EP2206170A1 - Procédé de dépôt de couches comportant des polyaromates non polaires - Google Patents

Procédé de dépôt de couches comportant des polyaromates non polaires

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Publication number
EP2206170A1
EP2206170A1 EP08844628A EP08844628A EP2206170A1 EP 2206170 A1 EP2206170 A1 EP 2206170A1 EP 08844628 A EP08844628 A EP 08844628A EP 08844628 A EP08844628 A EP 08844628A EP 2206170 A1 EP2206170 A1 EP 2206170A1
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EP
European Patent Office
Prior art keywords
different
linear
general formula
branched
radicals
Prior art date
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EP08844628A
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German (de)
English (en)
Inventor
Timo Meyer-Friedrichsen
Udo Guntermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Deutschland GmbH and Co KG
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HC Starck Clevios GmbH
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2425/18—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the invention relates to a process for coating non-polar polyaromatic-containing layers with conductive polymers, and to polymeric layers produced by this process.
  • polyaromatics e.g. alkyl-substituted polyfluorenes or polyalkylthiophenes.
  • fluorenes and fluorene copolymers for example poly (9,9-dioctylfluorene-co-bithiophene) (I)
  • the nonpolar alkyl substituents provide the necessary solubility in common organic solvents, on the other hand they can exert a directing effect on the order of the molecules in the thin layers produced therefrom, as for example in Adv. Mater. 2006, Vol. 18, p. 860. These order effects are necessary to allow the highest possible mobility of the charges in the semiconductor layers.
  • poly (3-alkylthiophenes) are used as copolymers of 3-alkylthiophenes with different alkyl groups, as this provides an advantage in solubility, and thus the applicability, of the polymers.
  • Methods for the preparation of poly (3-alkylthiophenes) are described, for example, in Handbook of Conducting Polymers, 3rd Edition, Volume Conjugated Polymers, Chapter 9.3.1 and the references cited therein.
  • Organic conductive materials are, for example, polyaniline (PANI) 5 polypyrroles (PPy) 5 poly (3,4-ethylenedioxythiophene) (PEDT) or poly (thienothiophene) (PTT).
  • PANI polyaniline
  • PPy polypyrroles
  • PEDT polyethylenedioxythiophene
  • PTT poly (thienothiophene)
  • the conductivity is usually achieved by positive charges, which are distributed over the polymer chain and compensated and stabilized by a corresponding counterion.
  • Polyelectrolytes may serve as counterions which at the same time make it possible to prepare stable dispersions or solutions of the conductive polymers in polar solvents such as water or short-chain alcohols.
  • Poly (3,4-ethylenedioxythiophene) is generally used in the form of an aqueous dispersion of a complex of PEDT (III) with polystyrenesulfonic acid (PSS) to PEDT: PSS, as described, for example, in EP 0440957.
  • PEDT III
  • PSS polystyrenesulfonic acid
  • PEDT PSS
  • the structure has ionic character.
  • the conductivity of the complex is generated by the doping of the PEDT chains with positive charges, which are stabilized by the sulfonic acid groups of the PSS and. ensure the charge neutrality.
  • An overview of the molecular structure and current fields of application of PEDT: PSS is described for example in J.Mater.Chem. 2005, Volume 15, p. 2077.
  • Y is a C] -Cjg alkylene radical.
  • dispersions or solutions with polyelectrolyte counterions such as, for example, poly (styrenesulfonic acid) can also be obtained from optionally substituted PANI (for example in Journal of tlie Electrochemical Society 1994, Volume 141 (6), p. 1409 and Polymer 1994, Volume 35 (15), P. 3193), PPy (for example in US 5665498) or PTT (for example in US 2004/0074779 and Synth. Metals 2005, volume 152, p. 177).
  • PANI for example in Journal of tlie Electrochemical Society 1994, Volume 141 (6), p. 1409 and Polymer 1994, Volume 35 (15), P. 3193
  • PPy for example in US 566549
  • PTT for example in US 2004/0074779 and Synth. Metals 2005, volume 152, p. 177.
  • PEDTiPSS is applied as a dispersion in polar solvents, preferably water, via appropriate application methods.
  • a very common application method is e.g. spin-coating method.
  • a particularly elegant method is the application by the ink-jet method (IEEE Transactions on Electron Devices, Volume 52, No. 9, 2005, p.
  • the dispersion is applied to the substrate in the form of very fine droplets and dried. This method allows to perform the patterning of the conductive layer during application. Depending on the composition of the dispersions, films with conductivities of up to 500 S / cm are achieved.
  • the manufacture of electronic components requires the direct coating of semiconducting materials such as polyalkylthiophenes with conductive layers such as PEDTiPSS.
  • semiconducting materials such as polyalkylthiophenes with conductive layers such as PEDTiPSS.
  • the source and drain electrodes are deposited on the semiconductor by the orthogonal polarities of the non-polar polymeric semiconductors such as poly (3-hexylthiophene-2 , 5-diyl) (P3HT), and the polar PEDT: PSS cause adhesion and wetting problems between these layers, which prevent a stable coating.
  • OFET structures are described in which PEDT: PSS source and drain electrodes are under a P3HT semiconductor layer (bottom-contacf mode). Statements about the adhesion stability of the layers obtained were not given.
  • Adhesion is usually determined by a "TESA test” in which a strip of pressure-sensitive adhesive roll is briefly pressed onto the layer and peeled off again, providing sufficient adhesion if the layer does not detach from the underlying layer.
  • the "top-contact” configuration in which the conductor tracks are applied to the semiconductor layer, is more favorable in terms of printing technology and function than the "bottom-contact” configuration.
  • the non-polar semiconductor layer must be printed with a polar PEDT: PSS dispersion, which is not possible due to the hydrophobic surface.
  • wetting agents such as Dynol 604, Surfynol 104 E, Zonyl FF 300 or Triton X-100 leads to a wetting of the non-polar surface, but the obtained PEDT: PSS layer passes the TESA test, regardless of the one used Coating method, such as spin coating or knife coating, not.
  • Other additives, such as crosslinking agents do not lead to an improvement in the adhesion of the PEDT: PSS to non-polar alkyl-substituted polyaromatic layers.
  • the object of the present invention was therefore to provide a method by which polar conductive polymer layers can be applied to nonpolar organic layers, such as semiconductor layers, for example, so that stable, adherent and functional structures are obtained. Such a method would enable the production of stable organic electronic devices.
  • non-polar polyaromatic-containing layers can be provided with a polar layer of at least one conductive polymer which is stable to adhesion if the non-polar layer is previously wetted with substituted alkanes.
  • the resulting layers of at least one conductive polymer pass the TESA test and are conductive.
  • the invention thus provides a process for the coating of non-polar polyaromatic containing layers with conductive polymers, characterized in that the non-polar layer is first wetted with substituted alkanes, and the layer thus obtained is then coated with at least one side-bearing polymer.
  • the non-polar polyaromatic-containing layers contain identical or different units of polyaromatics of the general formula (H)
  • Ar are identical or different aromatic units, preferably those consisting of thiophene, phenylene or fluorenyl units, particularly preferably thiophenyl units,
  • R is the same or different and is independently of the same or different, linear or branched C 4 -C 2 o-AIkylreste, mono- or polyunsaturated C 4 -C 2 o-A ⁇ kenylreste, or C ⁇ CarAralkylreste, preferably for linear or branched G f C 2 o-alkyl radicals, particularly preferably linear C 4 -C 20 -alkyl radicals,
  • n is an integer from 0 to 2
  • n is an integer of> 1, preferably from 1 to 1000, particularly preferably from 1
  • the non-polar polyaromatic-containing layer contains identical or different units of polyaromatics of the general formula (H-I)
  • n is an integer of> 1, preferably from 1 to 1000, particularly preferably from 1
  • - 800 most preferably from 1 to 400 and most preferably from 10 to 30.
  • the nonpolar polyaromatic-containing layers used in the process according to the invention may be conductive or semiconducting, preferably semiconducting.
  • At least one leirable polymer selected from the group consisting of an optionally substituted polythiophene, polyaniline or polypyrrole is preferably used for coating the nonpolar polyaromatic layers.
  • At least one conductive polymer particularly preferably comprises an optionally substituted polythiophene containing recurring units of the general formula (LI) or recurring units of the general formula (LO) or recurring units of the general formula (L-III) or recurring units of the general formulas (LI) and (L-II) or recurring units of the general formulas (LI) and (L-III) or recurring units of the general formulas (L-II) and (L-IO) or recurring units of the general formulas (LI), II) and (L-III):
  • R are identical or different and are each independently identical or different, linear or branched Ci-C 20 -A! Kylreste, mono- or polyunsaturated C 2 -C 20 alkenyl radicals, C 7 -C 2 o aralkyl radicals or H, preferably linear or branched particularly preferably represents C s - C 8 alkyl radicals, or together form an optionally substituted C 1 - C 1 alkylene radical, preferably a C 1 -alkylene radical.
  • Y has the meaning given above and p is an integer from 3 to 100, preferably from 5 to 50, most preferably from 8 to 20.
  • At least one conductive polymer comprises a polythiophene containing repeating units of the general formula (L-TV),
  • the above-mentioned polyhiophenes preferably carry H. at the end groups.
  • C 1 -C 4 -alkylene radicals are, for example, methylene, ethylene, n-propylene, or n-butylene.
  • 20 -alkyl represents for the purposes of the invention are linear or branched CrC 2 O- alkyl radicals such as methyl, ethyl, n- or iso-propyl, n-, äso-, sec- or tert-butyl, n-pentyl, 1- Methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1-methyldiylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-do
  • substituents of the C 1 -C 4 -alkylene radicals are numerous organic groups, for example alkylcycloalkyl, aryl, halogen, ether, thioether, disulfide, sulfoxide, sulfone, sulfonate, amino, Aldehyde, keto, carboxylic ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane groups and carboxylamide groups.
  • the conductive polymers or polythiophenes can be neuü-al or cationic. In preferred embodiments, they are cationic, with "cationic" referring only to the charges which are located on the polymer or polythiophene main chain
  • the polymers or polythiophenes can carry positive and negative charges in the structural unit, wherein the positive charges on the polymer or polythiophene main chain and the negative charges optionally substituted on the substituted by sulfonate or carboxylate groups Residues R are located.
  • the positive charges of the polymer or polythiophene main chain can be saturated in part or completely by the optionally present anionic groups on the radicals R.
  • the polymers or polythiophenes in these cases can be cationic, neutral or even anionic. Nevertheless, they are all considered as cationic polymers or polythiophenes in the context of the invention, since the positive charges on the polymer or Po ⁇ ythiophensburgkette are relevant.
  • the positive charges are not shown in the formulas because their exact number and position can not be determined properly. However, the number of positive charges is at least 1 and at most n, where n is the total number of all repeating units (equal or different) within the polymer or polythiophene.
  • Cationic polymers or polythiophenes are also referred to below as polycations.
  • the cationic polymers or polythiophenes require anions as counterions.
  • Suitable counteranones are preferably polymeric anions, also referred to below as polyanions, in question.
  • At least one conductive polymer and at least one counterion are used for the coating.
  • suitable polyisocyanates are anions of polymeric carboxylic acids, such as polyacrylic acids, polymethacrylic acid or polymaleic acids, or anions of polymeric sulfonic acids, such as polystyrenesulfonic acids and polyvinylsulfonic acids.
  • polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acid or polymaleic acids
  • polymeric sulfonic acids such as polystyrenesulfonic acids and polyvinylsulfonic acids.
  • These polycarboxylic and -sulfonic acids may also be copolymers of vinylcarboxylic and vinylsulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
  • polystyrene sulfonic acid PSS
  • the molecular weight of the polyanionic polyacids is preferably 1,000 to 2,000,000, more preferably 2,000 to 500,000.
  • the polyacids or their alkali salts are commercially available, e.g. Polystyrenesulphonic acids and polyacrylic acids, or else can be prepared by known processes (see, for example, Houben Weyl, Methoden der organischen Chemie, Vol. E 20 Macromolecular Substances, Part 2, (1987), p. 1141 and following).
  • Cationic polythiophenes which contain anions as counterions for charge compensation are also often referred to in the art as polythiophene / (poly) anion complexes.
  • 3,4-poly (ethylenedioxythiophene) and polystyrene sulfonate are used for the coating.
  • the coating with leirjähigen polymers is preferably carried out from solution or dispersion.
  • the polar dispersions or solutions of the conducting polymers may contain other ingredients such as wetting agents or crosslinkers.
  • Wetting agents are, for example, Dynol 604, Surfmol 104 E, Zonyl 104 E or Triton X-100.
  • Epoxysilanes such as Silquest A 187, isocyanates such as Crosslinker CX-100 or melamine resins such as Acraf ⁇ x ML, for example, can be used as crosslinkers.
  • aqueous dispersions or solutions preferably containing 3,4-polyalkylenedioxythiophenes
  • Suitable oxidizing agents and solvents are also those listed in EP 440 957 in question.
  • an aqueous dispersion or solution is understood as meaning a dispersion or solution which contains at least 50% by weight (% by weight) of water, preferably at least 90% by weight of water, and optionally contains solvents which Water - at least partially - are miscible, such as alcohols, eg Methanol, ethanol, n-propanol, isopropanol, butanol or octanol, glycols or glycol ethers, e.g. Ethylene glycol, diethylene glycol, propane, diol, propane 1,3-diol or dipropylene glycol dimethyl ether or ketones such as acetone or methyl ethyl ketone.
  • alcohols eg Methanol, ethanol, n-propanol, isopropanol, butanol or octanol
  • glycols or glycol ethers e.g. Ethylene glycol, diethylene glycol, propane, diol,
  • derivatives of the thiophenes listed above are, for example, dimers or trimers of these thiophenes. There are also higher molecular weight derivatives, ie tetramers, pentamers, etc. of the monomeric precursors as derivatives possible.
  • the derivatives can be composed of the same or different monomer units and can be used in pure form and mixed with one another and / or with the abovementioned thiophenes.
  • thiophenes and Thiophene derivatives are included within the meaning of the invention of the term thiophenes and thiophene derivatives, provided that in their polymerization, the same conductive polymers formed as in the above-listed thiophenes and thiophene derivatives.
  • Suitable solvents which may be mentioned are, in particular, the following organic solvents which are inert under the reaction conditions: aliphatic alcohols, such as methanol, ethanol, isopropanol and butanol; aliphatic ketones such as acetone and methyl ethyl ketone; aliphatic carboxylic acid esters such as Ess ⁇ gklareethylester and butyl acetate; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; Chlorohydrocarbons such as dichloromethane and dichloroethane; aliphatic nitriles such as acetonitrile, aliphatic sulfoxides and sulfones such as dimethylsulfoxide and sulfolane; aliphatic carboxylic acid
  • solvents are alcohols and water and mixtures containing alcohols or water or mixtures of alcohols and water.
  • Thiophenes which are liquid under the oxidation conditions, can also be polymerized in the absence of solvents.
  • the aqueous dispersion or solution may additionally contain at least one polymeric binder.
  • Suitable binders are polymeric, organic binders, for example polyvinyl alcohols, polyvinylpyrrolidones, polyvinyl chlorides, polyvinyl acetates, polyvinyl butyrates,
  • Polyacrylic acid esters polyacrylic acid amides, polymethacrylic acid esters, polymethacrylic acid amides,
  • Copolymers polybutadienes, polyolsoprenes, polystyrenes, polyethers, polyesters, polycarbonates, polyurethanes, polyamides, polyimides, polysulfones, melamine-formaldehyde resins, epoxy resins,
  • Silicone resins or celluloses are Silicone resins or celluloses.
  • the solids content of polymeric binder is between 0 and
  • R 3 is a linear or branched C 4 - C 2 o alkyl radical
  • Q is -OH, -N 4 R 5 R, -SH, -COO 4 R, -CON 4 R 5 R, -PO (O 4 R), -SO 3 4 R or -SO 2 N 4 R 5 R .
  • R 4 R and 5 R independently of one another represent optionally substituted, linear or branched C 1 -C 20 -alkyl radicals or H,
  • the substituted alkane of the general formula (A) is preferably alcohols, ie Q is -OH. Particular preference is given to primary alcohols having a linear alkyl radical 3 R, very particular preference to primary alcohols having a linear G f -C 2 -alkyl radical 3 R.
  • a linear or branched C 1 -C 20 -alkyl radical is, for example, 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-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonade
  • Suitable substituents of the C 1 -C 20 -alkyl radicals are numerous organic groups, for example alkyl, cycloalkyl, aryl, halogen, ethers, thioether, disulfide, sulfoxide, sulfone, sulfonate, amino, , Aldehyde, keto, carboxylic ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane groups and carboxylamide groups.
  • the substituted alkanes can be used as a single component or as a mixture of various substituted alkanes.
  • the unpoiare layer is preferably containing polyaromatics of the general formula (H) after wetting with the substituted alkane of general formula (A) at 40 to 200 0 C, preferably 60-150 ° C? very particularly preferably at 80 - 130 0 C annealed.
  • the nonpolar polyaromatic-containing layer treated with the substituted alkane of general formula (A) is then coated with a dispersion or solution containing at least one conductive polymer by, for example, doctoring, spin-coating or printing techniques such as inkjet printing.
  • the application of the substituted alkane and the polar solutions or dispersions to the nonpolar semiconductor layer can be carried out by the known methods, for example by spraying, dipping, printing and knife coating. Particularly preferred is the application by spin-coating and by ink-jet printing.
  • the invention furthermore relates to polymer layers produced by the process according to the invention, the use of these polymeric layers in electronic components such as field-effect transistors, light-emitting components such as organic luminescent diodes, or photovoltaic cells, lasers and sensors, and these electronic components.
  • the layers produced by the process of the invention may be further modified after application, for example by a temperature treatment, e.g. while passing through a liquid crystalline phase, or for structuring, e.g. by laser ablation.
  • polymeric semithamer compounds used were prepared by known methods from, for example, McCulIough et al. in J. Org. Chem. 1993, Vol. 58, p. 904 or US 6166172:
  • PEDTcPSS formatting weight 42.92 ⁇ % Baytron ® P from HC Starck GmbH, 2:58% by weight of N-methyl-2-pyrrolidinone, 0.86 wt .-% Silquest A 187 from GE-Bayer Silicones, 53.34 wt .-%. Isopropanol and 0.30 wt .-% Dynol 604 Air Products.
  • a 4-6 ⁇ m wet film layer of the formulation has a surface resistance of after drying
  • TESA test In the TESA test, a strip of a pressure-sensitive adhesive roll is briefly pressed onto the layer and pulled off again. Enough adhesion is given if the layer does not detach from the underlying layer.
  • a poly (3-hexylthiophene) coated PET film was wetted by spin-coating with a 4 ⁇ 6 ⁇ m thick wet film layer of commercially available 1-butanol. The wet film was annealed at 8O 0 C for 10 minutes. Subsequently, a layer of the PEDT: PSS formulation with a wet film thickness of 4 to 6 ⁇ m was applied by spin coating and then dried at 80 ° C.
  • the PEDT PSS layer had a surface resistance of 10 4 ⁇ / D.
  • the PEDT PSS layer passed the TESA test.
  • Example 2
  • a poly (3-hexylthiophene) coated PET film was wetted by spin-coating with a 4-6 ⁇ m thick wet film layer of commercially available 1-octanol.
  • the moist film was tempered at 130 ° C. for 10 minutes.
  • After a layer of the PEDTtPSS- formulation with a wet film thickness of 4 was - 6 microns coated by spin coating and then dried at 80 0 C.
  • the PEDTiPSS layer had a surface resistance of 10 4 ⁇ / o.
  • the PEDTiPSS-Schambat passed the TESA test.
  • a PET film coated with poly (3-alkylthiophene) consisting of a co-polymer of 90 mole% of commercially available 3-hexylthiophene and 10 mole% of commercially available 3-decylthiophene was prepared by lapping with a 4-6 ⁇ m thick wet film layer of commercially available 1-octanol wetted. The moist film was tempered at 130 ° C. for 10 minutes. Subsequently, a layer of the PEDT: PSS formulation with a wet film thickness of 4 - 6 microns was applied by aufschleudem and then dried at 80 0 C.
  • the PEDTrPSS layer had a surface resistance of 10 4 ⁇ / o.
  • the PEDT: PSS layer passed the TESA test.
  • a 4-6 ⁇ m thick wet film layer of the PEDT: PSS formulation was applied by spin-coating onto a poly (3-hexylthiophene) -coated PET film and then dried at 80 ° C.
  • a PET film coated with poly (3-alkylthiophene) consisting of a copolymer of 90 mol% of 3-hexylthiophene and 10 mol% of 3-decylthiophene was spin-coated onto a 4 to 6 ⁇ m thick wet film layer of the PEDTiPSS Formulation applied and then dried at 80 0 C.
  • the PEDT: PSS layer had a surface resistance of 10 * ⁇ / ö.
  • the PEDT: PSS layer did not pass the TESA test.
  • a PET film coated with poly (3-alkylthiophene) consisting of a copolymer of 90 mol% of 3-hexylthiophene and 10 mol% of 3-decylthiophene was spin-coated by a 4-6 ⁇ m thick wet film layer of a dispersion from 90 to 99 wt .-% of the PEDT: PSS Forraultechnik and 1 - 10 wt .-% of a further auxiliary additive applied and then dried at 80 0 C.
  • the auxiliary additives used and the results of the corresponding coating are listed in Table 1. In each case always 2 wt .-% of auxiliary additive was used.
  • the surface resistance of the PEDT: PSS layer was 10 * ⁇ / o in Comparative Examples 3 to 9, respectively.
  • a PET film coated with poly (3-alkylthiophene) consisting of a copolymer of 90 mol% of 3-hexylthiophene and 10 mol% of 3-decylthiophene was spin-coated onto a 4 to 6 ⁇ m thick wet film layer of the PEDT : PSS formulation containing 1 wt .-% octanol applied and then dried at 8O 0 C.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Thin Film Transistor (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un procédé de dépôt de couches comportant des polyaromates non polaires, avec des polymères conducteurs, ainsi que les couches polymères fabriquées suivant ce procédé.
EP08844628A 2007-11-01 2008-10-20 Procédé de dépôt de couches comportant des polyaromates non polaires Ceased EP2206170A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710052522 DE102007052522A1 (de) 2007-11-01 2007-11-01 Verfahren zur Beschichtung von unpolaren Polyaromaten enthaltenden Schichten
PCT/EP2008/064110 WO2009056462A1 (fr) 2007-11-01 2008-10-20 Procédé de dépôt de couches comportant des polyaromates non polaires

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EP2206170A1 true EP2206170A1 (fr) 2010-07-14

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EP (1) EP2206170A1 (fr)
JP (1) JP2011505681A (fr)
KR (1) KR20100126264A (fr)
DE (1) DE102007052522A1 (fr)
TW (1) TW200936655A (fr)
WO (1) WO2009056462A1 (fr)

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JP5650051B2 (ja) * 2011-05-09 2015-01-07 Ｊｘ日鉱日石エネルギー株式会社 有機半導体
CN102443250B (zh) * 2011-07-29 2013-07-17 常州大学 可交联聚（3,4-乙烯二氧噻吩）水分散体及制备方法
TWI460203B (zh) * 2011-12-30 2014-11-11 Eternal Materials Co Ltd 電解質材料調配物、由此形成之電解質材料組合物及其用途

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WO2009056462A1 (fr) 2009-05-07
TW200936655A (en) 2009-09-01
WO2009056462A9 (fr) 2009-09-24
JP2011505681A (ja) 2011-02-24
US20100304147A1 (en) 2010-12-02
KR20100126264A (ko) 2010-12-01
DE102007052522A1 (de) 2009-05-07

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