KR102632027B1 - Formulation of organic functional materials - Google Patents

Abstract

The present invention relates to formulations containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one carbonate group, and to electronic devices manufactured using such formulations. It's about.

Description

Formulation of organic functional materials

The present invention relates to a formulation containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one carbonate group, and an electroluminescence device prepared using such formulation. It's about devices.

Organic light emitting devices (OLEDs) have long been fabricated by vacuum deposition processes. Other technologies, such as inkjet printing, have recently been thoroughly investigated due to their advantages such as cost savings and scale-up potential. One of the main challenges in multilayer printing is identifying the relevant parameters to obtain a homogeneous deposition of ink on the substrate. To trigger these parameters, such as surface tension, viscosity or boiling point, some additives may be added to the formulation.

Many solvents have been proposed for inkjet printing of organic electronic devices. However, the number of important parameters that play a role during the deposition and drying process makes the choice of solvent very difficult. Therefore, formulations containing organic semiconductors used for film deposition by inkjet printing still require improvement. One object of the present invention is to provide a formulation of an organic semiconductor that allows controlled deposition to form an organic semiconductor layer with good layer properties and efficiency performance. A further object of the present invention is to provide a formulation of an organic semiconductor that provides good layer properties and efficiency performance by enabling uniform application of ink droplets on a substrate, for example when used in inkjet printing methods. will be.

The above objects of the present invention are directed to a formulation containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one carbonate group, preferably one carbonate group. This is resolved by providing

The inventors have surprisingly found that the use of an organic solvent containing at least one carbonate group as the first solvent allows complete control of the surface tension and the formation of a uniform and well-defined layer of functional materials with good layer properties and performance. It was found that it leads to effective ink deposition to form organic layers.

Figure 1 shows a device containing 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 an Al cathode. shows a typical layer structure.

Detailed Description of Embodiments

The invention relates to a formulation containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one carbonate group, preferably one carbonate group.

Preferred Embodiment

In a preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group-containing solvent according to general formula (I)

During the ceremony

R ¹ and R ² are the same or different at each occurrence and are selected from the group consisting of a straight-chain 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, 2 to 20 carbon atoms, A straight chain alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkenyloxy group having 2 to 20 carbon atoms. or a branched or cyclic alkynyl or alkynyloxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO -O-, -C=O-, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F), or has 4 to 14 carbon atoms or an aryl or heteroaryl group, which may form a fused heterocycle or aryl and may be substituted by one or more non-aromatic R ³ radicals, on the same ring or on two different rings, a plurality of substituents R ³ , together in turn, may form a monocyclic or polycyclic, aliphatic or aromatic ring system, which may be substituted by a plurality of substituents R ³ ; and

R ³ is the same or different at each occurrence and is a straight-chain 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, wherein one or more non-adjacent CH ₂ groups may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F ), or an aryl or heteroaryl group having 4 to 14 carbon atoms and which may be substituted with one or more non-aromatic R ³ radicals.

In a first more preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group-containing solvent according to general formula (I) wherein

R ¹ and R ² are the same or different at each occurrence and have 4 to 14 carbon atoms, or may form a fused heterocycle or aryl and may be substituted by one or more non-aromatic R ³ radicals. or a heteroaryl group, wherein, on the same ring or on two different rings, a plurality of substituents R ³ together form a monocyclic or polycyclic, aliphatic or aromatic ring system, which in turn may be substituted by a plurality of substituents R ³ It may be possible.

In a first most preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group containing solvent according to general formula (II)

During the ceremony

R ³ is the same or different at each occurrence and is a straight-chain 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, wherein one or more non-adjacent The CH ₂ group may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F. may; and

n is an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

In a second more preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group-containing solvent according to general formula (I) wherein

R ¹ is a straight-chain 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, a straight-chain alkenyl or alkenyloxy group having 2 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkynyloxy group having 2 to 20 carbon atoms, or a branched or cyclic alkenyloxy group having 3 to 20 carbon atoms or A cyclic alkynyl or alkynyloxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH =CH- or -C≡C- and one or more hydrogen atoms may be replaced by F; and

R ² is an aryl or heteroaryl group having 4 to 14 carbon atoms, which may form a fused heterocycle or aryl and which may be substituted by one or more non-aromatic R ³ radicals and which may be substituted on the same ring or by 2 On different rings, a plurality of substituents R ³ may together form a monocyclic or polycyclic, aliphatic or aromatic ring system, which in turn may be substituted by a plurality of substituents R ³ ;

In a second most preferred embodiment, the first organic solvent containing one carbonate group is a solvent containing carbonate groups according to general formula (III)

During the ceremony

R ¹ is a straight-chain 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, a straight-chain alkenyl or alkenyloxy group having 2 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkynyloxy group having 2 to 20 carbon atoms, or a branched or cyclic alkenyloxy group having 3 to 20 carbon atoms or A cyclic alkynyl or alkynyloxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH =CH- or -C≡C- and one or more hydrogen atoms may be replaced by F;

R ³ is the same or different at each occurrence and is a straight-chain 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, wherein one or more non-adjacent The CH ₂ group may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F. may; and

n is an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

In a third more preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group containing solvent according to general formula (I) wherein

R ¹ and R ² are the same or different at each occurrence and are selected from the group consisting of a straight-chain 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, 2 to 20 carbon atoms, A straight chain alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkenyloxy group having 2 to 20 carbon atoms. or a branched or cyclic alkynyl or alkynyloxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO -O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F.

In a third most preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group-containing solvent according to general formula (I) wherein

R ¹ and R ² are the same or different in each case and are a straight-chain 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.

In a fourth more preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group-containing solvent according to general formula (I) wherein

R ¹ is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched alkyl or alkoxy group having 3 to 20 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2 to 20 carbon atoms, or 3 A branched alkenyl or alkenyloxy group having from 2 to 20 carbon atoms, or a straight-chain alkynyl or alkynyloxy group having from 2 to 20 carbon atoms, or a branched alkynyl or alkynyl group having from 3 to 20 carbon atoms. an oxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH=CH- or -C ≡C- may be replaced and one or more hydrogen atoms may be replaced by F; and

R ² is a cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, a cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a cyclic alkynyl or alkynyl group having 3 to 20 carbon atoms. an oxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH=CH- or -C ≡C- and one or more hydrogen atoms may be replaced by F.

In a fourth most preferred embodiment, the first organic solvent containing one carbonate group is a carbonate group-containing solvent according to general formula (IV),

During the ceremony

R ¹ is a straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a straight-chain alkenyl group having 2 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms It is a branched alkenyl group, or a straight-chain alkynyl group having 2 to 20 carbon atoms, or a branched alkynyl group having 3 to 20 carbon atoms;

R ³ is the same or different at each occurrence and is a straight-chain 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, wherein one or more non-adjacent The CH ₂ group may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F. may; and

n is an integer of 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

Examples of preferred carbonate group containing solvents and their boiling points (BP) are shown in Table 1 below.

Preferably, the first solvent has a surface tension of ≧20 mN/m. More preferably, the surface tension of the first solvent ranges from 25 to 40 mN/m, and most preferably from 28 to 37.5 mN/m.

The content of the first solvent is preferably in the range of 50 to 100% by volume, more preferably in the range of 75 to 99% by volume and most preferably in the range of 90 to 99% by volume, based on the total amount of solvent in the formulation.

As a result, the content of the second solvent is preferably in the range from 0 to 50% by volume, more preferably in the range from 1 to 25% by volume and most preferably in the range from 1 to 10% by volume, based on the total amount of solvent in the formulation. am.

Preferably, the boiling point of the first solvent is in the range of 100 to 400°C, more preferably in the range of 200 to 400°C.

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

In one embodiment, the second solvent can be a different solvent than the first solvent, containing carbonate groups. Nevertheless, preferably, the second solvent does not contain carbonate groups.

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

Preferably, the second solvent may be selected from one of 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 heterocycles such as pyrrolidinone, pyridine, pyrazine; 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-dimethyltetraline, 1-benzothylene Ophene, thianaphthalene, 1-bromonaphthalene, 1-chloromethylnaphthalene, 1-ethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 1-methylindole, 2,3-benzofuran, 2,3-di Hydrobenzofuran, 2,3-dimethylanisole, 2,4-dimethylanisole, 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, butyl phenyl ether, cyclohexyl Benzene, decahydronaphthol, dimethoxytoluene, 3-phenoxytoluene, diphenyl ether, propiophenone, ethylbenzene, ethyl benzoate, hexylbenzene, indane, hexamethylindane, indene, isochroman, cumene, m- Cymene, mesitylene, methyl benzoate, o-, m-, p-xylene, propyl benzoate, propylbenzene, o-dichlorobenzene, pentylbenzene, phenethol, ethoxybenzene, phenyl acetate, p-cymene, propylene Ophenone, sec-butylbenzene, t-butylbenzene, thiophene, toluene, veratrol, monochlorobenzene, o-dichlorobenzene, pyridine, pyrazine, pyrimidine, pyrrolidinone, morpholine, dimethylacet-amide, dimethyl sulfoxide, decalin and/or mixtures of these compounds.

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

Preferably, the boiling point of the second solvent is in the range of 100 to 400°C, more preferably in the range of 150 to 350°C.

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

The content of at least one organic functional material in the formulation ranges from 0.001 to 20% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, and most preferably from 0.001 to 20% by weight, based on the total weight of the formulation. ranges from 0.3 to 5% by weight.

The formulation according to the invention preferably has a surface tension in the range from 10 to 50 mN/m and more preferably in the range from 25 to 40 mN/m.

Moreover, the formulation according to the invention preferably has a temperature range of 1 to 50 mPa ^. s range, more preferably 2 to 40 mPa ^. s range, and most preferably between 2 and 20 mPa ^. It has a viscosity in the s range.

Preferably, the organic solvent blend comprises a surface tension in the range of 15 to 80 mN/m, more preferably in the range of 20 to 60 mN/m and most preferably in the range of 25 to 40 mN/m. Surface tension can be measured using a FTA (First Ten Angstrom) 1000 contact angle goniometer at 20°C. Details of this method are provided by Roger P. Woodward, Ph.D. Available from First Ten Angstrom as published in “Surface Tension Measurements Using the Drop Shape Method.” Preferably, the surface tension can be determined using the soaking method. This measurement technique dispenses a drop from a needle in the bulk liquid or gas phase. The shape of the droplet is obtained from the relationship between surface tension, gravity, and density differences. When using the drop method, the surface tension is calculated from the shadow image of the pendant drop using http://www.kruss.de/services/education-theory/glossary/drop-shape-analysis do. Commonly used and commercially available high-precision droplet shape analysis tools, namely First Ten All surface tension measurements were performed using FTA100 from ngstrom. The surface tension is determined by the software FTA1000. All measurements were performed at room temperature ranging from 20°C to 22°C. Standard operating procedures include determination of the surface tension of each formulation using novel disposable droplet dispensing systems (syringes and needles). Each droplet is measured with 60 measurements over a duration of 1 minute, which are later averaged. For each formulation, three droplets were measured. The final value is the average of the above measurements. The tool is regularly cross-checked against various liquids with well-known surface tensions.

The viscosity of the formulations and solvents according to the invention is measured with a TA Instruments ARG2 rheometer over a shear rate range from 10 to 1000 s ^-1 using a 40 mm parallel plate geometry. Measurements were taken as averages from 200 to 800 s ^-1 , where temperature and shear rate were accurately controlled. The viscosity shown in Table 3 is the viscosity of each formulation measured at a temperature of 25°C. Each solvent was measured three times. The viscosity values mentioned were averaged over the above measurements.

The formulation according to the invention comprises 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 introduced between the anode and cathode of an electronic device.

The term organic functional material includes, in particular, organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light-absorbing compounds, organic light-sensitive compounds, organic photosensitisation agents and other organic photoactive compounds. represents a compound. The term organic functional materials therefore includes organometallic complexes of transition metals, rare earths, lanthanides and actinides.

Organic functional materials include fluorescent emitter, phosphorescent emitter, host material, matrix material, exciton blocking material, electron transport material, electron injection material, hole conductor material, hole injection material, n-dopant, p-dopant, wide It is selected from the group consisting of wide-band-gap materials, electron blocking materials, and hole blocking materials.

Preferred embodiments of organic functional materials are disclosed in detail in WO 2011/076314 A1, the content of which is incorporated herein by reference.

In a preferred embodiment, the organic functional material is an organic semiconductor selected from the group consisting of hole injection, hole transport, emission, electron transport and electron injection materials.

More preferably, the organic functional material is an organic semiconductor selected from the group consisting of hole injection and hole transport materials.

The organic functional materials may be compounds, polymers, oligomers or dendrimers with low molecular weight, where the organic functional materials may also be in the form of mixtures. Therefore, the formulation according to the invention may comprise two different compounds with low molecular weight, one compound with low molecular weight and one polymer or two polymers (blend).

Organic functional materials are often described through the properties of frontier orbitals, which are explained in more detail below. Molecular orbitals, especially also the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy levels and the energy of the lowest triplet state T ₁ or of the lowest excited singlet state S ₁ of the material are It is determined through quantum-chemical calculations. To calculate metal-free organic materials, first, geometry optimization is performed using the “ground state/quasi-empirical/default spin/AM1/charge 0/spin singlet” method. Energy calculations are then performed based on the optimized geometry. Here, the "TD-SCF/DFT/Default Spin/B3PW91" method using the "6-31G(d)" base set (charge 0, spin singlet) is used. For metal-containing compounds, the geometry is optimized via the “ground state/Hartree-Fock/default spin/LanL2MB/charge 0/spin singlet” method. Energy calculations are performed similarly to the method described above for organic materials, except that the "LanL2DZ" base set is used for metal atoms and the "6-31G(d)" base set is used for ligands. The energy calculation gives the HOMO energy level HEh or the LUMO energy level LEh in hartree units. The HOMO and LUMO energy levels in electron volts, calibrated based on cyclic voltammetry measurements, are then determined as follows:

For the purposes of this application, these values will be regarded as the HOMO and LUMO energy levels of the materials, respectively.

The lowest triplet state T ₁ is defined as the energy of the triplet state with the lowest energy resulting from the quantum chemical calculations described.

The lowest excited singlet state S ₁ is defined as the energy of the excited singlet state with the lowest energy resulting from the quantum-chemical calculations described.

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

Compounds with hole injection properties, also so-called herein hole injection materials, simplify or facilitate the transport of holes, i.e. positive charges, from the anode to the organic layer. Typically, the hole injecting material has a HOMO level at or above the anode level region, ie typically at least -5.3 eV.

Compounds with hole transport properties, also so-called herein hole transport materials, are generally capable of transporting holes, i.e. positive charges, injected from the anode or an adjacent layer, for example a hole injection layer. The hole transport material generally preferably has a high HOMO level of at least -5.4 eV. Depending on the structure of the electronic device, hole transport materials may also be used as hole injection materials.

Preferred compounds having hole injection and/or hole transport properties include, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thiamine. Trene, dibenzo-para-dioxine, phenoxathiin, carbazole, azulene, thiophene, pyrrole and furan derivatives, and also additional O-, S with high HOMO (HOMO = highest occupied molecular orbital) - or N-containing heterocycles are included.

Compounds with hole injection and/or hole transport properties include phenylenediamine derivatives (US 3615404), arylamine derivatives (US 3567450), amino-substituted chalcone derivatives (US 3526501), styrylanthracene derivatives (JP-A- 56-46234), polycyclic aromatic compounds (EP 1009041), polyarylalkane derivatives (US 3615402), fluorenone derivatives (JP-A-54-110837), hydrazone derivatives (US 3717462), acylhydrazone, stilbene derivatives (JP-A-61-210363), silazane derivative (US 4950950), polysilane (JP-A-2-204996), aniline copolymer (JP-A-2-282263), thiophene oligomer (JP Heisei 1 (1989) 211399), polythiophene, poly(N-vinylcarbazole) (PVK), polypyrrole, polyaniline and other electrically conductive macromolecules, porphyrin compounds (JP-A-63-2956965, US 4720432), aromatic dimethylidene type compounds, carbazole compounds, such as for example CDBP, CBP, mCP, aromatic tertiary amines and styrylamine compounds (US 4127412), such as for example triphenylamines of the benzidine type, triphenylamines of the styrylamine type and triphenylamine of the diamine type may be particularly mentioned. Also, arylamine dendrimers (JP Heisei 8 (1996) 193191), monomeric triarylamines (US 3180730), triarylamines containing at least one functional group containing one or more vinyl radicals and/or active hydrogen (US 3567450) and US 3658520), or tetraaryldiamine (two tertiary amine units linked through an aryl group) can be used. Additionally, more triarylamino groups may be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives, for example dipyrazino[2,3-f:2',3'-h]quinoxalinehexacarbonitrile.

Aromatic tertiary amines containing at least two tertiary amine units (US 2008/0102311 A1, US 4720432 and US 5061569), such as NPD (α-NPD = 4,4'-bis[N-(1-naph) til)-N-phenylamino]biphenyl) (US 5061569), TPD 232 (= 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-tolylamino phenyl)cyclohexane), 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"'-quarterphenyl, also tertiary amines containing carbazole units, for example TCTA (=4-(9H-carbazol-9-yl)-N,N- Preference is given to bis[4-(9H-carbazol-9-yl)phenyl]benzenamine) 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) is equally desirable.

Particularly preferred are the following triarylamine compounds of formula (TA-1) to (TA-12), which are described in EP 1162193 B1, EP 650 955 B1, Synth.Metals 1997 , 91(1-3), 209, DE 19646119 A1. , WO 2006/122630 A1, EP 1 860 097 A1, EP 1834945 A1, JP 08053397 A, US 6251531 B1, US 2005/0221124, JP 08292586 A, US 7399537 B2 , US 2006/006126 5 A1, EP 1 661 888 and WO It is disclosed in 2009/041635. The above compounds of formula (TA-1) to (TA-12) may also be substituted:

Further compounds that can be used as hole injection materials are disclosed in EP 0891121 A1 and EP 1029909 A1, and injection layers are generally disclosed in US 2004/0174116 A1.

These arylamines and heterocycles, which are generally used as hole injection and/or hole transport materials, give rise in the polymer to a HOMO of preferably greater than -5.8 eV (relative to the vacuum level), particularly preferably greater than -5.5 eV. .

Compounds with electron injection and/or electron transport properties include, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine. Azines, ketones, phosphine oxides and phenazine derivatives, as well as triarylboranes and further O-, S- or N-containing heterocycles with low LUMO (LUMO = lowest unoccupied molecular orbital).

Particularly suitable compounds for the electron transport and electron injection layer include metal chelates of 8-hydroxyquinoline (e.g. LiQ, AlQ ₃ , GaQ _{3 , MgQ 2} , ZnQ ₂ , InQ _{3 ,} ZrQ ₄ ), BAlQ, Ga oxinoids Complexes, 4-azaphenanthrene-5-ol-Be complex (US 5529853 A, see formula ET-1), butadiene derivative (US 4356429), heterocyclic optical brightener (US 4539507), benzimidazole Derivatives (US 2007/0273272 A1), such as for example TPBI (see US 5766779, formula ET-2), 1,3,5-triazines, for example spirobifluorenyltriazine derivatives (for example DE 102008064200), pyrene, anthracene, tetracene, fluorene, spirofluorene, dendrimer, tetracene (e.g. rubrene derivatives), 1,10-phenanthroline derivatives (JP 2003-115387, JP 2004-311184 , JP-2001-267080, WO 02/043449), silacyclopentadiene derivatives (EP 1480280, EP 1478032, EP 1469533), borane derivatives, such as Si-containing triarylborane derivatives (US 2007/0087219 A1, formula ET-3), pyridine derivatives (JP 2004-200162), phenanthrolines, especially 1,10-phenanthroline derivatives, such as for example BCP and Bphen, as well as several phenanthroles linked via biphenyl or other aromatic groups. lin (US-2007-0252517 A1) or phenanthroline linked to anthracene (US 2007-0122656 A1, see formulas ET-4 and ET-5).

Heterocyclic organic compounds, such as for example thiopyran dioxide, oxazole, triazole, imidazole or oxadiazole, are likewise suitable. Examples of the use of N-containing 5-membered rings include, for example, oxazoles, preferably 1,3,4-oxadiazoles, for example formulas ET-6, ET-7, ET-8 and ET- Compounds of 9 (especially those disclosed in US 2007/0273272 A1); Thiazoles, oxadiazoles, thiadiazoles, triazoles (see especially US 2008/0102311 A1 and Y.A. Levin, M.S. Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341), preferably compounds of the formula ET-10 , is a silacyclopentadiene derivative. Preferred compounds are of the formula (ET-6) to (ET-10):

Additionally, organic compounds such as derivatives of fluorenone, fluorenylidenemethane, perylenetetracarboxylic acid, anthraquinonedimethane, diphenoquinone, anthrone and anthraquinonediethylenediamine can be used.

2,9,10-substituted anthracene (with 1- or 2-naphthyl, and 4- or 3-biphenyl) or a molecule containing two anthracene units (see US 2008/0193796 A1, formula ET-11) is desirable. The connection of 9,10-substituted anthracene units to benzimidazole derivatives (see US 2006/147747 A and EP 1551206 A1, formulas ET-12 and ET-13) is also very advantageous.

Compounds capable of producing electron injection and/or electron transport properties preferably give rise to a LUMO below -2.5 eV (relative to the vacuum level), particularly preferably below -2.7 eV.

Formulations of the invention may also include an emitter. The term emitter refers to a material that enables a radiative transition to the ground state with emission of light after excitation, which can occur by any type of energy transfer. In general, two classes of emitters are known: fluorescent and phosphorescent emitters. The term fluorescent emitter refers to a material or compound in which a radiative transition from an excited singlet state to the ground state occurs. The term phosphorescent emitter refers to a luminescent material or compound, preferably containing a transition metal.

Emitters are also often called dopants when the dopant causes the properties described above in the system. In systems comprising a matrix material and a dopant, the dopant is taken to mean the component whose proportion in the mixture is smaller. Correspondingly, in systems comprising a matrix material and a dopant, the matrix material is taken to mean the component whose proportion in the mixture is greater. Accordingly, the term phosphorescent emitter can also be taken to mean, for example, a phosphorescent dopant.

Compounds capable of emitting light include, among others, fluorescent emitters and phosphorescent emitters. These are, in particular, stilbenes, stilbenamines, styrylamines, coumarins, rubrenes, rhodamines, thiazoles, thiadiazoles, cyanines, thiophenes, paraphenylenes, perylenes, phthalocyanines, porphyrins, ketones, quinolines and imines. , and compounds containing anthracene and/or pyrene structures. Compounds that are capable of emitting light with high efficiency from the triplet state even at room temperature, i.e. exhibiting electrophosphorescence instead of electrofluorescence, which often leads to an increase in energy efficiency, are particularly preferred. First, compounds containing heavy atoms with an atomic number greater than 36 are suitable for this purpose. Compounds containing d- or f-transition metals that satisfy the conditions mentioned above are preferred. Here, corresponding compounds containing elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt) are particularly preferred. Suitable functional compounds here are various complexes as described for example in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 2004/026886 A2.

Preferred compounds that can act as fluorescent emitters are described by way of example below. Preferred fluorescent emitters are selected from the class of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphine, styryl ethers and arylamines.

Monostyrylamine is taken to mean a compound containing one substituted or unsubstituted styryl group and at least one, preferably aromatic amine. Distyrylamine is taken to mean a compound containing two substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. Tristyrylamine is taken to mean a compound containing three substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. Tetrastyrylamine is taken to mean a compound containing four substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. The styryl group is particularly preferably stilbene, which may also be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamines or aromatic amines in the meaning of the present invention are understood to mean compounds containing a system of three substituted or unsubstituted aromatic or heteroaromatic rings directly bonded to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyrenamine, aromatic pyrenediamine, aromatic chrysenamine or aromatic chrysendiamine. Aromatic anthraceneamines are taken to mean compounds in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. Aromatic anthracenediamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 2,6- or 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined similarly, wherein the diarylamino group is bonded to the pyrene, preferably at the 1-position or 1,6-position.

Further preferred fluorescent emitters are indenofluorenamine or indenofluorenediamine, in particular those described in WO 2006/122630; benzoindenofluoreneamine or benzoindenofluorenediamine, especially as described in WO 2008/006449; and in particular dibenzoindenofluoreneamine or dibenzoindenofluorenediamine described in WO 2007/140847.

Examples of compounds from the styrylamine class that can be used as fluorescent emitters include substituted or unsubstituted tristilbenamine, or WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and This is a dopant described in WO 2007/115610. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Additional styrylamines can be found in US 2007/0122656 A1.

Particularly preferred styrylamine compounds are the compounds of the formula EM-1 described in US Pat. No. 7,250,532 B2 and the compounds of the formula EM-2 described in DE 10 2005 058557 A1:

Particularly preferred triarylamine compounds are those described in CN 1583691 A, JP 08/053397 A and US 6251531 B1, EP 1957606 A1, US 2008/0113101 A1, US 2006/210830 A, WO 2008/006449 and DE 102008035413. The disclosed formula EM- 3 to EM-15, and their derivatives:

Further preferred compounds that can be used as fluorescent emitters are naphthalene, anthracene, tetracene, benzanthracene, benzophenanthrene (DE 10 2009 005746), fluorene, fluoranthene, periplanthene, indenoperylene, phenanes. Trene, perylene (US 2007/0252517 A1), pyrene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US 4769292 , US 6020078, US 2007/0252517 A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamic acid ester, diketopyrrolopyrrole, acridone and quinacridone (US 2007/ 0252517 A1).

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

Rubrene, coumarin, rhodamine, quinacridone, such as for example DMQA (= N,N'-dimethylquinacridone), dicyanomethylenepyran, such as for example DCM (=4-(dicyanoethylene)- Equally preferred are derivatives of 6-(4-dimethylaminostyryl-2-methyl)-4H-pyran), thiopyran, polymethine, pyrylium and thiapyrylium salts, periplanthene and indenoperylene.

The blue fluorescent emitter is preferably a polyaromatic compound, such as for example 9,10-di(2-naphthylanthracene) and other anthracene derivatives, tetracene, xanthene, derivatives of perylene, such as for example 2 ,5,8,11 -tetra- t-butylperylene, phenylene, e.g. 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl, fluorene , fluoranthene, arylpyrene (US 2006/0222886 A1), arylenevinylene (US 5121029, US 5130603), bis(azinyl)imine-boron compound (US 2007/0092753 A1), bis(azinyl)methene compounds and carbostyryl compounds.

A further preferred blue fluorescent emitter is C.H. Chen et al.: “Recent developments in organic electroluminescent materials”, Macromol. 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 DE 102008035413.

Preferred compounds that can act as fluorescent emitters are described below by way of example.

Examples of phosphorescent emitters are revealed by WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP 1191613, EP 1191612, EP 1191614 and WO 2005/033244. In general, all phosphorescent complexes used according to the prior art for phosphorescent OLEDs and known to the person skilled in the art of organic electroluminescence are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without inventive steps.

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-phenyl It is an isoquinoline derivative or 2-phenylquinoline derivative. All these compounds may be substituted with fluoro, cyano and/or trifluoromethyl substituents, for example for blue color. The auxiliary ligand is preferably acetylacetonate or picolinic acid.

In particular, complexes of Pt or Pd with tetradentate ligands of formula EM-16 are suitable.

Compounds of formula EM-16 are described in more detail in US 2007/0087219 A1, and for explanation of substituents and indices in the above formula, reference is made to this specification for disclosure purposes. Additionally, Pt-porphyrin complexes with expanded ring systems (US 2009/0061681 A1) and Ir complexes, such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin -Pt(II), tetraphenyl-Pt(II) tetrabenzoporphyrin (US 2009/0061681 A1), 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)quinolinate-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, US 2001/0053462 A1, 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) (acetylacetonate), bis(2-(4',6'- Difluorophenyl)pyridinato-N,C ^2' )iridium(III) (picolinate) (FIrpic, blue), bis(2-(4',6'-difluorophenyl)pyridine To-N,C ^2' )Ir(III) (tetrakis(1-pyrazolyl)borate), tris(2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III), ( ppz) ₂ Ir(5phdpym) (US 2009/0061681 A1), (45ooppz) ₂ Ir(5phdpym) (US 2009/0061681 A1), derivatives of the 2-phenylpyridine-Ir complex, such as, for example, PQIr (= Iridium(III) bis(2-phenylquinolyl-N,C ^2' )acetylacetonate), tris(2-phenylisoquinolinato-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).

Trivalent lanthanides, such as, for example, complexes of 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 the phosphorescent complex of Pt(II), Ir(I), Rh(I) with maleonitrile dithiolate (Johnson et al., JACS 105, 1983, 1795), Re(I) tricarbonyl -diimine complexes (especially Wrighton, JACS 96, 1974, 998), Os(II) complexes with cyano ligands, and bipyridyl or phenanthroline ligands (Ma et al., Synth. Metals 94, 1998, 245) This is equally suitable.

Additional phosphorescent emitters with tridentate ligands are described in US 6824895 and US 10/729238. Red emitting phosphorescent complexes are found in US 6835469 and US 6830828.

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

Derivatives are described in US 7378162 B2, US 6835469 B2 and JP 2003/253145 A.

Furthermore, compounds of formula EM-18 to EM-21 (described in US 7238437 B2, US 2009/008607 A1 and EP 1348711) and their derivatives can be used as emitters.

Quantum dots can likewise be used as emitters; these materials are disclosed in detail in WO 2011/076314 A1.

Compounds used as host materials, especially with emitting compounds, include materials from various classes of materials.

The host material has a larger band gap between HOMO and LUMO than commonly used emitter materials. Additionally, preferred host materials exhibit properties of hole- or electron-transport materials. Furthermore, the host material can have both electron- and hole-transport properties.

The host material is also called a so-called matrix material in some cases, especially when the host material is used in combination with a phosphorescent emitter in an OLED.

Preferred host or co-host materials, especially used with fluorescent dopants, are those of the class of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobi according to EP 676461) fluorene or dinaphthylanthracene), especially oligoarylenes containing condensed aromatic groups, such as for example anthracene, benzanthracene, benzophenanthrene (DE 10 2009 005746, WO 2009/069566), phenanthrene, tetracene, coro Nene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, oligoarylenevinylene (e.g. DPVBi = 4,4 according to EP 676461 '-bis(2,2-diphenylethenyl)-1,1'-biphenyl or spiro-DPVBi), polypodal metal complexes (e.g. according to WO 04/081017), especially 8-hydride Metal complexes of hydroxyquinolines, for example AlQ ₃ (= aluminum(III) tris(8-hydroxyquinoline)) or bis(2-methyl-8-quinolinoleato)-4-(phenylphenolinoleto)aluminium , also imidazole chelates (US 2007/0092753 A1) and quinoline-metal complexes, aminoquinoline-metal complexes, benzoquinoline-metal complexes, hole-conducting compounds (for example according to WO 2004/058911), electron-conducting compounds, especially Ketones, phosphine oxides, sulfoxides, etc. (e.g. according to WO 2005/084081 and WO 2005/084082), atropisomers (e.g. according to WO 2006/048268), boronic acid derivatives (e.g. for example according to WO 2006/117052) or benzanthracene (for example according to WO 2008/145239).

Particularly preferred compounds that can serve as host or co-host materials are selected from the class of oligoarylenes, including anthracene, benzanthracene and/or pyrene, or atropisomers of these compounds. Oligoarylene in the meaning of the present invention is taken to mean a compound in which at least three aryl or arylene groups are bonded to each other.

Preferred host materials are selected in particular from compounds of formula (H-1):

wherein Ar ⁴ , Ar ⁵ and Ar ⁶ are, at each occurrence, identically or differently, an optionally substituted aryl or heteroaryl group having 5 to 30 aromatic ring atoms, and p ranges from 1 to 5. represents the integer of; The sum of π electrons in Ar ⁴ , Ar ⁵ and Ar ⁶ is at least 30 for p = 1, at least 36 for p = 2, and at least 42 for p = 3.

In the compounds of formula (H-1), the group Ar ⁵ particularly preferably represents anthracene, and the groups Ar ⁴ and Ar ⁴ are bonded at the 9- and 10-positions, where these groups may be optionally substituted. Very particularly preferably, at least one of the groups Ar ⁴ and/or Ar ⁶ is 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl, or 2-, 3-, 4-, 5- It is a condensed aryl group selected from , 6- or 7-benzanthracenyl. Anthracene-based compounds are described in US 2007/0092753 A1 and US 2007/0252517 A1, 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 (US 2008/0193796 A1), for example 10,10'-bis[1,1',4',1'']terphenyl-2-yl-9,9'- Bisanthracenyl is preferred.

Further preferred compounds are arylamines, styrylamines, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, bisbenzoxa Derivatives of zoline, oxazole, pyridine, pyrazine, imine, benzothiazole, benzoxazole, benzimidazole (US 2007/0092753 A1), for example 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 (US 5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethine, cinnamic acid ester, and fluorescent dye.

Derivatives of arylamines and styrylamines, for example TNB (=4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl) are particularly preferred. Metal-oxinoid complexes such as LiQ or AlQ ₃ can be used as co-hosts.

Preferred compounds with oligoarylene as matrix include US 2003/0027016 A1, US 7326371 B2, US 2006/043858 A, WO 2007/114358, WO 2008/145239, JP 3148176 B2, EP 1009044, US 2004/01838 3,W.O. 2005/061656 A1, EP 0681019B1, WO 2004/013073A1, US 5077142, WO 2007/065678 and DE 102009005746, where particularly preferred compounds are represented by formulas H-2 to H-8.

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

These compounds, which can also be used as structural elements in polymers, include CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (e.g. WO 2005/039246, US 2005/0069729, JP 2004/288381, according to EP 1205527 or WO 2008/086851), azacarbazole (e.g. according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/347160), ketone (e.g. according to WO 2004/093207 or DE 102008033943) (according to) , phosphine oxides, sulfoxides and sulfones (e.g. according to WO 2005/003253), oligophenylenes, aromatic amines (e.g. according to US 2005/0069729), amphiphilic matrix materials (e.g. according to WO 2007/137725 (according to DE 102008017591), silanes (e.g. according to WO 2005/111172), 9,9-diarylfluorene derivatives (e.g. according to DE 102008017591), azaboroles or boronic acid esters (e.g. according to WO 2006/117052) (according to WO 2007/063754), 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 according to DE 102009031021), diazaphosphole derivatives (for example according to DE 102009022858), triazole derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, disti Rylpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indole, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, car Bodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives, such as for example AlQ ₃ (which may also contain triarylaminophenol ligands) (US 2007/0134514 A1), metal complexes/polysilane compounds, and Included are thiophene, benzothiophene and dibenzothiophene derivatives.

Examples of preferred carbazole derivatives are mCP (=1,3-N,N-dicarbazolylbenzene (=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). Particularly preferred compounds are disclosed in US 2007/0128467 A1 and US 2005/0249976 A1 (formulas H-11 and H-13).

Preferred tetraaryl-Si compounds are described, for example, in US 2004/0209115, US 2004/0209116, US 2007/0087219 A1 and H. Gilman, E.A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120.

Particularly preferred tetraaryl-Si compounds are represented by formulas H-14 to H-21.

Particularly preferred compounds from group 4 for the preparation of matrices for phosphorescent dopants are disclosed in particular in DE 102009022858, DE 102009023155, EP 652273 B1, WO 2007/063754 and WO 2008/056746, where particularly preferred compounds have the formula H- Described as 22 to H-25.

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

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

Furthermore, compounds that improve the transition from the singlet state to the triplet state and are used as supports for functional compounds with emitter properties to improve the phosphorescence properties of such compounds can be used. For this purpose, carbazole and bridged carbazole dimer units (for example described in WO 2004/070772 A2 and WO 2004/113468 A1) are suitable. For this purpose, ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds (for example described in WO 2005/040302 A1) are also suitable.

n-dopant is taken here 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 WO 2005/086251 A2), P=N compounds (e.g. WO 2012/175535 A1, WO 2012/175219 A1) , naphthylenecarbodiimide (e.g. WO 2012/168358 A1), fluorene (e.g. WO 2012/031735 A1), free radicals and diradicals (e.g. EP 1837926 A1, WO 2007/107306 A1), pyridines (e.g. EP 2452946 A1, EP 2463927 A1), N-heterocyclic compounds (e.g. WO 2009/000237 A1) and acridine, as well as phenazines (e.g. US 2007/145355 A1).

Furthermore, the formulations may include wide band gap materials as functional materials. Wide band gap materials are taken to mean materials within the meaning of the disclosure of US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

Compounds used as wide band gap materials may have a band gap of 2.5 eV or more, preferably 3.0 eV or more, particularly preferably 3.5 eV or more. The band gap can be calculated using, in particular, the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

Furthermore, the formulation may include hole blocking material (HBM) as a functional material. Hole blocking materials refer to materials that prevent or minimize the transfer of holes (positive charge) in a multilayer system, especially when these materials are arranged in the form of layers adjacent to an emitting layer or a hole conducting layer. Typically, hole blocking materials have lower HOMO levels than hole transporting materials in adjacent layers. A hole blocking layer is often placed between the light emitting layer and the electron transport layer in OLED.

Basically any known hole blocking material can be used. In addition to other hole blocking materials described elsewhere in this application, advantageous hole blocking materials include metal complexes (US 2003/0068528), such as for example bis(2-methyl-8-quinolinoleato)(4-phenylphenolate) It is aluminum(III) (BAlQ). For this purpose, Fac-tris(1-phenylpyrazolato-N,C2)-iridium(III) (Ir(ppz) ₃ ) (US 2003/0175553 A1) is likewise used. Phenanthroline derivatives, such as for example BCP, or phthalimides, such as for example TMPP, can likewise be used.

Furthermore, advantageous hole blocking materials are described in WO 00/70655 A2, WO 01/41512 and WO 01/93642 A1.

Furthermore, the formulation may include electronic blocking material (EBM) as a functional material. Electron blocking materials refer to materials that prevent or minimize the transfer of electrons in a multilayer system, especially when such materials are disposed in the form of layers adjacent to an emitting layer or an electron conducting layer. Typically, electron blocking materials have higher LUMO levels than electron transport materials in adjacent layers.

Basically any known electron blocking material can be used. In addition to other electron blocking materials described elsewhere in this application, advantageous electron blocking materials are transition-metal complexes, such as Ir(ppz) ₃ (US 2003/0175553).

The electron blocking material may preferably be selected from amines, triarylamines and their derivatives.

Furthermore, the functional compounds that can be used as organic functional materials in the formulation preferably have a molecular weight of ≤ 3,000 g/mol, more preferably ≤ 2,000 g/mol and most preferably ≤ 1,000, if they are low molecular weight compounds. It is g/mol.

Additionally, functional compounds that are distinguished by a high glass transition temperature are of particular interest. In this regard, particularly preferred functional compounds that can be used as organic functional materials in formulations have a glass transition temperature, as determined according to DIN 51005, of ≧70°C, preferably ≧100°C, more preferably ≧125°C and Most preferably, those are ≧150°C.

The formulation may also include polymers as organic functional materials. The compounds described above as organic functional materials, which often have relatively low molecular weights, can also be mixed with polymers. Likewise, these compounds can be incorporated into polymers by covalent bonds. This is possible, in particular, with compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or by reactive polymerizable groups such as olefins or oxetane. They can be used as monomers for the preparation of corresponding oligomers, dendrimers or polymers. Here, oligomerization or polymerization preferably takes place via halogen functional groups or boronic acid functional groups, or via polymerizable groups. Polymers can also be crosslinked through this type of group. 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 units or structural elements described in the context of the compounds described above, especially those disclosed and extensively listed in WO 02/077060 A1, WO 2005/014689 A2 and WO 2011/076314 A1. Contains. These documents are incorporated herein by reference. Functional materials may come from, for example, 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 combining the properties described in relation to Groups 1 and 2;

Group 4: Structural elements with luminescent properties, especially 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 also the emission color of the resulting polymer;

Group 7: Structural elements typically used as backbone.

Since the structural elements here may also have various functions, an explicit designation need not be advantageous. For example, structural elements of group 1 may likewise serve as a backbone.

Polymers with hole transport or hole injection properties used as organic functional materials, containing structural elements of group 1, may preferably contain units corresponding to the hole transport or hole injection materials described above.

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 groups with high HOMO -, S- or N-containing heterocycle. These arylamines and heterocycles preferably have a HOMO greater than -5.8 eV (relative to vacuum level), particularly preferably greater than -5.5 eV.

In particular, polymers with hole transport or hole injection properties are preferred, which contain at least one of the repeating units of the formula HTP-1:

In the formula, the symbols have the following meanings:

Ar ¹ is, in each case identically or differently to a different repeating unit, a single bond, or a monocyclic or polycyclic aryl group which may be optionally substituted;

Ar ² is, in each case identically or differently for the different repeating units, a monocyclic or polycyclic aryl group, which may be optionally substituted;

Ar ³ is, in each case identically or differently for the different repeating units, a monocyclic or polycyclic aryl group, which may be optionally substituted;

m is 1, 2 or 3.

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

In the formula, the symbols have the following meanings:

R ^a in each occurrence, identically or differently, is H, substituted or unsubstituted aromatic or heteroaromatic group, alkyl, cycloalkyl, alkoxy, aralkyl, aryloxy, arylthio, alkoxycarbonyl, silyl or carboxyl group, halogen It is an atom, a cyano group, a nitro group, or a hydroxyl group;

r is 0, 1, 2, 3 or 4

s is 0, 1, 2, 3, 4 or 5.

In particular, polymers with hole transport or hole injection properties are preferred, which contain at least one of the repeating units of the formula HTP-2:

In the formula, the symbols have the following meanings:

T ¹ and T ² are independently selected from thiophene, selenophen, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, pyrrole and aniline; These groups may be substituted with one or more radicals R ^b ;

R ^b is independently in each case 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 , selected from optionally substituted silyl, carbyl or hydrocarbyl groups having 1 to 40 carbon atoms, which may be optionally substituted and optionally contain one or more heteroatoms;

R ⁰ and R ⁰⁰ are each independently H, or an optionally substituted carbyl or hydrocarbyl group having 1 to 40 carbon atoms, which may be optionally substituted and optionally contain one or more heteroatoms. ;

Ar ⁷ and Ar ⁸ , independently of each other, represent a monocyclic or polycyclic aryl or heteroaryl group, which may be optionally substituted, and is optionally substituted at the 2,3-position of one or both of the adjacent thiophene or selenophene groups. may be combined;

c and e are, independently of each other, 0, 1, 2, 3 or 4, where 1 < c + e ≤　is 6;

d and f are, independently of each other, 0, 1, 2, 3 or 4.

Preferred examples of polymers with hole transport or hole injection properties are described in particular in WO 2007/131582 A1 and WO 2008/009343 A1.

Polymers with electron injection and/or electron transport properties used as organic functional materials, containing structural elements of group 2, may preferably also contain units corresponding to the electron injection and/or electron transport materials described above. .

Further preferred structural elements of group 2, which have electron injection and/or electron transport properties, are for example pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline and phenazine groups, as well as triaryl groups. derived from a borane group or an additional O-, S- or N-containing heterocycle with a low LUMO level. These structural elements of group 2 preferably have a LUMO (relative to the vacuum level) of less than -2.7 eV, especially preferably of less than -2.8 eV.

The organic functional material may preferably be a polymer containing structural elements from group 3, in which structural elements that improve hole and electron mobility (i.e. structural elements from groups 1 and 2) are directly connected to each other. Some of these structural elements may act as emitters herein, where the emission color may be shifted, for example to green, red or yellow. Therefore, their use is advantageous for the generation of other emission colors or broadband emissions, for example by polymers that originally emit blue.

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

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

For this purpose, carbazole and linked carbazole dimer units (for example described in DE 10304819 A1 and DE 10328627 A1) are suitable. For this purpose, ketones, phosphine oxides, sulfoxides, sulfone and silane derivatives and similar compounds (for example described in DE 10349033 A1) are also suitable. Furthermore, preferred structural units can be derived from the compounds described above in relation to matrix materials used with phosphorescent compounds.

The further organic functional materials are preferably polymers containing units of group 6, which influence the morphology and/or the emission color of the polymer. These are those that, in addition to the polymers mentioned above, have at least one additional aromatic or another conjugated structure not taken into account among the groups mentioned above. Accordingly, these groups have no or little effect on charge-carrier mobility, non-organometallic complexes, or singlet-triplet transitions.

These types of structural units can influence the morphology and/or emission color of the resulting polymer. Therefore, depending on the structural units, these polymers can also be used as emitters.

Therefore, for fluorescent OLEDs, aromatic structural elements with 6 to 40 C atoms or also tolane, stilbene or bistyrylarylene derivative units are preferred, each of which may be substituted by one or more radicals. wherein 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'-naphthylylene, 4,4'-tolanylene. , It is particularly preferred to use groups derived from 4,4'-stilbenylene or 4,4"-bistyrylarylene derivatives.

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

These include, in particular, 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives (e.g. described in US 5962631, WO 2006/052457 A2 and WO 2006/118345A1) , 9,9-spirobifluorene derivatives (e.g. disclosed in WO 2003/020790 A1), 9,10-phenanthrene derivatives (e.g. disclosed in WO 2005/104264 A1), 9,10-di Hydrophenanthrene derivatives (e.g. disclosed in WO 2005/014689 A2), 5,7-dihydrodibenzoxepin derivatives, and cis- and trans-indenofluorene derivatives (e.g. disclosed in WO 2004/041901 A1 and binapthylene derivatives (e.g. described in WO 2006/063852 A1), and further units (e.g. WO 2005/056633 A1, EP 1344788 A1, WO 2007 /043495 A1, WO 2005/033174 A1, WO 2003/099901 A1 and DE 102006003710) are included.

Fluorene derivatives (e.g. disclosed in US 5,962,631, WO 2006/052457 A2 and WO 2006/118345 A1), spirobifluorene derivatives (e.g. disclosed in WO 2003/020790 A1), benzofluorene, di- The structural unit of group 7 is selected from benzofluorene, benzothiophene and dibenzofluorene groups, and their derivatives (e.g. disclosed in WO 2005/056633 A1, EP 1344788 A1 and WO 2007/043495 A1) Particularly desirable.

Particularly preferred structural elements of group 7 are represented by the general formula PB-1:

In the formula, symbols and exponents have the following meanings:

A, B and B' are each, also for different repeating units, identical or different, preferably -CR ^c R ^d -, -NR ^c -, PR ^c -, -O-, -S-, -SO A divalent selected from -, -SO ₂ -, -CO-, -CS-, -CSe-, -P(=O)R ^c -, -P(=S)R ^c - and -SiR ^c R ^d - It is strange;

R ^c and R ^d are independently in each case, 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 1 to 40 carbon atoms, which may be optionally substituted and optionally contain one or more heteroatoms, wherein the group R ^c and R ^d may optionally form a spiro group with the fluorene radical to which they are bound;

X is halogen;

R ⁰ and R ⁰⁰ are each independently H, or an optionally substituted carbyl or hydrocarbyl group having 1 to 40 carbon atoms (which may be optionally substituted and optionally contain one or more heteroatoms) am;

g is, at each occurrence, independently 0 or 1, and h is at each occurrence independently 0 or 1, wherein the sum of g and h in the subunit is preferably 1;

m is an integer ≥ 1;

Ar ¹ and Ar ² independently represent a monocyclic or polycyclic aryl or heteroaryl group, which may be optionally substituted, and is optionally bonded to the 7,8-position or 8,9-position of the indenofluorene group. It could be;

a and b are, independently of each other, 0 or 1.

When the groups R ^c and R ^d together with the fluorene group to which these groups are bonded form a spiro group, these groups preferably represent spirobifluorene.

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

In the formula, R ^c has the meaning described 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 )} a straight-chain, 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 The atoms may be optionally substituted with F or Cl and the groups R ⁰ , R ⁰⁰ and X have the meanings described above for formula PB-1.

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

In the formula, the symbols have the following meanings:

L is H, halogen, or an optionally fluorinated, linear or branched alkyl or alkoxy group having 1 to 12 C atoms, preferably H, F, methyl, i-propyl, t-butyl, n- represents pentoxy or trifluoromethyl; and

L' is an optionally fluorinated, linear or branched alkyl or alkoxy group having 1 to 12 C atoms and preferably represents n-octyl or n-octyloxy.

For carrying out the present invention, polymers containing more than one of the structural elements of groups 1 to 7 described above are preferred. Furthermore, it may be provided that the polymer preferably contains more than one of the structural elements from one of the groups described above, ie comprising a mixture of structural elements selected from one group.

In particular, in addition to at least one structural element (group 4) with luminescent properties, preferably at least one phosphorescent group, additionally selected from groups 1 to 3, 5 or 6, preferably from groups 1 to 3, as described above. Particular preference is given to polymers containing at least one additional structural element.

When present in the polymer, the proportions of the various classes of groups can be within a wide range known to those skilled in the art. The proportion of one class present in the polymer, in each case selected from the structural elements of groups 1 to 7 described above, is preferably ≥ 5 mol% in each case, particularly preferably ≥ 10 mol% in each case. If so, surprising benefits can be achieved.

The preparation of white-emitting copolymers is described in particular in detail in DE 10343606 A1.

To improve solubility, the polymer may contain corresponding groups. Preferably, it may be provided that the polymer contains substituents such that there are on average at least 2 non-aromatic carbon atoms per repeat unit, particularly preferably at least 4 and particularly preferably at least 8 non-aromatic carbon atoms. (mean here refers to number average). Here, individual carbon atoms can be replaced by O or S, for example. However, it is possible for a certain proportion, optionally all, of the repeating units to contain no substituents containing non-aromatic carbon atoms. Here, short-chain substituents are preferred, since long-chain substituents can have a negative effect on the layers that can be obtained using organic functional materials. The substituents preferably contain at most 12 carbon atoms, preferably at most 8 carbon atoms and particularly preferably at most 6 carbon atoms in the linear chain.

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

In a further embodiment, the polymer used as organic functional material may be a non-conjugated polymer with side chains, where this embodiment is particularly important in phosphorescent OLEDs based on polymers. In general, phosphorescent polymers can be obtained by free-radical copolymerization of vinyl compounds, which vinyl compounds contain at least one unit with a phosphorescent emitter and/or at least one charge transport unit, which is described in particular in US 7250226 It is disclosed in B2. Further phosphorescent polymers are described in particular in JP 2007/211243 A2, JP 2007/197574 A2, US 7250226 B2 and JP 2007/059939 A.

In a further preferred embodiment, the non-conjugated polymer contains backbone units connected to each other by spacer units. Examples of such triplet emitters based on non-conjugated polymers based on backbone units are disclosed, for example, in DE 102009023154.

In a further preferred embodiment, the non-conjugated polymer can be designed as a fluorescent emitter. Preferred fluorescent emitters based on non-conjugated polymers with side chains contain anthracene or benzanthracene groups in the side chains, or derivatives of these groups, such polymers being described for example in JP 2005/108556, JP 2005/285661 and It is disclosed in JP 2003/338375.

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

Furthermore, the functional compounds used as organic functional materials in the formulation preferably have a molecular weight M _w of ≥ 10,000 g/mol, particularly preferably ≥ 20,000 g/mol and particularly preferably ≥ 50,000 g/ in the case of polymeric compounds. It is mol.

Here, the molecular weight M _w of the polymer preferably ranges from 10,000 to 2,000,000 g/mol, particularly preferably from 20,000 to 1,000,000 g/mol and very particularly preferably from 50,000 to 300,000 g/mol. The molecular weight M _w is determined using GPC (=gel permeation chromatography) against an internal polystyrene standard.

The documents cited above for description of functional compounds are incorporated by reference into this application for purposes of disclosure.

The formulation according to the invention may comprise all organic functional materials essential for the production of the respective functional layers of the electronic device. If, for example, the hole transport, hole injection, electron transport or electron injection layer is built from exactly one functional compound, the formulation comprises exactly this compound as the organic functional material. If the release layer comprises an emitter, for example in combination with a matrix or host material, the formulation may be an organic functional material, precisely as described in more detail elsewhere in the present application, with the matrix or host material. Contains a mixture of sieves.

In addition to the above ingredients, the formulations according to the invention may also contain further additives and processing aids. These include, in particular, surface-active substances (surfactants), lubricants and greases, additives that modify viscosity, additives that increase conductivity, dispersants, hydrophobizers, adhesion promoters, flow improvers, anti-foaming agents, degassing agents, reactive or non-( Includes diluents, fillers, auxiliaries, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors, which may be non-reactive.

The invention further provides a method for producing the formulation according to the invention, wherein at least a first organic solvent containing at least one carbonate group and at least one organic functional material that can be used for the production of a functional layer of an electronic device are mixed. It is about manufacturing method.

The formulations according to the invention can be used for the production of layered or multilayered structures, where organic functional materials are present in the layers, as required for the production of desirable electronic or optoelectronic components, such as OLEDs.

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

The invention likewise relates to a method for producing electronic devices, in which the formulation according to the invention is applied to a substrate and dried.

Functional layers include, for example, flood coating, dip coating, spray coating, spin coating, screen printing, relief printing, gravure printing, rotary printing, roller coating, flexographic printing, offset printing. or by nozzle printing, preferably inkjet printing, on the substrate or on one of the layers applied to the substrate.

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

Furthermore, it may be provided that the process is repeated several times, with the formation of different or identical functional layers. Here, crosslinking of the formed functional layer can occur, preventing its dissolution, as disclosed for example in EP 0 637 899 A1.

The invention also relates to an electronic device obtainable by a method for manufacturing an electronic device.

The invention further relates to an electronic device, which has at least one functional layer comprising at least one organic functional material, obtainable by the above-mentioned method for manufacturing electronic devices.

An electronic device is taken to mean a device comprising an anode, a cathode and at least one functional layer between them, where this functional layer comprises at least one organic or organometallic compound.

Organic electronic devices are preferably organic electroluminescent devices (OLED), polymeric 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 light detector, organic photoreceptor, organic field-quench device (O-FQD), organic electric sensor, a light-emitting electrochemical cell (LEC) or an organic laser diode (O-laser), more preferably an organic electroluminescent device (OLED) or a polymeric electroluminescent device (PLED).

The active ingredient is generally an organic or inorganic material introduced between the anode and the cathode, wherein such active ingredient influences, maintains and/or improves the properties of the electronic device, such as its performance and/or its lifetime. Sikkim), for example charge injection, charge transport or charge blocking materials, especially emission materials and matrix materials. Accordingly, organic functional materials that can be used for the production of functional layers of electronic devices preferably include the active ingredients of the electronic device.

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

It is also preferred to use a mixture of two or more triplet emitters together with the matrix. The triplet emitter with a shorter wavelength emission spectrum serves here as a co-matrix for the triplet emitter with a longer wavelength emission spectrum.

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

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

The emitting layer of an organic electroluminescent device may also comprise a system comprising a plurality of matrix materials (mixed-matrix systems) and/or a plurality of dopants. In this case too, the dopant is generally the material with a smaller proportion in the system and the matrix material is the material with a larger proportion in the system. However, in individual cases, the proportion of individual matrix materials in the system may be smaller than the proportion of individual dopants.

The mixed-matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Here, one of the two materials is preferably a material with hole transport properties, and the other material is preferably a material with electron transport properties. However, the desired electron transport and hole transport properties of the mixed-matrix components may also be combined primarily or entirely in a single mixed-matrix component, where the additional mixed-matrix component(s) fulfill different functions. The two different matrix materials are used in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1 and most preferably 1:4 to 1:1. It may exist as rain. Mixed matrix systems are preferably employed in phosphorescent organic electroluminescent devices. Further details on mixed-matrix systems can be found, for example, in WO 2010/108579.

In addition to these layers, the organic electroluminescent device may also comprise further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation in each case. 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 conjugation. Here, one or more hole transport layers may be p-doped, for example with a metal oxide, such as MoO ₃ or WO ₃ , or a (per)fluorinated electron-deficient aromatic compound, and/or one or more electron transport layers may be n-doped. there is. Additionally, an intermediate layer that has an exciton blocking function and/or regulates charge balance, for example in electroluminescent devices, can be introduced between the two emitting layers. However, it should be pointed out that each of these layers does not necessarily need to be present. These layers may likewise be present upon use of the formulation according to the invention, as defined above.

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

Accordingly, the invention also relates to an electronic device comprising at least three layers, but in a preferred embodiment all of the above layers from hole injection, hole transport, emission, electron transport, electron injection, charge blocking and/or charge generation layers, It relates here to an electronic device, wherein at least one layer is obtained by the formulation used according to the invention. The thickness of the layer, for example the hole transport and/or hole injection layer, may preferably range from 1 to 500 nm, more preferably from 2 to 200 nm.

Furthermore, the device may comprise layers constructed from further low molecular weight compounds or polymers that are not applied by the use of the formulation according to the invention. It can also be prepared by evaporation of low molecular weight compounds in high vacuum.

It may also be desirable to use the compounds not as pure substances, but as mixtures (blends) with further polymeric, oligomeric, dendritic or low molecular weight substances of any desired type. These may, for example, improve electronic properties or they may emit themselves.

In a preferred embodiment of the invention, the formulation according to the invention comprises an organic functional material that is used as host material or matrix material in the release layer. The formulation herein may also comprise, in addition to the host material or matrix material, the emitter described above. The organic electroluminescent device here may include one or more emitting layers. If a plurality of emitting layers are present, they preferably have a plurality of emission maxima between 380 nm and 750 nm, so that an overall white emission is obtained, i.e. various emitting compounds capable of causing fluorescence or phosphorescence are used in the emitting layers. do. Very particular preference is given to a three-layer system, wherein the three layers exhibit blue, green and orange or red emission (for the basic structure, see for example WO 2005/011013). White emitting devices are suitable, for example, as backlighting of LCD displays or for general lighting applications.

Additionally, it is possible for multiple OLEDs to be arranged one above the other, which allows a further increase in efficiency with respect to light yield to be achieved.

To improve the coupling-out of light, in OLEDs the final organic layer on the light exit side can be in the form of, for example, nanofoam, which results in a decrease in the rate of total reflection. .

Furthermore, one or more layers are applied by a sublimation process, wherein the material is deposited in a vacuum sublimation apparatus at a pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar, more preferably less than 10 ^-7 mbar. Organic electroluminescent devices applied by are preferred.

Furthermore, 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 applied at a pressure of 10 ^-5 mbar to 1 bar. may be provided.

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

These layers can also be applied by processes in which compounds of formula (I), (II), (IIa), (III) or (IIIa) are not used. Here, preferably, an orthogonal solvent can be used, which dissolves the functional material of the layer to be applied, but does not dissolve the layer to which the functional material is applied.

A device usually includes a cathode and anode (electrodes). The electrodes (cathode, anode) are, for the purposes of the present invention, chosen such that their band energy corresponds as closely as possible to that of the adjacent organic layer in order to ensure highly efficient electron or hole injection.

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

The anode preferably comprises materials with a high work function. The anode preferably has a potential greater than 4.5 eV relative to vacuum. On the other hand, for this purpose, metals with a high redox potential, for example Ag, Pt or Au, are suitable. On the other hand, metal/metal oxide electrodes (eg Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. In some applications, at least one of the electrodes must be transparent to enable irradiation of organic materials (O-SC) or coupling out of light (OLED/PLED, O-laser). A preferred structure uses a transparent anode. Preferred anode materials herein are conductive, mixed metal oxides. ITO (indium tin oxide) or IZO (indium zinc oxide) are particularly preferred. Furthermore, conductively doped organic materials are preferred, especially conductively doped polymers, such as, for example, poly(ethylenedioxythiophene) (PEDOT) and polyaniline (PANI), or derivatives of these polymers. It is also preferred if a p-doped hole transport material is applied to the anode as a hole injection layer, where suitable p-dopants are metal oxides, for example MoO ₃ or WO ₃ , or (per)fluorinated electron-deficient aromatics. It is a compound. Additional suitable p-dopants are the compounds NPD9 or HAT-CN (hexacyanohexaazatriphenylene) from Novaled. This type of layer simplifies hole injection in materials with low HOMO, i.e. large values of HOMO.

In general, all materials used in the layers according to the prior art can be used in the further layers, and a person skilled in the art will be able to combine each of these materials with the materials according to the invention in an electronic device without inventive steps.

Since the lifespan of such devices is dramatically shortened in the presence of water and/or air, the devices themselves are correspondingly structured, provided with contacts and finally sealed, in a manner known per se, depending on the application.

The formulations according to the invention and the electronic devices obtainable therefrom, in particular organic electroluminescent devices, are distinguished over the prior art by one or more of the following surprising advantages:

1. Electronic devices obtainable using the formulation according to the invention show very high stability and a very long lifetime compared to electronic devices obtained using conventional methods.

2. Since the formulations according to the invention can be processed using conventional methods, cost advantages thereby can also be achieved.

3. The organic functional materials used in the formulation according to the present invention are not subject to any special restrictions, allowing the method of the present invention to be comprehensively used.

4. The coatings obtainable using the formulations of the invention show excellent quality, especially in terms of uniformity of the coating.

These advantages mentioned above are not accompanied by degradation of other electronic properties.

It should be pointed out that variations of the embodiments described herein fall within the scope of the present invention. Each feature disclosed in the present invention may be replaced by an alternative feature that can be used for the same, equivalent or similar purpose, unless explicitly excluded. Accordingly, each feature disclosed in the present invention, unless otherwise noted, should be regarded as an example of a generic series or as an equivalent or similar feature.

All features of the invention may be combined with one another in any way, as long as certain features and/or steps are not mutually exclusive. This applies in particular to the preferred features of the invention. Equally, features of non-essential combinations can be used separately (rather than in combination).

Additionally, it should be pointed out that many of the features of the invention, and particularly those of the preferred embodiments, are themselves inventive and should not be considered merely as part of the embodiments of the invention. For these features, independent protection may be sought as an alternative to, or in addition to, the respective inventions currently claimed.

The teachings regarding the technical operation disclosed in the present invention can be extracted and combined with other examples.

The invention is explained in more detail below with reference to working examples, but is not limited thereto.

Those skilled in the art will be able, using the detailed description, to make further electronic devices in accordance with the present invention and, therefore, to practice the invention within the scope of the claims, without devoting the ability to inventive step.

Work example

All worked examples presented below were made using the device structure shown in Figure 1. The hole injection layer (HIL) and hole transport layer (HTL) of all examples were fabricated by an inkjet printing process to achieve the desired thickness. For the release layer, the individual solvents used in Examples 1 and 2 are listed in Table 2 below:

Table 2: List of solvents used in Examples 1 and 2.

The viscosity of the formulations and solvents was measured using a TA Instruments ARG2 rheometer over a range of shear rates ranging from 10 to 1000 s ^-1 using a 40 mm parallel plate geometry. Measurements were taken as averages from 200 to 800 s ^-1 , where temperature and shear rate were accurately controlled. The viscosity shown in Table 3 is the viscosity of each formulation measured at a temperature of 25°C. Each solvent was measured three times. The viscosity values mentioned were averaged over the above measurements.

Preferably, the organic solvent blend may comprise a surface tension ranging from 15 to 80 mN/m, more preferably from 20 to 60 mN/m and most preferably from 25 to 40 mN/m. Surface tension can be measured using a FTA (First Ten Angstrom) 1000 contact angle goniometer at 20°C. Details of the method are provided by Roger P. Woodward, Ph.D. Available from First Ten Angstrom, as published in “Surface Tension Measurements Using the Drop Shape Method.” Preferably, the surface tension can be determined using the soaking method. All measurements are performed at room temperature ranging from 20°C to 22°C. For each formulation, three droplets were measured. The final value is the average of the above measurements. The tool was regularly cross-checked against a variety of liquids with well-known surface tensions.

Examples 1 and 2 were fabricated using the same architecture with HIL and HTL inkjet printed to achieve the same thickness. The solvent(s) used in EML are different and details are listed in Table 3.

Table 3: Details of formulations used in Examples 1 and 2

Description of the production process

The glass substrate covered with pre-structured ITO and bank material was cleaned in isopropanol using sonication, then in deionized water, then dried using an air-gun, followed by hot heating at 230°C. Annealed for 2 hours on the plate.

A hole injection layer (HIL) using PEDOT-PSS (Clevios Al4083, Heraeus) was inkjet printed on the substrate and dried in vacuum. The HIL was then annealed at 185°C in air for 30 min.

On top of the HIL, a hole transport layer (HTL) was inkjet printed, dried in vacuum, and annealed at 210 °C for 30 min in a nitrogen atmosphere. As a material for the hole transport layer, polymer HTM-1 was used. The structure of polymer HTM-1 is as follows:

The green emitting layer (G-EML) was also inkjet printed, vacuum dried, and annealed at 160 °C for 10 min in a nitrogen atmosphere. The ink for the green emitting layer contained, in all working examples, two host materials (i.e. HM-1 and HM-2) as well as one triplet emitter (EM-1). The materials were used in the following ratio: HM-1 : HM-2 : EM-1 = 2 : 2 : 1. The structure of these materials is as follows:

All inkjet printing processes were performed under yellow light and under ambient conditions.

The device was then transferred to a vacuum deposition chamber, where deposition of the hole blocking layer (HBL), electron transport layer (ETL) and cathode (Al) was performed using thermal evaporation. The device was then characterized in the glovebox.

ETM-1 was used as a hole blocking material for the hole blocking layer. The material has the following structure:

In the electron transport layer (ETL), a 50:50 mixture of ETM-1 and LiQ was used. LiQ is lithium 8-hydroxyquinolinate.

To measure OLED performance in current density-brightness-voltage performance, the device was driven by a sweeping voltage of -5V to 25V provided by a Keithley 2400 source measure unit. The voltage across the OLED device as well as the current through the OLED device were recorded by a Keithley 2400 SMU. The brightness of the device was detected with a calibrated photodiode. Photocurrent was measured with a Keithley 6485/E picoammeter. For spectra, the brightness sensor was replaced with a fiberglass connected to an Ocean Optics USB2000+ spectrometer.

Results and Discussion

Example 1

An inkjet printed OLED device was fabricated with the layer printed using tert-butyl phenyl carbonate as the solvent for the emissive layer. The structure of the pixelated OLED device is glass / ITO / HIL (40 nm) / HTM (20 nm) / EML (60 nm) / HBL (10 nm) / ETL (40 nm) / Al, where the banks are pixelated were pre-fabricated on a substrate to form the device. In this case, the green emitting material is dissolved in tert-butyl phenyl carbonate at a concentration of 12 mg/ml.

Luminance efficiency at 1000 cd/m ² is 65.32 cd/A. The efficiency of this OLED device is very good, and the voltage at 1000 cd/m ² is 7.35 V.

Example 2

An inkjet printed OLED device was fabricated with the layer printed using methyl phenyl carbonate as the solvent for the emissive layer. The structure of the pixelated OLED device is glass / ITO / HIL (40 nm) / HTM (20 nm) / EML (60 nm) / HBL (10 nm) / ETL (40 nm) / Al, where the banks are pixelated were pre-fabricated on a substrate to form the device. In this case, the green emitting material is dissolved in methyl phenyl carbonate at a concentration of 19 mg/ml.

Luminance efficiency at 1000 cd/m ² is 42.27 cd/A. The efficiency of this OLED device is good, and the voltage at 1000 cd/m ² is 10.56 V.

The measured values of all examples are summarized in Table 4 below.

Table 4: Measurements for Examples 1 and 2

Claims (23)

A formulation containing at least one organic functional material and at least a first organic solvent,
the first organic solvent contains one carbonate group,
The content of the first organic solvent is in the range of 50 to 100% by volume based on the total amount of solvent in the formulation,
The at least one organic functional material is a low molecular weight compound with a molecular weight of ≤ 3,000 g/mol,
The at least one organic functional material is an organic semiconductor selected from the group consisting of hole injection, hole transport, emission, electron transport and electron injection materials,
The first organic solvent has a boiling point in the range of 200 to 400 ° C,
The formulation ranges from 2 to 40 mPa ^. has a viscosity in the s range,
The first organic solvent, containing one carbonate group, is a carbonate group-containing solvent according to the general formula (I):

During the ceremony
R ¹ and R ² are the same or different at each occurrence and are selected from the group consisting of a straight-chain 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, 2 to 20 carbon atoms, A straight chain alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkenyloxy group having 2 to 20 carbon atoms. or a branched or cyclic alkynyl or alkynyloxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO -O-, -C=O-, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F), or has 4 to 14 carbon atoms or an aryl or heteroaryl group, which may form a fused heterocycle or aryl and may be substituted by one or more non-aromatic R ³ radicals, on the same ring or on two different rings, a plurality of substituents R ³ , together in turn, may form a monocyclic or polycyclic, aliphatic or aromatic ring system, which may be substituted by a plurality of substituents R ³ ; and
R ³ is the same or different at each occurrence and is a straight-chain 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, wherein one or more non-adjacent CH ₂ Groups may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F) , or an aryl or heteroaryl group having 4 to 14 carbon atoms and which may be substituted with one or more non-aromatic R ³ radicals. delete According to claim 1,
The first organic solvent, containing one carbonate group, is a carbonate group-containing solvent according to general formula (I)
During the ceremony
R ¹ and R ² are the same or different at each occurrence and have 4 to 14 carbon atoms, or may form a fused heterocycle or aryl and may be substituted by one or more non-aromatic R ³ radicals. or a heteroaryl group, wherein, on the same ring or on two different rings, a plurality of substituents R ³ together form a monocyclic or polycyclic, aliphatic or aromatic ring system, which in turn may be substituted by a plurality of substituents R ³ Possible formulation. According to claim 1,
The first organic solvent, containing one carbonate group, is a carbonate group-containing solvent according to general formula (I)
During the ceremony
R ¹ is a straight-chain 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, a straight-chain alkenyl or alkenyloxy group having 2 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkynyloxy group having 2 to 20 carbon atoms, or a branched or cyclic alkenyloxy group having 3 to 20 carbon atoms or A cyclic alkynyl or alkynyloxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH =CH- or -C≡C- and one or more hydrogen atoms may be replaced by F; and
R ² is an aryl or heteroaryl group having 4 to 14 carbon atoms, which may form a fused heterocycle or aryl and which may be substituted by one or more non-aromatic R ³ radicals and which may be substituted on the same ring or by 2 A plurality of substituents R ³ on the different rings may together form a monocyclic or polycyclic, aliphatic or aromatic ring system, which in turn may be substituted by a plurality of substituents R ³ . According to claim 1,
The first organic solvent, containing one carbonate group, is a carbonate group-containing solvent according to general formula (I)
During the ceremony
R ¹ and R ² are the same or different at each occurrence and are selected from the group consisting of a straight-chain 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, 2 to 20 carbon atoms, A straight chain alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a branched or cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a straight chain alkynyl or alkenyloxy group having 2 to 20 carbon atoms. or a branched or cyclic alkynyl or alkynyloxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO -O-, -C=O-, -CH=CH- or -C≡C- and one or more hydrogen atoms may be replaced by F. According to claim 1,
The first organic solvent, containing one carbonate group, is a carbonate group-containing solvent according to general formula (I)
During the ceremony
R ¹ is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched alkyl or alkoxy group having 3 to 20 carbon atoms, a straight-chain alkenyl or alkenyloxy group having 2 to 20 carbon atoms, or 3 A branched alkenyl or alkenyloxy group having from 2 to 20 carbon atoms, or a straight-chain alkynyl or alkynyloxy group having from 2 to 20 carbon atoms, or a branched alkynyl or alkynyl group having from 3 to 20 carbon atoms. an oxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH=CH- or -C ≡C- may be replaced and one or more hydrogen atoms may be replaced by F; and
R ² is a cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, a cyclic alkenyl or alkenyloxy group having 3 to 20 carbon atoms, or a cyclic alkynyl or alkynyl group having 3 to 20 carbon atoms. an oxy group, wherein one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ³ -, -CONR ³ -, -CO-O-, -C=O-, -CH=CH- or -C ≡C- and one or more hydrogen atoms may be replaced by F. According to claim 1,
The formulation of claim 1, wherein the first organic solvent has a surface tension of ≧25 mN/m. delete delete According to claim 1,
The formulation comprising at least one second solvent that is different from the first organic solvent. According to claim 10,
wherein the second solvent has a boiling point in the range of 100 to 400 °C. According to claim 10,
The formulation, wherein the at least one organic functional material has a solubility in the first organic solvent and the second solvent ranging from 1 to 250 g/l. According to claim 1,
The formulation has a surface tension ranging from 1 to 70 mN/m. delete According to claim 1,
A formulation, wherein the content of at least one organic functional material in the formulation ranges from 0.001 to 20% by weight, based on the total weight of the formulation. delete delete delete According to claim 1,
A formulation wherein the at least one organic semiconductor is selected from the group consisting of hole injection and hole transport materials. According to claim 19,
A formulation wherein the hole injection and hole transport material is a polymeric compound or a blend of polymeric and non-polymeric compounds. A process for preparing a formulation according to any one of claims 1, 3 to 7, 10 to 13, 15, 19 and 20, comprising:
A production method wherein the at least one organic functional material and the at least first organic solvent are mixed. A method of manufacturing an electroluminescent device, comprising:
depositing or printing the formulation according to any one of claims 1, 3 to 7, 10 to 13, 15, 19 and 20 onto a surface, followed by In drying, at least one layer of the electroluminescent device is produced. depositing or printing the formulation according to any one of claims 1, 3 to 7, 10 to 13, 15, 19 and 20 onto a surface, followed by An electroluminescent device, wherein at least one layer is produced upon drying.

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