JP2019523997A - Formulation of organic functional materials - Google Patents

Abstract

The present invention uses at least one organic functional material, a formulation containing at least a first organic solvent and a first organic solvent that is a 1,1-diphenylethylene derivative, and these formulations. It is related with the electronic device prepared by this.

Description

  The present invention relates to formulations containing a 1,1-diphenylethylene derivative as a first solvent, and further to electroluminescent devices prepared by using these formulations.

  Organic light emitting devices (OLEDs) have long been made by vacuum deposition processes. Other techniques, such as ink jet printing, have recently been thoroughly studied due to their advantages, such as cost savings and scalability. One of the main challenges in multilayer printing is identifying relevant parameters for obtaining uniform ink deposition on the substrate. Several additives can be added to the formulation to induce such parameters, such as surface tension, viscosity, or boiling point.

  Many solvents have been proposed in organic electronic devices for inkjet printing. However, the number of important parameters that play a role during the deposition and drying process makes solvent selection very difficult. Therefore, formulations containing organic semiconductors used for deposition by ink jet printing still need to be improved. One object of the present invention is to provide organic semiconductor formulations that allow controlled deposition to form organic semiconductor layers with good layer properties and efficiency performance. A further object of the present invention is an organic semiconductor formulation that, when used in, for example, an ink jet printing method, allows for the uniform application of ink droplets on a substrate, thereby providing good layer properties and efficiency performance. Is to provide.

Solution to the problem

  The above object of the present invention is solved by providing a formulation comprising a 1,1-diphenylethylene derivative as the first solvent.

  The inventors have surprisingly found that the use of an organic solvent containing a 1,1-diphenylethylene derivative as the first solvent allows complete control of surface tension and induces effective ink deposition. It has been discovered that it forms an organic layer of a highly uniform and well-defined functional material with good layer properties and performance.

FIG. 1 shows a substrate, ITO anode, hole injection layer (HIL), hole transport layer (HTL), green light emitting layer (G-EML), hole blocking layer (HBL), electron transport layer (ETL) and Al 1 shows a typical layer structure of a device containing a cathode. FIG. 2 shows the device performance of an OLED prepared according to Example 1. FIG. 3 shows the device performance of an OLED prepared according to Comparative Example 1.

Aspect description

  The present invention relates to a formulation containing at least one organic functional material and a 1,1-diphenylethylene derivative as a first solvent.

Preferred embodiment

  In the first preferred embodiment, the first organic solvent has the general formula (I)

(Where
R ¹ and R ² are the same or different at each occurrence and are F, Cl, Br, I, NO ₂ , CN, a linear alkyl or alkoxy group having 1-20 carbon atoms or 3-20 A branched or cyclic alkyl or alkoxy group having one carbon atom, wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, — CO—O—, —C═O—, —CH═CH—, or —C≡C—, where one or more hydrogen atoms may be replaced by F), or 4 An aryl or heteroaryl group having -14 carbon atoms and optionally substituted by one or more non-aromatic R ⁵ radicals, wherein the plurality of substituents R ⁵ are on the same ring or two different ring Of either a plurality of substituents R ⁵ aliphatic is mono- or may be polycyclic substituted by may together form an aromatic or heteroaromatic ring system;
R ³ and R ⁴ are the same or different at each occurrence and are H, F, Cl, Br, I, NO ₂ , CN, a linear alkyl or alkoxy group having 1-20 carbon atoms or 3 A branched or cyclic alkyl or alkoxy group having ˜20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ — , -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 optionally substituted by one or more non-aromatic R ⁵ radicals, wherein the plurality of substituents R ⁵ are on the same ring or 2 Two different Either on the ring, a plurality of substituents R ⁵ aliphatic is mono- or may be polycyclic substituted by may together form an aromatic or heteroaromatic ring system;
R ⁵ is the same or different in each case 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 (here Wherein one or more non-adjacent CH ₂ groups are replaced by —O—, —S—, —CO—O—, —C═O—, —CH═CH— or —C≡C—. Or one or more hydrogen atoms may be replaced by F), or may have 4 to 14 carbon atoms and be substituted by one or more non-aromatic R ⁵ radicals. A good aryl or heteroaryl group;
m and n are the same or different at each occurrence and are 0, 1, 2 or 3, preferably 0 or 1, more preferably 0)
1,1-diphenylethylene derivative.

In a first more preferred embodiment, the first organic solvent has the general formula (I)
(Where
R ¹ and R ² are the same or different at each occurrence 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 A group wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, —CO—O—, —C═O—, —CH = CH- or -C≡C- may be substituted);
R ³ and R ⁴ are the same or different at each occurrence and are H, a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl having 3 to 20 carbon atoms Or an alkoxy group (where one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, —CO—O—, —C═O—, May be replaced by -CH = CH- or -C≡C-);
R ⁵ is the same or different in each case 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 (here Wherein one or more non-adjacent CH ₂ groups are replaced by —O—, —S—, —CO—O—, —C═O—, —CH═CH— or —C≡C—. May be);
m and n are the same or different at each occurrence and are 0 or 1, preferably 0)
1,1-diphenylethylene derivative.

In a second more preferred embodiment, the first organic solvent has the general formula (I)
(Where
R ¹ and R ² are the same or different at each occurrence 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 A group wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, —CO—O—, —C═O—, —CH = CH- or -C≡C- may be substituted);
R ³ and R ⁴ are H;
R ⁵ is the same or different in each case 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 (here Wherein one or more non-adjacent CH ₂ groups are replaced by —O—, —S—, —CO—O—, —C═O—, —CH═CH— or —C≡C—. May be);
m and n are the same or different at each occurrence and are 0 or 1, preferably 0)
1,1-diphenylethylene derivative.

In the first most preferred embodiment, the first organic solvent has the general formula (I)
(Where
R ¹ and R ² are the same or different at each occurrence and are straight chain alkyl groups having 1-20 carbon atoms or branched or cyclic alkyl groups having 3-20 carbon atoms;
R ³ and R ⁴ are H;
m and n are the same or different at each occurrence and are 0 or 1, preferably 0)
1,1-diphenylethylene derivative.

  In a second most preferred embodiment, the first organic solvent is 1,1-diphenylethylene according to general formula (II).

  Examples of the most preferred 1,1-diphenylethylene derivatives and their boiling points (BP) are shown in Table 1 below.

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

  The content of the first solvent is preferably in the range of 50-100 vol%, more preferably in the range of 75-100 vol%, most preferably in the range of 90-100 vol%, based on the total amount of solvent in the formulation. .

  As a result, the content of the second solvent is preferably in the range of 0-50 vol%, more preferably in the range of 0-25 vol%, most preferably in the range of 0-10 vol%, based on the total amount of solvent in the formulation. It is a range.

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

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

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

  Preferably, the second solvent comprises the following groups: substituted and unsubstituted aromatic or linear esters such as ethyl benzoate, butyl benzoate; substituted and unsubstituted aromatic or linear ethers such as 3 -Phenoxytoluene or anisole; substituted or unsubstituted arene derivatives such as xylene; indane derivatives such as hexamethylindane; substituted and unsubstituted aromatic or linear ketones; substituted and unsubstituted heterocyclic compounds such as pyrrolidinone , Pyridine, pyrazine; one of the other fluorinated or chlorinated aromatic hydrocarbons.

  Particularly preferred second organic solvents are, for example, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,3-trimethylbenzene, 1,2,4,5. -Tetramethylbenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, 1,2-dihydronaphthalene, 1,2-dimethylnaphthalene, 1,3-benzodioxolane, 1,3-diisopropylbenzene 1,3-dimethylnaphthalene, 1,4-benzodioxane, 1,4-diisopropylbenzene, 1,4-dimethylnaphthalene, 1,5-dimethyltetralin, 1-benzothiophene, thiaphthalene, 1-bromonaphthalene, 1 -Chloromethylnaphthalene, 1-ethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 1-methyl Ruindole, 2,3-benzofuran, 2,3-dihydrobenzofuran, 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 Phosphorus, acetophenone, anisole, benzonitrile, benzothiazole, benzyl acetate, bromobenzene, butylbenzoate, butylphenyl ether, cyclohexylbenzene, decahydronaphthol, dimethoxytoluene, 3-phenoxytoluene, diphenylether, 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, phenetole, ethoxybenzene, phenyl acetate, p-cymene, propiophenone, sec-butylbenzene, t-butylbenze , Thiophene, toluene, veratrol, monochlorobenzene, o-dichlorobenzene, pyridine, pyrazine, pyrimidine, pyrrolidinone, morpholine, dimethylacetamide, 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 to form the second solvent.

  Preferably, the second solvent has a boiling point 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 preferably has a solubility in the range of 1 to 250 g / l, more preferably in the range of 1 to 50 g / l, with respect to the first and second solvents.

  The content of at least one organic functional material in the formulation is in the range of 0.001 to 20% by weight, preferably in the range of 0.01 to 15% by weight, more preferably, based on the total weight of the formulation. It is in the range of 0.1 to 10% by weight, most preferably in the range of 0.3 to 10% by weight.

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

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

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

Example formulations and solvent viscosities were measured over a shear rate range of 10-1000 s ⁻¹ using a TA instruments ARG2 rheometer using a 40 mm parallel plate structure. Measurements were used as an average of 200-800 s ⁻¹ where temperature and shear rate were precisely controlled. The viscosities shown in Table 3 are the viscosities of each formulation measured at a temperature of 25 ° C. and a shear rate of 500 s ⁻¹ . Each solvent is measured in triplicate. The stated viscosity values are averages of the above measurements.

  The formulation according to the invention comprises at least one organic functional material that can be used for the production of a functional layer of an electronic device. The functional material is generally an organic material introduced between the anode and cathode of the electronic device.

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

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

  Preferred embodiments of the organic functional material are disclosed in detail in WO2011 / 076314A1, which is hereby incorporated by reference.

  In a preferred embodiment, the organic functional material is an organic semiconductor selected from the group consisting of hole injection, hole transport, light 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 material can be a compound, polymer, oligomer or dendrimer having a low molecular weight, where the organic functional material may further be in the form of a mixture. Thus, a formulation according to the invention may comprise two different compounds having a low molecular weight, one compound having a low molecular weight and one polymer, or two polymers (blends).

Organic functional materials are often described by the properties of frontier orbits, which are described in more detail below. The molecular orbitals, especially the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO), their energy levels, and the energy of the lowest triplet state T ₁ or lowest excited singlet state S ₁ of the material Determined by calculation. In order to calculate a metal-free organic material, first, structure optimization is performed using the “ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet” method. Subsequently, an energy calculation is performed based on the optimized structure. The “TD-SCF / DFT / default spin / B3PW91” method with “6-31G (d)” basis set (charge 0, spin singlet) is used here. For metal-containing compounds, the structure is optimized by the “ground state / Hartley Fock / default spin / LanL2MB / charge 0 / spin singlet” method. The energy calculation is performed in the same manner as in the case of the organic substance described above, but the “LanL2DZ” basis set is used for metal atoms, and the “6-31G (d)” basis set is used for ligands. There is a difference that By the energy calculation, the HOMO energy level HEh or the LUMO energy level LEh is obtained in Hartree units. The HOMO and LUMO energy levels in electron volts calibrated with reference to cyclic voltammetry measurements are then determined as follows:
HOMO (eV) = ((HEh ^* 27.212) −0.9899) /1.1206
LUMO (eV) = ((LEh ^* 27.212) -2.0041) /1.385
For purposes of this application, these values will be considered as the HOMO and LUMO energy levels of the material, respectively.

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

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

  The method described here is independent of the software package used and always gives the same results. Examples of frequently used programs for this purpose are “Gaussian 09W” (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

  A compound having hole injection properties, also referred to herein as a hole injection material, simplifies or facilitates the transfer of holes, ie positive charges, from the anode to the organic layer. The hole injection material has a HOMO level that is above the region of the anode level, i.e. generally at least -5.3 eV.

  A compound having hole transport properties, also referred to herein as a hole transport material, is generally capable of transporting positive holes injected from an anode or an adjacent layer, such as a hole injection layer, that is, a positive charge. The hole transport material generally has a high HOMO level, preferably at least -5.4 eV. Depending on the structure of the electronic device, it may be possible to use a hole transport material as a hole injection material.

  Preferred compounds having hole injection and / or hole transport properties include, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para. -Additional O, S or N containing heterocyclic compounds with dioxins, phenoxathiyne, carbazole, azulene, thiophene, pyrrole, and furan derivatives, high HOMO (HOMO = highest occupied molecular orbital).

  As a compound having hole injection and / or hole transport properties, a phenylenediamine derivative (US3615404), an arylamine derivative (US3567450), an amino-substituted chalcone derivative (US3526501), a styrylanthracene derivative (JP-A-56-46234), Polycyclic aromatic compound (EP1009041), polyarylalkane derivative (US3615402), fluorenone derivative (JP-A-54-110837), hydrazone derivative (US3717462), acylhydrazone, stilbene derivative (JP-A-6210363) Silazane derivatives (US4950950), polysilanes (JP-A-2-204996), aniline copolymers (JP-A-2-282263), thiophene oligomers 1989) -211399), polythiophene, poly (N-vinylcarbazole) (PVK), polypyrrole, polyaniline, and other conductive polymers, porphyrin compounds (JP-A-63-295965, US 4720432), aromatic dimethylidene type Compounds, carbazole compounds such as CDBP, CBP, mCP, aromatic tertiary amines and styrylamine compounds (US 4127412) such as benzidine type triphenylamine, styrylamine type triphenylamine, and diamine type triphenyl Particular mention may be made of amines and the like. Arylamine dendrimers (JP-A-8 (1996) -193191), monomeric triarylamines (US3180730), triarylamines containing at least one functional group containing one or more vinyl radicals and / or active hydrogens ( It is also possible to use US 3567450 and US 3658520), or tetraaryldiamines (two tertiary amine units are linked via an aryl group). More triarylamino groups may be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives, and quinoline derivatives such as dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline hexacarbonitrile.

Aromatic tertiary amines containing at least two tertiary amine units (US 2008/010311 A1, US 4720432 and US 5061569), such as NPD (α-NPD = 4,4′-bis [N- (1-naphthyl) -N -Phenyl-amino] biphenyl) (US 5061569), TPD232 (= N, N′-bis- (N, N′-diphenyl-4-aminophenyl) -N, N-diphenyl-4,4′-diamino-1, 1′-biphenyl) or MTDATA (MTDATA or m-MTDATA = 4,4 ′, 4 ″ -tris [3-methylphenyl) phenylamino] -triphenylamine) (JP-A-4-308688), TBDB ( = N, N, N ', N'-tetra (4-biphenyl) -diaminobiphenylene), TAPC (= 1,1- (4-di-p-tolylaminophenyl) cyclo-hexane), TAPPP (= 1,1-bis (4-di-p-tolylaminophenyl) -3-phenylpropane), BDTAPVB (= 1,4- Bis [2- [4- [N, N-di (p-tolyl) amino] phenyl] vinyl] benzene), TTB (= N, N, N ′, N′-tetra-p-tolyl-4,4 ′ -Diaminobiphenyl), TPD (= 4,4′-bis [N-3-methylphenyl] -N-phenylamino) -biphenyl), N, N, N ′, N′-tetraphenyl-4,4 ″ '-Diamino-1,1', 4 ', 1'',4'',1'''-quaterphenyl and the like are preferred, as well as tertiary amines containing carbazole units, such as TCTA (= 4 -(9H-carbazol-9-yl) -N, N-bis [4- (9H- Carbazole-9-yl) phenyl] benzenamine) and the like are preferable. Similarly, hexaazatriphenylene compounds according to US 2007/0092755 A1 and phthalocyanine derivatives (eg H ₂ Pc, CuPc (= copper phthalocyanine), CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO) AlPc, (HO) GaPc, VOPc, TiOPc, MoOPc, GaPc—O—GaPc) are preferred.

  Triarylamine compounds of the following formulas (TA-1) to (TA-12) are particularly preferred, and EP1162193B1, EP650955B1, Synth. Metals 1997, 91 (1-3), 209, DE196646119A1, WO2006 / 122630A1, EP1860097A1, EP1834945A1, JP08053397A, US6251531B1, US2005 / 0221124, JP08292686A, US738916, 2006 The compounds of formulas (TA-1) to (TA-12) may be substituted.

  Further compounds that can be used as hole injection materials are described in EP0811121A1 and EP1029909A1, and the injection layer is generally described in US2004 / 0174116A1.

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

  Compounds having electron injection and / or electron transport properties include, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzoanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide, And phenazine derivatives, as well as triarylboranes, and additional O, S or N containing heterocyclic compounds with low LUMO (LUMO = lowest unoccupied molecular orbital).

Particularly suitable compounds for electron transport and electron injection layers are metal chelates of 8-hydroxyquinoline (eg LiQ, AlQ ₃ , GaQ ₃ , MgQ ₂ , ZnQ ₂ , InQ ₃ , ZrQ ₄ ), BAlQ, Ga oxinoid complexes, 4- Azaphenanthrene-5-ol-Be complex (see US5529853A, formula ET-1), butadiene derivative (US4356429), heterocyclic optical brightener (US4539507), benzimidazole derivative (US2007 / 0273272A1), such as TPBI (US5776679, 1,3,5-triazines such as spirobifluorenyltriazine derivatives (eg according to DE 102008064200), pyrenes, anthracenes, tetracenes, fluorenes, spiroflutes, etc. Rene, dendrimer, tetracene (for example, rubrene derivative), 1,10-phenanthroline derivative (JP2003-115387, JP2004-3118184, JP2001-267080, WO02 / 043449), silacyclopentadiene derivative (EP1480280, EP1478032, EP1469533), borane derivative, For example, triarylborane derivatives containing Si (US2007 / 0087219A1, see formula ET-3), pyridine derivatives (JP2004-200162), phenanthrolines, especially 1,10-phenanthroline derivatives such as BCP and Bphen, and also biphenyl or Some phenanthrolines linked via other aromatic groups (US2007-0252517A1 Or phenanthroline bound to anthracene is (US2007-0122656A1, wherein reference ET-4 and ET-5).

  Likewise suitable are heterocyclic organic compounds such as thiopyran dioxide, oxazole, triazole, imidazole or oxadiazole. Five-membered rings containing N, such as oxazole, preferably 1,3,4-oxadiazole, such as inter alia the formulas ET-6, ET-7, ET-8 and ET-9 disclosed in US2007 / 0273272A1 Examples of the use of thiazole, oxadiazole, thiadiazole, triazole are described in US 2008/010311 A1 and Y. A. Levin, M.M. S. See Skorobogatova, Khimiya Geterosiklichskih Soedinenii 1967 (2), 339-341, preferably a compound of formula ET-10, a silacyclopentadiene derivative. Preferred compounds are the following formulas (ET-6) to (ET-10):

  It is likewise possible to use organic compounds such as derivatives of fluorenone, fluorenylidenemethane, perylenetetracarbonic acid, anthraquinone dimethane, diphenoquinone, anthrone and anthraquinone diethylenediamine.

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

  Compounds capable of producing electron injection and / or electron transport properties preferably produce a LUMO of less than −2.5 eV (vs. vacuum level), particularly preferably less than −2.7 eV.

  The formulations of the present invention may include a light emitter. The term illuminant means a material that allows a radiative transition to the ground state with emission after excitation, which can occur by any type of energy transfer. In general, two classes of light emitters are known, namely fluorescent and phosphorescent emitters. The term fluorescent emitter means a material or compound that undergoes a radiative transition from an excited singlet state to a ground state. The term phosphorescent emitter means a luminescent material or compound that preferably contains a transition metal.

  If the dopant causes the above properties in the system, the phosphor is often referred to as a dopant. A dopant in a system that includes a matrix material and a dopant is taken to mean the component with the lower proportion of the mixture. Correspondingly, the matrix material in the system comprising the matrix material and the dopant is taken to mean the component with the higher proportion of the mixture. Thus, the term phosphorescent emitter can also be taken to mean, for example, a phosphorescent dopant.

  Compounds capable of emitting light include, inter alia, fluorescent emitters and phosphorescent emitters. These include, among others, stilbene, stilbeneamine, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene, phthalocyanine, porphyrin, ketone, quinoline, imine, anthracene and / or pyrene. Includes compounds containing structure. A compound that can emit light from a triplet state with high efficiency even at room temperature, that is, a compound that exhibits electrophosphorescence, which often causes an increase in energy efficiency, is not electrofluorescence. Suitable for this purpose are first compounds containing heavy atoms with atomic numbers greater than 36. A compound containing a d- or f-transition metal that satisfies the above conditions is preferred. Here, the corresponding compounds containing Group 8-10 elements (Ru, Os, Rh, Ir, Pd, Pt) are particularly preferred. Here, suitable functional compounds are various complexes described in, for example, WO02 / 068435A1, WO02 / 081488A1, EP123395A2 and WO2004 / 026886A2.

  Preferred compounds that can function as fluorescent emitters are described by the following examples. Preferred fluorescent emitters are selected from the classes of monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styryl ether, and arylamine.

  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 and may be further substituted. Corresponding phosphines and ethers are defined similarly to amines. An arylamine or aromatic amine in the sense of the present invention is taken to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines, or aromatic chrysene diamines. Aromatic anthracenamine is taken to mean a compound in which one diarylamino group is bonded directly to the anthracene group, preferably in the 9-position. Aromatic anthracenediamine is taken to mean a compound in which two diarylamino groups are bonded directly to the anthracene group, preferably in the 2,6 or 9,10 position. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysenediamines are defined similarly, where the diarylamino group is preferably attached to pyrene at the 1-position or 1,6-position.

  Further preferred fluorescent emitters are inter alia indenofluorenamine or indenofluorenamine as described in WO 2006/122630; in particular benzoindenofluorenamine or benzoindenofluorenilamine as described in WO 2008/006449; and especially as described in WO 2007/140847. Selected from dibenzoindenofluorenamine or dibenzoindenofluorenamine.

  Examples of compounds from the styrylamine class that can be used as fluorescent emitters are substituted or unsubstituted tristilbeneamines or dopants described in WO2006 / 000388, WO2006 / 058737, WO2006 / 000389, WO2007 / 0665549 and WO2007 / 115610. is there. Distyrylbenzene and distyrylbiphenyl derivatives are described in US Pat. Further styrylamines can be found in US2007 / 0122656A1.

  Particularly preferred styrylamine compounds are the compounds of formula EM-1 as described in US Pat. No. 7,250,532 B2 and the compounds of formula EM-2 as described in DE 102005058557A1:

  Particularly preferred triarylamine compounds are compounds of the formula EM-3 to EM-15 and their derivatives as disclosed in CN1588391A, JP08 / 053397A and US6251531B1, EP1957606A1, US2008 / 0113101A1, US2006 / 210830A, WO2008 / 006449, and DE102008035413 Is:

  Further preferred compounds that can be used as fluorescent emitters are naphthalene, anthracene, tetracene, benzoanthracene, benzophenanthrene (DE102009005746), fluorene, fluoranthene, perifuranthene, indenoperylene, phenanthrene, perylene (US2007 / 0252517A1), pyrene, chrysene, decacyclene. , Coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US4769292, US6020078, US2007 / 0252517A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamic acid ester , Diketopyrrolopyrrole, acridone, And it is selected from the derivatives of quinacridone (US2007 / 0252517A1).

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

  Similarly, derivatives of rubrene, coumarin, rhodamine, quinacridone, such as DMQA (= N, N′-dimethylquinacridone), dicyanomethylenepyran, such as DCM (= 4- (dicyanoethylene) -6- (4-dimethylaminostyryl). Preferred are thiopyran, polymethine, pyrylium and thiapyrylium salts, perifrantene, and indenoperylene, such as -2-methyl) -4H-pyran).

  The blue fluorescent emitter is preferably a polyaromatic compound such as 9,10-di (2-naphthylanthracene) and other anthracene derivatives such as tetracene, xanthene, perylene derivatives such as 2,5,8,11-tetra. -T-butylperylene and the like, phenylene such as 4,4'-bis (9-ethyl-3-carbazovinylene) -1,1'-biphenyl, fluorene, fluoranthene, arylpyrene (US2006 / 0222886A1), arylene vinylene (US51221029, US5130603), bis (azinyl) imine-boron compound (US2007 / 0092753A1), bis (azinyl) methene compound, and carbostyryl compound.

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

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

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

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

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

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

  In particular, Pt or Pd complexes having a tetradentate ligand of the formula EM-16 are suitable.

Compounds of formula EM-16 are described in more detail in US 2007/0087219 A1, where reference is made to this specification for purposes of disclosure for explanation of substituents and subscripts in the above formula. Further, Pt-porphyrin complexes having an extended ring system (US2009 / 0061681A1) and Ir complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin-Pt (II), tetraphenyl -Synthesis of Pt (II) tetrabenzoporphyrin (US2009 / 0061681A1), cis- bis ^{(2-phenylpyridinato--N, C 2 ') Pt (} II), cis- bis (2- (2'-thienyl) pyridinato ^{-N, C 3 ') Pt (} II), cis- bis (2- (2'-thienyl) - quinolinato ^{-N, C 5') Pt (} II), (2- (4,6- difluorophenyl) pyridinato ^{-N, C 2 ') Pt (} II) ( acetylacetonate), or tris ^{(2-phenylpyridinato--N, C 2') Ir (} III (= Ir _{(ppy) 3,} green), bis ^{(2-phenylpyridinato--N,} C 2) Ir (III) (acetylacetonate) (= Ir _{(ppy) 2} acetylacetonate, green, US2001 / 0053462A1 , Baldo, Thompson et al., Nature 403, (2000), 750-753), bis (1-phenylisoquinolinato--N, ^{C 2} ') (2- phenylpyridinato--N, ^{C 2')} iridium (III ), bis (2-phenylpyridinato--N, ^{C 2} ') (1-phenylisoquinolinato--N, ^{C 2')} iridium (III), bis (2- (2'-benzothienyl) pyridinato -N , C ³ ′) iridium (III) (acetylacetonate), bis (2- (4 ′, 6′-difluorophenyl) pyridinato-N, C ² ′) iridium (III) (picolinate) (FIrpic, blue), bis (2- (4 ′, 6′-difluorophenyl) pyridinato-N, C ² ′) Ir (III) (tetrakis (1-pyrazolyl) borate), tris (2- (biphenyl-3-yl) -4-tert-butylpyridine) iridium (III), (ppz) ₂ Ir (5 phdpym) (US2009 / 0061681A1), (45ooppz) ₂ Ir (5phdpym) (US2009 / 0061681A1) Derivatives of 2-phenylpyridine-Ir complexes, such as 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).

Also suitable are complexes of trivalent lanthanides such as Tb ³⁺ and Eu ³⁺ (J. Kido et al., Appl. Phys. Lett. 65 (1994), 2124, Kido et al., Chem. Lett. 657, 1990, US2007 / 0252517A1), or phosphorescent complexes of Pt (II), Ir (I), Rh (I) containing maleonitrile dithiolate (Johnson et al., JACS 105, 1983, 1795), Re (I) tricarbonyl-diimine complex (Especially Wrightton, JACS 96, 1974, 998), Os (II) complexes having a cyano ligand and a bipyridyl or phenanthroline ligand (Ma et al., Synth. Metals 94, 1998, 245).

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

  Particularly preferred compounds for use as phosphorescent dopants are, inter alia, US 2001/0053462 A1 and Inorg. Chem. 2001, 40 (7), 1704-1711, JACS2001, 123 (18), 4304-4312 and compounds of formula EM-17 and derivatives thereof.

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

  Furthermore, the compounds of formulas EM-18 to EM-21 and their derivatives as described in US Pat. No. 7,238,437 B2, US 2009/008607 A1 and EP 1348711 can be used as illuminants.

  Similarly, quantum dots can be used as light emitters, and these materials are disclosed in detail in WO2011 / 076314A1.

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

  Host materials generally have a larger band gap between HOMO and LUMO than the phosphor material used. In addition, preferred host materials exhibit properties of either hole or electron transport materials. Furthermore, the host material can have both electron and hole transport properties.

  The host material is sometimes also referred to as a matrix material, particularly when the host material is used in combination with a phosphorescent emitter in an OLED.

Preferred host materials or cohost materials used in particular with fluorescent dopants are oligoarylenes (for example 2,2 ′, 7,7′-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular condensed aromatic groups. Oligoarylenes containing, for example, anthracene, benzoanthracene, benzophenanthrene (DE102009005746, WO2009 / 069566), phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, etc. DPVBi = 4,4′-bis (2,2-diphenylethenyl) -1,1′-biphenyl or EP according to EP676461 Pyro-DPVBi), polypodal metal complexes (for example according to WO 04/081017), in particular metal complexes of 8-hydroxyquinoline, such as AlQ ₃ (= aluminum (III) tris (8-hydroxyquinoline)) or bis (2-methyl-8). -Quinolinolato) -4- (phenylphenolinolato) aluminum metal complexes that further contain an imidazole chelate (US2007 / 0092753A1), and quinoline metal complexes, aminoquinoline-metal complexes, benzoquinoline-metal complexes, positive Pore conducting compounds (eg according to WO 2004/058911), electron conducting compounds, in particular ketones, phosphine oxides, sulfoxides etc. (eg according to WO 2005/084081 and WO 2005/084082) (By e.g. WO2006 / 048268) the body, is selected from the class of boronic acid derivatives (e.g. by WO2006 / 117052) or (by e.g. WO2008 / 145 239) benzo anthracene.

  Particularly preferred compounds that can function as host materials or cohost materials are selected from the classes of oligoarylenes, including anthracene, benzoanthracene and / or pyrene, or atropisomers of these compounds. Oligoarylene in the sense of the present invention is intended to be understood as meaning a compound in which at least three aryl or arylene groups are bonded to one another.

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

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

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

  Further preferred compounds are arylamine, styrylamine, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, bisbenzoxazoline, oxazole, pyridine, pyrazine, imine , Derivatives of benzothiazole, benzoxazole, benzimidazole (US2007 / 0092753A1), such as 2,2 ′, 2 ″-(1,3,5-phenylene) tris [1-phenyl-1H-benzimidazole], aldazine, Stilbene, styrylarylene derivatives such as 9,10-bis [4- (2,2-diphenylethenyl) -phenyl] anthracene, and distyrylarylene Derivatives (US5121029), diphenylethylene, vinyl anthracene, diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethine, cinnamic acid esters, as well as fluorescent dyes.

Arylamine and styrylamine derivatives such as 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 cohosts.

  Preferable compounds containing oligoarylene as a matrix are US2003 / 0027016A1, US73326371B2, US2006 / 043858A, WO2007 / 114358, WO2008 / 145239, JP3148176B2, EP1009044, US2004 / 0163853, WO2005 / 061656, WO142 / 007 065678, and DE 102009005746, where particularly preferred compounds are described by the formulas H-2 to H-8.

  Further, compounds that can be used as a host or matrix include materials used with phosphorescent emitters.

These compounds can also be used as structural elements in the polymer, and CBP (N, N-biscarbazolylbiphenyl), carbazole derivatives (eg WO2005 / 039246, US2005 / 0069729, JP2004 / 288811, EP1205527 or WO2008 / 086851), azacarbazole (for example according to EP1617710, EP1617711, EP1731584 or JP2005 / 347160), ketone (for example according to WO2004 / 093207 or DE102008033943), phosphine oxide, sulfoxide and sulfone (for example according to WO2005 / 003253), oligophenylene, aromatic Amines (for example according to US 2005/0069729), Polar matrix materials (for example according to WO2007 / 137725), silanes (for example according to WO2005 / 111172), 9,9-diarylfluorene derivatives (for example according to DE1020080175591), azabolol or boronate esters (for example according to WO2006 / 117052), triazine derivatives (for example DE102008036982), indolocarbazole derivatives (for example according to WO2007 / 063754 or WO2008 / 056746), indenocarbazole derivatives (for example according to DE102009023155 and DE102009031021), diazaphosphole derivatives (for example according to DE102009022858), triazole derivatives, oxazole and Xazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indoles, hydrazones Derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carbodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives that may further contain a triarylaminophenol ligand, such as AlQ ₃ (US2007 / 0134514A1), metal complexes / Polysilane compounds and thiophene, benzothiophene and dibenzothiophene derivatives.

  An example of a preferred carbazole derivative is mCP (= 1,3-N, N-di-carbazolylbenzene (= 9,9 ′-(1,3-phenylene) bis-9H-carbazole)) (formula H-9 ), CDBP (= 9,9 ′-(2,2′-dimethyl [1,1′-biphenyl] -4,4′-diyl) bis-9H-carbazole), 1,3-bis (N, N ′) -Dicarbazolyl) benzene (= 1,3-bis (carbazol-9-yl) benzene), PVK (polyvinylcarbazole), 3,5-di (9H-carbazol-9-yl) biphenyl, and CMTTP (formula H-10 ). Particularly mentioned compounds are disclosed in US2007 / 0128467A1 and US2005 / 0249976A1 (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.P. Gilman, E .; A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120.

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

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

  With respect to functional compounds that can be used according to the invention and can function as host materials, substances containing at least one nitrogen atom are particularly preferred. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. Therefore, carbazole derivatives exhibit particularly high efficiency. Triazine derivatives provide an unexpectedly long lifetime for electronic devices.

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

  It is further possible to use compounds that improve the transition from the singlet state to the triplet state, are used to support functional compounds with luminescent properties and improve the phosphorescence properties of these compounds. Suitable for this purpose are in particular carbazole and bridged carbazole dimer units, as described, for example, in WO 2004/070772 A2 and WO 2004/113468 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds, as described, for example, in WO 2005/040302 A1.

Here, n-dopant is taken to mean a reducing agent, ie an electron donor. Preferred examples of n dopants include W (hpp) ₄ and other electron rich metal complexes according to WO 2005/086251 A2, P═N compounds (eg WO2012 / 175535A1, WO2012 / 175219A1), naphthylenecarbodiimides (eg WO2012 / 168358A1), fluorene (Eg WO2012 / 031735A1), free radicals and diradicals (eg EP1837926A1, WO2007 / 107306A1), pyridine (eg EP2452946A1, EP2463927A1), N-heterocyclic compounds (eg WO2009 / 000237A1), and acridine and phenazine (eg US2007 / 145355A1) ).

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

  The compound used as the wide band gap material can preferably 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 by the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), among others.

  Further, the formulation may include a hole blocking material (HBM) as a functional material. Hole blocking material means a material that prevents or minimizes the transmission of holes (positive charge) in a multilayer system, especially when the material is arranged in the form of a layer adjacent to a light emitting layer or hole conducting layer. . In general, hole blocking materials have a lower HOMO level than hole transport materials in adjacent layers. The hole blocking layer is often disposed between the light emitting layer and the electron transport layer in the OLED.

In principle, 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 (US2003 / 0068528), such as bis (2-methyl-8-quinolinolato) (4-phenylphenol). Lato) aluminum (III) (BAlQ). Fac-Tris (1-phenylpyrazolato-N, C2) -iridium (III) (Ir (ppz) ₃ ) has been used for this purpose as well (US2003 / 0175553A1). Phenanthroline derivatives such as BCP or phthalimides such as TMPP can be used as well.

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

  Furthermore, the formulation may include an electron blocking material (EBM) as a functional material. By electron blocking material is meant a material that prevents or minimizes the transfer of electrons in a multilayer system, particularly when the material is arranged in the form of a layer adjacent to a light emitting layer or an electron conducting layer. In general, the electron blocking material has a higher LUMO level than the electron transport material in the adjacent layer.

In principle, 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 (US2003 / 0175553).

  The electron blocking material can preferably be selected from amines, triarylamines, and derivatives thereof.

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

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

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

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

  The structural elements here may also have various functions, and a clear assignment need not be advantageous. For example, the structural elements of group 1 may function as a skeleton as well.

  The polymer having hole transport or hole injection properties used as an organic functional material containing a structural element from Group 1 preferably may contain units corresponding to the above hole transport or hole injection materials. Good.

  Further preferred structural elements of group 1 include, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, carbazoles, azulene, thiophene, pyrrole, and furan derivatives, and additional O, S, or N-containing heterocycles with high HOMO. It is a cyclic compound. These arylamines and heterocyclic compounds preferably have a HOMO greater than −5.8 eV (vs. vacuum level), particularly preferably greater than −5.5 eV.

  In particular, polymers with hole transport or hole injection properties containing at least one repeating unit of formula HTP-1 below are preferred:

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

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

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

  In particular, polymers with hole transport or hole injection properties containing at least one repeating unit of formula HTP-2 below are preferred:

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

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

  The polymer having electron injection and / or electron transport properties used as an organic functional material containing a structural element from group 2 may preferably contain units corresponding to the above electron injection and / or electron transport materials. Good.

  Further preferred structural elements of group 2 having electron injection and / or electron transport properties include, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline and phenazine groups, as well as triarylborane groups, or low LUMO groups. Derived from further O, S or N containing heterocyclic compounds having a position. These group 2 structural elements preferably have a LUMO of less than −2.7 eV (vs. vacuum level), particularly preferably less than −2.8 eV.

  The organic functional material can preferably be a polymer containing structural elements from group 3, where the structural elements that improve hole and electron mobility (ie structural elements from groups 1 and 2) are Are directly connected to each other. Some of these structural elements can function as light emitters, where the emission color may be shifted to eg green, red or yellow. Thus, their use is advantageous, for example, for the production of other emission colors or broadband emission by polymers that originally emit blue light.

  The polymer with luminescent properties used as an organic functional material containing structural elements from group 4 may preferably contain units corresponding to the luminescent material described above. Here, a polymer containing the above-mentioned luminescent metal complex containing a phosphorescent group, in particular a corresponding unit containing a group 8-10 element (Ru, Os, Rh, Ir, Pd, Pt) is preferred.

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

  Suitable for this purpose are in particular carbazole and linked carbazole dimer units, as described, for example, in DE 10304819 A1 and DE 10328627 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones and silane derivatives, as well as similar compounds, as described, for example, in DE 103 490 33 A1. Furthermore, preferred structural units may be derived from the compounds described above in connection with the matrix material used with the phosphorescent compound.

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

  This type of structural unit can affect the morphology or emission color of the resulting polymer. Thus, depending on the structural unit, these polymers can also be used as light emitters.

  Thus, in the case of fluorescent OLEDs, aromatic structural elements having 6 to 40 C atoms, or tolan, stilbene or bisstyrylarylene derivative units are preferred, each of which may be substituted by one or more radicals. . Here, 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6-, 2,7- or 4,9-pyrenylene, 3,9- or 3,10 -Peryleneylene, 4,4'-biphenylene, 4,4 "-terphenylylene, 4,4'-bi-1,1'-naphthylylene, 4,4'-tralenylene, 4,4'-stilbenylene, or 4,4 The use of groups derived from '' -bisstyrylarylene derivatives is particularly preferred.

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

  These include, among others, 4,5-dihydropyrene derivatives, 4,5,9,10-tetra-hydropyrene derivatives, fluorene derivatives, such as disclosed in WO2003 / 020790A1, which are disclosed, for example, in US5962631, WO2006 / 052457A2 9,9-spirobifluorene derivatives, such as the 9,10-phenanthrene derivatives disclosed in WO2005 / 104264A1, such as the 9,10-dihydrophenanthrene derivatives disclosed in WO2005 / 014689A2, such as WO2004 / 041901A1 and 5,7-Dihydrodibenzooxepin derivatives and cis- and trans-indenofluores disclosed in WO2004 / 113212A2 Including derivatives and for example binaphthylene derivatives disclosed in WO2006 / 063852A1, and for example, WO2005 / 056633A1, EP1344788A1, WO2007 / 043495A1, WO2005 / 033174A1, WO2003 / 099901A1 and additional units disclosed in DE102006003710.

  For example, fluorene derivatives disclosed in US 5,962,631, WO2006 / 052457A2 and WO2006 / 118345A1, for example spirobifluorene derivatives disclosed in WO2003 / 020790A1, such as disclosed in WO2005 / 056633A1, EP1344788A1 and WO2007 / 043495A1. Particularly preferred are the structural units of group 7 selected from the benzofluorene, dibenzofluorene, benzothiophene and dibenzofluorene groups and derivatives thereof.

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

(Where the symbols and subscripts have the following meanings:
A, respectively B and B ', also have the same or different for different repeating units, preferably ^{-CR c R d -, - NR} c -, - PR c -, - O -, - _{S -, - SO -, -} SO 2-, -CO -, - CS -, - cSe -, - P (= O) R c -, - P (= S) R c - and -SiR ^c R ^d - A divalent group selected from:
R ^c and R ^d each occur 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, optionally silyl substituted carbyl or hydrocarbyl group having one or more heteroatoms carbon atoms may also be 1 to 40, which contain optionally may be optionally substituted Wherein R ^c and R ^d may optionally form a spiro group with the fluorene radical to which they are attached;
X is a halogen;
R ⁰ and R ⁰⁰ are each independently H, or optionally substituted having 1 to 40 carbon atoms, which may be optionally substituted and optionally contain one or more heteroatoms. A carbyl or hydrocarbyl group which may be substituted;
g is independently 0 or 1 in each case, and h is independently 0 or 1 in each case, where the sum of g and h in the subunits is preferably 1. ;
m is an integer greater than or equal to 1;
Ar ¹ and Ar ² may be optionally substituted independently of each other, and optionally monocyclic or polycyclic aryl, which may be bonded to the 7,8-position or 8,9-position of indenofluorene, Represents a heteroaryl group;
a and b are independently 0 or 1).

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

  Particular preference is given to repeating units of the formula PB-1 selected from the group consisting of units of the formulas PB-1A to PB-1E:

(Wherein 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 radical R ^c ) .

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

  Particular preference is given to repeating units of the formula PB-1 selected from the group consisting of units of the formulas PB-1F to PB-1I:

Where 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 methyl, i-propyl, t-butyl , N-pentoxy or trifluoromethyl;
L ′ is an optionally fluorinated linear or branched alkyl or alkoxy group having 1 to 12 C atoms, preferably representing n-octyl or n-octyloxy).

  In practicing the present invention, polymers containing two or more of the structural elements of groups 1-7 are preferred. Furthermore, the polymer may preferably be defined as containing two or more of the structural elements from one group as described above, ie comprising a mixture of structural elements selected from one group.

  In particular, in addition to the luminescent properties, preferably at least one structural element (group 4) having at least one phosphorescent group, at least one further structural element from the above groups 1-3, 5 or 6 is additionally added. Polymers containing are particularly preferred, where these are preferably selected from groups 1 to 3.

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

  The preparation of white light-emitting copolymers is described in detail in DE 10343606 A1 among others.

  In order to improve the solubility, the polymer may contain a corresponding group. Preferably, the polymer contains substituents, so that on average at least 2 non-aromatic carbon atoms, particularly preferably at least 4 and particularly preferably at least 8 non-aromatic carbon atoms per repeating unit. There may be specified where the average relates to the number average. Here, individual carbon atoms may be replaced by, for example, O or S. However, it is possible that a certain proportion of any repeat unit optionally does not contain a substituent containing a non-aromatic carbon atom. Here, short chain substituents are preferred because long chain substituents may adversely affect layers that can be obtained using organic functional materials. The substituent preferably contains no more than 12 carbon atoms, preferably no more than 8 carbon atoms, particularly preferably no more than 6 carbon atoms in the straight chain.

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

  In a further aspect, the polymer used as the organic functional material can be a non-conjugated polymer with side chains, where this aspect is particularly important in the case of polymer-based phosphorescent OLEDs. In general, phosphorescent polymers can be obtained by free radical copolymerization of vinyl compounds, where these vinyl compounds are at least one unit having a phosphorescent emitter and, inter alia, disclosed in US Pat. No. 7,250,226 B2. And / or contain at least one charge transport unit. Further phosphorescent polymers are described inter alia in JP 2007/21243 A2, JP 2007/197574 A2, US 7250226 B2 and JP 2007 / 059939A.

  In a further preferred embodiment, the non-conjugated polymer contains skeletal units linked together by spacer units. Examples of such triplet emitters based on non-conjugated polymers based on backbone units are disclosed, for example, in DE102009023154.

  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 benzoanthracene groups, or derivatives of these groups in the side chain, where these polymers are for example JP 2005/108556, JP 2005/285661. And JP 2003/338375.

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

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

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

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

  The formulation according to the invention may comprise all the organic functional materials necessary for the production of the respective functional layer of the electronic device. For example, if the hole transport, hole injection, electron transport, or electron injection layer is precisely constructed from one functional compound, the formulation includes this compound exactly as an organic functional material. For example, if the emissive layer includes an emitter in combination with a matrix or host material, the formulation may include a mixture of the emitter and matrix or host material as the organic functional material, as described in more detail elsewhere herein. Including exactly.

  In addition to the above components, the formulations according to the invention may comprise further additives and processing aids. These include, among other things, surface active substances (surfactants), lubricants and greases, additives that adjust viscosity, additives that increase conductivity, dispersants, hydrophobizing agents, adhesion promoters, fluidity improvers Defoamers, deaerators, diluents, fillers, adjuvants, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles, and inhibitors that may be reactive or non-reactive including.

  The invention further relates to a method for preparing a formulation according to the invention, wherein at least a first organic solvent 1,1-diphenylethylene derivative and at least one organic function that can be used for the manufacture of a functional layer of an electronic device. The materials are mixed.

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

  The formulations of the present invention can preferably be used to form a functional layer on a substrate or 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 an electronic device, wherein the formulation according to the invention is applied to a substrate and dried.

  The functional layer is for example a substrate or a substrate by flood coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, rotary printing, roller coating, flexographic printing, offset printing or nozzle printing, preferably by ink jet printing. Can be produced on one of the applied layers.

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

  It may further be provided that the process is repeated several times with the formation of different or identical functional layers. Here, the functional layer to be formed can be crosslinked, for example, as disclosed in EP 0 633 899 A1 to prevent its decomposition.

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

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

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

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

  The active components are generally organic or inorganic materials introduced between the anode and the cathode, where these active components realize, maintain and / or achieve the properties of the electronic device, such as its performance and / or its lifetime. Or improve, for example, charge injection, charge transport or charge blocking materials, but particularly light emitting materials and matrix materials. Therefore, the organic functional material that can be used for the production of the functional layer of the electronic device preferably comprises the active component of the electronic device.

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

  More preferably, a mixture of two or more triplet emitters is used with the matrix. Here, the triplet light emitter having a short wavelength emission spectrum functions as a co-matrix for the triplet light emitter having a longer wavelength emission spectrum.

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

  Correspondingly, 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 case of a fluorescent light emitting layer. In the case of a phosphorescent light emitting layer, it is 3 to 15% by volume.

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

  The mixed matrix system preferably comprises 2 or 3 different matrix materials, more preferably 2 different matrix materials. Here, preferably, one of the two materials is a material having a hole transport property, and the other material is a material having an electron transport property. However, the desired electron transport and hole transport properties of the mixed matrix component may be primarily or completely combined in a single mixed matrix component, in which case the additional mixed matrix component (s) Fulfills the function. Here, the two different matrix materials are 1:50 to 1: 1, preferably 1:20 to 1: 1, more preferably 1:10 to 1: 1, most preferably 1: 4 to 1: 1. May be present in a ratio of Mixed matrix systems are preferably used in phosphorescent organic electroluminescent devices. Further details regarding mixed matrix systems can be found, for example, in WO2010 / 108579.

Apart from these layers, the organic electroluminescent device comprises further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, Exciton blocking layer, electron blocking layer, charge generation layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or organic or inorganic p / n junctions. Wherein one or more hole transport layers are p-doped with, for example, metal oxides such as MoO ₃ or WO ₃ or with (per) fluorinated electron-deficient aromatic compounds, and / or one or more The electron transport layer can be n-doped. It is likewise possible to introduce an intermediate layer between the two emissive layers, for example having an exciton blocking function and / or controlling the charge balance in the electroluminescent device. It should be pointed out, however, that each of these layers does not necessarily have to be present. These layers may be present as well when using the formulation according to the invention, as defined above.

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

  Accordingly, the present invention further includes at least three layers of hole injection, hole transport, light emission, electron transport, electron injection, charge blocking and / or charge generation layers, and in a preferred embodiment all of the layers are Including, but relates to an electronic device wherein at least one layer is obtained with a formulation to be used according to the invention. The thickness of the layer, for example the hole transport and / or hole injection layer, can preferably be in the range of 1 to 500 nm, more preferably in the range of 2 to 200 nm.

  The device may further comprise a layer constructed from a low molecular weight compound or polymer that has not been applied through the use of a formulation according to the invention. These can be produced by evaporation of low molecular weight compounds in high vacuum.

  In addition, it may be preferred not to use the compound to be used as a pure substance, but instead as a mixture (blend) with any desired type of further macromolecular, oligomeric, dendritic or low molecular weight substances. These may, for example, improve electronic properties or emit light themselves.

  In a preferred embodiment of the invention, the formulation according to the invention comprises an organic functional material used as a host material or matrix material in the light emitting layer. Here, the formulation may include the above-described phosphor in addition to the host material or matrix material. Here, the organic electroluminescent device may include one or more light emitting layers. When there are a plurality of light emitting layers, preferably they have a plurality of light emission maxima from 380 nm to 750 nm to produce white light emission as a whole, that is, various light emitting compounds capable of emitting fluorescence or phosphorescence emit light. Used for layer. A three-layer system is very particularly preferred, where the three layers exhibit blue, green, and orange or red emission (for example, see WO2005 / 011013 for the basic structure). White light emitting devices are suitable, for example, as backlighting for LCD displays or for general lighting applications.

  Multiple OLEDs can be placed one above the other to allow further efficiency gains with respect to the light yield to be realized.

  In order to improve the light coupling-out, the final organic layer on the light output side of the OLED can also result in a reduction in the percentage of total reflection, for example in the form of a nanofoam.

More preferred are organic electroluminescent devices in which one or more layers are applied by a sublimation process, wherein the material is less than 10 ⁻⁵ mbar, preferably less than 10 ⁻⁶ mbar, more preferably in a vacuum sublimation unit. Is applied by vapor deposition at a pressure of less than 10 ⁻⁷ mbar.

Furthermore, it may be provided that one or more layers of the electronic device according to the invention are applied by an OVPD (Organic Vapor Deposition) process or utilizing carrier gas sublimation, wherein the material is It is applied at a pressure of 10 ⁻⁵ mbar to 1 bar.

  Furthermore, the one or more layers of the electronic device according to the invention are from solution, for example by spin coating, or any desired printing process, for example screen printing, flexographic printing or offset printing, but particularly preferably LITI. It may be specified to be manufactured by (photo-induced thermal imaging, thermal transfer printing) or ink jet printing.

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

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

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

The anode preferably comprises a material having a high work function. The anode preferably has a potential in excess of 4.5 eV versus vacuum. Suitable for this purpose are on the one hand metals with a high redox potential, such as Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (eg Al / Ni / NiO _x , Al / PtO _x ) may also be preferred. In some applications, at least one of the electrodes must be transparent to facilitate either organic material irradiation (O-SC) or light coupling out (OLED / PLED, O-lasers). A preferred structure uses a transparent anode. The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Further preferred are conductive doped organic materials, in particular conductive doped polymers such as poly (ethylenedioxythiophene) (PEDOT) and polyaniline (PANI), or derivatives of these polymers. More preferably, a p-doped hole transport material is applied to the anode as a hole injection layer, where suitable p dopants are metal oxides such as MoO ₃ or WO ₃ , or (per) fluorinated electrons. It is a deficient aromatic compound. Further suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NDP9 from Novaled. This type of layer simplifies hole injection in materials with low HOMO, ie high values of HOMO.

  In general, any material as used for the layers according to the prior art can be used for the further layers, and the person skilled in the art can combine each of these materials with the material according to the invention without requiring inventive step in the electronic device. .

  Correspondingly, the devices are constructed in a manner known per se and, depending on the application, are provided with contacts, so that the lifetime of such devices is greatly shortened in the presence of water and / or air, so that they are finally sealed. Is done.

The formulations according to the invention and the electronic devices obtainable therefrom, in particular organic electroluminescent devices, are distinguished from the prior art by one or more of the following surprising advantages:
1. The electronic devices that can be obtained using the formulations according to the invention exhibit a very high stability and a very long lifetime compared to electronic devices obtained using conventional methods.
2. The formulations according to the invention can be processed using conventional methods, so that a cost advantage can be realized.
3. The organic functional materials used in the formulations according to the invention make it possible to use the method according to the invention comprehensively without any particular restrictions.
4). The coatings obtainable with the formulations according to the invention exhibit an excellent quality, in particular with regard to the uniformity of the coating.

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

  It should be pointed out that variations on the embodiments described herein are within the scope of the invention. Each feature disclosed in the present invention may be replaced by an alternative feature serving the same, equivalent or similar purpose, unless expressly excluded. Thus, each feature disclosed in the invention is to be considered as an example of a comprehensive series, or equivalent or similar features, unless otherwise specified.

  All of the features of the present invention can be combined with each other in any manner, as long as the particular features and / or steps are not mutually exclusive. This is particularly true for the preferred features of the present invention. Similarly, non-essential combination features can be used individually (and not combined).

  It should be further pointed out that many features, particularly those of preferred embodiments of the present invention, are inventive in their own right and should not be considered as only part of the embodiments of the present invention. For these features, independent protection may be sought in addition to or as an alternative to each invention claimed in the present invention.

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

  The present invention will be described in more detail below with reference to examples, but is not limited thereto.

  One skilled in the art can use this description to manufacture additional electronic devices according to the present invention without the need to use creative techniques, and thus can implement the present invention throughout the claimed scope.

[Example]
The embodiment presented below was made using the device structure shown in FIG. All example hole injection layers (HIL) and hole transport layers (HTL) were prepared by ink jet printing to achieve the desired thickness. For the emissive layer, the individual solvents used in Examples 1 and 2 are listed in Table 2 below:

Formulation and solvent viscosities were measured over a shear rate range of 10 to 1000 s ⁻¹ using a TA instruments ARG2 rheometer using a 40 mm parallel plate structure. Measurements were used as an average of 200-800 s ⁻¹ where temperature and shear rate were precisely controlled. The viscosities shown in Table 3 are the viscosities of each formulation measured at a temperature of 25 ° C. and a shear rate of 500 s ⁻¹ . Each solvent is measured in triplicate. The stated viscosity value is an average of the measured values.

  Preferably, the organic solvent blend can include a surface tension in the range of 15-80 mN / m, more preferably in the range of 20-60 mN / m, and most preferably in the range of 25-40 mN / m. The surface tension can be measured at 20 ° C. using a FTA (First Ten Angstrom) 1000 contact angle horn. Details of the method can be found in Roger P. Woodward, Ph. D. Available from First Ten Angstrom as published by “Surface Tensure Measurements Using the Drop Shape Method”. Preferably, the surface tension can be determined using a pendant drop method. All measurements were performed at room temperature ranging from 20 ° C to 22 ° C. Three drops are measured for each formulation. The final value is an average of the measured values. The tool is regularly cross-checked against various liquids with known surface tensions.

  Example 1 is made by using the same structure where HIL and HTL are inkjet printed to achieve the same thickness. The solvent (s) used for EML are different and details are given in Table 3.

Description of preparation method A glass substrate coated with prestructured ITO and bank material is cleaned using sonication in isopropanol and then in deionized water, then dried using an air gun, followed by hot plate Above, annealing was performed at 230 ° C. for 2 hours.

  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 in air at 185 ° C. for 30 minutes.

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

  The green light emitting layer (G-EML) was similarly ink-jet printed, vacuum dried, and annealed at 160 ° C. for 10 minutes in a nitrogen atmosphere. In all examples, the green light-emitting layer ink contained two host materials (ie, HM-1 and HM-2), and one triplet emitter (EM-1). The materials were used in the following ratio, HM-1: HM-2: EM-1 = 40: 40: 20. As can be seen from Table 3, only the solvent (s) differ from example to example. The structure of these materials is as follows:

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

  The device was then transferred to a vacuum evaporation chamber where the hole blocking layer (HBL), electron transport layer (ETL), and cathode (Al) were deposited using thermal evaporation. Next, the characteristics of the device were clarified in the glove box.

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

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

To measure OLED performance in current density-brightness-voltage performance, the device is driven with a sweep voltage of -5V to 25V supplied by a Keithley 2400 source measurement unit. The voltage across the OLED device and the current passing through the OLED device are recorded by the Keithley 2400 SMU. The brightness of the device is detected by a calibrated photodiode. The photocurrent is measured with a Keithley 6485 / E picoammeter. For the spectrum, the luminance sensor has been replaced by a glass fiber connected to an Ocean Optics USB2000 + spectrometer.
Results and Discussion Example 1
Inkjet printed OLED devices are prepared using a printed layer using 1,1-diphenylethylene as the solvent for the light emitting 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. Once created, a pixelated device is formed. In this case, the green luminescent material is dissolved in 1,1-diphenylethylene at a concentration of 14 mg / ml.

The luminance efficiency at 1000 cd / m ² is 39.25 cd / A. The efficiency of this OLED device is very good, the voltage at 1000 cd / m ² is 7.05V.

  The resulting film exhibits very good and uniform film forming characteristics, as can be seen from FIG.

Comparative Example 1
Inkjet printed OLED devices are prepared using a printed layer using 3-phenoxy-toluene 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. Once created, a pixelated device is formed. In this case, the green luminescent material is dissolved in 1,1-diphenylethylene at a concentration of 14 mg / ml.

The luminance efficiency at 1000 cd / m ² is 47.51 cd / A. The efficiency of this OLED device is very good, the voltage at 1000 cd / m ² is 9.79V.

  As can be seen from FIG. 3, the resulting film is inferior in film-forming properties compared to 1,1-diphenylethylene.

Claims (22)

  A formulation comprising at least one organic functional material and a 1,1-diphenylethylene derivative as a first solvent. The first organic solvent is represented by the general formula (I)
(Where
R ¹ and R ² are the same or different at each occurrence and are F, Cl, Br, I, NO ₂ , CN, a linear alkyl or alkoxy group having 1-20 carbon atoms or 3-20 A branched or cyclic alkyl or alkoxy group having one carbon atom, wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, — CO—O—, —C═O—, —CH═CH—, or —C≡C—, where one or more hydrogen atoms may be replaced by F), or 4 An aryl or heteroaryl group having -14 carbon atoms and optionally substituted by one or more non-aromatic R ⁵ radicals, wherein the plurality of substituents R ⁵ are on the same ring or two different ring Of either a plurality of substituents R ⁵ aliphatic is mono- or may be polycyclic substituted by may together form an aromatic or heteroaromatic ring system;
R ³ and R ⁴ are the same or different at each occurrence and are H, F, Cl, Br, I, NO ₂ , CN, a linear alkyl or alkoxy group having 1-20 carbon atoms or 3 A branched or cyclic alkyl or alkoxy group having ˜20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ — , -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 optionally substituted by one or more non-aromatic R ⁵ radicals, wherein the plurality of substituents R ⁵ are on the same ring or 2 Two different Either on the ring, a plurality of substituents R ⁵ aliphatic is mono- or may be polycyclic substituted by may together form an aromatic or heteroaromatic ring system;
R ⁵ is the same or different in each case 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 (here Wherein one or more non-adjacent CH ₂ groups are replaced by —O—, —S—, —CO—O—, —C═O—, —CH═CH— or —C≡C—. Or one or more hydrogen atoms may be replaced by F), or may have 4 to 14 carbon atoms and be substituted by one or more non-aromatic R ³ radicals. A good aryl or heteroaryl group;
m and n are the same or different at each occurrence and are 0, 1, 2 or 3, preferably 0 or 1, more preferably 0)
The formulation according to claim 1, which is a 1,1-diphenylethylene derivative according to claim 1. The first organic solvent is represented by the general formula (I)
(Where
R ¹ and R ² are the same or different at each occurrence 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 A group wherein one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, —CO—O—, —C═O—, —CH = CH- or -C≡C- may be substituted);
R ³ and R ⁴ are the same or different at each occurrence and are H, a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl having 3 to 20 carbon atoms Or an alkoxy group (where one or more non-adjacent CH ₂ groups are —O—, —S—, —NR ⁵ —, —CONR ⁵ —, —CO—O—, —C═O—, May be replaced by -CH = CH- or -C≡C-);
R ⁵ is the same or different in each case 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 (here Wherein one or more non-adjacent CH ₂ groups are replaced by —O—, —S—, —CO—O—, —C═O—, —CH═CH— or —C≡C—. May be);
m and n are the same or different at each occurrence and are 0 or 1, preferably 0)
The formulation according to claim 2, which is a 1,1-diphenylethylene derivative according to claim 1. The first organic solvent is represented by the general formula (I)
(Where
R ¹ and R ² are the same or different at each occurrence and are straight chain alkyl groups having 1-20 carbon atoms or branched or cyclic alkyl groups having 3-20 carbon atoms;
R ³ and R ⁴ are H;
m and n are the same or different at each occurrence and are 0 or 1, preferably 0)
4. A formulation according to claim 2 or 3, which is a 1,1-diphenylethylene derivative according to claim 1. The first organic solvent is represented by the general formula (II)
The formulation according to any one of claims 2 to 4, which is 1,1-diphenylethylene according to claim 1.   The formulation according to any one of claims 1 to 5, wherein the first solvent has a surface tension of 25 mN / m or more.   The formulation according to any one of claims 1 to 6, wherein the content of the first solvent is in the range of 50 to 100 vol% based on the total amount of the solvent in the formulation.   The formulation according to any one of the preceding claims, wherein the first solvent has a boiling point in the range of 100-400 ° C.   The formulation according to any one of claims 1 to 8, wherein the formulation comprises at least one second solvent different from the first solvent.   The formulation according to any one of the preceding claims, wherein the second solvent has a boiling point in the range of 100-400 ° C.   The formulation according to any one of claims 1 to 10, wherein the at least one organic functional material has a solubility in the range of 1 to 250 g / l in the first and second solvents.   12. Formulation according to any one of the preceding claims, wherein the formulation has a surface tension in the range of 1-70 mN / m.   The formulation according to any one of claims 1 to 12, wherein the formulation has a viscosity in the range of 1 to 50 mPa · s.   The content of the at least one organic functional material in the formulation is in the range of 0.001 to 20 wt% based on the total weight of the formulation. The formulation as described.   The at least one organic functional material is an organic conductor, an organic semiconductor, an organic fluorescent compound, an organic phosphorescent compound, an organic light absorbing compound, an organic photosensitive compound, an organic photosensitizer, and other organic photoactive compounds, 15. A formulation according to any one of the preceding claims, for example selected from the group consisting of transition metal, rare earth, lanthanide and organotin complexes of actinides.   The at least one organic functional material is a fluorescent light emitter, a phosphorescent light emitter, a host material, a matrix material, an exciton blocking material, an electron transport material, an electron injection material, a hole conduction material, a hole injection material, or an n dopant. 16. The formulation of claim 15, wherein the formulation is selected from the group consisting of: p dopant, wide band gap material, electron blocking material, and hole blocking material.   16. The formulation according to claim 15, wherein the at least one organic functional material is an organic semiconductor selected from the group consisting of hole injection, hole transport, light emission, electron transport and electron injection materials.   18. A formulation according to claim 17, wherein the at least one organic semiconductor is selected from the group consisting of hole injection, hole transport and luminescent materials.   19. The formulation of claim 18, wherein the hole injection and hole transport material is a polymeric compound or a blend of a polymeric compound and a non-polymeric compound.   20. A method for preparing a formulation according to any one of the preceding claims, wherein the at least one organic functional material and the at least first solvent are mixed.   An electroluminescent device wherein at least one layer of the electroluminescent device is prepared by depositing, preferably printing, and subsequently drying the formulation according to any one of claims 1-19 on a surface. How to prepare a cent device.   21. An electroluminescent device, wherein at least one layer is prepared by depositing, preferably printing and subsequently drying the formulation according to any one of claims 1-19.