CN109563402B - Preparation of organic functional materials - Google Patents

Abstract

The present invention relates to formulations comprising at least one organic functional material and at least one sulfamide or sulfanilamide as a first organic solvent, and electronic devices prepared by using these formulations.

Description

Preparation of organic functional materials

Technical Field

The present invention relates to formulations comprising a thioamide or a sulfonamide as first solvent, and electroluminescent devices prepared by using these formulations.

Background

Organic Light Emitting Devices (OLEDs) have long been manufactured by vacuum deposition methods. Other techniques such as inkjet printing have been thoroughly studied recently because they have advantages such as cost savings and scalability. One of the main challenges of multi-layer printing is to determine relevant parameters to obtain uniform ink deposition on the substrate. To trigger such parameters as surface tension, viscosity or boiling point, additives may be added to the formulation.

Technical problem and objects

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

Solution to the problem

The above object of the present invention is solved by providing a formulation comprising a sulfonamide or sulfamide as first solvent.

The invention has the advantages of

The inventors have surprisingly found that the use of an organic solvent containing a sulfonamide or sulfamide as first solvent enables a complete control of the surface tension and induces an efficient ink deposition to form organic layers of very uniform and clearly distinguishable functional materials having good layer properties and performance in electronic devices.

Drawings

Fig. 1 shows a typical layer structure of a device including 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.

Detailed Description

The invention relates to a preparation containing at least one organic functional material and a sulfonamide or sulfamide as first solvent.

Detailed description of the preferred embodiments

In a first preferred embodiment, the first organic solvent is a compound according to formula (I)

Wherein

R¹And R²Identical or different at each occurrence to a linear alkyl radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl radical having from 3 to 20 carbon atoms, in which one or more non-adjacent CH' s ₂The radicals being optionally substituted by-O-, -S-, -NR-⁶-、-CONR⁶-, -CO-O-, -C ═ O-, -CH ═ CH-or-C.ident.C-and in which one or more hydrogen atoms may be replaced by F, or aryl or heteroaryl radicals having from 2 to 60 carbon atoms, in which any of the abovementioned radicals may be replaced by one or more R⁶Is substituted by radicals, and wherein R¹And R²Or together may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;

x is-N (R)⁴)(R⁵) Or R³；

R³、R⁴And R⁵Identical or different at each occurrence to a linear alkyl radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl radical having from 3 to 20 carbon atoms, in which one or more non-adjacent CH' s₂The radicals being optionally substituted by-O-, -S-, -NR-⁶-、-CONR⁶-, -CO-O-, -C ═ O-, -CH ═ CH-or-C.ident.C-and in which one or more hydrogen atoms may be replaced by F, or aryl or heteroaryl radicals having from 2 to 60 carbon atoms, in which the abovementioned radicals may be replaced by one or more R⁶Is substituted by radicals in which R³And R⁴Or together may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system; and is provided with

R⁶In each case identical or different and is H, a linear alkyl or alkoxy radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy radical having from 3 to 20 carbon atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂Instead of, or as aromatic hydrocarbons having 2 to 14 carbon atomsA radical or a heteroaryl radical.

In a first more preferred embodiment, the first organic solvent is a sulfamide compound according to general formula (II)

Preferably, the substituent R¹、R²、R⁴And R⁵Are the same.

Further preferred are compounds of formula (II) wherein R is¹And R²Are identical and R⁴And R⁵Identical, but wherein the substituents R¹And R²With a substituent R⁴And R⁵Different.

Still more preferably R¹And R²Are different from each other, and R⁴And R⁵Identical, except that the substituents R¹And R²Both with the same substituent R⁴And R⁵Different.

Still more preferably R¹、R²、R⁴And R⁵Are different from each other.

In a second more preferred embodiment, the first organic solvent is a sulfonamide compound according to formula (III)

Preferably, the substituent R¹、R²And R³Are the same.

Further preferably R¹And R²Are identical to each other, and R³And R¹And R²Different.

Still more preferably R in the formula (III)¹And R²Are different from each other.

Still more preferred is R in formula (III)¹、R²And R³Are different from each other.

Preferably, R is¹、R²、R³、R⁴And R⁵Selected from linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein one or more non-adjacent CH groups₂The radicals being optionally substituted by-O-, -S-, -NR ⁶-、-CONR⁶-, -CO-O-, -C ═ O-, -CH ═ CH-or-C ≡ C-, and in which one or more hydrogen atoms may be replaced by F, where the above groups may be substituted by one or more R⁶And (4) substituting the group.

More preferably, R¹、R²、R³、R⁴And R⁵Selected from linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein one or more non-adjacent CH groups₂The radicals being optionally substituted by-O-, -S-, -NR⁶-、-CONR⁶-, -CO-O-, -C-O-, -CH-or-C.ident.C-and in which one or more hydrogen atoms may be replaced by F, where the above radicals may be substituted by one or more R⁶And (4) substituting the group.

Even more preferably, R¹、R²、R³、R⁴And R⁵Selected from linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein the above groups may be substituted by one or more R⁶And (4) substituting the group.

Most preferably, R¹、R²、R³、R⁴And R⁵Selected from linear alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, wherein the above groups may be substituted by one or more R⁶And (4) substituting the group.

Most preferably, R¹、R²、R³、R⁴And R⁵Selected from linear alkyl groups having 1 to 5 carbon atoms or branched or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the above groups may be substituted by one or more R ⁶And (4) substituting the group.

It is further preferred that R¹、R²、R³、R⁴And R⁵Is selected from the group consisting of having 1 toA linear alkyl group of 20 carbon atoms, preferably 1 to 5 carbon atoms, wherein the linear alkyl group may be substituted by one or more R⁶And (4) substituting the group.

It is also preferred that R¹、R²、R³、R⁴And R⁵Selected from branched or cyclic alkyl groups having from 3 to 20 carbon atoms, preferably from 3 to 15 carbon atoms, very preferably from 3 to 10 carbon atoms, particularly preferably from 3 to 8 carbon atoms and very particularly preferably from 3 to 6 carbon atoms, wherein even more preferably a branched alkyl group is present, wherein the above groups may be substituted by one or more R⁶And (4) substituting the group.

Preferred substituents R¹、R²、R³、R⁴And R⁵Is a group of the following formulae (R-1) to (R-23), wherein the dotted line indicates R¹、R²、R⁴And R⁵Bond to nitrogen atom or R³A bond to a sulfur atom, wherein these radicals may be substituted by one or more R⁶Is substituted by radicals, and wherein R⁶Preferably H.

In a particularly preferred embodiment, the substituents R⁶Is H.

Examples of the most preferred solvent compounds of formula (I) and their Boiling Point (BP) and Melting Point (MP) are shown in the table below.

Preferably, the first solvent has a surface tension of ≧ 20 mN/m. More preferably, the surface tension of the first solvent is in the range of 20 to 40 mN/m.

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

In one embodiment, the formulation according to the invention may comprise at least a second solvent, which is different from the first solvent. The second solvent is used together with the first solvent.

The content of the second solvent is preferably in the range of 0 to 50 vol%, more preferably in the range of 0 to 25 vol%, and most preferably in the range of 0 to 10 vol%, based on the total amount of solvents in the formulation.

Preferably, the first solvent has a boiling point of 400 ℃ or less. More preferably, the first solvent has a boiling point in the range from 100 ℃ to 400 ℃, very preferably in the range from 100 ℃ to 350 ℃, particularly preferably in the range from 150 ℃ to 350 ℃ and very particularly preferably in the range from 170 ℃ to 350 ℃. The boiling point is measured at 760 mmHg.

Suitable second solvents are preferably organic solvents, which include, inter alia, alcohols, aldehydes, ketones, ethers, esters, amides such as di-C_1-2Alkyl formamides, sulfur compounds, nitro compounds, hydrocarbons, halogenated hydrocarbons (e.g., chlorinated hydrocarbons), aromatic or heteroaromatic hydrocarbons, and halogenated aromatic or heteroaromatic hydrocarbons.

Preferably, the second solvent may be selected from one of the following groups: substituted and unsubstituted aromatic or linear esters such as ethyl benzoate, butyl benzoate; substituted and unsubstituted aromatic or straight chain ethers such as 3-phenoxytoluene or anisole; substituted or unsubstituted aromatic hydrocarbon derivatives such as xylene; indane derivatives such as hexamethylindan; substituted and unsubstituted aromatic or straight chain ketones; substituted and unsubstituted heterocyclic compounds such as pyrrolidones, esters of non-aromatic alcohols such as cyclohexyl hexanoate or menthyl isovalerate, cyclic or acyclic siloxanes, pyridines, pyrazines; 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-benzodioxolane

Alkane, 1, 4-diisopropylbenzene, 1, 4-dimethylnaphthalene, 1, 5-dimethyltetralin, 1-benzothiophene, thienylnaphthalene, 1-bromonaphthalene, 1-chloromethylnaphthalene, 1-ethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 1-methylindole, 2, 3-benzofuran, 2, 3-dihydrobenzofuran, 2, 3-dimethylanisole, 2, 4-dimethylanisole, 2, 5-dimethylanisole, 2, 6-dimethylnaphthalene, 2-bromo-3-bromomethylnaphthalene, 2-bromonaphthalene, 2-ethoxynaphthalene, 2-ethylnaphthalene, 2-isopropylanisole, 2-methylanisole, 2-bromonaphthalene, 1-methylnaphthalene, 1-benzothiophene, 1-thianaphthalene, 1-bromonaphthalene, 1-methylnaphthalene, 2, 3-methylindole, 2, 3-bromomethylnaphthalene, 2-bromonaphthalene, 2-ethoxynaphthalene, 2-ethylnaphthalene, 2-isopropylanisole, 2-methylanisole, 2-methylnaphthalene, 2-bromonaphthalene, and a, 2-methylindole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, 3-bromoquinoline, 3-methylanisole, 4-methylanisole, 5-decalactone, 5-methoxyindane, 5-methoxyindole, 5-tert-butyl-m-xylene, 6-methylquinoline, 8-methylquinoline, acetophenone, anisole, benzonitrile, benzothiazole, benzyl acetate, bromobenzene, butyl benzoate, butylphenyl ether, cyclohexylbenzene, cyclohexyl hexanoate, menthyl isovalerate, p-tolyl isobutyrate, decalin, dimethoxytoluene, 3-phenoxytoluene, diphenyl ether, propiophenone, ethylbenzene, ethyl benzoate, hexylbenzene, indane, hexamethylindane, indene, isochroman, isopropylbenzene, m-cymene, mesitylene, Methyl benzoate, o-xylene, m-xylene, p-xylene, propyl benzoate, propylbenzene, o-dichlorobenzene, pentylbenzene, phenetole, ethoxybenzene, phenyl acetate, p-cymene, propiophenone, sec-butylbenzene, tert-butylbenzene, thiophene, o-dimethoxybenzene, monochlorobenzene, o-dichlorobenzene, pyridine, pyrazine, pyrimidine, pyrrolidone, morpholine, dimethylacetamide, dimethylsulfoxide, decalin and/or mixtures of these compounds.

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

Preferably, the second solvent has a boiling point in the range of 100 ℃ to 400 ℃, more preferably in the range of 150 ℃ to 350 ℃.

The solubility of the at least one organic functional material in the first solvent and in the second solvent is preferably in the range of 1g/l to 50g/l, and more preferably in the range of 1g/l to 250 g/l. The solubility of organic materials in high-boiling solvents is determined according to ISO7579: 2009.

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

The formulations according to the invention have a surface tension which is preferably in the range from 10 to 70mN/m, and very preferably in the range from 10 to 50mN/m, and particularly preferably in the range from 15 to 40 mN/m.

Furthermore, the formulations according to the invention have a viscosity preferably in the range from 0.8 to 50mpa.s, very preferably in the range from 1 to 40mpa.s, particularly preferably in the range from 2 to 20mpa.s and very particularly preferably in the range from 2 to 10 mpa.s.

Preferably, the organic solvent blend comprises a surface tension in the range of 10 to 80mN/m, more preferably in the range of 15 to 60mN/m and most preferably in the range of 20 to 40 mN/m.

Surface tension can be measured at 20 ℃ using an FTA (First Ten Angstrom) 1000 contact Angle goniometer. Details of the Method are available from First Ten Angstrom corporation as disclosed by "Surface Measurements Using the Drop Shape Method" by Roger P.Woodward, Phd. Preferably, the surface tension can be determined using the pendant drop method. This measurement technique disperses droplets expelled from the needle in an integral liquid or gas phase. The shape of the droplet results from the relationship between surface tension, gravity and density differences. Surface tension was calculated from the shadow image of the hanging drop using the hanging drop method using http:// www.kruss.de/services/reduction-the/transparency/drop-shape-analysis. All surface tension measurements were made using a commonly used and commercially available high precision droplet shape analysis tool, FTA1000 from First Ten Angstrom. The surface tension is determined by the software FTA 1000. All measurements were performed at room temperature, which is in the range of 20 ℃ to 25 ℃. Standard operating procedures include determining the surface tension of each formulation using a new disposable drop dispensing system (syringe and needle). Each droplet was measured over a duration of 1 minute, sixty measurements were taken, and these measurements were then averaged. For each formulation, three droplets were measured. The final value is averaged over the measured values. The tool is periodically checked against a plurality of liquids having known surface tensions.

The TA instruments ARG2 rheometer was used at 10s^-1To 1000s^-1The viscosities of the formulations and solvents of the examples were measured using a 40mm parallel plate geometry over a range of shear rates. The measurement result is at 200s^-1And 800s^-1In which the temperature and shear rate are precisely controlled. The viscosities given in Table 3 are at a temperature of 25 ℃ and 500s^-1The viscosity of each formulation measured at a shear rate of (a). Each solvent was measured in triplicate. The viscosity value is the average of the measured values.

The formulations according to the invention comprise at least one organic functional material, which can be used for the production of functional layers of electronic devices. The functional material is typically an organic material introduced between the anode and the cathode of an electronic device, in particular an electroluminescent device.

The term organic functional material denotes especially organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light-absorbing compounds, organic photosensitive compounds, organic photosensitizers and other organic photoactive compounds. Furthermore, the term organic functional material encompasses organometallic complexes of transition metals, rare earth elements, lanthanides and actinides.

The organic functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, exciton blocking materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, n-type dopants, p-type dopants, wide band gap materials, electron blocking materials, and hole blocking materials.

Preferred embodiments of the organic functional material are disclosed in detail in WO 2011/076314 a1, which is incorporated by reference in the present application.

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

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

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

Organic functional materials are often described by the nature of the leading orbital, which will be described in more detail below. Molecular orbitals of materials, in particular the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), their energy levels and the lowest triplet state T₁Energy of or lowest excited singlet state S₁Can be determined via quantum chemical calculations. To calculate the metal-free organic species, a geometry optimization was first performed using the "ground state/semi-empirical/default spin/AM 1/charge 0/spin singlet" method. An energy calculation is then performed based on the optimized geometry. The "TD-SCF/DFT/default spin/B3 PW 91" method and "6-31G (d)" basis sets (Charge 0, spin singlet) are used herein. For metal-containing compounds, the geometry was optimized by the "ground state/hartley-fock/default spin/LanL 2 MB/charge 0/spin singlet" method. The energy calculation was carried out similarly to the above method for organic substances, except that the "LanL 2 DZ" group was used for the metal atoms, and For the ligands, groups "6-31G (d)" were used. Energy calculations give the HOMO energy level HEh or the LUMO energy level LEh in hartley. The HOMO and LUMO energy levels in electron volts calibrated against cyclic voltammetry measurements were thus determined as follows:

HOMO(eV)＝((HEh*27.212)-0.9899)/1.1206

LUMO(eV)＝((LEh*27.212)-2.0041)/1.385

for the purposes of this application, these values are considered to be the HOMO and LUMO energy levels of the material, respectively.

Lowest triplet state T₁Is defined as the energy of the triplet state with the lowest energy resulting from the quantum chemistry described.

Lowest excited singlet S₁Is defined as the energy of the excited singlet state with the lowest energy resulting from the quantum chemistry described.

The methods described herein are independent of the software package used and give the same results throughout. Examples of frequently used programs for this purpose are "Gaussian 09W" (Gauss Corp.) and Q-Chem 4.1(Q-Chem Corp.).

Compounds having hole-injecting properties, which are also referred to herein as hole-injecting materials, simplify or facilitate the transfer of holes (i.e., positive charges) from the anode into the organic layer. Generally, the hole injecting material has a HOMO level in the region of or above the anode level, i.e. typically at least-5.3 eV.

Compounds having hole transporting properties, which are also referred to herein as hole transporting materials, are capable of transporting holes, i.e., positive charges, that are typically injected from the anode or an adjacent layer, such as a hole injection layer. The hole transport material typically 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 injecting and/or hole transporting properties include, for example, triarylamines, benzidines, tetraaryl-p-phenylenediamines, triarylphosphines, phenothiazines, thiophenes

Oxazines, dihydrophenazines, thianthrenes, dibenzo-p-dioxanes

English and thiophene

Thia-and carbazoles,

Thiophene, pyrrole and furan derivatives and other O, S or N-containing heterocyclic compounds having a high HOMO (HOMO ═ highest occupied molecular orbital).

As the compound having ｃA hole injecting and/or hole transporting property, there may be mentioned, in particular, 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 derivatives (US 4950950), polysilanes (JP-A-2-204996), aniline copolymers (JP-A-2-282263), thiophene oligomers (JP pan 1(1989)211399), polythiophenes, poly (N-vinylcarbazole) (PVK), Polypyrrole, polyaniline and other conductive macromolecules, porphyrin compounds (JP- ｃA-63-2956965, US 4720432), aromatic dimethylene type compounds, carbazole compounds (e.g., CDBP, CBP, mCP), aromatic tertiary amines, and styrene amine compounds (US4127412) (e.g., benzidine type triphenylamine, styrene amine type triphenylamine, and diamine type triphenylamine). Arylamine dendrimers (JP hei 8(1996)193191), monomeric triarylamines (US 3180730), triarylamines containing one or more vinyl groups and/or at least one active hydrogen-containing functional group (US 3567450 and US 3658520) or tetraaryldiamines (two tertiary amine units linked via an aryl group) may also be used. More triarylamino groups may also be present in the molecule. Phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives, such as dipyrazino [2,3-f:2',3' -h ] quinoxaline hexacyanoferrate, are also suitable.

Preference is given to aromatic tertiary amines containing at least two tertiary amine units (U.S. Pat. No. 3, 2008/0102311, 1, U.S. Pat. No. 4720432 and U.S. Pat. No. 5061569), such as NPD (alpha-NPD ═ 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ═ 4]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- ｃA-4-308688), TBDB (═ N, N' -tetrakis (4-biphenyl) diaminobiphenyl), TAPC (═ 1, 1-bis (4-di-p-tolylaminophenyl) cyclohexane), TAPPP (═ 1, 1-bis (4-di-p-tolylaminophenyl) -3-phenylpropane), BDTAPVB (═ 1, 4-bis [2- [4- [ N, N-di (p-tolyl) amino group)]Phenyl radical]Vinyl radical]Benzene), TTB (═ N, N ' -tetra-p-tolyl-4, 4' -diaminobiphenyl), TPD (═ 4,4' -bis [ N-3-methylphenyl group)]-N-phenylamino) biphenyl), N ' -tetraphenyl-4, 4' -diamino-1, 1',4', 1',4', 1' -quaterphenyl, tertiary amines containing carbazole units such as TCTA (═ 4- (9H-carbazol-9-yl) -N, N-bis [4- (9H-carbazol-9-yl) phenyl)]Aniline). Preference is also given to hexaazaterphenyl compounds and phthalocyanine derivatives according to US 2007/0092755A1 (e.g. H) ₂Pc, CuPc (═ copper phthalocyanine), CoPc, NiPc, ZnPpc, Pdpc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, and Cl₂SiPc、(HO)AlPc、(HO)GaPc、VOPc、TiOPc、MoOPc、GaPc-O-GaPc)。

Particularly preferred are triarylamine compounds of the following formulae (TA-1) to (TA-12), which are disclosed in the following documents: EP 1162193B 1, EP 650955B 1, synth metals 1997,91(1-3),209, DE 19646119 a1, WO 2006/122630 a1, EP 1860097A 1, EP 1834945 a1, JP 08053397A, US 6251531B 1, US 2005/0221124, JP 08292586 a, US 7399537B 2, US 2006/0061265 a1, EP 1661888 and WO 2009/041635. The compounds of formulae (TA-1) to (TA-12) may also be substituted:

other compounds that can be used as hole injection materials are described in EP 0891121 a1 and EP 1029909 a1, and the injection layer is generally described in US 2004/0174116 a 1.

These arylamines and heterocyclic compounds, which are generally used as hole-injecting and/or hole-transporting materials, preferably produce HOMO in the polymer in a range of greater than-5.8 eV (relative to vacuum level), particularly preferably greater than-5.5 eV.

Compounds having electron-injecting and/or electron-transporting properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine,

Oxadiazoles, quinolines, quinoxalines, anthracenes, benzanthracenes, pyrenes, perylenes, benzimidazoles, triazines, ketones, phosphine oxides, and phenazine derivatives, as well as triarylboranes and other O, S or N-containing heterocyclic compounds having a low LUMO (LUMO ═ lowest unoccupied molecular orbital).

Particularly suitable compounds for the electron transport and electron injection layer are metal chelates of 8-hydroxyquinoline (e.g. LiQ, AlQ)₃、GaQ₃、MgQ₂、ZnQ₂、InQ₃、ZrQ₄) BALQ, Ga hydroxyquinoline complexes, 4-azaphenanthren-5-ol-Be complexes (US 5529853A, cf. formula ET-1), butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidazole derivatives (US 2007/0273272A 1) such as TPBI (US 5766779, cf. formula ET-2), 1,3, 5-triazines, for example spirobifluorenyltriazine derivatives (for example according to DE102008064200), pyrene, anthracene, tetracene, fluorene, spirofluorene, dendrimers, tetracenes (for example 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, for example Si-containing triarylborane derivatives (US 2007/0087219A 1, reference formula ET-3), pyridine derivatives (JP 2004-200162), phenanthrolines, in particular 1, 10-phenanthroline derivatives, such as BCP and Bphen, and phenanthrolines linked via biphenyl or other aromatic groupsQuinoline (US-2007-0252517A 1) or phenanthroline linked to anthracene (US 2007-0122656A 1, see formulae ET-4 and ET-5).

Heterocyclic organic compounds are likewise suitable, such as thiopyran dioxide, thiopyran dioxide,

Azole, triazole, imidazole or

Diazole. Examples of the N-containing five-membered rings used are

Oxazole, preferably 1,3,4-

Diazoles, for example compounds of formulae ET-6, ET-7, ET-8 and ET-9, which are disclosed in particular in US 2007/0273272A 1; thiazole,

Oxadiazoles, thiadiazoles, triazoles, in particular as described in U.S. Pat. Nos. 2008/0102311A1 and Y.A. Levin, M.S. Skorobogaova, Khimiya Geterotsilicheskikh Soedinenii 1967(2),339-341, preferably a compound of the formula ET-10, a silacyclopentadiene derivative. Preferred compounds are those of the formulae (ET-6) to (ET-10):

it is also possible to use organic compounds such as derivatives of fluorenone, fluorenylidene methane, perylenetetracarboxylic acid, anthraquinone dimethane, diphenoquinone, anthrone, and anthraquinone diethylenediamine.

Preferably 2,9, 10-substituted anthracenes (substituted with 1-or 2-naphthyl and 4-or 3-biphenyl) or molecules containing two anthracene units (U.S. Pat. No. 2008/0193796A 1, cf. formula ET-11). Furthermore, it is highly advantageous to attach 9, 10-substituted anthracene units to benzimidazole derivatives (U.S. Pat. No. 4, 2006/147747A and EP 1551206A 1, cf. formulae ET-12 and ET-13).

Compounds capable of generating electron injection and/or electron transport properties preferably generate LUMO below-2.5 eV (relative to vacuum level), particularly preferably below-2.7 eV.

The formulations of the invention may comprise a luminophore. The term luminophore denotes a material which, after excitation which can take place by transfer of any type of energy, can radiatively transition to the ground state and emit light. In general, two classes of emitters are known, namely fluorescent and phosphorescent emitters. The term fluorescent emitter denotes a material or compound in which a radiative transition from an excited singlet state to the ground state occurs. The term phosphorescent emitter preferably denotes a luminescent material or compound containing a transition metal.

The emitters are often also referred to as dopants, in which case the dopants give rise to the abovementioned properties in the system. The dopant in the system comprising the host material and the dopant means the component in the mixture in a smaller proportion. Accordingly, the host material in a system comprising a host material and a dopant means the component in the mixture in the greater proportion. Thus, the term phosphorescent emitter may also mean, for example, a phosphorescent dopant.

Compounds capable of emitting light include, inter alia, fluorescent emitters and phosphorescent emitters. These include, inter alia, compounds comprising the following structure: stilbene, stilbenediamine, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene, phthalocyanine, porphyrin, ketone, quinoline, imine, anthracene, and/or pyrene structures. Particularly preferred are compounds capable of emitting light from a triplet state with high efficiency even at room temperature, i.e., compounds exhibiting electrophosphorescence rather than electroluminescence, which generally cause an increase in energy efficiency. Suitable for this purpose are, above all, compounds containing heavy atoms having an atomic number of greater than 36. Preferred are compounds containing a d-or f-transition metal satisfying the above conditions. Here, the corresponding compounds containing elements from groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt) are particularly preferred. Suitable functional compounds here are, for example, complexes as described, for example, in WO 02/068435A 1, WO 02/081488A 1, EP 1239526A 2 and WO 2004/026886A 2.

Preferred compounds which can act as fluorescent emitters are described by way of example below. Preferred fluorescent emitters are selected from the following classes: monostyrenylamine, distyrenylamine, tristyrenylamine, tetraphenylethyleneamine, styrylphosphine, styrene ether, and arylamine.

By monostyrenylamine is meant a compound containing one substituted or unsubstituted styryl group and at least one amine, preferably an aromatic amine. Distyrene amines means compounds containing two substituted or unsubstituted styrene groups and at least one amine, preferably an aromatic amine. Tristyrylamine means a compound containing three substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. By tetraphenylethyleneamine is meant a compound containing four substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. The styryl radical is particularly preferably stilbene, which may also be substituted further. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine in the sense of the present invention means a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, preferably a fused ring system having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic pyrene diamines

Amines or aromatics

A diamine. By aromatic anthracenamine is meant a compound in which one diarylamino group is bonded directly to the anthracene group, preferably at the 9-position. Aromatic anthracenediaminesRefers to compounds in which two diarylamino groups are bonded directly to an anthracene group, preferably at the 2,6 or 9,10 positions. Aromatic pyrene amine, aromatic pyrene diamine, aromatic

Amines and aromatics

Diamines are defined analogously thereto, wherein the diarylamino groups are bonded to pyrene preferably in the 1-position or in the 1, 6-position.

Other preferred fluorescent emitters are selected from indenofluorenylamines or indenofluorenyldiamines, which are described in particular in WO 2006/122630; benzoindenofluoreneamines or benzindenofluorenediamines, which are described in particular in WO 2008/006449; and dibenzoindenofluoreneamines or dibenzoindenofluorenediamines, which are described in particular in WO 2007/140847.

Examples of compounds from the styrylamine class which can be used as fluorescent emitters are substituted or unsubstituted tristilbene amines or the dopants described in WO 2006/000388, WO 2006/058737, WO2006/000389, WO 2007/065549 and WO 2007/115610. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Other styrylamine can be found in US 2007/0122656 a 1.

Particularly preferred styrylamine compounds are compounds of the formula EM-1 described in US 7250532B 2 and compounds of the formula EM-2 described in DE 102005058557A 1:

particularly preferred triarylamine compounds are compounds of formulae EM-3 to EM-15 and derivatives thereof disclosed in CN 1583691A, JP 08/053397 a and US 6251531B 1, EP 1957606 a1, US 2008/0113101 a1, US 2006/210830A, WO 2008/006449 and DE 102008035413:

other preferred compounds which can be used as fluorescent emitters are selected from the following derivatives: naphthalene, anthracene, tetracene, benzanthracene, triphenylene (DE 102009005746), fluorene, fluoranthene, diindenoperylene, indenoperylene, phenanthrene, perylene (U.S. Pat. No. 3, 2007/0252517, 1), pyrene, perylene,

Decacycloalkene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (U.S. Pat. Nos. 4,69292, 6020078, 2007/0252517A 1), pyran, perylene, and mixtures thereof,

Azole, benzo

Oxazoles, benzothiazoles, benzimidazoles, pyrazines, cinnamates, diketopyrrolopyrroles, acridones and quinacridones (US 2007/0252517 a 1).

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

Derivatives of the following are also preferred: rubrene, coumarin, rhodamine, quinacridones, such as DMQA (═ N, N' -dimethylquinacridone), dicyanomethylenepyrans, such as DCM (═ 4- (dicyanoethylene) -6- (4-dimethylaminostyryl-2-methyl) -4H-pyran), thiopyrans, polymethines, pyrans

And thiopyran

Salts, diindenoperylenes and indenoperylenes.

The blue fluorescent emitters are preferably polycyclic aromatic compounds, such as 9, 10-bis (2-naphthylanthracene) and other anthracene derivatives, derivatives of tetracene, derivatives of xanthene, derivatives of perylene (such as 2,5,8, 11-tetra-tert-butylperylene), derivatives of phenylene radicals, such as 4,4 '-bis (9-ethyl-3-carbazolylidene) -1,1' -biphenyl, derivatives of fluorene, derivatives of fluoranthene, derivatives of arylpyrene (US2006/0222886 a1), derivatives of arylylidene (US 5121029, US5130603), derivatives of bis (azinyl) imine-boron compounds (US 2007/0092753 a1), derivatives of bis (azinyl) methylidene compounds and derivatives of quinolin-2-one compounds.

Other preferred blue fluorescent emitters are described in C.H. Chen et al, "Recent developments in organic electroluminescent materials" macromolecular. Symp. 125, (1997)1-48 and "Recent developments of molecular organic electroluminescent materials and devices" Mat.Sci.and Eng.R. (materials science and engineering reports), 39(2002), 143-.

Other preferred blue fluorescent emitters are hydrocarbons as disclosed in DE 102008035413.

Preferred compounds which can act as phosphorescent emitters are described by way of example below.

Examples of phosphorescent emitters are disclosed in WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614 and WO 2005/033244. In general, all phosphorescent complexes used for phosphorescent OLEDs according to the prior art and known to the person skilled in the art of organic electroluminescence are suitable, and the person skilled in the art is able to use other phosphorescent complexes without inventive effort.

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

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

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

Compounds of formula EM-16 are described in more detail in US 2007/0087219 a1, wherein the specification is referred to for disclosure purposes for the purpose of explaining the substituents and labels in the above formula. In addition, Pt-porphyrin complexes with enlarged ring systems (US 2009/0061681A 1) and Ir complexes, for example 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-porphyrin-Pt (II), tetraphenyl-Pt (II) tetraphenylporphyrin (US 2009/0061681A 1), cis-bis (2-phenylpyridinato-N, C²') Pt (II), cis-bis (2- (2' -thienyl) pyridinato-N, C³') Pt (II), cis-bis (2- (2' -thienyl) quinolinato-N, C⁵') Pt (II), (2- (4, 6-difluorophenyl) pyridinato-N, C²') Pt (II) (acetylacetonate), or tris (2-phenylpyridinato-N, C²')Ir(III)(＝Ir(ppy)₃Green light), bis (2-phenylpyridyl-N, C²) Ir (iii) (acetylacetonate) (═ ir (ppy)₂Acetylacetonate, green light, US 2001/0053462A 1, Baldo, Thompson et al, Nature 403, (2000),750-753), bis (1-phenylisoquinolinium-N, C²') (2-phenylpyridyl-N, C²') Iridium (III), bis (2-phenylpyridinato-N, C²') (1-phenylisoquinolino-N, C²') Iridium (III), bis (2- (2' -benzothienyl) pyridinato-N, C³') Iridium (III) (acetylacetonate), bis (2- (4',6' -difluorophenyl) pyridinato-N, C ²') Iridium (III) (picolinate) (FIrpic, blue light), bis (2- (4',6' -difluorophenyl) pyridinato-N, C²') Ir (III) (tetrakis (1-pyrazolyl) borate), tris (2- (biphenyl-3-yl) -4-tert-butylpyridinium) iridium (III), (ppz)₂Ir(5phdpym)(US2009/0061681 A1)，(45ooppz)₂Ir (5phdpym) (US 2009/0061681 a1), derivatives of 2-phenylpyridine-Ir complexes, such as PQIr (═ bis (2-phenylquinoline)quinoline-N, C²') Iridium acetylacetonate (III), tris (2-phenylisoquinolino-N, C) Ir (III) (Red light), bis (2- (2' -benzo [4, 5-a)]Thienyl) pyridinato-N, C³) Ir (acetylacetonate) ([ Btp)₂Ir(acac)]Red light, Adachi et al, appl. Phys. Lett. (applied physical bulletin) 78(2001), 1622-.

The following materials are also suitable: trivalent lanthanides, e.g. Tb³⁺And Eu³⁺Complexes of (j. Kido et al, appl. phys. lett.65(1994),2124, Kido et al, chem. lett. (promiscuous chemie) 657,1990, US 2007/0252517 a1), or pt (ii), ir (i), rh (i) phosphorescent complexes with maleonitriledithiolane (Johnson et al, JACS105,1983,1795), re (i) tricarbonyl-diimine complexes (in particular Wrighton, JACS 96,1974,998), os (ii) complexes with cyano ligands and bipyridine or phenanthroline ligands (Ma et al, synthetic metals 94,1998,245).

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

Particularly preferred compounds for use as phosphorescent dopants are, inter alia, the compounds of the formula EM-17 and derivatives thereof, described in US 2001/0053462A 1 and Inorg. chem. (inorganic chemistry) 2001,40(7),1704-1711, JACS 2001,123(18), 4304-4312.

Derivatives are described in US 7378162B 2, US 6835469B 2 and JP 2003/253145 a.

Furthermore, compounds of the formulae EM-18 to EM-21 described in US 7238437B 2, US 2009/008607A 1 and EP 1348711 and derivatives thereof can be used as luminophores.

Quantum dots can also be used as luminophores, these materials being disclosed in detail in WO2011/076314 a 1.

Compounds used as host materials, particularly with luminescent compounds, include materials from a variety of classes of substances.

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

In some cases, the host material is also referred to as a host material, particularly when the host material is used in combination with a phosphorescent emitter in an OLED.

Preferred host or co-host materials for use particularly with fluorescent dopants are selected from the following classes: oligomeric aromatic subunits (e.g. 2,2',7,7' -tetraphenylspirobifluorene according to EP 676461, or dinaphthylanthracene), especially those containing fused aromatic groups, e.g. anthracene, benzanthracene, triphenylene (DE 102009005746, WO 2009/069566), phenanthrene, tetracene, coronene, perylene,

Fluorene, spirofluorene, perylene, phthaloperylene, naphthoperylene, decacycloalkene, rubrene, oligomeric arylenevinylenes (e.g. DPVBi ═ 4,4 '-bis (2, 2-diphenylvinyl) -1,1' -biphenyl or spiro-DPVBi, according to EP 676461), polypental metal complexes (e.g. according to WO 04/081017), in particular metal complexes of 8-hydroxyquinolines, for example AlQ₃(═ tris (8-quinolinolato) aluminium (III)) or bis (2-methyl-8-quinolinolato) - (4-phenylphenoxy) aluminium, as well as imidazole chelates (US 2007/0092753a1) 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 (e.g. according to WO 2005/084081 and WO 2005/084082), atropisomers (e.g. according to WO 2006/048268), boronic acid derivatives (e.g. according to WO2006/117052), or benzanthracenes (e.g. according to WO 2008/145239).

Particularly preferred compounds that can serve as host materials or co-host materials are selected from the class of oligomeric aromatic subunits including anthracene, benzanthracene, and/or pyrene, or atropisomers of these compounds. In the sense of the present invention, oligomeric arylidene means a compound in which at least three aryl or arylidene groups are bonded to one another.

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

Ar⁴-(Ar⁵)_p-Ar⁶ (H-1)

wherein Ar⁴、Ar⁵、Ar⁶Identically or differently on each occurrence, is an aryl or heteroaryl group having 5 to 30 aromatic ring atoms, which groups may optionally be substituted, and p represents an integer in the range from 1 to 5; ar (Ar)⁴、Ar⁵And Ar⁶The sum of the pi electrons is at least 30 when p is 1, at least 36 when p is 2 and at least 42 when p is 3.

In the compound of formula (H-1), the group Ar⁵Particularly preferably anthracene, and the radical Ar⁴And Ar⁶Bonded at the 9 and 10 positions, where these groups may be optionally substituted. Very particularly preferably, the group Ar⁴And/or Ar⁶At least one of which is a fused aryl group selected from 1-or 2-naphthyl, 2-, 3-or 9-phenanthryl, or 2-, 3-, 4-, 5-, 6-or 7-benzanthryl. Anthracene-based compounds are described in US 2007/0092753A 1 and US 2007/0252517A 1, 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-diphenylvinyl) phenyl ] anthracene]Anthracene, 9, 10-diphenylanthracene, 9, 10-bis (phenylethynyl) anthracene, and 1, 4-bis (9' -ethynylanthracenyl) benzene. Preference is also given to compounds containing two anthracene units (U.S. Pat. No. 3, 2008/0193796, 1), for example 10,10' -bis [1,1',4',1 ] " ]Terphenyl-2-yl-9, 9' -dianthracene.

Other preferred compounds are derivatives of: arylamine, styrylamine, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, or the like,

Diazoles, dibenzoyl

Oxazoline,

Azoles, pyridines, pyrazines, imines, benzothiazoles, benzols

Azole, benzimidazoles (US 2007/0092753A1) such as 2,2' - (1,3, 5-phenylene) tris [ 1-phenyl-1H-benzimidazole]Aldazine, stilbene, styrylarylene derivatives, e.g. 9, 10-bis [4- (2, 2-diphenylvinyl) phenyl]Anthracene, and distyrylarylene derivatives (US 5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyrans, thiopyrans, diketopyrrolopyrroles, polymethines, cinnamates and fluorescent dyes.

Particularly preferred are derivatives of arylamines and styrylamine, such as TNB (═ 4,4' -bis [ N- (1-naphthyl) -N- (2-naphthyl) amino)]Biphenyl). Metal-hydroxyquinoline complexes (e.g. LiQ or AlQ)₃) May be used as a co-host.

Preferred compounds as substrates having oligomeric aromatic subunits are disclosed in US 2003/0027016A 1, US 7326371B 2, US 2006/043858A, WO2007/114358, WO 2008/145239, JP 3148176B 2, EP 1009044, US2004/018383, WO 2005/061656A 1, EP 0681019B1, WO 2004/013073A1, US 5077142, WO 2007/065678 and DE 102009005746, with particularly preferred compounds being described by the formulae H-2 to H-8.

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

These compounds which can also be used as structural elements in polymers include CBP (N, N-biscarbazolylbiphenyl), carbazole derivatives (for example according to WO 2005/039246, US2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851), azacarbazoles (for example according to EP 1617710. EP 1617711, EP 1731584 or JP2005/347160), ketones (for example according to WO 2004/093207 or according to DE102008033943), phosphine oxides, sulfoxides and sulfones (for example according to WO 2005/003253), oligophenylenes, aromatic amines (for example according to US 2005/0069729), bipolar matrix materials (for example according to WO 2007/137725), silanes (for example according to WO 2005/111172), 9, 9-diarylfluorene derivatives (for example according to DE 102008017591), azaboroles or borates (for example according to WO 2006/117052), triazine derivatives (for example according to DE 102008036982), indolocarbazole derivatives (for example according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (for example according to DE 102009023155 and DE 102009031021), diazaphosphole derivatives (for example according to DE 102009022858), triazole derivatives,

Azoles and

azole derivatives, imidazole derivatives, polycyclic arylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, aromatic tertiary amines, styrylamine, amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carbodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives such as AlQ₃It may also contain triarylaminophenol ligands (US 2007/0134514 a1), metal complexes/polysilane compounds and thiophene, benzothiophene and dibenzothiophene derivatives.

Examples of preferred carbazole derivatives are mCP (═ 1,3-N, N-dicarbazolylbenzene (═ 9,9'- (1, 3-phenylendiylidene) 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-bis (9H-carbazol-9-yl) biphenyl and CMTTP (formula H-10). Particular mention is made of the compounds disclosed in US 2007/0128467A 1 and US 2005/0249976A 1 (formulae H-11 and H-13).

Preferred tetraaryl-Si compounds are disclosed, for example, in US 2004/0209115, US2004/0209116, US 2007/0087219 a1 and h.gilman, e.a.zuech, Chemistry & Industry (london, uk), 1960,120.

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

Particularly preferred compounds from class 4 for the preparation of matrices for phosphorescent dopants are disclosed in particular in DE 102009022858, DE 102009023155, EP 652273B 1, WO2007/063754 and WO 2008/056746, with particularly preferred compounds being described by the formulae H-22 to H-25.

As for the functional compound which can be used according to the present invention and can serve as a host material, a substance containing at least one nitrogen atom is particularly preferable. It preferably includes aromatic amines, triazine derivatives and carbazole derivatives. The carbazole derivatives thus exhibit, in particular, surprisingly high efficiencies. The triazine derivatives provide unexpectedly long lifetimes for electronic devices.

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

It is also possible to use compounds which improve the transition from the singlet state to the triplet state and which are used to carry functional compounds having emitter properties, improving the phosphorescent properties of these compounds. In particular, carbazole and bridged carbazole dimer units are suitable for this purpose, as described, for example, in WO 2004/070772 a2 and WO 2004/113468 a 1. Ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds are also suitable for this purpose, as described, for example, in WO 2005/040302 a 1.

Herein, the n-type dopant means a reducing agent, i.e., an electron donor. Preferred examples of n-type dopants are W (hpp) according to WO 2005/086251A 2₄And other electron-rich metal complexes, P ═ N compounds (e.g. WO 2012/175535 a1, WO 2012/175219 a1), naphthalenylidene carbodiimides (e.g. WO 2012/168358 a1), fluorenes (e.g. WO 2012/031735a1), free and diradicals (e.g. EP 1837926 a1, WO 2007/107306 a1), pyridines (e.g. EP 2452946 a1, EP 2463927 a1), N-heterocyclic compounds (e.g. WO 2009/000237 a1) and acridines and phenazines (e.g. US 2007/145355 a 1).

Furthermore, the formulation may comprise a wide bandgap material as the functional material. By wide bandgap material is meant a material in the sense of the disclosure of US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.

The band gap of the compound used as the wide band gap material may preferably be 2.5eV or more, preferably 3.0eV or more, particularly preferably 3.5eV or more. The band gap can be calculated in particular by means of the energy levels of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO).

In addition, the formulation may contain a Hole Blocking Material (HBM) as a functional material. A hole-blocking material denotes a material which prevents or minimizes the transport of holes (positive charges) in a multilayer system, in particular if this material is arranged in layers adjacent to the light-emitting layer or the hole-conducting layer. In general, the HOMO level of the hole blocking material is lower than the HOMO level of the hole transporting material in the adjacent layer. The hole blocking layer is typically disposed between the light emitting layer and the electron transport layer in the OLED.

Essentially any known hole blocking material can be used. Except in the present applicationAmong other hole blocking materials described elsewhere, advantageous hole blocking materials are metal complexes (US2003/0068528), such as bis (2-methyl-8-quinolinol) (4-phenylphenoxy) aluminum (III) (BALQ). (III) the facial form of tris (1-phenylpyrazolato-N, C2) Iridium (III) (Ir (ppz)₃) Also for this purpose (US 2003/0175553A 1). Phenanthroline derivatives, such as BCP; or phthalimides such as TMPP.

Further, advantageous hole blocking materials are described in WO 00/70655 a2, WO 01/41512 and WO 01/93642 a 1.

In addition, the formulation may include an Electron Blocking Material (EBM) as a functional material. An electron-blocking material means a material which prevents or minimizes the transport of electrons in a multilayer system, in particular if this material is arranged in layers adjacent to the light-emitting layer or the electron-conducting layer. Generally, the LUMO energy level of an electron blocking material is higher than the LUMO energy level of an electron transporting material in an adjacent layer.

Essentially any known electron blocking material can be used. Among the other electron blocking materials described elsewhere in this application, advantageous electron blocking materials are transition metal complexes, such as Ir (ppz) ₃(US 2003/0175553)。

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

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

Furthermore, functional compounds characterized by a high glass transition temperature are of particular interest. In this connection, particularly preferred functional compounds which can be used as organic functional materials in the formulations are those which have a glass transition temperature, determined in accordance with DIN 51005, of > 70 ℃, preferably > 100 ℃, more preferably > 125 ℃ and most preferably > 150 ℃.

The formulation may also comprise a polymer as the organic functional material. It is also possible to mix the above-mentioned compounds, which generally have a relatively low molecular weight, as organic functional materials, with the polymer. These compounds can also be incorporated covalently into the polymer. This can be achieved in particular with compounds which are substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acids or boronic esters or reactive polymerizable groups such as alkenes or oxetanes. These can be used as monomers for the production of corresponding oligomers, dendrimers or polymers. Here, the oligomerization or polymerization is preferably carried out via halogen functions or boronic acid functions or via polymerizable groups. The polymers may also be crosslinked by such groups. The compounds and polymers according to the invention can be used as crosslinked or uncrosslinked layers.

The polymers which can be used as organic functional materials generally contain units or structural elements described under the meaning of the above-mentioned compounds, in particular units or structural elements disclosed and broadly listed in WO 02/077060A 1, WO 2005/014689A 2 and WO 2011/076314A 1. Which is incorporated by reference in the present application. The functional material may for example be from the following classes:

class 1: structural elements capable of producing hole injection and/or hole transport properties;

class 2: structural elements capable of generating electron injection and/or electron transport properties;

class 3: structural elements combining the properties described with respect to classes 1 and 2;

class 4: a structural element having a light-emitting property, particularly a phosphorescent group;

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

class 6: structural elements that affect the morphology or the emission color of the resulting polymer;

class 7: usually as structural elements of the skeleton.

The structural elements described here may also have a plurality of functions, so that an explicit classification is not necessarily advantageous. For example, the type 1 structural element may also serve as a skeleton.

The polymers having hole-transporting or hole-injecting properties containing structural elements from class 1 used as organic functional materials may preferably contain units corresponding to the hole-transporting or hole-injecting materials described above.

Further preferred structural elements of class 1 are, for example, triarylamines, benzidines, tetraaryl-p-phenylenediamines, carbazoles,

Thiophene, pyrrole and furan derivatives and other O, S or N containing heterocyclic compounds with a high HOMO. The HOMO of these arylamines and heterocyclic compounds is preferably higher than-5.8 eV (relative to the vacuum level), particularly preferably higher than-5.5 eV.

Particularly preferred are polymers having hole-transporting or hole-injecting properties which contain at least one repeating unit of the formula HTP-1:

wherein the symbols have the following meanings:

Ar¹aryl groups which are in each case, identically or differently, single-bonded or monocyclic or polycyclic for the different recurring units, which may be optionally substituted;

Ar²aryl groups which are in each case identical or different, monocyclic or polycyclic for different recurring units, which may be optionally substituted;

Ar³aryl radicals which are in each case, identically or differently, monocyclic or polycyclic for different recurring units, which may be optionally substituted;

m is 1, 2 or 3.

Particular preference is given to recurring units of the formula HTP-1 selected from units of the formulae HTP-1A to HTP-1C:

wherein the symbols have the following meanings:

R^abeing, identically or differently on each occurrence, H, a substituted or unsubstituted aromatic or heteroaromatic radical, alkyl, ring An alkyl group, an alkoxy group, an aralkyl group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a silyl group, or a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxyl group;

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

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

Particularly preferred are polymers having hole-transporting or hole-injecting properties which contain at least one repeating unit of the formula HTP-2:

-(T¹)_c-(Ar⁷)_d-(T²)_e-(Ar⁸)_f-HTP-2

wherein the symbols have the following meanings:

T¹and T²Independently selected from thiophene, selenophene, thieno [2,3-b ]]Thiophene, thieno [3,2-b ]]Thiophene, dithienothiophene, pyrrole and aniline, where these radicals may be substituted by one or more radicals R^bSubstitution;

R^bindependently at each occurrence, is selected from halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C (═ O) NR⁰R⁰⁰、-C(＝O)X、-C(＝O)R⁰、-NH₂、-NR⁰R⁰⁰、-SH、-SR⁰、-SO₃H、-SO₂R⁰、-OH、-NO₂、-CF₃、-SF₅An optionally substituted silyl, carbyl or hydrocarbyl group having 1 to 40 carbon atoms, which group may optionally be substituted and may optionally contain one or more heteroatoms;

R⁰and R⁰⁰Each independently is H or an optionally substituted carbyl or hydrocarbyl group having 1 to 40 carbon atoms, which group may optionally be substituted and may optionally contain one or more heteroatoms;

Ar⁷And Ar⁸Independently of one another, represent a monocyclic or polycyclic aryl or heteroaryl group, which groups may optionally be substituted and may optionally be bonded to one or two adjacent thiophene or selenophene groups at the 2,3 positions;

c and e are independently of each other 0, 1, 2,3 or 4, wherein 1< c + e.ltoreq.6;

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

Preferred examples of polymers having hole-transporting or hole-injecting properties are described in particular in WO 2007/131582a1 and WO 2008/009343a 1.

The polymer having electron injecting and/or electron transporting properties containing a structural element from the group 2 used as the organic functional material may preferably contain units corresponding to the above-mentioned electron injecting and/or electron transporting materials.

Other preferred structural elements of class 2 having electron injecting and/or electron transporting properties are derived from e.g. pyridine, pyrimidine, pyridazine, pyrazine,

Oxadiazoles, quinolines, quinoxalines and phenazines, and triarylborane groups or other O, S or N-containing heterocyclic compounds with a low LUMO energy level. The LUMO of these type 2 structural elements is preferably below-2.7 eV (relative to the vacuum level), particularly preferably below-2.8 eV.

The organic functional material may preferably be a polymer containing a structural element from group 3 in which structural elements for improving hole and electron mobility (i.e., structural elements from groups 1 and 2) are directly connected to each other. Here, some of these structural elements may act as luminophores, wherein the luminescence color may be converted to, for example, green, red or yellow. Their use is therefore advantageous for producing other emission colors or broadband emission, for example from originally blue-emitting polymers.

The polymer having a light-emitting property containing a structural element from the 4 th class used as the organic functional material may preferably contain a unit corresponding to the above-mentioned light-emitting material. Here, polymers containing phosphorescent groups, in particular the above-mentioned luminescent metal complexes, which contain corresponding units comprising elements from groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt) are preferred.

Polymers used as organic functional materials containing a type 5 unit that improves the transition from the so-called singlet state to the triplet state can be preferably used for carrying phosphorescent compounds, preferably polymers containing the above-mentioned type 4 structural elements. A polymer triplet matrix may be used herein.

In particular, carbazoles and linked carbazole dimer units as described, for example, in DE 10304819A 1 and DE 10328627A 1 are suitable for this purpose. Ketones, phosphine oxides, sulfoxides, sulfones and silane derivatives and similar compounds as described, for example, in DE 10349033A 1 are also suitable for this purpose. Furthermore, preferred building blocks may be derived from the compounds described above for the matrix materials used with the phosphorescent compounds.

The other organic functional material is preferably a polymer comprising units of class 6 which influence the morphology and/or the emission color of the polymer. In addition to the above polymers, these polymers are polymers not in the above class having at least one other aromatic structure or another conjugated structure. Thus, these classes have little or no effect on charge carrier mobility, non-organometallic complexes, or singlet-triplet transitions.

This type of structural unit can affect the morphology and/or the emission color of the resulting polymer. Depending on the structural unit, these polymers can therefore also be used as emitters.

Thus, in the case of fluorescent OLEDs, preference is given to aromatic structural elements having 6 to 40C atoms or additionally diphenylacetylene, stilbene or bisstyrylarylene derivative units, each of which may be substituted by one or more radicals. Particular preference is given here to using radicals derived from: 1, 4-phenylene, 1, 4-naphthylene, 1, 4-or 9, 10-anthracenylene, 1,6-, 2, 7-or 4, 9-pyrene, 3, 9-or 3, 10-perylene, 4,4' -biphenylene, 4,4' -terphenylene, 4,4' -bi-1, 1' -naphthylene, 4,4' -diphenylacetylene, 4,4' -stilbenylene or 4,4' -bisstyrylaryl-arylene derivatives.

The polymers used as organic functional materials preferably contain units of the 7 th class, which preferably contain aromatic structures having 6 to 40C atoms, which are frequently used as skeletons.

These include inter alia 4, 5-dihydropyrene derivatives, 4,5,9, 10-tetrahydropyrene derivatives, fluorene derivatives, which are disclosed for example in US 5962631, WO 2006/052457 a2 and WO 2006/118345a1, 9, 9-spirobifluorene derivatives, which are disclosed for example in WO 2003/020790a1, 9, 10-phenanthrene derivatives, which are disclosed for example in WO 2005/104264 a1, 9, 10-dihydrophenanthrene derivatives, which are disclosed for example in WO 2005/014689 a2, 5, 7-dihydrodibenzosuberylene derivatives and cis-and trans-indenofluorene derivatives, which are disclosed for example in WO 2004/041901 a1 and WO 2004/113412 a2, and binaphthylene derivatives, which are disclosed for example in WO 2006/063852 a1, and disclosed for example in WO 2005/056633a1, Other units in EP 1344788A1, WO 2007/043495A1, WO 2005/033174A1, WO 2003/099901A 1 and DE 102006003710.

Particularly preferred type 7 building blocks are selected from fluorene derivatives, as disclosed for example in US 5,962,631, WO 2006/052457 a2 and WO 2006/118345 a1, spirobifluorene derivatives, as disclosed for example in WO 2003/020790 a1, benzofluorene, dibenzofluorene, benzothiophene and dibenzofluorene groups and their derivatives, as disclosed for example in WO 2005/056633 a1, EP 1344788 a1 and WO 2007/043495 a 1.

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

wherein the symbols and indices have the following meanings:

A. b and B' are each, and identically or differently for different repeating units, divalent radicals, preferably selected from the group consisting of-CR^cR^d-、-NR^c-、-PR^c-、-O-、-S-、-SO-、-SO₂-、-CO-、-CS-、-CSe-、-P(＝O)R^c-、-P(＝S)R^c-and-SiR^cR^d-；

R^cAnd R^dIndependently at each occurrence, is selected from H, halo, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C (═ O) NR⁰R⁰⁰、-C(＝O)X、-C(＝O)R⁰、-NH₂、-NR⁰R⁰⁰、-SH、-SR⁰、-SO₃H、-SO₂R⁰、-OH、-NO₂、-CF₃、-SF₅Optionally substituted silyl, carbyl or hydrocarbyl groups having from 1 to 40 carbon atoms which may optionally be substituted and may optionally contain one or more heteroatoms, wherein the group R^cAnd R^dMay optionally form a spiro group with the fluorene group to which it is bonded;

x is halogen;

R⁰and R⁰⁰Each independently is H or an optionally substituted carbyl or hydrocarbyl group having 1 to 40 carbon atoms, which group may optionally be substituted and may optionally contain one or more heteroatoms;

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

m is an integer greater than or equal to 1;

Ar¹and Ar²Independently of one another, represent a monocyclic or polycyclic aryl or heteroaryl group, which may optionally be substituted and may optionally be bonded to the indenofluorene group at the 7,8 or 8,9 position; and is

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

If the group R is^cAnd R^dForms a spiro ring group with the fluorene group to which these groups are bonded, then this group preferably represents spirobifluorene.

Particular preference is given to recurring units of the formula PB-1 selected from units of the formulae PB-1A to PB-1E:

wherein R is^cHas the meaning described above for formula PB-1, R is 0, 1, 2, 3 or 4, and R^eHaving a radical R^cThe same meaning is used.

R^epreferably-F, -Cl, -Br, -I, -CN, -NO₂，-NCO，-NCS，-OCN，-SCN，-C(＝O)NR⁰R⁰⁰，-C(＝O)X，-C(＝O)R⁰，-NR⁰R⁰⁰An optionally substituted silyl, aryl or heteroaryl group having 4 to 40, preferably 6 to 20, C atoms, or a linear, branched or cyclic alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 20, preferably 1 to 12, C atoms, wherein one or more hydrogen atoms may optionally be substituted by F or Cl, and a group R ⁰、R⁰⁰And X has the meaning described above for formula PB-1.

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

wherein the symbols have the following meanings:

l is H, halogen or an optionally fluorinated linear or branched alkyl or alkoxy group having 1 to 12C atoms and preferably represents H, F, methyl, isopropyl, tert-butyl, n-pentyloxy or trifluoromethyl; and is provided with

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

For the practice of the present invention, polymers containing more than one of the above-mentioned structural elements of types 1 to 7 are preferred. Furthermore, it can be provided that the polymer preferably contains more than one structural element from one of the abovementioned classes, i.e. a mixture comprising structural elements from one of the classes.

In particular, polymers which, in addition to at least one structural element having a light-emitting property (class 4), preferably at least one phosphorescent group, additionally contain at least one further structural element of the abovementioned classes 1 to 3, 5 or 6, wherein the structural element is preferably selected from classes 1 to 3, are particularly preferred.

The proportions of the various classes of groups, if present in the polymer, may be within a wide range, where this is known to the person skilled in the art. A surprising advantage is achieved if the proportion of the one class present in the polymer, which is in each case selected from the abovementioned structural elements of classes 1 to 7, is preferably in each case > 5 mol%, particularly preferably in each case > 10 mol%.

The preparation of white-emitting copolymers is described in particular in detail in DE 10343606A 1.

To improve solubility, the polymers may contain corresponding groups. It can be preferably provided that the polymer contains substituents such that on average at least 2 non-aromatic carbon atoms, particularly preferably at least 4 non-aromatic carbon atoms and particularly preferably at least 8 non-aromatic carbon atoms are present per repeating unit, where average means number average. Individual carbon atoms herein may be replaced by O or S, for example. However, a particular proportion of, optionally all, the repeating units may be free of substituents containing non-aromatic carbon atoms. Here, short-chain substituents are preferable because long-chain substituents may have adverse effects on layers that can be obtained using organic functional materials. The substituents preferably contain up to 12 carbon atoms, preferably up to 8 carbon atoms and particularly preferably up to 6 carbon atoms in the straight chain.

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

In another embodiment, the polymer used as the organic functional material may be a non-conjugated polymer with side chains, wherein this embodiment is particularly important for polymer-based phosphorescent OLEDs. In general, phosphorescent polymers may be obtained by free-radical copolymerization of vinyl compounds, wherein these vinyl compounds contain at least one unit with a phosphorescent emitter and/or at least one charge transport unit, as disclosed in particular in US 7250226B 2. Other phosphorescent polymers are described in particular in JP 2007/211243A 2, JP 2007/197574A 2, US 7250226B 2 and JP 2007/059939A.

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

In another preferred embodiment, the non-conjugated polymer can be designed as a fluorescent emitter. Preferred fluorescent emitters based on non-conjugated polymers with side chains contain anthracene or benzanthracene groups or derivatives of these groups in the side chain, wherein these polymers are disclosed in e.g. JP2005/108556, JP 2005/285661 and JP 2003/338375.

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

Furthermore, in the case of polymeric compounds, the molecular weight M of the functional compounds used as organic functional materials in the preparation_wPreference is given to. gtoreq.10,000 g/mol, particularly preferably. gtoreq.20,000 g/mol and very particularly preferably. gtoreq.50,000 g/mol.

Here, the molecular weight M of the polymer_wPreferably in the range from 10,000g/mol to 2,000,000g/mol, particularly preferably in the range from 20,000g/mol to 1,000,000g/mol and very particularly preferably in the range from 50,000g/mol to 300,000 g/mol. Molecular weight M_wDetermined by means of GPC (gel permeation chromatography) against internal polystyrene standards.

The publications cited above, which describe functional compounds, are incorporated by reference into this application for the purpose of disclosure.

The formulations according to the invention may comprise all organic functional materials required for the manufacture of the corresponding functional layers of the electronic device. For example, if the hole transporting, hole injecting, electron transporting or electron injecting layer is built up from exactly one functional compound, the formulation contains exactly this compound as organic functional material. If the light-emitting layer comprises, for example, a combination of a luminophore and a matrix or host material, the formulation comprises exactly the mixture of luminophore and matrix or host material as organic functional material, as described in more detail elsewhere in this application.

In addition to the components, the formulations according to the invention may comprise further additives and processing aids. These include, inter alia, surface-active substances (surfactants), lubricants and greases, viscosity-regulating additives, conductivity-improving additives, dispersants, hydrophobicizing agents, adhesion promoters, flow improvers, defoamers, deaerators, reactive or nonreactive diluents, fillers, auxiliaries, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.

The invention furthermore relates to a process for preparing the formulations according to the invention, wherein the at least first organic solvent, the 1, 1-diphenylethylene derivative and the at least one organic functional material, which can be used for manufacturing functional layers of electronic devices, are mixed.

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

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

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

The functional layer can be produced, for example, by flood coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, rotary printing, roller coating, flexographic printing, offset printing or nozzle printing, preferably 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 carried out in order to remove the solvent from the above-mentioned continuous phase. Drying may preferably be carried out at a relatively low temperature for a relatively long time to avoid bubble formation and to obtain a uniform coating. The drying may preferably be carried out at a temperature in the range of from 80 ℃ to 300 ℃, more preferably from 150 ℃ to 250 ℃ and most preferably from 160 ℃ to 200 ℃. Here, the drying may preferably be at 10^-6In the range of mbar to 2 bar, more preferably in the range of 10^-2In the range of mbar to 1 bar and most preferably at 10^-1At a pressure in the range from mbar to 100 mbar. The temperature of the substrate may range from-15 ℃ to 250 ℃ during the drying process. The duration of drying depends on the degree of drying to be achieved, wherein small amounts of water can optionally be removed in combination with sintering at relatively high temperatures, sintering being preferably carried out.

It may also be provided that the process is repeated a plurality of times to form a plurality of functional layers that are different or the same. Here, crosslinking of the formed functional layer can be carried out to prevent its dissolution, as disclosed for example in EP 0637899 a 1.

The invention also relates to an electronic device, which is obtainable by a method of manufacturing an electronic device.

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

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

Active components are generally organic or inorganic materials introduced between the anode and the cathode, wherein these active components enable, maintain and/or improve the properties of the electronic device, such as its performance and/or its lifetime, for example charge injection, charge transport or charge blocking materials, but in particular light emitting materials and host materials. Thus, organic functional materials that may be used to fabricate functional layers of an electronic device preferably comprise the active components of the electronic device.

An organic electroluminescent device is one preferred embodiment of the present invention. The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer.

Furthermore, it is preferred to use mixtures of two or more triplet emitters with a matrix. The triplet emitter with the shorter-wave emission spectrum serves here as a co-host for the triplet emitter with the longer-wave emission spectrum.

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

Accordingly, the proportion of the dopant is preferably 0.1 to 50 vol%, more preferably 0.5 to 20 vol% and most preferably 0.5 to 8 vol% for the fluorescent light-emitting layer, and 3 to 15 vol% for the phosphorescent light-emitting layer.

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

The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Here, one of the two materials is preferably a material having a hole transporting property, and the other material is a material having an electron transporting property. However, the desired electron transporting and hole transporting properties of the mixed matrix component may also be combined primarily or entirely in a single mixed matrix component, with the other mixed matrix component or components fulfilling other functions. Here, the two different matrix materials may be present 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. The mixed matrix system is preferably used in phosphorescent organic electroluminescent devices. Further details regarding mixed matrix systems can be found, for example, in WO 2010/108579.

In addition to these layers, the Organic electroluminescent Device may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers, Charge-generating layers (IDMC 2003, Taiwan; Session 21OLED (5), T.Matsumoto, T.Nakada, J.endo, K.Mori, N.Kawamura, A.Yokoi, J.Kido, Multiphoron Organic EL Device Having Charge Generation Layer) and/or Organic or inorganic p/n junctions. Here, one or more hole transport layers may be used, for example, with metal oxides (e.g., MoO) ₃Or WO₃) Or p-type doped with a (per) fluorinated electron deficient aromatic compound and/or one or more electron transport layers may be n-type doped. An intermediate layer may also be introduced between the two light-emitting layers, which intermediate layer has, for example, an exciton blocking function and/or controls the charge balance in the electroluminescent device. However, it should be noted that each of these layers need not be present. As defined above, these layers may also be present when using the formulation according to the invention.

In another embodiment of the present invention, the device comprises a plurality of layers. The formulations according to the invention can preferably be used here for the production of hole-transport layers, hole-injection layers, electron-transport layers, electron-injection layers and/or light-emitting layers.

The invention therefore also relates to an electronic device comprising at least three layers, but in a preferred embodiment the electronic device comprises all of said layers from the group of hole injection, hole transport, light emission, electron transport, electron injection, charge blocking and/or charge generation layers, and wherein at least one layer has been obtained by means of a formulation to be used according to the invention. The thickness of the layer, e.g. the hole transporting and/or hole injecting layer, may preferably be in the range of 1nm to 500nm, more preferably in the range of 2nm to 200 nm.

The device may also comprise a layer built up from other low molecular weight compounds or polymers, which layer has not been applied by using the formulation according to the invention. These can also be made by evaporating low molecular weight compounds in a high vacuum.

In addition, it may be preferred to use compounds which are not used in pure form but in the form of mixtures (blends) with other polymers, oligomers, dendrimers or low molecular weight substances of any desired type. These may for example improve the electronic properties or emit light itself.

In a preferred embodiment of the present invention, the formulation according to the invention comprises an organic functional material which serves as host material or matrix material in the light-emitting layer. Here, the preparation may contain the above-described luminophores in addition to the host material or matrix material. Here, the organic electroluminescent device may include one or more light emitting layers. If a plurality of light emitting layers are present, these light emitting layers preferably have a plurality of light emission peaks between 380nm and 750nm, so that a plurality of light emitting compounds capable of emitting white light overall, that is, capable of emitting fluorescence or phosphorescence are used in the light emitting layers. Very particular preference is given to three-layer systems in which the three layers exhibit blue, green and orange or red luminescence (for the basic structure, see, for example, WO 2005/011013). White light emitting devices are for example suitable for use as backlights for LCD displays or for general lighting applications.

A plurality of OLEDs can also be arranged in a stacked manner, so that the efficiency with respect to the light output to be achieved is further increased.

In order to improve the coupling-out of light, the final organic layer on the light exit side in an OLED can, for example, also be in the form of a nanofoam, which leads to a reduction in the proportion of total reflection.

Also preferred are the following organic electroluminescent devicesPiece, wherein one or more layers are applied by means of a sublimation process, by passing them in a vacuum sublimation unit at a temperature below 10 deg.C^-5Mbar, preferably below 10^-6Mbar, more preferably below 10^-7Vapor deposition at a pressure of mbar to apply the material.

It may also be provided that one or more layers of the electronic device according to the invention are applied by means of the OVPD (organic vapor deposition) method or by means of carrier gas sublimation, where 10 is^-5The material is applied at a pressure of mbar to 1 bar.

It may also be provided that one or more layers of the electronic device according to the invention are produced from solution, for example by spin coating or by means of any desired printing method, such as screen printing, flexographic printing or offset printing, but particularly preferably LITI (photo-induced thermal imaging, thermal transfer) or inkjet printing.

These layers can also be applied by methods which do not use compounds of the formulae (I), (II), (III). Orthogonal solvents can preferably be used here which, although dissolving the functional material of the layer to be applied, do not dissolve the layer to which the functional material is applied.

The device typically comprises a cathode and an anode (electrode). For the purposes of the present invention, the electrodes (cathode, anode) are chosen such that their band energies correspond as closely as possible to the band energies of the adjacent organic layers, in order to ensure efficient electron or hole injection.

The cathode preferably comprises a metal complex, a metal with a low work function, a metal alloy or a multilayer structure comprising a plurality of metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). In the case of a multilayer structure, in addition to the metals, other metals having a relatively high work function, such as Ag and Ag nanowires (Ag NWs), can also be used, in which case combinations of metals, such as Ca/Ag or Ba/Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal fluorides or alkaline earth metal fluorides, and the corresponding oxides (examples)Such as LiF, Li₂O、BaF₂MgO, NaF, etc.). The layer thickness of this layer is preferably from 0.1nm to 10nm, more preferably from 0.2nm to 8nm, particularly preferably from 0.5nm to 5 nm.

The anode preferably comprises a material having a high work function. The anode preferably has an electrical potential greater than 4.5eV relative to vacuum. On the one hand, metals with a high redox potential, such as Ag, Pt or Au, are suitable for this purpose. On the other hand, metal/metal oxide electrodes (e.g., Al/Ni/NiO) may also be preferred_x、Al/PtO_x). For some applications, at least one of the electrodes must be transparent in order to facilitate the radiation (O-SC) or the out-coupling of light (OLED/PLED, O-laser) of the organic material. A preferred configuration uses a transparent anode. Preferred anode materials herein are conductive mixed metal oxides. Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) is particularly preferable. Furthermore, electrically conductive doped organic materials are preferred, in particular electrically conductive doped polymers such as poly (ethylenedioxythiophene) (PEDOT) and Polyaniline (PANI) or derivatives of these polymers. Furthermore, a p-type doped hole transport material is preferably applied to the anode as a hole injection layer, wherein a suitable p-type dopant is a metal oxide (e.g. MoO)₃Or WO₃) Or (per) fluorinated electron-deficient aromatic compounds. Other suitable p-type dopants are HAT-CN (hexacyanohexanazaterphenyl) or the compound NPD9 (from Novaled). This type of layer simplifies hole injection in materials with low HOMO (i.e., HOMO with large values).

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

Depending on the application, the components are correspondingly structured in a manner known per se, contact points are provided and finally hermetically sealed, since the lifetime of such components is drastically shortened in the presence of water and/or air.

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

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

2. The formulations according to the invention can be prepared and processed using conventional methods, so that cost advantages can also be achieved.

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

4. The coatings obtainable using the formulations of the invention exhibit excellent quality, especially with respect to the uniformity of the coating.

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

It should be noted that variations of the embodiments described in the present invention fall within the scope of the invention. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose, unless expressly excluded. Thus, unless otherwise specified, each feature disclosed in this disclosure should be viewed as a generic series of examples or as equivalent or similar features.

All features of the invention may be combined with each other in any manner, except where certain features and/or steps are mutually exclusive. This applies in particular to the preferred features of the invention. Likewise, features that are not necessarily combined may be used separately (rather than in combination).

It should also be noted that many of the features, particularly those of the preferred embodiments of the invention, are inventive in their own right and should not be considered as part of an embodiment of the invention only. Independent protection may be sought for these features in addition to, or as an alternative to, the presently claimed inventions.

The teachings of the disclosed technology acts can be refined and combined with other examples.

The present invention is illustrated in more detail below with reference to examples, but the present invention is not limited thereto.

A person skilled in the art will be able to use this description to manufacture other electronic devices according to the invention without inventive effort, whereby the invention can be implemented within the scope of the claims.

Example-device Performance

Two devices were fabricated using the device structure shown in fig. 1, in which the abbreviations ETL, EML, HTL, and HIL represent an electron transport layer, an emission layer, a hole transport layer, and a hole injection layer, respectively. The green light emitting layer (G-EML) was prepared using N, N-tetraethylthioamide (example 1) and 3-phenoxytoluene (reference example 1). The solvent used for the HTL, HTM-1 was 3-phenoxytoluene. Table 2 summarizes the concentration, viscosity and surface tension of the inks used as the green light emitting layer materials.

Table 2. concentration, viscosity and surface tension of the inks for G-EML.

The viscosity of the formulations and solvents was measured using a 1 ° cone-plate rotational rheometer (type: Haake MARS III rheometer from seemer Scientific), with precise control of temperature and shear rate. The viscosities given in Table 2 are at a temperature of 25 ℃ (+/-0.2 ℃) and 500s^-1The viscosity of each formulation measured at a shear rate of (a). The measurements were performed using the following settings: haake MARS III rheometer, bottom plate TMP60 and cone C60/1 ° Ti l.; n is a radical of ₂Supply with a back pressure of-1.8 bar; the sample volume was 1.3 ml. Each formulation was measured in triplicate. The viscosity value is the average of the measured values. Data processing was carried out according to DIN 1342-2 using the software "Haake RheoWin Job Manager". The device (Haake MARS III from seemer technologies) was calibrated periodically by seemer technologies and was calibrated by a certified standard factory before first use.

Surface tension measurements were performed using a high precision droplet shape analysis tool DSA100 from kruss GmbH. The surface tension was determined by the software "DSA 4" according to DIN 55660-1. All measurements were performed at room temperature ranging between 22 ℃ and 24 ℃. The standard procedure involved determining the surface tension (sample volume 0.3ml) of each formulation using a new disposable drop dispensing system (syringe and needle). Each droplet was measured over a one minute duration, sixty measurements were taken, and then averaged. For each formulation, three droplets were measured. The final value is the average taken over the measurements. The tool is periodically checked against a plurality of liquids having known surface tensions.

Description of the manufacturing method

The glass substrate covered with the pre-structured ITO and bank material was cleaned with ultrasound in isopropanol, then cleaned in de-ionised water, then dried using an air gun, and subsequently annealed on a hot plate at 230 ℃ for 2 hours.

A Hole Injection Layer (HIL) using PEDOT-PSS (Clevios Al4083, Heley) was ink jet printed onto a substrate and dried in vacuo. The HIL was then annealed in air at 185 ℃ for 30 minutes.

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

the green emitting layer (G-EML) was also inkjet printed, vacuum dried and annealed at 140 ℃ in a nitrogen atmosphere for 10 minutes. The ink for the green light emitting layer contained two host materials (i.e., HM-1 and HM-2) and one triplet emitter (EM-1) in all examples. The materials were used in the following ratios: HM-1: HM-2: EM-1: 40: 20. As can be seen from table 2 above, only the solvent differed between the examples. The structure of the material is as follows:

all inkjet printing processes were carried out under yellow light and ambient conditions.

The device was then transferred to a vacuum deposition chamber where the deposition of the common Hole Blocking Layer (HBL), Electron Transport Layer (ETL) and cathode (Al) was performed using thermal evaporation (see fig. 1). These devices were then characterized in a glove box.

In the Hole Blocking Layer (HBL), ETM-1 is used as a hole blocking material. 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 8-hydroxyquinoline lithium.

Finally, an Al electrode was vapor deposited. The devices were then packaged in a glove box and physically characterized in ambient air. Fig. 1 shows a device structure.

The device is driven by a constant voltage supplied by a Keithley 230 voltage source. The voltage across the device and the current through the device were measured with two Keithley 199 DMM multimeters. The SPL-025Y luminance sensor (a combination of a photodiode and a photon filter) is used to detect the luminance of the device. The photocurrent was measured with a Keithley 617 electrometer. For spectroscopy, the brightness sensor was replaced with a fiberglass connected to the spectrometer input. Device lifetime is measured at a given current using initial brightness. The brightness is then measured over time by a calibrated photodiode.

Results and discussion

Table 3 summarizes the device performance. The device in the examples (N, N-tetraethylsulfamide) shows good performance, which means good values of voltage, efficiency and lifetime. The performance of the device according to the invention is superior to that of the comparative example (reference example 1, comprising 3-phenoxytoluene). The solvent system provides an alternative to inkjet printing techniques to meet device requirements in terms of performance. It also provides the opportunity to use different print heads to assemble a variety of inkjet printers, since a wide variety of solvents from the series can be used.

Table 3: luminance efficiency, external quantum efficiency, operating voltage and device lifetime

Claims (14)

1. A formulation comprising at least one organic functional material and a first organic solvent, wherein the first organic solvent is a compound according to formula (II):

wherein

R¹And R²Identical or different at each occurrence to a linear alkyl radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl radical having from 3 to 20 carbon atoms, in which one or more non-adjacent CH' s₂The radicals being optionally substituted by-O-, -S-, -NR⁶-、-CONR⁶-, -CO-O-, -C ═ O-, -CH ═ CH-or-C ≡ C-and in which one or more hydrogen atoms may be replaced by F, or an aryl or heteroaryl group having 2 to 60 carbon atoms in which any of the above alkyl, aryl and heteroaryl groups may be substituted by one or more R ⁶Is substituted by radicals, and wherein R¹And R²And together may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system;

R⁴and R⁵Identical or different at each occurrence to a linear alkyl radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl radical having from 3 to 20 carbon atoms, in which one or more non-adjacent CH' s₂The radicals being optionally substituted by-O-, -S-, -NR-⁶-、-CONR⁶-, -CO-O-, -C ═ O-, -CH ═ CH-or-C ≡ C-and in which one or more hydrogen atoms may be replaced by F, or aryl or heteroaryl groups having 2 to 60 carbon atoms in which the above alkyl, aryl and heteroaryl groups may be replaced by one or more R⁶Substitution of radicals;

R⁶identical or different on each occurrence and is H, a straight-chain alkyl or alkoxy radical having from 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy radical having from 3 to 20 carbon atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO₂An aryl or heteroaryl group instead of, or having 4 to 14 carbon atoms;

wherein the at least one organic functional material is an organic semiconductor selected from hole injection, hole transport and light emitting materials;

wherein the first organic solvent has a boiling point in the range of 100 ℃ to 400 ℃, the first organic solvent being a liquid at room temperature;

Wherein the formulation has a mPa of between 0.8^.s to 50mPa^.Viscosity in the s range.

2. The formulation of claim 1, wherein R in formula (II)¹And R²Are the same.

3. The formulation of claim 1, wherein R¹、R²、R⁴And R⁵Selected from linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein one or more non-adjacent CH groups₂The radicals being optionally substituted by-O-, -S-, -NR⁶-、-CONR⁶-, -CO-O-, -C ═ O-, -CH ═ CH-or-C ≡ C-, and in which one or more hydrogen atoms may be replaced by F, where the above groups may be substituted by one or more R⁶And (4) substituting the group.

4. The formulation of claim 1, wherein R¹、R²、R⁴And R⁵Selected from linear alkyl groups having 1 to 20 carbon atoms, wherein the linear alkyl group may be substituted with one or more R⁶And (4) substituting the group.

5. The formulation of claim 1, wherein the first solvent has a surface tension of ≥ 20 mN/m.

6. The formulation of claim 1, wherein the first solvent is present in an amount ranging from 50% to 100% by volume, based on the total amount of solvent in the formulation.

7. The formulation of claim 1, wherein the first solvent has a boiling point in the range of 100 ℃ to 350 ℃.

8. The formulation of claim 1, wherein the formulation comprises at least one second solvent, the second solvent being different from the first solvent.

9. The formulation of claim 8, wherein the second solvent has a boiling point in the range of 100 ℃ to 400 ℃.

10. The formulation according to claim 8, wherein the solubility of the at least one organic functional material in the first and second solvents is in the range of 1 to 250 g/l.

11. The formulation of claim 1, wherein the formulation has a surface tension in the range of 10mN/m to 50 mN/m.

12. The formulation as claimed in claim 1, wherein the content of the 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.

13. The formulation of claim 1, wherein the hole injecting and hole transporting material is a polymeric compound or a blend of a polymeric compound and a non-polymeric compound.

14. A method for producing an electroluminescent device, wherein at least one layer of the electroluminescent device is produced in the following manner: depositing a formulation according to any one of claims 1 to 13 on a surface and subsequently drying.

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