WO2014127909A1 - Formulations comprenant des nanofils d'argent lavés et un pedot - Google Patents

Formulations comprenant des nanofils d'argent lavés et un pedot Download PDF

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WO2014127909A1
WO2014127909A1 PCT/EP2014/000436 EP2014000436W WO2014127909A1 WO 2014127909 A1 WO2014127909 A1 WO 2014127909A1 EP 2014000436 W EP2014000436 W EP 2014000436W WO 2014127909 A1 WO2014127909 A1 WO 2014127909A1
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conductive polymer
composition
silver nanowires
silver
solvent
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Wilfried LÖVENICH
Rüdiger Sauer
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Heraeus Deutschland GmbH and Co KG
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Heraeus Precious Metals GmbH and Co KG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • C—CHEMISTRY; METALLURGY
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    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09D139/08—Homopolymers or copolymers of vinyl-pyridine
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • Formulations comprising washed silver nanowires and PEDOT
  • the present invention relates to a process for the preparation of a composition which comprises a solvent, silver nanowires and a conductive polymer, the composition obtainable by this process, a composition which comprises a solvent, silver nanowires and a conductive polymer, a process for the production of an electrically conductive layer, the electrically conductive layer obtainable by this and the use of the compositions according to the invention.
  • Conductive polymers are increasingly gaining economic importance, since polymers have advantages over metals with respect to processability, weight and targeted adjustment of properties by chemical modification.
  • Examples of known ⁇ -conjugated polymers are polypyrroles, polythiophenes, polyanilines, polyacetylenes, polyphenylenes and poly(p-phenylene-vinylenes).
  • Layers of conductive polymers are employed in diverse industrial uses, e.g. as polymeric counter-electrodes in capacitors or for throughplating of electronic circuit boards.
  • the preparation of conductive polymers is carried out chemically or electrochemically by oxidation from monomeric precursors, such as e.g.
  • poly(3,4- ethylenedioxythiophene) (PEDOT or PEDT), which is described, for example, in EP 0 339 340 A2 and is prepared by chemical polymerization of 3,4- ethylenedioxythiophene (EDOT or EDT), and which has very high conductivities in its oxidized form.
  • PEDOT or PEDT poly(3,4- ethylenedioxythiophene)
  • EDOT or EDT 3,4- ethylenedioxythiophene
  • An overview of numerous poly(3,4-alkylenedioxythiophene) derivatives, in particular poly(3,4-ethylenedioxythiophene) derivatives, and their monomer units, syntheses and uses is given by L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik & J. R. Reynolds, Adv. Mater.
  • the dispersions disclosed for example in EP 0 440 957 A2, of PEDOT with polyanions, such as e.g. polystyrenesulphonic acid (PSS), have acquired particular industrial importance (PEDOT/PSS dispersions).
  • PEDOT/PSS dispersions Transparent, conductive films which have found a large number of uses, e.g. as a hole injection layer in organic light-emitting diodes (OLED) or as an intermediate layer in organic photovoltaic elements (OPV elements), can be produced from these dispersions. Due to the polyelectrolyte properties of PEDOT as a polycation and PSS as a polyanion, the PEDOT/PSS compositions are not a true solution, but rather a dispersion.
  • OLED and OPV elements as a rule comprise a layer of indium tin oxide (ITO) as a conductive substrate layer.
  • ITO indium tin oxide
  • efforts are currently being made to dispense with the use of ITO, since in contrast to conductive polymer layers, for example, this is not flexible.
  • the disadvantage of the PEDOT/PSS-comprising dispersions known from the prior art is, however, that the conductivity of these layers is too low for them to be employed not only as a hole injection layer in an OLED or as an intermediate layer between the ITO-coated substrate and the semiconductor layer in the standard construction of a P3HT : PCBM solar cell, but as a simultaneous substitute for the underlying ITO layer. So that layers comprising conductive polymers can replace the ITO layers in OLED and OPV elements, they must have a particularly high conductivity (or a low surface resistance), with at the same time a high transmission.
  • a polyol serves here both as a solvent and as a reducing agent for silver salts, preferably silver nitrate, a dispersing agent, such as polyvinylpyrrolidone (PVP), and a halide source being available.
  • PVP polyvinylpyrrolidone
  • the mixture of the components is chosen such that a specific growth of the wires along a preferred crystal axis develops.
  • Anisotropic conductive bars having an aspect ratio of at least 10 : 1 to 1,000 : 1 are formed by this means.
  • electrically conductive films of low surface resistance (SR) and high conductivity and a transparency of > 80 % can be achieved when the percolation threshold is exceeded.
  • SR surface resistance
  • These can be applied both to glass and especially to flexible substrates and show a constant conductivity even after bending.
  • suitable structuring these transparent electrodes can be used inter alia as an ITO substitute in electronic equipment, such as LCD or plasma screens, touch screens and organic light-emitting diodes.
  • the silver nanowires can be applied in the form of dispersions, for example by spin coating, spray coating or by "stamping on".
  • the silver nanowires are processed from a dispersion without a film-forming agent, the silver nanowires show only a poor adhesion to the surface and due to the loose bond they are often only inadequately in contact and show relatively high surface resistances. This makes it necessary to press the layers in order to increase the conductivity, and/or to cover them with a further layer, for example a layer of a Ti0 2 sol/gel (Yang et al. ACS Nano 2011, 5, 9,877-9,882).
  • Coatings with conductive materials, in particular conductive polymers, are furthermore proposed in the patent literature, as is described, for example in WO-A-2011/041232 or WOA-2008/131304.
  • a stamping process in which the dry silver nanowires are applied to a prefabricated PEDOT/PSS layer is also known (Peumans et al. Adv. Mater. 2011, 23, 2905-2910).
  • the approaches described above for application of a conductive layer comprising silver nanowires to a substrate are technically comparatively involved.
  • a simple application of conductive layers by means of simple coating processes is desirable for use on an industrial scale.
  • US-A-2012/0104374 describes the combining of a silver nanowire suspension with neutral to alkaline PEDOT/PSS materials and uses these formulations for coating by spin coating. However, the application contains no indications of the quality of the silver nanowires employed which is necessary for the preparation of mixtures with conductive polymers. US-A-2012/0104374 gives no information on the purity of the silver nanowires employed there, in particular not on the amount of non- conductive polymers which - due to the process for the production of silver nanowires - are conventionally adsorbed on the surface of the silver nanowires.
  • the present invention was based on the object of overcoming the disadvantages resulting from the prior art in connection with compositions comprising silver nanowires, in particular in connection with the use of such compositions for the production of conductive layers which are suitable as an ITO substitute.
  • the present invention was based on the object of providing a composition comprising silver nanowires, from which electrically conductive layers which are characterized by a low surface resistance with at the same time a high transmission and are therefore suitable as an ITO substitute material in an OLED, an OPV element or a touch screen can be produced in a simple manner on an industrial scale.
  • the compositions should be distinguished in particular by a particularly advantageous storage stability.
  • the present invention was furthermore based on the object of providing a process by means of which compositions which comprise silver nanowires and are advantageous in such a way can be prepared in a simple and reproducible manner.
  • a contribution towards achieving the abovementioned objects is made by a process for the preparation of a composition, preferably a dispersion, which comprises a solvent A, silver nanowires and a conductive polymer, comprising the process steps:
  • compositions which comprise electrically conductive polymers and have been prepared with silver nanowires which have first been purified by a washing process are distinguished in particular by a significantly improved storage stability compared with compositions which have been prepared with non-washed silver nanowires.
  • process step (i) of the process according to the invention silver salts are first reduced by means of a polyol serving as a solvent and reducing agent in the presence of a non-conductive polymer, and the silver nanowires formed by this procedure are then precipitated.
  • a polyol serving as a solvent and reducing agent in the presence of a non-conductive polymer
  • Process step (i) can accordingly include, for example, the part steps:
  • reaction mixture comprising a polyol, a non-conductive polymer which adsorbs on to a silver surface, a chemical which forms a halide and/or one which forms a pseudohalide and a chemical which forms a redox pair, chosen from the group consisting of bromine, iodine, copper, vanadium and mixtures thereof; (ib) the addition of a silver salt in an amount such that the concentration of silver in the reaction mixture is at least 0.5 wt.%, based on the total weight of the reaction mixture; the reduction of the silver salt at a temperature of the reaction mixture of at least 75 °C for the duration of the reaction; the separating off of the silver nano wires from the reaction mixture.
  • reaction mixture constituents a chemical which forms a halide and/or one which forms a pseudohalide
  • a chemical which forms a redox pair chosen from the group consisting of bromine, iodine, copper, vanadium and mixtures thereof overlap.
  • the chemicals bromine and iodine which form a redox pair are halogens which, in the form of one of their salts, are both a "salt of a halide” and a "chemical which forms a redox pair, chosen from the group consisting of bromine and iodine".
  • Preferred polyols are accordingly chosen from the group consisting of 1,2- ethanediol, 1 ,2-propanediol, 1,3 -propanediol, 1 ,2-butanediol, 1,3-butanediol, 1,4- butanediol, 2,3-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, triethanolamine, trihydroxymethyl- aminomethane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycols, dipropylene glycols and a polyethylene glycol which is liquid at the reaction temperature, such as, for example, polyethylene glycol 300.
  • Very particularly preferred polyols are chosen from the group consisting of glycerol, ethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, 1,2- butanediol, 1,3-butanediol, 1,4-butanediol and 2,3-butanediol, the use of ethylene glycol and glycerol being most preferred.
  • the non-conductive polymer which adsorbs on to the silver surface is required in the polyol process for formation of the desired wire-shaped morphology.
  • all those compounds which are mentioned in WO-A-2009/128973 on pages 19 to 27 (paragraphs [0095] to [01 16]) under the heading "Organic Protective Agent(s) (OPA)" can be employed as the non-conductive polymer.
  • Preferred non-conductive polymers which adsorb on to a silver surface are those having a weight-average molecular weight, preferably determined by gel permeation chromatography, of at least 100,000 g/mol, still more preferably at least 250,000 g/mol and most preferably at least 500,000 g/mol.
  • non-conductive polymers are chosen from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and mixtures of various grades (molecular weights) and copolymers of these polymers.
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • Suitable comonomers are e.g. N-vinylimidazole, vinyl acetate and vinylcaprolactam.
  • polyvinylpyrrolidone having a molecular weight of at least 100,000 g/mol, still more preferably at least 250,000 g/mol and most preferably at least 500,000 g/mol is most preferred as the non-conductive polymer.
  • the chemical which forms a halide is preferably a salt of a halide, particularly preferably NaCl, NaBr, Nal, KCl, KBr, KI or a mixture of at least two of these, or elemental bromine, elemental iodine or a mixture of at least two of these, while the chemical which forms the pseudohalide is preferably a salt of a pseudohalide, particularly preferably NaSCN, KSCN or a mixture of these.
  • the chemical which forms a redox pair is preferably elemental copper, elemental vanadium, a copper oxide, a vanadium oxide, a copper hydroxide, a vanadium hydroxide, a copper sulphate, a vanadium sulphate, a copper nitrate, a vanadium nitrate, a vanadium trichloride or a mixture of these compounds.
  • the chemical which forms a halide and the chemical which forms a redox pair are preferably already present in the reaction mixture provided in process step (ia). These chemicals (or at least one of these chemicals), however, can also be added only subsequently, for example together with or after the addition of the silver salt in process step (ib).
  • a silver salt is then added in an amount such that the concentration of silver in the reaction mixture is at least 0.5 wt.%, based on the total weight of the reaction mixture, it being possible for the silver salt to be added, for example, at a temperature of the reaction mixture of at least 75 °C, particularly preferably at least 100 °C.
  • AgN0 3 is preferred as the silver salt, and is added to the reaction in the form of a solution or directly as a solid.
  • a suitable solvent for the silver salt is, inter alia, the polyol employed in the reaction, that is to say preferably ethylene glycol and/or glycerol. The addition can take place all at once, in portions or continuously over a relatively long period of time.
  • the silver salt is added at the reaction temperature.
  • the silver salt is added in an amount which corresponds mathematically to a silver concentration of at least 0.5 wt.% in the reaction mixture.
  • silver is present in a concentration of at least 0.75 wt.%, more preferably of at least 1.0 wt.%, most preferably of at least 1.5 wt.%.
  • the silver salt is then reduced, this reduction preferably being carried out at a temperature of at least 75 °C, particularly preferably of at least 100 °C and still more preferably of at least 120 °C for the duration of the reaction.
  • the formation of the silver nanowires can be readily monitored visually when carrying out this process.
  • the reaction mixture can be allowed to cool. A reaction mixture comprising silver nanowires, on the surface of which at least some of the non-conductive polymer is adsorbed, is obtained.
  • the silver nanowires can then be separated off from this reaction mixture in a further part step (id), for example by precipitation after dilution of the reaction mixture by the addition of suitable solvents, such as, for example, acetone, tetrahydrofuran or ethyl acetate, or after addition of chemicals which modify the electrical double layer.
  • suitable solvents such as, for example, acetone, tetrahydrofuran or ethyl acetate, or after addition of chemicals which modify the electrical double layer.
  • suitable solvents such as, for example, acetone, tetrahydrofuran or ethyl acetate, or after addition of chemicals which modify the electrical double layer.
  • the silver nanowires are characterized by a length of from 1 ⁇ to 200 ⁇ , by a diameter of from 50 nm to 1,300 nm and by an aspect ratio (length : diameter) of at least 5 : 1, very particularly preferably by an aspect ratio in a range of from 10 : 1 to 1,000 : 1.
  • the non-conductive polymer adsorbed on the surface of the silver nanowires is at least partially removed to obtain purified silver nanowires.
  • process step (ii) it is preferable in this connection to remove in process step (ii) the non-conductive polymer adsorbed on the surface of the silver nanowires to an extent such that the weight ratio of silver : adsorbed non-conductive polymer is increased by a factor of at least 2, particularly preferably at least 5 and most preferably at least 10, starting from the weight ratio present after process step (i) has ended.
  • process step (ii) includes the following part steps:
  • Possible solvents B which are employed in process step (iia) and in which the non-conductive polymer adsorbed on the surface of the silver nanowires is at least partly soluble are, if polyvinylpyrrolidone is used as the non-conductive polymer, in particular water, alcohols, such as methanol or ethanol, or mixtures of these.
  • the silver nanowires it is furthermore preferable for the silver nanowires to be suspended at a temperature in a range of from 15 to 100 °C, particularly preferably in a range of from 20 to 50 °C for a duration of from 1 minute to 5 hours, particularly preferably for a duration of from 5 minutes to 60 minutes.
  • the silver nanowires prefferably be suspended in an amount of from 1 g to 100 g, particularly preferably in an amount of from 2.5 g to 25 g of solvent B per gram of silver nanowires obtained in process step (i), preferably per gram of the composition obtained in process step (id) after the silver nanowires have been separated off.
  • the separating off of the suspended silver nanowires in process step (iib) is preferably again carried out by processes known to the person skilled in the art, particularly preferably by centrifugation.
  • a continuous washing in which the silver nanowires obtained in process step (i) are brought into contact continuously with a solvent B in which the non- conductive polymer adsorbed on the surface of the silver nanowires is at least partly soluble is also conceivable. This can be carried out, for example, by dialysis.
  • the nitrogen content of the purified silver nanowires obtained in process step (ii) is less than 7 wt.%, particularly preferably less than 2.5 wt.% and most preferably less than 1 wt.%, in each case based on the total weight of the drying residue of the purified silver nanowires.
  • the purified silver nanowires are then brought into contact with a solvent A and a conductive polymer, but particularly preferably with a dispersion comprising a solvent A and a conductive polymer.
  • polythiophenes are particularly preferred as the conductive polymer, in particular polythiophenes having the general formula in which A represents an optionally substituted Ci-Cs-alkylene radical,
  • R represents a linear or branched, optionally substituted CrC 1 -alkyl radical, an optionally substituted C 5 -C 12 -cycloalkyl radical, an optionally substituted C 6 -C 14 -aryl radical, an optionally substituted C7-C 18 -aralkyl radical, an optionally substituted C C 4 -hydroxyalkyl radical or a hydroxyl radical, wherein 0 to 8 radicals R can be bonded to A and, in the case of more than one radical, can be identical or different.
  • the polythiophenes preferably in each case carry H on the end groups.
  • d-C 5 -alkylene radicals A are preferably methylene, ethylene, n-propylene, n-butylene or n-pentylene.
  • Ci-C 18 -alkyl R preferably represent linear or branched CrC 18 -alkyl radicals, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1-methylbutyl, 2- methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2- dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- nonyl, n-decyl, n-undecyl, n-dodecyl, n-do
  • Polythiophenes in which A represents an optionally substituted C 2 -C 3 -alkylene radical are particularly preferred.
  • Poly(3,4-ethylenedioxythiophene) is very particularly preferred as the polythiophene.
  • the polythiophenes can be neutral or cationic. In preferred embodiments they are cationic, "cationic" relating only to the charges on the polythiophene main chain.
  • the polythiophenes can carry positive and negative charges in the structural unit, depending on the substituent on the radicals R, the positive charges being on the polythiophene main chain and the negative charges optionally being on the radicals R substituted by sulphonate or carboxylate groups.
  • the positive charges of the polythiophene main chain can be partly or completely satisfied by the anionic groups optionally present on the radicals R. Overall, in these cases the polythiophenes can be cationic, neutral or even anionic.
  • the positive charges on the polythiophene main chain are the deciding factor.
  • the positive charges are not shown in the formulae, since their precise number and position cannot be determined absolutely. However, the number of positive charges is at least 1 and at most n, where n is the total number of all recurring units (identical or different) within the polythiophene.
  • the conductive polymer furthermore comprises a polyanion which is preferably based on polymers functionalized with acid groups.
  • Anions of polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acid or polymaleic acids, or of polymeric sulphonic acids, such as polystyrenesulphonic acids and polyvinylsulphonic acids, are possible in particular as the polyanion.
  • These polycarboxylic and -sulphonic acids can also be copolymers of vinylcarboxylic and vinylsulphonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
  • Polyanions which are furthermore possible are perfluorinated, colloid-forming polyanions, which are commercially obtainable, for example, under the name Nafion ® .
  • the molecular weight of the polymers which are functionalized with acid groups and supply the polyanions is preferably 1 ,000 to 2,000,000, particularly preferably 2,000 to 500,000.
  • the polymers functionalized with acid groups or their alkali metal salts are commercially obtainable, e.g. polystyrenesulphonic acids and polyacrylic acids, or can be prepared by known processes (see e.g. Houben Weyl, Methoden der organischen Chemie, vol. E 20 Makromolekulare Stoffe, part 2, (1987), p. 1141 et seq.).
  • Polymers functionalized with acid groups (polyanions) and polythiophenes, in particular polystyrenesulphonic acid and poly(3,4-ethylenedioxythiophene), can be present in the conductive polymer employed in process step (iii) in a weight ratio of from 0.5 : 1 to 50 : 1, preferably from 1 : 1 to 30 : 1, particularly preferably 2 : 1 to 20 : 1.
  • the weight of the electrically conductive polymers here corresponds to the weight of the monomers employed for the preparation of the conductive polymers, assuming that complete conversion takes place during the polymerization.
  • the conductive polymer employed in process step (iii) comprises complexes of a polythiophene and a polyanion, very particularly preferably PEDOT/PSS complexes.
  • Such complexes are obtainable by polymerizing the thiophene monomers, preferably 3,4-ethylenedioxythiophene, oxidatively in aqueous solution in the presence of the polyanions, preferably the polystyrenesulphonic acid.
  • Preferred solvents A are water, aliphatic alcohols, such as methanol, ethanol, i- propanol and n-butanol, aliphatic ketones, such as acetone and methyl ethyl ketone, aliphatic carboxylic acid esters, such as ethyl acetate and butyl acetate, aromatic hydrocarbons, such as toluene and xylene, aliphatic hydrocarbons, such as hexane, heptane and cyclohexane, chlorohydrocarbons, such as methylene chloride and dichloroethane, aliphatic nitriles, such as acetonitrile, aliphatic sulphoxides and sulphones, such as dimethylsulphoxide and sulpholane, aliphatic carboxylic acid amides, such as methylacetamide and dimethylformamide, or aliphatic and araliphatic ethers,
  • the purified silver nanowires obtained in process step (ii) are mixed in process step (iii) with an aqueous dispersion comprising, as the conductive polymer, complexes of a polythiophene and a polyanion, particularly preferably PEDOT/PSS complexes, and water as solvent A.
  • PEDOT/PSS dispersions which are suitable for this are commercially obtainable, for example, under the trade name CleviosTM.
  • the solids content of such dispersions is conventionally in a range of from 0.1 to 10 wt.%, particularly preferably in a range of from 1 to 5 wt.%.
  • the conductive polymer in the presence of the purified silver nanowires in that polymerizable precursors of the conductive polymer (e.g. 3,4-ethylenedioxythiophene in the case of poly(3,4- ethylenedioxythiophene) as the conductive polymer) are polymerized in the presence of the purified silver nanowires and in the presents of polyanions, such as polystyrenesulphonic acid.
  • polymerizable precursors of the conductive polymer e.g. 3,4-ethylenedioxythiophene in the case of poly(3,4- ethylenedioxythiophene) as the conductive polymer
  • the purified silver nanowires obtained in process step (ii) and the conductive polymer to be employed in process step (iii) in a relative amount such that the weight ratio of silver : conductive polymer in the composition is in a range of from 10 : 1 to 1 : 10, particularly preferably in a range of from 5 : 1 to 1 : 5 and most preferably in a range of from 2 : 1 to 1 : 2.
  • the above relative amounts stated relate to the weight ratio of silver : total amount of polythiophenes and polyanions.
  • the composition obtainable by the process according to the invention can optionally comprise further additives, such as, for example, additives which increase the conductivity, antioxidants, adhesion promoters, acids or bases for regulation of the pH, binders, crosslinking agents, surfactants or other additives known to the person skilled in the art as additives for PEDOT/PSS dispersions.
  • additives can in principle be added to the purified silver nanowires employed in process step (iii), the dispersions employed in process step (iii) comprising a conductive polymer, or the mixture of these two components obtained in process step (iii).
  • Surfactant is understood as meaning amphiphilic substances which have a hydrophilic head group and a hydrophobic part.
  • the hydrophilic group can be either ionic or nonionic in nature. Due the molecular structure and the tendency to accumulate at interfaces, this substance class lowers the interfacial tension and leads to improved wetting properties.
  • Suitable surfactants are, in particular, anionic surfactants, such as e.g. alkylbenzenesulphonic acids and salts, paraffinsulphonates, alcohol sulphonates, ether sulphonates, sulphosuccinates, phosphate esters, alkyl ether carboxylic acids or carboxylates, cationic surfactants, such as e.g.
  • nonionic surfactants such as e.g. linear alcohol ethoxylates, oxo alcohol ethoxylates, alkylphenol ethoxylates or alkyl polyglucosides.
  • Conductivity additives for polythiophenes which can be employed are polyalkylene glycols, in particular polyethylene glycols or polypropylene glycols, polyglycerols or mixtures of these, polyols, such as propylene glycol and ethylene glycol, sulphoxides, such as dimethylsulphoxide, carboxylic acid amides, such as methylacetamide, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, N-cyclohexylpyrrolidone, ionic liquids or sugars, such as sorbitol, the use of high- boiling solvents, such as DMSO or ethylene glycol, being very particularly preferred. Additions of from 2 to 5 wt.% of these additives to an aqueous PEDOT/PSS dispersion lead to a significant increase in conductivity in the film formation.
  • Antioxidants are reagents which prevent the oxidative degradation of materials, which is often promoted by UV light. In the case of a use of pol thiophenes as the conductive polymer, aromatic polyhydroxy compounds have proved suitable. Antioxidants which are particularly preferred according to the invention are gallic acid and the propyl esters of gallic acid, since they have an inhibiting effect in the conductive layers produced from the composition. Within a month, under the same storage conditions as the non-protected layer, the value can be kept below 60 ⁇ / ⁇ .
  • the amount in which the gallic acid or the propyl esters of gallic acid are employed in the process according to the invention is preferably in a range of from 0.001 to 5 wt.%, particularly preferably in a range of from 0.005 to 1 wt.% and most preferably in a range of from 0.01 to 0.2 wt.%, in each case based on the total weight of the composition obtained by the process according to the invention.
  • Possible adhesion promoters are, in particular, organofunctional silanes and hydrolysates thereof, e.g.
  • Suitable binders are polyalkylene glycols, polyvinyl acetate, polycarbonate, polyvinyl butyrate, polyacrylic acid esters, polymethacrylic acid esters, polystyrene, polyacrylonitrile, polyvinyl chloride, polybutadiene, polyisoprene, polyesters, silicones, and also pyrrole/acrylic acid ester, vinyl acetate/acrylic acid ester and ethylene/vinyl acetate copolymers which are soluble in organic solvents.
  • Preferred bases for regulation of the pH are, in addition to ammonia, alkali metal hydroxides and alkaline earth metal hydroxides, in particular amines, particularly preferably primary, secondary or tertiary amines in which the alkyl groups are chosen from the group consisting of methyl-, ethyl-, n-propyl- or iso-propyl-.
  • amines particularly preferably primary, secondary or tertiary amines in which the alkyl groups are chosen from the group consisting of methyl-, ethyl-, n-propyl- or iso-propyl-.
  • An example of a suitable amine is dimethylaminoethanol. It is furthermore preferable according to the invention to establish a pH in a range of from 2 to 7, very particularly preferably in a range of from 4 to 6 in the compositions.
  • composition preferably a dispersion, comprising a solvent, silver nano wires and a conductive polymer, which is obtainable by the process according to the invention.
  • Preferred solvents A, silver nano wires and conductive polymers in this context are those solvents A, silver nanowires and conductive polymers which have already been described above as preferred solvents A, silver nanowires and conductive polymer in connection with the process according to the invention.
  • the dispersion according to the invention can also comprise further additives, those additives which have already been mentioned above as preferred additives in connection with the process according to the invention being preferred.
  • the composition according to the invention preferably the dispersion according to the invention, like the composition obtainable by the process according to the invention, is distinguished in that less than 1.5 g, particularly preferably less than 1.0 g, still more preferably less than 0.85 g and most preferably less than 0.1 g of a non-conductive polymer per gram of silver are adsorbed on the surface of the silver nanowires in the composition.
  • a non-conductive polymer per gram of silver are adsorbed on the surface of the silver nanowires in the composition.
  • the nitrogen content, determined in the drying residue, of the silver nanowires in the composition to be less than 7 wt.%, particularly preferably less than 4 wt.% and most preferably less than 1 wt.%, in each case based on the total weight of the drying residue of the silver nanowires.
  • the nitrogen content, determined in the drying residue of the total composition, is preferably less than 1 wt.%) and particularly preferably less than 0.5 wt.%>, in each case based on the total weight of the drying residue of the composition.
  • the composition according to the invention is furthermore preferably distinguished in that it comprises the silver nanowires and the conductive polymer in a relative amount such that the weight ratio of silver : conductive polymer in the dispersion is in a range of from 10 : 1 to 1 : 10, particularly preferably in a range of from 5 : 1 to 1 : 5 and most preferably in a range of from 2 : 1 to 1 : 2.
  • the pH of the dispersion according to the invention is preferably in a range of from 2 to 7, particularly preferably in a range of from 4 to 6.
  • a substrate is first provided, the nature of the substrate depending on the intended purpose for which the composition obtainable by the process according to the invention or the composition according to the invention is employed.
  • the substrate can be, for example, a porous anode body provided with a dielectric layer.
  • the dispersion is employed, for example, for the production of a hole injection layer in an OLED, the substrate can be, for example, a transparent electrode, such as ITO.
  • Possible substrates are furthermore, in particular, films, particularly preferably polymer films, very particularly preferably polymer films of thermoplastic polymers, or glass plates.
  • a composition obtainable by the process according to the invention or a composition according to the invention is then applied to the substrate, it being possible for this application to be carried out by known processes, e.g. by spin coating, impregnation, pouring, dripping on, spraying, misting, knife coating, brushing or printing, for example by ink-jet, screen, gravure, offset or tampon printing, in a wet film thickness of from, for example, 0.5 ⁇ to 250 ⁇ , preferably in a wet film thickness of from 2 ⁇ to 50 ⁇ .
  • process step III at least some of solvent A is then removed from the composition to obtain an electrically conductive layer on the substrate, this removal preferably being carried out by a drying at a temperature in a range of from 20 °C to 200 °C of the substrate coated with the composition.
  • a contribution towards achieving the abovementioned objects is also made by the use of the composition obtainable by the process according to the invention or of the composition according to the invention for the production of an electrically conductive layer in an OLED, an OPV element, a touch screen, for shielding from electromagnetic radiation ("EMI shielding"), in sensofs or for the production of an IR reflection layer.
  • EMI shielding electromagnetic radiation
  • the use of the composition obtainable by the process according to the invention or of the composition according to the invention as an ITO substitute in an OLED, an OPV element or a touch screen is very particularly preferred.
  • the surface resistance (SR.) of the coatings is determined by means of the 4-point measurement method and stated in ⁇ /D.
  • the transmission of the coated substrates is determined on a 2-channel spectrometer (Lambda900, PerkinElmer).
  • the sample is measured in a photometer sphere (Ulbricht sphere), as a result of which scattered light and transmitted light are detected by the photodetector.
  • the transmission is thus understood as meaning 1 -absorption of the coating and of the substrate.
  • the transmission of the pure substrate is first measured. Melinex 506 films having a thickness of 175 ⁇ are used as the substrate. Thereafter, the coated substrate is measured.
  • the transmission spectra are recorded in the range of visible light, i.e. from 320 nm to 780 nm with a step width of 5 nm.
  • the standard colour value Y of the sample is calculated from the spectra in accordance with DIN 5033, taking as the basis a 10° observer angle and light type D65.
  • the internal transmission is calculated from the ratio of the standard colour values of the substrate with coating (Y) to that without coating (Y 0 ): The internal transmission corresponds to Y/Y 0 x 100 in per cent. For simplicity, only transmission is referred to the in the following. Determination of the figure of merit
  • the drying residue for determination of the nitrogen content in the silver nano wires is obtained by drying 2 g of silver nano wires at 100 °C in vacuo ( ⁇ 50 mbar) for 14 hours.
  • the determination of the element contents was performed at Currenta GmbH & Co. OHG as a commissioned analysis.
  • the measurement was performed on a LECO TruSpec apparatus (LECO Corporation, St. Joseph, USA), and the carbon and hydrogen content are determined with an IR measurement cell.
  • the nitrogen determination is carried out by means of a thermal conduction detector. Examples
  • Example 1 Synthesis of silver nanowires (according to the invention) Ethylene glycol (193 g, technical grade 98 %, Applichem Darmstadt) is initially introduced into a round-bottomed flask and heated, and polyvinylpyrrolidone (4.5 g, Luvitec K90, BASF, Ludwigshafen) is introduced while hot. A solution of silver nitrate (4.5 g, 63.5 % metal basis, Johnson Matthey, Enfield) in ethylene glycol (20.5 g) and a solution of vanadium chloride (9 mg, 99 %, Merck, Darmstadt) in ethylene glycol (2.5 g) are then added and the mixture is heated to 120 °C.
  • Ethylene glycol (193 g, technical grade 98 %, Applichem Darmstadt) is initially introduced into a round-bottomed flask and heated, and polyvinylpyrrolidone (4.5 g, Luvitec K90, BASF, Ludwigshafen) is introduced while hot.
  • Example 2 Precipitation - silver nanowires (according to the invention)
  • Example 3 Silver nanowires - 1st washing step (according to the invention)
  • Example 2 5 g of the acetone-moist precipitate from Example 2 (mixture 2) are suspended in 20 g of water and the suspension is homogenized by shaking. The homogeneous mixture is centrifuged at 2,500 rpm for 20 min. The supernatant is removed and discarded and the sediment is topped up with water to 5 g and the mixture homogenized by shaking (mixture 3).
  • Example 4 Silver nanowires - 2nd washing step (according to the invention) 5 g of the suspension from Example 3 are suspended in 20 g of water and the suspension is homogenized by shaking. The homogeneous mixture is centrifuged at 2,500 rpm for 20 min. The supernatant is removed and discarded and the sediment is topped up with water to 5 g and the mixture homogenized by shaking (mixture 4).
  • Example 5 Silver nanowires - 3rd washing step (according to the invention)
  • Example 6 CHN determination
  • Example 7 Formulation of silver nano wires + Clevios PH 1000 (according to the invention)
  • Example 8 Formulation of silver nano wires washed twice - Clevios PH 1000 (according to the invention)
  • Example 9 Formulation of silver nanowires washed 3 times - Clevios PH 1000 (according to the invention)
  • Example 10 Formulation without high-boiling substance, 0.4 % of silver nanowires
  • Example 11 Formulation without conductivity additive, 0.6 % of silver nanowires
  • Example 12 Storage stability of the formulation from Example 9
  • Example 9 The formulation obtained in Example 9 was applied, after 30 days of storage, to Melinex 506 films using 6 ⁇ spiral doctor blades from Erichsen. The coatings were dried at 120 °C for 5 min. Table 5: Storage stability of Clevios - nanowire formulations.
  • Example 13 Formulation from mixture 2 (0.6 % silver content)
  • Example 14 Storage stability of the formulation from Example 13
  • Example 13 The formulation obtained in Example 13 was applied, after 4 days of storage, to Melinex 506 films using a 12 ⁇ spiral doctor blade from Erichsen. The coatings were dried at 120 °C for 5 min.
  • Example 15 CHN analysis on dry residues of formulations.

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Abstract

L'invention concerne un procédé de préparation d'une composition comprenant un solvant A, des nanofils d'argent et un polymère conducteur. Le procédé comprend les étapes de traitement suivantes: (i) la réduction de sels d'argent au moyen d'un polyol utilisé comme solvant et agent réducteur en présence d'un polymère non conducteur, et la précipitation subséquente des nanofils d'argent ainsi formés pour obtenir des nanofils d'argent à la surface desquels au moins une partie du polymère non conducteur est adsorbée; (ii) l'élimination au moins partielle du polymère non conducteur adsorbé à la surface des nanofils d'argent pour obtenir des nanofils d'argent purifiés; (iii) la mise des nanofils d'argent purifiés au contact d'un solvant A et d'un polymère conducteur. L'invention concerne également les compositions pouvant être obtenues par ce procédé; une composition comprenant un solvant, des nanofils d'argent et un polymère conducteur; un procédé de production d'une couche électroconductrice pouvant être obtenue par ce procédé; et l'utilisation des compositions de l'invention.
PCT/EP2014/000436 2013-02-20 2014-02-18 Formulations comprenant des nanofils d'argent lavés et un pedot Ceased WO2014127909A1 (fr)

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CN109346610A (zh) * 2018-09-18 2019-02-15 张军 一种钙钛矿太阳能电池及其制备方法
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