US20050202274A1 - Polythiophene compositions for improving organic light-emitting diodes - Google Patents
Polythiophene compositions for improving organic light-emitting diodes Download PDFInfo
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- US20050202274A1 US20050202274A1 US11/054,584 US5458405A US2005202274A1 US 20050202274 A1 US20050202274 A1 US 20050202274A1 US 5458405 A US5458405 A US 5458405A US 2005202274 A1 US2005202274 A1 US 2005202274A1
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- NNOFCGFKHMESBG-UHFFFAOYSA-N CC1=C2OCOC2=C(C)S1 Chemical compound CC1=C2OCOC2=C(C)S1 NNOFCGFKHMESBG-UHFFFAOYSA-N 0.000 description 3
- 0 [1*]C1([2*])COC2=C(C)SC(C)=C2O1.[1*]C1([2*])COC2=C(C)SC(C)=C2OC1 Chemical compound [1*]C1([2*])COC2=C(C)SC(C)=C2O1.[1*]C1([2*])COC2=C(C)SC(C)=C2OC1 0.000 description 2
- VTWDEPQPVJEXDS-UHFFFAOYSA-N C.C.C.C.CC(F)(F)C(C)(F)F.CC(F)(F)C(C)(F)O[Rf]C(F)(F)C(F)(F)S(=O)(=O)O Chemical compound C.C.C.C.CC(F)(F)C(C)(F)F.CC(F)(F)C(C)(F)O[Rf]C(F)(F)C(F)(F)S(=O)(=O)O VTWDEPQPVJEXDS-UHFFFAOYSA-N 0.000 description 1
- QRMOFSMDGNTTJO-UHFFFAOYSA-N CC1=C2OCC(COCCCCS(=O)(=O)[O-])OC2=C(C)S1.CC1=C2OCC(COCCCS(=O)(=O)[O-])OC2=C(C)S1.CC1=C2OCC(OCCCCS(=O)(=O)[O-])COC2=C(C)S1.CC1=C2OCC(OCCCS(=O)(=O)[O-])COC2=C(C)S1.[H+].[H+].[H+].[H+] Chemical compound CC1=C2OCC(COCCCCS(=O)(=O)[O-])OC2=C(C)S1.CC1=C2OCC(COCCCS(=O)(=O)[O-])OC2=C(C)S1.CC1=C2OCC(OCCCCS(=O)(=O)[O-])COC2=C(C)S1.CC1=C2OCC(OCCCS(=O)(=O)[O-])COC2=C(C)S1.[H+].[H+].[H+].[H+] QRMOFSMDGNTTJO-UHFFFAOYSA-N 0.000 description 1
- WSXSIQXFVQCFLZ-UHFFFAOYSA-N CC1=C2OCCOC2=C(C)S1 Chemical compound CC1=C2OCCOC2=C(C)S1 WSXSIQXFVQCFLZ-UHFFFAOYSA-N 0.000 description 1
- YRIAURDNTQZQJJ-UHFFFAOYSA-N COC(F)(C(C)(F)F)C(F)(F)F Chemical compound COC(F)(C(C)(F)F)C(F)(F)F YRIAURDNTQZQJJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C13/00—Means for manipulating or holding work, e.g. for separate articles
- B05C13/02—Means for manipulating or holding work, e.g. for separate articles for particular articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
- B62D25/08—Front or rear portions
- B62D25/10—Bonnets or lids, e.g. for trucks, tractors, busses, work vehicles
- B62D25/12—Parts or details thereof
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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
Definitions
- the present invention relates to compositions/formulations containing polythiophenes and further polymers, their use, and electroluminescing arrangements containing hole-injecting layers containing these formulations.
- An electroluminescing arrangement is characterised in that when an electrical voltage is applied it emits light accompanied by a flow of current.
- Such arrangements have been known for a long time under the description “light-emitting diodes”) (LEDs).
- LEDs light-emitting diodes
- the emission of light is due to the fact that positive charges (“holes”) and negative charges (“electrons”) recombine with the emission of light.
- the LEDs conventionally used in technology all consist to a very large extent of inorganic semiconductor materials.
- EL arrangements have been known whose basic constituents are organic materials.
- organic EL arrangements generally contain one or more layers of organic charge transport compounds.
- the principal layer structure of an EL arrangement is as follows:
- an EL arrangement consists of two electrodes between which is arranged an organic layer that fulfils all functions, including the emission of light.
- EP-A 686 662 it is known to use special mixtures of conducting organic polymeric conductors such as poly(3,4-ethylenedioxythiophene) and for example polyhydroxy compounds or lactams as electrode in electroluminescent displays. It has been found in practice however that these electrodes do not have a sufficient conductivity, especially for large area displays. The conductivity is however sufficient for small displays (luminous area ⁇ 1 cm 2 ).
- polymeric organic conductors for example poly(3,4-ethylenedioxythiophene), as hole-injecting layers.
- the luminosity of the electroluminescing displays can thereby be significantly increased compared to structures that do not employ polymeric organic intermediate layers.
- the conductivity can be specifically adjusted by reducing the particle size of the poly(3,4-alkylenedioxythiophene) dispersions. In this way it is possible to prevent electrical crosstalk between adjacent address lines, especially in passive matrix displays (EP-A 1 227 529).
- the object of the present invention accordingly consisted in discovering and providing suitable materials for the production of such EL arrangements.
- a further object consisted in producing such EL arrangements from these materials.
- compositions/formulations comprising at least one optionally substituted polyaniline or polypyrrole or at least one polythiophene containing repeating units of the general formula (I), wherein
- substituted means if not otherwise indicated a substitution with chemical group selected from the group consisting of:
- repeating units of the general formula (I) may be identical or different within a polythiophene. Preferred are repeating units of the general formulae (I-a) and/or (I-b), wherein R 1 and R 2 have the meanings given hereinbefore for the general formula (I).
- Preferred embodiments of the present invention are such formulations containing at least one polythiophene containing repeating units of the formulae (I-a-1) and/or (I-b-1) and/or (I-a-2) and/or (I-b-2)
- radicals R 1 may in each case be identical or different and the radicals R 2 may in each case be identical or different, though preferably the radicals R 1 are in each case identical and the radicals R 2 are in each case identical.
- the polythiophene may be built up from repeating units of the general formula (I -a), (I-a-1) and/or (I-a-2) or from repeating units of the general formula (I-b), (1-b-1) and/or (I-b-2) or also from repeating units of the general formula (I-a) and (I-b), (I-a-1) and (I-b-1) and/or (I-a-2) and (I-b-2).
- the units of the general formula (I-a) and (I-b), (I-a-1) and (I-b-1) and/or (I-a-2) and (I-b-2) may be contained in arbitrary proportions in the polythiophene, though preferably the units of the general formula (I-a), (I-a-1) and/or (I-a-2) are contained in a proportion of 65 to 99.5%, particularly preferably in a proportion of 75 to 99% and most particularly preferably in a proportion of 75 to 85%, referred to the total content of repeating units in the polythiophene, and the units of the general formula (I-b), (I-b-1) and/or (I-b-2) are contained preferably in a proportion of 0.5 to 35%, particularly preferably in a proportion of 1 to 25% and most particularly preferably in a proportion of 15 to 25%, referred to the total number of repeating units in the polythiophene, with the proviso that the sum total of both proportion
- the polythiophene may however contain, in addition to the repeating units of the general formula (I), (I-a) and/or (I-b), (I-a-1) and/or (I-b-1) and/or (I-a-2) and/or (I-b-2), also other repeating units, for example repeating units of the general formulae (II) and/or (III), wherein
- radical R numerous organic groups are suitable, for example alkyl, cycloalkyl, aryl, halogen, ether, thioether, disulfide, sulfoxide, sulfone, amino, aldehyde, keto, carboxylic acid ester, cyano, akylsilane and alkoxysilane groups as well as carboxylamide groups.
- the polythiophene may contain, apart from the repeating units of the general formula (I), (I-a) and/or (I-b), (I-a-1) and/or (I-b-1) and/or (I-a-2) and/or (I-b-2), preferably also repeating units of the formula (IIIa), (3,4-ethylenedioxythiophene units)
- R 2 in the repeating units of the general formula (I), (I-a) and/or (I-b) denotes H.
- R 3 in the repeating units of the general formula (I), (I-a) and/or (I-b) denotes SO 3 ⁇ M + , where M + has the meaning mentioned hereinbefore for the general formula (I).
- the polythiophenes are copolymers of two or more different repeating units of the general formula (I)— here and hereinafter this is also understood to denote units of the general formulae (I-a) and/or (I-b) or (I-a-1) and/or (I-b-1) or (I-a-2) and/or (I-b-2)—or repeating units of the general formula (I) and (II) and/or (III)— here and hereinafter also understood to include units of the general formulae (III-a)—the repeating units may be contained randomly, alternatingly or as blocks in the copolymer.
- the coupling of the repeating units may be regioregular and/or non-regioregular.
- the repeating units of the general formulae (II) and/or (III), preferably of the formula (III-a), in a copolymer comprising structural units of formular (I) and (II) und/or (III) are contained in the copolymers preferably in a proportion of at most 50%, particularly preferably of at most 30%, referred to the total number of the repeating units in the copolymer.
- the repeating units of the general formula (I) are contained in the copolymers in a proportion of at least 50%, preferably in a proportion of at least 70%, referred to the total number of the repeating units.
- repeating units of the general formula (I-a) or (I-b) or (I-a) and (I -b) may be contained.
- Repeating units of the general formula (I-a) and (I-b) may be contained in arbitrary mixture ratios.
- Preferably repeating units of the general formula (I-a) are contained in a proportion of 65 to 100%, particularly preferably in a proportion of 75 to 99%, most particularly preferably in a proportion of 75 to 85%, referred to the total number of the repeating units of the general formula (I), and the repeating units of the general formula (I-b) are contained in a proportion of 0 to 35%, particularly preferably in a proportion of 1 to 25% and most particularly preferably in a proportion of 15 to 25%, referred to the total number of the repeating units of the general formula (I) in the copolymers, with the proviso that the sum total of both proportions is 100%.
- the polythiophenes preferably carry in each case H on the terminal groups.
- the polythiophenes contain in total n repeating units of the general formula (I) and optionally of the general formulae (II) and/or (III), where n is an integer from 2 to 1000, preferably 3 to 100, particularly preferably 4 to 15.
- Repeating units are understood within the context of the invention to denote units of the general formulae (I), (II) or (III), irrespective of whether they are contained once or more than once in the polythiophene.
- units of the general formulae (I), (II) or (III) are also understood to be repeating units even if they are contained only once in the polythiophene.
- Formulations according to the invention may also include those that contain, apart from at least one of the polythiophenes described hereinbefore containing repeating units of the general formula (I), also further conducting polymers, such as for example polyanilines or polypyrroles.
- the polymerisation of the corresponding monomeric compounds usually is carried out with suitable oxidising agents in suitable solvents.
- suitable oxidising agents are iron(III) salts, in particular FeCl 3 and iron(III) salts of aromatic and aliphatic sulfonic acids, H 2 O 2 , K 2 Cr 2 O 7 , K 2 S 2 O 8 , Na 2 S 2 O 8 , KMnO 4 , alkali metal perborates and alkali metal or ammonium persulfates or mixtures of these oxidising agents.
- suitable oxidising agents are described for example in “Handbook of Conducting Polymers” (Ed. Skotheim, T. A.), Marcel Dekker: New York, 1986, Vol. 1, 46-57.
- Particularly preferred oxidising agents are FeCl 3 , Na 2 S 2 O 8 and K 2 S 2 O 8 or mixtures thereof.
- the polymerisation is preferably carried out at a reaction temperature of ⁇ 20° to 100° C. Particularly preferred are reaction temperatures of 20° to 100° C.
- the reaction solution is then optionally treated with at least one ion exchanger.
- Suitable solvents are for example polar solvents such as for example water, alcohols such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerol or mixtures of these.
- aliphatic ketones such as acetone and methyl ethyl ketone
- aliphatic nitrites such as acetonitrile
- aliphatic and cyclic amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (NMP)
- ethers such as tetrahydrofuran (THF) as well as sulfoxides such as dimethyl sulfoxide (DMSO) or mixture of these solvents with one another or with the previously specified solvents.
- THF tetrahydrofuran
- DMSO dimethyl sulfoxide
- the resulting polythiophenes are readily soluble in the polar solvents or solvent mixtures.
- the formulations according to the invention contain at least one further polymer containing SO 3 ⁇ M + or COO ⁇ M + groups.
- Suitable polymers within the scope of the invention containing SO 3 ⁇ M + or COO ⁇ M + groups are preferably those that do not contain a completely conjugated main chain, hereinafter also briefly termed non-conjugated.
- these polymers are soluble in polar solvents such as water, alcohols such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerol, aliphatic ketones such as acetone and methyl ethyl ketone, aliphatic nitrites such as acetonitrile, aliphatic and cyclic amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (NMP), ethers such as tetrahydrofuran (THF) as well as sulfoxides such as dimethyl sulfoxide (DMSO) or mixtures containing these, preferably in water, alcohols such as methanol, ethanol, 2-propanol, n-propanol and n-butanol or mixtures thereof.
- polar solvents such as water, alcohol
- Suitable polymers containing SO 3 ⁇ M + or COO ⁇ M + groups that may be mentioned by way of example are polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acid or polymaleic acids, or polymeric sulfonic acids such as polystyrenesulfonic acids and polyvinylsulfonic acids. Also suitable are copolymers of vinylcarboxylic and vinylsulfonic acids with other polymerisable monomers such as acrylic acid esters and styrene, or polymers containing partially fluorinated or perfluorinated SO 3 ⁇ M + or COO ⁇ M + groups.
- polystyrenesulfonic acid poly(styrenesulfonic co-maleic acid), poly(vinylsulfonic acid) or commercially obtainable polymers that contain sulfonic acid groups and CF 2 groups, such as for example Nafion®, (copolymer of tetrafluoroethylene and of the fluorovinylether of poly(hexafluoro propylene oxide)mono(tetrafluoro vinyl sulfonic acid)ethers).
- Nafion® copolymer of tetrafluoroethylene and of the fluorovinylether of poly(hexafluoro propylene oxide)mono(tetrafluoro vinyl sulfonic acid)ethers.
- the formulation according to the invention contains as at least one polymer containing SO 3 ⁇ M + or COO ⁇ M + groups, a partially fluorinated or perfluorinated polymer containing SO 3 ⁇ M + or COO ⁇ M + groups.
- Such polymers containing partially fluorinated or perfluorinated SO 3 M + or COO ⁇ M + groups are for example those containing repeating units of the formulae (IV-a) and (IV-b), wherein R f denotes a radical with at least one, preferably 1 to 30, repeating unit(s) of the formula (IV-c)
- Such perfluorinated polymers are for example the polymers obtainable commercially under the trade name Nafion® or in dissolved form under the trade name Liquion®.
- the formulation according to the invention contains Nafion® (copolymer of tetrafluoroethylene and of the fluorovinylether of poly(hexafluoro propylene oxide)mono(tetrafluoro vinyl sulfonic acid)ethers) as at least one polymer containing SO 3 ⁇ M + or COO ⁇ M + groups.
- Nafion® copolymer of tetrafluoroethylene and of the fluorovinylether of poly(hexafluoro propylene oxide)mono(tetrafluoro vinyl sulfonic acid)ethers
- the formulation according to the invention contains at least two polymers containing SO 3 ⁇ M + or COO ⁇ M + groups.
- the formulation according to the invention contains copolymers of tetrafluroethylene and sulfonic acid or carboxyl functional perfluorinated ethylene (e.g., Nafion® PFSA polymers) and polystyrenesulfonic acid (PSS) as polymers containing SO 3 ⁇ M + or COO ⁇ M + groups.
- the molecular weight of the polyacids is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
- the polyacids or their alkali metal salts are commercially available, for example polystyrenesulfonic acids and polyacrylic acids, or may however also be produced by known processes (see for example Houben Weyl, Methoden der organischen Chemie, Vol. E 20 Makromolekulare Stoffe, Part 2, (1987), p. 1141 ff.).
- the formulations according to the invention contain, referred to one part by weight of polythiophene(s) containing repeating units of the general formula (I), preferably 1 to 30 parts by weight, particularly preferably 2 to 15 parts by weight of the polymer or polymers containing SO 3 ⁇ M + or COO ⁇ M + groups.
- the formulations according to the invention contain the polythiophene or polythiophenes containing repeating units of the general formula (I) and the polymer or polymers containing SO 3 ⁇ M + or COO ⁇ M + groups, in a weight ratio of polythiophene(s) to polymer(s) containing SO 3 ⁇ M + or COO ⁇ M + groups of 1 to 2 (1:2) to 1 to 15 (1:15), in particular 1 to 3 (1:3) to 1 to 15 (1:15).
- This ratio of polythiophene(s) to polymer(s) containing SO 3 ⁇ M + or COO ⁇ M + groups may be adjusted directly by mixing the two components.
- formulations according to the invention may preferably contain at least one polar diluent.
- Polar diluents (solvents) within the scope of the invention are understood to mean diluents with a solubility parameter 6 of 16 MPa 1/2 and above, preferably 19 MPa 1/2 and above.
- solubility parameters as a rule takes place at standard temperature (20° C.).
- solubility parameters see J. Brandrup et al., Polymer Handbook, 4 th Edition, 1999, VII/675-VII/688. Solubility parameters are tabulated, for example in J. Brandrup et al., Polymer Handbook, 4 th Edition, 1999, VII/688-VII/697.
- Preferred polar diluents are water, alcohols such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerol, aliphatic ketones such as acetone and methyl ethyl ketone, aliphatic nitrites such as acetonitrile, aliphatic and cyclic amides such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (NMP), ethers such as tetrahydrofuran (THF) as well as sulfoxides such as dimethyl sulfoxide (DMSO) or mixtures containing these.
- Particularly preferred polar solvents are water, alcohols or mixtures containing these, most particularly preferred being water, methanol, ethanol, n-propanol, 2-propanol or n-butanol
- Such new formulations containing at least one polar diluent preferably contain 99.99 to 80 wt. %, particularly preferably 99.8 to 95 wt. % of polar diluent(s) and have a solids content of 0.01 to 20 wt. %, particularly preferably 0.2 to 5 wt. %, i.e. they contain in total 0.01 to 20 wt. %, particularly preferably 0.2 to 5 wt. % of polythiophene(s), polymer(s) containing SO 3 ⁇ M + or COO ⁇ M + groups, and optionally further components such as e.g. binders, crosslinking agents and/or surfactants in dissolved and/or dispersed form.
- the viscosity at 20° C. of the new formulations containing at least one polar diluent is typically between the viscosity of the diluent and 200 mPas, preferably ⁇ 100 mPas.
- the desired amount of diluent can be removed from the formulations by distillation, preferably in vacuo, or by other methods, e.g. filtration.
- Organic, polymeric binders and/or organic, low molecular weight crosslinking agents or surfactants may also be added to the formulations according to the invention.
- Suitable binders are described for example in EP-A 564 911.
- polyvinylcarbazole silanes such as Silquest® A187 (OSi specialities) or surfactants such as the fluorinated surfactant FT 248 (Bayer AG, tetraethylammonium salt of perfluoro octyl sulfonic acid).
- the formulations preferably contain only minor amounts of ionic impurities within the limits as described in EP-A 991 303. Preferably the formulations contain less than 1000 ppm of ionic impurities.
- the formulations according to the invention may be produced in various ways. For example, it is possible to mix at least one polythiophene with at least one polymer containing SO 3 ⁇ M + or COO ⁇ M + groups and optionally add at least one diluent to this mixture, and preferably dissolve it completely or partially in at least one diluent. It is also possible to dissolve at least one polythiophene beforehand in at least one diluent and to dissolve at least one polymer containing SO 3 ⁇ M + or COO ⁇ M + groups beforehand in at least one diluent and then to mix the two solutions. The diluent or diluents may then optionally be completely or partially removed from this mixture, for example by distillation or by other methods.
- the formulations according to the invention by first of all producing the polythiophene or polythiophenes by polymerisation of the corresponding monomeric compounds with at least one suitable oxidising agent in at least one suitable solvent, wherein either the solvent corresponds to one of the polar diluents listed hereinbefore or an appropriate exchange of solvent or addition of further solvents may take place after completion of the polymerisation.
- the formulations according to the invention are outstandingly suitable for the production of hole-injecting or hole-transporting layers in EL arrangements, organic solar cells, organic laser diodes, organic thin film transistors or organic field effect transistors, and for the production of electrodes or electrically conducting coatings.
- the present invention accordingly also provides for the use of the formulations according to the invention for the production of hole-injecting layers in EL arrangements, and for the production of electrodes or electrically conducting coatings.
- EL arrangements with a hole-injecting layer containing a formulation according to the invention are characterised by a high luminosity (luminous intensity) and a significantly longer service life than known EL arrangements.
- the present invention accordingly also provides EL arrangements comprising a hole-injecting layer on the basis of a formulation according to the invention.
- Preferred are those EL arrangements comprising at least two electrodes, at least one of which is optionally mounted on an optionally transparent substrate, at least one emitter layer between the two electrodes and at least one hole-injecting layer between one of the two electrodes and the emitter layer, characterised in that the hole-injecting layer contains a formulation according to the invention.
- At least one of the current-conducting electrodes consists of a transparent and conducting material.
- Suitable as such transparent and conducting electrode materials are for example
- an electrode that does not consist of one of the transparent and conducting materials listed hereinbefore, then it is preferably a metal electrode, in particular a metal cathode.
- Suitable materials for metal cathodes are those commonly used for electrooptical structures and known to the person skilled in the art. Suitable as metal cathodes are preferably those of metals with a low work function such as Mg, Ca, Ba or metal salts such as LiF.
- Suitable as optionally transparent substrate are for example glass, very thin glass (flexible glass) or plastics, preferably plastics films.
- plastics are: polycarbonates, polyesters such as e.g. PET and PEN (polyethylene terephthalate and polyethylene naphthalenedicarboxylate), copolycarbonates, polyacrylate, polysulfone, polyether sulfone (PES), polyimide, polyethylene, polypropylene or cyclic polyolefins and cyclic olefin copolymers (COC), hydrogenated styrene polymers or hydrogenated styrene copolymers.
- PET and PEN polyethylene terephthalate and polyethylene naphthalenedicarboxylate
- copolycarbonates polyacrylate
- polysulfone polyether sulfone
- PES polyether sulfone
- COC cyclic olefin copolymers
- hydrogenated styrene polymers or hydrogenated styrene copolymers hydrogenated styrene copolymers.
- Suitable polymer substrates may for example be films such as polyester films, PES films from Sumitomo, or polycarbonate films from Bayer AG (Makrofol®).
- a bonding agent layer may be arranged between the substrate and the electrode.
- Suitable bonding agents are for example silanes.
- Preferred are epoxysilanes, such as for example 3-glycidoxypropyltrimethoxysilane (Silquest® A187, OSi specialities).
- Other bonding agents with hydrophilic surface properties may also be used.
- a thin layer of PEDT:PSS is described as a suitable bonding agent for PEDT (Hohnholz et al., Chem. Commun. 2001, 2444-2445).
- the emitter layer of the EL arrangement according to the invention contains at least one emitter material.
- Suitable emitter materials are those commonly used for electrooptical structures and known to the person skilled in the art.
- Suitable emitter materials are preferably conjugated polymers such as polyphenylenevinylenes and/or polyfluorenes, such as the polyparaphenylenevinylene derivatives and polyfluorene derivatives described for example in WO-A 90/13148, or emitters from the class of low molecular weight emitters, also termed “small molecules” in specialist circles, such as aluminium complexes, e.g. tris(8-hydroxy-quinolinato)aluminium (Alq 3 ), fluorescing dyes, e.g. quinacridones, or phosphorescing emitters, e.g. Ir(ppy) 3 .
- Emitter materials are described for example in DE-A 196 27 071.
- EL arrangement electroluminescing layer structure
- charge-injecting e.g. electron-injecting, charge-transporting or charge-blocking intermediate layers.
- charge-injecting e.g. electron-injecting, charge-transporting or charge-blocking intermediate layers.
- charge-transporting or charge-blocking intermediate layers Such layer composites are known to the person skilled in the art and are described for example in J. R. Sheats et al., Science 273, (1996), 884.
- a layer may also perform several tasks.
- the emitter materials listed hereinbefore may be used in combination with a hole-transporting intermediate layer between the hole-injecting and emitter layer (cf. e.g. U.S. Pat. No. 4,539,507 and U.S. Pat. No. 5,150,006).
- EL arrangements may be produced for example by applying an electrode from solution or by vapour deposition on a substrate.
- metal oxide electrodes or semi-transparent metal film electrodes are preferably applied by vapour deposition, whereas semi-transparent, conducting polymer electrodes are preferably applied from solution to the substrate.
- a bonding agent may optionally be applied—by vapour deposition or from solution—before application of the electrode material to the substrate.
- substrates coated with electrode material are also already commercially obtainable (e.g. K-Glas, ITO-coated glass substrates).
- the hole-injecting layer may then be applied to the electrode, which advantageously takes place from solution in the case of the EL arrangements according to the invention with a hole-injecting layer containing a formulation according to the invention.
- the further layers are then applied from solution or by vapour deposition, depending on the material used, to the hole-injecting layer in the order specified in the introduction, bearing in mind that individual layers may be omitted.
- the layer arrangement is then contacted and encapsulated.
- a formulation according to the invention is applied as a film to an electrode, preferably the base electrode.
- Suitable solvents are the polar diluents specified above, preferably water, alcohols or mixtures of the latter.
- Suitable alcohols are for example methanol, ethanol, n-propanol, 2-propanol and n-butanol.
- the formulation according to the invention may be uniformly distributed on the electrode by techniques such as spin coating, casting, knife application, pressure application, curtain casting, etc.
- the layers may then be dried at room temperature or temperatures of up to 300° C., preferably 100° to 200° C.
- the formulation according to the invention may also preferably be applied in a structured manner by techniques such as inkjet application.
- This technique is known to the person skilled in the art and is described, with the use of water-soluble and dispersed polythiophenes such as 3,4-polyethylenedioxythiophene:polystyrenesulfonic acid (PEDT:PSS), for example in Science, Vol. 279, 1135, 1998 and DE-A 198 41 804.
- formulations according to the invention are filtered through a filter before the application.
- Formulations that can be filtered particularly well are for example obtained if, referred to one part by weight of polythiophene(s) containing repeating units of the general formula (I), there are preferably used 1 to 30 parts by weight, particularly preferably 2 to 15 parts by weight of the polymer(s) containing SO 3 ⁇ M + or COO ⁇ M + groups, and most particularly preferably the formulations according to the invention contain the polythiophene(s) containing repeating units of the general formula (I) and the polymer(s) containing SO 3 ⁇ M + or COO ⁇ M + groups, in a weight ratio of polythiophene(s) to polymer(s) containing SO 3 ⁇ M + or COO ⁇ M + groups of 1 to 2 to 1 to 15.
- the thickness of the hole-injecting layer is for example 3 to 500 nm, preferably 10 to 200 nm.
- a hole-injecting layer containing a formulation according to the invention may be tested in a special assembly of such an EL arrangement according to the invention.
- the hole-injecting layer is applied by means of a spin coater to a wet chemically cleaned ITO substrate. The layer is then dried at 100°-200° C. for 5 minutes. The layer thickness is 20-300 nm.
- a 1 wt. % solution of a polyfluorene-based emitter material Green 1300 LUMATIONTM from Dow Chemical Company
- the thickness of the emitter layer is typically 60-120 nm.
- the organic light-emitting diodes according to the invention are characterised by a long service life, high luminosity, low applied voltages and a high rectification ratio.
- EDT-S mixture of 80% of 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonic acid and 20% of 4-(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)-1-butanesulfonic acid) as sodium salt
- N 2 a protective gas atmosphere
- the sodium salt of the EDT-S used was prepared from Baytron® M OH VP CH 8020 (mixture of 80% of 2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl-methanol and 20% of 3,4-dihydro-2H-thieno-[3,4-b][1,4]dioxepin-3-ol, H. C. Starck GmbH) similarly to the procedure described by Chevrot et al., J. Electroanal. Chem. 1998, 443, pp. 217-226.
- the product consists of 80% of 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonic acid and 20% of 4-(3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-3-yl)-1-butanesulfonic acid, in each case as the sodium salt.
- the PEDT-S solution from Example 1 is mixed with different amounts of a solution of polystyrenesulfonic acid (PSS) in H 2 O (HAPPS VP AI 4061, solids content 5.88 wt. %, H. C. Starck GmbH).
- Weight Ratio PEDT-S:PSS Composition of the Solution for Stage 2 1:1 21.1 g of PEDT-S solution with 1.45 wt. % solids content, 5.2 g of PSS solution with 5.88 wt. % solids content, 1:2.5 10.55 g of PEDT-S solution with 1.45 wt. % solids content, 6.37 g of PSS solution with 5.88 wt. % solids content, 1:6 10.55 g of PEDT-S solution with 1.45 wt. % solids content, 15.61 g of PSS solution with 5.88 wt. % solids content,
- OLED organic light-emitting diode
- ITO-coated glass (Merck Balzers AG, FL, Part. No. 253 674 XO) is cut into 50 mm ⁇ 50 mm size pieces (substrates). The substrates are then cleaned in a 3% aqueous mucasol solution in an ultrasound bath for 15 minutes. Following this the substrates are rinsed with distilled water and spin-dried in a centrifuge. This rinsing and drying procedure is repeated 10 times. The ITO-coated sides are cleaned for 10 minutes in a UV/ozone reactor (PR-100, UVP Inc., Cambridge, GB) immediately before the coating.
- UV/ozone reactor PR-100, UVP Inc., Cambridge, GB
- Example 2.1 About 10 ml of the mixture according to the invention from Example 2.1 are filtered (Millipore HV, 0.45 ⁇ m). The cleaned ITO-coated substrate is placed on a paint application centrifuge and the filtered solution is distributed on the ITO-coated side of the substrate. The supernatant solution is then spun off by rotating the plate at 1200 rpm for a period of 30 seconds. Following this the coated substrate is dried for 5 minutes at 200° C. on a hotplate. The layer thickness is 85 nm (Tencor, Alphastep 500).
- a metal cathode is vapour deposited on the emitter layer.
- the substrate is placed together with the emitter layer downwards on a perforated mask (hole diameter 2.5 mm).
- the vapour deposition rates are 10 ⁇ /sec for Ba and 20 ⁇ /sec for Ag.
- the two electrodes of the organic LED are connected (contacted) via electrical leads to a voltage source.
- the positive pole is connected to the ITO electrode and the negative pole to the metal electrode.
- the dependence of the OLED current and elecroluminescence intensity (detection by means of a photodiode (EG&G C30809E) on the voltage are recorded.
- Example 2.1 The formulation according to the invention from Example 2.1 is used to construct an organic light-emitting diode (OLED).
- OLED organic light-emitting diode
- ITO substrates coated over the whole surface instead of ITO substrates coated over the whole surface (cf. Example 3, process step 1.), structured ITO substrates are used.
- the ITO structures consist of 2.0 mm wide strips insulated from one another.
- the structuring of the ITO was carried out by a conventional photoresist technique followed by etching in FeCl 3 solution.
- the metal cathode is vapour deposited through a strip mask that is aligned perpendicular to the ITO strips.
- the width of the strips is 2 mm.
- the active luminous area at the point of intersection of the two electrodes is 4 mm 2 .
- a special alternating voltage is applied to the arrangements for the service life measurements.
- the frequency of the alternating voltage is 100 Hz.
- a constant current of 640 ⁇ A flows during the positive half-wave, whereas a voltage of ⁇ 10 V is applied during the negative half-wave.
- the cycle ratio of positive to negative half-wave is 50:50.
- the integral area current density is 8 mA/cm 2 .
- the EL arrangement according to the invention with the hole-injecting layer containing the formulation according to the invention proves to be more efficient also under pulsed electrical control and has a significantly longer service life than the EL arrangements with the hole-injecting layer of known material PEDT:PSS (OLEDs from Comparison Examples 4.1 and 4.2).
- Example 2.1 The formulation according to the invention from Example 2.1 is used to construct an organic light-emitting diode (OLED).
- OLED organic light-emitting diode
- Example 2.2 The formulation according to the invention from Example 2.2 is used to construct an organic light-emitting diode (OLED).
- OLED organic light-emitting diode
- the two OLEDs according to the invention from Examples 5.1 and 5.2 have longer service lives than the OLED from Comparison Example 5.3 with the known material PEDT:PSS in the hole-injecting layer. It is also shown that the use of the formulation according to the invention from Example 2.1 (weight ratio of PEDT:S to Nafion® of 1:6) for the production of a hole-injecting layer leads to even longer service lives of the resulting EL arrangement according to the invention in operation than when using the formulation according to the invention from Example 2.2 (weight ratio of PEDT:S to Nafion® of 1:2.5).
- OLEDs organic light-emitting diodes
- ITO substrates coated over the whole surface instead of ITO substrates coated over the whole surface (cf. Example 3, process step 1.), structured ITO substrates are used.
- the ITO structures consist of 2.0 mm wide strips insulated from one another.
- the structuring of the ITO was carried out by a conventional photoresist technique followed by etching in FeCl 3 solution.
- Example 3 instead of the solution from Example 2.1, in process step 2, Example 3, the solutions from Example 2.3 are used in each case.
- the metal cathode is vapour deposited through a strip mask that is aligned perpendicular to the ITO strips.
- the width of the strips is 1 mm.
- the active luminous area at the point of intersection of the two electrodes is 2 mm 2 .
- OLEDs organic light-emitting diodes
- the solids content of the solution from Example 1 is increased to 5.12. wt. % by concentration by evaporation on a rotary evaporator (PEDT-S solution).
- PEDT-S solution concentration by evaporation on a rotary evaporator
- a comparison of the OLEDs from Example 6 and Comparison Example 6.1 shows that an OLED with a hole-injecting layer of pure PEDT-S has lower luminous densities at a comparable area current and thus a lower efficiency than OLEDs with a hole-injecting layer produced from the formulations according to the invention from Example 2.3.
- the comparison shows that the efficiency can be significantly raised by increasing the weight ratio of PEDT-S:SS from 1:1 to 1:2.5 or 1:6.
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4539507A (en) * | 1983-03-25 | 1985-09-03 | Eastman Kodak Company | Organic electroluminescent devices having improved power conversion efficiencies |
US5111327A (en) * | 1991-03-04 | 1992-05-05 | General Electric Company | Substituted 3,4-polymethylenedioxythiophenes, and polymers and electro responsive devices made therefrom |
US5150006A (en) * | 1991-08-01 | 1992-09-22 | Eastman Kodak Company | Blue emitting internal junction organic electroluminescent device (II) |
US5578249A (en) * | 1992-06-30 | 1996-11-26 | Nitto Denko Corporation | Process for producing electrically conductive organic polymer composition |
US5965281A (en) * | 1997-02-04 | 1999-10-12 | Uniax Corporation | Electrically active polymer compositions and their use in efficient, low operating voltage, polymer light-emitting diodes with air-stable cathodes |
US5995273A (en) * | 1998-02-25 | 1999-11-30 | Ashwin-Ushas Corporation | Electrochromic display device |
US6206937B1 (en) * | 1996-04-04 | 2001-03-27 | Matsushita Electric Industrial Co., Ltd. | Solid electrolytic capacitors comprising a conductive layer made of a polymer of pyrrole or its derivative and method for making the same |
US20020136923A1 (en) * | 2001-01-26 | 2002-09-26 | Friedrich Jonas | Electroluminescent arrangements |
US20030149171A1 (en) * | 2001-12-20 | 2003-08-07 | Agfa-Gevaert | 3,4-alkylenedioxy-thiophene copolymers |
US6635729B1 (en) * | 2000-02-03 | 2003-10-21 | Bayer Aktinegesellschaft | Process for the preparation of water-soluble π-conjugated polymers |
US20040044214A1 (en) * | 2002-08-23 | 2004-03-04 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
US20040102577A1 (en) * | 2002-09-24 | 2004-05-27 | Che-Hsiung Hsu | Water dispersible polythiophenes made with polymeric acid colloids |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8909011D0 (en) | 1989-04-20 | 1989-06-07 | Friend Richard H | Electroluminescent devices |
EP0418504B1 (en) | 1989-07-25 | 1995-04-05 | Matsushita Electric Industrial Co., Ltd. | Organic semiconductor memory device having a MISFET structure and its control method |
DE4211461A1 (de) | 1992-04-06 | 1993-10-07 | Agfa Gevaert Ag | Antistatische Kunststoffteile |
EP0686662B2 (de) | 1994-05-06 | 2006-05-24 | Bayer Ag | Leitfähige Beschichtungen |
DE19627071A1 (de) | 1996-07-05 | 1998-01-08 | Bayer Ag | Elektrolumineszierende Anordnungen |
CN1130956C (zh) | 1996-07-29 | 2003-12-10 | 剑桥显示技术有限公司 | 具有电极保护的场致发光元件 |
DE19824215A1 (de) | 1998-05-29 | 1999-12-02 | Bayer Ag | Elektrochrome Anordnung auf Basis von Poly-(3,4-ethylendioxy-thiophen)-Derivaten in der elektrochromen und der ionenspeichernden Funktionsschicht |
DE19839947A1 (de) * | 1998-09-02 | 2000-03-09 | Bayer Ag | Elektrolumineszierende Anordnungen mit Thiophencarboxylat-Metallkomplexen |
DE19841804A1 (de) * | 1998-09-12 | 2000-03-16 | Bayer Ag | Leiterbahnen aus Polyalkylendioxythiophen |
DE19841803A1 (de) | 1998-09-12 | 2000-03-16 | Bayer Ag | Hilfsschichten für elektrolumineszierende Anordnungen |
NO314525B1 (no) | 1999-04-22 | 2003-03-31 | Thin Film Electronics Asa | Fremgangsmåte ved fremstillingen av organiske halvledende innretninger i tynnfilm |
JP2001131150A (ja) | 1999-10-29 | 2001-05-15 | Toyota Central Res & Dev Lab Inc | 有機電界発光素子及びビニルピリジン誘導体化合物 |
KR20030053529A (ko) * | 2000-11-22 | 2003-06-28 | 바이엘 악티엔게젤샤프트 | 분산성 중합체 분말 |
EP1231250A1 (en) | 2001-02-07 | 2002-08-14 | Agfa-Gevaert | Manufacturing of a thin film inorganic light emitting diode |
EP1231251A1 (en) | 2001-02-07 | 2002-08-14 | Agfa-Gevaert | Thin film inorganic light emitting diode |
DE10111790A1 (de) * | 2001-03-12 | 2002-09-26 | Bayer Ag | Neue Polythiophen-Dispersionen |
EP1323763A1 (en) * | 2001-12-20 | 2003-07-02 | Agfa-Gevaert | 3,4-Alkylenedioxy-thiophene copolymers |
JP4363050B2 (ja) * | 2002-01-31 | 2009-11-11 | 住友化学株式会社 | 有機エレクトロルミネッセンス素子 |
WO2004018560A1 (en) * | 2002-08-23 | 2004-03-04 | Agfa-Gevaert | Layer configuration with improved stability to sunlight exposure |
JP2004085389A (ja) | 2002-08-27 | 2004-03-18 | Toshio Fukuda | 爽快目覚し時計システム |
-
2004
- 2004-02-10 DE DE102004006583A patent/DE102004006583A1/de not_active Withdrawn
-
2005
- 2005-01-28 EP EP05001766A patent/EP1564250B1/de not_active Not-in-force
- 2005-01-28 DE DE502005009439T patent/DE502005009439D1/de active Active
- 2005-01-28 AT AT05001766T patent/ATE465216T1/de not_active IP Right Cessation
- 2005-02-04 TW TW094103490A patent/TWI379866B/zh not_active IP Right Cessation
- 2005-02-07 CA CA002496173A patent/CA2496173A1/en not_active Abandoned
- 2005-02-07 KR KR1020050011163A patent/KR20060041802A/ko not_active Application Discontinuation
- 2005-02-08 MX MXPA05001554A patent/MXPA05001554A/es active IP Right Grant
- 2005-02-08 IL IL166738A patent/IL166738A/en not_active IP Right Cessation
- 2005-02-09 RU RU2005103299/04A patent/RU2382809C2/ru not_active IP Right Cessation
- 2005-02-09 US US11/054,584 patent/US20050202274A1/en not_active Abandoned
- 2005-02-09 JP JP2005032962A patent/JP4860933B2/ja not_active Expired - Fee Related
- 2005-02-16 CN CNA2005100090371A patent/CN1654542A/zh active Pending
-
2011
- 2011-06-30 US US13/173,547 patent/US8334331B2/en not_active Expired - Fee Related
-
2012
- 2012-07-05 KR KR1020120073206A patent/KR101359205B1/ko not_active IP Right Cessation
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4539507A (en) * | 1983-03-25 | 1985-09-03 | Eastman Kodak Company | Organic electroluminescent devices having improved power conversion efficiencies |
US5111327A (en) * | 1991-03-04 | 1992-05-05 | General Electric Company | Substituted 3,4-polymethylenedioxythiophenes, and polymers and electro responsive devices made therefrom |
US5150006A (en) * | 1991-08-01 | 1992-09-22 | Eastman Kodak Company | Blue emitting internal junction organic electroluminescent device (II) |
US5578249A (en) * | 1992-06-30 | 1996-11-26 | Nitto Denko Corporation | Process for producing electrically conductive organic polymer composition |
US6206937B1 (en) * | 1996-04-04 | 2001-03-27 | Matsushita Electric Industrial Co., Ltd. | Solid electrolytic capacitors comprising a conductive layer made of a polymer of pyrrole or its derivative and method for making the same |
US5965281A (en) * | 1997-02-04 | 1999-10-12 | Uniax Corporation | Electrically active polymer compositions and their use in efficient, low operating voltage, polymer light-emitting diodes with air-stable cathodes |
US5995273A (en) * | 1998-02-25 | 1999-11-30 | Ashwin-Ushas Corporation | Electrochromic display device |
US6635729B1 (en) * | 2000-02-03 | 2003-10-21 | Bayer Aktinegesellschaft | Process for the preparation of water-soluble π-conjugated polymers |
US20020136923A1 (en) * | 2001-01-26 | 2002-09-26 | Friedrich Jonas | Electroluminescent arrangements |
US20030149171A1 (en) * | 2001-12-20 | 2003-08-07 | Agfa-Gevaert | 3,4-alkylenedioxy-thiophene copolymers |
US20040044214A1 (en) * | 2002-08-23 | 2004-03-04 | Agfa-Gevaert | Layer configuration comprising an electron-blocking element |
US20040102577A1 (en) * | 2002-09-24 | 2004-05-27 | Che-Hsiung Hsu | Water dispersible polythiophenes made with polymeric acid colloids |
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US7557369B2 (en) * | 2004-07-29 | 2009-07-07 | Samsung Mobile Display Co., Ltd. | Display and method for manufacturing the same |
US20060022219A1 (en) * | 2004-07-29 | 2006-02-02 | Werner Humbs | Display and method for manufacturing the same |
WO2007084569A3 (en) * | 2006-01-20 | 2008-01-24 | Plextronics Inc | Electrostatic coatings and articles comprising polythiophenes |
US20090155579A1 (en) * | 2006-01-20 | 2009-06-18 | Plextronics, Inc. | Electrostatic coatings and articles comprising polythiophenes |
JP2009523632A (ja) * | 2006-01-20 | 2009-06-25 | プレックストロニクス インコーポレーティッド | ポリチオフェンを含む、静電気コーティングおよび物品 |
US20070221916A1 (en) * | 2006-03-24 | 2007-09-27 | Merck Patent Gmbh | Organic semiconductor formulation |
US8314416B2 (en) | 2006-03-24 | 2012-11-20 | Merck Patent Gmbh | Organic semiconductor formulation |
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US20080213594A1 (en) * | 2006-12-28 | 2008-09-04 | Che-Hsiung Hsu | Laser (230nm) ablatable compositions of electrically conducting polymers made with a perfluoropolymeric acid applications thereof |
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Also Published As
Publication number | Publication date |
---|---|
US8334331B2 (en) | 2012-12-18 |
TWI379866B (en) | 2012-12-21 |
IL166738A (en) | 2008-12-29 |
US20110257277A1 (en) | 2011-10-20 |
DE502005009439D1 (de) | 2010-06-02 |
JP4860933B2 (ja) | 2012-01-25 |
DE102004006583A1 (de) | 2005-09-01 |
KR20120093119A (ko) | 2012-08-22 |
EP1564250A1 (de) | 2005-08-17 |
CN1654542A (zh) | 2005-08-17 |
ATE465216T1 (de) | 2010-05-15 |
KR20060041802A (ko) | 2006-05-12 |
JP2005226072A (ja) | 2005-08-25 |
CA2496173A1 (en) | 2005-08-10 |
IL166738A0 (en) | 2006-01-15 |
RU2382809C2 (ru) | 2010-02-27 |
RU2005103299A (ru) | 2006-07-20 |
MXPA05001554A (es) | 2005-08-12 |
TW200606210A (en) | 2006-02-16 |
KR101359205B1 (ko) | 2014-02-06 |
EP1564250B1 (de) | 2010-04-21 |
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