In some embodiments, the particle-free platinum conductive ink composition is applied to a nonpolar polymer substrate. In some embodiments, the particle-free platinum conductive ink composition is applied to a glass substrate. In some embodiments, the particle-free platinum conductive ink composition is applied to a ceramic substrate.
  • the particle-free platinum conductive ink composition is applied to an elastomer. In some embodiments, the particle-free platinum conductive ink composition is applied to a 3D substrate.
  • the particle-free platinum conductive ink composition of the instant methods has a concentration of about 0.1-50 weight percent platinum of the ink composition. In some embodiments, the ink composition of the instant methods has a concentration of about 0.1-40 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 1-30 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 1-20 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 1-10 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 5-15 weight percent platinum of the ink composition.
  • the ink composition has a concentration of about 0.1 weight percent, about 0.2 weight percent, about 0.3 weight percent, about 0.4 weight percent, about 0.5 weight percent, about 0.6 weight percent, about 0.7 weight percent, about 0.8 weight percent, about 0.9 weight percent, about 1 weight percent, about 2 weight percent, about 3 weight percent, about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, about 11 weight percent, about 12 weight percent, about 13 weight percent, about 14 weight percent, about 15 weight percent, about 16 weight percent, about 17 weight percent, about 18 weight percent, about 19 weight percent, or about 20 weight percent platinum of the ink composition.
  • the ink composition of the instant methods has a concentration of at least about 0.1 weight percent, about 0.2 weight percent, about 0.3 weight percent, about 0.4 weight percent, about 0.5 weight percent, about 0.6 weight percent, about 0.7 weight percent, about 0.8 weight percent, about 0.9 weight percent, 1 weight percent, about 2 weight percent, about 3 weight percent, about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, about 11 weight percent, about 12 weight percent, about 1 weight percent, about 14 weight percent, about 15 weight percent, about 16 weight percent, about 17 weight percent, about 18 weight percent, about
  • the ink composition has a concentration of at most about 40 weight percent, about 39 weight percent, about 38 weight percent, about 37 weight percent, about 36 weight percent, about 35 weight percent, about 34 weight percent, about 33 weight percent, about 32 weight percent, 31 weight percent, about 30 weight percent, about 29 weight percent, about 28 weight percent, about 27 weight percent, about 26 weight percent, about 25 weight percent, about 24 weight percent, about 23 weight percent, about 22 weight percent, about 21 weight percent, about 20 weight percent, about 19 weight percent, about 18 weight percent, about 17 weight percent, about 16 weight percent, about 15 weight percent, about 14 weight percent, about 13 weight percent, or about 12 weight percent platinum of the ink composition.
  • the ink composition of the instant methods has a concentration of about 0.1-50 weight percent platinum of the ink composition. In some embodiments, the ink composition of the instant methods has a concentration of about 0.1- 40 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 1-30 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 1-
  • the ink composition has a concentration of about 1-10 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 5- 15 weight percent platinum of the ink composition. In some embodiments, the ink composition has a concentration of about 0.1 weight percent, about 0.2 weight percent, about 0.3 weight percent, about 0.4 weight percent, about 0.5 weight percent, about 0.6 weight percent, about 0.7 weight percent, about 0.8 weight percent, about 0.9 weight percent, 1 weight percent, about 2 weight percent, about 3 weight percent, about 4 weight percent, about 5 weight percent, about 6 weight percent, about 7 weight percent, about 8 weight percent, about 9 weight percent, about 10 weight percent, about 11 weight percent, about 12 weight percent, about 13 weight percent, about 14 weight percent, about 15 weight percent, about 16 weight percent, about 17 weight percent, about 18 weight percent, about 19 weight percent, or about 20 weight percent platinum of the ink composition.
  • the particle- free platinum conductive ink compositions of the disclosure are decomposed on a substrate to form a conductive structure on the substrate.
  • the particle-free platinum conductive ink composition is decomposed by heating the composition at a temperature of about 270 °C or less.
  • the conductive ink composition is decomposed by heating the composition at a temperature of about 260 °C or less, about 250 °C or less, about 240 °C or less, about 230 °C or less, about 220 °C or less, about 210 °C or less, about 200 °C or less, about
  • the conductive ink composition is heated by a heat source.
  • heat sources include an IR lamp, oven, or a heated substrate.
  • the conductive ink composition is decomposed by exposing the composition to a light source at a wavelength from about 100 nm to about 1500 nm. In some embodiments, the conductive ink composition is decomposed by exposing the composition to a light source such as a Xenon lamp or IR lamp at a wavelength from about 100 nm to about 1000 nm. In some embodiments, the conductive ink composition is decomposed by exposing the composition to a light source at a wavelength from about 100 nm to about 700 nm. In some embodiments, the conductive ink composition is decomposed by exposing the composition to a light source at a wavelength from about 100 nm to about 500 nm.
  • the conductive ink composition is decomposed by exposing the composition to a light source at a wavelength from about 100 nm to about 300 nm. In some embodiments, the conductive ink composition is decomposed by exposing the composition to a light source at a wavelength of about 100 nm, about 200 nm, about 300 nm, about 400 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, or about 1000 nm.
  • the conductive ink composition is decomposed by a combination of heating the reducible metal complex, for example at any of the abovelisted temperatures, and exposing the composition to a light source, for example at any of the above-listed wavelengths.
  • the electrical conductivity of the conductive structures is measured. In some embodiments, the electrical conductivity of the conductive structures is about IxlO -6 Ohm-cm or greater. In some embodiments, the electrical conductivity of the conductive structures is from about 1x10 6 Ohm-cm to about 8x10 4 Ohm-cm. In some embodiments, the electrical conductivity of the conductive structures is from about 3x1 O’ 6 Ohm-cm to about 6xl0 -6 Ohm-cm.
  • the electrical conductivity of the conductive structures is at least about IxlO -6 Ohm-cm, about 2xl0 -6 Ohm-cm, about 3xl0 -6 Ohm-cm, about 4xl0 -6 Ohm- cm, about 5xl0 -6 Ohm-cm, about 6xl0 -6 Ohm-cm, about 7xl0 -6 Ohm-cm, about 8xl0 -6 Ohm-cm, about 9xl0 -6 Ohm-cm, about IxlO -5 Ohm- cm, about 2xl0 -5 Ohm-cm, about 3xl0 -5 Ohm-cm, about 4xl0 -5 Ohm-cm, about 5xl0 -5 Ohm-cm, about 6xl0 -5 Ohm-cm, about 7xl0 -5 Ohm-cm, about 8xl0 -5 Ohm-cm, about 9xl0 -5 Ohm-cm, about IxlO -6 Ohm-
  • the electrical conductivity of the conductive structures is at most about 8xl0 -4 Ohm-cm, 7xl0 -4 Ohm -cm, about 6xl0 4 Ohm-cm, about 5xl0 -4 Ohm- cm, about 4xl0 4 Ohm-cm, about 3xl0 -4 Ohm-cm, about 2xl0 -4 Ohm-cm, or about IxlO -4 Ohm-cm, about 9xl0 -5 Ohm-cm, about 8xl0 -5 Ohm-cm, about 7xl0 -5 Ohm-cm, about 6xl0 -5 Ohm-cm, about 5xl0 -5 Ohm-cm, about 4xl0 -5 Ohm-cm, about 3xl0 -5 Ohm-cm, about 2xl0 -5 Ohm-cm, about IxlO -5 Ohm-cm, about 9xl0 -6 Ohm-cm, about 8xl0 -4 Ohm-
  • the ink compositions of the instant disclosure can be used in various printing applications, including slot die coating, spin coating, roll-to-roll printing, including gravure, flexography, rotary screen printing, screen printing, aerosol jet printing, inkjet printing, airbrushing, Mayer rod coating, flood coating, 3D printing, and electrohydrodynamic painting.
  • the inks can be used in inkjet printing, dip coating, and spray coating.
  • patterns can be created using photolithography to create a mask to etch the platinum from certain areas, thereby creating high-fidelity features.
  • the ink compositions are used in aerosol jet printing applications to print conductive structures comprising platinum metal.
  • This method which is also known as maskless mesoscale materials deposition or M3D (see, e.g., U.S. Patent No. 7,485,345), involves atomization of the particle-free ink composition, via ultrasonic or pneumatic techniques, to generate droplets of micrometer scale.
  • the aerosolized ink is combined with a carrier gas and directed via a flowhead onto a substrate where the ink is ultimately cured to a conductive structure.
  • the ink compositions are compatible with many nonpolar polymer substrates, glasses, and ceramic substrates, where polar complexes do not wet particularly well.
  • the ink composition is applied to a polymer substrate.
  • the ink composition is applied to a nonpolar polymer substrate.
  • the ink composition is applied to a glass substrate.
  • the ink composition is applied to a ceramic substrate.
  • the ink composition is applied to an elastomer. In some embodiments, the ink composition is applied to a 3D substrate.
  • the film Upon a 100 pL drop-cast deposition onto glass or wafer substrate, the film was thermally treated to 80°C on a hot plate for 10 minutes to which the film turns to an off- white color. The film was annealed in a binder oven at 200°C for 30 minutes, exhibiting a white to red to metallic gray transitional sequence, denoting that the platinum complex has decomposed into a metallic, conductive structure. Using a multimeter for resistance measurements, the platinum film had an electrical resistance of 178 to 400 Ohms after 30 minutes at 1.1 to 1.9 cm in diameter respectively. The electrical resistance may vary depending on the printing method and thermal decomposition appliance used to characterize the porous platinum ink.
  • the ink was annealed in a binder oven for 1 hour at 230°C and on a hot plate at 200°C, exhibiting a red to black to metallic gray-black transitional sequence, denoting that the platinum complex has decomposed fully into a native, conductive platinum network.
  • the platinum film had an electrical sheet resistance of 19 Ohms/square (OPS) after 1 hour at 230°C in a binder oven and 48 OPS after 1 hour on a hot plate at 200°C.
  • OPS Ohms/square
  • the electrical resistance may vary depending on the printing method and thermal decomposition appliance used to characterize the dense platinum ink.
  • the prepared ink can be blade/bar coated onto various substrates such as glass, polyimide etc. Alternatively, the ink can also be aerosol jetted onto the substate of choice depending on the application.
  • Typical annealing method includes heating for 1 h at 230 °C in convection oven or on a hot plate at 200 °C for 1 h.
  • the ink exhibits a red to black to metallic gray-black transition leaving a smooth reflective surface during the annealing sequence, denoting that the platinum complex has converted into its metallic form.
  • FIG. 1A shows the reflection of a camera photographing a 3x2 inch glass slide coated with platinum ink using a 20 um blade, cured at 200 °C for 1 h.
  • the platinum film had an electrical sheet resistance of 19 Ohms/square ( Z ) after 1 hour at 230 °C in a binder oven and 48 Q/ after 1 hour on a hot plate at 200 °C.
  • the electrical resistance may vary depending on the printing method and thermal decomposition appliance used to characterize the dense platinum ink. Scanning microscope imaging of the surface (FIG. IB, at 25K magnified optical image) and edge (FIG. 1C, at 10.5K magnification SEM imaging) reveal a tightly packed structure forming a dense film.
  • the prepared ink can be blade/bar coated onto various substrates such as glass, polyimide etc. Alternatively, the ink can also be aerosol jetted onto the substate of choice depending on the application.
  • the low curing ink was blade coated on glass slides and annealed inside convection oven for at 150 °C for 1 h to form a dense film of metallic platinum.
  • the electrical resistance may vary depending on the printing method and thermal decomposition appliance used to characterize the dense platinum ink.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne des compositions d'encre à décomposition organométallique (MOD) conductrice contenant du platine. L'invention concerne également des procédés de préparation des compositions d'encre conductrice, des procédés de formation de structures conductrices à partir des compositions d'encre conductrice, et des structures conductrices formées à partir des compositions d'encre conductrice, comprenant des films de platine conducteurs denses. Les compositions d'encre conductrice comprennent de préférence un métal de platine, un premier agent complexant bidenté et un solvant. Des films de platine conducteurs peuvent être formés à partir des compositions d'encre à basse température et peuvent par conséquent être utilisés sur divers substrats, y compris des substrats de choix pour des applications électroniques.
PCT/US2023/073121 2022-08-30 2023-08-30 Compositions d'encre au platine et procédés de revêtement conducteur à basse température WO2024050387A2 (fr)

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PL1853671T3 (pl) * 2005-03-04 2014-01-31 Inktec Co Ltd Tusze przewodzące i sposób ich wytwarzania
WO2015160938A1 (fr) * 2014-04-17 2015-10-22 Electroninks Incorporated Compositions d'encre conductrice
WO2016017836A1 (fr) * 2014-07-30 2016-02-04 (주)피이솔브 Encre conductrice
JP2018154806A (ja) * 2017-03-15 2018-10-04 Dic株式会社 金属微粒子分散体、導電性インク、および電子デバイス
WO2019028435A1 (fr) * 2017-08-03 2019-02-07 Electroninks Incorporated Compositions d'encre conductrice comprenant du palladium et leurs procédés de fabrication
US20210307163A1 (en) * 2018-08-03 2021-09-30 Electroninks Incorporated Conductive materials and their methods of preparation by metallization with metal complex conductive ink compositions
US20230064831A1 (en) * 2020-01-30 2023-03-02 Liquid X Printed Metals, Inc. Force sensor controlled conductive heating elements

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