WO2016037964A1 - Couche optiquement active améliorée et procédé pour la réaliser - Google Patents

Couche optiquement active améliorée et procédé pour la réaliser Download PDF

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Publication number
WO2016037964A1
WO2016037964A1 PCT/EP2015/070344 EP2015070344W WO2016037964A1 WO 2016037964 A1 WO2016037964 A1 WO 2016037964A1 EP 2015070344 W EP2015070344 W EP 2015070344W WO 2016037964 A1 WO2016037964 A1 WO 2016037964A1
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Prior art keywords
light
group
ligand
emitting layer
branched
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PCT/EP2015/070344
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German (de)
English (en)
Inventor
Daniel Volz
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Cynora Gmbh
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Publication of WO2016037964A1 publication Critical patent/WO2016037964A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • C—CHEMISTRY; METALLURGY
    • 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, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a method for applying a light-emitting layer S to the surface of a component T, comprising applying a composition Z1 comprising at least one Cu (I) salt and a composition Z2 comprising at least one uncomplexed ligand L which is Cu (I) under complexing to the surface of the device T, forming a Cu (I) complex which emits light in the visible region of the electromagnetic spectrum at room temperature from the excited singlet state S1 according to the singlet harvesting mechanism can. Furthermore, the present invention comprises a light-emitting layer S comprising the Cu (I) complex as emitter compound E and either uncomplexed Cu (I) or a non-complexed ligand L.
  • Organo-chemical compound based optoelectronic devices such as organic light emitting diodes (OLEDs), light emitting electrochemical cells (LECs), organic lasers, organic solar cells ( English: “organic solar cells” (OSCs) and optical sensors, are increasingly gaining practical importance, especially OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.
  • OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.
  • OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.
  • OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.
  • OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.
  • OLEDs and LECs are promising components in electronic devices, such as screens, but also in the lighting technology.
  • OLEDs and LECs are promising components in electronic devices, such as screens, but also
  • ISC rate intersystem crossing rate
  • Cu (I) salt and ligand need not necessarily be reacted in a stoichiometric ratio with each other.
  • An excess of Cu (I) salt or ligand (s) can bring further technical advantages, such as increased stability and / or increased lifespan.
  • a first aspect of the present invention relates to methods for applying a light-emitting layer S on the surface of a component T, comprising the steps of: (i) providing:
  • composition Z1 comprising at least one complexed or uncomplexed Cu (I) salt and optionally a coordinating solvent
  • composition Z2 containing at least one uncomplexed ligand L capable of reacting with Cu (I) to complex, and optionally
  • composition Z3 comprising at least one host molecule W which can form a matrix for the light-emitting layer S;
  • compositions Z1, Z2 and optionally Z3 applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T, wherein the Cu (I) complexes with the ligand L or several of the ligands L and thereby forms a Cu (I) complex, which is at room temperature can emit light in the visible region of the electromagnetic spectrum at the excited singlet level according to the singlet harvesting mechanism.
  • the Cu (I) complex formed represents an emitter compound E which is capable of emitting light to the ground state (SO) by fluorescence, therefore by relaxation of an excited singlet state (such as S1), with the energy gap ⁇ between the excited singlet state S1 and the excited triplet state T1 is so small that even at room temperature (20 ° C) energy from the excited T1 state to the overlying S1 state can be transmitted by reverse intersystem crossing (RISC). Therefore, preferably, the energy gap ⁇ between S1 and T1 (the singlet-triplet energy splitting, AE (S1-T1)) is not greater than 3000 cm "1, more preferably not greater than 2500 cm" 1, more preferably not greater than 2000 cm " 1. Optionally, AE (S1-T1) is not even more than 1500 cm "1 or not more than 1000 cm " 1 .
  • the process may here be application from the gas phase or from the liquid phase (also “liquid processing”, “film processing” or “wet processing”) .
  • the liquid processing is also understood as an in situ procedure, and can also be referred to as "chemistry in the layer”.
  • the compositions Z1, Z2 and optionally Z3 are not mixed together before application to the surface, but applied independently of each other, therefore not combined with each other.
  • the compositions Z1, Z2 and optionally Z3 optionally intermix or otherwise come into contact with each other
  • the compositions Z1, Z2 and optionally Z3 are each liquid
  • the compositions Z1, Z2 and optionally Z3 are each evaporable without being destroyed Alternatively, one or more of the compositions Z1, Z2 and / or optionally Z3 fl SSGIs and others to be destroyed without evaporierbar.
  • the method according to the invention also makes it possible to produce light-emitting layers S comprising sparingly soluble Cu (I) complexes which, although obtainable by conventional production methods, are not yet processable into light-emitting layers S since the application fails as a layer.
  • Such materials are often initially dissolved in the course of the reaction, often accumulate during the synthesis after isolation in substance as insoluble substances and can not be brought back into solution in the heat after completion of crystallization.
  • the light-emitting layer S is preferably not thicker than 1 mm, more preferably not thicker than 0.1 mm, more preferably not thicker than 10 ⁇ , even more preferably not thicker than 1 ⁇ , in particular not thicker than 0.1 ⁇ .
  • the emitter compound E in the context of the present invention in the broadest sense is to be understood as any optically active compound which is able to emit light under certain conditions in an opto-electronic device. Accordingly, the emitter connection E can actually be used to generate light. But it can also be used differently, for example to absorb light and convert it into electrical energy.
  • a component T comprising at least one light-emitting layer S is typically built in or on the opto-electronic device.
  • the light-emitting layer S is supplied with electrical or chemical energy in the optoelectronic device, in particular electrical energy is supplied.
  • electricity can be connected, wherein the current flow through the light-emitting layer S, the emitter compounds E contained therein excites so that so-called excitons arise that can relax under the emission of light in the ground state.
  • the component T as used herein can be broadly any technical element that supports the light-emitting layer S.
  • the structure depends on which type of opto-electronic device the component T is provided.
  • a component T preferably has a (largely) planar surface onto which compositions Z1 and Z2 and optionally Z3 can be applied.
  • the surface of the component T, to which the compositions Z1, Z2 and optionally Z3 are applied may be any surface of the component T.
  • the compositions Z1, Z2 and optionally Z3 are applied depends on which opto-electronic device, the component T is to be used.
  • the surface is preferably either a hole-conducting layer (eg comprising an electron-rich heteroaromatic, such as a triarylamine and / or a carbazole, such as tris (4-carbazoyl-9-ylphenyl) amine (TCTA)) or an electron conduction layer (eg comprising an electron-deficient compound such as a benzimidazole, pyridine, triazole, phosphine oxide or sulfone or a star-shaped heterocycle such as 1, 3,5-tri (1-phenyl-1H-benzo [d ] imidazole-2- yl) phenyl (TPBi)).
  • a hole-conducting layer eg comprising an electron-rich heteroaromatic, such as a triarylamine and / or a carbazole, such as tris (4-carbazoyl-9-ylphenyl) amine (TCTA)
  • an electron conduction layer eg comprising an electron-deficient compound such
  • the composition Z1 consists only or largely of one or more Cu (I) salt (s).
  • the Cu (I) salt (s) is / are uncomplexed.
  • this Cu (l) salt is already (partially) complexed, but can be further complexed by the ligand L from composition Z2.
  • the composition Z1 contains one or more other components, such as besides the at least one salt of a non-complexed Cu (I) and at least one solvent in which the at least one salt is soluble.
  • Particular preference is given here to those coordinating solvents in which both Z1 and Z2 and optionally Z3 are soluble.
  • a coordinating solvent is, for example, a solvent selected from the group consisting of tetrahydrothiophene, benzonitrile, pyridine, a nitrile (eg acetonitrile), a thioether, trihydrofuran, triarylamine and toluene. It is also possible to use combinations of different solvents. Very particular preference is given to acetonitrile.
  • a Cu (I) salt contained in the composition Z1 may be a Cu (I) salt having any anion.
  • the salt of Cu (I) is preferably a halide salt (especially a salt with CI " anions), a cyanide salt (hence a salt with CN anions), a thiocyanate salt (hence a salt with SCN ' anions), a thiolate salt ( therefore, a salt with RS " anions, wherein R is any organic radical having 1-40 carbon atoms, preferably an unsubstituted or substituted Ci-2o-alkyl radical, an unsubstituted or substituted C2-2o-Alkyenrest, an unsubstituted or substituted C2-2o Alkynyl, unsubstituted or substituted phenyl, unsubstituted or substituted phenyl or benzyl, unsubstituted
  • the composition Z2 consists only or largely of one or more ligands L.
  • the composition Z2 also contains one or more other components such as at least one solvent in which the ligand L is soluble.
  • Each ligand L is preferably low molecular weight, therefore L preferably has a molecular weight of not more than 5 kDa, more preferably not more than 2 kDa, especially not more than 1 kDa. Often the molecular weight is not greater than 500 kDa.
  • coordinating solvents are preferred, such as those selected from the group consisting of the group consisting of tetrahydrothiophene, benzonitrile, pyridine, a nitrile (e.g., acetonitrile), a thioether, trihydrofuran, triarylamine, and toluene. It is also possible to use combinations of different solvents.
  • the dissolved, at least one ligand L can then be applied in liquid form to the surface of the component T.
  • the ligand L is preferably an organochemical ligand, therefore predominantly consists of carbon, nitrogen, phosphorus and hydrogen.
  • the ligand L may be one which can form a monodentate or a bidentate Cu (I) complex with the Cu (I).
  • the Cu (I) complex may be homoleptic (like ligands) or heteroleptic (different ligands).
  • a ligand L may be one as described in WO 2013/072508, WO 2013/007709, WO 2013/007710 or WO 2013/014066. These documents also describe how such a ligand L can be prepared and how a Cu (I) complex can be formed therefrom.
  • the ligand L may be any ligand capable of complexing the Cu (I) alone or together with other ligands.
  • a ligand L may be selected from the group consisting of: 4-Methyl-2- (diphenylphosphino) -pyridine (MePyrPHOS), 4-heptyl-2- (diphenylphosphino) -pyridine, 4-butyne-1-yl (diphenylphosphino) -pyridine
  • the ligand L is particularly preferably MePyrPHOS.
  • a ligand may be used as illustrated in embodiments below. Particularly preferred embodiments are also shown in the experimental examples below.
  • the composition Z3, if present, contains at least one host molecule W and optionally at least one solvent in which the host molecule W is soluble.
  • solvents in which both Z1 and Z2 and optionally Z3 are soluble are soluble. Therefore, coordinating solvents are preferred in which both Z1 and Z2 and optionally Z3 are soluble or which are miscible with a solvent in which they are soluble. Therefore, coordinating solvents are preferred such as those selected from the group consisting of: tetrahydrothiophene, benzonitrile, pyridine, acetonitrile, trihydrofuran, triarylamine and toluene. Very particular preference is given to acetonitrile.
  • the dissolved at least one host molecule W can then be applied in liquid form to the surface of the component T.
  • the step (i) of providing can be done in any way.
  • the at least one Cu (I) salt and the at least one ligand L can each be used as such (for example in coevaporation) or they can be dissolved.
  • compositions Z1, Z2 and / or optionally Z3 may also contain solvents.
  • compositions Z1, Z2 and / or optionally Z3 can then optionally be commercially available.
  • a ligand L, a Cu (I) salt and / or a host molecule W may then be dissolved in a suitable solvent, respectively, to obtain the respective composition.
  • the step (ii) applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T can be carried out in any desired manner.
  • the at least one Cu (I) salt and the at least one ligand L can be co-evaporated with one another in vacuo and sublimated on the surface.
  • Such a step may be that of Liu et al., Chem. Mater. 2014, 26 (7), 2368-2373 and Liu ei a /., J. Am. Chem. Soc. 201 1, 133, 3700-3703 or WO 2012/016074 described, with the difference that other complexes are formed in the context of the present invention and also ligand L can be used in excess.
  • the Cu (I) complexes can also be formed from the liquid phase.
  • step (ii) may then be spin coating, dropcasting, slot casting, curtain casting, a rolling process, or a printing process (eg, inkjet printing, gravure, or knife coating).
  • compositions Z1, Z2 and / or optionally Z3 may also contain a vaporizable organic solvent, such as a solvent selected from the group consisting of: Tetrahydrofuran, dioxane, chlorobenzene, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, gamma-butyrolactone, N-methylpyrollidinone, ethoxyethanol, xylene, toluene, anisole, phenetole, acetonitrile, tetrahydrothiophene, benzonitrile, pyridine, trihydrofuran, triarylamine and PGMEA (propylene glycol monoethyl ether acetate).
  • a solvent selected from the group consisting of: Tetrahydrofuran, dioxane, chlorobenzene, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, gamma-butyrolactone, N
  • liquid composition Z1, Z2 and / or optionally Z3 to be applied to the surface can also be admixed with agents for improving the flow properties.
  • agents for improving the flow properties are well known to those skilled in the art.
  • such an agent or component may be selected from the group consisting of: polyethyloxides (polyethylene glycols), polyethylenediamines, polyacrylates (eg polymethyl methacrylate (PMMA), polyacrylic acid and their salts (superabsorbents)), substituted or unsubstituted polystyrenes (eg polyhydroxystyrene), polyvinyl alcohols , Polyesters or polyurethanes, polyvinylcarbazoles, polytriaryamines, polythiophenes and
  • compositions in the liquid phase produce a wet phase containing a Cu (I) complex or the composition Z, which can then be dried and / or cured by means of customary processes known in the art.
  • compositions Z1, Z2 and optionally Z3 in the liquid phase By applying the compositions Z1, Z2 and optionally Z3 in the liquid phase to the surface of the component T, a wet film is formed in which Cu (I), in place of the Cu (I) contained in Z1, is present in situ (in situ). Salt and ligand (s) L of Z2 which form Cu (I) complexes which are emitter compounds E.
  • the Cu (I) complex formed from the one or more Cu (I) salt (s) and the one or more ligand (s) L may, in principle, take on any conceivable stoichiometry. It is preferably a complex having a stoichiometry selected from the group consisting of Cu (I) 2L 2 , Cu (I) 2 L 3 , Cu (I) Li, Cu (I) I L 2 , Cu (L) i L 3 , Cu (I) i L 4 , Cu (I) 2 Li and Cu (I) 2 L 4 .
  • L represents only the organochemical ligands L, the similar (homoleptic) or may be different (heteroleptic) ligands. Any inorganic ions are not included in the aforementioned stoichiometry.
  • a complex containing two Cu (I) eg, Cu (I) 2L 2 or Cu (I) 2L 3
  • the Cu (I) complex preferably has one of the following structures (a), (b) or (c):
  • X and X ' are each independently of one another a suitable anionic ligand, for example an anion selected from the group consisting of CI “ , Br “ , I “ , SCN “ , CN “ , RS “ , RSe “ , RR'N “ , RR'P “ and RC ⁇ C " are present,
  • a Ci-20-alkyl radical eg, methyl, ethyl, n-propyl, iso-propyl
  • a further step (iii) of drying and / or curing the coating S obtained by the application on the surface of the component T can follow the method described above.
  • This step (iii) can in principle be arbitrary.
  • the drying may optionally be carried out under reduced pressure and / or under elevated temperature.
  • the drying can be carried out at atmospheric pressure and 50 ° C.
  • the drying can be carried out at atmospheric pressure and a temperature of 50-60 ° C, in particular 60 ° C.
  • the curing may be accompanied by a polymerization, such as an acrylic resin, in which the compounds are embedded.
  • the ligand L can be chemically bound covalently or noncovalently with one or more host molecules, as described, for example, in WO 2013/007709 and WO 2013/007710.
  • a method is preferred in which the following steps are used to apply a light-emitting layer S on the surface of a component T:
  • the Cu (I) complex formed is one which can emit light in the visible spectrum of light (hence in the wavelength range of 350 to 950 nm, especially 400 to 800 nm) according to the singlet harvesting mechanism ,
  • the Cu (I) complex in the powder or film state has a photoluminescence quantum efficiency of at least 50%. More preferably, the Cu (I) complex in the powder or film state has a photoluminescence quantum efficiency of at least 60% or at least 70%.
  • the Cu (I) complex has a singlet-triplet energy splitting AE (S1-T1) of not more than 3000 cm -1 , preferably not more than 2500 cm -1, and more preferably not more than 2000 cm " 1 on.
  • AE (S1-T1) is even no more than 1500 cm "1, or not more than 1000 cm" 1.
  • uncomplexed Cu (I) or uncomplexed ligand L in the light-emitting layer S may allow so-called self-healing of such a layer.
  • a loss of Cu (I) from the Cu (I) complex can be counterbalanced by uncomplexed Cu (I).
  • compositions Z1 and Z2 are chosen such that an excess of at least 0.1 mol%, preferably at least 0.5 mol%, more preferably at least 1 mol%, in particular at least 5 mol% of Cu (L) is applied to ligand L on the surface of the component T.
  • an excess as used herein represents the corresponding excess of one component over the other component in the applied and obtained light-emitting layer S.
  • Cu (I) salts in particular of copper halides such as Cul, CuCl or CuBr, an excess of these can contribute to an increase in the conductivity.
  • compositions Z1 and Z2 are chosen such that an excess of at least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, in particular at least 20 mol% of ligand L to Cu (l) is applied to the surface of the component T.
  • a stoichiometry can be selected which achieves (almost) complete complexation of the Cu (I) and of the ligand (s) L, and thus (almost) no uncomplexed Cu (I) and (almost) no uncomplexed ligand L is present in the obtained light-emitting layer S.
  • the step (ii) of applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T may be carried out by any method.
  • co-evaporation followed by vacuum sublimation, spin coating, dropcasting, slot casting, curtain casting, rolling or printing processes e.g., inkjet printing
  • inkjet printing may be employed.
  • the step (ii) of applying the compositions Z1, Z2 and optionally Z3 to the surface of the component T is carried out by coevaporation in vacuo and subsequent sublimation from the gas phase or by spin coating in the liquid phase.
  • a light-emitting layer S is preferably an organochemical light-emitting layer S which consists predominantly of organic materials, ie of hydrocarbon compounds, where the hydrocarbon compounds may be substituted by heteroatoms such as nitrogen, phosphorus, oxygen and / or halogens. At least one of the hydrocarbon compounds represents a ligand L in the context of the invention.
  • the light-emitting layer S preferably contains a Cu (I) complex of Cu (I) and at least one ligand L, and at least one host compound W, and optionally non-complexed Cu (l) salt or ligands L.
  • the light-emitting layer S can also fluorescent polymers (eg Superyellow (SY)), photoluminescent nanoparticles (such as silicon), quantum dots, cadmium selenide and / or exciplexes ( Optional complexes diluted with host molecules ("hosts") If the uncomplexed Cu (I) salt or ligand L is present, the light-emitting layer S can, as described above, have very particularly positive properties exhibit.
  • the present invention also includes a light-emitting layer S containing:
  • Such a light-emitting layer S is preferably produced in accordance with the method according to the invention.
  • the light-emitting layer S may optionally additionally contain a dye F.
  • the light-emitting layer S additionally contains a dye F.
  • a dye F is not a Cu (I) complex according to the present invention.
  • the dye F can also be a fluorescent and / or phosphorescent dye F, which can shift the emission and / or absorption spectrum of the light-emitting layer S.
  • diphoton effects can also be used, therefore absorbing two photons with half the energy of the absorption maximum.
  • a fluorescent and / or phosphorescent dye F usually a bathochromic effect is achieved (for example by heat loss). However, a hypsochromic effect can also be achieved (for example by diphoton effects).
  • the light emitting layer S may contain an ionic liquid or a combination of two or more ionic liquids.
  • an ionic liquid or combination of two or more ionic liquids may be selected from the group consisting of:
  • Methyl imidazolium hexafluorophosphates eg 1-alkyl-3-methylimidazolium hexafluorophosphates such as, for example, 1-methyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-propyl-3-methylimide dzolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolinium hexafluorophosphate), dimethylimidazolium hexa-fluorophosphates (eg, 1-alkyl-2,3-dimethylimidazolium hexafluorophosphates such as 1-butyl-2,3 dimethyl imidazolium hexafluorophosphate), 3-methylimidazolium hexafluorophosphates (eg
  • the light-emitting layer S may contain one or more electrolytes, such as KCF3SO3.
  • the stoichiometry between Cu (I) and ligand (s) L in the light-emitting layer can be optionally chosen so that all the Cu (I) and the entire ligand L are complexed in Cu (I) complexes.
  • uncomplexed Cu (I) or non-complexed ligand L is present in the light-emitting layer S.
  • the presence of uncomplexed Cu (I) or uncomplexed ligand L in the light-emitting layer S may enable self-healing of such.
  • a loss of Cu (I) from the Cu (I) complex can be compensated by uncomplexed Cu (I).
  • the light-emitting layer S at least 0.1 mol%, preferably at least 0.5 mol%, more preferably at least 1 mol%, in particular at least 5 mol% of the total Cu (l) as non- complexed Cu (I).
  • At least 1 mol%, preferably at least 5 mol%, more preferably at least 10 mol%, in particular at least 20 mol% of the total ligand L is present in the light-emitting layer S as uncomplexed ligand L.
  • an opto-electronic device including a light-emitting layer S according to the present invention.
  • An optoelectronic device according to the invention is preferably an organochemical optoelectronic device in which the light emitting layer S consists at least predominantly of organic materials. These may consist of hydrocarbon compounds, wherein the hydrocarbon compounds may be substituted with heteroatoms such as nitrogen, phosphorus, oxygen and / or halogens.
  • the light-emitting layer S is to be understood in the broadest sense as described above. Therefore, the light-emitting layer S, as described above, a Cu (l) complex of at least one Cu (l) salt and at least one ligand L as the emitter compound E, and optionally one or more host molecules W.
  • the proportion of Cu (l ) Complex in the light-emitting layer S may be 0.1 to 100%. Accordingly, the light-emitting layer S may consist entirely or largely of the Cu (I) complex or else the Cu (I) complex only as a small or large proportion in addition to other compounds (such as one or more unbound salt (s) of the Cu ( l) and / or other metals, one or more unbound ligands L or one or more host molecules W).
  • the proportion of Cu (I) complex in the light-emitting layer S is preferably more than 30% by weight, more than 40% by weight, more than 50% by weight. %, more than 60 wt .-%, more than 70 wt .-%, more than 80 wt .-% or more than 90 wt .-%.
  • the opto-electronic device may be opaque, semi-transparent or (substantially) transparent.
  • the optoelectronic device can be any optoelectronic device that includes a light emitting layer S according to the invention.
  • the optoelectronic device is an organic light emitting diode (OLED), an organic laser, an organic solar cell (OSC) or an optical sensor.
  • the optoelectronic device is particularly preferably an organic light-emitting diode (OLED) or an organic solar cell (OSC).
  • An organic solar cell (OSC) may also be referred to as an organochemical photovoltaic device (OPV).
  • An optical sensor may, for example, be an optical sensor which measures the light intensity. Also, the optical sensor may optionally determine the light intensity of light of a particular wavelength range. An optical sensor may also be part of an array of optical sensors (hence an array), as used, for example, as an image sensor in a digital camera.
  • the optoelectronic device is an organic light emitting diode (OLED), a light emitting electrochemical cell (LEC), an organic solar cell (OSC) or an optical sensor
  • the optoelectronic device can optionally also be designed as a thin layer, the total not thicker than 5 mm, not thicker than 2 mm, not thicker than 1 mm, not thicker than 0.5 mm, not thicker than 0.25 mm, not thicker than 100 ⁇ or not thicker than 10 ⁇ .
  • the optoelectronic device may also have a thickness in the range of 8-9 ⁇ , 7-8 ⁇ , 6-7 [im, 5-6 [im, 4-5 [im, 3-4 [im, 2-3 im, 1 -2 [im or less than 1 [im.
  • either the anode layer A or the cathode layer C must be largely, preferably (almost) completely transparent to the light to be coupled out.
  • Anode layer A usually consists to a large part or (almost) completely of one or more (largely) transparent conductive oxides ("transparent conductive oxides", TCOs)
  • transparent conductive oxides TCOs
  • Such an anode layer A can be, for example, indium tin oxide, aluminum zinc Oxide, fluorine-tin oxide, indium-zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene.
  • the anode layer A can also be composed of one or more of the abovementioned materials, more preferably the anode consists of indium-tin-oxide (ITO) (usually (InO) o, 9 (SnO 2) o, i).
  • ITO indium-tin-oxide
  • the roughness of the transparent, conductive oxides used in the anode layer A can be compensated for by the use of an additional hole injection layer (HIL)
  • the hole injection layer can facilitate the injection of positive quasi charge carriers by preventing the transfer of the carrier from the transparent, Poly-3,4-ethylenedioxythiophene (PEDOT), polystyrene sulfonate (PSS), MoO 2 , V 2 O 5 or Cul, especially a mixture of PEDOT and PSS, can be used in the hole injection layer can also prevent the diffusion of metals from the anode layer A in the transition in the hole line layer.
  • PEDOT Poly-3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonate
  • MoO 2 , V 2 O 5 or Cul especially a mixture of PEDOT and PSS
  • a hole transport layer (HTL) is typically arranged, in which case any hole conductor can be used, for example electron-rich heteroaromatics such as triarylamines or carbazoles can be used as hole conductors Function and bridge the energy barrier to the light emitting layer S (emitter layer, English, "layer", EML, or "light emitting layer", LEL)
  • Hole conduction layer may also be referred to as an electron blocking layer (EBL)
  • the hole conductors have high triplet energies
  • the hole conduction layer as a hole conductor may be a star-shaped heterocycle such as tris (4-carbazoyl-9-ylphenyl) amine (TCTA).
  • the light-emitting layer S which in the context of the present invention contains at least one Cu (I) complex of at least one Cu (I) salt and at least one ligand L, is applied to the hole-conducting layer.
  • the light-emitting layer S can also consist of this Cu (I) complex.
  • the composition of a light-emitting layer S will be described in detail above.
  • an electron transport layer can be applied to the light-emitting layer S.
  • Any electron conductor can be used here, for example electron-deficient compounds such as benzimidazoles, pyridines, triazoles, oxadiazoles (for example 1, 3,
  • the electron conduction layer may be a star-shaped heterocycle as an electron conductor, such as 1,3,5-tri (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl (TPBi).
  • the electron transport layer can be used for energetic leveling between cathode layer C and light-emitting layer S.
  • a cathode layer C is applied, which may consist of a metal or a metal alloy, for example Al, Au, Ag , Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd and / or Mi shingles or alloys of two or more of these metals.
  • the cathode layer C may consist of largely optically nontransparent metals, such as Mg, Ca or Al.
  • the cathode layer C may also contain graphite and / or carbon nanotubes (CNTs)
  • the anode layer A should be as transparent as possible.
  • the cathode layer C may also consist largely of semitransparent materials such as nanoscale silver wires.
  • the cathode layer can be vapor-deposited, for example, in a high vacuum.
  • a thin protective layer may optionally be applied between the cathode layer C and the ETL.
  • This may for example contain lithium fluoride, cesium fluoride and / or silver and may optionally be applied by vapor deposition.
  • OLEDs can also be produced, for example, as illuminated foils, as luminous labels in smart packaging or as innovative design elements, and can also be used in cell recognition and analysis.
  • An OLED preferably comprises at least the following layers:
  • anode layer A preferably comprising indium tin oxide, indium zinc oxide, PbO, SnO, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and / or doped polythiophene; S) a light-emitting layer S according to the present invention.
  • a cathode layer C preferably comprising Al, Ca, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd and / or mixtures or alloys of two or more of these metals,
  • an anode layer A in particular one comprising indium tin oxide
  • ETL an electron conduction layer
  • a cathode layer C preferably comprising Al, Ca and / or Mg. preferably in the arrangement A) - HTL) - S) - ETL) - C), wherein the layers either directly adjoin or still one or more layer (s) may be therebetween.
  • the electrons migrate in operation from the cathode towards the anode, which provides the holes (hence positive quasi charge carriers).
  • the optoelectronic device according to the invention is an organic solar cell (OSC)
  • OSC organic solar cell
  • the device comprises the Cu (I) complex of Cu (I) and L according to the invention as constituent of an absorber layer on Cu (I) complex in the absorber layer is preferably between 30 and 100 wt .-%.
  • two electrodes are also provided for OSCs. Between these, the absorber layer is arranged, in which the Cu (I) complex described in the present application is used.
  • the above-described Cu (I) complex can emit light, therefore serving as emitter compound E.
  • the ⁇ distance between the first excited triplet state T1 and the singlet ground state SO and the first excited singlet state S1 and the singlet ground state SO can be varied so that it is possible to vary the wavelength of the emitted light.
  • Cu (I) complexes which have a mono- or bidentate ligand L, excellent results have been achieved in this regard.
  • the opto-electronic device is an OSC, it may be a single-layer or multi-layer OSC.
  • a single-layer OSC can have the following layers:
  • ITO indium tin oxide
  • a metal or a metal alloy such as Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W, Pd and / or mixtures or alloys of two or more of these metals, Carbon nanotubes (CNTs) and / or nanoscale silver wires, in particular Mg, Ca or Al,
  • the single-layer OSC is typically applied to one substrate (such as the first electrode layer) and protected on the other outside with a protective layer.
  • a multilayer OSC can be constructed in accordance with an OLED, wherein the layer S in the OSC is referred to as the absorber layer S, but otherwise the light-emitting layer S can correspond to an OLED and thus is also able to emit light under suitable conditions.
  • An optoelectronic device can also be used to emit light. Accordingly, another aspect of the invention includes a method of producing light of a particular wavelength, comprising the step of providing an opto-electronic device according to the present invention.
  • the wavelength of the emitted light can also be adjusted to short-wave emission, so that blue light is emitted.
  • the present invention also includes a method of producing blue, green, yellow, orange or red emission.
  • light in the range of 400-800 nm may be emitted, such as in the range of 400-500 nm, 450-550 nm, 500-600 nm, 550-650 nm, 600-700 nm, 650 -750 nm and / or 700-800 nm.
  • the opto-electronic device according to the present invention is an OSC
  • it can also be used, for example, as a roll-up solar cell (for mobile applications such as smartphones, laptops, tablets, etc.), as an architectural element (eg wall or roof cladding element) or as Component in the traffic engineering area (eg in the automotive, aircraft, train, and / or ship area) are used.
  • Such products, which contain the opto-electronic device according to the invention, are the subject of the present invention.
  • a further aspect of the invention relates to a process according to the present invention in which a Cu (I) complex is formed, which has a structure according to one of the following formulas A or A 'and in analogy to the complexes described above, in a light-emitting Layer S, can be used in an optoelectronic device and a method of generating light as described herein. Examples of corresponding complexes are also given in WO 2013/007707 (see, for example, Examples 1 -6 thereof). According to formulas A and A ', the complexes described herein can be used to form complexes which emit singlet harvesting mechanism (and TADF, thermally activated delayed fluorescence).
  • Formula A Formula A ', in which the L, L 'and Z-containing ligand ( ⁇ _ ⁇ ⁇ _') is a neutral, bidentate ligand bound to the Cu via non-ionic groups; in which the D, [B] n and N " comprehensive ligand (D A N ⁇ ) is bound via an anionic group to the Cu, wherein D is a radical having at least one substituent D * selected from the group consisting of a divalent carbene C * , N, O, P, S, As and Sb or consists of D * ,
  • R u and R u are each independently a radical of up to 40 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R ', - ⁇ ( ⁇ ) ⁇ , -COOH, -OR', -NR 'R' ', - SiR'R' R *, -GeR'R'R ' ", -SR', -SOR ', -SO 2 R' and other donor and acceptor groups, such as carboxylates and their esters and CF 3 groups, wherein R ', R * and R r are independently selected from the group consisting of H, OH, NH 2 , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci -2 o- alkyl, Ci -2 o- heteroalkyl, C 2-2 o alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-
  • At least one carbon atom is between N " and D *, wherein one or more substituents of D and / or N " with B may optionally form cyclic, aliphatic, conjugated, aromatic and / or fused systems;
  • T is CR W or nitrogen
  • R w is a radical selected from the group consisting of hydrogen, halogen, -R v , -OC (O) R v , -COOH, -OR v , -NR V R V , -SiR v R v R v " , -GeR v R v R v , -SR V , - SOR v , -SO2R v and other donor and acceptor groups, such as carboxylates and their esters and CF 3 groups, wherein R v , R v and R v are independently selected from the group consisting of H, OH, NH 2 , NHR V " , NHR V ' R V"" , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-2o-alkyl, Ci-20-heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substitute
  • R v and R v are independently selected from each other from the group consisting of OH, NH 2, halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C 5 - 2o-heteroaryl, C 7 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C 7- 32-Heteroalkylarylalkylrest wherein two or more of the radicals.
  • R v , R v , R v and R w may optionally also form one or more fused ring systems, where T may optionally form one or more ring systems with one or more B; where n is the integers from 1 to 9; each of L and L 'is independently a substituent attached to the Cu, wherein L contains a substituent L * and L' contains a substituent L ' * , wherein L * and L' * are independently selected from the group consisting of a divalent carbene C * , N, O, P, S, As and Sb and L * and L ' * each form a bond to the Cu, wherein L contains one or more, preferably three, substituents attached to L * and wherein L 'contains one or more, preferably three, substituents attached to L * ', those attached to L * and L ' * Substituents independently of one another are each a substituent having up to 40 carbon atoms, selected from the group consisting of a linear, branched
  • two or more Z L and L ' may connect to each other.
  • residue D of the D, [B] n and N ' ' comprising ligand (N "A D) of formula A or A ' is selected from the group consisting of (wherein the ligand has not more than 20 carbon atoms):
  • each R is independently selected from the group consisting of hydrogen, deuterium, halogen, -R -OR s s, -OC (O) -R s, -NR S R S, -SiR s R s R s ", -GeR s R s R s, - SR 8, -SOR and -SO 2 R s s may be connected wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, -R -OR s s, -OC (O) -R s, -NR S R S , -SiR s R s R s " , -Ge R s R s R s" , -SR 8 , -SOR s and -SO 2 R s s may be connected wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, -R -OR s s, -OC (O)
  • R 1 is a radical selected from the group consisting of hydrogen, deuterium, halogen, -R k , -OC (O) R k , -COOH, -OR k , -NR k R k , -SiR k R k R k " , - GeR k R k R k " , -SR k , -SOR k , -SO 2 R k and other donor and acceptor groups such as carboxylates and their esters and CF 3 - groups, wherein R k , R k and R k are independent of each other are selected from the group consisting of H, OH, NH 2 , NR s R s , NHR s , a halogen, a substituted or un
  • the carbene C * of the D, [B] n and N " comprising ligand (N " A D) of the formula A or A ' is part of a structure selected from the group consisting of:
  • the two dots ":" represent a divalent carbene which coordinates to the Cu atom and the structure is linked to one of the sites marked # with B, the other one selecting the other site indicated by #, then with a residue from the group consisting of hydrogen, halogen, -OR g, -O- C (O) -R g, -NR g R g, -SiR g R g R g ', -GeR g R g R g', -SR 9 , -SOR 9 and -SO 2 R 9 , wherein each R is independently selected from the group consisting of hydrogen, deuterium, halogen, -R 9 , -OR 9 , -OC (O) -R 9 , -NR 9 R 9 , -SiR 9 R 9 R 9 , - GeR 9 R 9 R 9 , -SR 9 , -SOR 9 and -SO 2 R 9 , wherein R g , R g and
  • R e , R e and R e are independently selected from the group consisting of H, OH, NH 2 , NR s R s , NHR s , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o alkenyl, Ci-io-heteroalkenyl and a substituted or unsubstituted C6-2o-aryl, C 5- 2o-heteroaryl, C 7- 32-arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C 7- 32-Heteroalkylarylalkylrest, the / R e, R e, R e and R f optionally may also result in fused ring systems, where z for the integers 1, 2, 3 o the 4 stands.
  • the ligand ⁇ _ ⁇ ⁇ _ 'of the formulas A and A' is a bidentate ligand of the form LG-L ', wherein G is a substituted or unsubstituted C 1-6 alkylene, C 2-8 alkenylene, C 2- s alkynylene or arylene group, -R d -NR d -, -NR d ' - R d -, -R d -NR d -R d -, -R d -SiR d " R d" -R d -, -R d -SiR d ' R d " -, -SiR d' R d" -, -R d -GeR d " R d" -R d -, -R d -GeR d " R d" -R d -, -R d -GeR d
  • the fragment X b or an unsaturated or aromatic N-heterocyclic unit having 4 to 8 ring atoms which is selected from the group consisting of pyridyl, pyrimidyl, pyridazyl, pyrazyl, pyranyl, cumaryl, pteridyl, thiophenyl, benzothiophenyl, Furyl, benzofuryl,
  • fragment X b is selected from the group consisting of:
  • R az is a radical selected from the group consisting of hydrogen, halogen, -R ay , -OC (O) R ay , -COOH, ay -OR, -NR R ay ay ', - SiR R ay ay' R ay ", -GeR R ay ay 'R ay", -SR ay, ay -SOR, -SO 2 R ay and other donor and acceptor groups such as carboxylates and their esters and CF 3 groups, wherein R ay , R ay and R ay "are independently selected from the group consisting of H, OH, NH 2 , NR s R s , NHR s ,
  • the two dots ":" represent a divalent carbene which coordinates to the Cu atom and the structure is linked to one of the sites marked # with B, the other one selecting the other site indicated by # with a residue from the group consisting of hydrogen, halogen, -OR g, -OC (O) -R g, -NR g R g, -SiR g R g R g ', -GeR g R g R g', -SR 9, - SOR 9 and -SO 2 R 9 may be substituted, wherein the radicals R, R 9 , R 9 , R 9 and Y and z are as defined above.
  • a further aspect of the invention relates to a process according to the present invention in which a Cu (I) complex is formed, which has a structure according to the following formula B and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein.
  • a Cu (I) complex is formed, which has a structure according to the following formula B and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein.
  • Examples of such complexes are also shown in WO 2013/007707 (Formulas I and A thereof) and in WO 2010/031485 (see, for example, Formulas II, IV and VI-IX thereof).
  • Formula B in which the L, L 'and Z-containing ligand (L A U) is a neutral, bidentate ligand bonded to the Cu via non-ionic groups; in which the ligand ( ⁇ ⁇ ⁇ ) comprising the ring systems A and A 'and the bridging ligand Z' can optionally be bonded to the Cu via an anionic group, the ligand ⁇ ⁇ ⁇ then neutralizing the positive charge of the Cu (I) can; wherein the ring systems A and A 'have one of the following structures:
  • R a and R a are each independently a radical having up to 20 carbon atoms, independently of one another selected from the group consisting of hydrogen, halogen, -R c , -OC (O) R c , -COOH, -OR c , -NR C R C , -SiR c R c
  • R ub " and R ub" are each independently a radical of up to 40 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R r , -OC (O) R r , -COOH, -OR r , -NR * 'R' "'- SiR' 'R'
  • Me is a methyl radical and Ph ür a phenyl radical.
  • a further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula C and in analogy to the complexes described above, in a light-emitting layer S, in an opto-electronic Apparatus and a method for generating light as described herein can be used.
  • a metal (I) complex is formed, which has a structure according to the following formula C and in analogy to the complexes described above, in a light-emitting layer S, in an opto-electronic Apparatus and a method for generating light as described herein can be used.
  • Examples of such complexes are also shown in WO 2014/102079 (see, for example, Formulas A and I-IX thereof).
  • a spacer unit S for example a Ci-io-alkylene group
  • an improvement in the solubility of the metal complex can be achieved by at least one of the ligands EnD and E'nD 'carries a corresponding substituent.
  • a further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula D and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in European Patent Application No. EP14164815.
  • R 1 and R 2 each independently represent a group selected from the group consisting of alkyl, aryl, heteroaryl, -OR 3 , -SR 3 , -SeR 3 , -H and -D each having up to 20 carbon atoms wherein R 3 is an alkyl, aryl, heteroaryl, each having up to 20 carbon atoms, -H or -D; and wherein at least one of the radicals R-R '''and / or G1 and / or G1 is substituted by at least one non-complexed ionic group, preferably with an ammonium group, a carboxyl group, a sulfonate group, a phosphonate group, in particular substituted with -SO 3 ' is.
  • the ring systems G1 and G2 are each preferably a five- or six-membered heteroaromatic ring system which is optionally substituted by further radicals such as R, R '; R ", R '", R a and / or R a may be substituted or fused with other aromatic rings.
  • a further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula E and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein. Examples of such complexes are also shown in WO 2013/014066 (see, for example, Formula IV thereof).
  • M and M ' are independently selected from the group consisting of Cu, Ag and Au, especially both Cu; wherein X and X 'are independently selected from the group consisting of Cl, Br, I, CN, OCN, SCN, Ci.io-alkynyl and azide.
  • the two bidentate ligands EnD and E'nD ' can also be linked to one another via a spacer unit S (for example a Ci-io-alkylene group), resulting in a tetradentate ligand.
  • a spacer unit S for example a Ci-io-alkylene group
  • an improvement in the solubility of the metal complex can be achieved by at least one of the ligands EnD and E'nD 'carries a corresponding substituent.
  • a further aspect of the invention relates to a process according to the present invention in which a metal (I) complex is formed, which has a structure according to the following formula F and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein.
  • a metal (I) complex is formed, which has a structure according to the following formula F and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein.
  • Examples of such complexes are also shown in WO 2013/017675 (see, for example, Formula A thereof).
  • Formula F wherein X and X 'each independently are selected from the group consisting of Cl, Br, I, CN, OCN, SCN, Ci-i0 alkynyl, and azide; where Z and Z 'independently represent a covalent bridge comprising at least two carbon and / or nitrogen atoms, where P is phosphorus and N is nitrogen; in which the ligand (PnN) comprising P, Z and N and the ligand ( ⁇ 'comprising P, Z' and N) is in each case an N-heterocycle-substituted phosphine ligand which has a structure according to formula G:
  • E is a carbon or nitrogen atom
  • E ' is a carbon or nitrogen atom which is not bonded to a hydrogen atom
  • R is an optionally substituted, optionally branched Ci-20-alkyl radical, preferably a C6-2o-alkyl radical or an optionally alkylated C6-2o-aryl radical, in particular phenyl, wherein a substitution in this case is a substitution with a or more halogens (eg, F, Cl, Br, and / or I), silane groups, ether groups, or optionally in turn substituted alkyl, alkenyl, and / or alkynyl groups; in which R 'and R "are independently selected from the group consisting of alkyl groups, preferably C6-2o-alkyl groups, which may also be branched or cyclic, or
  • Aryl or heteroaryl groups which may be optionally substituted with alkyl groups, halogens (eg, F, Cl, Br and / or I), silane groups or ether groups, wherein R 'and R "are each directly bonded to the phosphorus atom of the phosphane ligand in which R '"is selected from the group consisting of alkyl groups, preferably C6-2o-alkyl groups, which may also be branched or cyclic, or aryl or heteroaryl groups which are optionally substituted by alkyl groups, Halogens (eg, F, Cl, Br and / or I), silane groups or ether groups may be substituted,
  • R '"with Z can also form a ring system, therefore an aliphatic or aromatic heterocycle, wherein Z, Z' and Z x are each independently selected from the group consisting of a substituted or unsubstituted C 1-6 -alkylene, 2- C 8 alkenylene, C 2- 8 alkynylene, or arylene, -R a -NR a '-, -NR a' -R a -, -R a -NR a "-R a -, -R a -SiR a " R a" R a -, -R a -SiR a ' R a' -, -SiR a " R a" - R a -, -R a -OR a -, -R a -CO -R a -, -R a -CO- OR a -, -R a -O-CO-OR
  • R a and R a are independently each are each a radical having up to 20 carbon atoms, independently of one another selected from the group consisting of hydrogen, deuterium, halogen, -R c , -OC (O) R c , -COOH, -OR c , - NR C R C , -SiR c R c R c " -SR
  • a further aspect of the invention relates to a process according to the present invention in which a Cu (I) complex is formed, which has a structure according to the following formula H and in analogy to the complexes described above, in a light-emitting layer S, in an optoelectronic device and a method of generating light as described herein.
  • Examples of such complexes are also shown in WO 2013/072508 (see, for example, Formula A thereof), WO 2010/149748 (see, for example, Formula A thereof), and WO 2013/001086 (see, for example, Formula A thereof).
  • R c , R c and R c are independently selected from the group consisting of H, OH, NH 2 , NHR a , NR a " R a"' , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20 alkyl, Ci-2O heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C 5- 2o-heteroaryl, C 7- 32 arylalkyl, C6-3i-heteroarylalkyl, Ce-33 AI ky I a ry I a I ky I residue and a C 7- 32-Heteroalkylarylalkylrest,
  • radicals R c , R c ' , R c " , R d , R d' , R d" and R d " can optionally also lead to fused ring systems, where L and L 'are also bonded together and as in formula A above or as defined below according to formula K, in which the N * , Z and E-comprising ligand (EnN * ) may be a bidentate ligand according to the structure of formula K:
  • Y ' is a carbon or nitrogen atom substituted with a hydrogen atom
  • E * is selected from the group consisting of P, N, As, Sb, a divalent carbene C * , O and S; wherein the dotted bond is a single or double bond; wherein N represents a nitrogen atom incorporated in an imine group, the
  • heteroaromatic group comprising N, Y, Y ' and Z x
  • the heteroaromatic group is preferably selected from the group consisting of pyridyl, pyrimidyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, which may be optionally substituted (for example with one or more of the substituents of the above-mentioned group) and / or may be fused to other groups of the complex in which R u and R v are independently selected from the group consisting of alkyl groups, preferably C 6-2o-alkyl Groups which may also be branched or cyclic, or aryl or heteroaryl groups, which may be optionally substituted with alkyl groups, halogens (eg, F, Cl, Br and / or I), silane or ether groups; are each selected independently from one another in the x Z and Z is selected from the group consisting of
  • substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl radicals, linear, branched or cyclic heteroalkyl radicals, Aryl radicals, heteroaryl radicals, linear, branched or cyclic alkenyl radicals, linear, branched or cyclic alkynyl radicals and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF 3 groups may be substituted, wherein the substituents with each other optional form a cyclized and / or fused structure, wherein R a and R a are each independently a radical having up to 20 carbon atoms, independently selected from the group consisting of hydrogen, deuterium, halogen, -R c , -OC (O ) R c , -COOH, -OR c , - NR C R C , -SiR c R
  • heteroaromatic group is preferably selected from the group consisting of pyridyl, pyrimidyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, which may be optionally substituted (for example with one or more of the substituents of the aforementioned group) and / or with other groups of the complex can be fused
  • the ligands L and L 'according to formula H are monodentate ligands having up to 42 carbon atoms.
  • FIG. 2 represents the excitation and emission spectrum of the metal complex MK2 (solid line) and the emission spectrum of the metal complex MK1 (dashed line).
  • compositions Z1 and Z2 to a surface of a component T is exemplified by the formation of a Cu (I) complex of copper iodide (Cul) as the salt of the metal M and 4-methyl-2- (diphenylphosphino) pyridine (MePyrPHOS) shown as ligand L1.
  • a Cu (I) complex of copper iodide (Cul) as the salt of the metal M
  • MePyrPHOS 4-methyl-2- (diphenylphosphino) pyridine
  • Ligand L1 metal complex MK1 The synthesis of ligand L1 is analogous to WO 2013/007710. Furthermore, the synthetic route can also be taken from WO 2013/072508 and WO 2013/007709.
  • the emission spectrum of a light-emitting layer S which consisted of a metal complex MK1 thus produced on the surface in situ, was compared with that from a metal complex synthesized and purified by bulk synthesis (classical synthesis in the reaction vessel in solution) MK1 passed (Fig. 1). It showed almost identical spectra, which shows that the metal complexes MK1 were made similar. After three days of standing at room temperature, there was no visual change.
  • Ligand L4 (ligand L5) (ligand L6) (ligand L7) (ligand L7)
  • Table 3 shows the emission characteristics of the obtained films.
  • the aim of the optimization was to shift the emission color to blue, which is why mainly electron-rich pyridines were used. Due to the expected higher quantum efficiency, bromide was chosen as the counterion.
  • amine-containing substituents are not a favorable tool for manipulating the emission color: the oxidation sensitivity of the dissolved complexes is markedly higher than for amine-free complexes.
  • the solutions degraded within minutes after combining copper salt with the ligands, resulting in dark green discoloration was observed with the naked eye. The decomposition was probably due to oxidation with atmospheric oxygen.
  • the electron-rich pyridines destabilize by coordination via the amine nitrogen Cu (I) and favor the oxidation to Cu (II) (HSAB concept).
  • Cu (I) complex formed by the process which has one of the following structures (I) to (VII):
  • X is selected from the group consisting of halide (preferably I, Br or Cl), CN, SCN, OCN, SPh and an acetylide (preferably a phenylacetylide), especially where X is a halide; where the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a radical having up to 40 carbon atoms, preferably those independently selected from the group consisting of -R r , -OC (O) R r , -COOH, -OR r , -NR ⁇ 'R' "'- SiR' R ,,, r" R t, -GeR ' "R r” R t -SR "', -SOR r,
  • each E represents N, P, As or Sb; and wherein Z is any divalent group, preferably a selected those from the group consisting of -R ub - -R ub -NR ub -, -NR ub "-R ub -, -R ub -NR ub -R ub -, - R ub -SiR ub " R ub"' R ub' -, R ub -SiR ub " R ub”' -, -SiR ub " R ub” - R ub -, R ub -GeR ub " R ub "'-R ub' -, -R ub - GeR ub” R ub '-, -GeR ub "
  • R ub and R ub are each independently a radical of up to 40 carbon atoms selected from the group consisting of a linear, branched or cyclic alkylene radical, a linear, branched or cyclic heteroalkylene radical, an arylene radical, a heteroarylene radical, a linear, branched one or cyclic alkenylene radical and a linear, branched or cyclic alkynylene radical,
  • substituents selected from the group consisting of halogens, deuterium, linear, branched or cyclic alkyl, linear, branched or cyclic heteroalkyl, aryl, heteroaryl, linear, branched or cyclic alkenyl, linear, branched or cyclic alkynyl and other donor and acceptor groups such as amines, phosphines, carboxylates and their esters and CF 3 groups, may be substituted, wherein the substituents may optionally form together a cyclized and / or fused structure, wherein R ub " and R ub" are each independently a radical having up to 40 carbon atoms, independently selected from the group consisting of hydrogen, halogen, -R r, -OC (O) R r, -COOH, -OR r, -NR * 'R' "'- SiR' '' FF 'R', -GeFfFff
  • R r , R r and R * are independently selected from the group consisting of H, OH, NH 2 , a halogen, a substituted or unsubstituted, linear, branched or cyclic Ci-20-alkyl, Ci-2o heteroalkyl, C2-2o-alkenyl, Ci-io-Heteroalkenylrest and a substituted or unsubstituted C6-2o-aryl, C 5- 2o-heteroaryl, C 7 32 arylalkyl, C6-3i-heteroarylalkyl, Cs-33-Alkylarylalkylrest and a C 7- 32-Heteroalkylarylalkylrest.
  • CuCI, CuBr, CuI, CuCN, CuSCN, CuOCN, CuBH 4 , CuSPh and Cu-C ⁇ C-Ph are particularly preferably used as copper salts.
  • radicals in one of the structures of the formulas (I) to (VII) are defined as follows: R 1 "6 : in each case H or a Ci-io-alkyl;
  • R 7 and R 8 are each an aryl radical, in particular phenyl
  • R 9 and R 10 are each an alkyl radical, especially a methyl radical, or together with the N or E to which they are attached, forming a ring system such as a piperidyl, piperidyl or morpholinyl ring;
  • R 11 and R 12 are each phenyl
  • R 13 and R 14 are each an alkyl radical, in particular a methyl radical, or together with the N or E to which they are attached, a ring system such as a piperidyl, piperidyl or
  • R 15 "18 in each case an aryl radical, in particular phenyl;
  • halide in particular I, Br or Cl
  • ligands L selected from:
  • ligands L selected from:
  • a ligand L of the following formula can be used:
  • a ligand L of the following formula can be used:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un procédé pour appliquer une couche électroluminescente S sur la surface d'un composant T, consistant à appliquer une composition Z1 contenant au moins un sel de Cu(I) et une composition Z2 contenant au moins un ligand non complexé L qui peut réagir avec le Cu(I) en formant un complexe, sur la surface du composant T, ce qui donne lieu à la formation d'un complexe Cu(I) pouvant émettre de la lumière dans la gamme visible du spectre électromagnétique à température ambiante à partir de l'état de singulet excité, selon le mécanisme de récolte de singulets. L'invention concerne également une couche électroluminescente S comprenant le complexe Cu(I) en tant que composé émetteur E et soit du Cu(I) non complexé soit un ligand non complexé L.
PCT/EP2015/070344 2014-09-08 2015-09-07 Couche optiquement active améliorée et procédé pour la réaliser WO2016037964A1 (fr)

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CN108997382A (zh) * 2018-06-29 2018-12-14 湖北大学 含有二甲基噻吩双齿膦配体的卤化亚铜配合物及其合成方法和应用

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN108997382A (zh) * 2018-06-29 2018-12-14 湖北大学 含有二甲基噻吩双齿膦配体的卤化亚铜配合物及其合成方法和应用
CN108997382B (zh) * 2018-06-29 2020-09-29 湖北大学 含有二甲基噻吩双齿膦配体的卤化亚铜配合物及其合成方法和应用

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