JP2023552761A - Methods for ink-based and inkjet printing - Google Patents

Abstract

The present application describes a first formulation comprising: a) at least one first film-forming organic functional material and at least one first organic solvent; b) at least one first organic functional material; 2 and at least one second organic solvent, the ink system comprising: (i) the first and second organic solvents are different from each other; (ii) the first film-forming organic functional material has a dissolution time in the second organic solvent of more than 15 minutes, preferably more than 30 minutes, more preferably more than 60 minutes, and the dissolution time is at room temperature. An ink system is provided, characterized in that the concentration of the first film-forming organic functional material in the second organic solvent is 7 g/L.

Description

field of invention

The present invention is in the field of inkjet printing and relates to ink systems. The invention also relates to an inkjet printing method by application of the mentioned ink system. The invention furthermore relates to a method for producing functional layers of organic light emitting diodes (OLEDs) and for producing OLEDs, in particular full-color OLED displays, by carrying out the mentioned inkjet printing method.

OLED (organic light emitting diode) displays are extremely thin, lightweight, and energy efficient. These displays deliver perfect images from any viewing angle, with exceptional color vibrancy and extremely high contrast. Due to their low energy consumption, small OLED displays are well suited for use in portable devices, such as smartphones, digital frames and digital cameras. OLED displays are suitable for televisions, monitors, large area video walls and automotive applications. Flexible or rollable displays for everyone are not just a pipe dream, they are already in development.

OLED displays consist of an array of individually controlled light emitting elements or pixels. For full-color displays, each pixel consists of red, green, and blue (RGB) subpixels that can be individually controlled to collectively produce the desired image. In this regard, there are two main approaches to RGB color patterning in OLED displays: (a) side-by-side RGB OLEDs; (b) white OLEDs with added color filters. In the first approach, each pixel consists of RGB OLED sub-pixels and all light output of each device contributes directly to the final image unaltered; in the latter, three white OLED sub-pixels Combined with color filters.

The basic OLED cell structure forming an RGB OLED generally consists of depositing organic semiconductor molecules between conductive electrodes on a glass or flexible film substrate. When a current flows between the electrodes, electrons and holes are injected into the organic semiconductor, and when they recombine in pairs, excitons are generated and the organic molecules become electrically excited. Organic molecules return from their electrically excited state to their ground state by emitting light. The color of the emitted light is determined by the molecular structure of the semiconductor used. Specifically, the OLED stack includes multiple functional organic layers, including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer and an electron injection layer. All of these layers are located between the anode and cathode.
OLED structure breakdown:
- Substrate (can be plastic, glass or metal foil) - is the base of the OLED.
- Anode (which may or may not be transparent, depending on the type of OLED) - carries a positive charge and injects holes (lack of electrons) into the organic layers that make up the OLED device.
- Hole injection layer (HIL) - Deposited on top of the anode, this layer receives holes from the anode and injects them deeper into the device.
- Hole Transport Layer (HTL) - This layer assists in the transport of holes across this layer so that they can reach the emissive layer.
- Emissive Layer (EML) - The heart of the device and where the light originates, the emissive layer consists of a color-defining phosphor doped into the host. A luminescent layer is a layer in which electrical energy is directly converted into light.
- Electron transport layer (ETL) - assists in the transport of electrons across this layer so that they can reach the emissive layer.
- Electron injection layer (EIL) - This layer receives electrons from the cathode and injects them deeper into the device.
- Cathode (may or may not be transparent, depending on the type of OLED) - carries a negative charge and injects electrons into the organic layers that make up the OLED device.
OLED Structure The side-by-side approach provides better power consumption efficiency because the entire light output of each device is utilized for image generation. However, this approach requires assembling RGB OLEDs side-by-side on the same substrate. As organic semiconductors are generally not amenable to photolithographic methods due to being easily damaged by solvents, assembling OLEDs of different materials on the same substrate is a challenge due to the thermal isolation of OLED materials using a shadow mask. It can be done only by vapor deposition or, in the case of polymers and solution processable small molecule materials, only through printing-based techniques, such as inkjet printing.

Display manufacturers have great interest in OLEDs for display applications. There is particular interest in inkjet printed OLEDs because of their great potential for higher performance and potentially lower manufacturing costs. The advantages of using inkjet techniques are very precise positioning, control of ink volume, and potentially high throughput for high volume production. To sustain high productivity, a maximum number of inks are printed in the same cycle of manufacture, eg all three emissive layer materials (inks) are printed and dried at the same time.

To optimize performance for each color, display manufacturers tend to select the best inks from different ink suppliers, containing different deposition materials and different solvent systems. However, this may result in poor pixel profiles, especially if the layers in adjacent pixels are formed by different solvent systems. Specifically, as described below, during the drying process of two or more different solvents, one of the solvent vapors affects the adjacent pixel, causing the formation of the adjacent pixel to change as shown in Figure 1. Damage to film formation occurs, including premature deposition of film material or even dewetting of adjacent pixels.

Improved methods are applied to prevent adverse solvent interactions during the drying process. Specifically, one ink (ink A at pixel A) is first printed and dried by vacuum drying to form a film, as described below. Another ink (ink B at pixel B) is then printed and dried by vacuum drying. However, a problem with this approach may still be that the film at pixel A is affected by solvent vapor during printing or drying, as shown in FIG.

In view of this, the prior art provides ink systems to prevent the negative effects of the solvent of one ink on films formed from other inks, thus achieving uniform film formation. It is urgently needed.

This application contains the following ingredients:
a) a first formulation comprising at least one first film-forming organic functional material and at least one first organic solvent;
b) an ink system comprising or consisting of a second formulation comprising at least one second film-forming organic functional material and at least one second organic solvent;
(i) the first and second organic solvents are different from each other;
(ii) the first film-forming organic functional material has a dissolution time in the second organic solvent of more than 15 minutes, preferably more than 30 minutes, more preferably more than 60 minutes, and the dissolution time is at room temperature. , 7 g/L of the first film-forming organic functional material in the second organic solvent.

In a preferred embodiment, the ink system of the present application further comprises a third formulation comprising at least one third film-forming organic functional material and at least one third organic solvent; The organic solvent is different from the first and second organic solvents, and the first and second film-forming organic functional materials are both in the third solvent for more than 15 minutes, preferably for more than 30 minutes. Preferably it has a dissolution time of more than 60 minutes, the dissolution time being determined at room temperature and at a concentration of 7 g/L.

The invention further provides a method for inkjet printing, comprising:
a) preparing the substrate;
b) printing a first formulation of the ink system of claim 1 onto a first type of pixel;
c) drying the first formulation in the first type of pixels;
d) printing a second formulation of the ink system of claim 1 on a second type of pixel, and e) drying the second formulation on the second type of pixel, or The present invention relates to a method comprising the above.

The invention furthermore relates to a method for producing a functional layer of an organic light emitting diode (OLED), in which the functional layer is formed by an inkjet printing method according to the invention or by using said inkjet printing method and by other deposition techniques, e.g. It relates to a method produced by carrying out a combination with vacuum evaporation/deposition.

This application also
a) preparing a pair of electrodes;
b) a method for manufacturing an OLED comprising or consisting of the step of providing a functional layer between electrodes, the method comprising:
The present invention relates to a method in which at least one functional layer is produced by implementing the inkjet printing method of the invention.

Surprisingly, it has been found that by application of the method according to the present application, the profile of the first type of pixels remains smooth and uniform during the printing and drying process of the second formulation. As a result, printing yield and efficiency can be increased. Furthermore, by application of the method according to the present application, the functional layers of organic light emitting diodes (OLEDs) obtained have a long lifetime.

FIG. 6 illustrates a case where one of the solvent vapors affects an adjacent pixel during a drying process of two or more different solvents. Indicates when printing or drying is affected by solvent vapor. Show profile comparison.

Detailed description of the invention

Inks - Formulation According to the present application, the first formulation, the second formulation and optionally the third formulation are different in that the solvents are different from each other.

According to the present application, the term "at least" is understood as one, two, three, four, five and more.

According to the present application, the term film-forming organic functional material includes, inter alia, organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light-absorbing compounds, organic photosensitive compounds, organic photosensitizers, and Represents other organic photoactive compounds. The term organic functional material further includes organometallic complexes of transition metals, rare earths, lanthanides, and actinides.

The film-forming organic functional material preferably includes a fluorescent emitter, a phosphorescent emitter, a host material, a matrix material, an exciton blocking material, an electron transport material, an electron injection material, a hole transport material, a hole injection material, and an n-dopant. , p-dopants, wide band gap materials, electron blocking materials, and hole blocking materials.

Preferred embodiments of the film-forming organic functional material are further disclosed in detail in WO2011/076314A1.

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

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

Film-forming organic functional materials are often described in terms of frontier orbital properties, which are described in more detail below. Molecular orbitals, especially the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy levels, and the energy of the lowest triplet state T ₁ or the lowest excited singlet state S ₁ of a material can be determined using quantum chemistry. It can be evaluated based on calculations. To calculate these properties for metal-free organic materials, structure optimization is first performed using the "ground state/semi-empirical/default spin/AM1/charge 0/spin singlet" method. Energy calculations are then performed based on the optimized structure. The "TD-SCF/DFT/default spin/B3PW91" method with the "6-31G(d)" basis set (charge 0, spin singlet) is used here. For metal-containing compounds, the structure is optimized by the "ground state/Hartree-Fock/default spin/LanL2MB/0 charge/spin singlet" method. Energy calculations are performed in the same way as for organic substances described above, except that for metal atoms, the "LanL2DZ" basis set is used, and for ligands, the "6-31G(d)" basis set is used. There is a difference in that. The energy calculation yields the HOMO energy level HEh or the LUMO energy level LEh in Hartree units. The HOMO and LUMO energy levels in electron volts, calibrated with reference to cyclic voltammetry measurements, are then determined as follows:
HOMO (eV) = ((HEh ^* 27.212) - 0.9899) / 1.1206
LUMO (eV) = ((LEh ^* 27.212) - 2.0041) / 1.385
For purposes of this application, these values will be considered the HOMO and LUMO energy levels of the material, respectively.

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

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

The method described here is independent of the software package used and always gives the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem4.1 (Q-Chem, Inc.).

Compounds with hole-injecting properties, also referred to herein as hole-injecting materials, simplify or promote the transfer of holes, ie, positive charges, from the anode to the organic layer. The hole-injecting material has a HOMO level that lies above the region of the anode level, ie generally at least -5.3 eV.

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

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

Compounds with hole injection and/or hole transport properties include phenylenediamine derivatives (US3615404), arylamine derivatives (US3567450), amino-substituted chalcone derivatives (US3526501), styryl anthracene derivatives (JP-A-56-46234), Polycyclic aromatic compounds (EP1009041), polyarylalkane derivatives (US3615402), fluorenone derivatives (JP-A-54-110837), hydrazone derivatives (US3717462), acylhydrazone, stilbene derivatives (JP-A-61-210363) , silazane derivatives (US4950950), polysilanes (JP-A-2-204996), aniline copolymers (JP-A-2-282263), thiophene oligomers (JP-A-1989-211399), polythiophene, poly(N- vinylcarbazole) (PVK), polypyrrole, polyaniline, and other conductive polymers, porphyrin compounds (JP-A-63-2956965, US4720432), aromatic dimethylidene type compounds, carbazole compounds such as CDBP, CBP, mCP, etc. Particular mention may be made of aromatic tertiary amines and styrylamine compounds (US 4,127,412), such as triphenylamine of the benzidine type, triphenylamine of the styrylamine type and triphenylamine of the diamine type. Arylamine dendrimers (JP 8 (1996)-193191), monomeric triarylamines (US3180730), triarylamines containing at least one functional group containing one or more vinyl radicals and/or active hydrogen ( US 3,567,450 and US 3,658,520) or tetraaryl diamines (in which the two tertiary amine units are linked via an aryl group). More triarylamino groups may be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives, such as dipyrazino[2,3-f:2',3'-h]quinoxaline hexacarbonitrile.

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

Triarylamine compounds of the following formulas (TA-1) to (TA-12) are particularly preferred, and are those described in EP1162193B1, EP650955B1, Synth. Metals1997, 91(1-3), 209, DE19646119A1, WO2006/122630A1, EP1860097A1, EP1834945A1, JP08053397A, US6251531B1, US2005/0221124, JP082925 86A, US7399537B2, US2006/0061265A1, EP1661888, and WO2009/041635. The compounds of formulas (TA-1) to (TA-12) may be substituted.

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

These arylamines and heterocyclic compounds commonly utilized as hole-injecting and/or hole-transporting materials preferably have a voltage above −5.8 eV (vs. vacuum level) in the polymer, particularly preferably This results in a HOMO greater than -5.5 eV.

Compounds with electron-injecting and/or electron-transporting properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide and Phenazines and their derivatives, as well as triarylboranes and further O-, S- or N-containing heterocyclic compounds with low LUMO (LUMO=lowest unoccupied molecular orbital).

Compounds which are particularly suitable for electron transporting and electron injecting layers are metal chelates of 8-hydroxyquinoline (eg LiQ, AlQ ₃ , GaQ ₃ , MgQ ₂ , ZnQ ₂ , InQ ₃ , ZrQ ₄ ), BAlQ, Ga oxinoid complexes, 4-Azaphenanthren-5-ol-Be complexes (US5529853A, see formula ET-1), butadiene derivatives (US4356429), heterocyclic optical brighteners (US4539507), benzimidazole derivatives (US2007/0273272A1), for example TPBI ( US 5766779, formula ET-2), 1,3,5-triazines, such as spirobifluorenyl triazine derivatives (e.g. according to DE 102008064200), pyrene, anthracene, tetracene, fluorene, spirofluorene, dendrimers, tetracene (e.g. rubrene derivatives) ), 1,10-phenanthroline derivatives (JP2003-115387, JP2004-311184, JP2001-267080, WO02/043449), silacyclopentadiene derivatives (EP1480280, EP1478032, EP1469533), borane derivatives, e.g. Si-containing triary Ruborane derivative (US2007/0087219A1, see formula ET-3), pyridine derivatives (JP2004-200162), phenanthroline, especially 1,10-phenanthroline derivatives, such as BCP and Bphen, further linked via biphenyl or other aromatic groups. (US2007-0252517A1) or phenanthroline linked to anthracene (US2007-0122656A1, see formulas ET-4 and ET-5).

Also suitable are heterocyclic organic compounds, such as thiopyrane dioxide, oxazole, triazole, imidazole or oxadiazole. N-containing five-membered rings, such as oxazole, preferably 1,3,4-oxadiazole, such as formulas ET-6, ET-7, ET-8 and ET-9 as disclosed inter alia in US 2007/0273272A1 Examples of the use of thiazoles, oxadiazoles, thiadiazoles, triazoles are inter alia US 2008/0102311A1 and Y. A. Levin, M. S. Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967(2), 339-341, preferably a compound of formula ET-10, a silacyclopentadiene derivative. Preferred compounds are the following formulas (ET-6) to (ET-10):

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

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

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

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

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

Compounds capable of emitting light include fluorescent emitters and phosphorescent emitters, among others. These contain inter alia stilbenes, stilbenamines, styrylamines, coumarins, rubrene, rhodamines, thiazoles, thiadiazoles, cyanines, thiophenes, paraphenylenes, perylenes, phthalocyanines, porphyrins, ketones, quinolines, imines, anthracene and/or pyrene structures. Contains compounds that Particular preference is given to compounds that can emit light from the triplet state with high efficiency even at room temperature, ie exhibit electrophosphorescence rather than electrofluorescence, which often results in increased energy efficiency. Suitable for this purpose are first of all compounds containing heavy atoms with an atomic number greater than 36. Compounds containing d- or f-transition metals that satisfy the above conditions are preferred. Particular preference is given here to corresponding compounds containing elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt). Suitable functional compounds here are, for example, the various complexes described in WO02/068435A1, WO02/081488A1, EP1239526A2 and WO2004/026886A2.

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

Monostyrylamine is taken to mean a compound containing one substituted or unsubstituted styryl group and at least one, preferably aromatic amine. Distyrylamine is taken to mean a compound containing two substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. Tristyrylamine is taken to mean a compound containing three substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. Tetrastyrylamine is taken to mean a compound containing four substituted or unsubstituted styryl groups and at least one, preferably aromatic amine. The styryl group is particularly preferably a stilbene, which may be further substituted. Corresponding phosphines and ethers are defined analogously to amines. Arylamine or aromatic amine in the sense of the present invention is taken to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyreneamine, aromatic pyrenediamine, aromatic chrysenamine, or aromatic chrysenediamine. Aromatic anthracene amines are taken to mean compounds in which one diarylamino group is bonded directly to the anthracene group, preferably in the 9-position. Aromatic anthracene diamine is taken to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 2,6 or 9,10 position. Aromatic pyreneamines, pyrenediamines, chrysenamines, and chrysendiamines are similarly defined, where the diarylamino group is preferably attached to the pyrene in the 1- or 1,6-position.

Further preferred fluorescent emitters are indenofluorene amines or indenofluorenediamines as described in particular in WO 2006/122630; benzoindenofluorenamines or benzoindenofluorene amines as described in particular in WO 2008/006449; and in particular as described in WO 2007/140847 selected from dibenzoindenofluorenamine or dibenzoindenofluorenediamine.

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

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

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

Further preferred compounds which can be used as fluorescent emitters are naphthalene, anthracene, tetracene, benzanthracene, benzophenanthrene (DE102009005746), fluorene, fluoranthene, periflanthene, indenoperylene, phenanthrene, perylene (US2007/0252517A1), pyrene, chrysene, decacyclene. , coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US4769292, US6020078, US2007/0252517A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamate ester , diketopyrrolopyrrole, acridone, and derivatives of quinacridone (US2007/0252517A1).

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

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

The blue fluorescent emitter is preferably a polyaromatic compound, such as 9,10-di(2-naphthylanthracene) and other anthracene derivatives, derivatives of tetracene, xanthene, perylene, such as 2,5,8,11-tetra -t-butylperylene, phenylene, for example 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl, fluorene, fluoranthene, arylpyrene (US2006/0222886A1), arylene vinylene (US5121029, US5130603), bis(azinyl)imine-boron compound (US2007/0092753A1), bis(azinyl)methene compound, and carbostyryl compound.

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

A further preferred blue fluorescent emitter has the following formula (1) as disclosed in WO2010/012328A1:

(In the formula, the following applies to the symbols and subscripts used:
Ar ¹ , Ar ² , Ar ³ are the same or different at each occurrence and are aryl or heteroaryl having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R ¹ a group with the proviso that Ar ² does not represent anthracene, naphthacene or pentacene;
X is the same or different at each occurrence, BR ² , C(R ² ) ₂ , Si(R ² ) ₂ , C=O, C=NR ² , C=C(R ² ) ₂ , O , S, S=O, _SO2 , ^NR2 , ^PR2 , P(=O) ^R2 and P(=S) ^R2 ;
R ¹ and R ² are the same or different each time they appear, and are H, D, F, Cl, Br, I, N(Ar ⁴ ) ₂ , C(=O) Ar ⁴ , P(=O) (Ar ⁴ ) ₂ , S(=O)Ar ⁴ , S(=O) ₂ Ar ⁴ , CR ² =CR ² Ar ⁴ , CHO, CR ³ =C(R ³ ) ₂ , CN, NO ₂ , Si( R ³ ) ₃ , B(OR ³ ) ₂ , B(R ³ ) ₂ , B(N(R ³ ) ₂ ) ₂ , OSO ₂ R ³ , straight-chain alkyl, alkoxy or a thioalkoxy group or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is (optionally substituted by one or more radicals R ³ ) (wherein in each case one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , Ge( ^R3 ) ₂ , Sn( ^R3 ) ₂ , C=O, C=S, C=Se, C= ^NR3 , P(=O) ^R3 , SO, _SO2 , ^NR3 , O, S or CONR ³ ; one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ ), or from 5 to 60 an aromatic or heteroaromatic ring system with aromatic ring atoms, which in each case may be substituted by one or more radicals R ³ , or a combination of these systems; The substituents R ¹ or R ² may mutually form a monocyclic or polycyclic aliphatic or aromatic ring system;
R ³ is the same or different at each occurrence and is H, D or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms;
Ar ⁴ is an aromatic or heteroaromatic ring having from 5 to 30 aromatic ring atoms, which may be the same or different at each occurrence and may be substituted by one or more non-aromatic radicals R ¹ system; where two radicals Ar on the same nitrogen or phosphorus atom may be bonded to each other by a single bond or a bridge X;
m and n are 0 or 1, provided that m+n=1;
p is 1, 2, 3, 4, 5 or 6;
Here, Ar ¹ , Ar ² and X together form a 5-membered or 6-membered ring, Ar ² , Ar ³ and X together form a 5- or 6-membered ring, However, either all of the symbols X in the compound of formula (1) are bonded to a 5-membered ring, or all of the symbols X in the compound of formula (1) are bonded to a 6-membered ring. ;
the sum of all π electrons in the groups Ar ¹ , Ar ² and Ar ³ is at least 28 when p=1, at least 34 when p=2 and at least 40 when p=3; , at least 46 when p=4, at least 52 when p=5 and at least 58 when p=6;
Here n = 0 or m = 0 means that the corresponding group X is not present and instead hydrogen or substituent R ¹ is bonded to the corresponding positions of Ar ² and Ar ³ )
is a hydrocarbon.

A further preferred blue fluorescent emitter has the following formula (2) as disclosed in WO2014/111269A2:

(In the formula:
Ar ¹ is an aryl or heteroaryl group having from 6 to 18 aromatic ring atoms, which may be the same or different at each occurrence and may be substituted by one or more radicals R ¹ ;
Ar ² is an aryl or heteroaryl group having 6 aromatic ring atoms, which are the same or different at each occurrence and which may be substituted by one or more radicals R ² ;
X ¹ is the same or different at each occurrence, BR ³ , C(R ³ ) ₂ , -C(R ³ ) ₂ -C(R ³ ) ₂ -, -C(R ³ ) ₂ -O -, -C(R ³ ) ₂ -S-, -R ³ C=CR ³ -, -R ³ C=N-, Si(R ³ ) ₂ , -Si(R ³ ) ₂ -Si(R ³ ) ₂ -, C=O, O, S, S=O, SO ₂ , NR ³ , PR ³ or P(=O)R ³ ;
R ¹ , R ² and R ³ are the same or different each time they appear, and are H, D, F, Cl, Br, I, C(=O)R ⁴ , CN, Si(R ⁴ ) ₃ , N(R ⁴ ) ₂ , P(=O)(R ⁴ ) ₂ , OR ⁴ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , straight-chain alkyl with 1 to 20 C atoms or an alkoxy group or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, in which each of the groups mentioned above one or more CH ₂ groups in the groups mentioned above may be substituted by a radical R ⁴ of -R ⁴ C=CR ⁴ -, -C≡C-, Si(R ⁴ ) ₂ , C=O, C=NR ⁴ , -C(=O)O-, -C(=O)NR ⁴ -, NR ⁴ , P(=O)(R ⁴ ), -O-, -S-, SO or an aromatic or heteroaromatic ring _system having from 5 to 30 aromatic ring atoms (which may be substituted by one or more radicals R ⁴ ), or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms (which may be replaced by one or more radicals R 4 ); Here, two or more radicals R ³ may be bonded to each other or may form a ring);
R ⁴ is the same or different at each occurrence, H, D, F, Cl, Br, I, C(=O)R ⁵ , CN, Si(R ⁵ ) ₃ , N(R ⁵ ) ₂ , P(=O)(R ⁵ ) ₂ , OR ⁵ , S(=O)R ⁵ , S(=O) ₂ R ⁵ , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or 3 to A branched or cyclic alkyl or alkoxy group having 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, in which the groups mentioned above are each substituted by one or more radicals R ⁵ and one or more CH ₂ groups in the groups mentioned above may be -R ⁵ C=CR ⁵ -, -C≡C-, Si(R ⁵ ) ₂ , C=O, C= replaced by NR ⁵ , -C(=O)O-, -C(=O)NR ⁵ -, NR ⁵ , P(=O)(R ⁵ ), -O-, -S-, SO or SO ₂ ), or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, optionally substituted in each case by one or more radicals R ⁵ (where two or more The radical R ⁴ may be bonded to each other or may form a ring);
R ⁵ is the same or different at each occurrence and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms (wherein, in addition, one The above H atoms may be replaced by D or F); where two or more substituents R ⁵ may be bonded to each other and may form a ring;
Here, at least one of the two groups Ar ¹ must contain 10 or more aromatic ring atoms;
Here, if one of the two groups Ar ¹ is a phenyl group, the other of the two groups Ar ¹ must not contain more than 14 aromatic ring atoms)
is a hydrocarbon.

A further preferred blue fluorescent emitter has the following formula (3) as disclosed in WO2018/007421A1:

(In the formula, the following applies to the symbols and subscripts used:
Ar ¹ represents an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, which may be the same or different at each occurrence and may be substituted in each case by one or more radicals R ¹ ; , where at least one of the groups Ar ¹ in formula (1) has 10 or more aromatic ring atoms;
Ar ² represents an aryl or heteroaryl group having 6 aromatic ring atoms, which may be the same or different at each occurrence and may be substituted in each case by one or more radicals R ¹ ;
Ar ³ , Ar ⁴ are the same or different at each occurrence and are aromatic groups having from 5 to 25 aromatic ring atoms, which in each case may be substituted by one or more radicals R ¹ ; or represents a heteroaromatic ring system;
E is the same or different at each occurrence, -BR ⁰ -, -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -O-, -C(R ⁰ ) ₂ -S-, -R ⁰ C=CR ⁰ -, -R ⁰ C=N-, Si(R ⁰ ) ₂ , -Si(R ⁰ ) ₂ -Si( R ⁰ ) ₂ -, -C(=O)-, -C(=NR ⁰ )-, -C(=C(R ⁰ ) ₂ )-, -O-, -S-, -S(=O) -, -SO ₂ -, -N(R ⁰ )-, -P(R ⁰ )- and -P((=O)R ⁰ )-, and the two groups E are cis- or May be in trans-position;
R ⁰ and R ¹ are the same or different each time they appear, and are H, D, F, Cl, Br, I, CHO, CN, N(Ar ⁵ ) ₂ , C(=O)Ar ⁵ , P (=O)(Ar ⁵ ) ₂ , S(=O)Ar ⁵ , S(=O) ₂ Ar ⁵ , NO ₂ , Si(R ² ) ₃ , B(OR ² ) ₂ , OSO ₂ R ² , 1 A straight-chain alkyl, alkoxy or thioalkyl group with ~40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group with 3 to 40 C atoms, each of which can be formed by one or more radicals R ² optionally substituted) (wherein in each case one or more non-adjacent CH ₂ groups are R ² C=CR ² , C≡C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, P(=O)(R ² ), SO, SO ₂ , O, S or CONR ² , one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), in each case one or more radicals R ² may be substituted 5 An aromatic or heteroaromatic ring system having ~60 aromatic ring atoms, or an aryloxy group having from 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R ² (wherein , two adjacent substituents R ⁰ and/or two adjacent substituents R ¹ are monocyclic or polycyclic aliphatic ring systems or aromatic groups optionally substituted by one or more radicals R ² . may form a group ring system);
^R2 is the same or different at each occurrence, H, D, F, Cl, Br, I, CHO, CN, N( ^Ar5 ) _2, C(=O) ^Ar5 , P(=O )(Ar ⁵ ) ₂ , S(=O)Ar ⁵ , S(=O) ₂ Ar ⁵ , NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , OSO ₂ R ³ , 1 to 40 pieces straight-chain alkyl, alkoxy or thioalkyl groups having from 3 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having from 3 to 40 C atoms, each of which is substituted by one or more radicals R ³ ) (wherein in each case one or more non-adjacent CH ₂ groups are R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , Ge(R ³ ) ₂ , Optionally replaced by Sn(R ³ ) ₂ , C=O, C=S, C=Se, P(=O)(R ³ ), SO, SO ₂ , O, S or CONR ³ , one The above H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), in each case from 5 to 60 which may be substituted by one or more radicals R ³ aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R ³ , where 2 two adjacent substituents R ² may form a monocyclic or polycyclic aliphatic or aromatic ring system optionally substituted by one or more radicals R ³ ;
R ³ is the same or different at each occurrence and is H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having from 1 to 20 C atoms or from 3 to 20 A branched or cyclic alkyl, alkoxy or thioalkyl group having 3 C atoms, in each case one or more non-adjacent CH ₂ groups being replaced by SO, SO ₂ , O, S. one or more H atoms may be replaced by D, F, Cl, Br or I) or represents an aromatic or heteroaromatic ring system with 5 to 24 C atoms;
Ar ⁵ is in each case aromatic or heteroaromatic having from 5 to 24 aromatic ring atoms, preferably from 5 to 18 aromatic ring atoms, optionally substituted by one or more radicals R ³ It is a family ring system;
n is an integer from 1 to 20;
Where n is equal to 1 and at least one of the groups Ar ³ or Ar ⁴ represents a phenyl group, the compound of formula (1) has at least one group R ⁰ or R ¹ , which , represents a straight-chain alkyl group with 2 to 40 C atoms or a branched or cyclic alkyl group with 3 to 40 C atoms, each of which is substituted by one or more radicals R ² good)
is a hydrocarbon.

Preferred compounds capable of functioning as phosphorescent emitters are described by the following examples.

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

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

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

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

Compounds of formula EM-16 are described in more detail in US 2007/0087219A1, to which reference is now made for disclosure purposes for an explanation of substituents and subscripts in the above formula. Furthermore, Pt-porphyrin complexes with extended ring systems (US2009/0061681A1) and Ir complexes, such as 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin-Pt(II), Tetraphenyl-Pt(II) tetrabenzoporphyrin (US2009/0061681A1), cis-bis(2-phenylpyridinato-N,C ² ')Pt(II), cis-bis(2-(2'-thienyl) Pyridinato-N,C ³ ')Pt(II), cis-bis(2-(2'-thienyl)-quinolinato-N,C ⁵ ')Pt(II), (2-(4,6-difluorophenyl) Pyridinato-N,C ² ′)Pt(II) (acetylacetonate), or tris(2-phenylpyridinato-N,C ² ′)Ir(III) (=Ir(ppy) ₃ , green), bis (2-phenylpyridinato-N,C ² )Ir(III) (acetylacetonate) (=Ir(ppy) _{2acetylacetonate} , green, US2001/0053462A1, Baldo, Thompson et al., Nature 403, (2000), 750-753), bis(1-phenylisoquinolinato-N,C ² ')(2-phenylpyridinato-N,C ² ')iridium(III), bis(2-phenylpyridinato-N, C ² ′) (1-phenylisoquinolinato-N,C ² ′)iridium(III), bis(2-(2′-benzothienyl)pyridinato-N,C ³ ′)iridium(III) (acetylacetonate ), bis(2-(4′,6′-difluorophenyl)pyridinato-N,C ² ′)iridium(III)(picolinate) (FIrpic, blue), bis(2-(4′,6′-difluorophenyl) ) Pyridinato-N, ^C2 ')Ir(III) (tetrakis(1-pyrazolyl)borate), tris(2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III), (ppz) ₂ Ir(5phdpym) (US2009/0061681A1), (45ooppz) ₂ Ir(5phdpym) (US2009/0061681A1), derivatives of 2-phenylpyridine-Ir complexes, such as PQIr (=iridium(III) bis(2-phenylquinolyl) -N,C ² ') acetylacetonate), tris(2-phenylisoquinolinato-N,C)Ir(III) (red), bis(2-(2'-benzo[4,5-a] thienyl)pyridinato-N,C ³ )Ir(acetylacetonate) ([Btp ₂ Ir(acac)], red, Adachi et al., Appl. Phys. Lett. 78 (2001), 1622-1624).

Also suitable are complexes of trivalent lanthanides, such as Tb ³⁺ and Eu ³⁺ (J. Kido et al., Appl. Phys. Lett. 65 (1994), 2124; Kido et al., Chem. Lett. 657, 1990; US2007/0252517A1), or phosphorescent complexes of Pt(II), Ir(I), Rh(I) containing maleonitrile dithiolate (Johnson et al., JACS105, 1983, 1795), Re(I) tricarbonyl-diimine complexes (Wrighton, JACS 96, 1974, 998, among others), Os(II) complexes with cyano and bipyridyl or phenanthroline ligands (Ma et al., Synth. Metals 94, 1998, 245).

Further phosphorescent emitters with tridentate ligands are described in US 6,824,895 and US 10/729,238. Red emitting phosphorescent complexes are found in US6835469 and US6830828.

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

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

Furthermore, compounds of formulas EM-18 to EM-21 and their derivatives as described in US7238437B2, US2009/008607A1 and EP1348711 can be utilized as luminescent materials.

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

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

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

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

Preferred host or cohost materials, particularly utilized with fluorescent dopants, are oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene, or dinaphthylanthracene according to EP 676 461), especially those containing fused aromatic groups. Containing oligoarylenes such as anthracene, benzanthracene, benzophenanthrene (DE102009005746, WO2009/069566), phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, oligoarylene vinylenes (e.g. DPVBi = 4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl or spiro-DPVBi) according to EP 676461, polypodal metal complexes (e.g. according to WO 04/081017), especially metals of 8-hydroxyquinoline complexes, such as AlQ ₃ (=aluminum(III) tris(8-hydroxyquinoline)) or metal complexes of bis(2-methyl-8-quinolinolato)-4-(phenylphenolinolato)aluminum, furthermore 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, especially ketones, phosphine oxides, sulfoxides, etc. (e.g. according to WO2005/084081 and WO2005/084082), atropisomers (e.g. according to WO2006/048268), boronic acid derivatives (e.g. according to WO2006/117052) or benzanthracenes (e.g. according to WO2008/145239).

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

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

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

In the compound of formula (H-1), the Ar ⁵ group particularly preferably represents anthracene, the Ar ⁴ and Ar ⁶ groups being bonded in the 9 and 10 positions, where these groups optionally May be replaced. Very particularly preferably, at least one of the Ar ⁴ and/or Ar ⁶ groups is 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl or 2-, 3-, 4-, 5-, 6 - or 7-benzanthracenyl. Anthracene-based compounds are described in US2007/0092753A1 and US2007/0252517A1, such as 2-(4-methylphenyl)-9,10-di-(2-naphthyl)anthracene, 9-(2-naphthyl)-10 -(1,1'-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene, and 1,4-bis(9'-ethynylanthracenyl)benzene. Compounds containing two anthracene units (US2008/0193796A1), such as 10,10'-bis[1,1',4',1'']terphenyl-2-yl-9,9'-bisanthracenyl is also preferable.

Further preferred compounds are arylamines, styrylamines, fluoresceins, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarins, oxadiazoles, bisbenzooxazolines, oxazoles, pyridines, pyrazines, imines , benzothiazole, benzoxazole, derivatives of benzimidazole (US2007/0092753A1), such as 2,2',2''-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole], aldazine, Stilbenes, styrylarylene derivatives such as 9,10-bis[4-(2,2-diphenylethenyl)-phenyl]anthracene, and distyrylarylene derivatives (US5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran , diketopyrrolopyrrole, polymethine, cinnamate ester, and fluorescent dye.

Particular preference is given to derivatives of arylamines and styrylamines, such as TNB (=4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl). Metal oxinoid complexes such as LiQ or AlQ ₃ can be used as cohosts.

Preferred compounds containing oligoarylene as a matrix are US2003/0027016A1, US7326371B2, US2006/043858A, WO2007/114358, WO2008/145239, JP3148176B2, EP1009044, US2004/018383, WO 2005/061656A1, EP0681019B1, WO2004/013073A1, US5077142, WO2007/ 065678, and DE 102009005746, in which particularly preferred compounds are described by formulas H-2 to H-8.

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

These compounds can also be utilized as structural elements in polymers, such as CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (e.g. WO2005/039246, US2005/0069729, JP2004/288381, EP1205527 or WO2008/ 086851), azacarbazoles (e.g. according to EP1617710, EP1617711, EP1731584 or JP2005/347160), ketones (e.g. according to WO2004/093207 or DE102008033943), phosphine oxides, sulfoxides and sulfones (e.g. according to WO2005/00325) 3), oligophenylene, aromatic Amines (e.g. according to US 2005/0069729), dipolar matrix materials (e.g. according to WO 2007/137725), silanes (e.g. according to WO 2005/111172), 9,9-diarylfluorene derivatives (e.g. according to DE 102008017591), azaboroles or boronate esters (e.g. Triazine derivatives (e.g. according to DE102008036982), indolocarbazole derivatives (e.g. according to WO2007/063754 or WO2008/056746), indenocarbazole derivatives (e.g. according to DE102009023155 and DE102009031021), diazaphos hole derivatives (e.g. according to DE102009022858), Triazole derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, thiopyrane dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carbodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives which may further contain triarylaminophenol ligands, such as AlQ ₃ (US 2007/ 0134514A1), metal complexes/polysilane compounds, and thiophene, benzothiophene and dibenzothiophene derivatives.

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

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

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

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

Regarding the film-forming functional compounds that can be utilized according to the invention and can function as host materials, substances containing at least one nitrogen atom are particularly preferred. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. Carbazole derivatives therefore exhibit particularly surprisingly high efficiencies. Triazine derivatives provide unexpectedly long lifetimes for electronic devices.

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

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

n-dopant is here taken to mean a reducing agent, ie an electron donor. Preferred examples of n-dopants are W(hpp) ₄ and other electron-rich metal complexes according to WO2005/086251A2, P=N compounds (e.g. WO2012/175535A1, WO2012/175219A1), naphthylene carbodiimide (e.g. WO2012/168358A1), fluorene (e.g. WO2012/031735A1), free radicals and diradicals (e.g. EP1837926A1, WO2007/107306A1), pyridine (e.g. US2007/145355A1 ).

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

The compound utilized as a wide band gap material can preferably have a band gap of 2.5 eV or more, preferably 3.0 eV or more, particularly preferably 3.5 eV or more. The bandgap can be calculated by the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), among others.

Additionally, the formulation may include a hole blocking material (HBM) as a film-forming functional material. Hole-blocking material means a material that prevents or minimizes the transmission of holes (positive charges) in a multilayer system, especially if this material is arranged in the form of a layer adjacent to a light-emitting layer or a hole-conducting layer. . Generally, hole-blocking materials have lower HOMO levels than hole-transporting materials in adjacent layers. A hole blocking layer is often placed between the emissive layer and the electron transport layer in OLEDs.

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

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

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

In principle, it is possible to utilize any known electron blocking material. In addition to other electron blocking materials described elsewhere in this application, advantageous electron blocking materials are transition metal complexes, such as Ir(ppz) ₃ (US2003/0175553).

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

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

Of particular interest are also functional compounds characterized by a high glass transition temperature. In this context, particularly preferred functional compounds which can be utilized as film-forming organic functional materials in the formulations have a glass transition temperature determined according to DIN 51005 of 70°C or higher, preferably 100°C or higher, more preferably 125°C or higher; Most preferably the temperature is 150°C or higher.

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

Polymers that can be used as film-forming organic functional materials often contain units or structural elements as described in the context of the above compounds, in particular those disclosed and extensively described in WO 02/077060A1, WO 2005/014689A2 and WO 2011/076314A1. do. Functional materials can come from, for example, the following classes:
Group 1: structural elements capable of generating hole injection and/or hole transport properties;
Group 2: structural elements capable of producing electron injection and/or electron transport properties;
Group 3: Structural elements that combine the characteristics described in relation to Groups 1 and 2;
Group 4: structural elements with luminescent properties, in particular phosphorescent groups;
Group 5: structural elements that improve the transition from the so-called singlet state to the triplet state;
Group 6: structural elements that influence the morphology or emission color of the resulting polymer;
Group 7: Structural elements typically used as scaffolds.

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

Polymers with hole-transporting or hole-injecting properties utilized as film-forming organic functional materials containing structural elements from group 1 preferably contain units corresponding to the above-mentioned hole-transporting or hole-injecting materials. You may.

Further preferred structural elements of group 1 are, for example, triarylamines, benzidines, tetraaryl-para-phenylenediamines, carbazoles, azulenes, thiophenes, pyrroles and furans and their derivatives, as well as further O, S or N with high HOMO. It is a containing heterocyclic compound. These arylamines and heterocyclic compounds preferably have a HOMO of more than -5.8 eV (vs. vacuum), particularly preferably more than -5.5 eV.

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

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

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

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

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

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

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

Polymers with electron injection and/or electron transport properties utilized as film-forming organic functional materials containing structural elements from group 2 preferably contain units corresponding to the above-mentioned electron injection and/or electron transport materials. You may.

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

The film-forming organic functional material may preferably be a polymer containing structural elements from Group 3, wherein structural elements that improve hole and electron mobility (i.e. structures from Groups 1 and 2) elements) are directly connected to each other. Some of these structural elements can function as emitters, where the emitted color may be shifted to green, red or yellow, for example. Their use is therefore advantageous, for example, for the production of other emission colors or broadband emission by naturally blue-emitting polymers.

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

Polymers utilized as film-forming organic functional materials containing units of group 5 that improve the transition from the so-called singlet state to the triplet state can preferably be utilized to support phosphorescent compounds, and are preferably Polymers containing structural elements of Group 4 above. Here, a polymeric triplet matrix can be used.

Suitable for this purpose are in particular carbazole and linked carbazole dimer units, as described for example in DE 10304819A1 and DE 10328627A1. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides, sulfones and silane derivatives, as described, for example, in DE 103 49 033 A1, and similar compounds. Additionally, preferred structural units may be derived from the compounds described above in connection with matrix materials utilized with phosphorescent compounds.

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

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

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

The polymers utilized as film-forming organic functional materials preferably contain units of group 7, preferably aromatic structures with 6 to 40 C atoms, often used as a backbone.

These include, inter alia, 4,5-dihydropyrene derivatives, 4,5,9,10-tetra-hydropyrene derivatives, fluorene derivatives, as disclosed in e.g. 9,9-spirobifluorene derivatives disclosed in WO2005/104264A1, such as 9,10-dihydrophenanthrene derivatives disclosed in WO2005/014689A2, such as 9,10-dihydrophenanthrene derivatives disclosed in WO2004/041901A1 and 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives as disclosed in WO2004/113412A2, and binaphthylene derivatives as disclosed in e.g. WO2006/063852A1, and e.g. It includes further units as disclosed in WO2007/043495A1, WO2005/033174A1, WO2003/099901A1 and DE102006003710.

Fluorene derivatives such as those disclosed in US 5,962,631, WO2006/052457A2 and WO2006/118345A1, e.g. spirobifluorene derivatives as disclosed in WO2003/020790A1, e.g. WO2005/056633A1, EP1344788A1 and WO2007/04349 Disclosed to 5A1 Particularly preferred are structural units of group 7 selected from benzofluorene, dibenzofluorene, benzothiophene and dibenzofluorene groups and derivatives thereof.

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

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

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

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

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

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

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

(In the formula, the symbols have the following meanings:
L is H, halogen or an optionally fluorinated straight-chain or branched alkyl or alkoxy group having 1 to 12 C atoms, preferably methyl, i-propyl, t-butyl , represents n-pentoxy or trifluoromethyl;
L' is an optionally fluorinated straight-chain or branched alkyl or alkoxy group having 1 to 12 C atoms, preferably n-octyl or n-octyloxy).

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

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

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

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

In order to improve the solubility, the polymers may contain corresponding groups. Preferably, the polymer contains substituents so that each repeating unit has an average of at least 2 non-aromatic carbon atoms, particularly preferably at least 4, particularly preferably at least 8 non-aromatic carbon atoms. exist, where it may be defined that the average relates to a number average. Here, individual carbon atoms may be replaced by O or S, for example. However, it is also possible that a certain proportion, and optionally all, of the repeating units do not contain substituents containing non-aromatic carbon atoms. Here, short-chain substituents are preferred, since long-chain substituents can have a negative effect on the layers that can be obtained using organic functional materials. The substituents preferably contain in the straight chain up to 12 carbon atoms, preferably up to 8 carbon atoms, particularly preferably up to 6 carbon atoms.

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

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

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

In a further preferred embodiment, the non-conjugated polymer can be designed as a fluorescent emitter. Preferred fluorescent emitters based on non-conjugated polymers with side chains contain anthracene or benzanthracene groups, or derivatives of these groups, in the side chains, where these polymers are e.g. and JP2003/338375.

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

Furthermore, when the functional compound used as the film-forming organic functional material in the formulation is a polymer compound, it is preferably 10,000 g/mol or more, more preferably 25,000 g/mol or more, and most preferably 50 g/mol or more. ,000 g/mol or _more .

Here, the molecular weight M _w of the polymer is preferably in the range of 10,000 to 2,000,000 g/mol, more preferably in the range of 25,000 to 1,000,000 g/mol, and most preferably in the range of 50,000 to It is in the range of 500,000 g/mol. The molecular weight M _w is determined by GPC (=gel permeation chromatography) against internal polystyrene standards.

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

Besides the abovementioned components, the formulations according to the invention may also contain further additives and processing aids. These include, inter alia, surface-active substances (surfactants), lubricants and greases, viscosity-adjusting additives, conductivity-increasing additives, dispersants, hydrophobizing agents, adhesion promoters, flow improvers. , defoamers, deaerators, diluents that may be reactive or non-reactive, fillers, auxiliaries, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles, and inhibitors. including.

In a preferred aspect of the present application, at least one first film-forming organic functional material, at least one second film-forming organic functional material, and optionally at least one third film-forming organic functional material The materials are different from each other.

Preferably, according to the present application, the first film-forming organic functional material is a polymer and the second film-forming organic functional material is a compound having a low molecular weight, and vice versa.

According to the present application, the first solvent of the first ink, the second solvent of the second ink and optionally the third solvent of the third ink are different from each other and are preferably organic solvents; Organic solvents include, inter alia, ketones, ethers, esters, amides, such as di-C _1-2 -alkylformamides, sulfur compounds, nitro compounds, hydrocarbons, halogenated hydrocarbons (for example chlorinated hydrocarbons), aromatic or heteroaromatic hydrocarbons (eg naphthalene derivatives), and halogenated aromatic or heteroaromatic hydrocarbons.

Preferably, the first, second and optionally third solvents are of the following group: substituted and unsubstituted aromatic or linear ethers such as 3-phenoxytoluene or anisole; substituted or unsubstituted arene derivatives; For example, cyclohexylbenzene; substituted or unsubstituted indanes, such as hexamethylindane; substituted and unsubstituted aromatic or linear ketones, such as dicyclohexylmethanone; substituted and unsubstituted heterocyclic compounds, such as pyrrolidinone, pyridine, pyrazine ; other fluorinated or chlorinated aromatic hydrocarbons, substituted or unsubstituted naphthalenes, such as alkyl-substituted naphthalenes, such as 1-ethylnaphthalene.

Particularly preferred first, second and optionally third solvents are, for example, 1-ethylnaphthalene, 2-ethylnaphthalene, 2-propylnaphthalene, 2-(1-methylethyl)-naphthalene, 1-(1-methyl ethyl)-naphthalene, 2-butylnaphthalene, 1,6-dimethylnaphthalene, 2,2'-dimethylbiphenyl, 3,3'-dimethylbiphenyl, 1-acetylnaphthalene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1,2,4-trichlorobenzene, 1,2-dihydronaphthalene, 1,2-dimethylnaphthalene, 1,3 -Benzodioxole, 1,3-diisopropylbenzene, 1,3-dimethylnaphthalene, 1,4-benzodioxane, 1,4-diisopropylbenzene, 1,4-dimethylnaphthalene, 1,5-dimethyltetralin, 1- Benzothiophene, thianaphthalene, 1-bromonaphthalene, 1-chloromethylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 2-bromo-3-bromomethylnaphthalene, 2-bromomethyl-naphthalene, 2-bromonaphthalene, 2- Ethoxynaphthalene, 2-isopropyl-anisole, 3,5-dimethyl-anisole, 5-methoxyindane, 5-methoxyindole, 5-tert-butyl-m-xylene, 6-methylquinoline, 8-methylquinoline, acetophenone, benzo Thiazole, benzyl acetate, butyl phenyl ether, cyclohexylbenzene, decahydronaphthol, dimethoxytoluene, 3-phenoxytoluene, diphenyl ether, propiophenone, hexylbenzene, hexamethylindane, isochroman, phenyl acetate, propiophenone, veratrol, These are pyrrolidinone, N,N-dibutylaniline, cyclohexylhexanoate, menthyl isovalerate, dicyclohexylmethanone, ethyllaurate, and ethyldecanoate.

The first, second and optionally third solvents have a temperature in the range of 100 to 400°C, preferably in the range of 200 to 350°C, more preferably in the range of 225 to 325°C, most preferably in the range of 250 to 300°C. It has a boiling point.

The first, second and optional third film-forming organic functional materials each have a solubility in the corresponding organic solvent of 5 g/l or more, preferably 10 g/l or more.

The content of at least one first, second or optional third film-forming organic functional material in the corresponding formulation is in each case from 0.001 to 20% by weight, based on the total weight of the formulation. preferably in the range of 0.01 to 10% by weight, more preferably in the range of 0.1 to 5% by weight, most preferably in the range of 0.3 to 5% by weight.

Furthermore, the first, second or optional third formulations of the invention each preferably have a pressure in the range of 0.8 to 50 mPa·s, more preferably in the range of 1 to 40 mPa·s, most preferably in the range of 2 to 40 mPa·s. It has a viscosity in the range of 15 mPa·s.

The viscosity of the formulations and solvents according to the invention is measured using a 1° cone plate rotary rheometer of the Discovery AR3 type (Thermo Scientific). This device allows precise control of temperature and shear rate. Viscosity measurements are carried out at a temperature of 25.0° C. (+/−0.2° C.) and a shear rate of 500 s ⁻¹ . Each sample is measured three times and the measurements obtained are averaged.

The first, second or optional third formulation of the invention each preferably has a have a range of surface tensions.

Preferably, the first, second or optional third organic solvent each has a molecular weight in the range of 15 to 70 mN/m, more preferably in the range of 10 to 50 mN/m, most preferably in the range of 20 to 40 mN/m. Including surface tension.

Surface tension can be measured at 20° C. using a FTA (First Ten Angstrom) 1000 contact angle goniometer. Details of the method can be found in Roger P. Woodward, Ph. D. As published by "Surface Tension Measurements Using the Drop Shape Method," available from First Ten Angstrom. Preferably, surface tension can be determined using the pendant drop method. This measurement technique dispenses droplets from a needle in a bulk liquid or gas phase. The shape of a droplet is derived from the relationship between surface tension, gravity, and density difference. Using the pendant drop method, visit http://www. cruss. Surface tension is calculated from the pendant drop shadow image using de/services/education-theory/glossary/drop-shape-analysis. All surface tension measurements were performed using a commonly used and commercially available high-precision droplet shape analysis tool, namely FTA1000 from First Ten Angstrom. Surface tension is determined by software FTA1000. All measurements were performed at room temperature, ranging from 20°C to 25°C. Standard operating procedures include determination of the surface tension of each formulation using a new disposable droplet dispensing system (syringe and needle). Each droplet is measured over a 1 minute duration with 60 measurements later averaged. Three drops are measured for each formulation. The final value is the average of the measured values. The tool is periodically cross-checked against various liquids with known surface tensions.

Preferably, according to the present application, the first solvent, the second solvent and optionally the third solvent are different from each other and may be selected from the solvents or mixtures thereof listed in Table 1 below.

Optionally, the solvents of the first, second and third solvents may be a mixture of solvents, where the predominant solvent is as described above and the remaining solvents are commonly used predominant solvents. It is a co-solvent for the solvent.

According to the present application, the first film-forming organic functional material in the second solvent has a dissolution time of more than 15 minutes, preferably more than 30 minutes, more preferably more than 60 minutes.

According to the present application, the dissolution time of the first film-forming organic functional material in the second solvent fulfills ISO standard 7579:2009, which describes the determination of solubility by photometric or gravimetric methods. It is judged by. Photometric techniques are recommended here.

Dissolution testing was performed as described below. The experiments were designed with a particular focus on being easily reproducible. The material to be analyzed (ie, the first film-forming material) was weighed into a clear glass flask. The solvent or preformed solvent mixture (second solvent) was then added in one portion to the solid mixture calculated to reach a final concentration of 7 g/L. The mixture was stirred at 600 rpm at room temperature (25° C.) using a magnetic stirrer until complete dissolution as judged by visual inspection of the mixture. Near the end of the dissolution test, the mixture can be additionally examined under illumination perpendicular to the line of sight to help identify undissolved particles. The "time of dissolution", referred to in this application and sometimes also referred to as "dissolution time", _tDISS , is measured using a chronometer and is the time of dissolution of the solvent until the last piece of material disappears into solution. The time between the addition of and the start of stirring is quantified. The dissolution rate is determined by dividing 7 g/L by the time until complete dissolution is obtained ("dissolution time").
Substrate According to the present invention, the substrate used in the inkjet printing method may be made from any suitable material commonly used in the field of inkjet printing.

In a preferred embodiment of the inkjet printing method, the substrate used should be a transparent material selected from the group comprising glass, plastic, metal foil or flexible membrane.

In another preferred embodiment of the inkjet printing method, printing is performed on a substrate on which all or a subset of sub-pixels are deposited.
Drying According to the invention, drying of the printed pixels is carried out by commonly used drying methods, including vacuum drying under reduced pressure. Alternative drying methods include thermal evaporation of solvents, hot air or infrared drying, and others.

Drying is performed at room temperature or from about 0°C to about 50°C.

Drying is carried out at a pressure below 1013 mbar, preferably below 1 mbar.
Pixels According to the invention, a second formulation is printed in a second sub-pixel adjacent to the first sub-pixel.
Functional Layers According to the present invention, the functional layers of an OLED include a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL). or a combination thereof.

In one preferred embodiment of the method for manufacturing functional layers of an OLED, the functional layers consist of HIL, HTL and EML, which are provided successively on the substrate.

According to the present application, the OLED is a full color OLED.

The examples below provide a detailed description of the invention and its construction.

[example]
Example 1
Determination of the dissolution time of a polymer as a hole transport material (HTL) when the first film-forming material is in a different second solvent Hole transport material (HTL) polymer ( Polymer P1) was used. The target concentration for the dissolution experiment was 7 g/l. Solvents were classified according to the dissolution time t _DISS at 25°C and characterized by the type of dissolution as shown in Tables 3a and 3b below.

Comparison of the profile of pixels formed by polymer P1 before and after printing the second ink Example 2
Determination of the dissolution time of small molecule blend SM-1 when the second film-forming material is in different first and second solvents Small molecule blend SM-1 as described in the device assembly example of WO2017/102048A1 1 was used. The target concentration for the dissolution experiment was 7 g/l. Solvents were classified according to the dissolution time t _DISS at 25°C and characterized by type of dissolution, as shown in Table 4a below, using the classification described in Table 3b above.

Example 3
Determination of the dissolution time of small molecule blend SM-2 when the film-forming materials are in different first and second solvents. Consisting of a 95/5 (wt/wt) mixture of host H1 and emitter E1. Small molecule blend SM-2 was used. The structure of H1 is given below, and the light emitter used was the material described as D2 in the device assembly example of WO2018/007421A1.

The target concentration for the dissolution experiment was 7 g/l. Solvents were classified according to the dissolution time t _DISS at 25°C and characterized by type of dissolution, as shown in Table 5a below, using the classification described in Table 3b above.

Example 4
A pixelated substrate is provided having adjacent first and second pixels. A first ink containing 20 mg/mL of polymer P1 from the ink with 3-phenoxytoluene as the first solvent is inkjet printed onto the first pixel. The substrate was subjected to drying at room temperature and under reduced pressure of 10 ⁻⁵ mBar. A second ink comprising an ink with 20 mg/mL SM-2 in 3-phenoxytoluene (3-PT) is then inkjet printed onto the second pixel. The substrate was subjected to drying at room temperature and under reduced pressure of 10 ⁻⁵ mBar. The profile of the first pixel before and after printing the second ink was characterized by a profilometer. Membrane profiles were measured using a KLA-Tencor Corporation Alpha-step D120 with a 2 μm needle.

Example 5
Example 4 was repeated, except that the second ink was replaced by 20 mg/mL SM-2 in menthyl isovalerate, and drying of the second ink was carried out at room temperature and at a reduced pressure of 10 ⁻⁵ mBar. .

Example 6
Example 4 was repeated, except that the second ink was replaced by 20 mg/mL SM-2 in 2-phenoxyethanol (2-PEN), and the drying of the second ink was carried out at room temperature and at 10 ^-5 mBar. Performed under reduced pressure.

Example 7
Example 6 was repeated, except that the second ink was replaced by 20 mg/mL SM-1 in 2-phenoxyethanol (2-PEN), and the drying of the second ink was carried out at room temperature and at 10 ^-5 mBar. Performed under reduced pressure.

Comparative example 1
A pixelated substrate is provided having adjacent first and second pixels. A first ink containing 20 mg/mL of SM-1 from the ink with 3-phenoxytoluene as the first solvent is inkjet printed onto the first pixel. The substrate was subjected to drying at room temperature and under reduced pressure of 10 ⁻⁵ mBar. A second ink comprising an ink with 20 mg/mL SM-2 in 3-phenoxytoluene (3-PT) is then inkjet printed onto the second pixel. The substrate was subjected to drying at room temperature and at a pressure of 10 ⁻⁵ mBar. The profile of the first pixel before and after printing the second ink was characterized by a profilometer. Membrane profiles were measured using a KLA-Tencor Corporation Alpha-step D120 with a 2 μm needle.

A comparison of the profiles is shown in Figure 3.

If the dissolution time of the first film-forming material in the second solvent is more than 15 minutes, preferably more than 30 minutes, more preferably more than 60 minutes, the profile of the first pixel is different from that of the second ink. It can be seen that it remained smooth, stable and uniform before and after drying.

Claims (14)

The following ingredients:
a) a first formulation comprising at least one first film-forming organic functional material and at least one first organic solvent;
b) an ink system comprising a second formulation comprising at least one second film-forming organic functional material and at least one second organic solvent;
(i) the first and second organic solvents are different from each other;
(ii) the first film-forming organic functional material has a dissolution time in the second organic solvent of more than 15 minutes, preferably more than 30 minutes, more preferably more than 60 minutes; , at room temperature, the concentration of the first film-forming organic functional material in the second organic solvent is 7 g/L. further comprising a third formulation comprising at least one third film-forming material and at least one third organic solvent, wherein the third organic solvent Ink system according to claim 1, characterized in that it is different from an organic solvent. 3. The ink system according to claim 1, wherein the first, second, and optional third film-forming organic functional materials are different from each other. 4. The method of claim 1, wherein the first, second and optional third film-forming organic functional materials are selected from low molecular weight compounds, polymers, oligomers or dendrimers, or mixtures thereof. The ink system according to any one of item 1. Ink system according to claim 4, characterized in that the low molecular weight compound has a molecular weight of 3,000 g/mol or less, preferably 2,000 g/mol or less, more preferably 1,000 g/mol or less. Ink system according to claim 4, characterized in that the polymer has a molecular weight M _w of 10,000 g/mol or more, preferably 25,000 g/mol or more, more preferably 50,000 g/mol or more. The content of the at least one first, second and optional third film-forming organic functional material in the corresponding formulation is from 0.001 to 0.001, respectively, based on the total weight of the formulation. Characterized by a range of 20% by weight, preferably a range of 0.01 to 10% by weight, more preferably a range of 0.1 to 5% by weight, most preferably a range of 0.3 to 5% by weight. , the ink system according to any one of claims 1 to 6. Said first, second and optionally third organic solvents may have a temperature in the range of 100 to 400°C, preferably in the range of 200 to 350°C, more preferably in the range of 225 to 325°C, most preferably in the range of 250 to 300°C. Ink system according to any one of claims 1 to 7, characterized in that it has a boiling point in the range. The first, second and optional third film-forming organic functional materials each have a solubility in the corresponding organic solvent of 5 g/l or more, preferably 10 g/l or more, The ink system according to any one of claims 1 to 8. Said first, second and optional third formulations each have a viscosity in the range of 0.8 to 50 mPa·s, preferably in the range of 1 to 40 mPa·s, more preferably in the range of 2 to 15 mPa·s. The ink system according to any one of claims 1 to 9, characterized in that it has the following. Said first, second and optional third formulations each have a surface tension in the range of 10 to 70 mN/m, preferably in the range of 15 to 50 mN/m, more preferably in the range of 20 to 40 mN/m. The ink system according to any one of claims 1 to 10, characterized in that it comprises: Ink system according to any one of claims 1 to 11, characterized in that the first, second and third organic solvents further comprise a co-solvent. A method for inkjet printing, the method comprising:
a) preparing the substrate;
b) printing a first formulation of the ink system according to claim 1 onto pixels of a first type;
c) drying the first formulation in the first type of pixel;
d) printing a second formulation of the ink system according to claim 1 on a second type of pixel; and e) drying the second formulation on the second type of pixel. including methods. a) preparing a pair of electrodes;
b) providing a functional layer between the electrodes, the method for manufacturing an OLED comprising:
14. A method, characterized in that at least one functional layer is produced by the method of claim 13.