WO2012143109A1 - Amines fluorées en tant que sam dans des del organiques - Google Patents

Amines fluorées en tant que sam dans des del organiques Download PDF

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Publication number
WO2012143109A1
WO2012143109A1 PCT/EP2012/001631 EP2012001631W WO2012143109A1 WO 2012143109 A1 WO2012143109 A1 WO 2012143109A1 EP 2012001631 W EP2012001631 W EP 2012001631W WO 2012143109 A1 WO2012143109 A1 WO 2012143109A1
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Prior art keywords
layer
fluorinated
layer body
alkyl radical
body according
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PCT/EP2012/001631
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English (en)
Inventor
Wilfried LÖVENICH
Stephan Kirchmeyer
Andreas Elschner
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Heraeus Precious Metals Gmbh & Co. Kg
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Priority to EP12716243.6A priority Critical patent/EP2700112A1/fr
Priority to KR1020137030843A priority patent/KR20140032406A/ko
Publication of WO2012143109A1 publication Critical patent/WO2012143109A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a layer body, a process for obtaining a layer body, the layer body obtainable by this process, electronic components comprising a layer body as well as the use of a fluorinated amine.
  • An electro-luminescent device is characterised in that it gives out light under a flow of electrical current when an electrical voltage is applied.
  • Such devices have been known for a long time under the name “light emitting diodes” (LEDs).
  • LEDs light emitting diodes
  • the emission of light arises when positive charges (holes) and negative charges (electrons) recombine with the emission of light.
  • LEDs employed in technology are composed predominantly of inorganic semiconductor materials.
  • EL-devices have been known whose fundamental constitu- ents are organic materials.
  • These organic EL-devices contain, as a rule, one or more layers of organic charge-transport compounds.
  • the fundamental layer composition of an EL-device is, for example, as follows: 1 carrier, substrate
  • an EL device consists of two electrodes between which there is an organic layer which performs all of the functions, including the emission of light.
  • DE-A-10 2009 031 677 recommends employing func- tionalised polysulphones instead of PSS as the polyanions for balancing the charge of the cati- onic polythiophenes.
  • metal oxides such as, for example, ITO and their use in OLEDs.
  • the present invention was based on the object of overcoming the disadvantages present in the state of the art in connection with OLEDs, in particular in connection with OLEDs comprising hole injection layers comprising conductive polymers, in particular hole injection layers com- 10 prising polythiophenes and polyanions functionalised with acid groups.
  • the present invention was particularly based on the object of providing a layer body comprising conductive polymers, in particular conductive polymers comprising polythiophenes and polyanions functionalised with acid groups, which is, for example, suitable as the hole injection layer in an OLED and which is less susceptible to degradation as compared to the hole 5 injection layers known from the state of the art.
  • the present invention was also based on the object of providing a process for the production of such a layer body, which enables the production of more stable (with respect to degradation) hole injection layers, comprising conductive polymers, in particular comprising conductive 0 polymers comprising polythiophenes and polyanions functionalised with acid groups, using the simplest possible process techniques, without thereby adversely influencing the electrical properties of such layers.
  • the process should in particular also enable the production of OLEDs with particularly longer life spans.
  • the present invention was also based on the object of providing OLEDs which are characterised by a particularly long life span, where the longer life span should, in particular, manifest itself in that the time taken for the light intensity of the OLED at a constant electrical current to halve is as long as possible.
  • a layer body at least comprising a first layer comprising a conductive polymer
  • fluorinated amines on a surface of a conductive polymer in particular on a surface of a conductive polymer comprising a polythiophene and a polymer functionalised with acid groups, for example on a PEDOT : PSS surface, can form a self as- S0 Marveld monolayer (SAM).
  • SAM Self as- S0 Marveld monolayer
  • the layer body according to the invention comprises a first layer which comprises a conductive polymer.
  • conductive polymers are all those polymers which exhibit an electrical conductivity, such as, for example, conductive polymers based on optionally substituted poly- anilines, optionally substituted polypyrroles or optionally substituted polythiophenes, polymers based on optionally substituted polythiophenes being particularly preferred.
  • the conductive polymer in the first layer comprises preferably cationic polythiophene and a preferably anionic polymer functionalised with acid groups.
  • the polythiophene is preferably a polythiophene with repeating units of the general formula (I) or (II) or a combination of units of the general formulas (I) and (II), preferably a polythiophene with repeating units of the general formula (II):
  • A stands for an optionally substituted C]-C 5 -alkylene radical
  • R stands for a linear or branched, optionally substituted Ci-Cis-alkyl radical, an optionally substituted C 5 -Ci 2 -cycloalkyl radical, an optionally substituted C6-Ci 4 -aryl radical, an optionally substituted C 7 -Ci 8 -aralkyl radical, an optionally substituted C1 -C4- hydroxyalkyl radical or a hydroxyl radical,
  • x stands for a whole number from 0 to 8 and in the case where multiple radicals R are connected to A, these can be identical or different.
  • polythiophenes with repeating units of the general formula (II), wherein A stands for an optionally substituted C 2 -C3-alkylene radical and x stands for 0 or 1.
  • L5 Especially preferred as polythiophene is poly(3,4-ethylenedioxythiophene), which is optionally substituted.
  • the prefix poly- is to be understood as meaning that more than one identical or different repeating units of the general formulas (I) and/or (II) are contained in
  • the polythiophene can also comprise other repeating units, it being preferred that at least 50 %, particularly preferred that at lease 75 % and most preferred that at least 95 % of all repeating units of the polythiophene exhibit the general formula(s) (I) and/or (II), preferably the general formula (II).
  • the polythiophenes contain in total n repeating units of the general for-
  • the repeating units of the general formula(s) (I) and/or (II), preferably of the general formula (II), within a polythiophene can each be identical or different. Polythiophenes with identical repeating units of the general formula (II) are preferred.
  • Ct-C 5 -Alkylene radicals A are preferably methylene, ethylene, n-propylene, n-butylene or n-pentylene.
  • 8 -alkyl R preferably stand for linear or branched Ci-C] 8 -alkyl radicals such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, 1 ,2-
  • C5-C] 2 -cycloalkyl radicals R stand, for example, for cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl.
  • C 5 -C 14 -aryl radicals R stand, for example, for phenyl or naphthyl.
  • C 7 -Ci 8 - aralkyl radicals R stand, for example, for benzyl, o-, m-, p- tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-,
  • radical A and/or the radical R numerous organic groups are possible, such as, for example, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halogen, ether, thi- 15 oether, disulphide, sulphoxide, sulphone, sulphonate, amino, aldehyde, ketone, carboxylic acid ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane groups as well as carboxylamide groups.
  • the polythiophenes can be neutral or cationic. In preferred embodiments they are cationic, >0 "cationic" referring only to the charges which reside on the polythiophene main chain.
  • the polythiophenes can carry positive and negative charges in the structural unit, the positive charges being on the polythiophene main chain and the negative charges, were applicable, being on the radicals R substituted with sulphonate or carbonate groups.
  • the positive charges of the polythiophene chain can thereby be partially or >5 fully balanced by the optionally present anionic groups on the radicals R. Considered as a whole the polythiophenes can be, in these cases, cationic, neutral or even anionic.
  • the first layer also comprises a polyanion based on polymers functionalised with acid groups.
  • polyanion is anions of polymeric carboxylic acids, such as polyacrylic acids, polymethacrylic acid 5 or polymaleic acids, or polymeric sulphonic acids, such as polystyrene sulphonic acids and polyvinylsulphonic acids.
  • the polycarboxylic and polysulphonic acids can also be copolymers of vinylcarboxylic and vinylsulphonic acids with other polymerisable monomers, such as acrylic acid esters and styrene. It is particularly preferable for the first layer to contain an anion of a polymeric carboxylic or sulphonic acid for compensation of the positive charge of the polio ythiophene.
  • polyanion is the anion of the polystyrene sulphonic acid (PSS) which, where polythiophene is used, preferably poly(3,4-ethylenedioxythiophene), is preferably present bound as a complex in the form of the PEDOT : PSS complexes known from the state of
  • PSS polystyrene sulphonic acid
  • Such complexes are obtainable by oxidative polymerisation of the thiophene monomers, preferably 3,4-ethylenedioxythiophene, in an aqueous solution in the presence of the polystyrene sulphonic acid.
  • the molecular weight of the polymers functionalised with acid groups which supply the poly- !0 anions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
  • the polymers functionalised with acid groups or their alkali salts are commercially available, e.g. polystyrene sulphonic acids and polyacrylic acids, or can be produced by known processes (see e.g. Houben Weyl, Methoden der organischen Chemie, vol. E 20 Makromolekulare Stoffe, Part 2, (1987), p. 1141 et seq.).
  • Polymers functionalised with acid groups (polyanions) and polythiophene, in particular polystyrene sulphonic acid and poly(3,4-ethylenedioxythiophene), can be present in the first layer in a weight ratio from 0.5 : 1 to 50 : 1, preferably from 1 : 1 to 30 : 1, particularly preferably from 2 : 1 to 20: 1.
  • the weight of the electrically conductive polymers here corresponds to the 10 weight of the monomers employed for the production of the conductive polymers, assuming that complete conversion takes place during the polymerisation.
  • the polystyrene sulphonic acid is present in excess by weight compared with the polythiophene, in particular poly(3,4- ethylenedioxythiophene) .
  • the first layer consists at least 40 % by weight, particularly preferably at least 55 % by weight and most preferably at least 70 % by weight, of the polythiophene and the polymer functional ised with acid groups, particularly preferably of PEDOT : PSS, the proportion in each case being relative to the total weight of the first layer.
  • the layer thickness of the first layer preferably lies in a range from 1 nm to 10 ⁇ , particularly preferably in a range from lO nm to 500 nm and most preferably in a range from 20 nm to 200 nm. s 5
  • the layer body according to the invention comprises a further layer following the first layer, which comprises a fluorinated amine, it being particularly preferable according to the invention if this further layer is one which forms a self assembled monolayer (SAM).
  • SAM self assembled monolayer
  • a self assembled monolayer generally forms spontaneously on dipping a substrate into a fluid comprising the fluorinated amine. It is an organised layer con-
  • SAMs exhibit a defined layer thickness, normally a layer thickness in the range from roughly 0.1 to 2 nm.
  • the fluorinated amines can be fluorinated or perfluorinated (i.e. the hydrogen atoms in the alkyl chains of the amine can be completely or partially replaced with fluorine atoms). It is preferred, however, for at least 40 %, particularly preferably at least 55 %, and most preferably at least 70 % of the hydrogen atoms in the amine to be replaced with fluorine atoms.
  • the amines can be primary, secondary or tertiary amines.
  • the fluorinated amine it is particularly preferred for the fluorinated amine to exhibit the general formula (III) R
  • R 1 , R 2 and R 3 can, independently of each other, stand for a hydrogen atom, for a C]- C 20 -alkyl radical, preferably for a Ci-Ci 5 -alkyl radical, particularly preferably for a CpCio- alkyl radical, or for a fluorinated CrC ⁇ -alkyl radical, preferably for a fluorinated CrCi 5 -alkyl radical, particularly preferably for a fluorinated d-C 10 -alkyl radical, wherein at least one of the radicals R 1 , R 2 and R 3 stands for a fluorinated Ci-C 20 -alkyl radical, preferably for a fluori- ⁇ nated Ci-Ci 5 -alkyl radical and particularly preferably for a fluorinated Ci-Qo-alkyl radical.
  • fluorinated comprises perfluorinated as well as polyfluorinated alkyl radicals.
  • alkyl radicals and fluorinated alkyl radicals can be straight chained or 15 branched and can optionally also comprise cyclic units, straight chain alkyl radicals being particularly preferred.
  • fluorinated amines are polyfluorinated or perfluorinated methyla- mine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylmethyla- mine, ethyldimethylamine, diethylmethyl amine, propylamine, dipropylamine, tripropylamine, >0 butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexyla- mine, dihexylamine, trihexyl amine, heptylamine, diheptylamine, triheptylamine, octylamine, dioctylamine, trioctylamine, nonylamine, dinonylamine, trinonylamine, decylamine, didecyl- amine, tridecylamine, undecylamine, diund
  • fluorinated amines are perfluorotripentylamine, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-l-decylamine (also known as ⁇ , ⁇ ,- 2H,2H-perfluorodecylamine) or 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-l-octylamine (also known as ⁇ , ⁇ -perfluorooctylamine).
  • the further layer can also comprise mixtures of at least two different fluorinated amines.
  • a contribution to achieving the objects named at the beginning is also made by a process for the production of a layer body comprising the process steps i) the application of a conductive polymer to a substrate to obtain a first layer; ii) the application of a fluorinated amine to the first layer to obtain a further layer.
  • a conductive polymer is applied to a substrate to obtain a first layer.
  • the substrate can be one which is furnished with a preferably transparent base electrode, the substrate itself preferably also being transparent.
  • Glass, PET or other transparent plastics, for example can be employed as transparent substrate, onto which a transparent electrically conductive electrode is then introduced, such as e.g. an electrode made of indium - tin oxide (ITO), doped zinc- or tin oxide or a conductive polymer.
  • a transparent electrically conductive electrode such as e.g. an electrode made of indium - tin oxide (ITO), doped zinc- or tin oxide or a conductive polymer.
  • transparent plastic substrates are, for example, polycarbonates, polyesters, such as e.g.
  • PET and PEN polyethyleneterephthalate and polyeth- ylenenaphthalinedicarboxylate
  • copolycarbonates polyacrylates, polysulphones, polyether- sulphones (PES), polyimides, polyethylene, polypropylene, cyclic polyolefins or cyclic olefin copolymers (COC), hydrated styrene polymers or hydrated styrene copolymers.
  • Suitable polymer bases can, for example, also be films such as polyester films, PES films from the Sumitomo company or polycarbonate films from the Bayer AG company (Makrofol®). According to the invention, ITO coated glass is particularly preferred as substrate.
  • the conductive polymer is deposited onto such a substrate or onto the electrode layer which has been applied to such a substrate to obtain the first layer of the layer body according to the invention, particularly preferred conductive polymers here being those conductive polymers which have already been described at the outset as preferred conductive polymer in connection with the layer body according to the invention.
  • particularly preferred according to the invention is a conductive polymer comprising a polythiophene, particularly preferably PEDOT, and a polymer functionalised with acid groups, particularly preferably PSS, the use of PEDOT : PSS complexes as conductive polymer being particularly preferable here also.
  • the conductive polymer is preferably introduced to the substrate in the form of a dispersion comprising the conductive polymer and a dispersing agent, particularly preferably in the form of a dispersion comprising polythiophene, a polymer functionalised with acid groups and a dispersing agent, especially preferably in the form of a PEDOT : PSS dispersion, with at least partial subsequent removal of dispersion agent to obtain the first layer.
  • a dispersing agent particularly preferably in the form of a dispersion comprising polythiophene, a polymer functionalised with acid groups and a dispersing agent, especially preferably in the form of a PEDOT : PSS dispersion, with at least partial subsequent removal of dispersion agent to obtain the first layer.
  • the application of the dispersion can be carried out, for example, using known processes, e.g.
  • the at least partial removal of the dispersing agent is preferably effected by drying at a temperature in a range from 20°C to 200°C, in which connection it can be advantageous to at least partially remove the supernatant dispersion prior to the drying processes, for example by spinning off.
  • dispersions comprising a polythiophene, a polymer functionalised with acid groups and a dispersing agent is basically described in EP-A-1 122 274 or US 5,11 1,327.
  • the polymerisation of the appropriate monomelic compounds is carried out in the presence of polymers functionalised with acid groups, 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 sulphonic acids, H 2 0 2 , 2 Cr 2 0 7 , 2 S 2 0 8 , Na 2 S 2 0 , KMn0 4 , alkali perborates and alkali or ammonium persulphates 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 0 and K 2 S 2 0 8 or mixtures thereof.
  • the polymerisation is preferably carried out at a reaction temperature of from -20 to 100°C. Particularly preferable 5 are reaction temperatures of from 20 to 100°C.
  • the reaction solution is optionally subsequently treated with at least one ion exchanger.
  • Suitable solvents are e.g. polar solvents such as, for example, water, alcohols such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerine 0 or mixtures of these.
  • polar solvents such as, for example, water, alcohols such as methanol, ethanol, 2-propanol, n-propanol, n-butanol, diacetone alcohol, ethylene glycol, glycerine 0 or mixtures of these.
  • aliphatic ketones such as acetone and methylethyl ketone
  • aliphatic nitriles 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 sulphoxides such as dimethylsulphoxide (DMSO) or mixture of these with each other or with those solvents previously specified.
  • THF tetrahydrofuran
  • DMSO dimethylsulphoxide
  • the dispersions preferably exhibit a solid content in a range from 0.01 to 20 % by weight, and particularly preferably in a range from 0.2 to 5 % by weight, i.e. they contain in total 0.01 to 20 % by weight, particularly preferably 0.2 to 5 % by weight of polythiophene(s), preferably PEDOT, with polymer functionalised with acid groups, preferably PSS, and optionally further ⁇ components, such as e.g. binding agents, cross-linking agents and/or surfactants, in dissolved and/or dispersed form.
  • polythiophene(s) preferably PEDOT
  • polymer functionalised with acid groups preferably PSS
  • optionally further ⁇ components such as e.g. binding agents, cross-linking agents and/or surfactants, in dissolved and/or dispersed form.
  • the viscosity at 20°C of the dispersions employed for production of the first layer preferably lies between the viscosity of the dispersing agent and 200 mPas, preferably between the vis- :5 cosity of the dispersing agent and 100 mPas.
  • the desired amount of dispersing agent can be removed from the dispersion through distillation, preferably in a vacuum or by other processes, e.g. ultra filtration.
  • organic, polymeric binding agents and/or organic low-molecular cross-linking agents or surfactants can be added to the dispersion.
  • Appropriate binding agents are, for example, described in EP-A 564 91 1. Examples in this regard are polyvinylcarbazole, silanes, such as Silquest ® A187 (Fa. OSi Specialities) or surfactants, such as the fluoro-surfactant FT 248 (Bayer AG).
  • a fluorinated amine is then introduced onto the first layer to obtain a further layer, it being particularly preferable if a SAM forms with the application of the fluorinated amine onto the first layer in process step ii).
  • Preferred fluorinated amines in this connection are those fluorinated amines which have already been described at the beginning as preferred fluorinated amines in connection with the layer body according to the invention
  • the application of the fluorinated amines onto the first layer is preferably effected by dissolving the fluorinated amines in a suitable non-polar solvent, for example in an ether such as tert- butyl ether, and then coating the first layer with the solution so obtained, where the application of the solution onto the first layer can, once more, be carried out using known process, e.g.
  • spin coating impregnation, pouring, dripping, spraying, misting on, knife coating, brushing or printing, for example ink-jet, screen, Intaglio, offset or tampon printing.
  • an exposure time in a range of 1 second to 120 minutes, particularly preferably 1 to 15 minutes at a temperature in a range preferably from 10 to 60°C, particularly preferably from 20 to 30°C, an excess of fluorinated amine can be removed, for example by spinning off the supernatant solution.
  • the process conditions for the application of the fluorinated amine onto the first layer should preferably be selected such that a SAM layer of the fluorinated amine forms on the first, conductive polymer comprising layer, preferably on the layer comprising PEDOT : PSS.
  • the concentration of fluorinated amine in the solution employed for introducing the fluorinated amine onto the first layer preferably lies in a range from 0.1 to 20 % by weight, particularly preferably in a range from 1 to 10 % by weight, in each case in relation to the total weight of the solu- tion.
  • the process according to the invention can comprise further process steps.
  • process step ii such as, for example, iii) the application of a hole transport layer onto the layer obtained in process step ii); iv) the application of an emitter layer onto the hole transport layer; v) the application of an electron injection layer onto the emitter layer; vi) the application of a cathode layer onto the electron injection layer.
  • the hole injection layer or the hole transport layer can also be designated as electron blocking layer. If the electron injection layer has the ability to block hole transport, then the electron injection layer can also be designated as hole blocking layer.
  • Possible hole transport layers are, for example, layers comprising polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives with aromatic amine in the side or main chain, pyrazoline derivatives, aryl amine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene and derivatives thereof, polyarylamine or derivatives thereof, polypyrrole or derivatives thereof, poly p- phenylenevinylene) or derivatives thereof and poly(2,5-thienylenevinylene) or derivatives thereof.
  • Particularly preferred as hole transport layer is NPB (N,N'-bis(naphthalene-l-yl)- N,N ' -bis(phenyl)benzidine.
  • Suitable materials for the emitter layer are conjugated polymers such as polyphenylene- vinylenes and/or polyfluorenes, for example, the polyparaphenylenevinylene derivatives and polyfluorene derivatives described in WO-A-90/13148, or emitters from the class of low molecular emitters, also termed , mall molecules" in technical circles, such as aluminium com- plexes, such as, for example, tris(8-hydroxyquinolinato)aluminium (Alq 3 ), fluorescence dyes, e.g. quinacridones, or phosphorescent emitters such as, for example, Ir(ppy) 3 .
  • Further suitable materials for the emitter layer are described e.g. in DE-A-196 27 071. Particularly preferred as emitter layer, according to the invention, is tris(8-hydroxyquinolinato)aluminium (Alq 3 ).
  • the injection layer are single Ca layers or a stack structure consisting of a Ca layer and another layer, which consists of one or more materials selected from the group LA and IIA metals of the periodic table, excluding Ca, which exhibit a work function from 1.5 to 3.0 eV, and oxides, halogenides and carbonates thereof.
  • group IA metals of the periodic ⁇ table which exhibit a work function from 1.5 to 3.0 eV, and oxides, halogenides and carbonates thereof are lithium, lithium fluoride, sodium oxide, lithium oxide and lithium carbonate.
  • group IIA metals of the periodic table excluding Ca, which exhibit a work function from 1.5 to 3.0 eV, and oxides, halogenides and carbonates thereof, are strontium, magnesium oxide, magnesium fluoride, strontium fluoride, barium fluoride, strontium
  • Particularly suitable materials for the cathode layer are transparent or translucent materials with a relatively low work function (preferably lower than 4.0 eV).
  • metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium
  • Cs Be, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminium (Al), scandium (Sc), vanadium (V), Zn, yttrium (Y), indium (In), cerium (Ce), samarium (Sm), Eu, Tb and ytterbium (Yb); alloys consisting of two or more of these metals; alloys consisting of one or more of these metals and one or more metals selected from Au, Ag, Pt, Cu, manganese (Mn), titanium (Ti), cobalt (Co), nickel (Ni), wolfram (W) and tin (Sn); graphite or graphite
  • intercalation compounds such as, for example, ITO and tin oxide.
  • metal oxides such as, for example, ITO and tin oxide.
  • aluminium is particularly preferable as the cathode layer.
  • the application of the further layers, in particular of the hole transport layer, of the emitter layer, of the electron injection layer and of the cathode injection layer can be carried out in a 30 manner known to a person skilled in the art, preferably through vapour coating such as is described, for instance, in WO-A-2009/0170244.
  • a contribution to the solution of the objects named at the outset is also made by a layer body, particularly preferably an OLED or an OPV element, which is/are obtainable by the process according to the invention.
  • an electronic component comprising a layer body according to the invention or a layer body obtainable by the process according to the invention, this component preferably being an OLED or an OPV element, particularly preferably an OLED.
  • the layer formation of the OLED can take any form known to the person skilled in the art, preferably, however, with the hole injecting layer replaced by the layer body according to the invention wherein the further layer of fluorinated amine, preferably the further SAM layer of fluorinated amine, is present in the boundary region between the hole injecting layer and the hole transport layer or, where no separate hole transport layer is present, then in the boundary region between the hole injecting layer and the emitter layer.
  • the further layer of fluorinated amine preferably the further SAM layer of fluorinated amine
  • the OLED according to the invention can, for example, exhibit any of the following layer structures (a) to (h):
  • hole injection layer/ hole transport layer/ 0 at least one emitter layer/ electron injection layer/ cathode
  • hole injection layer at least one emitter layer/ SO electron transport layer/ electron injection layer/ cathode;
  • the hole injection layer corresponding in each case to the layer body according to the invention or the layer body obtainable by the process according to the invention and in each case arranged in a such a way, that the further layer of fluorinated amine, preferably the further SAM of fluorinated amine is facing the hole injection layer or emitter layer.
  • the layer structures (a) to (h) can be embodied either with the anode located next to the substrate, the substrate being, for example, glass or a transparent plastic film, or with the cathode located next to the substrate.
  • anode layer hole transport layer, emitter layer, electron injection layer and cathode layer, those layers already mentioned at the outset in connection with the process according to the invention as preferred anode layer, hole transport layer, emitter layer, electron injection layer and cathode layer are again preferred.
  • the electron transport layer can consist of materials such as, for example, oxadiazol derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoan- thraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives and metal complexes of 8-hydroxyquinoline or
  • an OLED which is formed of the following layers: anode layer/first layer of the layer body according to the invention or of the layer body obtainable using the process according to the invention/further layer 5 of the layer body according to the invention or of the layer body obtainable according to the invention/optional hole transport layer/optional emitter layer/optional electron injection layer/cathode layer.
  • a contribution to the solution of the objects named at the outset is also made by the use of a 0 fluorinated amine for the improvement of the life span of electronic components which comprise layers of a conductive polymer, preferably layers comprising PEDOT : PSS complexes, the electronic component preferably being an OLED, especially preferably an OLED formed of the following layers: anode/hole injection layer/layer of the fluorinated amine, preferably SAM layer of the fluorinated amine/hole transport layer/emitter layer/electron injection lay- 5 er/cathode.
  • the hole injection layer preferably comprises a conductive polymer, particularly preferably complexes of PEDOT : PSS.
  • the time taken for the light intensity of the OLEDs at a constant electrical current to halve serves as a measure of the life span of the OLEDs.
  • Preferred fluorinated amines in this connection are similarly those fluorinated amines which !0 have already been described at the outset as preferred fluorinated amines in connection with the layer body according to the invention.
  • Example 1 SAM layer of lH,lH,2H,2H-perfluorodecylamine (according to the invention)
  • SAM-1 will be used for building an organic light emitting diode (OLED).
  • OLED organic light emitting diode
  • ITO-coated glass is cut into 50 mm ⁇ 50 mm pieces (substrates) and structured into four parallel lines, each 2 mm wide and 5 cm long with Photoresist and an etching solution. Then the substrates are freed from the remains of the Photoresist, cleaned in an ultrasonic bath with 0.3 % Mucasol solution, rinsed with distilled water and centrifuged dry in a centrifuge. Directly before coating the ITO-coated sides are cleaned in a UV/Ozone reac-
  • the aqueous dispersion, Clevios ® P AI4083 (Heraeus Clevios GmbH, Leverkusen), is 5 filtered through a syringe filter (Millipore HV, 0.45 ⁇ ).
  • the cleaned ITO-coated substrate is placed on a spin coater (Carl Siiss, RC13) and approximately 5 ml of the filtered solution are distributed over the ITO-coated side of the substrate. Subsequently, the supernatant solution is spun off by rotating the plate at 1000 U/min over a period of 30 s. Then the thusly coated substrate is dried for 5 minutes at 200 °C on a hotplate.
  • the layer !0 thickness is 50 nm (Tencor, Alphastep 500).
  • the thusly coated substrate is transferred into a vapour deposition apparatus (Univex 350, Leybold).
  • a vapour deposition apparatus Univex 350, Leybold.
  • 60 nm of a hole transport layer of NPB (N,N'-bis(naphthalene-l- yl)-N,N'-bis(phenyl)benzidine) and then 50 nm of an emitter layer of A1Q3 (tris-(8- hydroxyquinoline)aluminum) (Sensient, Bitterfeld) are sequentially vapour deposited at a pressure of 10-3 Pa and at a vapour deposition rate of 1 A/sec.
  • the layer system is transferred into a glove box with an N 2 atmosphere and an integrated vapour deposition apparatus (Edwards) and metal electrodes are applied by
  • the substrate is placed on a shadow mask with the layer system facing downwards.
  • the shadow mask contains rectangular slits with a width of 2 mm which are orientated perpendicular to the ITO stripes.
  • a 0.5 nm thick LiF layer and subsequently a 200 nm thick Al layer are sequentially vapour deposited.
  • the vapour deposition rates are 1 A/s for LiF and 10 A s
  • the surface area of the individual OLEDs is 4.0 mm 2 .
  • the two electrodes of the organic LED are connected to a power supply with electric !0 leads (contacted).
  • the positive terminal is connected to the ITO electrode, the negative terminal with the metal electrode.
  • the procedure is as that for example 1 with the difference that in point 1.3 ap- proximately 5 ml of the solution SAM-2 consisting of 0.1 g perfluorotripentylamine (Fluroinert FC 70, Sigma Aldrich) in 10 g tert.- butylmethyl ether is distributed onto the coated substrate which now lies, once again, on the spin coater. After an exposure time of approximately 3 min the supernatant solution is spun off at 3000 U/min for 30 s. The layer thickness of the entire coating remains unchanged after this process step and is 50 nm.
  • SAM-2 consisting of 0.1 g perfluorotripentylamine (Fluroinert FC 70, Sigma Aldrich) in 10 g tert.- butylmethyl ether
  • Table 1 shows an evaluation of the characteristic curves as well as the life span of the OLEDs produced in example 1-4.
  • the characteristic curves were evaluated at a light intensity of 1000 cd/m 2 and show that the voltage is significantly lower when SAM layers SAM-1 and SAM-2 are used than in the con- trol test or with the material SAM-3.
  • the life span test which is carried out at a constant current density of 3.84 mA/cm 2 , shows that the OLEDs with the SAM layers SAM-1 and SAM-2 according to the invention are significantly more stable than those without.
  • the value t 2 gives the time at which half of the original light intensity (L0) is reached.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un corps en couches comprenant au moins une première couche constituée d'un polymère conducteur, et une autre couche épousant la première couche et comprenant une amine fluorée. L'invention concerne également un procédé de fabrication d'un corps fluoré, dont celui susdécrit, ainsi que des composants électroniques comprenant ce corps en couche et l'utilisation d'amines fluorées.
PCT/EP2012/001631 2011-04-21 2012-04-16 Amines fluorées en tant que sam dans des del organiques WO2012143109A1 (fr)

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EP12716243.6A EP2700112A1 (fr) 2011-04-21 2012-04-16 Amines fluorées en tant que sam dans des del organiques
KR1020137030843A KR20140032406A (ko) 2011-04-21 2012-04-16 OLEDs에서 SAM으로서 불소화 아민

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DE102011018480.5 2011-04-21
DE102011018480A DE102011018480A1 (de) 2011-04-21 2011-04-21 Fluorierte Amine als SAM in OLEDs
US201161480433P 2011-04-29 2011-04-29
US61/480,433 2011-04-29

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TW201307062A (zh) 2013-02-16

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