JP7247231B2 - Formulation of organic functional material - Google Patents

Description

The present invention relates to formulations containing at least one organic functional material and at least first and second organic solvents, wherein said first organic solvent is an adamantane derivative; , to electroluminescent devices prepared by using these formulations.
BACKGROUND OF THE INVENTION Organic light emitting devices (OLEDs) have long been made by vacuum deposition processes.
Other techniques, such as inkjet printing, have recently been extensively investigated because of their advantages, such as potential cost reduction and scalability. One of the main challenges in multilayer printing is to identify the relevant parameters for obtaining uniform ink deposition on the substrate. Some additives can be added to the formulation to induce such parameters, such as surface tension, viscosity, or boiling point.
SUMMARY OF THE INVENTION A number of solvents have been proposed in organic electronic devices for inkjet printing. However, the number of important parameters that play a role during the deposition and drying process makes solvent selection very difficult. Therefore, there is still a need for improvement in formulations containing organic semiconductors used for deposition by inkjet printing. One object of the present invention is to provide formulations of organic semiconductors that allow controlled deposition to form organic semiconductor layers with good layer properties and efficiency performance. A further object of the present invention is a formulation of an organic semiconductor that enables uniform application of ink droplets on a substrate, for example when used in ink jet printing methods, thereby resulting in good layer properties and efficiency performance. is to provide
Solution to Problem The above object of the present invention is a formulation comprising at least one organic functional material and at least first and second organic solvents, wherein said first organic solvent is an adamantane derivative. One solution is to provide a formulation.
Effect of the Invention The inventors have surprisingly found that the use of an adamantane derivative organic solvent as the first solvent enables complete control of surface tension and induces effective ink deposition, resulting in good It has been discovered to form organic layers of uniform and well-defined functional materials with layer properties and performance.

FIG. 1 shows a substrate, an ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a green emitting layer (G-EML), a hole blocking layer (HBL), an electron transport layer (ETL) and Al. A typical layer structure of a device containing a cathode is shown. 2 shows the film profile of Comparative Example 1. FIG. 3 shows the film profile of Example 1. FIG. 4 shows the film profile of Example 2. FIG. 5 shows the film profile of Example 3. FIG. FIG. 6 shows the film profile of Example 4. 7 shows the film profile of Example 5. FIG. 8 shows the film profile of Example 6. FIG. 9 shows the film profile of Example 9. FIG. 10 shows the film profile of Example 10. FIG. DESCRIPTION OF THE EMBODIMENTS The present invention relates to formulations containing at least one organic functional material and at least first and second organic solvents, wherein said first organic solvent is an adamantane derivative. . Preferred Embodiment In a first preferred embodiment, the first organic solvent is represented by general formula (I)

(In the formula,
X is either CR or N, preferably CR;
R is the same or different at each occurrence, H, D, F, CN, NO ₂ , N(R ¹ ) ₂ , Si(R ¹ ) ₃ , straight chain having 1-20 carbon atoms Alkyl, alkoxy or thioalkoxy groups, branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, straight chain alkenyl or alkynyl groups having 2 to 20 carbon atoms or 3 to 20 A branched or cyclic alkenyl or alkynyl group having carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ¹ -, -CONR ¹ -, -S ( O) optionally replaced by ₂ -O-, -Si(R ¹ ) ₂ -, -CO-O-, -C=O-, -CR ¹ =CR ¹ - or -C≡C-, 1 one or more hydrogen atoms may be replaced by D, F, CN or NO ₂ ), or an aryl or heteroaryl group having 5 to 60 ring atoms, or having 5 to 40 ring atoms an aryloxy or heteroaryloxy group, or an arylalkyl or heteroarylalkyl group having 5 to 40 ring atoms, which are optionally substituted by one or more non-aromatic R ¹ radicals; Two substituents R on the same ring together form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system optionally substituted by multiple substituents R ¹ may;
R ¹ is the same or different in each case and is a linear alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms (here and one or more non-adjacent _CH2 groups are replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- one or more hydrogen atoms may be replaced by F), or having 4 to 14 carbon atoms and substituted by one or more non-aromatic R ¹ radicals good aryl or heteroaryl groups)
is an adamantane derivative by

In a first more preferred aspect, the first organic solvent is represented by general formula (I)
(In the formula,
X is CR;
R and ^R1 are as defined above)
is an adamantane derivative by

In a second more preferred aspect, the first organic solvent is represented by general formula (I)
(In the formula,
X is N;
R and ^R1 are as defined above)
is an adamantane derivative by

In a first most preferred embodiment, the first organic solvent is represented by general formula (II)

(In the formula,
R and ^R1 are as defined above)
is an adamantane derivative by

Preferably, in general formula (II):
R is the same or different at each occurrence, H, D, F, CN, NO ₂ , N(R ¹ ) ₂ , Si(R ¹ ) ₃ , straight chain having 1-20 carbon atoms Alkyl, alkoxy or thioalkoxy groups, branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, straight chain alkenyl or alkynyl groups having 2 to 20 carbon atoms or 3 to 20 A branched or cyclic alkenyl or alkynyl group having carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ¹ -, -CONR ¹ -, -S ( O) optionally replaced by ₂ -O-, -Si(R ¹ ) ₂ -, -CO-O-, -C=O-, -CR ¹ =CR ¹ - or -C≡C-, 1 one or more hydrogen atoms may be replaced by D, F, CN or NO ₂ ),
R ¹ is the same or different in each case and is a linear alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms (here and one or more non-adjacent _CH2 groups are replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F).

Examples of preferred adamantane derivatives and their boiling points (BP) are shown in Table 1 below.

Preferably, the first organic solvent has a surface tension of 20 mN/m or more. More preferably, the surface tension of the first organic solvent is in the range of 25-40 mN/m, most preferably in the range of 28-37.5 mN/m.

The content of the first organic solvent is preferably in the range of 0.1-30% by weight, more preferably in the range of 0.5-25% by weight, most preferably 1% by weight, based on the total amount of solvents in the formulation. ~20% by weight.

As a result, the content of the second organic solvent is preferably in the range of 70-99.9% by weight, more preferably in the range of 75-99.5% by weight, based on the total amount of solvents in the formulation, It is preferably in the range of 80 to 99% by weight.

Preferably, the first organic solvent has a boiling point in the range 100-400°C, more preferably in the range 150-350°C.

The formulation according to the invention in one preferred embodiment comprises at least a second organic solvent different from the first organic solvent. A second organic solvent is used with the first organic solvent.

In one aspect, the second organic solvent can be an adamantane derivative that is different from the first organic solvent. However, preferably the second organic solvent is not an adamantane derivative.

Suitable second organic solvents are preferably inter alia alcohols, aldehydes, ketones, ethers, esters, amides such as di-C _1-2 -alkylformamides, sulfur compounds, nitro compounds, hydrocarbons, halogenated hydrocarbons (eg , chlorinated hydrocarbons), aromatic or heteroaromatic hydrocarbons, and halogenated aromatic or heteroaromatic hydrocarbons.

Preferably, the second organic solvent is selected from the following group: substituted and unsubstituted aromatic or linear esters such as ethyl benzoate, butyl benzoate; substituted and unsubstituted aromatic or linear ethers such as 3-phenoxytoluene or anisole; substituted or unsubstituted arene derivatives such as xylene; indane derivatives such as hexamethylindane; substituted and unsubstituted aromatic or linear ketones; substituted and unsubstituted heterocyclic compounds such as pyrrolidinone, pyridine, pyrazine; and one of other fluorinated or chlorinated aromatic hydrocarbons.

Particularly preferred second organic solvents are, for example, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,3-trimethylbenzene, 1,2,4,5 -tetramethylbenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, 1,2-dihydronaphthalene, 1,2-dimethylnaphthalene, 1,3-benzodioxolane, 1,3-diisopropylbenzene , 1,3-dimethylnaphthalene, 1,4-benzodioxane, 1,4-diisopropylbenzene, 1,4-dimethylnaphthalene, 1,5-dimethyltetralin, 1-benzothiophene, thianaphthalene, 1-bromonaphthalene, 1 -chloromethylnaphthalene, 1-ethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 1-methylindole, 2,3-benzofuran, 2,3-dihydrobenzofuran, 2,3-dimethylanisole, 2,4-dimethyl Anisole, 2,5-dimethylanisole, 2,6-dimethylanisole, 2,6-dimethylnaphthalene, 2-bromo-3-bromomethylnaphthalene, 2-bromomethylnaphthalene, 2-bromonaphthalene, 2-ethoxynaphthalene, 2 -ethylnaphthalene, 2-isopropylanisole, 2-methylanisole, 2-methylindole, 3,4-dimethylanisole, 3,5-dimethylanisole, 3-bromoquinoline, 3-methylanisole, 4-methylanisole, 5- Decanolide, 5-methoxyindane, 5-methoxyindole, 5-tert-butyl-m-xylene, 6-methylquinoline, 8-methylquinoline, acetophenone, anisole, benzonitrile, benzothiazole, benzyl acetate, bromobenzene, butyl Benzoate, butylphenyl ether, cyclohexylbenzene, decahydronaphthol, dimethoxytoluene, 3-phenoxytoluene, diphenyl ether, propiophenone, ethylbenzene, ethylbenzoate, hexylbenzene, indane, hexamethylindane, indene, isochroman, cumene, m - cymene, mesitylene, methylbenzoate, o-, m-, p-xylene, propylbenzoate, propylbenzene, o-dichlorobenzene, pentylbenzene, phenetole, ethoxybenzene, phenylacetate, p-cymene, propiophenone , sec-butylbenzene, t-butylben Zen, thiophene, toluene, veratrol, monochlorobenzene, o-dichlorobenzene, pyridine, pyrazine, pyrimidine, pyrrolidinone, morpholine, dimethylacetamide, dimethylsulfoxide, decalin, and/or mixtures of these compounds.

These solvents can be used individually or as a mixture of two, three, or more solvents to form the second solvent.

Preferably, the second organic solvent has a boiling point in the range 100-400°C, more preferably in the range 150-350°C.

The at least one organic functional material preferably has a solubility in the range of 1-250 g/l, more preferably in the range of 1-50 g/l, in the first and second organic solvents.

The content of at least one organic functional material in the formulation is in the range of 0.001-20% by weight, preferably in the range of 0.01-10% by weight, more preferably in the range of 0.01-10% by weight, based on the total weight of the formulation. It is in the range of 0.1-5% by weight, most preferably in the range of 0.3-5% by weight.

The formulations according to the invention preferably have a surface tension in the range 10-50 mN/m, more preferably in the range 25-40 mN/m.

Furthermore, the formulations according to the invention preferably have a viscosity in the range 1 to 50 mPa.s, more preferably in the range 2 to 40 mPa.s, most preferably in the range 2 to 20 mPa.s.

Preferably, the organic solvent blend has a surface tension in the range of 15-80 mN/m, more preferably in the range of 20-60 mN/m, most preferably in the range of 25-40 mN/m. Surface tension can be measured at 20° C. using an FTA (First Ten Angstrom) 1000 contact angle goniometer. Details of the method can be found in Roger P.; Woodward, Ph.D. D. Available from First Ten Angstrom as published by "Surface Tension Measurements Using the Drop Shape Method". Preferably, surface tension can be determined using the pendant drop method. This measurement technique dispenses droplets from a needle in the bulk liquid or gas phase. The droplet shape is derived from the relationship between surface tension, gravity, and density difference. Using the pendant drop method, http://www. kruss. Surface tension is calculated from shadow images of pendant drops using de/services/education-theory/glossary/drop-shape-analysis. All surface tension measurements were performed using a commonly used and commercially available high-precision drop shape analysis tool, First Ten Angstrom's FTA1000. Surface tension is determined by the software FTA1000. All measurements were performed at room temperature, which ranged from 20°C to 22°C. A standard operating procedure involves determination of the surface tension of each formulation using a new disposable drop dispensing system (syringe and needle). Each drop is measured over a duration of 1 minute with 60 measurements averaged afterwards. Three drops are measured for each formulation. The final value is the average of the measurements. Tools are regularly cross-checked against various liquids with known surface tensions.

The viscosities of formulations and solvents were measured using a TA instruments ARG2 rheometer over a shear rate range of 10-1000 s ⁻¹ using a 40 mm parallel plate configuration. Measurements were used as averages from 200 to 800 s ⁻¹ where temperature and shear rate were precisely controlled. Each solvent is measured in triplicate. The stated viscosity values are the average of the above measurements.

The formulations according to the invention contain at least one organic functional material that can be used for the production of functional layers of electronic devices. Functional materials are generally organic materials that are introduced between the anode and cathode of electronic devices.

The term organic functional material means, inter alia, organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light absorbing compounds, organic photosensitive compounds, organic photosensitizers, and other organic photoactive compounds. do. The term organic functional material further includes organometallic complexes of transition metals, rare earths, lanthanides and actinides.

Organic functional materials include fluorescent emitters, phosphorescent emitters, host materials, matrix materials, exciton blocking materials, electron transport materials, electron injection materials, hole transport materials, hole injection materials, n dopants, p dopants, wide It is selected from the group consisting of bandgap materials, electron blocking materials, and hole blocking materials.

Preferred aspects of organic functional materials are disclosed in detail in WO2011/076314A1, which document is hereby incorporated by reference into the present application.

In preferred embodiments, the organic functional material is an organic semiconductor selected from the group consisting of hole-injecting, hole-transporting, luminescent, electron-transporting and electron-injecting materials.

More preferably, the organic functional material is an organic semiconductor selected from the group consisting of hole-injecting and hole-transporting materials.

The organic functional material can be a compound, polymer, oligomer or dendrimer having a low molecular weight, where the organic functional material can also be in the form of a mixture. Thus, formulations according to the invention may comprise two different compounds with low molecular weight, one compound and one polymer with low molecular weight, or two polymers (blends).

Organic functional materials are often described by the properties of frontier orbitals, which are described in more detail below. Molecular orbitals, especially the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), their energy levels and the energy of the lowest triplet state _T1 or lowest excited singlet state _S1 of a material are determined by quantum chemistry Determined by calculation. To calculate the metal-free organic material, first a geometry optimization is performed using the "ground state/semi-empirical/default spin/AM1/zero charge/spin singlet" method. An energy calculation is then performed based on the optimized structure. The 'TD-SCF/DFT/default spin/B3PW91' method with the '6-31G(d)' basis set (zero charge, spin singlet) is used here. For metal-containing compounds, the structure is optimized by the "ground state/Hartley Fock/default spin/LanL2MB/zero charge/spin singlet" method. Energy calculations are performed in the same manner as for organic substances described above, but for metal atoms the 'LanL2DZ' basis set is used and for ligands the '6-31G(d)' basis set is used. There is a difference that Energy calculations yield the HOMO energy level HEh or the LUMO energy level LEh in Hartree units. The HOMO and LUMO energy levels in electron volts, calibrated with reference to cyclic voltammetry measurements, are then determined as follows:
HOMO (eV) = ((HEh ^* 27.212)-0.9899)/1.1206
LUMO (eV) = ((LEh ^* 27.212)-2.0041)/1.385
For the purposes of this application, we will consider these values to be the HOMO and LUMO energy levels of the material, respectively.

The lowest triplet state _T1 is defined as the energy of the triplet state with the lowest energy resulting from the described quantum chemical calculations.

The lowest excited singlet state _S1 is defined as the energy of the excited singlet state with the lowest energy resulting from the described quantum chemical calculations.

The method described here is independent of the software package used and always gives the same result. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

Compounds with hole-injecting properties, also referred to herein as hole-injecting materials, simplify or facilitate the movement of holes, ie positive charges, from the anode to the organic layer. A hole-injecting material has a HOMO level that is above the region of the anode level, ie, typically at least −5.3 eV.

A compound with hole-transporting properties, also referred to herein as a hole-transporting material, is generally capable of transporting holes, ie positive charges, injected from the anode or an adjacent layer, such as a hole-injecting layer. Hole-transporting materials generally have a high HOMO level, preferably at least -5.4 eV. Depending on the structure of the electronic device, it may also be possible to use the hole-transporting material as the hole-injecting material.

Preferred compounds with hole-injecting and/or hole-transporting properties include, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, triarylphosphines, phenothiazines, phenoxazines, dihydrophenazines, thianthrene, dibenzo-para - dioxin, phenoxathiin, carbazole, azulene, thiophene, pyrrole and furan derivatives, further O, S or N containing heterocyclic compounds with high HOMO (HOMO=highest occupied molecular orbital).

As compounds with hole-injecting and/or hole-transporting properties, phenylenediamine derivatives (US3615404), arylamine derivatives (US3567450), amino-substituted chalcone derivatives (US3526501), styrylanthracene derivatives (JP-A-56-46234), Polycyclic aromatic compounds (EP1009041), polyarylalkane derivatives (US3615402), fluorenone derivatives (JP-A-54-110837), hydrazone derivatives (US3717462), acylhydrazones, stilbene derivatives (JP-A-61-210363) , silazane derivative (US4950950), polysilane (JP-A-2-204996), aniline copolymer (JP-A-2-282263), thiophene oligomer (JP-A-1 (1989)-211399), polythiophene, poly(N- vinylcarbazole) (PVK), polypyrrole, polyaniline, and other conductive polymers, porphyrin compounds (JP-A-63-2956965, US4720432), aromatic dimethylidene-type compounds, carbazole compounds such as CDBP, CBP, mCP, aromatic Particular mention may be made of group tertiary amine and styrylamine compounds (US Pat. No. 4,127,412), such as the benzidine type of triphenylamine, the styrylamine type of triphenylamine, and the diamine type of triphenylamine. Arylamine dendrimers (JP-A-8 (1996)-193191), monomeric triarylamines (US3180730), triarylamines containing one or more vinyl radicals and/or at least one functional group containing active hydrogen ( US 3,567,450 and US 3,658,520), or tetraaryldiamines (two tertiary amine units linked via an aryl group) can also be used. More triarylamino groups may be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives, and quinoline derivatives such as dipyrazino[2,3-f:2',3'-h]quinoxaline hexacarbonitrile.

Aromatic tertiary amines containing at least two tertiary amine units (US2008/0102311A1, US4720432 and US5061569) such as NPD (α-NPD = 4,4'-bis[N-(1-naphthyl)-N -phenyl-amino]biphenyl) (US5061569), TPD232 (=N,N'-bis-(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1, 1′-biphenyl) or MTDATA (MTDATA or m-MTDATA=4,4′,4″-tris[3-methylphenyl)phenylamino]-triphenylamine) (JP-A-4-308688), TBDB ( =N,N,N',N'-tetra(4-biphenyl)-diaminobiphenylene), TAPC (=1,1-bis(4-di-p-tolylaminophenyl)cyclo-hexane), TAPPP (=1 , 1-bis(4-di-p-tolylaminophenyl)-3-phenylpropane), BDTAPVB (= 1,4-bis[2-[4-[N,N-di(p-tolyl)amino]phenyl ]vinyl]benzene), TTB (=N,N,N′,N′-tetra-p-tolyl-4,4′-diaminobiphenyl), TPD (=4,4′-bis[N-3-methylphenyl ]-N-phenylamino)-biphenyl), N,N,N′,N′-tetraphenyl-4,4′″-diamino-1,1′,4′,1″,4″,1 '''-Quaterphenyl and the like are preferred, as well as tertiary amines containing carbazole units such as TCTA(=4-(9H-carbazol-9-yl)-N,N-bis[4-(9H -carbazol-9-yl)phenyl]benzenamine) and the like are preferred. Similarly, hexaazatriphenylene compounds according to US 2007/0092755 A1 and phthalocyanine derivatives (e.g. H ₂ Pc, CuPc (=copper phthalocyanine), CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc--O--GaPc) are preferred.

Triarylamine compounds of the following formulas (TA-1) to (TA-12) are particularly preferred, and EP1162193B1, EP650955B1, Synth. Ｍｅｔａｌｓ １９９７、９１（１－３）、２０９、ＤＥ１９６４６１１９Ａ１、ＷＯ２００６／１２２６３０Ａ１、ＥＰ１８６００９７Ａ１、ＥＰ１８３４９４５Ａ１、ＪＰ０８０５３３９７Ａ、ＵＳ６２５１５３１Ｂ１、ＵＳ２００５／０２２１１２４、ＪＰ０８２９２５８６Ａ、ＵＳ７３９９５３７Ｂ２、ＵＳ２００６／００６１２６５Ａ１、ＥＰ１６６１８８８、およびＷＯ２００９／０４１６３５に開示されている。 Said compounds of formulas (TA-1) to (TA-12) may be optionally substituted.

Further compounds that can be used as hole injection materials are described in EP0891121A1 and EP1029909A1, injection layers are generally described in US2004/0174116A1.

These arylamines and heterocyclic compounds, commonly used as hole-injecting and/or hole-transporting materials, preferably exceed −5.8 eV (vs. vacuum level) in the polymer, particularly preferably Resulting in a HOMO greater than -5.5 eV.

Compounds with electron-injecting and/or electron-transporting properties are, for example, pyridines, pyrimidines, pyridazines, pyrazines, oxadiazoles, quinolines, quinoxalines, anthracenes, benzanthracenes, pyrenes, perylenes, benzimidazoles, triazines, ketones, phosphine oxides, and phenazine derivatives, as well as triarylboranes and further O-, S- or N-containing heterocyclic compounds with low LUMO (LUMO=lowest unoccupied molecular orbital).

Particularly suitable compounds for the electron-transporting and electron-injecting layers are metal chelates of 8-hydroxyquinoline (eg LiQ, AlQ ₃ , GaQ ₃ , MgQ ₂ , ZnQ ₂ , InQ ₃ , ZrQ ₄ ), BAlQ, Ga oxinoid complexes, 4- Azaphenanthrene-5-ol-Be complexes (US5529853A, see formula ET-1), butadiene derivatives (US4356429), heterocyclic optical brighteners (US4539507), benzimidazole derivatives (US2007/0273272A1) such as TPBI (US5766779, 1,3,5-triazines, for example spirobifluorenyltriazine derivatives (for example according to DE 102008064200), pyrenes, anthracenes, tetracenes, fluorenes, spirofluorenes, dendrimers, tetracenes (for example rubrene derivatives), 1,10-phenanthroline derivatives (JP2003-115387, JP2004-311184, JP2001-267080, WO02/043449), silacyclopentadiene derivatives (EP1480280, EP1478032, EP1469533), borane derivatives such as Si-containing triarylborane derivatives (US2007 /0087219A1, see Formula ET-3), pyridine derivatives (JP2004-200162), phenanthrolines, especially 1,10-phenanthroline derivatives such as BCP and Bphen, and also some bound via biphenyl or other aromatic groups. phenanthroline (US2007-0252517A1) or phenanthroline bound to anthracene (US2007-0122656A1, see formulas ET-4 and ET-5).

Also suitable are heterocyclic organic compounds such as thiopyran dioxide, oxazole, triazole, imidazole or oxadiazole. Five-membered rings containing N, such as oxazole, preferably 1,3,4-oxadiazoles, such as formulas ET-6, ET-7, ET-8 and ET-9 disclosed inter alia in US 2007/0273272 A1 compounds of; A. Levin, M. S. See Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967(2), 339-341, preferably compounds of formula ET-10, silacyclopentadiene derivatives. Preferred compounds are the following formulas (ET-6) to (ET-10):

It is likewise possible to use derivatives of organic compounds such as fluorenone, fluorenylidenemethane, perylenetetracarbonate, anthraquinonedimethane, diphenoquinone, anthrone and anthraquinonediethylenediamine.

Preferred are 2,9,10-substituted anthracenes (with 1- or 2-naphthyl and 4- or 3-biphenyl) or molecules containing two anthracene units (see US2008/0193796A1, formula ET-11). Also very advantageous is the attachment of 9,10-substituted anthracene units to benzimidazole derivatives (see US2006/147747A and EP 1551206A1, formulas ET-12 and ET-13).

Compounds capable of producing electron-injecting and/or electron-transporting properties preferably yield a LUMO of less than -2.5 eV (vs. vacuum level), particularly preferably less than -2.7 eV.

The formulations of the invention may also contain phosphors. The term emitter means a material that allows radiative transitions to the ground state with luminescence after excitation, which can occur by any type of energy transfer. Generally, two classes of emitters are known: fluorescent and phosphorescent emitters. The term fluorescent emitter means a material or compound that undergoes a radiative transition from an excited singlet state to the ground state. The term phosphorescent emitter means a luminescent material or compound that preferably contains a transition metal.

Emitters are often referred to as dopants when the dopant induces the above properties in the system. Dopant in a system comprising matrix material and dopant is taken to mean the minor component of the mixture. Correspondingly, matrix material in a system comprising matrix material and dopant is taken to mean the higher proportion component of the mixture. The term phosphorescent emitter can thus also be taken to mean, for example, a phosphorescent dopant.

Compounds capable of emitting light include, among others, fluorescent emitters and phosphorescent emitters. These contain inter alia stilbenes, stilbeneamines, styrylamines, coumarins, rubrenes, rhodamines, thiazoles, thiadiazoles, cyanines, thiophenes, paraphenylenes, perylenes, phthalocyanines, porphyrins, ketones, quinolines, imines, anthracenes and/or pyrene structures. Contains compounds that Particularly preferred are compounds that can emit from the triplet state with high efficiency even at room temperature, ie exhibit electrophosphorescence rather than electrofluorescence, which often leads to increased energy efficiency. Suitable for this purpose are primarily compounds containing heavy atoms with an atomic number greater than 36. Compounds containing d- or f-transition metals satisfying the above conditions are preferred. Corresponding compounds containing elements of groups 8-10 (Ru, Os, Rh, Ir, Pd, Pt) are particularly preferred here. Suitable functional compounds here are the various complexes described, for example, in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 2004/026886 A2.

Preferred compounds that can function as fluorescent emitters are described by the following examples. Preferred fluorescent emitters are selected from the class of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphines, styryl ethers, and arylamines.

A monostyrylamine is taken to mean a compound which contains one substituted or unsubstituted styryl group and at least one, preferably aromatic amine. A distyrylamine is taken to mean a compound which contains two substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. A tristyrylamine is taken to mean a compound containing three substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. A tetrastyrylamine is taken to mean a compound which contains four substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. The styryl group is particularly preferably stilbene and may be further substituted. Corresponding phosphines and ethers are defined analogously to the amines. Arylamines or aromatic amines in the sense of the invention are taken to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly attached to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthracenamine is taken to mean a compound in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. Aromatic anthracenediamines are taken to mean compounds in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 2,6 or 9,10 positions. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, wherein the diarylamino groups are preferably attached to the pyrene in the 1- or 1,6-position.

Further preferred fluorescent emitters are indenofluorenamines or indenofluorenediamines, especially as described in WO2006/122630; benzoindenofluorenamines or benzoindenofluorenediamines, especially as described in WO2008/006449; dibenzoindenofluoreneamine or dibenzoindenofluorenediamine.

Examples of compounds from the class of styrylamines that can be used as fluorescent emitters are substituted or unsubstituted tristilbenamines or dopants as described in WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549 and WO2007/115610. be. Distyrylbenzene and distyrylbiphenyl derivatives are described in US5121029. Additional styrylamines can be found in US2007/0122656A1.

Particularly preferred styrylamine compounds are the compound of formula EM-1 described in US7250532B2 and the compound of formula EM-2 described in DE102005058557A1:

Particularly preferred triarylamine compounds are compounds of formula EM-3 to EM-15 and derivatives thereof disclosed in CN1583691A, JP08/053397A and US6251531B1, EP1957606A1, US2008/0113101A1, US2006/210830A, WO2008/006449 and DE102008035413. is:

Further preferred compounds that can be used as fluorescent emitters are naphthalene, anthracene, tetracene, benzanthracene, benzophenanthrene (DE 102009005746), fluorene, fluoranthene, periflanthene, indenoperylene, phenanthrene, perylene (US 2007/0252517 A1), pyrene, chrysene, decacyclene. , coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US4769292, US6020078, US2007/0252517A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamate , diketopyrrolopyrroles, acridones, and derivatives of quinacridones (US2007/0252517A1).

Among anthracene compounds, 9,10-substituted anthracenes, such as 9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene, are particularly preferred. 1,4-bis(9'-ethynylanthracenyl)-benzene is also a preferred dopant.

Similarly, derivatives of rubrene, coumarin, rhodamine, quinacridones such as DMQA (=N,N'-dimethylquinacridone), dicyanomethylenepyrans such as DCM (=4-(dicyanoethylene)-6-(4-dimethylaminostyryl) -2-methyl)-4H-pyran), thiopyrans, polymethines, pyrylium and thiapyrylium salts, periflanthenes, and indenoperylenes are preferred.

Blue fluorescent emitters are preferably polyaromatic compounds such as 9,10-di(2-naphthylanthracene) and other anthracene derivatives, derivatives of tetracene, xanthene, perylene such as 2,5,8,11-tetra -t-butylperylene and the like, phenylenes such as 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl, fluorene, fluoranthene, arylpyrene (US2006/0222886A1), arylenevinylene (US5121029, US5130603), bis(azinyl)imine-boron compounds (US2007/0092753A1), bis(azinyl)methene compounds, and carbostyryl compounds.

Further preferred blue fluorescent emitters are C.I. H. Chen et al.: "Recent developments in organic electroluminescent materials" Macro-mol. Symp. 125, (1997) 1-48 and "Recent progress of molecular organic electroluminescent materials and devices" Mat. Sci. and Eng. R, 39 (2002), 143-222.

Further preferred blue fluorescent emitters are the hydrocarbons disclosed in DE102008035413.

Preferred compounds that can function as phosphorescent emitters are described by the following examples.

Examples of phosphorescent emitters are disclosed by WO00/70655, WO01/41512, WO02/02714, WO02/15645, EP1191613, EP1191612, EP1191614 and WO2005/033244. In general, all phosphorescent complexes such as those used in phosphorescent OLEDs according to the prior art and known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to formulate further phosphorescent complexes without inventive step. can be used.

The phosphorescent metal complex preferably contains Ir, Ru, Pd, Pt, Os or Re, more preferably Ir.

Preferred ligands are 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives, 1-phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives, or 2-phenylquinoline derivatives. All these compounds may be substituted for the blue color, eg by fluoro, cyano and/or trifluoromethyl substituents. The ancillary ligand is preferably acetylacetonate or picolinic acid.

Particularly suitable are complexes of Pt or Pd with tetradentate ligands of formula EM-16.

The compound of formula EM-16 is described in more detail in US 2007/0087219 A1, to which reference is made here for purposes of disclosure for the explanation of the substituents and subscripts in the above formula. Additionally, Pt-porphyrin complexes with extended ring systems (US2009/0061681A1) and Ir complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin-Pt(II), Tetraphenyl-Pt(II) tetrabenzoporphyrin (US2009/0061681A1), cis-bis(2-phenylpyridinato-N,C ² ')Pt(II), cis-bis(2-(2'-thienyl) pyridinato-N,C ³ ′)Pt(II), cis-bis(2-(2′-thienyl)-quinolinato-N,C ⁵ ′)Pt(II), (2-(4,6-difluorophenyl) pyridinato-N,C ² ′)Pt(II) (acetylacetonate) or tris(2-phenylpyridinato-N,C ² ′)Ir(III) (=Ir(ppy) ₃ , green), bis (2-phenylpyridinato-N,C ² )Ir(III) (acetylacetonate) (=Ir(ppy) ₂ acetylacetonate, green, US2001/0053462A1, Baldo, Thompson et al., Nature 403, (2000) , 750-753), bis(1-phenylisoquinolinato-N,C ² ′)(2-phenylpyridinato-N,C ² ′)iridium(III), bis(2-phenylpyridinato-N ,C ² ′)(1-phenylisoquinolinato-N,C ² ′)iridium(III), bis(2-(2′-benzothienyl)pyridinato-N,C ³ ′)iridium(III) (acetylaceto nate), bis(2-(4′,6′-difluorophenyl)pyridinato-N,C ² ′)iridium(III) (picolinate) (FIrpic, blue), bis(2-(4′,6′-difluoro Phenyl)pyridinato-N,C ² ′)Ir(III) (tetrakis(1-pyrazolyl)borate), tris(2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III), (ppz ) ₂ Ir(5phdpym) (US2009/0061681A1), (45ooppz) _2Ir (5phdpym) (US2009/0061681A1), derivatives of 2-phenylpyridine-Ir complexes such as PQIr (=iridium(III) bis(2-phenylquino lyl-N,C ² ')acetylacetonate), tris(2-phenylisocyanate) Norinato-N,C)Ir(III) (red), bis(2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C ³ )Ir (acetylacetonate) ([Btp ₂ Ir (acac)], red, Adachi et al., Appl. Phys. Lett. 78 (2001), 1622-1624).

Also suitable are complexes of trivalent lanthanides, such as Tb ³⁺ and Eu ³⁺ (J. Kido et al., Appl. Phys. Lett. 65 (1994), 2124; Kido et al., Chem. Lett. 657, 1990; US 2007/0252517 A1), or phosphorescent complexes of Pt(II), Ir(I), Rh(I) with maleonitrile dithiolate (Johnson et al., JACS 105, 1983, 1795), Re(I) tricarbonyl-diimine complexes (Inter alia Wrighton, JACS 96, 1974, 998), Os(II) complexes with cyano ligands and bipyridyl or phenanthroline ligands (Ma et al., Synth. Metals 94, 1998, 245).

Further phosphorescent emitters with tridentate ligands are described in US6824895 and US10/729238. Red-emitting phosphorescent complexes are found in US6835469 and US6830828.

Particularly preferred compounds for use as phosphorescent dopants are described inter alia in US 2001/0053462 A1 and Inorg. Chem. 2001, 40(7), 1704-1711, JACS 2001, 123(18), 4304-4312 and compounds of formula EM-17 and derivatives thereof.

Derivatives are described in US7378162B2, US6835469B2 and JP2003/253145A.

Furthermore, the compounds of formula EM-18 to EM-21 and their derivatives described in US7238437B2, US2009/008607A1 and EP1348711 can be used as emitters.

Quantum dots can likewise be used as emitters and these materials are disclosed in detail in WO2011/076314A1.

In particular, compounds used as host materials in conjunction with emissive compounds include materials from various classes of substances.

The host material generally has a larger bandgap between HOMO and LUMO than the emitter material used. In addition, preferred host materials exhibit the properties of either hole or electron transport materials. Additionally, the host material can have both electron and hole transport properties.

A host material is sometimes also called a matrix material, especially when the host material is used in combination with a phosphorescent emitter in an OLED.

Preferred host or co-host materials, especially for use with fluorescent dopants, are oligoarylenes (for example 2,2′,7,7′-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), especially fused aromatic groups. Containing oligoarylenes such as anthracene, benzoanthracene, benzophenanthrene (DE102009005746, WO2009/069566), phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, etc., oligoarylenevinylenes (for example DPVBi according to EP 676461 = 4,4′-bis(2,2-diphenylethenyl)-1,1′-biphenyl or spiro-DPVBi), polypodal metal complexes (for example according to WO 04/081017), especially metals of 8-hydroxyquinoline complexes, for example metal complexes of AlQ ₃ (=aluminium(III) tris(8-hydroxyquinoline)) or bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum, additionally imidazole chelates (US 2007/0092753 A1), and quinoline metal complexes, aminoquinoline-metal complexes, benzoquinoline-metal complexes, hole-conducting compounds (for example according to WO2004/058911), electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides, etc. (eg according to WO2005/084081 and WO2005/084082), atropisomers (eg according to WO2006/048268), boronic acid derivatives (eg according to WO2006/117052) or benzanthracenes (eg according to WO2008/145239).

Particularly preferred compounds capable of functioning as host or co-host materials are selected from the class of oligoarylenes, including anthracene, benzanthracene and/or pyrene, or atropisomers of these compounds. An oligoarylene in the sense of the invention is intended to be understood as meaning a compound in which at least three aryl or arylene groups are attached to one another.

Preferred host materials are selected especially from compounds of formula (H-1)

(wherein Ar ⁴ , Ar ⁵ and Ar ⁶ are the same or different at each occurrence and are optionally substituted aryl or heteroaryl groups having 5 to 30 aromatic ring atoms; and p represents an integer ranging from 1 to 5; the sum of π electrons in Ar ⁴ , Ar ⁵ and Ar ⁶ is at least 30 if p=1, at least 36 if p=2, p= 3 is at least 42).

In compounds of formula (H-1), the Ar ⁵ group particularly preferably represents anthracene, the Ar ⁴ and Ar ⁶ groups are bonded at the 9 and 10 positions, wherein these groups optionally may be substituted. Very particularly preferably at least one of the Ar ⁴ and/or Ar ⁶ groups is 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl or 2-, 3-, 4-, 5-, 6- is a condensed aryl group selected from - or 7-benzoanthracenyl. Anthracene-based compounds are described in US2007/0092753A1 and US2007/0252517A1, for example 2-(4-methylphenyl)-9,10-di-(2-naphthyl)anthracene, 9-(2-naphthyl)-10 -(1,1′-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene, and 1,4-bis(9′-ethynylanthracenyl)benzene. Compounds containing two anthracene units (US2008/0193796A1) such as 10,10'-bis[1,1',4',1'']terphenyl-2-yl-9,9'-bisanthracenyl is also preferred.

Further preferred compounds are arylamines, styrylamines, fluoresceins, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarins, oxadiazoles, bisbenzoxazolines, oxazoles, pyridines, pyrazines, imines , benzothiazole, benzoxazole, derivatives of benzimidazole (US2007/0092753A1) such as 2,2′,2″-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole], aldazine, Stilbene, styrylarylene derivatives such as 9,10-bis[4-(2,2-diphenylethenyl)-phenyl]anthracene and distyrylarylene derivatives (US5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran , diketopyrrolopyrroles, polymethines, cinnamates, and fluorescent dyes.

Derivatives of arylamines and styrylamines such as TNB (=4,4′-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl) are particularly preferred. Metal oxinoid complexes such as LiQ or _AlQ3 can be used as cohosts.

オリゴアリーレンをマトリックスとして含む好ましい化合物が、ＵＳ２００３／００２７０１６Ａ１、ＵＳ７３２６３７１Ｂ２、ＵＳ２００６／０４３８５８Ａ、ＷＯ２００７／１１４３５８、ＷＯ２００８／１４５２３９、ＪＰ３１４８１７６Ｂ２、ＥＰ１００９０４４、ＵＳ２００４／０１８３８３、ＷＯ２００５／０６１６５６Ａ１、ＥＰ０６８１０１９Ｂ１、ＷＯ２００４／０１３０７３Ａ１、ＵＳ５０７７１４２、ＷＯ２００７／ 065678, and DE 102009005746, where particularly preferred compounds are described by formulas H-2 to H-8.

Additionally, compounds that can be used as hosts or matrices include materials that are used with phosphorescent emitters.

These compounds can also be used as structural elements in polymers, CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (for example WO2005/039246, US2005/0069729, JP2004/288381, EP1205527 or 086851), azacarbazoles (for example according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/347160), ketones (for example according to WO 2004/093207 or DE 102008033943), phosphine oxides, sulfoxides and sulfones (for example according to WO 2005/003253, aromatics), oligophenylenes Amines (for example according to US 2005/0069729), bipolar matrix materials (for example according to WO 2007/137725), silanes (for example according to WO 2005/111172), 9,9-diarylfluorene derivatives (for example according to DE 102008017591), azaboroles or boronic esters (for example WO 2006/117052), triazine derivatives (e.g. according to DE 102008036982), indolocarbazole derivatives (e.g. according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (e.g. according to DE 102009023155 and DE 102009031021), diazaphosphole derivatives (e.g. 050D8021) triazole derivatives, oxazoles and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carbodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives which may further contain triarylaminophenol ligands, such as AlQ ₃ (US2007/ 0134514 A1), metal complexes/polysilane compounds, and thiophene, benzothiophene and dibenzothiophene derivatives.

An example of a preferred carbazole derivative is mCP (=1,3-N,N-di-carbazolylbenzene (=9,9′-(1,3-phenylene)bis-9H-carbazole)) (formula H-9 ), CDBP (=9,9′-(2,2′-dimethyl[1,1′-biphenyl]-4,4′-diyl)bis-9H-carbazole), 1,3-bis(N,N′ -dicarbazolyl)benzene (=1,3-bis(carbazol-9-yl)benzene), PVK (polyvinylcarbazole), 3,5-di(9H-carbazol-9-yl)biphenyl, and CMTTP (formula H-10) ). Compounds of particular mention are disclosed in US2007/0128467A1 and US2005/0249976A1 (formulas H-11 and H-13).

Preferred tetraaryl-Si compounds are described, for example, in US2004/0209115, US2004/0209116, US2007/0087219A1, and H.I. Gilman, E. A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120.

Particularly preferred tetraaryl-Si compounds are described by formulas H-14 through H-21.

Particularly preferred compounds from group 4 for the preparation of matrices for phosphorescent dopants are disclosed inter alia in DE102009022858, DE102009023155, EP652273B1, WO2007/063754 and WO2008/056746, wherein particularly preferred compounds are of the formulas H-22 to Described by H-25.

For functional compounds that can be used according to the invention and can act as host materials, substances containing at least one nitrogen atom are particularly preferred. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. Therefore, carbazole derivatives in particular show surprisingly high efficiency. Triazine derivatives provide unexpectedly long lifetimes for electronic devices.

It may also be preferred to use a plurality of different matrix materials, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material, as a mixture. Equally preferred is the use of mixtures of charge transporting matrix materials and electrically inactive matrix materials which, if not to a significant extent, participate in charge transport, as described, for example, in WO 2010/108579. .

It is further possible to use compounds that improve the transition from the singlet state to the triplet state and are used to support functional compounds with emissive properties and improve the phosphorescent properties of these compounds. Suitable for this purpose are in particular carbazole and bridged carbazole dimer units, as described for example in WO2004/070772A2 and WO2004/113468A1. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds, as described, for example, in WO2005/040302A1.

An n-dopant here is taken to mean a reducing agent, ie an electron donor. Preferred examples of n-dopants are W(hpp) ₄ and other electron-rich metal complexes according to WO2005/086251A2, P=N compounds (e.g. WO2012/175535A1, WO2012/175219A1), naphthylene carbodiimides (e.g. (e.g. WO2012/031735A1), free radicals and diradicals (e.g. EP1837926A1, WO2007/107306A1), pyridines (e.g. EP2452946A1, EP2463927A1), N-heterocyclic compounds (e.g. WO2009/000237A1), and acridine and phenazine (e.g. US2007/1433) ).

Additionally, the formulation may include a wide bandgap material as a functional material. A wide bandgap material is taken to mean a material within the meaning of the disclosure of US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

The compounds used as wide bandgap materials can preferably have a bandgap of 2.5 eV or more, preferably 3.0 eV or more, particularly preferably 3.5 eV or more. The bandgap can be calculated by, among other things, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

Additionally, the formulation may include a hole blocking material (HBM) as a functional material. By hole-blocking material is meant a material that prevents or minimizes the transport of holes (positive charges) in multilayer systems, especially when this material is arranged in the form of a layer adjacent to the light-emitting layer or the hole-conducting layer. . Generally, hole-blocking materials have a lower HOMO level than hole-transporting materials in adjacent layers. A hole-blocking layer is often placed between the light-emitting layer and the electron-transporting layer in an OLED.

In principle it is possible to use any known hole blocking material. In addition to other hole-blocking materials described elsewhere in this application, advantageous hole-blocking materials include metal complexes (US2003/0068528) such as bis(2-methyl-8-quinolinolato)(4-phenylpheno Rath)aluminum (III) (BAlQ) and the like. Fac-tris(1-phenylpyrazolato-N,C2)-iridium(III) (Ir(ppz) ₃ ) has likewise been used for this purpose (US2003/0175553A1). Phenanthroline derivatives, such as BCP, or phthalimides, such as TMPP, can be used as well.

Further advantageous hole blocking materials are described in WO00/70655A2, WO01/41512 and WO01/93642A1.

Additionally, the formulation may include an electron blocking material (EBM) as a functional material. Electron-blocking material means a material that prevents or minimizes the transport of electrons in a multilayer system, especially if this material is arranged in the form of a layer adjacent to the light-emitting layer or the electron-conducting layer. Generally, electron blocking materials have a higher LUMO level than electron transporting materials in adjacent layers.

In principle it is possible to use any known electron blocking material. Advantageous electron blocking materials, in addition to other electron blocking materials described elsewhere in this application, are transition metal complexes such as Ir(ppz) ₃ (US 2003/0175553).

Electron blocking materials can preferably be selected from amines, triarylamines and derivatives thereof.

Furthermore, when the functional compound that can be used as an organic functional material in the formulation is a low molecular weight compound, it is preferably 3,000 g/mol or less, more preferably 2,000 g/mol or less, and most preferably 1,000 g/mol. It has the following molecular weight.

Also of particular interest are functional compounds characterized by a high glass transition temperature. In this context, particularly preferred functional compounds that can be used as organic functional materials in formulations have a glass transition temperature of 70° C. or higher, preferably 100° C. or higher, more preferably 125° C. or higher, most preferably 125° C. or higher, determined according to DIN 51005. 150° C. or higher.

The formulation may further comprise a polymer as organic functional material. The compounds described above as organic functional materials often have relatively low molecular weights and can also be mixed with polymers. It is likewise possible to incorporate these compounds covalently into polymers. This is possible in particular with compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronate esters, or by reactive polymerizable groups such as olefins or oxetanes. They can be used as monomers for the preparation of corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization here preferably takes place via halogen or boronic acid functionalities or via polymerizable groups. Furthermore, it is possible to crosslink the polymer via groups of this type. The compounds and polymers according to the invention can be used as crosslinked or non-crosslinked layers.

Polymers that can be used as organic functional materials often contain the units or structural elements described in the context of the above compounds, inter alia those disclosed and extensively described in WO02/077060A1, WO2005/014689A2 and WO2011/076314A1. These are incorporated herein by reference. Functional materials can originate, for example, from the following classes:
Group 1: Structural elements capable of producing hole-injection and/or hole-transport properties;
Group 2: Structural elements capable of producing electron-injection and/or electron-transport properties;
Group 3: Structural elements that combine the properties described in relation to Groups 1 and 2;
Group 4: Structural elements with luminescent properties, in particular phosphorescent groups;
Group 5: Structural elements that improve the transition from the so-called singlet state to the triplet state;
Group 6: Structural elements that influence the morphology or emission color of the resulting polymer;
Group 7: Structural elements typically used as scaffolds.

Structural elements here may also have different functions, and no clear assignment need be advantageous. For example, Group 1 structural elements may function as scaffolds as well.

Polymers with hole-transporting or hole-injecting properties used as organic functional materials containing structural elements from group 1 may preferably contain units corresponding to the hole-transporting or hole-injecting materials described above. good.

Further preferred structural elements of group 1 are, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, carbazoles, azulenes, thiophenes, pyrroles, and furan derivatives, and further O-, S- or N-containing hetero- It is a cyclic compound. These arylamines and heterocyclic compounds preferably have a HOMO above -5.8 eV (vs. vacuum level), particularly preferably above -5.5 eV.

Especially preferred are polymers with hole-transporting or hole-injecting properties containing at least one repeat unit of the formula HTP-1 below:

(Wherein the symbols have the following meanings:
Ar ¹ is in each case the same or different for different repeating units and is a single bond or an optionally substituted monocyclic or polycyclic aryl group;
Ar ² is in each case the same or different for different repeat units and is an optionally substituted monocyclic or polycyclic aryl group;
Ar ³ is in each case the same or different for different repeat units and is an optionally substituted monocyclic or polycyclic aryl group;
m is 1, 2 or 3).

Particularly preferred are repeating units of HTP-1 selected from the group consisting of units of the formulas HTP-1A to HTP-1C:

(Wherein the symbols have the following meanings:
R ^a is the same or different at each occurrence and is H, substituted or unsubstituted aromatic or heteroaromatic group, alkyl, cycloalkyl, alkoxy, aralkyl, aryloxy, arylthio, alkoxycarbonyl, silyl or carboxyl group , a halogen atom, a cyano group, a nitro group, or a hydroxy group;
r is 0, 1, 2, 3 or 4;
s is 0, 1, 2, 3, 4 or 5).

Especially preferred are polymers with hole-transporting or hole-injecting properties containing at least one repeat unit of formula HTP-2:

(Wherein the symbols have the following meanings:
T ¹ and T ² are independently selected from thiophene, selenophene, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, pyrrole and aniline, wherein these the group may be substituted by one or more radicals R ^b ;
R ^b is halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰ R ⁰⁰ , -C(=O)X, -C( ═O) R ⁰ , —NH ₂ , —NR ⁰ R ⁰⁰ , —SH, —SR ⁰ , —SO ₃ H, —SO ₂ R ⁰ , —OH, —NO ₂ , —CF ₃ , —SF ₅ , optional independently from an optionally substituted silyl, carbyl or hydrocarbyl group having from 1 to 40 carbon atoms, optionally substituted with and optionally containing one or more heteroatoms selected;
R ⁰ and R ⁰⁰ are each independently H or optionally substituted and optionally substituted having 1 to 40 carbon atoms, optionally containing one or more heteroatoms a carbyl or hydrocarbyl group which may be
Ar ⁷ and Ar ⁸ are, independently of each other, optionally substituted and optionally bonded at the 2,3-position of one or both of the adjacent thiophene or selenophene groups, monocyclic or polycyclic represents a cyclic aryl or heteroaryl group;
c and e are independently of each other 0, 1, 2, 3 or 4, where 1<c+e≦6;
d and f are independently of each other 0, 1, 2, 3 or 4).

Preferred examples of polymers with hole-transporting or hole-injecting properties are described inter alia in WO2007/131582A1 and WO2008/009343A1.

Polymers with electron-injecting and/or electron-transporting properties used as organic functional materials containing structural elements from group 2 may preferably also contain units corresponding to the electron-injecting and/or electron-transporting materials described above. good.

Further preferred structural elements of group 2 with electron-injecting and/or electron-transporting properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline and phenazine groups, also triarylborane groups, or low LUMO levels. derived from additional O-, S- or N-containing heterocyclic compounds having positions. These group 2 structural elements preferably have a LUMO of less than -2.7 eV (vs. vacuum level), particularly preferably less than -2.8 eV.

The organic functional material can preferably be a polymer containing structural elements from group 3, wherein structural elements improving hole and electron mobility (i.e. structural elements from groups 1 and 2) are , are directly coupled to each other. Some of these structural elements can act as emitters, where the emission color can be shifted to green, red or yellow, for example. Their use is therefore advantageous, for example, for the production of other emission colors or broadband emission by naturally blue-emitting polymers.

Polymers with luminescent properties which are used as organic functional materials containing structural elements from group 4 may preferably contain units corresponding to the emitter materials described above. Preference is given here to polymers containing the aforementioned luminescent metal complexes containing corresponding units containing phosphorescent groups, in particular elements of groups 8-10 (Ru, Os, Rh, Ir, Pd, Pt).

Polymers used as organic functional materials containing units of group 5 that improve the transition from the so-called singlet state to the triplet state can preferably be used to support phosphorescent compounds, preferably the above groups It is a polymer containing 4 structural elements. A polymer triplet matrix can be used here.

Suitable for this purpose are, in particular, carbazole and linked carbazole dimer units as described, for example, in DE 103 04 819 A1 and DE 103 28 627 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones and silane derivatives, as described, for example, in DE 103 49 033 A1, and similar compounds. Additionally, preferred structural units can be derived from the compounds described above in connection with the matrix material used with the phosphorescent compound.

Further organic functional materials are preferably polymers containing units of group 6 which influence the morphology or emission color of the polymer. Besides the polymers mentioned above, these are those which have at least one further aromatic or another conjugated structure not counted in the above groups. Thus, these groups have little or no effect on charge carrier mobility, non-organometallic complexes, or singlet-triplet transitions.

Structural units of this type can influence the morphology or emission color of the resulting polymer. Depending on the structural units, these polymers can therefore also be used as emitters.

For fluorescent OLEDs, therefore, aromatic structural elements with 6 to 40 C atoms or trans-, stilbene- or bisstyrylarylene derivative units are preferred, each of which may be substituted by one or more radicals. . Here, 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6-, 2,7- or 4,9-pyrenylene, 3,9- or 3,10 -perylenylene, 4,4'-biphenylene, 4,4''-terphenylylene, 4,4'-bi-1,1'-naphthylene, 4,4'-tranylene, 4,4'-stilbenylene, or 4,4 Particular preference is given to using groups derived from ''-bisstyrylarylene derivatives.

The polymers used as organic functional materials preferably contain units of group 7 and preferably aromatic structures with 6 to 40 C atoms which are often used as backbones.

These are inter alia 4,5-dihydropyrene derivatives, 4,5,9,10-tetra-hydropyrene derivatives, fluorene derivatives, for example disclosed in WO2003/020790A1, for example in US5962631, WO2006/052457A2 and WO2006/118345A1. 9,9-spirobifluorene derivatives such as those disclosed in WO2005/104264A1, such as 9,10-phenanthrene derivatives disclosed in WO2005/014689A2, such as 9,10-dihydrophenanthrene derivatives disclosed in WO2004/041901A1 and 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives disclosed in WO2004/113412A2 and binaphthylene derivatives disclosed for example in WO2006/063852A1 and for example WO2005/056633A1, EP1344788A1, Including further units disclosed in WO2007/043495A1, WO2005/033174A1, WO2003/099901A1 and DE102006003710.

Fluorene derivatives disclosed for example in US 5,962,631, WO2006/052457A2 and WO2006/118345A1, e.g. spirobifluorene derivatives disclosed in WO2003/020790A1, e.g. Structural units of group 7 selected from benzofluorene, dibenzofluorene, benzothiophene and dibenzofluorene groups and their derivatives are particularly preferred.

A particularly preferred group 7 structural element is represented by the general formula PB-1:

(wherein the signs and subscripts have the following meanings:
A, B and B' are each also the same or different for different repeating units, preferably -CR ^c R ^d -, -NR ^c -, -PR ^c -, -O-, - S-, -SO-, -SO _2- , -CO-, -CS-, -CSe-, -P(=O)R ^c -, -P(=S)R ^c - and -SiR ^c R ^d - is a divalent group selected from;
R ^c and R ^d at each occurrence are H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(=O)NR ⁰ R ⁰⁰ , —C(=O) X, —C(=O)R ⁰ , —NH ₂ , —NR ⁰ R ⁰⁰ , —SH, —SR ⁰ , —SO ₃ H, —SO ₂ R ⁰ , —OH, —NO ₂ , —CF ₃ , —SF ₅ , an optionally substituted silyl, carbyl or hydrocarbyl group having from 1 to 40 carbon atoms, optionally substituted and optionally containing one or more heteroatoms wherein R ^c and R ^d may optionally form a spiro group with the fluorene radical to which they are attached;
X is halogen;
R ⁰ and R ⁰⁰ are each independently H or optionally substituted and optionally substituted and optionally containing one or more heteroatoms having 1 to 40 carbon atoms a carbyl or hydrocarbyl group which may be
g is independently 0 or 1 at each occurrence and h is independently 0 or 1 at each occurrence, wherein the sum of g and h in the subunit is preferably 1 ;
m is an integer of 1 or more;
Ar ¹ and Ar ² independently of each other are optionally substituted monocyclic or polycyclic aryl optionally bonded to the 7,8- or 8,9-position of the indenofluorene or representing a heteroaryl group;
a and b are 0 or 1 independently of each other).

When the R ^c and R ^d groups form a spiro group with the fluorene group to which they are attached, this group preferably represents spirobifluorene.

Particularly preferred are repeat units of formula PB-1 selected from the group consisting of units of formulas PB-1A to PB-1E:

(wherein R ^c has the meaning given above for formula PB-1, r is 0, 1, 2, 3 or 4 and R ^e has the same meaning as the radical R ^c ) .

R ^e is preferably -F, -Cl, -Br, -I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰ R ⁰⁰ , -C (=O)X, -C(=O)R ⁰ , -NR ⁰ R ⁰⁰ , optionally substituted silyl, aryl or hetero with 4 to 40, preferably 6 to 20 C atoms an aryl group or a linear, branched or cyclic alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 20, preferably 1 to 12 C atoms, wherein , one or more hydrogen atoms may optionally be replaced by F or Cl, and the R ⁰ , R ⁰⁰ groups and X have the meanings given above for formula PB-1.

Particularly preferred are repeat units of formula PB-1 selected from the group consisting of units of formulas PB-1F to PB-1I:

(Wherein the symbols have the following meanings:
L is H, halogen or an optionally fluorinated linear or branched alkyl or alkoxy group with 1 to 12 C atoms, preferably methyl, i-propyl, t-butyl , representing n-pentoxy or trifluoromethyl;
L′ is an optionally fluorinated linear or branched alkyl or alkoxy group with 1 to 12 C atoms, preferably representing n-octyl or n-octyloxy).

Polymers containing two or more of the structural elements of groups 1-7 above are preferred for the practice of this invention. Furthermore, it may be provided that the polymer preferably contains two or more of the structural elements from one group above, ie comprises a mixture of structural elements selected from one group.

In particular, besides at least one structural element (group 4) having luminescent properties, preferably at least one phosphorescent group, at least one further structural element of groups 1 to 3, 5 or 6 above can be added. Particular preference is given to polymers containing, wherein these are preferably selected from groups 1-3.

The proportions of the various classes of groups, when present in the polymer, can be within wide ranges, where these are known to those skilled in the art. If in each case the proportion of one class present in the polymer selected from structural elements of groups 1 to 7 above is preferably in each case 5 mol % or more, particularly preferably in each case 10 mol % or more , amazing benefits can be achieved.

The preparation of white-emitting copolymers is described in detail inter alia in DE 103 43 606 A1.

To improve solubility, the polymer may contain corresponding groups. Preferably, the polymer contains substituents so that an average of at least 2 non-aromatic carbon atoms, particularly preferably at least 4 and especially preferably at least 8 non-aromatic carbon atoms per repeat unit It may be specified that there is, where the average relates to the number average. Here individual carbon atoms can be replaced by O or S, for example. However, it is possible that a certain proportion, optionally all repeat units, do not contain substituents containing non-aromatic carbon atoms. Short-chain substituents are preferred here, since long-chain substituents can adversely affect the layers obtainable with organic functional materials. The substituents preferably contain up to 12 carbon atoms, preferably up to 8 carbon atoms, particularly preferably up to 6 carbon atoms in the straight chain.

The polymers used as organic functional materials according to the invention can be random, alternating or regioregular copolymers, block copolymers, or combinations of these copolymer morphologies.

In a further aspect, the polymer used as the organic functional material can be a non-conjugated polymer with side chains, where this aspect is particularly important for polymer-based phosphorescent OLEDs. In general, phosphorescent polymers can be obtained by free-radical copolymerization of vinyl compounds, wherein these vinyl compounds have at least one unit with a phosphorescent emitter and /or contain at least one charge transport unit. Further phosphorescent polymers are described inter alia in JP2007/211243A2, JP2007/197574A2, US7250226B2 and JP2007/059939A.

In a further preferred embodiment, the non-conjugated polymer contains backbone units linked together by spacer units. Examples of such triplet emitters based on non-conjugated polymers based on backbone units are disclosed in DE 10 2009 023 154, for example.

In a further preferred embodiment, non-conjugated polymers can be designed as fluorescent emitters. Preferred fluorescent emitters based on non-conjugated polymers with side chains contain anthracene or benzoanthracene groups, or derivatives of these groups, in side chains, where these polymers are for example JP 2005/108556, JP 2005/285661 and JP2003/338375.

These polymers can often be used as electron or hole transport materials, where they are preferably designed as non-conjugated polymers.

Furthermore, the functional compound used as the organic functional material in the formulation is preferably 10,000 g/mol or more, particularly preferably 20,000 g/mol or more, particularly preferably 50,000 g/mol or more, in the case of a polymer compound. of molecular weight _Mw .

Here, the molecular weight M _w of the polymer is preferably in the range from 10,000 to 2,000,000 g/mol, particularly preferably in the range from 20,000 to 1,000,000 g/mol, very particularly preferably 50,000 g/mol. 000 to 300,000 g/mol. The molecular weight _Mw is determined by GPC (=gel permeation chromatography) against internal polystyrene standards.

The publications cited above for descriptions of functional compounds are hereby incorporated by reference for the purpose of disclosure.

The formulations according to the invention may contain all the organic functional materials required for the production of the respective functional layers of the electronic device. For example, if the hole-transporting, hole-injecting, electron-transporting or electron-injecting layer is constructed precisely from one functional compound, the formulation contains precisely this compound as the organic functional material. For example, if the emissive layer comprises an emitter in combination with a matrix or host material, the formulation may include a mixture of emitter and matrix or host material as the organic functional material, as described in more detail elsewhere in this application. contain exactly.

Besides the aforementioned ingredients, the formulations according to the invention may comprise further additives and processing aids. These are, inter alia, surface-active substances (surfactants), lubricants and greases, viscosity-regulating additives, conductivity-increasing additives, dispersants, hydrophobizing agents, adhesion promoters, flow improvers , defoamers, deaerators, diluents which may be reactive or non-reactive, fillers, adjuvants, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles, and inhibitors including.

The present invention further relates to a method of preparing a formulation according to the invention, wherein a first organic solvent which is at least an adamantane derivative, a second organic solvent and at least one Kinds of organic functional materials are mixed.

The formulations according to the invention can be used for the production of layers or multilayer structures in which organic functional materials are present in the layers, such as those required for the production of preferred electronic or optoelectronic components, such as OLEDs.

The formulations of the invention can preferably be used to form a functional layer on a substrate or one of the layers applied to a substrate. The substrate may or may not have a bank structure.

The invention likewise relates to a method of manufacturing an electronic device, wherein the formulation according to the invention is applied to a substrate and dried.

The functional layer is applied to the substrate or substrates by, for example, flood coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, rotary printing, roller coating, flexographic printing, offset printing or nozzle printing, preferably inkjet printing. can be manufactured on one of the layers applied to the

After applying the formulation according to the invention onto a substrate or an already applied functional layer, a drying step can be carried out in order to remove the solvent from the continuous phase. Drying can preferably be carried out at relatively low temperatures and over relatively long periods of time to avoid bubble formation and to obtain a uniform coating. Drying may preferably be carried out at a temperature in the range of 80-300°C, more preferably 150-250°C, most preferably 160-200°C. Here, drying may preferably be carried out at pressures in the range from 10 ⁻⁶ mbar to 2 bar, more preferably in the range from 10 ⁻² mbar to 1 bar, most preferably in the range from 10 ⁻¹ mbar to 100 mbar. During the drying process, the temperature of the substrate can vary from -15°C to 250°C. The drying time depends on the degree of drying to be achieved, where a small amount of water can optionally be removed at a relatively high temperature in combination with sintering and should preferably be done.

It may further be provided that the process is repeated several times with formation of different or identical functional layers. Here, the functional layer formed can be cross-linked, for example as disclosed in EP 0 637 899 A1, to prevent its degradation.

The invention further relates to an electronic device obtainable by the method for manufacturing an electronic device.

The invention further relates to an electronic device having at least one functional layer comprising at least one organic functional material obtainable by the method for manufacturing an electronic device described above.

Electronic device is taken to mean a device comprising an anode, a cathode and at least one functional layer therebetween, wherein the functional layer comprises at least one organic or organometallic compound.

Organic electronic devices are preferably organic electroluminescent devices (OLED), polymer electroluminescent devices (PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O -TFT), organic light emitting transistor (O-LET), organic solar cell (O-SC), organic photovoltaic (OPV) cell, organic optical detector, organic photoreceptor, organic field quenching device (O-FQD) , an organic electrical sensor, a light emitting electrochemical cell (LEC) or an organic laser diode (O-laser), more preferably an organic electroluminescent device (OLED) or a polymer electroluminescent device (PLED).

Active ingredients are generally organic or inorganic materials introduced between the anode and cathode, where these active ingredients achieve, maintain and/or achieve the properties of the electronic device, such as its performance and/or its lifetime. or enhance, for example, charge injection, charge transport or charge blocking materials, but especially luminescent materials and matrix materials. Therefore, the organic functional materials that can be used for the production of functional layers of electronic devices preferably comprise active ingredients of electronic devices.

Organic electroluminescent devices are a preferred embodiment of the invention. An organic electroluminescent device includes a cathode, an anode, and at least one emissive layer.

It is further preferred to use mixtures of two or more triplet emitters with the matrix. Here, triplet emitters with short wavelength emission spectra act as a comatrix for triplet emitters with longer wavelength emission spectra.

In this case, the proportion of the matrix material in the light-emitting layer is preferably 50 to 99.9% by volume, more preferably 80 to 99.5% by volume, most preferably 92 to 99.5% by volume for the fluorescent light-emitting layer. and 85 to 97% by volume for the phosphorescent emitting layer.

Correspondingly, the dopant proportion is preferably 0.1 to 50% by volume, more preferably 0.5 to 20% by volume, most preferably 0.5 to 8% by volume for the fluorescent emitting layer. , 3 to 15% by volume in the case of the phosphorescent emitting layer.

The light-emitting layer of an organic electroluminescent device may further comprise a system comprising multiple matrix materials (mixed matrix system) and/or multiple dopants. Again, the dopant is generally the material with the lower proportion in the system and the matrix material is the material with the higher proportion in the system. However, in individual cases, the proportion of individual matrix materials in the system may be lower than the proportion of individual dopants.

Mixed matrix systems preferably comprise two or three different matrix materials, more preferably two different matrix materials. Here, preferably one of the two materials is a material with hole transport properties and the other material is a material with electron transport properties.
However, the desired electron-transporting and hole-transporting properties of the mixed matrix component may be combined primarily or completely by a single mixed matrix component, in which case the further mixed matrix component(s) may be combined with other fulfill a function. wherein the two different matrix materials are 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 to 1:1 may be present in the ratio of Mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices. Further details regarding mixed matrix systems can be found, for example, in WO2010/108579.

Apart from these layers, the organic electroluminescent device may comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, Exciton blocking layer, electron blocking layer, charge generating layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. .Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and/or organic or inorganic p/n junctions. Here, p-doping one _{or more} hole-transporting layers with e.g. It is possible to n-dope the electron transport layer. It is likewise possible to introduce an intermediate layer between the two emitting layers, for example having an exciton blocking function and/or controlling the charge balance in the electroluminescent device. However, it should be pointed out that each of these layers need not necessarily be present. These layers may likewise be present during the use of the formulations according to the invention, as defined above.

In a further aspect of the invention, the device comprises multiple layers. Here, the formulations according to the invention can preferably be used for the production of hole-transport, hole-injection, electron-transport, electron-injection and/or emission layers.

Accordingly, the present invention further comprises at least three layers of hole-injecting, hole-transporting, light-emitting, electron-transporting, electron-injecting, charge blocking and/or charge generating layers, and in preferred embodiments all of said layers. electronic devices in which at least one layer is obtained by the formulation to be used according to the invention. The thickness of a layer, eg a hole-transporting and/or hole-injecting layer, may preferably be in the range 1-500 nm, more preferably in the range 2-200 nm.

The device may further comprise layers built up from low molecular weight compounds or polymers that have not been applied using the formulations according to the invention. They can be prepared by evaporation of low molecular weight compounds in high vacuum.

In addition, it may be preferable to use the compounds to be used not as pure substances, but instead as mixtures (blends) with further polymeric, oligomeric, dendritic or low molecular weight substances of any desired type. These may, for example, have improved electronic properties and may themselves emit light.

In a preferred embodiment of the invention, the formulations according to the invention contain organic functional materials used as host or matrix material in the light-emitting layer. Here, the formulations may contain the emitters mentioned above in addition to the host or matrix material. Here, the organic electroluminescent device may comprise one or more emissive layers. When multiple emissive layers are present, they preferably have multiple emission maxima between 380 nm and 750 nm to produce an overall white emission, i.e., various emissive compounds capable of fluorescence or phosphorescence emit light. Used for layers. Very particular preference is given to three-layer systems, wherein the three layers exhibit blue, green and orange or red emission (for the basic structure see eg WO2005/011013). White light emitting devices are suitable, for example, as backlighting for LCD displays or for general lighting applications.

Multiple OLEDs can also be arranged one above the other, allowing a further increase in efficiency with respect to the light yield to be achieved.

To improve light coupling-out, the final organic layer on the light output side in the OLED can also be in the form of, for example, a nanofoam to provide a reduced percentage of total internal reflection.

Further preferred are organic electroluminescent devices in which one or more layers are applied by a sublimation process, wherein the material is below 10 ⁻⁵ mbar, preferably below 10 −6 mbar, more preferably below 10 ⁻⁶ mbar in a vacuum sublimation unit. is applied by vapor deposition at pressures below 10 ⁻⁷ mbar.

Further, it may be provided that one or more layers of the electronic device according to the invention are applied by an OVPD (organic vapor phase deposition) process or with the aid of carrier gas sublimation, wherein the material is It is applied at a pressure of 10 ⁻⁵ mbar to 1 bar.

Furthermore, one or more layers of the electronic device according to the invention can be produced from solution, such as by spin coating, or by any desired printing process, such as screen printing, flexographic printing or offset printing, but particularly preferably LITI (light-induced thermal imaging, thermal transfer printing) or manufactured by inkjet printing.

These layers may be applied by methods in which compounds of formula (I) or (II) are not used. Orthogonal solvents can preferably be used here which dissolve the functional material of the layer to be applied but not the layer to which the functional material is applied.

A device typically includes a cathode and an anode (electrodes). The electrodes (cathode, anode) are, for the purposes of the present invention, such that their band energies are as close as possible to the band energies of the adjacent organic layers in order to ensure highly efficient electron or hole injection. selected for

The cathode preferably comprises a metal complex, a metal with a low work function, a metal alloy or various metals such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg , Yb, Sm, etc.). In the case of multilayer structures, further metals with a relatively high work function, such as Ag and Ag nanowires (AgNWs) can also be used in addition to said metals, in which case metal combinations such as Ca/Ag or Ba/Ag etc. are commonly used. It may also be preferable to introduce a thin intermediate layer of material with a high dielectric constant between the metallic cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline earth metal fluorides, as well as the corresponding oxides (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, etc.). The layer thickness of this layer is preferably 0.1 to 10 nm, more preferably 0.2 to 8 nm, most preferably 0.5 to 5 nm.

The anode preferably comprises a material with a high work function. The anode preferably has a potential of greater than 4.5 eV versus vacuum. Suitable for this purpose are metals which on the one hand have a high redox potential, such as Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (eg Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. Depending on the application, at least one of the electrodes must be transparent to facilitate either irradiation of organic materials (O-SC) or coupling out of light (OLED/PLED, O-lasers). A preferred construction uses a transparent anode. Preferred anode materials herein are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Further preferred are conductive doped organic materials, especially conductive doped polymers such as poly(ethylenedioxythiophene) (PEDOT) and polyaniline (PANI), or derivatives of these polymers. It is further preferred to apply a p-doped hole-transporting material as hole-injecting layer to the anode, where suitable p-dopants are metal oxides such as _MoO3 or _WO3 , or (per)fluorinated electron It is a deficient aromatic compound. Further suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. A layer of this kind simplifies hole injection in materials with low HOMO, ie high values of HOMO.

In general, all such materials as are used for layers according to the prior art can be used for further layers and the person skilled in the art can combine each of these materials with the material according to the invention without inventive steps in electronic devices. .

Correspondingly, the devices are constructed in a manner known per se and, depending on the application, are provided with contacts and are finally hermetically sealed, since the lifetime of such devices is greatly reduced in the presence of water and/or air. be done.

The formulations according to the invention and the electronic devices obtainable therefrom, in particular organic electroluminescent devices, are distinguished from the prior art by one or more of the following surprising advantages:
1. The electronic devices obtainable using the formulations according to the invention exhibit a very high stability and a very long lifetime compared to electronic devices obtained using conventional methods.
2. The formulations according to the invention can be processed using conventional methods, as a result of which cost advantages can be realized.
3. The organic functional materials used in the formulations according to the invention allow the comprehensive use of the method of the invention without any particular restrictions.
4. The coatings obtainable with the formulations of the invention exhibit excellent qualities, especially with regard to coating uniformity.

These above advantages are not accompanied by a reduction in other electronic properties.

It should be pointed out that variations of the described aspects of the invention are included within the scope of the invention.
Each feature disclosed in this invention, unless expressly excluded, may be replaced by alternative features serving the same, equivalent or similar purpose. Therefore, each feature disclosed in the present invention should be considered an example of a generic series or equivalent or similar features unless otherwise specified.

All features of the invention may be combined with each other in any manner, unless specific features and/or steps are mutually exclusive. This applies in particular to preferred features of the invention. Similarly, non-essential combination features may be used individually (and not in combination).

It should also be pointed out that many features, particularly those of preferred embodiments of the invention, are inventive in themselves and should not be considered as part of the embodiments of the invention. Independent protection may be sought for these features in addition to or alternative to each invention claimed in the present invention.

The teachings of the technical acts disclosed by the present invention can be extracted and combined with other examples.

The invention is explained in more detail below with reference to the examples, without it being restricted thereby.

A person skilled in the art can use this description to manufacture further electronic devices according to the invention without having to use creative techniques and thus practice the invention throughout the scope of the claims.

[example]
Film Formation As shown in Table 2, nine inks were made for the hole injection layer (HIL). The ink was inkjet printed and the film profile was measured after drying. The results are shown in Figures 2-10. The solvent 3-phenoxytoluene was chosen as a reference solvent (comparative example) and shows a uniform film profile. By adding adamantane derivatives (adamantane-1-sulfonic acid methyl ester and ethyladamantane-1-carboxylate), the film profile shows a uniform organic layer, slightly better than the comparative example. Another primary solvent, butyl benzoate, was chosen for further proof of concept. Addition of 10% adamantane derivative to butyl benzoate makes the film profile flatter compared to this reference solvent.

Film profiles were measured using a KLA-Tencor Corporation profilometer Alpha-step D120 with a 2 μm stylus. A flatness index was calculated by the following formula and used to determine flatness.

(In the formula,
H _edge is the height of the pixel edge of
H _center is the height of the pixel center. )
A film is considered flat if the flatness index is 10% or less.

Claims (18)

A formulation comprising at least one organic functional material and at least first and second organic solvents,
The first organic solvent has the general formula (I)

( In the formula,
X is CR;
R is the same or different at each occurrence, H, D, F, CN, NO ₂ , N(R ¹ ) ₂ , Si(R ¹ ) ₃ , straight chain having 1-20 carbon atoms Alkyl, alkoxy or thioalkoxy groups, branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, straight chain alkenyl or alkynyl groups having 2 to 20 carbon atoms or 3 to 20 A branched or cyclic alkenyl or alkynyl group having carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ¹ -, -CONR ¹ -, -S ( O) optionally replaced by ₂ -O-, -Si(R ¹ ) ₂ -, -CO-O-, -C=O-, -CR ¹ =CR ¹ - or -C≡C-, 1 one or more hydrogen atoms may be replaced by D, F, CN or NO 2), or an aryl or heteroaryl group having 5 to 60 ring atoms, or having 5 to 40 ring _atoms an aryloxy or heteroaryloxy group, or an arylalkyl or heteroarylalkyl group having 5 to 40 ring atoms, which are optionally substituted by one or more non-aromatic R 1 radicals ^; Two substituents R on the same ring together form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system optionally substituted by multiple substituents R ¹ may;
R ¹ is the same or different in each case and is a linear alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms (here and one or more non-adjacent CH2 _groups are replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- one or more hydrogen atoms may be replaced by F), or having 4 to 14 carbon atoms and substituted by one or more non-aromatic R 1 ^radicals good aryl or heteroaryl groups)
is an adamantane derivative by
the content of the first organic solvent is in the range of 0.5 to 25% by weight, based on the total amount of solvent in the formulation;
The content of the second organic solvent is in the range of 75-99.5% by weight based on the total amount of solvent in the formulation
formulation. The first organic solvent has the general formula (II)

(wherein R and ^R1 are as defined in claim 1)
2. The formulation of claim 1 , which is an adamantane derivative according to. 3. A formulation according to claim 1 or 2 , wherein said first organic solvent has a surface tension of 20 mN/m or more. A formulation according to any preceding claim, wherein said first organic solvent has a boiling point in the range of 100-400 °C. Formulation according to any one of the preceding claims, wherein said formulation comprises at least one second organic solvent different from said first organic solvent. A formulation according to any preceding claim, wherein said second organic solvent has a boiling point in the range of 100-400°C. Formulation according to any one of the preceding claims, wherein said at least one organic functional material has a solubility in said first and said second organic solvent ranging from 1 to 250 g/l. . Formulation according to any one of the preceding claims, wherein said formulation has a surface tension in the range from 10 to 50 mN/m. Formulation according to any one of the preceding claims, wherein the formulation has a viscosity in the range from 1 to 50 mPa·s. 10. The method according to any one of claims 1 to 9 , wherein the content of said at least one organic functional material in said formulation is in the range of 0.001 to 20% by weight based on the total weight of said formulation. Formulation as described. wherein the at least one organic functional material is an organic conductor, an organic semiconductor, an organic fluorescent compound, an organic phosphorescent compound, an organic light absorbing compound, an organic photosensitive compound, an organic photosensitizer, and other organic photoactive compounds; Formulation according to any one of claims 1 to 10 , for example selected from the group consisting of organometallic complexes of transition metals, rare earths, lanthanides and actinides. The at least one organic functional material is a fluorescent emitter, a phosphorescent emitter, a host material, a matrix material, an exciton blocking material, an electron transport material, an electron injection material, a hole transport material, a hole injection material, and an n-dopant. , p-dopants, wide bandgap materials , electron blocking materials, and hole blocking materials. 12. The formulation of claim 11 , wherein said at least one organic functional material is an organic semiconductor selected from the group consisting of hole-injecting, hole-transporting, luminescent, electron-transporting and electron-injecting materials. 14. The formulation of claim 13 , wherein said at least one organic semiconductor is selected from the group consisting of hole-injecting and hole-transporting materials. 15. The formulation of claim 14 , wherein the hole-injecting and hole-transporting material is a polymeric compound or a blend of polymeric and non-polymeric compounds. A method of producing a formulation according to any preceding claim, wherein said at least one organic functional material and said at least first and second organic solvents are mixed. Producing an electroluminescent device, wherein at least one layer of the electroluminescent device is prepared by depositing a formulation according to any one of claims 1 to 15 on a surface followed by drying Method. Electroluminescent device, wherein at least one layer is produced by depositing a formulation according to any one of claims 1 to 15 on a surface and subsequently drying.

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