WO2004019346A1 - Configuration de couche comprenant un element de blocage d'electrons - Google Patents

Configuration de couche comprenant un element de blocage d'electrons Download PDF

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WO2004019346A1
WO2004019346A1 PCT/EP2003/050341 EP0350341W WO2004019346A1 WO 2004019346 A1 WO2004019346 A1 WO 2004019346A1 EP 0350341 W EP0350341 W EP 0350341W WO 2004019346 A1 WO2004019346 A1 WO 2004019346A1
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polymer
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layer configuration
poly
hydrogen
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Hieronymus Andriessen
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Agfa Gevaert NV
Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/58—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing copper, silver or gold
    • C09K11/582—Chalcogenides
    • C09K11/584—Chalcogenides with zinc or cadmium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
    • 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
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a layer configuration comprising an electron-blocking element.
  • Polythiophenes have been studied extensively due to their interesting electrical and/or optical properties. Polythiophenes become electrically conducting upon chemical or electrochemical oxidation or reduction. Their ultimately achievable electrical conductivity is determined by their chemical composition, the stereoregularity of the polymerization of the thiophene monomers in the polythiophene chain and by their ⁇ -conjugation lengths. Such stereoregularity problems do not arise when unsubstituted thiophenes or thiophenes substituted in the 3- and 4-positions with identical groups axe polymerized.
  • WO 00/65653 discloses a method in the fabrication of an organic thin-film semiconducting device, wherein the semiconducting device comprises an electrode arrangement with electrodes contacting a semiconducting organic material, and wherein the method is characterized by depositing a first layer of a conducting or semiconducting material in the form of a combination of a conducting and a semiconducting material in the form of a patterned or non-patterned layer on an insulating substrate, such that at least a portion of the substrate is covered by the first layer; modifying the work function of the conducting layer and/or semiconducting material of the first layer by depositing a second layer of a conducting polymer with a work function higher than that of the material in the first layer such that the layer of the conducting polymer mainly covers the first layer or is conformal with the latter, whereby the combination of the first layer and the second layer constitutes the anode of the electrode arrangement and the work function of the anode becomes substantially equal to that of the conducting polymer, depositing a third layer
  • the conducting polymer in the second layer is a doped conjugated polymer e.g. poly (3, 4-ethylenedioxythiophene) (PEDOT) , a copolymer which includes the monomer 3, 4-ethylenedioxythiophene, substituted poly (thiophenes ) , substituted poly (thiophenes) , substituted poly (pyrroles) , substituted poly (anilines) or copolymers thereof, with .the dopant being preferably poly (4-styrene sulphonate) (PSS) .
  • PES poly (4-styrene sulphonate
  • WO 00/06665 discloses an electroluminescent device comprising a light-emitting organic film, arranged between an anode material and a cathide material such that under an applied voltage, the device is forward biased and holes are injected from the anode material into the organic film adjacent to the anode material and electrons are injected from the cathode material into the organic film adjacent to the cathode material, resulting in light emission from the light—emitting organic film; wherein the device additionally comprises a solution-processed film of a blend of an acid-functional non-conductive polymer e.g. polymers having pendant groups selected from sulfonic acid, sulfinic acid, carboxylic acid,
  • an acid-functional non-conductive polymer e.g. polymers having pendant groups selected from sulfonic acid, sulfinic acid, carboxylic acid,
  • phosphoric acid. phosphonic acid, phosphimc acid, and -N+ (R) H where R is selected from hydrogen, C 1 -C 20 hydrocarbyl, hydroxy, alkoxy, and aryloxy, and a conductive polymer positioned between the anode material and the light-emitting organic film, wherein the weight ratio of non-conducting to conducting polymer is at least 0.75:1.
  • WO 00/0665 specifically discloses the following non- conductive polymers: sulfonated polyphenylenes, pol yphenylenes bearing carboxylic acid functional groups, poly (styrene sulfonic acid), poly (2—acrylamido-2-methyl-l-propanesulfonic acid), polyacrylic acid, polymethacrylic acid or a mixture thereof.
  • US 5,111,327 discloses an electro-responsive polymer comprising chemically combined repeat units selected from the class consisting of,
  • EP-A 1 1 22 274 discloses a proces s for preparing water- soluble C-conj ugated polymers , characterized in that the monomer thiophene derivative according to formula ( I )
  • WO 01/78464 discloses in an organic/polymer electroluminescent (EL) device which comprises: a transparent substrate; a semitransparent electrode deposited on the transparent substrate; a hole-injecting layer positioned on the semitransparent electrode; an emissive layer made of an organic EL-material, positioned on the hole-injecting layer; and electron-injecting layer positioned on the electron-injecting layer, the improvement comprising that single-ion conductors are employed for the hole- injecting layer and the electron-injecting layer.
  • EL organic/polymer electroluminescent
  • single-ion conductor which in plain language means a conductor of a single ion, although claim 9 teaches that the single ion conductor can be a single-cation conductor or a single anion conductor and claim 10 teaches that such single ion conductors can be represented as a general formula (I) or (II), comprising ether chain [(-CH 2 ) n O ⁇ ] such as polyethylene oxide or polypropylene oxide in the main chain, and contains anions such as SO 3 , COO or I in the main side
  • a " C + wherein, EO represents ethylene oxide; Non-EO represents non- ethylene oxide; PO represents propylene oxide; Non-PO represents non-propylene oxide; A represents anion; C represents cation; m+n ll and n represents a real number more than 0 and less than 1.
  • ionic polyurethane possesses good mechanical properties and 0 high ionic conductivity with a single-ion transport character
  • SIC s are generally of two different types: one is a polymer blend of an ionomer and polyether which usually possesses poor mechanical properties and the other is the copolymer of an oligomeric ionomer with polyether.
  • 5 incorporation of the SIC s with soft and hard blocks into the EL devices dramatically improves not only luminance but also the efficiency and that SCC s possess electron-injecting and hole- blocking properties and SAC s possess hole-injecting and electron- blocking properties .
  • SCC s possess electron-injecting and hole- blocking properties
  • SAC s possess hole-injecting and electron- blocking properties .
  • R is aryl, C ⁇ - ⁇ s-alkyl or hydrogen; R is hydrogen or - (CH 2 ) s -0- (CH 2 ) p -S0 3 ⁇ M + ; R 3 is - (CH 2 ) ⁇ -0- (CH 2 ) p -S0 3 _ M + ; M + is a cation; m and n are independently a whole number from 0 to 3; s is a whole number from 0 to 10; and p is a whole number from 1 to 18, and a second polymer different from the first polymer and selected from the group consisting of optionally quaternized polyamine-polymers , polysulpho-polymers, polyphosphoric acids and polyphosphoric acid salts between a positive electrode and a material capable of hole transport improves the device performance by increasing the lifetime and in the case of light emitting diodes the reducing the optimum voltage .
  • a layer configuration on a support comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene) s and poly (3, 4 -dialkoxythiophene) s containing a first polymer containing structural units according to formula (I) :
  • R 1 is aryl, C ⁇ - 18 - lkyl or hydrogen; R2 is hydrogen or -
  • Figure 1 is a schematic representation of a side view and a top view of the layer configuration used in devices 2 to 14 and 16 to 37 and the circuit used for obtaining electroluminescence in which :
  • A represent s a poly (ethylene terephthalate ) support
  • C represent s an electron blocking layer
  • D represents an electroluminescent layer co ntaining ZnS : Cu nano- particles and a binder ;
  • F represent s conductive silver paste dots f or contacting
  • G represent s IV-power source ( Power Supply ES 030-5 of Delta
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n- propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and terrtiarry-butyl; for five carbon atoms: n-pentyl, 1, 1-dimethyl- propyl, 2 , 2-dimethylpropyl and 2-methyl-butyl etc.
  • aqueous for the purposes of the present invention means containing at least 60% by volume of water, preferably at least 80% by volume of water, and optionally containing water- miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; me t oxypr opanol ; and ketones e.g. 2-propanone and 2-butanone etc.
  • alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc.
  • glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; me t oxypr opanol
  • ketones
  • element as used in disclosing the present invention means a single layer containing both the first polymer and the second polymer or two contiguous layers wherein the innermost layer of the element with respect to the support contains the first polymer and the outermost layer with respect to the support contains the second polymer.
  • polymer includes homopolymers, copolymers, terpolymers, graft polymers and block copolymers and both chain and condensation polymers.
  • PEDOT-S represents poly [4- (2, 3-dihydro- thieno [3,4- ] [1,4] dioxin-2-ylmethoxy) -butane-1-sulphonic acid] .
  • PSS poly(styrene sulphonic acid) or poly (styrenesulphonate) .
  • tosylate represents p-toluenesulphonate .
  • the abbreviation HTs represents p-toluenesulphonic acid and Ts or tosylate represents p-toluenesulphonate.
  • non-photoactive element as used in disclosing the present invention means an element which is not photoactive, where photoactive means either capable of reacting to light or capable of emitting light.
  • poly (3, 4-alkylenedioxythiophene) as used in disclosing the present invention means a polythiophene in which the 3 and 4 positions in the thiophene ring are linked by a -0- alkylene-O- group, where the term alkylene means a saturated hydrocarbon group containing the carbon atoms linking the two oxygen atoms in the -O-alkylene-O- group and also saturated hydrocarbon groups containing the carbon atoms linking the two oxygen atoms in the -O-al ylene-O- group in which these carbon atoms are covalently linked with one or more alkyl groups .
  • polysulfo-polymer as used in disclosing the present invention means a polymer with more than one sulphonic acid group>s with the exclusion of the first polymer according to formula (I) .
  • the passage "material capable of transporting holes” as used in disclosing the present invention means a material into which holes can be injected and through which holes can be transported, preferably having a hole mobility > 10 cm V s and particularly preferably having a hole mobility > 10 cm V s as measured by time of flight techniques or in a field effect transistor .
  • aspects of the present invention are reali zed with a layer configuration on a support , the layer configuration comprising a non-photoactive element exclusive of poly ( 3 , 4- alkylenedioxythiophene ) s and poly ( 3 , 4-dialkoxythiophene ) s , the element containing a firs t polymer containing structural units according to formula (I ) :
  • the weight ratio of the second polymer to the first polymer is in the range of 1:1 to 20:1.
  • the element further contains a surfactant .
  • the element further contains a binder .
  • the element further contains a crross-linking agent.
  • the layer configuration is a transistor .
  • the layer configuration is an electroluminescent device.
  • the element is preferably prepared by spincoating the coating oxr coatings from aqueous or solvent media. Solutions or dispersions for spincoating preferably have viscosities of about 2 to 3 cP meaning that up to 95% of the solution is spun off i.e. not deposited during the spincoating process. If the element is prepared by the application of two coatings the first coating is preferably dried in a drying cupboard before the second coating is applied. Depending upon the ingredients and solvents/dispersion media used in the two coatings the two coatings will form a single homogeneous layer after the second coating or two identifiable layers .
  • the first polymer contains structural units according to formula (I) :
  • the first polymer is a polytriiophene according to formula (II)
  • R is aryl, C ⁇ -i8 _ alkyl or hydrogen; R is hydrogen or -
  • the first polymer is poly[4- (2, 3 — dihydro-thieno [3, 4-b] [1, 4] dioxin-2-ylmethoxy ) -butane-1- sulphonic acid] .
  • Organic polymer containing structural units according to formula (I) can be polymerized chemically or electrochemically .
  • Chemical polymerization can be carried out oxidatively or reductively.
  • the oxidation agents used for the oxidative polymerisation of pyrrole such as described for example in Journal of the American Chemical Society, volume 85, pages 454-458 (1963) and J .
  • the inexpensive and easily accessible oxidation agents such as iron (III) salts such as FeCl 3 , the iron (111) salts of organic acids, e.g. Fe (OTs) 3 , H 2 0 2 , K 2 Cr2 ⁇ 7, alkali and ammonium persu Iphates, alkali perborates and potassium permanganate are used in the oxidative polymerization.
  • oxidative polymerization of thiophenes requires 2.25 equivalents of oxidation agent per mole thiophene of formula (I) [see e.g. J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988) ] . In practice an excess of 0.1 to 2 equivalents of oxidation agent is used per polymerizable unit. The use of persulphates and iron (III) salts has the great technical advantage that they do not act corrosively. Furthermore, in the presence of particular additives oxidative polymerization of the thiophene compounds according to formula (I) proceeds so slowly that the thiophenes and oxidation agent can be brought together as a solution or paste and applied to the substrate to be treated. After application of such solutions or pastes the oxidative polymerization can be accelerated by heating the coated substrate as disclosed in US 6,001,281 and WO 00/14139 herein incorporated by reference .
  • Reductive polymerization can be performed using the Stille (organotin) or Suzuki (organoboron) routes described in 2002 by Appperloo et al . in Chem. Eur. Journal, volume 8, pages 2384-2396, and as disclosed in 2001 in Tetrahedron Letters, volume 42, pages 155-157 and in 1998 in Macromolecules, volume 31, pages 2047-2056 respectively or with nickel complexes as disclosed in 1999 in Bull. Chem. Soc. Japan, volume 72, page 621 and in 1998 in Advanced Materials, volume 10, pages 93-116.
  • Structural units according to formula (I) can be chemically or electrochemically copolymerized with other thiophene monomer, such as optionally substituted 3, 4-dialkoxythiophenes e.g. optionally substituted 3, 4-alkylenedioxythiophenes, or polymerizable heterocyclic compounds such as pyrrole.
  • thiophene monomer such as optionally substituted 3, 4-dialkoxythiophenes e.g. optionally substituted 3, 4-alkylenedioxythiophenes, or polymerizable heterocyclic compounds such as pyrrole.
  • aspects of the present invention are realized with a layer configuration on a s upport, the layer configuration comprising a non-photoactive element exclusive of poly ( 3 , 4-alkylenedioxy- thiophene ) s and poly ( 3 , 4-dialkoxythiophene ) s , the element conta ining a first polymer containing structural units according to formu la ( I ) :
  • R is aryl, C ⁇ - 18 -alkyl or hydrogen; R is hydrogen or -
  • Optionally quaternized polyamine-polymers include both optionally quaternized aliphatic polyamine-polymers, e.g. polyallylamine hydrochloride and polymers with optionally quaternized nitrogen-containing heteroaromatic groups, e.g. homopolymers and copolymers of optionally substituted vinylpyridines, vinyldipyridyls, vinylquinolines, vinylisoquinolines, vinylacridines, vinylpyridazines, vinylpyrimidines, vinylpyrazines, vinyltriazine, vinylcinnolines, vinylphthalazines, vinylquinazolines, vinylquinoxalines, vinylpteridines, vinyloxadiazole and vinyloxazole .
  • optionally quaternized aliphatic polyamine-polymers e.g. polyallylamine hydrochloride and polymers with optionally quaternized nitrogen-containing heteroaromatic groups, e.g. homopolymers and copolymers of optionally substituted vinylpyridine
  • the optionally quaternized polyamine-polymer is an optionally quaternized polyvinylpyridine or a copolymer of an optionally quaternized vinyl pyridine .
  • Suitable polyamine-polymers, according to the present invention include:
  • aspects of the present invention are realized with a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s and poly ( 3 , -dialkoxythiophene) s, the element containing a first polymer containing structural units according to formula ( I ) :
  • X and Y are independently 0,S, N-R , Z is -(CH 2 ) m ⁇ CR R " (CH 2 ) n -;
  • R 1 is aryl, C ⁇ - 18 -a.lkyl or hydrogen;
  • R2 is hydrogen or -
  • Suitable polysulpho-polymers include:
  • aspects of the present invention are realized with a layer configuration on a support, the layer configuration comprising a non-photoactive element exclusive of poly (3, 4-alkylenedioxy- thiophene)s and poly (3, 4-dialkoxythiophene) s, the element containing a first polymer containing structural units according to formula (I) : in which X and Y are independently 0,S, N-R 1, Z is -(CH 2 ) m -CR2R3-
  • R 1 is aryl, C ⁇ -i 8 ⁇ lkyl or hydrogen; R2 is hydrogen or -
  • Polyphosphoric acids include diphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, metaphosphoric acid and "polyphosphoric acid” .
  • Polyphosphoric acid may be prepared by heating H 3 P ⁇ 4 with sufficient P 4 O 10 (phosphoric anhydride) or by heating H 3 P ⁇ 4 to remove water.
  • a P 4 ⁇ ]_o H 2 0 mixture containing 72.74% P 4 O 10 corresponds to pure H 3 P0 4 , but the usual commercial grades of the acid contain more water.
  • pyrophosphoric acid forms along with P 3 through P Q polyphosphoric acids.
  • Triphosphoric acid appears at 71.7% P 2 O 5 (H 5 P 0]_o) an d tetraphosphoric acid (HgP 4 ⁇ 3 ) at about 75.5% P 2 O 5 .
  • Such linear polyphosphoric acids have 2 to 15 phosphorus atoms, which each bear a strongly acidic OH group.
  • the two terminal P atoms are each bonded to a weakly acidic OH group.
  • Cyclic polyphosphoric acids or metaphosphoric acids, H n P n 0 3rl; . which are formed from low- molecular polyphosphoric acids by ring closure, have a comparatively small number of ring atoms (n 3-8) .
  • Each atom in the ring is bound to one strongly acidic OH group.
  • High linear and cyclic polyphosphoric acids are present only at acid concentrations above 82% P 2 0s.
  • Commercial phosphoric acid has a 82 to 85% by weight P 2 O 5 content. It consists of about 55% tripolyphosphoric acid, the remainder being H 3 P ⁇ 4 and other polyphosphoric acids.
  • a polyphosphoric acid suitable for use according to the present invention is a 84% (as P 2 O 5 ) polyphosphoric acid supplied by ACROS (Cat. No. 19695-0025) .
  • the element further contains a non-ionic surfactant e.g. etho>ylated/fluoroalkyl surfactants, polyethoxylated silicone surfactants, polysiloxane/polyether surfactants, ammonium salts of perfluoroalkylcarboxylic acids, polyethoxylated surfactants and fluorine-containing surfactants .
  • a non-ionic surfactant e.g. etho>ylated/fluoroalkyl surfactants, polyethoxylated silicone surfactants, polysiloxane/polyether surfactants, ammonium salts of perfluoroalkylcarboxylic acids, polyethoxylated surfactants and fluorine-containing surfactants .
  • Suitable non-ionic surfactants include:
  • Surfactant no. 01 ZONYLTM FSN, a 40% by weight solution of
  • Surfactant no. 03 ZONYLTM FS3O0, a 40% by weight aqueous solution of a fluorinated surfactant, from DuPont;
  • Surfactant no. 04 ZONYLTM FSO, a 50% by weight solution of a mixture of ethoxylated non-ionic fluoro- surfactant with the formula:
  • Surfactant no. 06 TegoglideTM 410, a polysiloxane-polymer copolymer surfactant, from Goldschmidt;
  • Surfactant no. 08 FLUORADTMFC431: CF 3 (CF 2 ) 7 S ⁇ 2 (C 2 H 5 )N-CH 2 CO-(OCH 2 CH 2 ) n OH from 3M;
  • Surfactant no. 09 FLUORADTMFC126, a mixture of the ammonium salts of perfluorocarboxylic acids, from 3M;
  • Surfactant no. 10 Polyoxyethylene-10-lauryl ether
  • Surfactant no. 11 FLUORADTMFC430, a 98.5% active fluoroaliphatic ester from 3M; According to an eleventh embodiment of the layer configuration, according to the present invention, the element further contains an anionic surfactant.
  • Suitable anionic surfactants include :
  • Surfactant no . 12 ZONYLTM 7950 , a fluorinated surfactant, from
  • Surfactant no. 13 ZONYLTM FSA, 25% by weight solution of
  • Surfactant no. 14 ZONYLTM FSE, a 14% by weight solution of
  • Surfactant no. 16 ZONYLTM FSP, a 35% by weight solution of
  • Surfactant no. 17 ZONYLTM UR: [F (CF 2 CF 2 ) 1 _ CH 2 CH 2 0] X P (0) (OH) y where x
  • Surfactant no. 18 ZONYLTM TBS: a 33% by weight solution of
  • Surfactant no. 19 ammonium salt of perfluoro-octanoic acid from 3M
  • the layer configuration further comprises a layer or layers of one or more electroluminescent compound (s) .
  • This electroluminescent compound can be pure organic (organic light emitting devices) , hybrid (inorganic and organic) or pure inorganic (inorganic light emitting devices) .
  • the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor belongs to the class of II-VI semiconductors e.g.
  • ZnS or is a combination of group II elements with oxidic anions, the most common being silicates, phosphates, carbonates, germanates, stannates, borates, vanadates, tungstates and oxysulphates .
  • Typical dopants are metals and all the rare earths e.g. Cu, Ag, Mn, Eu, S , Tb and Ce.
  • the layer configuration further comprises a layer of an electroluminescent phosphor, wherein the electroluminescent phosphor is ZnS doped with manganese, copper or terbium or CaGa 2 S 4 doped with cerium.
  • the layer configuration further comprises a dielectric layer.
  • any dielectric material may be used in the dielectric layer, with yttria and barium titanate being preferred e.g. the barium titanate paste LUXPRINTTM type 7153E high K dielectric insulator supplied by DuPont and the barium titanate paste ELECTRODAGTM EL-040 supplied by Acheson.
  • a positive ion exchanger may be incorporated into the dielectric layer to capture any ions dissolving escaping from the phosphor of the light-emitting layer.
  • the amount of ion exchanger in the dielectric layer has to be optimized so that it has a maximum effectiveness in reducing black spots while not reducing the initial brightness level.
  • the ion exchanger may be organic or inorganic. Suitable inorganic ion exchangers are hydrated antimony pentoxide powder, titanium phosphate, salts of phosphoric acid and silicic acid and zeolite.
  • the support is transparent or translucent.
  • the support is paper, polymer film, glass or ceramic.
  • the support is a transparent or translucent polymer film .
  • a transparent or translucent support suitable for use with the electroconductive or antistatic layers, according to the present invention may be rigid or flexible and consist of a glass, a glass —polymer laminate, a polymer laminate, a thermoplastic polymer or a duroplastic polymer.
  • thin flexible supports are those made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, with poly (ethylene terephthalate) or poly (ethylene naphthalene-1, 4-dicarboxylate) being particularly preferred.
  • the layer configuration is an electroluminescent device.
  • the layer configuration is a light emitting diode.
  • Thin film electroluminescent devices are all characterized by one (or more) electroluminescent active layer (s) sandwiched between two electrodes .
  • a dielectric layer may also be part of the sandwich.
  • Thin film ELDs can be subdivided into organic and inorganic based ELDs .
  • Organic-based thin film ELDs can be subdivided into low molecular weight organic devices including ologomers (Organic Light Emitting Diodes (OLEDs) ) and high molecular weight organic devices (Polymer Light Emitting Diodes (PLEDs) .
  • the inorganic ELDs on the other hand can be further subdivided into the High Voltage Alternating Current (HV-AC) ELDs and the Low Voltage Direct Current (LV-DC) ELDs.
  • the LV-DC ELDs include Powder ELDs (DC-PEL Devices or DC-PELDs) and thin film DC-ELDs, hereinafter called Inorganic Light Emitting Diodes (ILEDs) .
  • the basic construction of organic ELDs comprises following layer arrangement : a transparent substrate (glass or flexible plastic), a transparent conductor, e.g. Indium Tin Oxide (ITO) , a hole transporting layer, a luminescent layer, and a second electrode, e.g. a Ca, Mg/Ag or Al/Li electrode.
  • a transparent substrate glass or flexible plastic
  • ITO Indium Tin Oxide
  • a hole transporting layer e.g. Indium Tin Oxide (ITO)
  • a hole transporting layer and the luminescent layer are 10- 50 nm thick and applied by vacuum deposition
  • the hole transporting layer is usually about 40 nm thick and the luminescent layer is usually about 100 nm thick and applied by spin coating or other non-vacuum coating techniques .
  • a direct voltage of 5-10 V is applied between the electrodes and light emission results from holes and electrons being injected from the positive and negative electrodes respectively combining in the luminescent layer to produce the energy to excite the luminescent
  • the hole transporting layer and electroluminescent layer consist of low molecular organic compounds, N,N' -diphenyl- 1, 1 ' -biphenyl-4, 4' -diamine (TPD) can, for example be used as the hole transporter and aluminium (III) 8-hydroxyquinoline complex (Al ⁇ q 3 ) , polyaromatics (anthracene derivatives, perylene derivatives and stilbene derivatives) and polyhetero-aromatics (oxazoles, oxadiazoles, thiazoles etc.) can be used as electroluminescent compounds .
  • TPD N,N' -diphenyl- 1, 1 ' -biphenyl-4, 4' -diamine
  • TPD N,N' -diphenyl- 1, 1 ' -biphenyl-4, 4' -diamine
  • TPD N,N' -diphenyl- 1, 1 ' -biphenyl-4, 4
  • electroluminescent compounds that can be used are polymers like the non-conjugated polyvinylcarbazole derivatives (PV ) or conjugated polymers like poly (p-phenylene vinylenes) (PPV) , polyfluorenes , poly (3-alkylthiophene) , poly (p-phenylene ethynylenes) etc.
  • PV polyvinylcarbazole derivatives
  • conjugated polymers like poly (p-phenylene vinylenes) (PPV) , polyfluorenes , poly (3-alkylthiophene) , poly (p-phenylene ethynylenes) etc.
  • Low voltage DC PEL Devices generally comprise a transparent substrate, a transparent conductor (ITO), a doped ZnS phosphor layer (20 ⁇ m) , and a top electrode of evaporated aluminium.
  • the phosphor layer is applied by means of the doctor blade technique or screen printing on an ITO conducting layer.
  • an aluminium electrode is applied by evaporation.
  • ITO positive a direct current voltage of several volts
  • holes start moving towards the aluminium electrode, thereby creating an insulating region (about 1 ⁇ m in thickness) next to the ITO layer within one minute or so. This results in a current drop which is associated with the onset of light emission. This process has been called the forming process.
  • Hybrid LEDs inorganic emitting so-called quantum dots are used in combination with organic polymers with charge transporting properties and in some cases also emitting properties.
  • Hybrid LEDs with CdSe nano particles have been reported by Colvin et al . [see Nature, volume 370, pages 354-357, (1994)], Dabbousi et al . [see Appl. Phys. Lett., volume 66, pages 1316-1318 (1995), and Gao et al . [see J. Phys. Chem. B, volume 102, pages 4096-4103 (1998)]; and with ZnS:Cu nano crystals have been reported by Huang et al . [see Appl. Phys. Lett., volume 70, pages 2335-2337 (1997)] all included herein by reference.
  • the layer configuration is a photovoltaic device.
  • the layer configuration further comprises at least one photovoltaic layer.
  • the photovoltaic layer may be organic layer, a hybrid inorganic and organic layer or an inorganic layer.
  • the layer configuration is a solar cell.
  • Photovoltaic devices incorporating the layer configuration can be of two types: the regenerative type which converts light into electrical power leaving no net chemical change behind in which current-carrying electrons are transported to the anode and the external circuit and the holes are transported to the cathode where they are oxidized by the electrons from the external circuit and the photosynthetic type in which there are two redox systems one reacting with the holes at the surface of the semiconductor electrode and one reacting with the electrons entering the counter-electrode, for example, water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode .
  • the hole transporting medium may be a liquid electrolyte supporting a redox reaction, a gel electrolyte supporting a redox reaction, an organic hole transporting material, which may be a low molecular weight material such as 2, 2 ' , 7, 7' -tetrakis (N, N-di-p-methoxyphenyl— amine) 9, 9' -spirobifluorene (OMeTAD) or triphenylamine compounds or a polymer such as PPV-derivatives, poly (N-vinylcarbazole) etc., or inorganic semiconductors such as Cul, CuSCN etc.
  • the charge transporting process can be ionic as in the case of a liquid electrolyte or gel electrolyte or electronic as in the case of organic or inorganic hole transporting materials.
  • Such regenerative photovoltaic devices can have a variety of internal structures in conformity with the end use. Conceivable forms are roughly divided into two types: structures which receive light from both sides and those which receive light from one side.
  • An example of the former is a structure made up of a transparently conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer and a transparent counter electrode electrically conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer having interposed therebetween a photosensitive layer and a charge transporting layer.
  • Such devices preferably have their sides sealed with a polymer, an adhesive or other means to prevent deterioration or volatilization of the inside substances.
  • the external circuit connected to the electrically-conductive substrate and the counter electrode via the respective leads is well-known.
  • Organic photovoltaic layers of the layer configuration, according to the present invention are, for example, mixtures of fullerene molecules (as electron acceptor and electron transporter) with conjugated polymers (e.g. substituted polyphenylenevinylene (PPV) (as light absorber and hole transporter) [see Brabec et al . , Adv. Funct. Mater., volume 11(1), pages 15 - 26 (2001)]. In 1995 Halls et al . reported in Nature, volume 376, page 498 the successful use of acceptor-type conjugated polymers instead of fullerenes .
  • conjugated polymers e.g. substituted polyphenylenevinylene (PPV) (as light absorber and hole transporter)
  • the layer configuration can be incorporated in hybrid photovoltaic compositions such as described in 1991 by Graetzel et al . in Nature, volume 353, pages 737-740, in 1998 by U. Bach et al . [see Nature, volume 395, pages 583-585 (1998)] and in 2002 by W. U. Huynh et al . [see Science, volume 295, pages 2425-2427 (2002)].
  • at least one of the components is inorganic (e.g. nano- Ti0 2 as electron transporter, CdSe as light absorber and electron transporter) and at least one of the components is organic (e.g. triphenylamine as hole transporter or poly (3-hexylthiophene) as hole transporter) .
  • the layer configuration further comprises a layer with one or more of the electron transporting or hole transporting components described above, but within such a configuration that it can be used as a transistor.
  • the semiconductor can be n-type, p-type or both (ambipolar transistor) and can be either organic or inorganic.
  • Layer configurations comprising an element, according to the present invention, between a positive electrode and a material capable of hole transport and capable of reducing hole-electron recombination at the positive electrode can be used in a wide range of electronic devices such as photovoltaic devices, solar cells, batteries, capacitors, light emitting diodes, organic and inorganic electroluminescent devices, smart windows, electrochromic devices, sensors for organic and bio-organic materials and field effect transistors [see also chapter 10 of the Handbook of Oligo- and Polythiophenes, Edited by D. Fichou, Wiley-VCH, We ' inheim (1999) ] .
  • a 70/30 molar mixture of 2-acetoxymethyl-2 , 3-dihydro- thieno [3,4-J ] [1, 4] dioxine-5, 7-dicarboxylic acid dimethyl ester and 3 — acetoxy-3, 4-dihydro-2H-thieno [3, 4-j ] [1, 4] dioxepine-6, 8- dicarboxylic acid dimethyl ester was obtained by performing the reaction between 3, 4-dihydroxythiophene-2, 5-dicarboxylic acid dimethyl ester and epibromohydrin as described in US 5,111,327.
  • Triethylamine 80 mL was subsequently added after which acetyl chloride (43 mL) was added dropwise, constantly keeping the reaction around 25 °C by slight cooling. After addition the mixture was stirred for another hour at 25°C.
  • Solutions 1 and 2 at room temperature were added simultaneously w both at a flow rate of 500 mL/min to solution 3, held at room temperature and stirred at 150O rpm for 60s.
  • 1000 mL of the resulting dispersion 1000 mL of a 1% polyphosphoric acid solution adjusted to pH 6 with ammonium hydroxide was added and the dispersion was concentrated to 1000 mL by means ultraf iltration
  • ITO indium tin oxide
  • PET poly (ethylene terephthalate)
  • each ITO/PET sheet contained a band of 2 cm of conductive ITO in the middle.
  • soluit ions/dispersions were prepared by stirring the ingredients in Table 1 together and then adjusting the pH, or not, as indicated therein _
  • Solutions 5, 7 and 8 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in element thicknesses of about 5 to 10 nm, thereby producing the substrates for devices 3, 4 and 5 respectively.
  • Solutions 4, 6 and 9 were spincoated on patterned ITO/PET at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in element thicknesses of about 100 nm, thereby producing the substrates for devices 2, 6 and 7 respectively.
  • the thicknesses were measured with a DEKTAKTM profilometer with the element spincoated on glass. Similar element thicknesses can be expected on ITO/PET.
  • the electroluminescent nano ZnS : Cu-dispersion was spincoated for 6 seconds at 1000 rpm followed by 50 seconds at 2000 rpm.
  • the electroluminescent nano ZnS : Cu-dispersion was applied to the substrates of devices 2 to 25 in the same way on top of the particular blocking element used.
  • the resulting layers were then dried at 50 C C for 10 minutes, a electroluminescent ZnS:Cu-layer thickness of 100 nm being thereby obtained.
  • the devices exhibited electroluminescence with a ⁇ max of 490 nm.
  • a forward bias was applied and the voltage was increased so as to keep the
  • the lifetime of the light emitting device was taken to be the time between application of the optimum voltage and the moment no further electroluminescence could be observed.
  • the optimum voltage was that voltage at which maximum light output was observed.
  • the substrate of light e itting device 8 was prepared by spincoating solution 4 on the patterned ITO/PET sheet at 800 rpm for 6 s and then at 1500 rpm for 50 s to produce a 100 nm thick coating after drying at 40°C for 10 minutes. Then the resulting coating was spincoated with solution 5 at 800 rpm for 6 s and then at 4000 rpm for 50 s and the resulting element dried at 40°C for 10 minutes to give a total element thickness of ca. 105 nm, since the water in solution 5 does not substantially redisperse the PEDOT-S coating.
  • the substrate of light emitting device 9 was prepared by spincoating solution 4 on the patterned ITO/PET sheet at 800 rpm for 6 s and then at 1500 rpm for 50 s to produce a 100 nm thick coating after drying at 40°C for 10 minutes. Then the resulting coating was spincoated with solution 6 at 800 rpm for 6 s and then at 1500 rpm for 50 s and the resulting element dried at 40°C for 10 minutes to give an additional ca. 100 nm thickness resulting in a total element thickness of ca . 200 nm, since the water in solution 6 does not substantially redisperse the PEDOT-S coating.
  • Light emitting elements 8 and 9 were prepared from substrates
  • Light emitting devices 10 and 11 were prepared as described for Devices 2 to 6 except that the patterned ITO electrode was coated with elements incorporating POLY-02. Solutions 10 to 12 used for preparing these elements are given below in Table 4. Solutions 10 and 12 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 4000 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in element thicknesses of about 5 to 10 nm thereby producing the substrates for Devices 10 and 11 respectively.
  • the substrate of light emitting device 12 was prepared by spincoating solution 11 on patterned ITO/PET at 800 rpm for 6 s and then at 1500 rpm for 50 s to produce a 100 nm thick element after drying at 40°C for 10 minutes.
  • the substrate of light emitting device 13 was prepared by spincoating solution 4 on the patterned ITO/PET sheet at 800 rpm for 6 s and then at 1500 rpm for 50 s to produce a 100 nm thick coating after drying at 40°C for 10 minutes. Then the resulting coating was spincoated with solution 10 at 800 rpm for 6 s and then
  • the substrate of light emitting device 14 was prepared by
  • Light emitting elements 12 to 14 were prepared from substrates 12 to 14 by applying the electroluminescent nano ZnS : Cu-dispe rsion
  • Devices 15 to 19 were prepared as described for Devices 2 to 6 except that the patterned ITO electrode was coated with elements incorporating poly (styrenesulphonic acid) .
  • Solutions 13 to 17, used for preparing these elements, are given below in Table 7.
  • Solutions 13, 14, 16 and 17 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then at 1500 rpm for 50 s and the elements dried at 40°C for 10 minutes. This resulted in element thicknesses of about 100 nm thereby producing the substrates for devices 16, 17, 18 and 19 respectively.
  • Table 7 Table 7:
  • the substrate of device 20 was prepared by spincoating solution 13 on the patterned ITO/PET sheet at 800 rpm for 6 s and then at 1500 rpm for 50 s to produce a 100 nm thick coating after drying at 40°C for 10 minutes.
  • the resulting coating was then spincoated with solution 15 at 800 rpm for 6 s and then at 4000 rpm for 50 s and the resulting element dried at 40°C for 10 minutes to give a total element thickness of ca . 105 nm, since the water in solution 15 does not substantially redisperse the PEDOT-S coating.
  • the substrate of device 21 was prepared by spincoating solution 15 at 8O0 rpm for 6 s and then at 4000 rpm for 50 s and the resulting element dried at 40 °C for 10 minutes to give an element thickness of 5 to 10 nm.
  • the substrate of device 22 was prepared by spincoating solution 14 on the patterned ITO/PET sheet at 800 rpm for 6 s and then at 1500 rpm for 50 s to produce a 100 nm thick coating after drying at 40 °C for 10 minutes. Then the resulting coating was spincoated with solution 16 at 800 rpm for 6 s and then at 1500 rpm for 50 s and the resulting element dried at 40 °C for 10 minutes to give an additional ca . 100 nm thickness resulting in a total element thickness of ca. 200 nm, since the water in solution 14 does not substantially redisperse the PEDOT-S coating.
  • Light emitting elements 20 and 22 were prepared from device substrates 20 and 22 by applying the electroluminescent nano ZnS : Cu-dispersion and aluminium electrode as described for light emitting devices 2 to 7.
  • Light emitting devices 23 to 31 were prepared as described for Devices 1 to 6 except that the patterned ITO electrode was coated with PEDOT—S layers incorporating polyphosphoric acid, an 84% polyphosphoric acid from ACROS (Cat. No. 19695-0025). Solutions 18 to 27 used for preparing these layers are given below in Table 10.
  • Solutions 18, 19, 20 and 21 were spincoated on patterned ITO/PET sheets at 800 rpm for 6 s and then 4000 rpm for 50 s and the layers dried at 40°C for 10 minutes. This resulted in a layer thickness of about 5 to 10 nm thereby producing the substrates for Devices 23, 24, 25 and 26 respectively. Solutions 22, 23, 24, 25 and 26 were spincoated on patterned
  • ITO/PET at 800 rpm for 6 s and then 1500 rpm for 50 s and the layers dried at 40°C for 10 minutes. This resulted in a layer thickness of about 10O nm.
  • the substrates for Devices 27, 28, 29, 30 and 31 respectively were thereby produced.
  • the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention.
  • various modi ications may be made within the scope of the invention.

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Abstract

L'invention se rapport à la configuration d'une couche sur un support qui est dotée d'un élément non photoactif constitué essentiellement de poly(3,4-alkylènedioxythiophène)s et de poly(3,4-dialkoxythiophène)s. Cet élément contient un premier polymère qui comprend des motifs représentés par la formule (I) dans laquelle X et Y représentant individuellement O, S, N-R1 ; z représente -(CH2)m-CR2R3(CH2)n-; R1 représente aryle, C1-18-alkyle ou hydrogène; R2 représente hydrogène ou (CH2)s-O-(CH2)p-S03-M+; R3 représente -(CH2)s-0-(CH2)p-S03-M+; M+ représente un cation; m et n représentent individuellement un nombre entier compris entre 0 et 3; s représente un nombre entier compris entre 0 et 10; et p représente un nombre entier compris entre 1 et 18 ; et un second polymère différent du premier et qui est sélectionné dans le groupe comprenant :polyamine-polymères éventuellement quaternarisés, polysulpho-polymères, acides polyphosphoriques et sels d'acides polyphosphoriques. La surface d'un premier côté de l'élément avoisine une électrode positive et la surface du côté opposé de l'élément avoisine un matériau apte au transport de trous.
PCT/EP2003/050341 2002-08-23 2003-07-29 Configuration de couche comprenant un element de blocage d'electrons Ceased WO2004019346A1 (fr)

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EP3037497A1 (fr) * 2014-12-23 2016-06-29 Heraeus Deutschland GmbH & Co. KG Procédé de production de polythiophènes fonctionnalisés
WO2016102129A1 (fr) * 2014-12-23 2016-06-30 Heraeus Deutschland GmbH & Co. KG Procédé de production de polythiophènes fonctionnalisés
US10767003B2 (en) 2014-12-23 2020-09-08 Heraeus Deutschland GmbH & Co. KG Process for producing functionalized polythiophenes

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