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Definitions

• the present invention relates to a composition comprising a compound of formula (H1 ) and a compound of formula (H2).
• the present invention furthermore relates to a formulation comprising a composition comprising a compound of formula (H1 ) and a formula (H2) and a solvent.
• the present invention relates to an electronic device comprising such a composition.
• the development of functional compounds for use in electronic devices is currently the subject of intensive research.
• the aim is, in particular, the development of compounds with which improved properties of electronic devices in one or more relevant points can be achieved, such as, for example, power efficiency and lifetime of the device as well as colour coordinates of the emitted light.
• the term electronic device is taken to mean, inter alia, organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light- emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).
• OICs organic integrated circuits
• OFETs organic field-effect transistors
• OLETs organic thin-film transistors
• OLETs organic light- emitting transistors
• OSCs organic solar cells
• OFQDs organic field-quench devices
• OLEDs organic light-emitting electrochemical cells
• O-lasers organic laser diodes
• OEDs organic electroluminescent devices
• OLEDs Of particular interest is the provision of compounds for use in the last- mentioned electronic devices called OLEDs.
• the general structure and the functional principle of OLEDs are known to the person skilled in the art and are described, for example, in US 4539507.
• the emitter compound is generally employed in the emitting layer in combination with a second compound, which serves as matrix compound or host compound.
• An emitter compound here is taken to mean a compound which emits light during operation of the electronic device.
• a host compound in this case is taken to mean a compound which is present in the mixture in a greater proportion than the emitter compound.
• the term matrix compound and the term host compound can be used synonymously.
• the host compound preferably does not emit light.
• the emitter compound is typically the component present in smaller amount, i.e. in a smaller proportion than the other compounds present in the mixture of the emitting layer.
• the emitter compound is also referred to as dopant.
• Hosts compounds for fluorescent emitters that are known from the prior art are a multiplicity of compounds.
• the emitting layer may comprise one host compound or more.
• Host compounds comprising a mixture of deuterated and non-deuterated host compounds are known from the prior art (for example in WO 2020/080416).
• further host materials or further combinations of host materials for fluorescent emitters which may be employed in OLEDs and lead to OLEDs having very good properties in terms of lifetime, colour emission and efficiency. More particularly, there is a need for host materials or combinations of host materials for fluorescent emitters combining very high efficiencies, very good lifetime and very good thermal stability.
• an OLED may comprise different layers, which may be applied either by vapour deposition in a vacuum chamber or by processing from a solution.
• the processes based on vapour deposition lead to very good results, but they might be complex and expensive. Therefore, there is also a need for compositions comprising OLED materials that can be easily and reliably processed from a solution. More particularly, there is a need for compositions comprising OLED materials that can be deposited as homogeneous films during the fabrication of OLEDs when processed from a formulation, more particularly from a solution like an ink.
• the materials should have good solubility properties in the solution that comprises them and the deposited films comprising OLED materials should be as smooth as possible after the drying step leading to the removing of the solvent.
• the deposited layer form a smooth and homogenous film as layer thickness inhomogeneities cause uneven luminance distributions with areas of thinner film thickness showing increased luminance and thicker areas with reduced luminance, which leads to a decrease of the OLED ' s quality.
• the OLEDs comprising the films processed form a solution should exhibit good performances, for example in terms of lifetime, operating voltage and efficiency.
• the present invention is thus based on the technical object of providing compositions comprising OLED materials, which are suitable for use in electronic devices, such as OLEDs, more particularly as a matrix component for fluorescent emitters.
• the present invention is also based on the technical object of providing compositions comprising OLED materials, which are particularly suitable for solution processing.
• the present invention is also based on the technical object of providing processes.
• compositions comprising a compound of formula (H1 ) and a compound of formula (H2) as defined below are eminently suitable for use in electronic devices.
• they achieve one or more, preferably all, of the above-mentioned technical objects.
• the present application thus relates to a composition
• a composition comprising: a first host material of formula (H1 ),
• Gi is an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R x ;
• Y stands on each occurrence, identically or differently, for C-R Y or N; with the proviso that Y stands for C when it is bonded to a group Ant2;
• Anti is a group of formula (A1 ): where the dashed bond in formula (A1) indicates the bonding position to the group Gi, and where the group Anti might be bonded to Gi at any free position;
• Ant2 is a group of formula (A2):
• Ar A1 , Ar B1 , Ar AS , Ar BS are, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals
• R stands on each occurrence, identically or differently, for FI, D, F, Cl,
• Ar is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R ' ;
• R ' stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CFI2 groups may be replaced by SO, SO2, O, S and where one or more FI atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms; and n is on each occurrence, identically or differently, 0 or 1 ; wherein when n is 0, then the corresponding Ar AS or Ar BS is absent, and the anthracene group is directly bonded to a group Gi or G2; m is 0 or 1 ; characterized in that the compound of formula (H 1 ) comprises at least one deuterium
• a deuterium atom is also called “D” here.
• An aryl group in the sense of this invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; a heteroaryl group in the sense of this invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom.
• the heteroatoms are preferably selected from N, O and S. This represents the basic definition. If other preferences are indicated in the description of the present invention, for example with respect to the number of aromatic ring atoms or the heteroatoms present, these apply.
• An aryl group or heteroaryl group here is taken to mean either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine or thiophene, or a condensed (annellated) aromatic or heteroaromatic polycycle, for example naphthalene, phenanthrene, quinoline or carbazole.
• a condensed (annellated) aromatic or heteroaromatic polycycle in the sense of the present application consists of two or more simple aromatic or heteroaromatic rings condensed with one another.
• An aryl or heteroaryl group which may in each case be substituted by the above-mentioned radicals and which may be linked to the aromatic or hetero aromatic ring system via any desired positions, is taken to mean, in particular, groups derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, - IQ - benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothio- phene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5
• aryloxy group in accordance with the definition of the present invention is taken to mean an aryl group, as defined above, which is bonded via an oxygen atom.
• An analogous definition applies to heteroaryloxy groups.
• An aromatic ring system in the sense of this invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms, more preferably 6 to 20 C atoms.
• a heteroaromatic ring system in the sense of this invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom.
• the heteroatoms are preferably selected from N, O and/or S.
• An aromatic or heteroaromatic ring system in the sense of this invention is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but instead in which, in addition, a plurality of aryl or hetero aryl groups may be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, an sp 3 -hybridised C, Si, N or O atom, an sp 2 -hybridised C or N atom or an sp-hybridised C atom.
• systems such as 9,9’-spirobifluorene, 9,9’-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be taken to be aromatic ring systems in the sense of this invention, as are systems in which two or more aryl groups are connected, for example, by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.
• systems in which two or more aryl or heteroaryl groups are linked to one another via single bonds are also taken to be aromatic or heteroaromatic ring systems in the sense of this invention, such as, for example, systems such as biphenyl, terphenyl or diphenyltriazine.
• An aromatic or heteroaromatic ring system having 5 - 60 aromatic ring atoms, which may in each case also be substituted by radicals as defined above and which may be linked to the aromatic or heteroaromatic group via any desired positions, is taken to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, naphtha- cene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenyl- ene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydro pyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spir
• a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms in which, in addition, individual H atoms or CH2 groups may be substituted by the groups mentioned above under the definition of the radicals, is preferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, cyclooct
• 2-ethylhexyloxy pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoro- methylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenyl- thio, butenylthio,
• the above-mentioned formulation is also intended to be taken to mean that, in the case where one of the two radicals represents hydrogen, the second radical is bonded at the position to which the hydrogen atom was bonded, with formation of a ring. This is illustrated by the following scheme:
• Adjacent radicals in the sense of the present invention are radicals which are bonded to atoms which are linked directly to one another or which are bonded to the same atom.
• the molecular weight (Mw) of the compound of formula (H 1 ) is Mw > 350 g/mol, preferably Mw > 380 g/mol, more preferably Mw > 400 g/mol, even more preferably Mw > 450 g/mol.
• the group Gi is selected from a group of one of the following formulae: where: X stands on each occurrence, identically or differently, for C-R x or N; with the proviso that X stands for C when it is bonded to a group Anti;
• R° stands on each occurrence, identically or differently, for H, D, F, CN, a straight-chain alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, even more preferably 6 to 18 aromatic ring atoms which may in each case be substituted by one or more radicals R; where two adjacent substituents R° may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R;
• R x , R have the same meaning as above.
• E 1 , E 2 , E 3 , E 4 stand on each occurrence, identically or differently, for a single bond, -0- or -S-; with the proviso that one of the groups E 1 and E 3 is a single bond and the other group is -0- or -S- and one of the groups E 4 and E 2 is a single bond and the other group is -0- or -S-. More preferably, E 1 and E 2 stand for -0- or -S- and E 3 and E 4 stand for a single bond.
• (G1-1) to (G1-12) the following structures are preferred: (G1-1), (G1-3), (G1-4), (G1-5), (G1-7), (G1-9), (G1-10), (G1- 11) and (G1-12).
• the following structures are particularly preferred: (G1-1), (G1-3), (G1-4), (G1-5,) (G1-9), (G1-10).
• the compound of formula (H1) is selected from compounds of the following formulae:
• the host material (H1 ) is preferably selected from the compounds of formulae (G1-1-1 ), (G1-2-1 ), (G1-3-1 ), (G1-4-1 ), (G1-4-2), (G1-5-1 ), (G1-6-êt c 1 ), (G1-7-1 ), (G1-8-1 ), (G1-9-1 ), (G1-9-3), (G1 -10-1 ), (G1 -10-3), (G1 -11 -1 ), (G1-11-3), (G1-12-1 ), (G1-12-3).
• the host material (H1) is very preferably selected from the compounds of formulae (G1 -1 -1 ), (G1 -3-1 ), (G1 -4-1 ), (G1 - 4-2), (G1-5-1 ), (G1-7-1 ) (G1-9-1 ), (G1 -10-1 ), (G1-11-1) and (G1 -12-1 ).
• the index m in formula (H1 ) is equal to 0 and the first host compound of formula (H1) comprises only one group Anti.
• the following groups are very preferred: (G1-1-1 ), (G1-1-2), (G1- 2-3), (G 1-2-4) , (G1-3-1 ), (G1-4-2), (G1-4-3), (G1-4-4), (G1-5-2), (G1-5-3), (G1-5-4), (G1-7-1 ), (G1-7-2), (G1-8-1 ) , (G1-8-2) , (G1-8-3) , (G1-9-1 ), (G1- 10-1 ), (G1-12-1 )
• the groups Ar A1 and Ar B1 are on each occurrence, identically or differently, selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, triphenylene, fluoranthene, tetracene, chrysene, benzanthracene, benzophenanthracene, pyrene or perylene, dibenzofuran, carbazole and dibenzothiophene, each of which may be substituted by one or more radicals R at any free positions; and where Ar A1 , Ar B1 might also be a combination of two or more of the previously cited groups.
• the groups Ar A1 and Ar B1 are on each occurrence, identically or differently, selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthalene, phenanthrene, each of which may be substituted by one or more radicals R at any free positions.
• the group Anti is a group of one of the formulae (A1 -1 ) to (A1 -5):
• R A1 to R A8 stand on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
• R A1 to R A8 are selected from FI and D.
• R A9 to R A21 stand on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
• R A9 to R A21 are selected from H and D.
• the group Anti is a group of one of the formulae (A1-1-D) to Formula (A1-5-D) where x is an integer from 0 to 8, more preferably from 1 to 8; y1 is an integer from 0 to 5, more preferably from 1 to 5; y2 is an integer from 0 to 4, more preferably from 1 to 4; y3 is an integer from 0 to 3, more preferably from 1 to 3; z is an integer from 0 to 7, more preferably from 1 to 7.
• the index x stands for 8
• the anthracene group in formula (A1-1-D) comprises 8 deuterated atoms, which means that the anthracene group in formula (A1-1-D) it is fully deuterated.
• the compound of formula (H1) comprises at least one deuterium atom.
• the at least one deuterium atom can be a substituent on the group Anti or Gi.
• the at least one deuterium atom is a substituent on a group Anti.
• At least one deuterium atom is a substituent on a group Anti, it is preferred that: - In formula (A1 ): at least one radical R A1 to R A8 stands for a deuterium atom or at least one radical R in the group Ar A1 stands for a deuterium atom;
• At least one radical R A1 to R A8 stands for a deuterium atom or at least one radical R A9 to R A21 stands for a deuterium atom;
• the at least one deuterium atom is a substituent on a group Gi.
• At least one radical R x stands for a deuterium atom. More particularly, it is preferred that at least 10% of the substituent R x present in a group Gi stand for a deuterium atom. More preferably, at least 20% of the substituent R x present in a group Gi stand for a deuterium atom, or at least 30 of the substituent R x present in a group Gi stand for a deuterium atom, or at least 40 % of the substituent R x present in a group Gi stand for a deuterium atom, or at least 50 % of the substituent R x present in a group Gi stand for a deuterium atom, or at least 60 % of the substituent R x present in a group Gi stand for a deuterium atom, or at least 70 % of the substituent R x present in a group Gi stand for a deuterium atom, or at least 80 % of the substituent R x present in a group Gi stand for a deuterium atom.
• R x stand on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be sub stituted by one or more radicals R. More preferably, R x is selected from FI and D.
• the compound of formula (H 1 ) is at least 10% deuterated with deuterium atoms being substituents on a group Gi, on a group Anti or on both groups Gi and Anti. This means that at least 10% of the available hydrogen atoms in the compound of formula (H 1 ) are replaced by a deuterium atom. More preferably, the compound of formula (FH1 ) is at least 20% deuterated, or at least 30 % deuterated, or at least 40 % deuterated, or at least 50 % deuterated, or at least 60 % deuterated, or at least 70 % deuterated, or at least 80 % deuterated, or at least 90 % deuterated.
• the group G2 is selected from a group of one of the following formulae: where: Y stands on each occurrence, identically or differently, for C-R Y or N; with the proviso that Y stands for C when it is bonded to a group Ant2; and where the symbols R Y has the same meaning as above; and R B0 has the same meaning as above.
• R B0 stands on each occurrence, identically or differently, for H, a straight-chain alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 20, more preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R; where two adjacent substituents R B0 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R.
• the groups (G2-1 ) to (G2-5) are preferred.
• the compound of formula (H2) is selected from the groups of the following formulae:
• the following compounds are preferred: (G2-1-1), (G2-2-1), (G2-4-1), (G2-5-1), (G2-5-2), more preferred are (G2-1-1), (G2-2-1), (G2-5-1), (G2-5-2) and very preferred are (G2-1-1), (G2-2-1).
• R Y stands on each occurrence, identically or differently, for H, F, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10
• R Y stands on each occurrence, identically or differently, for H, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be sub stituted by one or more radicals R. More preferably, R Y stands for H.
• the group Ant2 is preferably a group of one of the formulae (A2-1 ) to (A2-5):
• R B1 to R B8 stand on each occurrence, identically or differently, for H, F, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
• R B1 to R B8 stand on each occurrence, identically or differently, for H, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be sub stituted by one or more radicals R.
• R B1 to R B8 stand for H.
• R B9 to R B21 stand on each occurrence, identically or differently, for H, F, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
• R B9 to R B21 stand on each occurrence, identically or differently, for H, F, a straight-chain alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 6 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
• the groups AR AS and AR BS stands on each occurrence, identically or differently, for phenyl, biphenyl, fluorene, spirobifluorene, naphthalene, phenanthrene, anthracene, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, benzopyridine, benzopyridazine, benzopyrimidine and quinazoline, each of which may be substituted by one or more radicals R.
• the groups AR AS and AR BS stands on each occurrence, identically or differently, for phenyl, biphenyl or naphthalene, each of which may be substituted by one or more radicals R.
• R stands on each occurrence, identically or differently, for H, D,
• a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R ' , where in each case one or more non-adjacent CH2 groups may be replaced by R ' C CR ' , CoC, O or S and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring systems having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R ' .
• Ar is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 25, very more preferably 6 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R ’ ;
• R ’ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl group having 1 to 10 C atoms or branched or cyclic alkyl group having 3 to 10 C atoms, where in each case one or more FI atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 18 C atoms.
• the composition comprises a first host material of formula (FH1 ), a second host material of formula (FH2) and a dopant material.
• the dopant material is preferably a fluorescent emitter.
• the composition comprises at least one fluorescent emitter, which comprises at least one of the following group: - an arylamine containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen;
• the composition comprises at least one fluorescent emitter of one of the following formulae (E-1 ), (E-2), (E-3) or (E-4) as depicted below:
• Ar 10 , Ar 11 , Ar 12 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; with the proviso that at least one group Ar 10 , Ar 11 , Ar 12 is an aromatic or heteroaromatic ring system having 10 to 40 aromatic ring atoms, containing at least one condensed aryl or heteroaryl group consisting of 2 to 4 aromatic rings condensed with one another, where the aromatic or heteroaromatic ring system may be substituted by one or more radicals
• R has the same definition as above; and e is 1 , 2, 3 or 4; more preferably, e is 1 ;
• Ar 20 , Ar 21 , Ar 22 are on each occurrence, identically or differently, an aryl or heteroaryl group having 6 to 30 aromatic ring atoms, which may in each 25 case also be substituted by one or more radicals R;
• R° stands on each occurrence, identically or differently, for H, D, F, a straight- chain alkyl group having 1 to 20 , preferably 1 to 10 C atoms or branched or a cyclic alkyl group having 3 to 20, preferably 3 to 10 C atoms, each of 35 which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH2 groups may be replaced by 0 or S and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring systems having 5 to 40, preferably 5 to 30, more preferably 6 to 18 aromatic ring atoms, which may in each case be sub stituted by one or more radicals R, where two adjacent radicals R°, may form an aliphatic or aromatic ring system together, which may be substituted by one or more radicals R,
• Ar 30 , Ar 31 , Ar 32 stand on each occurrence, identically or differently, for a substituted or unsubstituted aryl or heteroaryl group having 5 to 22, preferably 5 to 18, more preferably 6 to 14 aromatic ring atoms; E 30 stands for B or N;
• E 31 , E 32 , E 33 stand on each occurrence, identically or differently, for 0, S,
• Ar 40 , Ar 41 , Ar 42 stand on each occurrence, identically or differently, for a substituted or unsubstituted aryl or heteroaryl group having 5 to 22, preferably 5 to 18, more preferably 6 to 14 aromatic ring atoms; E 41 , E 42 , E 43 stand on each occurrence, identically or differently, for 0, S,
• R° has the same definition as above; i, g, h are on each occurrence, identically or differently, 0 or 1 , with the proviso that i + g + h > 1 .
• the fluorescent emitter of formula (E-1 ) comprises at least one group Ar 10 , Ar 11 or Ar 12 , preferably Ar 10 , which is selected from the groups of formulae (Ar 10 -1 ) to (Ar 10 -24): where the groups Ar 10 -1 to Ar 10 -24 may be substituted at all free positions by one or more radicals R; and where
• the emitters of formula (E-1 ) comprise a group Ar 10 selected from the groups of formulae (Ar 10 -15) to (Ar 10 - 22), wherein d is preferably equal to 1 and wherein preferably at least one group Ar 11 , Ar 12 is selected from the groups of formulae (Ar 10 -15) to (Ar 10 -22).
• the emitter of formula (E-1 ) is selected from the emitters of formulae (E-1 -1 ) to (E-1 -6), where the symbols have the same meaning as above and where: f is 0, 1 or 2; and the benzene rings represented above in the compounds of formulae (E-1-1) to (E-1-6) may be substituted at all free positions by one or more radicals R.
• the compounds of formula (E-1) are selected from the compounds of formulae (E-1-1 -A) to (E-1-6-A), where the symbols and indices have the same meaning as above and where the benzene rings represented above in the compounds of formulae (E-1-1- A) to (E-1 -6-A) may be substituted at all free positions by one or more radicals
• the fluorescent emitter of formula (E-2) is selected from fluorescent emitters of formula (E-2-1 ) to (E-2-43), where the groups of formulae (E-2-1 ) to (E-2-43) may be substituted at all free positions by one or more radicals R; and where E 20 has the same definition as above.
• E 20 is C(R°)2.
• the compounds of formula (E-2) are preferably selected from the compounds of formulae (E-2-32) to (E-2-43).
• the compounds of formula (E-2) are selected from the compounds (E-2-32-A) to (E-2-43-A): where the symbols have the same meaning as above and where the benzene and naphthalene rings represented above in the compounds of formulae (E- 2-32-A) to (E-2-43-A) may be substituted at all free positions by one or more radicals R.
• the fluorescent emitter of formula (E-3) is selected from fluorescent emitters of formula (E-3-1),
• the fluorescent emitter of formula (E-3) is selected from fluorescent emitters of formula (E-3-2),
• Formula (E-3-3) Formula (E-3-4) where the symbols and indices have the same meaning as above.
• the fluorescent emitter of formula (E-4) is selected from fluorescent emitters of formula (E-4-1) or (E-4-2),
• the fluorescent emitter of formula (E-4) is selected from fluorescent emitters of formula (E-4-1-A) or (E-4-2-A), where the symbols have the same meaning as above.
• the fluorescent emitter of formula (E-1 ), (E-2), (E-3) or (E-4) comprises a group RS, wherein the group RS is selected:
• R 22 , R 23 , R 24 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 25 , and where two of radicals R 22 , R 23 , R 24 or all radicals R 22 , R 23 , R 24 may be joined to form a (poly)cyclic alkyl group, which may be substituted by one or more radicals R 25 ;
• R 25 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms; with the proviso that at each occurrence at least one of radicals R 22 , R 23 and R 24 is other than H, with the proviso that at each occurrence all of radicals R 22 , R 23 and R 24 together have at least 4 carbon atoms and with the proviso that at each occurrence, if two of radicals R 22 , R 23 , R 24 are H, the remaining radical is not a straight-chain; or from branched or cyclic alkoxy groups represented by the general following formula (RS-b)
• R 26 , R 27 , R 28 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 25 as defined above, and where two of radicals R 26 , R 27 , R 28 or all radicals R 26 , R 27 , R 28 may be joined to form a (poly)cyclic alkyl group, which may be substituted by one or more radicals R 25 as defined above; with the proviso that at each occurrence only one of radicals R 26 , R 27 and R 28 may be H; from aralkyl groups represented by the general following formula (RS-c)
• R 29 , R 30 , R 31 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 , or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals
• R 32 and where two or all of radicals R 29 , R 30 , R 31 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R 32 ;
• R 32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R 29 , R 30 and R 31 is other than H and that at each occurrence at least one of radicals R 29 , R 30 and R 31 is or contains an aromatic ring system having at least 6 aromatic ring atoms;
• R 40 to R 44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 , or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 32 , and where two or more of radicals R 40 to R 44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R 32 as defined above; or
• Ar 50 , Ar 51 stand on each occurrence, identically or differently, for an aromatic or heteroaromatic ring systems having 5 to 40, preferably 5 to 30, more preferably 6 to 18 aromatic ring atoms, which may in each case be sub stituted by one or more radicals R. More preferably, Ar 50 , Ar 51 are selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, anthracene, phenanthrene, triphenylene, fluoranthene, dibenzofuran, carbazole and dibenzothiophene, which may in each case be substituted by one or more radicals R.
• At least one group Ar 50 or Ar 51 is a fluorene, which may be substituted by one or more radicals R. More particularly, it is preferred that at least one group Ar 50 stands for a group of formula (Ar50-2) and/or at least one group Ar 51 stands for a group of formula (Ar51-2), where the dashed bonds in formula (Ar50-2) indicate the bonding to the fluorescent emitter and to a group Ar 50 or Ar 51 ; and the dashed bond in formula (Ar51-2) indicates the bonding to Ar 50 ;
• E 4 is selected from -C(R 0a )2-, -Si(R 0a )2-, -0-, -S- or -N(R 0a )-, preferably - C(R 0a ) 2 ;
• R 0a stands on each occurrence, identically or differently, for H, D, F, CN, a straight-chain alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R; where two adjacent substituents R 0a may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R, which has the same meaning as above; and the groups of formulae (Ar50-2) and (Ar51-2) may be substituted at each free position by a group R, which has the same meaning as above.
• the group RS is preferably located at a position, where it replaces R, R° or R ' .
• fluorescent emitters which may be employed in the composition comprising the compounds of formulae (H1 ) and (H2) are aromatic anthra- cenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines.
• An aromatic anthracenamine is taken to mean a compound in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position.
• An aromatic anthracenediamine is taken to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position.
• Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously thereto, where the diarylamino groups are preferably bonded to the pyrene in the 1 -position or in the 1 ,6-position.
• Further preferred emitters are bridged triarylamines, for example in accordance with WO 2019/111971 , WO201 9/240251 and WO 2020/067290.
• emitters are indenofluorenamines or indenofluorenediamines, for example in accordance with WO 2006/108497 or WO 2006/122630, benzoindenofluorenamines or benzoindenofluorenediamines, for example in accordance with WO 2008/ 006449, and dibenzoindenofluorenamines or dibenzoindenofluorene- diamines, for example in accordance with WO 2007/140847, and the indenofluorene derivatives containing condensed aryl groups which are disclosed in WO 2010/012328.
• Still further preferred emitters are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers connected via heteroaryl groups like in WO 2016/150544 or phenoxazine derivatives as disclosed in WO 2017/028940 and WO 2017/028941.
• Preference is likewise given to the pyrenarylamines disclosed in WO 2012/048780 and WO 2013/185871.
• very suitable fluorescent emitters are the indenofluorene derivatives disclosed in WO 2018/007421 and the dibenzofuran derivatives disclosed in WO 2019/076789.
• the compound of formula (H1 ) and the compound of formula (H2) are present together in the composition, preferably in a homogeneous mixture.
• the compound of formula (H1 ) is present in the composition in a proportion equal to or superior to 1 % by weight of the composition. More preferably, the compound of formula (H1 ) is present in the composition in a proportion of 1 - 99 %, preferably 10 - 95 %, more preferably 20 - 90 %, particularly preferably 30 - 85%, very particularly preferably 40 - 80%.
• the compound of formula (H2) is present in the composition in a proportion equal to or superior to 1 % by weight of the composition. More preferably, the compound of formula (H2) is present in the composition in a proportion of 1 - 99 %, preferably 5 - 90 %, more preferably 10 - 80 %, particularly preferably 15 - 70%, very particularly preferably 20 - 60%.
• the composition according to the invention further comprises at least one fluorescent emitter.
• the fluorescent emitter is present in the composition in a proportion of 0.1 and 50.0%, preferably between 0.5 and 20.0%, particularly preferably between 1.0 and 10.0%.
• the specifications of the proportions in % are, for the purposes of the present application, taken to mean % by vol. if the compounds are applied from the gas phase and % by weight if the compounds are applied from solution.
• formulations of the compositions according to the invention are necessary. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose.
• the solvents are preferably selected from organic and inorganic solvents, more preferably organic solvents.
• the solvents are very preferably selected from hydrocarbons, alcohols, esters, ethers, ketones and amines.
• Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-TFIF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3- phenoxytoluene, (-)-fenchone, 1 ,2,3,5-tetramethylbenzene, 1 ,2,4,5-tetra- methylbenzene, 1-methylnaphthalene, 1-ethylnaphthalene, decylbenzene, phenyl naphthalene, menthyl isovalerate, para tolyl isobutyrate, cyclohexal hexanoate, ethyl para toluate, ethyl ortho toluate, ethyl meta toluate, decahydronaphthalene, ethyl 2-
• the present invention therefore furthermore relates to a formulation com prising a compound formula (H1 ) and a compound of formula (H2) according to the invention and at least one solvent.
• the solvent may be one of the above-mentioned solvents or a mixture of these solvents.
• the proportion of the organic solvent in the formulation according to the invention is preferably at least 60% by weight, preferably at least 70% by weight and more preferably at least 80% by weight, based on the total weight of the formulation.
• a formulation in accordance with the present invention can be employed for the production of a layer or multilayered structure in which the organofunc- tional materials are present in layers, as are required for the production of preferred electronic or opto-electronic components, such as OLEDs.
• the formulation of the present invention can preferably be employed for the formation of a functional layer comprising a composition according to the present invention on a substrate or on one of the layers applied to the substrate.
• Still further object of the invention is a process for the production of an electronic device, wherein at least one layer is obtained from the application of a formulation of the present invention.
• a formulation according to the invention is applied to a substrate or to another layer and then dried.
• the functional layer obtained from the formulation according to the invention can be produced, for example, by flood coating, dip coating, spray coating, spin coating, screen printing, relief printing, gravure printing, rotary printing, roller coating, flexographic printing, offset printing or nozzle printing, preferably ink-jet printing on a substrate or one of the layers applied to the substrate.
• a drying step can be carried out in order to remove the solvent.
• the drying step comprises a vacuum drying, which is preferably followed by an annealing of the layer.
• the vacuum drying here can preferably be carried out at a pressure in the range from 10 7 mbar to 1 bar, particularly preferably in the range from 10 -6 mbar to 1 bar.
• the vacuum drying is preferably carried out at a temperature in the range from 10 to 40°C, more preferably 15 to 30°C.
• the vacuum drying step is preferably followed by a thermal annealing of the layer.
• the thermal annealing of the layer preferably takes places at a temperature of from 120°C to 180°C, preferably from 130°C to 170°C, more preferably 140°C to 160°C.
• the present invention relates to a process for the production of an electronic device comprising at least one layer comprising a composition according to the present invention, wherein the process comprises the following steps: a) Preparation of a formulation according to the invention; b) Application of the formulation prepared in step a) on a substrate or on another layer in order to form a layer comprising a composition according to the present invention; c) Drying of the layer in order to remove the solvent.
• the formulation is applied by processing from a liquid phase, more preferably via a coating method or a printing method, very more preferably by a printing method, particularly preferably by an inkjet printing method.
• Another object of the invention is an electronic device, which comprises anode, cathode and at least one functional layer in between, where this functional layer comprises a composition according to the invention.
• this functional layer comprises a composition according to the invention.
• the at least one functional layer comprising a composition according to the invention is an emitting layer.
• the electronic device is preferably selected from organic electroluminescent device (OLEDs), organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices. More preferably, the electronic device is an organic electroluminescent device (OLED).
• OLEDs organic electroluminescent device
• the organic electroluminescent device comprises a cathode, an anode and at least one emitting layer, which comprises a composition according to the invention. Apart from these layers, it may also comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generation layers. It is likewise possible for interlayers, which have, for example, an exciton-blocking function, to be introduced between two emitting layers. However, it should be pointed out, that each of these layers does not necessarily have to be present.
• the organic electroluminescent device here may comprise one emitting layer or a plurality of emitting layers.
• a plurality of emission layers are present, these preferably have in total a plurality of emission maxima between 380 nm and 750 nm, resulting overall in white emission, i.e. various emitting compounds which are able to fluoresce or phosphoresce are used in the emitting layers.
• various emitting compounds which are able to fluoresce or phosphoresce are used in the emitting layers.
• Particular preference is given to systems having three emitting layers, where the three layers exhibit blue, green and orange or red emission (for the basic structure see, for example, WO 2005/011013).
• These can be fluorescent or phosphorescent emission layers or hybrid systems, in which fluorescent and phosphorescent emission layers are combined with one another.
• the electronic device concerned may comprise a single emitting layer comprising the composition according to the invention or it may comprise two or more emitting layers.
• composition according to the present invention may comprise one or more further matrix materials.
• Preferred further matrix materials are selected from the classes of the oligoarylenes (for example 2,2‘,7,7‘-tetraphenylspirobifluorene in accordance with EP 676461 or dinaphthylanthracene), in particular the oligoarylenes containing condensed aromatic groups, the oligoarylenevinylenes (for example DPVBi orspiro-DPVBi in accordance with EP 676461 ), the polypodal metal complexes (for example in accordance with WO 2004/081017), the hole-conducting compounds (for example in accordance with WO 2004/058911 ), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc.
• the oligoarylenes for example 2,2‘,7,7‘-tetraphenylspirobifluorene in accordance with EP 676461 or dinaphthylanthracene
• Particularly preferred matrix materials are selected from the classes of the oligoarylenes, comprising naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these com pounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides.
• Very particularly preferred matrix materials are selected from the classes of the oligoarylenes, comprising anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds.
• An oligoarylene in the sense of this invention is intended to be taken to mean a compound in which at least three aryl or arylene groups are bonded to one another.
• Suitable charge-transport materials are, for example, the com pounds disclosed in Y. Shirota et al. , Chem. Rev. 2007, 107(4), 953-1010, or other materials as are employed in these layers in accordance with the prior art.
• Materials which can be used for the electron-transport layer are all materials as are used in accordance with the prior art as electron-transport materials in the electron-transport layer. Particularly suitable are aluminium complexes, for example Alq3, zirconium complexes, for example Zrq4, lithium complexes, for example LiQ, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives.
• aluminium complexes for example Alq3, zirconium complexes, for example Zrq4
• lithium complexes for example LiQ
• benzimidazole derivatives triazine derivatives
• pyrimidine derivatives pyridine derivatives
• pyrazine derivatives quinoxaline derivatives
• quinoline derivatives quinoline
• suitable materials are derivatives of the above-mentioned compounds, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.
• Preferred hole-transport materials which can be used in a hole-transport, hole-injection or electron-blocking layer in the electroluminescent device according to the invention are indenofluorenamine derivatives (for example in accordance with WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example in accordance with WO 01/049806), amine derivatives containing condensed aromatic rings (for example in accordance with US 5,061 ,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (for example in accordance with WO 08/006449), dibenzoindenofluorenamines (for example in accordance with WO 07
• the cathode of the organic electroluminescent device preferably comprises metals having a low work function, metal alloys or multilayered structures comprising various metals, such as, for example, alkaline-earth metals, alkali metals, main-group metals or lanthanoids (for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali metal or alkaline- earth metal and silver, for example an alloy comprising magnesium and silver.
• further metals which have a relatively high work function such as, for example, Ag or Al
• lithium quinolinate (LiQ) can be used for this purpose.
• the layer thickness of this layer is preferably between 0.5 and 5 nm.
• the anode preferably comprises materials having a high work function.
• the anode preferably has a work function of greater than 4.5 eV vs. vacuum. Suitable for this purpose are on the one hand metals having a high redox potential, such as, for example, Ag, Pt or Au.
• metal/metal oxide electrodes for example AI/Ni/NiOx, Al/PtOx
• at least one of the electrodes must be transparent or partially transparent in order to facilitate either irradiation of the organic material (organic solar cells) or the coupling-out of light (OLEDs, O-lasers).
• Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers.
• the device is appropriately (depending on the application) structured, pro vided with contacts and finally sealed, since the lifetime of the devices according to the invention is shortened in the presence of water and/or air.
• the organic electroluminescent device according to the invention is characterised in that one or more layers are coated by means of a sublimation process, in which the materials are applied by vapour deposition in vacuum sublimation units at an initial pressure of less than 10 5 mbar, preferably less than 10 6 mbar.
• the initial pressure it is also possible here for the initial pressure to be even lower, for example less than 10 7 mbar.
• an organic electroluminescent device char acterised in that one or more layers are coated by means of the OVPD (organic vapour phase deposition) process or with the aid of carrier-gas sublimation, in which the materials are applied at a pressure of between 10 5 mbar and 1 bar.
• OVPD organic vapour phase deposition
• carrier-gas sublimation in which the materials are applied at a pressure of between 10 5 mbar and 1 bar.
• OVJP organic vapour jet printing
• an organic electroluminescent device characterised in that one or more layers are produced from solution, such as, for example, by spin coating, or by means of any desired printing process, such as, for example, screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or ink-jet printing.
• Soluble compounds of the formula (I) are necessary for this purpose. High solubility can be achieved through suitable substitution of the compounds.
• hybrid processes in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapour deposition.
• the electronic devices comprising one or more compounds according to the invention can be employed in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (for example light therapy).
• the raw material is dissolved in toluene and filtered through a filter plug (silica, toluene) to give a yellow solid, which is further purified by several crystallizations out of toluene/heptane to give a pale yellow solid (HPLC >99.9).
• the remaining solvents are removed by sublimation (10 -5 bar at 330°C).
• Host H2 The syntheses of the hosts of formula (H2) are known to the person skilled in the art and are described, for example, in WO 2009/100925, WO 2018/150832 and KR2018131963. Further syntheses examples are described below: Synthesis of compound H2-1 :
• the precipitate is purified by hot extraction over aluminum oxide (toluene) and further purified by crystallization out of toluene/ethanol and toluene/heptane up to a purity of >99.9 by FIPLC.
• the remaining solvents are removed by tempering at 300 °C at 10-5 bar for 2 hours. Yield: 4.9 g (7.2 mmol, 23%) of a pale yellow solid
• Glass substrates covered with pre-structured ITO (50nm) and bank material are cleaned using ultrasonication in de-ionized water.
• the substrates are dried using an air-gun and subsequently annealed on a hot plate at 230°C for 2 hours.
• a hole-injection layer (H IL) is inkjet-printed onto the substrate with a thickness of 20nm and dried in vacuum.
• the H IL ink has a solid concentration of 6 g/l.
• the H IL is then annealed at 220°C for 30 minutes. Inkjet-printing and annealing of the HIL is carried out in air.
• As the HIL material a hole transporting, cross-linkable polymer and a p-doped salt are dissolved in 3- phenoxy toluene. The materials are described i.e. in WO2016/107668, WO201 3/081052 and EP2325190.
• a hole-transport layer is inkjet-printed under ambient conditions, dried in vacuum and annealed at 225°C for 30 minutes in argon atmosphere.
• the hole-transport layer is either the polymer of the structure shown in Table 1 (HTM1 ), which is synthesized in accordance with W02013156130 or the polymer HTM2 (Table 1 ), which is synthesized in accordance with WO2018/114882.
• the polymer is dissolved in 3-phenoxy toluene, so that the solution typically has a solid content of approx. 5 g/l if, as here, the layer thickness of 20nm which is typical for a device, is to be achieved by means of inkjet printing.
• the emission layer comprises a matrix material (one host compound or two host compounds) and a dopant as described in Table 2 below.
• the mixture for the emission layer is dissolved in 3-phenoxy toluene.
• the solids content of such solutions is about 10 mg/ml if, as here, the layer thickness of 30nm which is typical for a device is to be achieved by means of inkjet-printing.
• the blue emissive layer (B-EML) is also inkjet-printed, then vacuum dried and annealed at 150°C for 10 minutes. Inkjet-printing is done in ambient atmosphere, whereas the annealing is done in argon atmosphere.
• the devices that are prepared according to Figure 4a, are used in order to evaluate the EML film homogeneity.
• ETL1 consists of ETM1 (10nm film thickness)
• ETL2 consists of a 1 :1 volume% mixture of ETM1 and ETM2 (35nm film thickness).
• the electron injection layer consists of ETM2 (1 nm) and the cathode is aluminum (1 OOnm).
• Table 1 The structures are shown in Table 1 .
• the devices After evaporation, the devices are encapsulated in a glovebox in argon atmosphere.
• Table 1 Structures of the materials of the solution processed layers. b) Evaluation of emissive film homogeneity
• the present invention addresses the topic of EML film homogeneity and device performance.
• the first step for the evaluation is thereby the examination of the film homogeneity.
• the stack shown in Figure 4a is used. Processing is stopped after the EML deposition.
• the films are prepared as described in part a).
• the composition of the EML is shown in Table 2a and Table 2b.
• the peak-to-valley difference R p-V which indicates the maximum height difference within the layer (equation 1 ) and the root-mean-squared roughness RMS, in which z t corresponds to the profile height at position i and z to the average profile height (equation 2).
• Example PE1 which comprises a host mixture according to the invention, shows significantly reduced R p-v and RMS values compared to PR1, where only host component 2 is used, and therefore corresponds to a much smoother film ( Figure 1 and 3). Furthermore, while example PE1 exhibits similar R p-v and RMS values as reference PR2, it leads to significantly better OLED performance as shown in Table 5a (DE1 vs. DR1).
• the R p-v and RMS values are significantly lower as for the respective single host EMLs based on host component 1 (PE2 vs. PR4, PE3 vs. PR6, PE4 and PE5 vs.
• the electroluminescence spectra, current/voltage/luminous density characteristic curves (IUL characteristic curves) assuming Lambert emission characteristics and the (operating) lifetime are recorded.
• the IUL characteristic curves are used to determine characteristic figures of merit such as external quantum efficiency (in %) at a certain luminance.
• the devices are driven with constant voltages at each step of an applied voltage ramp.
• the device lifetime is measured under a given current corresponding to an initial luminance.
• the luminance is then measured over time by a calibrated photodiode.
• Table 5a Blue EML mixtures to use for device examples with 1% E2
• Table 5b Blue EML mixtures to use for device examples with 5% E4
• the present invention i.e. a mixed host EML
• a smooth film with good homogeneity and a good device performance EQE and LT
• Table 6b Blue EML mixtures to use for device examples with 1% E1
• Table 6c Blue EML mixtures to use for device examples with 3% E1

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• 2022
  • 2022-04-06 EP EP22720999.6A patent/EP4320649A1/de not_active Withdrawn
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