KR102486614B1 - Formulation of organic functional materials - Google Patents

Abstract

The present invention relates to a formulation containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one [2.2.1]bicyclic-group, It relates to electronic devices manufactured using the formulation.

Description

Formulation of organic functional materials

The present invention relates to a formulation containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one [2.2.1]bicyclic-group, It relates to an electroluminescent device made using the formulation.

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

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

The above objects of the present invention are a formulation containing at least one organic functional material and at least a first organic solvent, wherein the first organic solvent contains at least one [2.2.1]bicyclic-group, preferably one [2.2.1] It is solved by providing the formulation, which contains a bicyclic-group.

Surprisingly, the inventors found that the use of an organic solvent containing at least one [2.2.1]bicyclic-group as the first solvent enables complete control of the surface tension and produces a uniform and uniform layer of functional materials with good layer properties and performance. It has been found that this leads to effective ink deposition for forming well-defined organic layers.

1 shows a device containing a substrate, an ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a green emission layer (G-EML), a hole blocking layer (HBL), an electron transport layer (ETL) and an Al cathode. shows a typical layered structure of
2 and 3 show the device performance of OLEDs prepared according to Working Examples 1 and 2.

DETAILED DESCRIPTION OF EMBODIMENTS

The present invention is a formulation containing at least one organic functional material and at least a first organic solvent, said first organic solvent comprising at least one [2.2.1]bicyclic-group, preferably one [2.2.1 ] to the above formulation, containing a bicyclic-group.

preferred embodiment

In a first preferred embodiment, the first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group-containing solvent according to general formula (I).

during the ceremony

R ¹ to R ¹² are identical or different at each occurrence and are H, D, F, Cl, Br, I, NO ₂ , CN, a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or 3 to 20 carbon atoms A branched or cyclic alkyl or alkoxy group having atoms wherein one or more adjacent or non-adjacent CH ₂ groups are fused to form a cyclic structure having 3 to 10 C atoms, and one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ¹³ -, -CONR ¹³ -, -CO-O-, -O-CO-, -C=O-, =CO, -CH=CH- or -C≡C- or one or more hydrogen atoms may be replaced by F), or an aryl or heteroaryl group having 4 to 14 carbon atoms and may be substituted by one or more non-aromatic R ¹³ radicals, on the same ring or A plurality of substituents R ¹³ on two different rings may together in turn form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R ¹³ ;

R ¹³ , identical or different at each occurrence, is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ group may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F) , or an aryl or heteroaryl group having 4 to 14 carbon atoms and which may be substituted with one or more non-aromatic R ¹³ radicals.

In a first more preferred embodiment, the first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group-containing solvent according to general formula (II).

In the formula, R ¹ to R ¹² have the meanings as described above for general formula (I).

In a first most preferred embodiment, the first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group-containing solvent according to general formula (II), wherein

R ¹ and R ⁷ to R ¹⁰ are H;

R ² , R ³ , R ⁵ , R ⁶ , R ¹¹ and R ¹² , identical or different at each occurrence, are H or a straight chain alkyl or alkoxy group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms A branched or cyclic alkyl or alkoxy group having

R ⁴ is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein one or more adjacent or non-adjacent CH ₂ groups are fused to form 3 to 10 carbon atoms. form a cyclic structure with C atoms and one or more nonadjacent CH ₂ groups are -O-, -S-, -NR ¹³ -, -CONR ¹³ -, -CO-O-, -O-CO-, -C =O-, =CO, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F), or have from 4 to 14 carbon atoms and have one or more an aryl or heteroaryl group which may be substituted by a non-aromatic R ¹³ radical and linked through an alkylene group having 1 to 10 carbon atoms or through an alkenylene group having 2 to 10 carbon atoms, on the same ring or A plurality of substituents R ¹³ on two different rings may together in turn form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R ¹³ ;

In a second more preferred embodiment, the first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group-containing solvent according to formula (IIIa) or (IIIb) to be.

In the formula, R ¹ to R ¹² have the meanings as described above for general formula (I).

In a second most preferred embodiment, the first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group containing solvent according to formula (IIIa) or (IIIb) and here

R ³ , R ⁴ , R ⁵ or R ⁹ or R ⁴ and R ⁷ are straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms or branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, wherein One or more adjacent or non-adjacent CH ₂ groups are fused to form a cyclic structure having 3 to 10 C atoms, and one or more non-adjacent CH ₂ groups are -O-, -S-, -NR ¹³ -, -CONR ¹³ - , -CO-O-, -O-CO-, -C=O-, =CO, -CH=CH- or -C≡C-, wherein one or more hydrogen atoms are 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 ¹³ radicals, wherein a plurality of substituents R ¹³ on the same ring or on two different rings together in turn may form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R ¹³ ;

The rest of R ¹ to R ¹² are H,

R ¹³ has the meaning as described above for general formula (I).

In a third most preferred embodiment, the first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group-containing solvent according to general formula (II), wherein

R ⁵ is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein one or more adjacent or non-adjacent CH ₂ groups are fused to form 3 to 10 carbon atoms. form a cyclic structure with C atoms and one or more nonadjacent CH ₂ groups are -O-, -S-, -NR ¹³ -, -CONR ¹³ -, -CO-O-, -O-CO-, -C =O-, =CO, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F), or have from 4 to 14 carbon atoms and have one or more an aryl or heteroaryl group which may be substituted by a non-aromatic R ¹³ radical, and a plurality of substituents R ¹³ on the same ring or on two different rings together in turn may form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system; and may be substituted by a plurality of substituents R ¹³ ;

Except for R ⁵ , R ¹ to R ¹² are H;

R ¹³ has the meaning as described above for general formula (I).

[2.2.1] It should be noted that solvents containing bicyclic groups may exist in the form of at least two isomers. These isomers are encompassed by the formulas (I), (II), (IIIa) and (IIIb) mentioned above.

For example, solvents containing a [2.2.1]bicyclic group according to formula (II) in which R ¹ to R ¹² have the meanings as described above with respect to formula (I) have formulas (IIa) and It contains the following two isomers according to (IIb):

Further, solvents containing a [2.2.1]bicyclic group according to general formulas (IIIa) or (IIIb) in which R ¹ to R ¹² have the meanings as described above with respect to general formula (I), respectively, have the formula ( IIIa1) and (IIIa2) and the following two isomers according to (IIIb1) and (IIIb2):

Examples of preferred [2.2.1]bicyclic group-containing solvents and their boiling points (BP) are shown in Table 1 below.

Table 1: Preferred [2.2.1] bicyclic group containing solvents and their boiling points (BP).

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

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

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

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

Formulations according to the invention, in one preferred embodiment, comprise at least a second solvent different from the first solvent. A second solvent is used together with the first solvent.

In one embodiment, the second solvent may be a [2.2.1]bicyclic-group containing solvent, which is different from the first solvent. Nevertheless, preferably, the second solvent does not contain [2.2.1] bicyclic groups.

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

Preferably, the second solvent may be selected from one of 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 heterocycles such as pyrrolidinone, pyridine, pyrazine; Other fluorinated or chlorinated aromatic hydrocarbons.

Particularly preferred second organic solvents are for example 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,3-trimethylbenzene, 1,2,4,5 -Tetramethylbenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, 1,2-dihydronaphthalene, 1,2-dimethylnaphthalene, 1,3-benzodioxolane, 1,3 -Diisopropylbenzene, 1,3-dimethylnaphthalene, 1,4-benzodioxane, 1,4-diisopropylbenzene, 1,4-dimethylnaphthalene, 1,5-dimethyltetraline, 1-benzothiocyanate Opene, thianaphthalene, 1-bromonaphthalene, 1-chloromethylnaphthalene, 1-ethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 1-methylindole, 2,3-benzofuran, 2,3-di Hydrobenzofuran, 2,3-dimethylanisole, 2,4-dimethylanisole, 2,5-dimethylanisole, 2,6-dimethylanisole, 2,6-dimethylnaphthalene, 2-bromo-3- Bromomethylnaphthalene, 2-bromomethylnaphthalene, 2-bromonaphthalene, 2-ethoxynaphthalene, 2-ethylnaphthalene, 2-isopropylanisole, 2-methylanisole, 2-methylindole, 3,4 -Dimethylanisole, 3,5-dimethylanisole, 3-bromoquinoline, 3-methylanisole, 4-methylanisole, 5-decanolide, 5-methoxyindane, 5-methoxyindole, 5 -tert-butyl-m-xylene, 6-methylquinoline, 8-methylquinoline, acetophenone, anisole, benzonitrile, benzothiazole, benzyl acetate, bromobenzene, butyl benzoate, butyl phenyl ether, cyclohexyl Benzene, decahydronaphthol, dimethoxytoluene, 3-phenoxytoluene, diphenyl ether, propiophenone, ethylbenzene, ethyl benzoate, hexylbenzene, indane, hexamethylindane, indene, isochroman, cumene, m- Cemente, mesitylene, methyl benzoate, o-, m-, p-xylene, propyl benzoate, propylbenzene, o-dichlorobenzene, pentylbenzene, phenetole, ethoxybenzene, phenyl acetate, p-cymene, propyi Ophenone, sec-butylbenzene, t-butylbenzene, thiophene, toluene, veratrol, monochlorobenzene, o-dichlorobenzene, pyridine, pyrazine, pyrimidine, pyrrolidinone, morpholine, dimethylacetamide, dimethyl Sulfoxide, decalin and/or these It is a mixture of compounds.

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

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

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

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 10% by weight, more preferably in the range of 0.1 to 5% by weight, and most preferably in the range of 0.1 to 5% by weight, based on the total weight of the formulation. is in the range of 0.3 to 5% by weight.

Formulations according to the invention preferably have a surface tension in the range of 10 to 50 mN/m and more preferably in the range of 25 to 40 mN/m.

In addition, the formulation according to the present invention is preferably 1 to 50 mPa ^. s range, more preferably from 2 to 40 mPa ^. s range, and most preferably from 2 to 20 mPa ^. s range of viscosity.

ngstrom 사의 FTA100 을 사용하여, 모든 표면 장력 측정이 수행되었다. 표면 장력은 소프트웨어 FTA1000 에 의해 결정된다. 모든 측정은 20℃ 내지 22℃ 범위의 실온에서 수행되었다. 표준 작업 절차는, 새로운 일회용 액적 디스펜싱 시스템 (시린지 및 니들) 을 사용한 각각의 제형의 표면 장력의 결정을 포함한다. 각각의 액적은 1 분의 지속기간에 걸친 60 회 측정으로 측정되고, 이는 이후 평균내어진다. 각각의 제형에 대하여, 3 개의 액적을 측정하였다. 최종 값은 상기 측정값에 대하여 평균낸 것이다. 상기 도구는 널리 공지된 표면 장력을 갖는 다양한 액체에 대하여 규칙적으로 교차-점검하였다.Preferably, the organic solvent blend comprises a surface tension in the range of 15 to 80 mN/m, more preferably in the range of 20 to 60 mN/m and most preferably in the range of 25 to 40 mN/m. Surface tension can be measured using a FTA (First Ten Angstrom) 1000 contact angle goniometer at 20 °C. Details of the method can be found in Roger P. Woodward, Ph.D. Available from First Ten Angstrom, as published in "Surface Tension Measurements Using the Drop Shape Method". Preferably, the surface tension can be measured using the drop method. This measurement technique dispenses drops from a needle in the bulk liquid or gas phase. The shape of the droplet is obtained from the relationship between surface tension, gravity and density difference. When using the drop method, surface tension is calculated from shadow images of pendant droplets using http://www.kruss.de/services/education-theory/glossary/drop-shape-analysis. A commonly used and commercially available high-precision droplet shape analysis tool, namely First Ten

All surface tension measurements were performed using an FTA100 from ngstrom. Surface tension is determined by software FTA1000. All measurements were performed at room temperature in the range of 20 °C to 22 °C. Standard operating procedure involves the determination of the surface tension of each dosage form using a new disposable droplet dispensing system (syringe and needle). Each droplet is measured for 60 measurements over a duration of 1 minute, which are then averaged. For each formulation, 3 droplets were measured. Final values are averaged over these measurements. The tool was regularly cross-checked against a variety of liquids with well-known surface tensions.

The viscosity of formulations according to the present invention and solvents were measured using a TA Instruments ARG2 rheometer over a range of shear rates ranging from 10 to 1000 s ⁻¹ using a 40 mm parallel plate geometry. Measurements were taken as an average from 200 to 800 s ⁻¹ , at which time temperature and shear rate were accurately controlled. Each solvent was measured 3 times. The stated viscosity values have been averaged over these measurements.

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

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

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

A preferred embodiment of the organic functional material is disclosed in detail in WO 2011/076314 A1, the contents of which are hereby incorporated by reference.

In a preferred embodiment, the organic functional material is an organic semiconductor selected from the group consisting of hole injecting, hole transporting, emitting, electron transporting and electron injecting materials.

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

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

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

For the purposes of this application, these values should be considered as the material's respective HOMO and LUMO energy levels.

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

The lowest excited singlet state 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 commonly used programs for this purpose are “Gaussian09W” (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

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

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

Preferred compounds having hole injection and/or hole transport properties include, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, triarylphosphines, phenothiazines, phenoxazines, dihydrophenazines, thians threne, dibenzo-para-dioxin, phenoxathiine, carbazole, azulene, thiophene, pyrrole and furan derivatives, and also further O-, S with high HOMO (HOMO=highest occupied molecular orbital) - or an N-containing heterocycle.

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

Aromatic tertiary amines containing at least two tertiary amine units (US 2008/0102311 A1, US 4720432 and US 5061569), such as for example NPD (α-NPD = 4,4′-bis[N-(1- naphthyl)-N-phenylamino]biphenyl) (US 5061569), TPD 232 (= N,N'-bis-(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl- 4,4'-diamino-1,1'-biphenyl) or MTDATA (MTDATA or m-MTDATA = 4,4',4"-tris[(3-methylphenyl)phenylamino]triphenylamine) (JP- A-4-308688), TBDB (= N, N, N', N'-tetra (4-biphenyl) diaminobiphenylene), TAPC (= 1,1-bis (4-di-p-tolyl aminophenyl)cyclohexane), TAPPP (= 1,1-bis(4-di-p-tolylaminophenyl)-3-phenylpropane), BDTAPVB (= 1,4-bis[2-[4-[N, N-di(p-tolyl)amino]phenyl]vinyl]benzene), TTB (= N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl), TPD (= 4,4'-bis[N-3-methylphenyl]-N-phenylamino)biphenyl), N,N,N',N'-tetraphenyl-4,4'''-diamino-1,1',4',1'',4'',1'''-quaterphenyl, likewise containing carbazole units, tertiary amines such as for example TCTA (= 4-(9H-carbazol-9-yl) -N,N-bis[4-(9H-carbazol-9-yl)phenyl]benzenamine) is preferred 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) is likewise preferred.

Particular preference is given to the following triarylamine compounds of the formulas (TA-1) to (TA-12), which are described in EP 1162193 B1, EP 650 955 B1, Synth.Metals 1997 , 91(1-3), 209, DE 19646119 A1 , WO 2006/122630 A1, EP 1 860 097 A1, EP 1834945 A1, JP 08053397 A, US 6251531 B1, US 2005/0221124, JP 08292586 A, US 7399537 B2 , US 2006/0061268 A1, and US 2006/0061268 A1 2009/041635. The compounds of formulas (TA-1) to (TA-12) may also be substituted:

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

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

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

Compounds particularly suitable 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 oxinoids complex, 4-azaphenanthrene-5-ol-Be complex (see US 5529853 A, formula ET-1), butadiene derivative (US 4356429), heterocyclic optical brightener (US 4539507), benzimidazole derivatives (US 2007/0273272 A1), for example TPBI (see US 5766779, formula ET-2), 1,3,5-triazines, for example spirobifluorenyltriazine derivatives (eg DE 102008064200 ), pyrene, anthracene, tetracene, fluorene, spirofluorene, dendrimers, tetracene (e.g. rubrene derivatives), 1,10-phenanthroline derivatives (JP 2003-115387, JP 2004-311184, JP-2001-267080, WO 02/043449), silacyclopentadiene derivatives (EP 1480280, EP 1478032, EP 1469533), borane derivatives, such as for example Si-containing triarylborane derivatives (US 2007/0087219 A1, formula ET -3), pyridine derivatives (JP 2004-200162), phenanthrolines, especially 1,10-phenanthroline derivatives, such as for example BCP and Bphen, as well as several phenanthrolines linked via biphenyls or other aromatic groups. (US-2007-0252517 A1) or phenanthroline linked to anthracene (see US 2007-0122656 A1, formulas ET-4 and ET-5).

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

Derivatives of organic compounds such as fluorenone, fluorenylidenemethane, perylenetetracarboxylic acid, anthraquinone dimethane, diphenoquinone, anthrone and anthraquinonediethylenediamine may also be used.

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

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

The dosage form of the present invention may also contain an emitter. The term emitter denotes a material that allows for a radiative transition to the ground state with emission of light following excitation, which can occur by any type of energy transfer. Generally, two classes of emitters are known: fluorescent and phosphorescent emitters. The term fluorescent emitter refers to a material or compound in which a radiative transition from an excited singlet state to a ground state occurs. The term phosphorescent emitter denotes a light emitting material or compound that preferably contains a transition metal.

An emitter is often referred to as a dopant when the dopant causes the properties described above in the system. In a system comprising a matrix material and a dopant, dopant is taken to mean the component with a smaller proportion in the mixture. Correspondingly, matrix material in a system comprising a matrix material and a dopant is taken to mean the component in which the proportion in the mixture is greater. Thus, the term phosphorescent emitter can also be taken to mean, for example, a phosphorescent dopant.

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

Preferred compounds capable of serving as fluorescent emitters are described as examples below. Preferred fluorescent emitters are selected from the classes of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphines, styryl ethers and arylamines.

Monostyrylamine is taken to mean a compound containing one substituted or unsubstituted styryl group and at least one, preferably aromatic amine. Distyrylamine is taken to mean a compound containing two substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. Tristyrylamine is taken to mean a compound containing three substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. Tetrastyrylamine is taken to mean a compound containing four substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. The styryl group is particularly preferably a stilbene, which may also be further substituted. The corresponding phosphines and ethers are defined analogously to amines. An arylamine or aromatic amine in the meaning of the present invention is taken to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to the nitrogen. At least one of the above aromatic or heteroaromatic ring systems is preferably a condensed ring system, preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyreneamine, aromatic pyrendiamine, aromatic chrysenamine or aromatic chrysendiamine. Aromatic anthraceneamines are taken to mean compounds in which one diarylamino group is bonded directly to the anthracene group, preferably in the 9-position. Aromatic anthracenediamine is understood 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, pyrendiamines, chryseneamines and chryssendiamines are similarly defined, wherein the diarylamino group is bonded to the pyrene, preferably at the 1- or 1,6-position.

Further preferred phosphor emitters are indenofluorenamines or indenofluorenediamines described in particular in WO 2006/122630; the benzoindenofluorenamines or benzoindenofluorenediamines described in particular in WO 2008/006449; and in particular the dibenzoindenofluorenamines or dibenzoindenofluorenediamines described in WO 2007/140847.

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

Particularly preferred styrylamine compounds are compounds of formula EM-1 described in US 7250532 B2 and compounds of formula EM-2 described in DE 10 2005 058557 A1:

Particularly preferred triarylamine compounds are of the formula EM- 3 to EM-15, and their derivatives:

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

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

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

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

A more preferred blue fluorescent emitter is C.H. Chen et al.: "Recent developments in organic electroluminescent materials", Macromol. Symp. 125, (1997) 1-48 and "Recent progress of molecular organic electroluminescent materials and devices", Mat. Sci. and Eng. R, 39 (2002), 143-222.

More preferred blue fluorescent emitters are the hydrocarbons disclosed in DE 102008035413.

Preferred compounds capable of serving as fluorescent emitters are described below as examples.

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

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

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

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

Compounds of the formula EM-16 are described in more detail in US 2007/0087219 A1, to which substituents and exponents in the formula are described, this specification is incorporated for disclosure purposes. Also, Pt-porphyrin complexes with an enlarged ring system (US 2009/0061681 A1) and Ir complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrins -Pt(II), tetraphenyl-Pt(II) tetrabenzoporphyrin (US 2009/0061681 A1), cis-bis(2-phenylpyridinato-N,C ² ')Pt(II), cis-bis (2-(2′-thienyl)pyridinato-N,C ³ ′)Pt(II), cis-bis(2-(2′-thienyl)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, US 2001/0053462 A1, Baldo, Thompson et al., Nature 403, (2000), 750-753), bis(1-phenylisoquinolinato-N,C ^2' )( 2-phenylpyridinato-N,C ^2' )iridium(III), bis(2-phenylpyridinato-N,C ^2' )(1-phenylisoquinolinato-N,C ^2' ) Iridium(III), bis(2-(2'-benzothienyl)pyridinato-N,C ^3' )iridium(III) (acetylacetonate), bis(2-(4',6'- Difluorophenyl)pyridinato-N,C ^2' )iridium(III) (picolinate) (FIrpic, blue), bis(2-(4',6'-difluorophenyl)pyridine Sat-N,C ^2′ )Ir(III) (tetrakis(1-pyrazolyl)borate), tris(2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III), ( ppz) ₂ Ir (5phdpym) (US 2009/0061681 A1), (45ooppz) ₂ -Ir (5phdpym) (US 2009/0061681 A1), derivatives of 2-phenylpyridine-Ir complexes, such as, for example, PQIr ( = iridium(III) bis(2-phenylquinolyl-N,C ^2' )acetylacetonate), tris(2-phenylisoquinolinato-N,C)Ir(III) (red), bis(2-(2'-benzo[4,5-a]thienyl)pyridi Nato-N,C ³ )Ir (acetylacetonate) ([Btp ₂ Ir(acac)], red, Adachi et al. Appl. Phys. Lett . 78 (2001), 1622-1624).

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

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

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

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

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

Quantum dots can likewise be used as emitters, such materials being disclosed in detail in WO 2011/076314 A1.

Compounds used as host materials, particularly with emissive compounds, include materials from various classes of materials.

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

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

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

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

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

In the formula, Ar ⁴ , Ar ⁵ , Ar ⁶ are, in each case, identically or differently, an optionally substituted aryl or heteroaryl group having 5 to 30 aromatic ring atoms, and p is in the range of 1 to 5; Represents an integer of; The sum of π electrons in Ar ⁴ , Ar ⁵ and Ar ⁶ is at least 30 when p = 1, at least 36 when p = 2, and at least 42 when p = 3.

In the compound of formula (H-1), the group Ar ⁵ particularly preferably represents anthracene, and the groups Ar ⁴ and Ar ⁴ are bonded at the 9- and 10-positions, wherein these groups may optionally be substituted. With very particular preference, at least one of the groups Ar ⁴ and/or Ar ⁶ is 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl, or 2-, 3-, 4-, 5- , a condensed aryl group selected from 6- or 7-benzanthracenyl. Anthracene-based compounds are described in US 2007/0092753 A1 and US 2007/0252517 A1, for example 2-(4-methylphenyl)-9,10-di-(2-naphthyl)anthracene, 9-(2- naphthyl)-10-(1,1'-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10 -bis(phenylethynyl)anthracene and 1,4-bis(9'-ethynylanthracenyl)benzene. Compounds containing 2 anthracene units (US 2008/0193796 A1), for example 10,10'-bis[1,1',4',1'']terphenyl-2-yl-9,9'- Bisanthracenyl is preferred.

More preferred compounds are arylamine, styrylamine, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, and bisbenzoxazoline. , oxazoles, pyridines, pyrazines, imines, benzothiazoles, benzoxazoles, derivatives of benzimidazoles (US 2007/0092753 A1), e.g. 2,2',2"-(1,3,5-phenyl len)tris[1-phenyl-1H-benzimidazole], aldazine, stilbene, styrylarylene derivatives such as 9,10-bis[4-(2,2-diphenylethenyl)phenyl] anthracene, and distyrylarylene derivatives (US 5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethine, cinnamic acid esters and fluorescent dyes.

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

Preferred compounds with oligoarylene as matrix are disclosed in US 2003/0027016 A1, US 7326371 B2, US 2006/043858 A, WO 2007/114358, WO 2008/145239, JP 3148176 B2, EP 1009044, US 2004/018383, WO 2005/061656 A1, EP 0681019B1, WO 2004/013073A1, US 5077142, WO 2007/065678 and DE 102009005746, where particularly preferred compounds are described by the formulas H-2 to H-8.

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

Such compounds which can also be used as structural elements in polymers include CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (e.g. WO 2005/039246, US 2005/0069729, JP 2004/288381, according to EP 1205527 or WO 2008/086851), azacarbazoles (eg according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/347160), ketones (eg according to WO 2004/093207 or DE 102008033943) , phosphine oxides, sulfoxides and sulfones (eg according to WO 2005/003253), oligophenylenes, aromatic amines (eg according to US 2005/0069729), bipolar matrix materials (eg according to WO 2007/137725 ), silanes (eg according to WO 2005/111172), 9,9-diarylfluorene derivatives (eg according to DE 102008017591), azabolol or boronic acid esters (eg WO 2006/117052 according to), triazine derivatives (eg according to DE 102008036982), indolocarbazole derivatives (eg according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (eg according to DE 102009023155 and according to DE 102009031021), diazaphosphole derivatives (eg according to DE 102009022858), triazole derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, disti Rilpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carboxylic Bodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives, such as for example AlQ ₃ (which is also triarylaminophenol may contain polyol ligands) (US 2007/0134514 A1), metal complex/polysilane compounds, and thiophene, benzothiophene and dibenzothiophene derivatives.

An example of a preferred carbazole derivative is mCP (= 1,3-N,N-dicarbazolylbenzene (= 9,9'-(1,3-phenylene)bis-9H-carbazole)) (formula H- 9), CDBP (= 9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole), 1,3-bis(N ,N'-dicarbazolyl)benzene (= 1,3-bis(carbazol-9-yl)benzene), PVK (polyvinylcarbazole), 3,5-di(9H-carbazol-9-yl) biphenyl and CMTTP (Formula H-10). Particularly preferred compounds are disclosed in US 2007/0128467 A1 and US 2005/0249976 A1 (Formulas H-11 and H-13).

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

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

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

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

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

Further, a compound that improves the transition from the singlet state to the triplet state and is used for the support of a functional compound having emitter properties to improve the phosphorescent properties of such a compound can be used. For this purpose, in particular carbazole and bridged carbazole dimer units (described for example in WO 2004/070772 A2 and WO 2004/113468 A1) are suitable. For this purpose, ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds (described for example in WO 2005/040302 A1) are also suitable.

Herein n-dopants are taken to mean reducing agents, ie electron donors. Preferred examples of n-dopants are W(hpp) ₄ and other electron-rich metal complexes (according to WO 2005/086251 A2), P=N compounds (eg WO 2012/175535 A1, WO 2012/175219 A1) , naphthylenecarbodiimides (eg WO 2012/168358 A1), fluorenes (eg WO 2012/031735 A1), free radicals and diradicals (eg EP 1837926 A1, WO 2007/107306 A1), pyridines (eg EP 2452946 A1, EP 2463927 A1), N-heterocyclic compounds (eg WO 2009/000237 A1) and acridines as well as phenazines (eg US 2007/145355 A1).

Furthermore, formulations may include wide band gap materials as functional materials. Wide band gap materials are taken to mean materials in the meaning of the disclosure of US Pat. No. 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

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

Furthermore, the formulation may contain a hole blocking material (HBM) as a functional material. A hole blocking material refers to a material that prevents or minimizes the transfer of holes (positive charge) in a multilayer system, especially when such material is disposed in the form of a layer adjacent to an emissive layer or a hole conducting layer. In general, the hole blocking material has a lower HOMO level than the hole transporting material in the adjacent layer. A hole blocking layer is often placed between the emissive layer and electron transport layer in OLEDs.

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

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

Furthermore, the formulation may contain an electron blocking material (EBM) as a functional material. An electron blocking material refers to a material that prevents or minimizes the transfer of electrons in a multilayer system, especially when such material is disposed in the form of a layer adjacent to a light emitting layer or an electron conducting layer. Generally, the electron blocking material has a higher LUMO level than the electron transporting material in the adjacent layer.

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

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

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

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

The formulation may also contain polymers as organic functional materials. The compounds described above as organic functional materials, often having a relatively low molecular weight, can also be mixed with polymers. Likewise, these compounds can be incorporated into polymers by means of covalent bonds. This is possible, in particular, with compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acids or boronic acid esters, or by reactive polymerizable groups such as olefins or oxetanes. They can be used as monomers for the preparation of corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization here preferably takes place via halogen functions or boronic acid functions or via polymerisable groups. It is also possible to crosslink polymers through groups of this type. The compounds and polymers according to the invention can be used as cross-linked or non-cross-linked layers.

Polymers usable as organic functional materials are often the units or structural elements described in the context of the compounds described above, especially those disclosed and extensively listed in WO 02/077060 A1, WO 2005/014689 A2 and WO 2011/076314 A1. contain These documents 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: Structural elements combining the properties described in relation to groups 1 and 2;

Group 4: Structural elements with luminescent properties, in particular phosphorescent groups;

Group 5: Structural elements that improve the transition from the so-called singlet state to the triplet state;

Group 6: Structural elements that influence the morphology of the resulting polymer or also the emission color;

Group 7: Structural elements typically used as backbones.

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

A polymer having hole transport or hole injection properties used as an organic functional material, containing structural elements of Group 1, may preferably contain units corresponding to the hole transport or hole injection materials described above.

More preferred structural elements of group 1 are, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, carbazoles, azulenes, thiophenes, pyrrole and furan derivatives, and further O- , S- or N-containing heterocycles. These arylamines and heterocycles preferably have a HOMO of 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 of the repeating units of the formula HTP-1, are preferred:

In the formula, the symbols have the following meanings:

Ar ¹ is, identically or differently for different repeating units in each case, a single bond or a mono- or polycyclic aryl group which may optionally be substituted;

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

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

m is 1, 2 or 3;

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

In the formula, the symbols have the following meanings:

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

r is 0, 1, 2, 3 or 4;

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

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

In the formula, the symbols have the following meanings:

T ¹ and T ² are thiophene, selenophene, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, dithienothiophene, pyrrole and aniline (these groups are one or more radicals optionally substituted with R ^b );

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

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

Ar ⁷ and Ar ⁸ are, independently of each other, a monocyclic or polycyclic aryl or heteroaryl group (which may be optionally substituted, optionally bonded to one or both of adjacent thiophene or selenophene groups at the 2,3-position may be);

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

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

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

A polymer having electron injection and/or electron transport properties used as an organic functional material, containing structural elements of group 2, may preferably contain units corresponding to the electron injection and/or electron transport materials described above. .

More preferred structural elements of group 2, which have electron injecting and/or electron transporting properties, are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline and phenazine groups, as well as triarylboranes. groups or further O-, S- or N-containing heterocycles with low LUMO levels. These structural elements of group 2 preferably have a LUMO of less than -2.7 eV (relative to the vacuum level), particularly preferably less than -2.8 eV.

The organic functional material may preferably be a polymer containing structural elements of group 3, in which structural elements improving hole and electron mobility (ie structural elements of groups 1 and 2) are directly connected to each other. Some of these structural elements may serve herein as an emitter, wherein the emission color may be shifted, for example to green, red or yellow. Its use is therefore advantageous for the production of broadband emission or other emission colors, for example by polymers that inherently emit blue.

A polymer having light emitting properties used as an organic functional material containing structural elements of Group 4 may preferably contain units corresponding to the emitter materials described above. Polymers containing phosphorescent groups, in particular emissive metal complexes described above containing corresponding units containing elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt) are preferred.

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

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

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

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

Thus, for fluorescent OLEDs, aromatic structural elements having 6 to 40 carbon atoms or also tolane, stilbene or bisstyrylarylene derivative units are preferred, each of which may be substituted with one or more radicals. Wherein, 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6-, 2,7- or 4,9-pyrenylene, 3,9- Or 3,10-perylenylene, 4,4'-biphenylene, 4,4"-terphenylylene, 4,4'-bi-1,1'-naphthylylene, 4,4'-tolanylene , It is particularly preferred to use groups derived from 4,4'-stilbenzylene or 4,4"-bisstyrylarylene derivatives.

Polymers used as organic functional materials preferably contain units of Group 7, which contain aromatic structures with 6 to 40 C atoms often used as backbones.

These include in particular 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives (as described for example in US 5962631, WO 2006/052457 A2 and WO 2006/118345A1). , 9,9-spirobifluorene derivatives (eg disclosed in WO 2003/020790 A1), 9,10-phenanthrene derivatives (eg disclosed in WO 2005/104264 A1), 9,10-di hydrophenanthrene derivatives (eg disclosed in WO 2005/014689 A2), 5,7-dihydrodibenzoxepin derivatives, and cis- and trans-indenofluorene derivatives (eg WO 2004/041901 A1 and described in WO 2004/113412 A2), and binapthylene derivatives (eg described in WO 2006/063852 A1), and further units (eg WO 2005/056633 A1, EP 1344788 A1, WO 2007/ 043495 A1, WO 2005/033174 A1, WO 2003/099901 A1 and DE 102006003710).

fluorene derivatives (eg disclosed in US 5,962,631, WO 2006/052457 A2 and WO 2006/118345 A1), spirobifluorene derivatives (eg disclosed in WO 2003/020790 A1), benzofluorene, di Structural units of group 7 selected from benzofluorene, benzothiophene and dibenzofluorene groups, and derivatives thereof (for example disclosed in WO 2005/056633 A1, EP 1344788 A1 and WO 2007/043495 A1) particularly preferred.

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

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

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

R ^c and R ^d are each independently 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 substituted silyl, carbyl or hydrocarbyl groups having 1 to 40 carbon atoms, which may be optionally substituted and may optionally contain one or more heteroatoms, wherein the groups R ^c and R ^d may optionally form a spiro group having a fluorene radical to which they are bonded;

X is halogen;

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

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

m is an integer ≥ 1;

Ar ¹ and Ar ² are, independently of each other, a monocyclic or polycyclic aryl or heteroaryl group (which may be optionally substituted, and may be optionally bonded to the 7,8-position or 8,9-position of the indenofluorene group present);

a and b are each independently 0 or 1.

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

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

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

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

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

In the formula, the symbols have the following meanings:

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

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

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

In particular, in addition to at least one structural element having luminescent properties (group 4), preferably at least one phosphorescent group, additionally selected from groups 1 to 3, 5 or 6, preferably from groups 1 to 3, described above. Especially preferred are polymers containing at least one additional structural element that is

When present in the polymer, the proportions of the various classes of groups may be in wide ranges known to those skilled in the art. wherein the proportion of one class present in the polymer, selected in each case from the structural elements of groups 1 to 7 described above, is preferably in each case ≥ 5 mol %, particularly preferably in each case ≥ 10 mol %. In this case, surprising advantages can be achieved.

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

To improve solubility, the polymers may also contain corresponding groups. Preferably, it may be provided that the polymer contains substituents such that there are on average at least 2 non-aromatic carbon atoms per repeat unit, particularly preferably at least 4 and particularly preferably at least 8 non-aromatic carbon atoms. (average here is about number average). Here, individual carbon atoms can be replaced by, for example, O or S. However, a certain proportion, optionally all, of the repeating units may not contain substituents containing non-aromatic carbon atoms. Here, short-chain substituents are preferred, since long-chain substituents may adversely affect the layer obtainable using the organic functional material. Substituents preferably contain at most 12 carbon atoms, preferably at most 8 carbon atoms and particularly preferably at most 6 carbon atoms in the linear chain.

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

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

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

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

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

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

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

The documents cited above for descriptions of functional compounds are incorporated herein by reference for purposes of disclosure.

A formulation according to the present invention may contain all organic functional materials necessary for the manufacture of each functional layer of an electronic device. If, for example, the hole transport, hole injection, electron transport or electron injection layer is constructed from exactly one functional compound, the formulation includes exactly this compound as the organic functional material. When the release layer comprises the release agent in combination with, for example, a matrix or host material, the formulation is, as an organic functional material, precisely the matrix or host material and the release agent, as described in more detail elsewhere in this application. Contains a mixture of sieve.

In addition to the above configurations, formulations according to the present invention may also contain further additives and processing aids. These include, inter alia, surface-active substances (surfactants), lubricants and greases, viscosity-modifying additives, conductivity-increasing additives, dispersants, hydrophobizers, adhesion promoters, flow improvers, antifoaming agents, degassing agents, reactivity or ratio ( Diluents, fillers, auxiliaries, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors, which may be non-reactive.

The present invention further relates to a method for preparing a formulation according to the present invention, comprising at least a first organic solvent containing at least one [2.2.1] bicyclic group and at least one organic solvent usable for the production of a functional layer of an electronic device. It relates to a manufacturing method in which organic functional materials are mixed.

Formulations according to the invention can be used for the production of layers or multi-layer structures, in which organic functional materials are present in layers, as required for the production of desirable electronic or optoelectronic components, such as OLEDs.

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

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

The functional layer may be, for example, flood coating, dip coating, spray coating, spin coating, screen printing, relief printing, gravure printing, rotational printing, roller coating, flexography printing, offset printing or by nozzle printing, preferably inkjet printing, on the substrate or on one of the layers applied to the substrate.

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

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

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

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

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

The organic electronic device is preferably an organic electroluminescent device (OLED), a polymeric 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 Photo Detector, Organic Photoreceptor, Organic Field-Quenched Device (O-FQD), Organic Electric The sensor, a light emitting electrochemical cell (LEC) or an organic laser diode (O-Laser), more preferably an organic electroluminescent device (OLED) or a polymeric electroluminescent device (PLED).

The active component is generally an organic or inorganic material introduced between the anode and the cathode, wherein the active component affects, maintains and/or improves the properties of the electronic device, e.g. its performance and/or its lifetime. ), for example charge injection, charge transport or charge blocking materials, in particular emissive materials and matrix materials. Therefore, organic functional materials that can be used for the production of functional layers of electronic devices preferably contain active components of electronic devices.

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

It is also preferred to use a mixture of two or more triplet emitters together with the matrix. Triplet emitters with shorter-wave emission spectra serve here as a co-matrix for triplet emitters with longer-wave emission spectra.

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

Therefore, the proportion of the 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 for the fluorescence emission layer, and 3 to 15% by volume for the phosphorescence emission layer. is the volume %.

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

The mixed-matrix system preferably includes 2 or 3 different matrix materials, more preferably 2 different matrix materials. Here, one of the two materials is preferably a material having hole transport properties, and the other material is a material having electron transport properties. However, the desired electron transport and hole transport properties of the mixed-matrix components may also be primarily or entirely combined in a single mixed-matrix component, where additional mixed-matrix component(s) fulfill different functions. The two different matrix materials are mixed in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1 and most preferably 1:4 to 1:1. may exist as rain. Mixed matrix systems are preferably employed in phosphorescent organic electroluminescent devices. Further details on mixed-matrix systems can be found, for example, in WO 2010/108579.

In addition to these layers, the organic electroluminescent device may also have 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 layers, electron blocking layers, 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. Here, one or more hole transport layers may be p-doped, for example with a metal oxide, such as MoO ₃ or WO ₃ , or (per)fluorinated electron deficient aromatic compounds, and/or one or more electron transport layers may be n-doped. there is. In addition, an intermediate layer having an exciton blocking function and/or adjusting the charge balance, for example in an electroluminescent device, may be introduced between the two emissive layers. However, it should be pointed out that each of these layers need not necessarily be present. These layers may likewise be present when using the formulations according to the invention, as defined above.

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

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

In addition, the device may comprise layers built up of additional low molecular weight compounds or polymers not covered by the use of the formulations according to the invention. It can also be prepared by evaporation of low molecular weight compounds in high vacuum.

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

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

It is also possible for a plurality of OLEDs to be arranged one above the other, which allows a further increase in efficiency in terms of light yield to be achieved.

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

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

Furthermore, one or more layers of the electronic device according to the invention are applied by means of an OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier-gas sublimation, wherein the material is applied at a pressure between 10 ⁻⁵ mbar and 1 bar. may be provided.

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

Such a layer may also be applied by a process in which compounds of formulas (I), (II), (IIIa) or (IIIb) are not used. Preferably, an orthogonal solvent can be used here which dissolves the functional material of the layer to be applied, but does not dissolve the layer to which the functional material is applied.

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

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

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

In general, any material used for a layer according to the prior art may be used for a further layer, and a person skilled in the art will be able to combine each such material with a material according to the invention in an electronic device without inventiveness.

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

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

1. The electronic devices obtainable using the formulations according to the present invention exhibit very high stability and very long lifetime compared to electronic devices obtained using conventional methods.

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

3. The organic functional material used in the formulation according to the present invention is not subject to any particular limitation, so that the method of the present invention can be used comprehensively.

4. Coatings obtainable using the formulations of the present invention exhibit excellent quality, especially in uniformity of the coating.

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

It should be pointed out that variations of the embodiments described herein fall within the scope of the present invention. Each feature disclosed herein may be replaced by an alternative feature serving the same, equivalent or similar purpose, unless expressly excluded. Accordingly, each feature disclosed herein is to be regarded as an example of a generic series, or as an equivalent or similar feature, unless stated otherwise.

All features of the present invention may be combined with each other in any way, provided that certain features and/or steps are not mutually exclusive. This applies in particular to preferred features of the present invention. Equally, features in non-essential combinations may be used separately (not in combination).

It should also be pointed out that many features of the present invention, and features of particularly preferred embodiments, are inventive in themselves and should not be regarded as merely part of the embodiments of the present invention. For these features, independent protection may be sought as an alternative to, or in addition to, each invention currently claimed.

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

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

Those skilled in the art will be able, using the detailed description, to manufacture additional electronic devices in accordance with the present invention, without exercising their inventive ability, and thus to practice the invention throughout the claimed scope.

working example

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

Viscosity of formulations and solvents were measured using a TA Instruments ARG2 rheometer over a range of shear rates ranging from 10 to 1000 s ⁻¹ using a 40 mm parallel plate geometry. Measurements were taken as an average from 200 to 800 s ⁻¹ , at which time temperature and shear rate were accurately controlled. Each solvent was measured in triplicate. Viscosity values stated are averaged over these measurements.

Preferably, the organic solvent blend may comprise a surface tension in the range of 15 to 80 mN/m, more preferably in the range of 20 to 60 mN/m and most preferably in the range of 25 to 40 mN/m. Surface tension can be measured using a FTA (First Ten Angstrom) 1000 contact angle goniometer at 20 °C. Details of the method can be found in Roger P. Woodward, Ph.D. Available from First Ten Angstrom, as published in "Surface Tension Measurements Using the Drop Shape Method". Preferably, the surface tension can be determined using the drop method. All measurements are performed at room temperature in the range of 20 °C to 22 °C. For each formulation, 3 droplets were measured. Final values are averaged over these measurements. The tool was regularly cross-checked for a variety of liquids with well-known surface tensions.

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

Description of the production process

Glass substrates covered with pre-structured ITO and bank material were sonicated in isopropanol, then rinsed with deionized water, dried using an air-gun, and subsequently on a hotplate at 230°C. Annealed 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 at 185°C for 30 minutes in air.

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

The green emitting layer (G-EML) was also inkjet printed, vacuum dried and annealed at 160°C for 10 minutes in a nitrogen atmosphere. The ink for the green emitting layer contained one triplet emitter (EM-1) as well as two host materials (ie, HM-1 and HM-2) in all working examples. The materials were used in the following ratio: HM-1 : HM-2 : EM-1 = 40 : 40 : 20. As can be seen in Table 3, only the solvent(s) differed between the examples. The structure of this material is as follows:

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

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

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

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

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

Results and Discussion

Example 1

An inkjet printed OLED device was prepared with the printed layer using isobornyl acetate 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, whereby the bank is formed on the substrate was pre-fabricated to form a pixelated device. In this case, the green release material is dissolved in isobornyl acetate at a concentration of 14 mg/ml.

2 shows the current density-luminance-voltage (ILV) and luminance efficiency for Example 2. The luminance efficiency at 1000 cd/m ² is 46.31 cd/A. The efficiency of this OLED device is very good, and the voltage at 1000 cd/m ² is 8.02 V.

Example 2

An inkjet printed OLED device was prepared with the layer printed using pencil acetate as the solvent for the release 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, whereby the bank is formed on the substrate was pre-fabricated to form a pixelated device. In this case, the green release material is dissolved in pencil acetate at a concentration of 14 mg/ml.

3 shows the current density-luminance-voltage (ILV) and luminance efficiency for Example 2. The luminance efficiency at 1000 cd/m ² is 53.26 cd/A. The efficiency of this OLED device is very good, and the voltage at 1000 cd/m ² is 8.15 V.

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

Claims (22)

A formulation containing at least one organic functional material and at least a first organic solvent,
the first organic solvent contains one [2.2.1]bicyclic-group;
Said first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group containing solvent according to the general formula (I)

during the ceremony
R ¹ to R ¹² are identical or different at each occurrence and are H, D, F, Cl, Br, I, NO ₂ , CN, a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or 3 to 20 carbon atoms A branched or cyclic alkyl or alkoxy group having atoms wherein one or more non-adjacent CH ₂ groups are -NR ¹³ -, -CONR ¹³ -, -CO-O-, -O-CO-, -C=O-, = CO, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F), or one or more non-aromatic R ¹³ radicals having 4 to 14 carbon atoms is an aryl or heteroaryl group which may be substituted by, and a plurality of substituents R ¹³ on the same ring or on two different rings may together in turn form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system, which is a plurality of substituents may be substituted by R ¹³ ;
R ¹³ , identical or different at each occurrence, is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ group may be replaced by -CO-O-, -C=O-, -CH=CH- or -C≡C-, and one or more hydrogen atoms may be replaced by F), or 4 to 14 carbon atoms is an aryl or heteroaryl group which may be substituted with one or more non-aromatic R ¹³ radicals;
The at least one organic functional material is a fluorescent emitter, a phosphorescent emitter, a host material, a matrix material, an exciton blocking material, an electron transport material, an electron injection material, a hole transport material, a hole injection material, an n-dopant, a p-dopant, A formulation characterized in that it is selected from the group consisting of wide-band-gap materials, electron blocking materials and hole blocking materials. According to claim 1,
Said first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group containing solvent according to the general formula (II)

wherein R ¹ to R ¹² have the meanings as described for general formula (I) above. According to claim 2,
Said first organic solvent containing one [2.2.1]bicyclic-group is a [2.2.1]bicyclic-group containing solvent according to general formula (II)
during the ceremony
R ⁵ is a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH ₂ groups are -NR ¹³ -, -CONR ¹³ -, -CO-O-, -O-CO-, -C=O-, =CO, -CH=CH- or -C≡C-, and one or more hydrogen atoms are replaced by F may be substituted), or an aryl or heteroaryl group having 4 to 14 carbon atoms and which may be substituted by one or more non-aromatic R ¹³ radicals, wherein a plurality of substituents R ¹³ on the same ring or on two different rings are together in turn form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by a plurality of substituents R ¹³ ;
Except for R ⁵ , R ¹ to R ¹² are H;
Characterized in that R ¹³ has the meaning as described for general formula (I) above. According to claim 1,
The formulation of claim 1, wherein the first organic solvent has a surface tension of ≥ 25 mN/m. According to claim 1,
The formulation, characterized in that the content of the first organic solvent is in the range of 50 to 100% by volume based on the total amount of the solvent in the formulation. According to claim 1,
The formulation, characterized in that the first organic solvent has a boiling point in the range of 100 to 400 ℃. According to claim 1,
Wherein the formulation comprises at least one second solvent different from the first organic solvent. According to claim 7,
The formulation, characterized in that the second solvent has a boiling point in the range of 100 to 400 ℃. According to claim 7,
wherein said at least one organic functional material has a solubility in said first organic solvent and said second solvent in the range of 1 to 250 g/l. According to claim 1,
The formulation, characterized in that the formulation has a surface tension in the range of 1 to 70 mN / m. According to claim 1,
The formulation is 1 to 50 mPa ^. A formulation characterized in that it has a viscosity in the s range. According to claim 1,
A formulation, characterized in that the content of at least one organic functional material in the formulation ranges from 0.001 to 20% by weight based on the total weight of the formulation. According to claim 1,
The formulation of claim 1, wherein the at least one organic functional material is an organic semiconductor selected from the group consisting of hole injecting, hole transporting, emitting, electron transporting and electron injecting materials. According to claim 13,
wherein at least one organic semiconductor is selected from the group consisting of hole injecting and hole transporting materials. 15. The method of claim 14,
Wherein the hole injection and hole transport material is a polymeric compound or a blend of a polymeric compound and a non-polymeric compound. A method for producing the dosage form according to any one of claims 1 to 15,
The method of claim 1, wherein the at least one organic functional material and the at least first organic solvent are mixed. As a method for manufacturing an electroluminescent device,
16. An electroluminescent device, characterized in that at least one layer of said electroluminescent device is produced by depositing, or printing, a formulation according to any one of claims 1 to 15 on a surface, followed by drying. manufacturing method. 16. An electroluminescent device, characterized in that at least one layer is produced by depositing, or printing, a formulation according to any one of claims 1 to 15 on a surface, followed by drying. delete delete delete delete

Images